Metal oxides doped with precious metal nanoparticles, and methods and applications for producing precious metal nanoparticles.

Abstract

This invention employs an Al-rich or Zn-rich intermetallic compound containing a doped noble metal element as a precursor, and reacts the intermetallic compound containing the doped noble metal element with the base solution at atmospheric pressure near the boiling point of the base solution, thereby achieving high-efficiency atmospheric-pressure production of nanometal oxides doped with noble metal nanoparticles of different crystalline properties. Simultaneously, a method for producing noble metal nanoparticles based on the nanometal oxides doped with noble metal nanoparticles is also provided. The production method of this invention is characterized by a simple process, easy operation, high efficiency, and low cost, and the produced products can be used in a wide range of applications, such as composite materials, catalyst materials, ceramic materials, refractory materials, advanced electronic materials, battery materials, discoloration materials, wave-absorbing materials, wastewater decomposition materials, sterilization materials, paints, pigments, thermal spray materials, and sensors.

Description

[Technical Field]

[0001] The present invention relates to the technology of nanomaterials, and more particularly to metal oxides doped with noble metal nanoparticles, methods for producing noble metal nanoparticles, and the use of the same. [Background technology]

[0002] Currently, conventional methods for producing metal nanooxides doped with precious metal nanoparticles primarily employ a strategy of first producing nanometal oxides and then mixing them with precious metal nanoparticles produced by other methods to dope them. In materials produced through such a two-step process, the doped precious metal nanoparticles adhere to the nanometal oxide matrix mainly by physicoadsorption. Furthermore, this mechanical mixing and physicoadsorption method is not only unfavorable for atomic-scale physicochemical interactions between the doped precious metal elements and the nanometal oxide particle matrix, but also easily leads to the detachment and separation of the doped precious metal nanoparticles from the nanometal oxide particle matrix, resulting in unstable material properties and degradation. In addition, conventional manufacturing methods have limitations on the particle size of the precious metal nanoparticles that can be produced, so the precious metal nanoparticles that can be produced generally have large particle sizes, making it difficult to produce dispersed precious metal nanoparticles with particle sizes of 10 nm or less and to physically mix them with nanometal oxides. Moreover, conventional manufacturing methods cannot obtain nanometal oxides doped with ultrafine precious metal nanoparticles or precious metal atoms / atomic clusters, nor can they improve the thermal stability of the nanometal oxide matrix through embedding doping. Therefore, the development of a new method for producing nanometal oxides doped with ultrafine precious metal nanoparticles that is rapid, efficient, under mild conditions, and suitable for large-scale production is of great positive significance.

[0003] Precious metal nanoparticles exhibit many unique properties in optics, electricity, magnetism, and catalysis that differ from conventional materials due to their special surface effects, quantum size effects, quantum tunneling effects, and Coulomb blocking effects. Therefore, they are widely used in fields such as optoelectronic devices, wave-absorbing materials, and high-efficiency catalysts. Currently, methods for manufacturing precious metal nanoparticles are classified into solid-phase, liquid-phase, and gas-phase methods depending on the state of the material. Solid-phase methods mainly include mechanical grinding, ultrasonic grinding, thermal decomposition, and explosive methods. Liquid-phase methods mainly include precipitation, alcohol salt methods, carbonyl methods, spray heating and drying, freeze-drying, electrolysis, and chemical coagulation. Gas-phase methods mainly include gas-phase reaction methods, plasma methods, high-temperature plasma methods, evaporation, and chemical vapor deposition. While there are many methods for manufacturing precious metal nanoparticles, each has its limitations, and large-scale mass production is particularly difficult. Therefore, developing new manufacturing methods for precious metal nanoparticles that enable large-scale production is equally important. [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] Based on this, there is a need to provide a method for producing nanometal oxides doped with precious metal nanoparticles that is simple in process, has a rapid and efficient reaction, operates under mild conditions, and is suitable for large-scale production, in order to address the above technical challenges. Furthermore, there is a need to provide a method for producing precious metal nanoparticles based on this method. [Means for solving the problem]

[0005] The present invention comprises, in order, the following embodiments:

[0006] In a first embodiment, a method for producing nanometal oxides doped with noble metal nanoparticles, characterized by comprising the following manufacturing steps:

[0007] Step 1: Provide an initial alloy, the initial alloy comprising M, T, and A component elements, where the M element comprises at least one of Cr, V, Nb, Ta, W, Mo, Mn, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; the T element comprises at least one of Al and Zn; and the A element mainly consists of noble metal elements comprising at least one of Au, Pt, Pd, Ru, Rh, Os, Ir, Re, Ag, and Cu; the solidification structure of the initial alloy mainly comprises an MTA intermetallic compound, or / or an MT(A) intermetallic compound in which the A component elements are solid-solved; and the composition of the initial alloy is mainly A x T y M z Here, x, y, and z are the atomic percentage content of the corresponding elements, and 0 <x≦15%、40%≦y<95%、5%≦z<60%である。

[0008] Step 2: The initial alloy is subjected to a hydrogen deposition and de-T reaction with a base solution. By controlling the temperature and concentration of the base solution, the reaction interface moves inward from the surface of the initial alloy at an average rate exceeding 2 μm / min. During the reaction, the initial alloy undergoes nanofragmentation through the hydrogen deposition and de-T reaction, and through the reconstruction of its shape and composition, it generates M-containing solid products having at least one dimension of 500 nm or less in the three-dimensional direction. Simultaneously with the hydrogen deposition and de-T reaction, A element atoms in the original initial alloy intermetallic compound are rearranged by diffusion to form A-containing nanoparticles.

[0009] Step 3: After the hydrogen deposition and de-T reaction is completed, the solid product in the reaction system is collected to obtain nanooxide M doped with A-containing nanoparticles, the nanooxide M consisting of A-containing nanoparticles and a nanooxide M matrix, where the A-containing nanoparticles include at least one of A nanoparticles and nanooxide A particles, and the particle size range of the A-containing nanoparticles is 0.25 nm to 100 nm, the nanooxide M matrix includes at least one of low-crystalline nanooxide M, crystalline nanooxide M, and hydrated nanooxide M, where hydrated nanooxide M specifically refers to nanohydroxylated M, and the nanooxide M matrix has a shape in which the scale of at least one dimension in the three-dimensional direction is 500 nm or less.

[0010] In step 1 above,

[0011] Furthermore, the above-mentioned M element includes at least one of Cr, V, Nb, Ta, W, Mo, Mn, Y, and Gd.

[0012] Furthermore, the above M includes Cr, M includes V, M includes Nb, M includes Ta, M includes W, M includes Mo, and M includes Mn.

[0013] Furthermore, the above-mentioned M element includes at least one of Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.

[0014] Furthermore, the above element T contains Al, and furthermore, element T is Al.

[0015] Furthermore, the above element T contains Zn, and furthermore, element T is Zn.

[0016] Note: Regardless of the type of precious metal element, the types of precious metal elements in this invention include Au, Pt, Pd, Ru, Rh, Os, Ir, Re, Ag, and Cu.

[0017] Furthermore, the above element A includes at least one of Au, Pt, Pd, Ru, Rh, Os, Ir, Re, and Ag.

[0018] Furthermore, the above element A includes at least one of Au, Pt, Pd, Ru, Rh, Os, Ir, and Re.

[0019] Furthermore, 0.01% ≤ x ≤ 12%, and furthermore, 0.1% ≤ x ≤ 10%, and furthermore, 0.3% ≤ x ≤ 8%.

[0020] Furthermore, 45% ≤ y ≤ 94.5%, furthermore, 45% ≤ y ≤ 81%, furthermore, 45% ≤ y ≤ 76%, and furthermore, 49% ≤ y ≤ 76.

[0021] Furthermore, 5% ≤ z ≤ 54.5%, 19% ≤ z ≤ 54.5%, 24% ≤ z ≤ 54.5%, and 24% ≤ z ≤ 50%.

[0022] Furthermore, x <zである。

[0023] Furthermore, the initial alloy is produced by solidifying an alloy molten material containing three elements: A, T, and M. During the solidification process of the alloy, a solidification structure is formed mainly consisting of MTA intermetallic compounds, and / or MT(A) intermetallic compounds in which element A is dissolved.

[0024] Furthermore, the solidification rate of the initial alloy molten material is 0.01 K / s ~ 10 8 It is K / s.

[0025] Furthermore, the solidification rate of the initial alloy molten material is 1K / s~10 8 It is K / s.

[0026] Furthermore, when the A content is low, element A generally exists as a solid solution in the MT(A) intermetallic compound, where the MT(A) intermetallic compound has almost the same crystal structure as the MT intermetallic compound except that element A is in solid solution, and the solid solution form includes at least one of interstitial solid solution and substitutional solid solution.

[0027] Furthermore, the MT(A) intermetallic compound in which element A is in solid solution means that element A exists in the interstitial gaps of the MT(A) intermetallic compound in the form of interstitial atoms, or that element A substitutes for the M or T atomic positions in the lattice of the MT(A) intermetallic compound in the form of substitution atoms.

[0028] Furthermore, the above-mentioned MT(A) intermetallic compound is defined as having the phase composition of the intermetallic compound as the MT(A) intermetallic compound phase, that is, the XRD physical phase analysis results of the above-mentioned MT(A) intermetallic compound are essentially the same as the XRD physical phase analysis results of the MT intermetallic compound (solid solution atoms do not affect the change in the properties of the phase structure), and the main stoichiometric relationships of the MT intermetallic compound phase are MT4, MT3, and M4T. 11 This means including at least one of MT2, M5T8, M3T8, M2T3, and MT.

[0029] Furthermore, the above MT(A) intermetallic compound may be a single-phase compound such as an NbAl3 or (Nb-Ta)Al3 intermetallic compound in which Au is dissolved, or it may be a multiphase intermetallic compound composed of different M subelements and T elements, such as a composite multiphase intermetallic compound consisting of TaAl3 and YAl3 in which Au is dissolved.

[0030] Furthermore, when the A content is high, in addition to solid-solubilizing in the MT(A) intermetallic compound, the A element may also form an MTA intermetallic compound with a crystal structure completely different from that of the MT(A) intermetallic compound.

[0031] Whether element A exists as a solid solution in the MT(A) intermetallic compound or directly in the MTA intermetallic compound, element A atoms are dispersed in the corresponding intermetallic compound; that is, the corresponding intermetallic compound does not contain a phase or aggregates of element A that are mainly composed of element A.

[0032] Preferably, the initial alloy does not contain the T phase. The T phase is, that is, a phase mainly composed of the T element.

[0033] Furthermore, the shape of the initial alloy described above has an average size greater than 4 μm in any of the three dimensions.

[0034] Furthermore, the shape of the initial alloy described above has an average size greater than 10 μm in any of the three dimensions.

[0035] Furthermore, the shape of the initial alloy described above has an average size greater than 15 μm in any of the three dimensions.

[0036] Furthermore, the shape of the initial alloy described above includes at least one of granular, filamentous, strip-like, ribbon-like, and sheet-like forms.

[0037] Furthermore, if the initial alloy is in the form of a ribbon, it can be manufactured by a method including molten strip casting.

[0038] Furthermore, if the initial alloy is granular, a larger initial alloy ingot can be produced by casting, and then crushed to obtain initial alloy particles or powder.

[0039] In step 2 described above,

[0040] Furthermore, the above base solution includes at least one of the following solutions: NaOH, KOH, LiOH, RbOH, CsOH, Ba(OH)2, Ca(OH)2, and Sr(OH)2.

[0041] Furthermore, the solvent of the above-mentioned base solution contains water, and preferably, the solvent of the above-mentioned base solution is water.

[0042] Furthermore, the concentration of the base in the above base solution is 3 to 30 mol / L, more preferably 5.1 to 30 mol / L, more preferably 5.1 to 15 mol / L, and even more preferably 7 to 15 mol / L.

[0043] Furthermore, the amount of base in the base solution reacting with the initial alloy is in excess, and the volume of the base solution is more than five times the volume of the initial alloy, allowing the reaction to proceed at a higher base concentration at all times.

[0044] Furthermore, the volume of the above-mentioned base solution is more than 10 times the volume of the initial alloy.

[0045] Furthermore, the volume of the above-mentioned base solution is more than 20 times the volume of the initial alloy.

[0046] Furthermore, the temperature of the base solution is the reaction temperature between the initial alloy and the base solution.

[0047] Furthermore, under specific base concentration conditions, the temperature T1 of the base solution should be such that the reaction interface in the hydrogen deposition / de-T reaction step progresses from the initial alloy surface to the interior at an average rate of 2 μm / min or more, and that the reaction process ensures the initial alloy is nano-fragmented through the hydrogen deposition / de-T reaction. In other words, the temperature T1 and concentration of the base solution are determined by the hydrogen deposition / de-T reaction rate or the hydrogen deposition / de-T reaction time (the reaction time is determined by determining the reaction rate and the initial alloy size, and the hydrogen deposition / de-T reaction time is the time required for the reaction to proceed until a gas that cannot be seen with the naked eye is generated), and the reaction effect. Therefore, when limiting the reaction conditions using the reaction rate value, the temperature T1 and concentration range of the base solution are also indirectly limited.

[0048] Furthermore, an average rate of 2 μm / min is the critical reaction rate at which the initial alloy undergoes nanofragmentation due to hydrogen deposition and de-T reactions during the reaction process.

[0049] Furthermore, the occurrence of the above nano-fragmentation refers to the fragmentation of the initial alloy into a single intermediate or product having at least one dimension less than 500 nm in the three-dimensional direction, through hydrogen deposition and de-T reactions.

[0050] Furthermore, the occurrence of the above nano-fragmentation refers to the fragmentation of the initial alloy into a single intermediate or product having at least one dimension less than 250 nm in the three-dimensional direction, through hydrogen deposition and de-T reactions.

[0051] Furthermore, the temperature of the above base solution is T1, and T1 ≥ 60°C.

[0052] Furthermore, if M in the initial alloy consists mainly of one or more elements from Cr, V, Nb, Ta, W, Mo, and Mn, then T1 ≥ 60°C.

[0053] Furthermore, if M in the initial alloy consists mainly of one or more elements from Cr, V, Nb, Ta, W, and Mo, then T1 ≥ 60°C.

[0054] Furthermore, if the initial alloy contains one or more elements from among Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu as its main component, then T1 > 100°C.

[0055] Furthermore, if M in the above initial alloy contains one of Cr, V, Nb, Ta, W, Mo, Mn, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and T contains Zn, then T1 ≥ 60°C.

[0056] Furthermore, if M in the above initial alloy contains one of Cr, V, Nb, Ta, W, Mo, Mn, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and T contains at least one of Al and Zn, then T1 > 100°C.

[0057] Furthermore, the reaction between the initial alloy and the base solution is carried out at atmospheric pressure or high pressure.

[0058] Furthermore, the reaction between the initial alloy and the base solution is carried out in a sealed container.

[0059] In a sealed container, when the pressure inside the container exceeds 1 atm, it becomes a high pressure. At the same time, if the gas generated by the reaction inside the container cannot be discharged, it may become an even higher pressure.

[0060] Furthermore, when performing a reaction in a sealed container, first, the initial alloy and the base solution are separately placed inside the sealed container. When the temperature of the base solution reaches the set reaction temperature, the initial alloy and the base solution are brought into contact to carry out the reaction.

[0061] Furthermore, inside the sealed container, the temperature of the base solution may exceed the boiling point temperature at normal pressure.

[0062] Furthermore, 100 °C < T1 ≤ T f溶液 where the reaction between the initial alloy and the hot base solution is carried out at normal pressure. Here, T f溶液 is the boiling point temperature of the base solution involved in the reaction under normal pressure.

[0063] Furthermore, the above normal pressure refers to the atmospheric pressure when not using a sealed container.

[0064] Furthermore, the above reaction is carried out under a normal pressure environment. Normal pressure generally refers to 1 standard atmosphere, and the boiling point of water at this time corresponds to 100 °C. When a base is dissolved in water, the boiling point temperature of the aqueous base solution at 1 standard atmosphere is higher than 100 °C, and the higher the concentration of the base, the higher the boiling point. For example, the boiling point Tf溶液 of a sodium hydroxide aqueous solution with a molar concentration of 5 mol / L is about 108 °C, and the boiling point Tf溶液 of a sodium hydroxide aqueous solution with a molar concentration of 7 mol / L is about 11២C, and the boiling point Tf溶液 of a sodium hydroxide aqueous solution with a molar concentration of 10 mol / L is about 119 °C, and the boiling point Tf溶液 of a sodium hydroxide aqueous solution with a molar concentration of 12 mol / L is about 128 °C, and the boiling point Tf溶液 of a sodium hydroxide aqueous solution with a molar concentration of 15 mol / L is about 14២C, and the boiling point Tf溶液 of a sodium hydroxide aqueous solution with a molar concentration of 17 mol / L is about 148 °C, and the boiling point Tf溶液It is approximately 160°C, and is the boiling point of a 25 mol / L sodium hydroxide aqueous solution. Tf溶液 It is approximately 180°C, and is the boiling point of a 10 mol / L potassium hydroxide aqueous solution. Tf溶液 It is approximately 125°C, and the boiling point of a 12 mol / L potassium hydroxide aqueous solution. Tf溶液 It is approximately 136°C, and is the boiling point of a 15 mol / L potassium hydroxide aqueous solution. Tf溶液 The temperature is approximately 150°C.

[0065] Furthermore, 101℃≦T1≦T f溶液 Furthermore, 105℃≦T1≦T f溶液 That is the case.

[0066] Furthermore, 101℃≦T f溶液 -5℃≦T1≦T f溶液 Furthermore, 101℃≦T f溶液 -2℃≦T1≦T f溶液 That is the case.

[0067] More preferably, the temperature of the base solution is T f溶液 Therefore, T1 = T f溶液 That is the case.

[0068] The reaction solution can be heated to its boiling point (T) at the highest temperature it can reach under normal pressure. f溶液 Therefore, once that temperature is reached, further heating will not raise the temperature of the solution. Further heating will only cause it to boil. Instead, to raise the reaction temperature, a higher boiling point can be obtained by increasing the concentration of the base solution. Thus, the boiling point is the easiest, simplest, and most precise temperature to control. Furthermore, the reaction time required for a reaction at the boiling point at the same concentration is shorter than the reaction time required for reactions at other temperatures below the boiling point.

[0069] During the reaction between the initial alloy and the base solution, the MTA intermetallic compound, or / or the MT(A) intermetallic compound in the initial alloy, undergoes nanofragmentation through vigorous hydrogen deposition and de-T reactions, and further undergoes reconstruction of its shape and composition, generating M-containing solid products on a nanoscale. In this process, the T element (Al, Zn), being an amphoteric metal, reacts with the high-temperature concentrated base solution to form a salt, which then dissolves in the base solution.

[0070] Furthermore, a characteristic of the hydrogen deposition and de-T reaction is that the T element in the initial alloy dissolves in the solution, and hydrogen is deposited simultaneously.

[0071] During the hydrogen deposition and de-T reaction, element A atoms in the original initial alloy metal compound evolve primarily into A-containing nanoparticles through diffusion dislocations. Simultaneously, the generated M-containing solid product binds to the A-containing nanoparticles, enabling a one-step in-situ doping of the M-containing solid product with A-containing nanoparticles. Furthermore, in the reaction step of step 2, while the T element dissolves in the base solution, the initial alloy undergoes nanofragmentation by a vigorous hydrogen deposition-de-T reaction, undergoing reconstruction of its shape and composition to produce an M-containing solid product in which at least one dimension in the three-dimensional direction does not exceed 500 nm.

[0072] Furthermore, the intensity of the hydrogen deposition and de-T reaction is related to the rate at which the reaction interface advances from the initial alloy surface to the interior per unit time. The higher the base concentration and the higher the temperature of the base solution, the faster the reaction interface advances, and the more vigorous the reaction becomes.

[0073] Furthermore, ultrasound is applied during the hydrogen deposition and de-T reaction described above, and the sonication further enhances the nano-fragmentation effect and reaction rate.

[0074] Furthermore, the above ultrasound is 20kHz~10 6 It has a frequency of kHz.

[0075] For example, when the NaOH concentration is 10 mol / L, during the reaction between the initial alloy mainly composed of the intermetallic compound Al3Nb(Au) with dissolved Au and the base solution, the hydrogen evolution and de-T reaction interface advances from the surface of the initial alloy towards the inside at the following rate:

[0076] When 60°C ≤ T1 ≤ 80°C, the average advancing rate of the above reaction interface is about 2 μm / min to 7 μm / min.

[0077] When 80°C ≤ T1 ≤ 90°C, the average advancing rate of the above reaction interface is about 7 μm / min to 15 μm / min.

[0078] When 90°C < T1 ≤ 100°C, the average advancing rate of the above reaction interface is about 15 μm / min to 30 μm / min.

[0079] When 100°C < T1 ≤ 110°C, the average advancing rate of the above reaction interface is about 30 μm / min to 50 μm / min.

[0080] When 110°C < T1 < 119°C, the average advancing rate of the above reaction interface is about 50 μm / min to 120 μm / min.

[0081] T1 = T f溶液 In this case, the average advancing rate of the above reaction interface exceeds 120 μm / min.

[0082] Furthermore, during the above reaction, the reaction interface advances from the surface of the initial alloy towards the inside at an average rate of 7 μm / min or more.

[0083] Furthermore, the above reaction interface advances from the surface of the initial alloy towards the inside at an average rate of 15 μm / min or more.

[0084] Furthermore, the above reaction interface advances from the surface of the initial alloy towards the inside at an average rate of 30 μm / min or more.

[0085] Furthermore, under specific base concentration conditions, the temperature of the base solution should be such that the reaction interface in the hydrogen deposition / de-T reaction process progresses from the initial alloy surface to the interior at an average rate of 2 μm / min or more, and that the reaction process nano-fragments the initial alloy through the hydrogen deposition / de-T reaction. Therefore, under different initial alloy conditions or base solution conditions, if the reaction interface during the hydrogen deposition / de-T reaction progresses at a rate of 2 μm / min or more, the required reaction solution temperature may be lower than 60°C, and especially when sonication is supplemented, the required reaction solution temperature may be even lower.

[0086] Furthermore, the occurrence of the above-mentioned nanofragmentation means that, through hydrogen deposition and de-T reactions, the initial alloy at the reaction interface is fragmented into nanoscale intermediates and products, while at the same time, nanoscale M-containing solid products are generated through the reconstruction of their shape and composition. In this process, the vigorous release of hydrogen due to the hydrogen deposition and de-T reactions promotes the nanofragmentation of intermediates and products, as well as the diffusion distribution of the products in the base solution after they leave the reaction interface.

[0087] Furthermore, the occurrence of nanofragmentation means that the size of the M-containing solid product is smaller than the size of the initial alloy before the occurrence of nanofragmentation.

[0088] Furthermore, the above-mentioned shape reconstruction means that the nanoscale M-containing solid product obtained from the hydrogen deposition-detox reaction is not simply a physical fragment of a nanoporous structure (ligament), but undergoes shape changes in addition to being a physical fragment.

[0089] Furthermore, the above-mentioned M-containing solid product has particle dispersibility.

[0090] Furthermore, different valence states of M in the above nano-oxidized M correspond to different nano-oxidized M. For example, the oxidized Mn can be MnO or MnO2.

[0091] Furthermore, the size of the M-containing solid product is less than 0.25 times the size of the initial alloy before the occurrence of nanofragmentation.

[0092] Furthermore, the size of the M-containing solid product is less than 0.05 times the size of the initial alloy before the occurrence of nanofragmentation.

[0093] Furthermore, the occurrence of the above nano-fragmentation means that the initial alloy in the reaction process is fragmented into intermediates or products with at least one dimension in the three-dimensional direction less than 500 nm by hydrogen deposition and de-T reaction.

[0094] Furthermore, the shape of the M-containing solid product described above has at least one dimension in the three-dimensional direction that is less than 500 nm.

[0095] Furthermore, the shape of the M-containing solid product described above has at least one dimension in the three-dimensional direction that is less than 250 nm.

[0096] Furthermore, the shape of the M-containing solid product described above has at least one dimension in the three-dimensional direction that is less than 150 nm. Furthermore, the shape of the M-containing solid product includes at least one of the following: film-like, granular, plate-like, ribbon-like, tubular, and aggregated, where aggregated refers to a state in which extremely fine microstructures with inconspicuous edges are aggregated.

[0097] Furthermore, even though the M-containing solid products are softly aggregated with each other, they are not firmly bound together by a three-dimensional continuous rigid reticular structure, and maintain the shape of the original initial alloy.

[0098] Furthermore, the shape of the M-containing solid product is completely different from that of the initial alloy, and its particle size is clearly fragmented and smaller.

[0099] Furthermore, if the M-containing solid product is mainly in the form of a film, its thickness is 0.25 nm to 30 nm, and the average area of ​​the film is 100 nm. 2 Larger.

[0100] Furthermore, if the M-containing solid product is mainly granular, its particle size range is 1.5 nm to 500 nm, preferably 1.5 nm to 200 nm, and preferably 1.5 nm to 100 nm.

[0101] Furthermore, when the above-mentioned M-containing solid product is mainly in the form of a plate, its thickness is 1.5 nm to 100 nm, preferably 5 nm to 30 nm, more preferably 5 nm to 20 nm, and the average area of ​​the plate is 100 nm. 2 Larger.

[0102] Furthermore, if the M-containing solid product is mainly in the form of aggregates, the size of the microstructure of these aggregates is between 0.25 nm and 15 nm.

[0103] Furthermore, if the M-containing solid product is mainly tubular or rod-shaped, it includes tubular or rod-shaped forms, and its diameter is in the range of 2 nm to 200 nm, more preferably in the range of 2 nm to 50 nm, and its aspect ratio is greater than 2. When the aspect ratio is extremely large, the tubular or rod-shaped form can be considered fibrous.

[0104] Furthermore, the above-mentioned M-containing solid product includes at least one of low-crystalline nanooxide M, crystalline nanooxide M, and hydrated nanooxide M.

[0105] Furthermore, the above-mentioned low-crystalline nanooxide M includes amorphous nanooxide M.

[0106] Since nanooxide M can be considered as a composite of nanooxide M and H2O, nanooxide M can be obtained by heating and dehydrating at a relatively low temperature. Therefore, hydrated nanooxide M is nanooxide M.

[0107] Furthermore, the above nanooxide M may be a single nanooxide M, or it may be a composite nanooxide M composed of different M subelements, such as a composite nanometal oxide consisting of oxide Y and oxide Ta (both Y and Ta are subelements of element M).

[0108] Furthermore, the degree of nanofragmentation and shape reconstruction described above are related to the temperature of the base solution; the higher the temperature of the base solution, the greater the degree of fragmentation and the smaller the particle size of the M-containing solid product.

[0109] Furthermore, if the degree of nanofragmentation needs to be increased, it can be supplemented with ultrasonic treatment.

[0110] Furthermore, when the temperature is 60°C ≤ T1 ≤ 100°C, the degree of nano-fragmentation and shape reconstruction is high, and the degree of fragmentation and shape reconstruction increases as the temperature increases.

[0111] Furthermore, 100℃ <T1<T f溶液 In this case, the degree of nano-fragmentation and shape reconstruction is very high, and essentially complete fragmentation can be achieved.

[0112] Preferably, T1 = T f溶液 In this case, the degree of nano-fragmentation and shape reconstruction is highest and most complete. This is because gas expansion due to the nucleation and growth of a large amount of boiling gas on the solid product at the boiling temperature greatly accelerates the fragmentation and shape reconstruction process.

[0113] Furthermore, the nanoscale M-containing solid products generated by the reconstruction of shape and composition during the reaction process do not remain at the original initial alloy reaction interface, but rather diffuse further into the base solution through diffusion and convection of the base solution as they are formed.

[0114] Furthermore, the reconstruction of the shape and composition described above means that the product obtained after the hydrogen deposition and de-T reaction of the initial alloy and nano-fragmentation undergoes a dramatic change in shape and composition, resulting in a nanoscale M-containing solid product with a composition and shape completely different from the initial alloy on a micron or millimeter scale, and which is significantly fragmented.

[0115] Furthermore, the shape of the generated nanoscale M-containing solid product is not primarily a three-dimensional continuous network nanoporous structure or a porous skeletal structure.

[0116] Furthermore, the three-dimensional continuous network nanoporous structure or porous framework structure refers to a nanoporous structure or porous framework structure obtained by a general dealloying reaction, in which the three-dimensional continuous network porous band has rigidity in the three-dimensional direction, and its shape remains unchanged under the action of gravity or surface tension. Although it is not ruled out that aggregates formed by the aggregation of M-containing solid product particles manufactured in this application without heat treatment and sintering may have similar properties to the nanoporous structure or porous framework structure under TEM or SEM observation, the soft aggregate connections between particles lack rigidity, the shape of the aggregate is variable under the action of gravity or surface tension, and it can also be dispersed by dispersion.

[0117] Furthermore, the above hydrogen deposition and de-T reaction converts the initial alloy, which is on a micron or millimeter scale, into a large number of nanoscale M-containing solid products through a stepwise nano-fragmentation and shape reconstruction process from the surface inward.

[0118] Furthermore, the reaction of the initial alloy with the high-temperature base solution, especially when T1 > 100°C, is crucial for the production of nanoscale M-containing nanosolid products with fine morphology. In Comparative Example 1, an initial alloy powder mainly composed of an Al3Nb(Au) intermetallic compound in which Au is dissolved was reacted with a 10 mol / L NaOH solution at 25°C for 2 hours under atmospheric pressure (average propulsion speed at the reaction interface was 0.5 μm / min or less). The shape of the original initial alloy powder remained almost unchanged before and after the reaction, remaining as the original fragmented, angular powdery particles of micron size. Moreover, at lower reaction temperatures, the microstructure is mainly fragmented at the nanoscale, and instead of producing M-containing solid products with a structurally reconstructed structure, it generates a microscopically rigid nanoporous structure. A nanoporous structure is produced that remains rigid in the microstructure. This nanoporous structure forms an appearance that matches the shape of the original alloy powder, including its angular shape, through a three-dimensional network structure, and its particle size is still equivalent to that of the original alloy powder, mainly on the micrometer scale. Therefore, the reaction between the initial alloy and the base solution occurring at lower temperatures near room temperature is completely different from the reaction of the present invention, and the morphology of the product is also completely different.

[0119] In particular, the reaction takes place at atmospheric pressure, preferably at the boiling point temperature T of the base solution. f溶液 When this occurs, the solution composition of the reaction system undergoes a distinctly special change, which manifests as follows: in the temperature range below the boiling point of the base solution, the solvent exists mainly as liquid water; however, at or near the boiling point of the base solution, the solvent contains not only liquid water and gaseous water produced by boiling, but also critical water in which the transition from liquid water to gaseous water is underway. Furthermore, according to the principle of heterogeneous nucleation, the presence of reactants in the solution and pre-formed nanoscale reaction products provides numerous boiling and evaporating particles, placing the reaction system entirely in a special environment of boiling and evaporation. In this special environment, the content and state of dissolved atmospheric gases (oxygen, nitrogen) in the water are also extremely special (because the large amount of hydrogen produced in the reaction of T and the base changes the saturation partial pressure conditions of the dissolved gases in the water). Specifically, the reaction of MTA or MT(A) intermetallic compounds with a high-temperature base solution generates a large amount of hydrogen during the process of removing T from the alloy. This rapidly generated hydrogen gas, along with the large amount of water vapor produced by heterogeneous nucleated boiling evaporation, acts on the hydrogen deposition / T removal reaction interface. The resulting intense expansion effect further accelerates the continuous nano-fragmentation and shape and composition reconstruction process of the initial alloy at the reaction interface. Additionally, T salts dissolved in the base solution also alter the material composition of the reaction solution system. Many of these properties of the solution at its boiling point provide a very specific reaction environment. Under this specific reaction environment, a special reaction process occurs, and the initial alloy undergoes efficient nano-fragmentation and shape / composition reconstruction through the hydrogen deposition / T removal reaction. Therefore, it becomes difficult to stabilize the three-dimensional network continuous nanoporous structure generally produced by de-alloying reactions at low temperatures or room temperature. Instead, a special nano-fragmentation process and shape / composition reconstruction process produce nanoscale fragmented M-containing solid products. Furthermore, because the boiling point of a specific base solution is constant, temperature control can be performed with extreme precision, making it extremely easy and precise to control the form and composition of the product.

[0120] Furthermore, while a solid product containing M is generated by the hydrogen deposition and de-T reaction, the element A atoms in the original initial alloy metal compound undergo diffusion dislocations to mainly generate A-containing nanoparticles. Simultaneously, the generated M-containing solid product binds to the A-containing nanoparticles, thereby achieving a one-step in-situ doping of the M-containing solid product with A-containing nanoparticles.

[0121] Furthermore, the composition of the A-containing nanoparticles includes at least one of Au, Pt, Pd, Ru, Rh, Os, Ir, Re, Ag, and Cu.

[0122] Furthermore, if the element A in the A-containing nanoparticles is mainly composed of at least one of Ag and Cu, then the A-containing nanoparticles include at least one of Ag nanoparticles, silver oxide nanoparticles, Cu nanoparticles, and copper oxide nanoparticles.

[0123] Since Cu and Ag have relatively weak oxidation resistance among precious metals, if the element A in A-containing nanoparticles is mainly composed of at least one of Ag and Cu, then at least one of Ag nanoparticles, Cu nanoparticles, silver oxide nanoparticles, or copper oxide nanoparticles may also be included. If the element A in A-containing nanoparticles consists only of small amounts of Ag and Cu, then Ag and Cu are generally dissolved in A nanoparticles made of other inert elements, and in this case, the dissolved Ag and Cu are not easily oxidized.

[0124] Furthermore, the composition of the A-containing nanoparticles described above includes at least one of Au, Pt, Pd, Ru, Rh, Os, Ir, and Re.

[0125] Furthermore, the A-containing nanoparticles include at least one of A nanoparticles and nano-oxidized A particles. If an A-containing nanoparticle does not contain nano-oxidized A particles, then the A-containing nanoparticle is an A nanoparticle.

[0126] Furthermore, the method for doping the A-containing nanoparticles into the M-containing solid product includes at least one of an in-situ embedding method and a physicoadsorption method.

[0127] Furthermore, the method of doping the above A-containing nanoparticles into the M-containing solid product includes in-situ embedding doping.

[0128] Furthermore, the method of doping the above A-containing nanoparticles into the M-containing solid product mainly includes in-situ embedding doping.

[0129] Furthermore, 0 < x ≤ 15%. When the content of x is low, the doping mode of A-containing nanoparticles into the M-containing solid product is mainly in-situ embedding. When the content of x is high, the doping mode of A-containing nanoparticles into the M-containing solid product includes in-situ embedding and physical adsorption. However, due to the different types and ratios of M, T, and A elements, the critical value of x for the start of physical adsorption is also different. For example, when an Al 78 Cr 19 Ag3 alloy is used as the raw material, with x = 3%, the doping of the M-containing solid product by Ag-containing nanoparticles is still mainly in-situ embedding, and when an Al 77 Cr 18 Ag5 alloy is used as the raw material and x = 5%, the doping mode of Ag-containing nanoparticles into the M-containing solid product includes both in-situ embedding and physical adsorption. When an Al 79 Cr 19.5 Au 1.5 alloy is used as the raw material and x = 1.5%, the doping mode of Au-containing nanoparticles into the M-containing solid product includes both in-situ embedding and physical adsorption. In the present invention, it has been found that the A element existing in solid solution in the M-T(A) intermetallic compound or the A element atoms existing in the M-T-A intermetallic compound mainly change into A-containing substantially spherical nanoparticles during hydrogen precipitation and de-T reaction. And the A-containing nanoparticles generated after this change are generally doped into the M-containing solid product by in-situ embedding.

[0130] The above-mentioned in-situ embedding means that A-containing nanoparticles are embedded and dispersed within the M-containing solid product by in-situ embedding; that is, the A-containing nanoparticles are formed in situ by being partially or completely encapsulated by the M-containing solid product, without relying on external addition or mixing for embedding. The A-containing nanoparticles produced by the above-mentioned in-situ embedding cannot move freely within the M-containing solid product and are not easily detached. The above-mentioned in-situ means that the A-containing nanoparticles are produced simultaneously with the M-containing solid product, and rather than transporting the A-containing nanoparticles from another location and then compound-doping them with the M-containing solid product, the A-containing nanoparticles are produced while being directly compound-doped with the M-containing solid product in situ.

[0131] The above-mentioned physical adsorption means that A-containing nanoparticles are dispersed in the M-containing solid product by simple physical mixing. The physically adsorbed A-containing nanoparticles can move within the M-containing solid product and may also be detached and re-adsorbed by van der Waals forces. Furthermore, the shape of the A-containing nanoparticles is mainly spherical, substantially spherical, and short rod-shaped, at least one of these.

[0132] Furthermore, the particle size range of the A-containing nanoparticles is 0.25 nm to 100 nm.

[0133] Furthermore, the particle size range of the A-containing nanoparticles is 0.50 nm to 50 nm.

[0134] Furthermore, when the A-containing nanoparticles have a particle size range of 0.25 nm to 2 nm and are embedded in the M-containing solid product in situ, the A-containing nanoparticles within this particle size range are embedded in the M-containing solid product in the form of atoms or atomic clusters.

[0135] When the particle size range of the A-containing nanoparticles is less than 2 nm and they are embedded in the M-containing solid product in situ, it is difficult to observe the A-containing nanoparticles using observation methods. In this case, element A is embedded in the M-containing solid product in the form of atoms or atomic clusters, and the size of the corresponding atoms or atomic clusters becomes the size of the A-containing nanoparticles.

[0136] In step 3 above,

[0137] The reaction time required for the hydrogen deposition and dehydrogenation reaction to be completed can be determined by the end of hydrogen deposition; the dehydrogenation reaction can be considered complete when the deposition of gas due to the reaction is no longer visible to the naked eye.

[0138] In addition to the base concentration and the temperature of the base solution, the reaction time required for the complete removal of element T from the initial alloy by the hydrogen deposition and de-T reaction depends on the shape of the initial alloy. The smaller the initial alloy powder particles, or the thinner the initial alloy ribbon, the shorter the time required to complete the hydrogen deposition and de-T reaction, and conversely, the longer the time required to complete the hydrogen deposition and de-T reaction. Based on the average rate of reaction at the reaction interface and the size of the initial alloy, the minimum reaction time t required to complete the hydrogen deposition and de-T reaction can be calculated. For example, if the initial alloy is a ribbon of thickness d and the average rate of reaction at the reaction interface is v, then assuming that the reaction proceeds from both the top and bottom of the ribbon, t = 0.5d / v. Similarly, if the initial alloy is a particle of diameter d and the average rate of reaction at the reaction interface is v, then t = 0.5d / v.

[0139] In one embodiment, an initial alloy ribbon of an NbAl3 intermetallic compound containing Au as a solid solution reacts with a 10 mol / L NaOH solution at its boiling point (the boiling point is approximately 119°C), and the average reaction rate of the reaction interface of the initial alloy ribbon is approximately 120 μm / min. That is, for an initial alloy ribbon with a thickness of 40 μm, the hydrogen deposition and de-algalization reaction can be completed in 10 seconds; for an initial alloy ribbon with a thickness of 20 μm, the hydrogen deposition and de-algalization reaction can be completed in 5 seconds; and even for an initial alloy sphere with a particle size of 5 mm, the hydrogen deposition and de-algalization reaction can be completed in 21 minutes.

[0140] Furthermore, the reaction time for the above hydrogen precipitation / de-T reaction is 10s to 59min, furthermore, the reaction time for the above hydrogen precipitation / de-T reaction is 10s to 29min, furthermore, the reaction time for the above hydrogen precipitation / de-T reaction is 10s to 9.9min, furthermore, the reaction time for the above hydrogen precipitation / de-T reaction is 10s to 4.9min, furthermore, the reaction time for the above hydrogen precipitation / de-T reaction is 10s to 1min, and furthermore, the reaction time for the above hydrogen precipitation / de-T reaction is 10s to 30s.

[0141] Furthermore, the reaction time for the above hydrogen deposition / de-T reaction may be as short as 10 seconds.

[0142] Clearly, as T1 increases, the thickness of the initial alloy decreases and the grain size decreases, which shortens the required hydrogen deposition and de-T reaction time, while conversely, the reaction time increases.

[0143] Once the hydrogen deposition and de-T reaction is complete, extending the time the reaction system is held at the original reaction temperature ensures that the M-containing solid product remains a nanoscale product with dispersed particles. However, if the holding time is sufficiently long, the morphology of the M-containing solid product may change to some extent. In other words, if the reaction time between the initial alloy and the hot base solution far exceeds the required minimum hydrogen deposition and de-T reaction time t, even if it is only a few hours, it is possible to obtain an M-containing solid product, although its morphology may change to some extent.

[0144] The solid product in the reaction system is recovered to obtain nano-oxide M mainly doped with A-containing nanoparticles. Here, the M-containing solid product described in Step 2 is a nano-oxide M product, and the solid product refers to a solid product containing the M-containing solid product and A-containing nanoparticles.

[0145] Furthermore, the above nano-oxide M has particle dispersibility.

[0146] Furthermore, M in different valence states in the above nano-oxide M corresponds to different nano-oxide Ms. For example, manganese oxide can be MnO or MnO2.

[0147] Furthermore, the size of the above nano-oxide M is less than 0.25 times the size of the initial alloy before nano-fragmentation occurs.

[0148] Furthermore, the size of the above nano-oxide M is less than 0.05 times the size of the initial alloy before nano-fragmentation occurs, and the above size is the volume size.

[0149] Furthermore, the shape of the above nano-oxide M is such that at least one dimension in the three-dimensional direction does not exceed 500 nm.

[0150] Furthermore, the shape of the above nano-oxide M is such that at least one dimension in the three-dimensional direction does not exceed 250 nm.

[0151] Furthermore, the shape of the above nano-oxide M is such that at least one dimension in the three-dimensional direction does not exceed 150 nm.

[0152] Furthermore, the step of recovering the solid product in the above reaction system includes separating, washing, and drying the solid product in the reaction system.

[0153] Furthermore, the step of separating and recovering the solid product in the above reaction system includes any one of the following steps a) or b):

[0154] a) Add a large amount of cold solvent (e.g., water) to the reaction system to rapidly lower the temperature of the solid product and base solution in the reaction system as described in step 2, and at the same time lower the concentration of the base solution in the reaction system. After dilution and lowering the temperature, solid-liquid separation is performed. It is clear that the base solution after lowering the concentration and temperature is safer, and the morphology of the product is also guaranteed to be stable.

[0155] b) The high-temperature base solution in the reaction system is filtered and separated together with the solid product using a filtration device (e.g., a filter mesh), thereby lowering the temperature of the solid product and achieving solid-liquid separation.

[0156] Furthermore, the washing step includes washing the solid product with a dilute acid solution, and this washing includes removing residual base from the solid product.

[0157] Furthermore, the shape of the nano-oxide M includes at least one of the following: film-like, granular, plate-like, ribbon-like, tubular, and aggregate-like, where the aggregate-like is a state in which extremely fine microstructures with inconspicuous edges are aggregated.

[0158] Furthermore, even though the nano-oxide M molecules are softly aggregated with each other, they are not rigidly bonded together by a three-dimensional continuous rigid network structure, thus maintaining the shape of the original initial alloy.

[0159] Furthermore, the shape of the nano-oxide M changes depending on reaction conditions such as different reaction temperatures, base concentrations, different initial alloy compositions, and differences in the time for which the reaction conditions are maintained after the completion of the hydrogen deposition and de-T reaction. The shape of the nano-oxide M may change from being predominantly one shape to being predominantly another, or it may not change at all or may only change slightly. However, regardless of the change in shape, it includes at least one of the following: film-like, granular, plate-like, ribbon-like, tubular-rod-like, and aggregate-like.

[0160] Furthermore, the shape of the nano-oxide M described above is completely different from that of the initial alloy, and its particle size is clearly fragmented and smaller.

[0161] Furthermore, when the nano-oxidized M is mainly in the form of a film, its thickness is 0.25 nm to 30 nm, and the average area of the film is larger than 100 nm 2 than that.

[0162] Furthermore, when the nano-oxidized M is mainly in the form of particles, its particle size range is 1.5 nm to 500 nm, preferably 1.5 nm to 200 nm, and preferably 1.5 nm to 100 nm.

[0163] Furthermore, when the nano-oxidized M is mainly in the form of plates, its thickness is 1.5 nm to 100 nm, preferably 5 nm to 30 nm, more preferably 5 nm to 20 nm, and the average area of the plate is larger than 100 nm 2 than that.

[0164] Furthermore, when the nano-oxidized M is mainly in the form of tubular or rod-shaped, it includes tubular or rod-shaped, and its diameter is in the range of 2 nm to 200 nm, more preferably in the range of 2 nm to 50 nm, and its aspect ratio is greater than 2. When the aspect ratio is extremely large, the tubular or rod-shaped can be regarded as fibrous.

[0165] Furthermore, when the nano-oxidized M is mainly in the form of aggregates, the size of the fine structure of the aggregates is 0.25 nm to 15 nm.

[0166] Furthermore, the nano-oxidized M includes at least one of low-crystalline nano-oxide M, crystalline nano-oxide M, and hydrated nano-oxide M.

[0167] Furthermore, the low-crystalline nano-oxide M includes amorphous nano-oxide M.

[0168] Since the nano-oxide M can be regarded as a composite of the nano-oxide M and H2O, the nano-oxide M can be obtained by heat dehydration treatment at a relatively low temperature. Therefore, the hydrated nano-oxide M described in the present invention is the nano-oxide M.

[0169] Furthermore, the above nanooxide M may be a single nanooxide M, or it may be a composite nanooxide M composed of different M subelements, such as a composite nanometal oxide consisting of oxide Y and oxide Ta (both Y and Ta are subelements of element M).

[0170] Furthermore, the composition of the A-containing nanoparticles includes at least one of Au, Pt, Pd, Ru, Rh, Os, Ir, Re, Ag, and Cu.

[0171] Furthermore, if the element A in the A-containing nanoparticles is mainly composed of at least one of Ag and Cu, then the A-containing nanoparticles include at least one of Ag nanoparticles, silver oxide nanoparticles, Cu nanoparticles, and copper oxide nanoparticles.

[0172] When the element A in A-containing nanoparticles consists only of small amounts of Ag and Cu, the Ag and Cu are generally dissolved in the A nanoparticles made up of other inert elements A, and in this case, the dissolved Ag and Cu are not easily oxidized.

[0173] Furthermore, the composition of the A-containing nanoparticles described above includes at least one of Au, Pt, Pd, Ru, Rh, Os, Ir, and Re.

[0174] Furthermore, the A-containing nanoparticles include at least one of A nanoparticles and nano-oxidized A particles. For example, if A is Ag, the A-containing nanoparticles include at least one of Ag nanoparticles and nano-oxidized Ag particles.

[0175] Furthermore, the method for doping the above-mentioned A-containing nanoparticles into a nano-oxidized M matrix includes at least one of an in-situ embedding method and a physicoadsorption method.

[0176] Furthermore, the method of doping the above-mentioned A-containing nanoparticles into a nano-oxidized M matrix includes in-situ embedding doping.

[0177] Furthermore, when the x content is low, the doping method of A-containing nanoparticles into the nano-oxidized M matrix is ​​mainly in-situ embedding, while when the x content is high, the doping method of A-containing nanoparticles into the nano-oxidized M matrix includes in-situ embedding and physicoadsorption.

[0178] The doping described above does not mean that the A-containing nanoparticles are impurities; it simply indicates that the nano-oxide M matrix is ​​not just nano-oxide M, but nano-oxide M containing other components.

[0179] Furthermore, the method for doping the above-mentioned A-containing nanoparticles into a nano-oxidized M matrix is ​​primarily in-situ embedding doping.

[0180] The above-mentioned in-situ embedding means that A-containing nanoparticles are embedded and dispersed in a nano-oxide M matrix by in-situ embedding, that is, A-containing nanoparticles are formed in situ by being partially or completely encapsulated by the nano-oxide M matrix, and do not rely on external addition or external mixing to embed them. The A-containing nanoparticles produced by the above-mentioned in-situ embedding cannot move freely in the nano-oxide M matrix and are not easily detached. This in-situ embedding is achieved by simultaneously embedding the A-containing nanoparticles and simultaneously forming the nano-oxide M matrix during the hydrogen deposition and de-T reaction process. The above-mentioned in-situ means that the A-containing nanoparticles are generated simultaneously with the nano-oxide M matrix, and rather than transporting the A-containing nanoparticles from another location and then compound-doping them with the nano-oxide M matrix, the A-containing nanoparticles are generated while being directly compound-doped with the nano-oxide M matrix in situ. The above-mentioned partial encapsulation means that a portion of the A-containing nanoparticles is embedded in the nano-oxide M matrix, while the portion remains external.

[0181] The above-mentioned physical adsorption means that A-containing nanoparticles are dispersed in the nano-oxide M matrix by simple physical mixing and adsorption. The physically adsorbed A-containing nanoparticles can move within the nano-oxide M matrix and may also be re-adsorbed after being detached by van der Waals forces.

[0182] Furthermore, the shape of the A-containing nanoparticles is mainly spherical, substantially spherical, and short rod-shaped, at least one of these.

[0183] Furthermore, the particle size range of the A-containing nanoparticles is 0.25 nm to 100 nm.

[0184] Furthermore, the particle size range of the A-containing nanoparticles is 0.50 nm to 50 nm.

[0185] Furthermore, when the A-containing nanoparticles have a particle size range of 0.25 nm to 2 nm and are embedded in a nano-oxide M matrix in situ, the A-containing nanoparticles within this particle size range are embedded in the nano-oxide M matrix in the form of atoms or atomic clusters.

[0186] When the above-mentioned A-containing nanoparticles have a particle size range of 0.25 nm to 2 nm and are embedded in a nano-oxide M matrix in situ, it is difficult to observe the corresponding A-containing nanoparticles using observation methods. In this case, the corresponding A element is embedded in the nano-oxide M matrix in the form of atoms or atomic clusters, and the size of the corresponding atoms or atomic clusters corresponds to the size of the corresponding A-containing nanoparticles.

[0187] Furthermore, the thermal stability of the nanometal oxides doped with the aforementioned precious metal nanoparticles is higher than that of the corresponding nanooxide matrix manufactured under similar conditions.

[0188] Furthermore, when the particle size range of the A-containing nanoparticles includes 0.25 nm to 2 nm, the A-containing nanoparticles significantly improve the thermal stability of the corresponding nanooxide M matrix. Specifically, when the corresponding nanooxide M matrix is ​​low in crystallinity or amorphous, embedded A-containing nanoparticles (particle size in the range of 0.25 nm to 2 nm) existing in the form of atoms or atomic clusters significantly improve the thermal stability of the low in crystallinity or amorphous nanooxide M matrix, and its crystallization temperature increases significantly (see Comparative Example 2). The clear increase in the thermal stability of the corresponding doped nanooxide M matrix is ​​key to determining whether the doped A-containing nanoparticles are embedded as atoms or atomic clusters.

[0189] In a second embodiment, the present invention also relates to a method for producing a nanometal oxide doped with noble metal nanoparticles, characterized by heat-treating a nanometal oxide M doped with A-containing nanoparticles produced by the production method described in the first embodiment to obtain a nanometal oxide M doped with A-containing nanoparticles with increased crystallinity.

[0190] Furthermore, the above heat treatment temperature is 300°C to 2000°C, furthermore, the above heat treatment temperature is 400°C to 2000°C, and furthermore, the above heat treatment temperature is 500°C to 2000°C.

[0191] Furthermore, the above heat treatment time is 1 min to 24 hours, and furthermore, the above heat treatment time is 5 min to 24 hours.

[0192] Furthermore, the heat treatment time is 30 min to 24 h.

[0193] It is understood that extending the heat treatment time and increasing the heat treatment temperature will increase the degree of crystallinity of the resulting heat-treated product until it is completely crystallized.

[0194] Furthermore, during the heat treatment process, changes in the form and / or composition of nano-oxide M may occur, where compositional changes include changes in the valence state of M in nano-oxide M (e.g., from low-valence M to high-valence M) or changes in the arrangement structure of oxide atoms.

[0195] Furthermore, if the nano-oxide M matrix produced by the manufacturing method described in the first embodiment is in a crystalline state, grain growth occurs after heat treatment.

[0196] Furthermore, if the nano-oxide M matrix produced by the manufacturing method described in the first embodiment is partially crystalline, further crystallization and grain growth occur after thermal treatment.

[0197] Furthermore, if the nano-oxide M matrix produced by the manufacturing method described in the first embodiment is partially amorphous, partial or complete crystallization and grain growth occur after heat treatment.

[0198] Furthermore, if the nanooxide M matrix produced by the manufacturing method described in the first embodiment is hydrated nanooxide M, the hydrated nanooxide M changes to nanooxide M after heat treatment, and then further crystallization and grain growth of the nanooxide M occur.

[0199] Furthermore, the nanooxide M matrix with increased crystallinity may be a single nanooxide M, or it may be a composite nanooxide M composed of different M subelements, such as a composite nanometal oxide consisting of nanooxide Y and nanooxide Ta (both Y and Ta are subelements of element M).

[0200] Furthermore, during the heat treatment process, the valence state of element M in the nanooxide M matrix can change, for example, from a low-valence M to a high-valence M.

[0201] Furthermore, the shape of the nanooxide M matrix with increased crystallinity includes at least one of the following: film-like, granular, plate-like, ribbon-like, tubular, and sintered aggregates.

[0202] Furthermore, after heat treatment, the shape of the nanooxide M matrix, whose crystallinity has increased, changes, for example, from aggregated aggregates before heat treatment to a film-like structure, or from a film-like structure before heat treatment to a granular structure.

[0203] Furthermore, when the nano-oxide M matrix with increased crystallinity is in the form of a film, its thickness is 1 nm to 50 nm, more preferably 2 nm to 10 nm, and the average area of ​​the film is 50 nm. 2 Larger.

[0204] Furthermore, when the shape of the nanooxide M matrix with increased crystallinity is granular, the particle size range is 3 nm to 500 nm, preferably 3 nm to 250 nm, more preferably 3 nm to 150 nm, even more preferably 3 nm to 75 nm, even more preferably 3 nm to 30 nm, and even more preferably 3 nm to 15 nm.

[0205] Furthermore, when the shape of the nanooxide M matrix with increased crystallinity is plate-like, its thickness is 3 nm to 200 nm, preferably 6 nm to 75 nm, preferably 6 nm to 40 nm, more preferably 6 nm to 25 nm, and the average area of ​​the plate is 100 nm. 2 Larger.

[0206] Furthermore, when the shape of the nanooxide M matrix with increased crystallinity is ribbon-like, its diameter range is 3 nm to 60 nm, and its aspect ratio is greater than 2.

[0207] Furthermore, when the shape of the nanooxide M matrix with increased crystallinity is tubular or rod-shaped, it includes tubular or rod-shaped forms, with a diameter in the range of 2 nm to 200 nm, and an aspect ratio greater than 2. When the aspect ratio is extremely large, the tubular or rod-shaped form can be considered fibrous.

[0208] Furthermore, when the shape of the nanooxide M matrix with increased crystallinity is a sintered aggregate, the particle size increases significantly due to the formation of the sintered aggregate, and the particle size range is 5 nm to 1 mm.

[0209] Furthermore, the crystallinity of the nanooxide M matrix with increased crystallinity is related to the time and temperature of the heat treatment; the higher the temperature and the longer the time, the higher the crystallinity.

[0210] Furthermore, the crystallinity of the nanooxide M matrix with increased crystallinity is 20% or higher, furthermore, the crystallinity of the nanooxide M matrix with increased crystallinity is 50% or higher, and furthermore, the crystallinity of the nanooxide M matrix with increased crystallinity is 95% or higher.

[0211] Furthermore, after heat treatment, the particle size of the A-containing nanoparticles is greater than or equal to the particle size of the A-containing nanoparticles before heat treatment.

[0212] Furthermore, the particle size of A-containing nanoparticles after heat treatment is larger than the particle size of A-containing nanoparticles before heat treatment.

[0213] Specifically, during the heat treatment process, when A-containing nanoparticles bond and grow before heat treatment, their particle size increases after heat treatment.

[0214] Furthermore, the composition of the A-containing nanoparticles includes at least one of Au, Pt, Pd, Ru, Rh, Os, Ir, Re, Ag, and Cu.

[0215] Furthermore, if the element A in the A-containing nanoparticles is mainly composed of at least one of Ag and Cu, then the A-containing nanoparticles include at least one of Ag nanoparticles, silver oxide nanoparticles, Cu nanoparticles, and copper oxide nanoparticles.

[0216] Furthermore, the composition of the A-containing nanoparticles described above includes at least one of Au, Pt, Pd, Ru, Rh, Os, Ir, and Re.

[0217] Furthermore, the above-mentioned A-containing nanoparticles include at least one of A nanoparticles and nano-oxidized A particles.

[0218] Furthermore, the method for doping the above-mentioned A-containing nanoparticles into a nanooxide M matrix with increased crystallinity includes at least one of an in-situ embedding method and a physicoadsorption method.

[0219] Furthermore, the method of doping the above A-containing nanoparticles into a nanooxide M matrix with increased crystallinity includes in-situ embedding doping.

[0220] Furthermore, when the x content is low, the doping method of A-containing nanoparticles into the nanooxide M matrix with increased crystallinity is mainly in-situ embedding, while when the x content is high, the doping method of A-containing nanoparticles into the nanooxide M matrix with increased crystallinity includes in-situ embedding and physicoadsorption.

[0221] Furthermore, the method for doping the above-mentioned A-containing nanoparticles into a nanooxide M matrix with increased crystallinity is primarily in-situ embedding doping.

[0222] The above-mentioned in-situ embedding means that A-containing nanoparticles are embedded and dispersed in a nano-oxide M matrix with increased crystallinity by in-situ embedding; that is, A-containing nanoparticles are formed in situ by being partially or completely encapsulated in a nano-oxide M matrix with increased crystallinity, without relying on external addition or mixing for embedding. The A-containing nanoparticles produced by the above in-situ embedding cannot move freely in the nano-oxide M matrix with increased crystallinity and are not easily detached.

[0223] The above-mentioned physical adsorption means that, through simple physical mixing, A-containing nanoparticles are dispersed in a nano-oxide M matrix with increased crystallinity. The physically adsorbed A-containing nanoparticles can move within the nano-oxide M matrix with increased crystallinity, and may also be re-adsorbed after being detached by van der Waals forces.

[0224] Furthermore, the shape of the A-containing nanoparticles is mainly spherical, substantially spherical, and short rod-shaped, at least one of these.

[0225] Furthermore, the particle size range of the A-containing nanoparticles is 0.25 nm to 200 nm, furthermore, the particle size range of the A-containing nanoparticles is 0.25 nm to 100 nm, and furthermore, the particle size range of the A-containing nanoparticles is 0.5 nm to 75 nm.

[0226] Furthermore, when the A-containing nanoparticles have a particle size range of 0.5 nm to 2 nm and are embedded in-situ in a nano-oxide M matrix with increased crystallinity, the A-containing nanoparticles within this particle size range are embedded in the nano-oxide M matrix with increased crystallinity in the form of atoms or atomic clusters.

[0227] Furthermore, when the particle size range of the A-containing nanoparticles includes 0.5 nm to 2 nm, the A-containing nanoparticles significantly improve the thermal stability of the corresponding nanooxide M matrix. Specifically, if the corresponding nanooxide M matrix is ​​in a low-crystallinity or amorphous state before heat treatment, embedded A-containing nanoparticles, existing in the form of atoms or atomic clusters, significantly improve the thermal stability of the low-crystallinity or amorphous nanooxide M matrix, and its crystallization temperature increases significantly. Even after heat treatment at a specific temperature, for example, 600°C for 2 hours, certain nanooxide M matrices do not undergo significant crystallization. However, in this case, while the nanooxide M matrix may not show clear crystallization, the doped A-containing nanoparticles generally fuse and grow.

[0228] When the heat treatment temperature is low or the heat treatment time is short, if the A-containing nanoparticles have a particle size range of 0.5 nm to 2 nm and are embedded in-situ in a nano-oxide M matrix with increased crystallinity, it is difficult to observe A-containing nanoparticles within this particle size range using observation methods. In this case, the corresponding A element is embedded in the highly crystallinity oxide M nanomatrix in the form of atoms or atomic groups, and the size of the corresponding atoms or atomic clusters in this case becomes the size of the corresponding A-containing nanoparticles.

[0229] In a third aspect, the present invention also relates to a method for producing nanometal oxides doped with noble metal nanoparticles, characterized by comprising the following manufacturing steps:

[0230] Step 1: Provide an initial alloy, the initial alloy comprising M, T, and A component elements, where the M element comprises at least one of Cr, V, Nb, Ta, W, Mo, Mn, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; the T element comprises at least one of Al and Zn; and the A element mainly consists of noble metal elements comprising at least one of Au, Pt, Pd, Ru, Rh, Os, Ir, Re, Ag, and Cu; the solidification structure of the initial alloy mainly comprises an MTA intermetallic compound, or / or an MT(A) intermetallic compound in which the A component elements are solid-solved; and the composition of the initial alloy is mainly A x T y M z Here, x, y, and z are the atomic percentage content of the corresponding elements, and 0 <x≦15%、40%≦y<95%、5%≦z<60%である。

[0231] Step 2: Mix the above initial alloy with a base solution at a temperature of T1, where T s溶液 <T1≦T f溶液 And, T f溶液 T is the boiling point temperature of the base solution involved in the reaction at normal pressure. s溶液 This is the freezing point temperature of the base solution involved in the reaction at atmospheric pressure.

[0232] Step 3: Place the mixture of the initial alloy and the base solution in a sealed container and treat at a temperature T2 higher than atmospheric pressure for a certain period of time. Collect the product to obtain a nanooxide M doped with A-containing nanoparticles whose morphology and / or composition has changed compared to before high-pressure treatment. The nanooxide M comprises A-containing nanoparticles and a nanooxide M matrix, and the above T2 > T f溶液 The above A-containing nanoparticles comprise at least one of A nanoparticles and nanooxide A particles, the particle size range of the A-containing nanoparticles is 0.25 nm to 100 nm, the above nanooxide M matrix comprises at least one of low-crystalline nanooxide M, crystalline nanooxide M, and hydrated nanooxide M, where hydrated nanooxide M specifically refers to nanohydroxylated M, and the above modified nanooxide M matrix has a shape in which the scale of at least one dimension in the three-dimensional direction is 500 nm or less.

[0233] Step 1 described above is identical to Step 1 in the method for producing a metal oxide doped with noble metal nanoparticles as described in the first embodiment, including the detailed descriptive portion corresponding to Step 1. Therefore, the detailed description of Step 1 will not be repeated in this specification.

[0234] In step 2 described above,

[0235] Furthermore, the above base solution includes at least one of the following solutions: NaOH, KOH, LiOH, RbOH, CsOH, Ba(OH)2, Ca(OH)2, and Sr(OH)2.

[0236] Furthermore, the solvent of the above-mentioned base solution contains water, and preferably, the solvent of the above-mentioned base solution is water.

[0237] Furthermore, the concentration of the base in the above base solution is 3 to 30 mol / L, more preferably 5.1 to 30 mol / L, more preferably 5.1 to 15 mol / L, and even more preferably 7 to 15 mol / L.

[0238] Furthermore, the amount of base in the base solution mixed with the initial alloy is in excess, the volume of the base solution is more than 5 times the volume of the initial alloy, furthermore, the volume of the base solution is more than 10 times the volume of the initial alloy, and furthermore, the volume of the base solution is more than 20 times the volume of the initial alloy.

[0239] It is understood that the initial alloy and the base solution at temperature T1 undergo a hydrogen deposition and de-T reaction while mixing, and that the reaction rate increases as the temperature of the base solution and the concentration of the base solution increase.

[0240] If the reaction interface in the hydrogen deposition and de-T reaction step progresses from the initial alloy surface into the interior at an average rate of 2 μm / min or more, this is the situation described in step 2 of the first embodiment. See step 2 of the first embodiment for details. In this case, the initial alloy undergoes nanofragmentation during the reaction process by hydrogen deposition and de-T reaction, undergoing reconstruction of shape and composition to produce M-containing solid products in which at least one dimension in the three-dimensional direction does not exceed 500 nm. Simultaneously with the hydrogen deposition and de-T reaction, atoms of element A in the intermetallic compound of the initial alloy undergo diffusion dislocation to form A-containing nanoparticles. These A-nanoparticle-doped nano-oxidized M are subjected to the subsequent high-temperature, high-pressure reaction step 3, where their form and / or composition are similarly modified. Thus, step 2 encompasses the situation described in step 2 of the first embodiment, i.e., performing the processing of step 3 after the situation described in step 2 of the first embodiment remains within the scope of the protection of the third embodiment. Here, the above modification means changing the form and / or composition of the nano-oxide M doped with the A nanoparticles obtained in step 2, and the above compositional change includes a change in the valence state of M in the nano-oxide M matrix (e.g., a change from low-valence Mn to high-valence Mn) or a change in the atomic arrangement structure in the nano-oxide M.

[0241] If step 3 is present, whether or not nanofragmentation occurs in step 2, or whether or not the hydrogen deposition / de-T reaction is completed after mixing the initial alloy with the base solution as described in step 2, does not fundamentally affect the outcome of the reaction in step 3. This is because the reaction in step 3 is carried out at a longer time, higher temperature, and higher pressure, regardless of the product obtained in step 2, and therefore undergoes morphological and / or compositional modification in step 3.

[0242] Furthermore, in step 2 described above, the initial alloy and the base solution at temperature T1 undergo a hydrogen deposition-de-T reaction while mixing, and the reaction interface advances inward from the surface of the initial alloy at an average rate of less than 2 μm / min during the hydrogen deposition-de-T reaction.

[0243] Furthermore, T s溶液 ≤T1 < 60℃, and furthermore, T s溶液 ≤T1 < 80℃.

[0244] In step 3 above,

[0245] Furthermore, the mixture of the initial alloy and the base solution has no limit to the extent to which the initial alloy undergoes hydrogen deposition and de-T reaction. Therefore, the solid material in the mixture may be the initial alloy, or it may be a product of the initial alloy after partial or complete hydrogen deposition and de-T reaction, including a product that undergoes sufficient nano-fragmentation, or a nanoporous product that does not undergo sufficient nano-fragmentation.

[0246] A specific operational step comprising placing the mixture of the above initial alloy and base solution into a sealed container, the step including at least one of the following two methods:

[0247] a) The mixture of the initial alloy and base solution from step 2 is placed directly into a sealed container and treated at a temperature T2 higher than atmospheric pressure.

[0248] b) First, the solid material in the mixture of the initial alloy and base solution from step 2 is separated from the base solution, mixed with a new base solution, placed in a sealed container, and treated at a temperature higher than atmospheric pressure T2. At this time, the new base solution may be the same as the original base solution, or a different type of base solution may be used. Furthermore, the concentration of the new base solution is 0.1 mol / L to 30 mol / L, and furthermore, the concentration of the new base solution is 5 mol / L to 30 mol / L.

[0249] Furthermore, the above pressure is above normal pressure and less than 100 MPa, and furthermore, the above pressure is above normal pressure and less than 20 MPa.

[0250] Furthermore, T f溶液 <T2≦500℃であり、さらに、T f溶液 <T2≦300℃である。

[0251] Furthermore, the processing time at a T2 temperature higher than atmospheric pressure is 1 min to 2 hours, and the processing time is 1 min to 30 minutes.

[0252] Furthermore, the processing time for the above is 1 min to 10 min.

[0253] The process described in Step 3, like the strong base hydrothermal method, involves reactions under strongly basic, high-temperature, and high-pressure conditions, but there is a significant difference between the two: the precursor used in the strong base hydrothermal method is generally a crystalline oxide with a small specific surface area, so it takes a long time (e.g., several tens of hours) to first cleave the OM bond and then recombine it to achieve modification. In contrast, in the modification process of the present invention, the precursor used is basically the initial alloy raw material, and even if it has changed into an oxide M matrix before modification (mixing or heating process), in most cases, before modification it is either a low-crystalline nano-oxide M matrix with an ultra-high specific surface area, or even if it is a crystalline nano-oxide M matrix, it is in a state with a very high specific surface area. The higher the specific surface area, the higher the substitution energy, and the easier the modification. Therefore, the heat treatment time required to modify the nano-oxide M matrix of the present invention is shortened, energy consumption is reduced, efficiency is improved, and a product with a completely different morphology can be obtained. Naturally, even after the modification is complete and reaction equilibrium is reached, the modification process time can be extended to obtain the product of the corresponding modification process by the present invention.

[0254] Furthermore, the modified nano-oxide M matrix includes at least one of low-crystalline nano-oxide M, crystalline nano-oxide M, and hydrated nano-oxide M. Here, the hydrated nano-oxide M specifically refers to nano-hydroxylated M.

[0255] Furthermore, the above-mentioned low-crystalline nano-oxide M is mainly amorphous nano-oxide M.

[0256] Since nano-oxidized M can be considered as a composite of nano-oxidized M and H2O, nano-oxidized M can be obtained by heating and dehydrating at a relatively low temperature. Therefore, hydrated nano-oxidized M is nano-oxidized M.

[0257] Furthermore, different valence states of M in the above nano-oxidized M correspond to different nano-oxidized M. For example, the oxidized Mn can be MnO or MnO2.

[0258] Furthermore, the degree of crystallinity of the modified nano-oxidized M matrix is ​​related to the time, temperature, and pressure of the modification process; the higher the temperature, the longer the time, and the higher the pressure, the higher the degree of crystallinity. Therefore, the high-temperature, high-pressure modification is a method to improve the crystallinity of the modified product and obtain a new product morphology without significantly reducing the high specific surface area of ​​the reaction product.

[0259] Furthermore, the shape of the modified nano-oxidized M matrix includes at least one of the following: film-like, aggregate, granular, plate-like, ribbon-like, and tubular / rod-like.

[0260] Furthermore, the characteristic changes in the modified nano-oxide M matrix compared to the nano-oxide M matrix produced at the end of the hydrogen deposition-de-T reaction include at least one of the following: larger particle size, lower specific surface area, and increased crystallinity.

[0261] Furthermore, the M element in the modified nano-oxidized M matrix mainly exists in a high-valence state.

[0262] Furthermore, the crystallinity of the modified nano-oxide M matrix increases by 50% compared to before high-pressure treatment. For example, if the crystallinity before high-pressure treatment is 10% and the crystallinity of the modified nano-oxide M matrix is ​​16%, the crystallinity of the modified nano-oxide M matrix increases by (16%-10%) / 10%=60% compared to before high-pressure treatment.

[0263] Furthermore, the crystallinity of the modified nano-oxide M matrix exceeds 20%, and furthermore, the crystallinity of the modified nano-oxide M matrix exceeds 50%.

[0264] Furthermore, the shape of the modified nano-oxidized M matrix described above is such that at least one dimension in the three-dimensional direction does not exceed 500 nm.

[0265] Furthermore, the shape of the modified nano-oxidized M matrix described above is such that at least one dimension in the three-dimensional direction does not exceed 250 nm.

[0266] Furthermore, when the modified nano-oxide M matrix is ​​mainly granular, its particle size range is 3 nm to 500 nm, preferably 3 nm to 200 nm, and preferably 3 nm to 100 nm.

[0267] Furthermore, when the modified nano-oxide M matrix is ​​mainly plate-shaped, its thickness is 2 nm to 120 nm, preferably 5 nm to 30 nm, and more preferably 5 nm to 20 nm, and the average area of ​​the plate is 100 nm. 2 Larger.

[0268] Furthermore, when the shape of the modified nano-oxide M matrix is ​​mainly ribbon-like, its diameter range is 3 nm to 50 nm, and its aspect ratio is greater than 2.

[0269] Furthermore, when the shape of the modified nano-oxidized M matrix is ​​mainly tubular or rod-shaped, it includes tubular or rod-shaped forms, with a diameter range of 3 nm to 200 nm, more preferably 3 nm to 50 nm, and an aspect ratio greater than 2. When the aspect ratio is extremely large, the tubular or rod-shaped form can be considered fibrous.

[0270] Furthermore, the modified nano-oxide M matrix may be a single nano-oxide M, or it may be a composite nano-oxide M composed of different M sub-elements, such as a composite nano-metal oxide consisting of oxide Y and oxide Ta (both Y and Ta are sub-elements of element M).

[0271] Furthermore, the composition of the A-containing nanoparticles includes at least one of Au, Pt, Pd, Ru, Rh, Os, Ir, Re, Ag, and Cu.

[0272] Furthermore, if the element A in the A-containing nanoparticles is mainly composed of at least one of Ag and Cu, then the A-containing nanoparticles include at least one of Ag nanoparticles, silver oxide nanoparticles, Cu nanoparticles, and copper oxide nanoparticles.

[0273] Furthermore, the composition of the A-containing nanoparticles described above includes at least one of Au, Pt, Pd, Ru, Rh, Os, Ir, and Re.

[0274] Furthermore, the A-containing nanoparticles include at least one of A nanoparticles and nano-oxidized A particles.

[0275] Furthermore, the method for doping the above-mentioned A-containing nanoparticles into a modified nano-oxidized M matrix includes at least one of an in-situ embedding method and a physicoadsorption method.

[0276] Furthermore, the method of doping the above-mentioned A-containing nanoparticles into a modified nano-oxidized M matrix includes in-situ embedding doping.

[0277] Furthermore, when the x content is low, the doping method of A-containing nanoparticles into the modified nano-oxidized M matrix is ​​mainly in-situ embedding, while when the x content is high, the doping method of A-containing nanoparticles into the modified nano-oxidized M matrix includes in-situ embedding and physicoadsorption.

[0278] The above-mentioned in-situ embedding means that A-containing nanoparticles are embedded and dispersed in a modified nano-oxide M matrix by in-situ embedding; that is, A-containing nanoparticles are formed in situ by being partially or completely encapsulated by the modified nano-oxide M matrix, without relying on external addition or mixing for embedding. The A-containing nanoparticles produced by the above in-situ embedding cannot move freely within the modified nano-oxide M matrix and are not easily detached.

[0279] The above-mentioned physical adsorption means that A-containing nanoparticles are dispersed in the modified nano-oxide M matrix by simple physical mixing, and the physically adsorbed A-containing nanoparticles can move, desorb, or re-adsorb within the modified nano-oxide M matrix.

[0280] Furthermore, when A-containing nanoparticles are bound to a modified nano-oxide M matrix by physical adsorption, the position of the A-containing nanoparticles within the modified nano-oxide M matrix is ​​not fixed, and the A-containing nanoparticles can detach from one modified nano-oxide M matrix and re-adsorb to another. When A-containing nanoparticles are bound to a modified nano-oxide M matrix by in-situ embedding, the position of the A-containing nanoparticles within the modified nano-oxide M matrix is ​​fixed, and the A-containing nanoparticles are embedded within the modified nano-oxide M matrix.

[0281] Furthermore, the shape of the A-containing nanoparticles is mainly spherical, substantially spherical, and short rod-shaped, at least one of these.

[0282] Furthermore, the particle size range of the A-containing nanoparticles is 0.25 nm to 100 nm.

[0283] Furthermore, the particle size range of the A-containing nanoparticles is 0.50 nm to 75 nm.

[0284] Furthermore, when the A-containing nanoparticles have a particle size range of 0.5 nm to 2 nm and are embedded in a modified nano-oxide M matrix in situ, the A-containing nanoparticles within this particle size range are embedded in the modified nano-oxide M matrix in the form of atoms or atomic clusters.

[0285] When the above A-containing nanoparticles have a particle size range of 0.5 nm to 2 nm and are embedded in a modified nano-oxide M matrix in situ, it is difficult to observe the A-containing nanoparticles using observation methods. In this case, the relevant A element is embedded in the modified nano-oxide M matrix in the form of atoms or atomic clusters, and the size of the corresponding atoms or atomic clusters corresponds to the size of the relevant A-containing nanoparticles.

[0286] In a fourth aspect, the present invention also relates to a method for producing noble metal nanoparticles, characterized by dissolving a nano-oxide M matrix in a solid product produced by the production method described in any one of the first to third aspects by an etching solution reaction, thereby obtaining A nanoparticles mainly composed of an inert noble metal element, while retaining the inert noble metal element in the A nanoparticles in the solid product without dissolving. Herein, the composition of the A nanoparticles includes at least one of Au, Pt, Pd, Ru, Rh, Os, Ir, Re, and Ag.

[0287] Furthermore, the selection criterion for the etching solution is that it can remove the nano-oxide M matrix while retaining the inert noble metal A nanoparticles.

[0288] Furthermore, the etching solutions mentioned above are mainly acidic solutions.

[0289] Furthermore, the above acid solution contains at least one of the following: hydrochloric acid, nitric acid, sulfuric acid, acetic acid, phosphoric acid, oxalic acid, picric acid, oleic acid, perchloric acid, and hydrofluoric acid. In addition, the concentration of the acid solution is 0.1 mol / L to 30 mol / L.

[0290] Since precious metals are inert, they generally do not react well with acidic solutions. The matrix of the final product produced by the manufacturing method described in any one of the first to third embodiments is generally an oxide matrix, and when it is in the form of nanoscale, particularly low-crystalline aggregates, it can react with a certain concentration and type of etching solution and dissolve in the etching solution. When the nano-oxide M matrix dissolves, inert precious metal A nanoparticles are freely detached, and a colloidal solution of inert precious metal A nanoparticles is obtained. Further solid-liquid separation yields A nanoparticles mainly composed of inert precious metal A.

[0291] The applicant has found that while certain nanoscale crystalline nanooxides M are poorly reactable and soluble in acidic solutions, such nanooxides M are readily reactable and soluble in acids when they are low-crystallinity on a nanoscale, especially when they exhibit aggregated forms.

[0292] Furthermore, the particle size range of the A-containing nanoparticles is 2 nm to 300 nm.

[0293] Furthermore, the particle size range of the A-containing nanoparticles is 3 nm to 150 nm.

[0294] Furthermore, the shape of the A-containing nanoparticles is mainly spherical, substantially spherical, and short rod-shaped, at least one of these.

[0295] Furthermore, since A nanoparticles can coalesce and grow after being detached from nanooxide M particles, the higher particle size range of the manufactured A nanoparticles is greater than the higher particle size range of the original embedded doped A nanoparticles.

[0296] Furthermore, the number of A element types contained in the manufactured A nanoparticles is less than or equal to the number of A element types contained in the original doped A nanoparticles.

[0297] Specifically, if the original A nanoparticles are mainly composed of inert A elements (e.g., Au, Pt) before being reacted with the etching solution, the etching solution cannot dissolve these inert A elements. In this case, the number of A element types contained in the manufactured inert A nanoparticles will be equal to the number of A element types contained in the original doped A nanoparticles.

[0298] If the original A nanoparticles contain inert A elements and a considerable amount of other relatively active A elements (e.g., Cu) before reacting with the etching solution, the etching solution may also dissolve these relatively active A elements. In this case, the number of A element types in the produced inert A nanoparticles will be less than the number of A element types in the original doped A nanoparticles. For example, if the A nanoparticles in the doped nano-oxide M consist of Au-Cu and have a high Cu content, then a higher concentration of acid solution or a longer reaction time can remove Cu from the Au-Cu nanoparticles in addition to removing the nano-oxide M matrix, thereby obtaining Au nanoparticles.

[0299] In a fifth aspect, the present invention also relates to a nanometal oxide doped with noble metal nanoparticles, characterized in that it is manufactured by a manufacturing method described in any one of the first to third aspects, the properties of which are detailed in the first to third aspects. Its specific features are as follows: The metal oxide doped with noble metal nanoparticles comprises noble metal nanoparticles and a nanometal oxide matrix, wherein the molar percentage content of the noble metal nanoparticles is lower than the molar percentage content of the nanometal oxide matrix. The noble metal nanoparticles are A-containing nanoparticles, mainly composed of noble metal element A, and containing at least one of Au, Pt, Pd, Ru, Rh, Os, Ir, Re, Ag, and Cu. The above A-containing nanoparticles comprise at least one A nanoparticle and nano-oxidized A particles, and the above nanometal oxide matrix is ​​nano-oxidized M, where the element M comprises at least one of Cr, V, Nb, Ta, W, Mo, Mn, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. The above nano-oxidized M comprises at least one of low-crystalline nano-oxidized M, crystalline nano-oxidized M, and hydrated nano-oxidized M, where the above hydrated nano-oxidized M specifically refers to nano-hydroxylated M. A method of doping the above nano-oxidized M matrix with A-containing nanoparticles comprises in-situ embedding doping, i.e., A-containing nanoparticles are formed in situ by being partially or completely encapsulated by the nano-oxidized M matrix, the particle size range of the A-containing nanoparticles is 0.25 nm to 200 nm, and the above nano-oxidized M matrix has a shape in which the scale of at least one dimension in the three-dimensional direction is 500 nm or less.

[0300] Furthermore, twice the molar percentage content of the A-containing nanoparticles is lower than the molar percentage content of the nano-oxidized M matrix.

[0301] Furthermore, in nano-oxide M doped with the above-mentioned A-containing nanoparticles, the crystallization temperature of the nano-oxide M matrix is ​​higher compared to nano-oxide M that is not doped with noble metals. In other words, even with the same low degree of crystallinity of nano-oxide M, when A-containing nanoparticles are doped using the in-situ embedding method, a higher temperature is required for complete crystallization to occur.

[0302] Furthermore, the above nano-oxide M matrix has particle dispersibility. Furthermore, the shape of the above nano-oxide M matrix is ​​such that at least one dimension in the three-dimensional direction does not exceed 250 nm.

[0303] Furthermore, the shape of the above nano-oxide M matrix is ​​such that at least one dimension in the three-dimensional direction does not exceed 150 nm.

[0304] Furthermore, different valence states of M in the above nano-oxidized M correspond to different nano-oxidized M. For example, the oxidized Mn can be MnO or MnO2.

[0305] Furthermore, the shape of the nano-oxide M matrix includes at least one of the following: film-like, granular, plate-like, ribbon-like, tubular, and aggregate-like.

[0306] Furthermore, if the shape of the above nano-oxide M matrix is ​​mainly film-like, its thickness is 0.25 nm to 50 nm, and the average area of ​​the film is 50 nm. 2 Larger.

[0307] Furthermore, when the shape of the nano-oxide M matrix is ​​mainly granular, the particle size range is 1.5 nm to 500 nm, preferably 1.5 nm to 200 nm, and preferably 1.5 nm to 100 nm.

[0308] Furthermore, when the shape of the above nano-oxide M matrix is ​​mainly plate-like, its thickness is 1.5 nm to 200 nm, preferably 5 nm to 30 nm, more preferably 5 nm to 20 nm, and the average area of ​​the plate is 100 nm. 2 Larger.

[0309] Furthermore, if the shape of the above nano-oxide M matrix is ​​mainly tubular or rod-shaped, it includes tubular or rod-shaped forms, its diameter range is 2 nm to 200 nm, and its aspect ratio is greater than 2.

[0310] Furthermore, if the shape of the above-mentioned nano-oxide M matrix is ​​mainly aggregates, the size of the aggregate microstructure is 0.25 nm to 15 nm.

[0311] Furthermore, when the shape of the above nano-oxide M matrix is ​​mainly that of a sintered aggregate, its particle size increases significantly due to sintering and aggregation, and the particle size range is 5 nm to 1 mm.

[0312] Furthermore, the method for doping the above-mentioned A-containing nanoparticles into a nano-oxidized M matrix includes at least one of an in-situ embedding method and a physicoadsorption method.

[0313] Furthermore, the method of doping the above-mentioned A-containing nanoparticles into a nano-oxidized M matrix includes in-situ embedding doping.

[0314] Furthermore, the method for doping the above A-containing nanoparticles into a nano-oxide M matrix is ​​primarily in-situ embedding doping, i.e., the A-containing nanoparticles are formed in situ by being partially or completely encapsulated by the nano-oxide M matrix. This in-situ embedding is achieved during the hydrogen deposition and de-T reaction process, while the A-containing nanoparticles and the nano-oxide M matrix are formed simultaneously.

[0315] Furthermore, the shape of the A-containing nanoparticles is mainly spherical, substantially spherical, and short rod-shaped, at least one of these.

[0316] Furthermore, the particle size range of the A-containing nanoparticles is 0.25 nm to 100 nm.

[0317] Furthermore, the particle size range of the A-containing nanoparticles is 0.25 nm to 50 nm.

[0318] Furthermore, when the A-containing nanoparticles have a particle size range of 0.25 nm to 2 nm and are embedded in a nano-oxide M matrix in situ, the A-containing nanoparticles within this particle size range are embedded in the nano-oxide M matrix in the form of atoms or atomic clusters.

[0319] Furthermore, in-situ doping with the A-containing nanoparticles improves the thermal stability of the corresponding nano-oxide M matrix. Specifically, when the corresponding nano-oxide M matrix is ​​in a low-crystallinity or amorphous state, the in-situ doped A-containing nanoparticles significantly improve the thermal stability of the low-crystallinity or amorphous nano-oxide M matrix. In other words, compared to a low-crystallinity or amorphous nano-oxide M that is not doped with A-containing nanoparticles, a higher temperature is required for complete crystallization in the same heat treatment time (see Comparative Example 2).

[0320] Furthermore, the preferred particle size range for in-situ embedded doped A-containing nanoparticles to improve the thermal stability of the above nano-oxide M matrix is ​​0.25 nm to 10 nm.

[0321] Furthermore, in order to improve the thermal stability of the above nano-oxide M matrix, in-situ embedded doped A-containing nanoparticles are provided, having a preferred particle size range of 0.25 nm to 2 nm, and the A-containing nanoparticles exist in the form of atoms or atomic clusters.

[0322] In a sixth aspect, the present invention also relates to applications of nanometal oxide composite materials, catalyst materials, ceramic materials, refractory materials, advanced electronic materials, battery materials, color-changing materials, wave-absorbing materials, wastewater decomposition materials, sterilizing materials, paints, pigments, thermal spray materials, and sensors, in which noble metal nanoparticles produced by the manufacturing method described in any one of the first to third aspects above are doped.

[0323] In a seventh aspect, the present invention also relates to the application of nanometal oxides doped with noble metal nanoparticles produced by the manufacturing method described in any one of the first to third aspects to home decor paints, antibacterial sprays, and antifouling paints, wherein the component composition of the noble metal nanoparticles comprises at least one of Cu and Ag.

[0324] For use in decorative residential paints, the invention is characterized by mixing nanometal oxides doped with noble metal nanoparticles containing Cu and / or Ag as a paint additive with other components of the paint, and applying them together to the surfaces of furniture, fixtures, and walls to achieve an antibacterial effect.

[0325] For use as a disinfectant spray, the antibacterial effect is achieved by mixing nanometal oxides doped with noble metal nanoparticles containing Cu and / or Ag with other liquid spray components and spraying them together onto furniture, utensils, fabrics, and wall surfaces through a spray carrier.

[0326] The antifouling coating is characterized by using nanometal oxides doped with noble metal nanoparticles containing Cu and / or Ag as an antifouling agent, replacing the antibacterial and antifouling components (e.g., cuprous oxide powder) in conventional antifouling coatings (e.g., antifouling paints) to achieve an antifouling effect.

[0327] Furthermore, the above Ag exists as at least one of Ag, Ag2O, and AgO, and the above Cu exists as at least one of Cu, Cu2O, and CuO.

[0328] In an eighth aspect, the present invention also relates to the application of nanometal oxides doped with noble metal nanoparticles produced by the manufacturing method described in any one of the first to third aspects to antimicrobial fabrics, wherein the component composition of the noble metal nanoparticles includes at least one of Cu and Ag.

[0329] Furthermore, the above application is characterized in that, after dispersing nanometal oxides doped with noble metal nanoparticles containing Cu and / or Ag, the material is attached to or coated on the surface of the fabric, or mixed with the fabric and knitted, thereby enabling the fabric to acquire antibacterial and germicidal effects and capabilities.

[0330] Furthermore, the above Ag exists as at least one of Ag, Ag2O, and AgO, and the above Cu exists as at least one of Cu, Cu2O, and CuO.

[0331] In a ninth aspect, the present invention also relates to a nanometal oxide doped with A nanoparticles, characterized by having the following features: the A nanoparticle doped metal oxide comprises A nanoparticles and a nanometal oxide matrix, wherein the molar percentage content of A nanoparticles is lower than the molar percentage content of the nanometal oxide matrix. The A nanoparticles are A-containing nanoparticles, mainly composed of element A, and containing at least one of Au, Pt, Pd, Ru, Rh, Os, Ir, Re, Ag, Cu, Fe, Ni, and Co. The A-containing nanoparticles comprise at least one of A nanoparticles and nano-oxidized A particles, and the nanometal oxide matrix is ​​nano-oxidized M, wherein element M contains at least one of Cr, V, Nb, Ta, W, Mo, Mn, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. The above nano-oxide M comprises at least one of low-crystalline nano-oxide M, crystalline nano-oxide M, and hydrated nano-oxide M, where the above hydrated nano-oxide M specifically refers to nano-hydroxylated M. A method of doping the above nano-oxide M matrix with A-containing nanoparticles comprises in-situ embedding doping, i.e., A-containing nanoparticles are formed in situ by being partially or completely encapsulated by the nano-oxide M matrix, the particle size range of the A-containing nanoparticles being 0.25 nm to 200 nm, and the above nano-oxide M matrix having a shape in which the scale of at least one dimension in the three-dimensional direction is 500 nm or less.

[0332] Furthermore, the above-mentioned A nanoparticles are A-containing nanoparticles, with element A as the main component and containing at least one of Au, Pt, Pd, Ru, Rh, Os, Ir, Re, Ag, Cu, and Fe.

[0333] Furthermore, the above-mentioned A nanoparticles are A-containing nanoparticles, with element A as the main component and containing at least one of Ag and Cu.

[0334] Furthermore, the above-mentioned A nanoparticles are A-containing nanoparticles, with element A as the main component and containing at least one of Au, Pt, Pd, Ru, Rh, Os, Ir, Re, Ag, Cu, and Fe.

[0335] Furthermore, element A is a noble metal element, and nanoparticles A are noble metal nanoparticles.

[0336] Furthermore, the A-containing nanoparticles include at least one of A nanoparticles and nano-oxidized A particles. For example, if A is Ag, the A-containing nanoparticles include at least one of Ag nanoparticles and nano-oxidized Ag particles.

[0337] Furthermore, nano-oxidized A particles are nanoparticles of oxidized A. For example, if A is Cu, then nano-oxidized A particles are nano-oxidized Cu particles containing at least one nano-Cu2O particle and a nano-CuO particle.

[0338] Furthermore, twice the molar percentage content of the A-containing nanoparticles is lower than the molar percentage content of the nano-oxidized M matrix.

[0339] Furthermore, in nano-oxide M doped with the above-mentioned A-containing nanoparticles, the crystallization temperature of the nano-oxide M matrix is ​​higher compared to nano-oxide M not doped with element A. In other words, even with the same low degree of crystallinity of nano-oxide M, when A-containing nanoparticles are doped using the in-situ embedding method, a higher temperature is required for complete crystallization to occur.

[0340] Furthermore, the above nano-oxide M matrix has particle dispersibility.

[0341] Furthermore, the shape of the above nano-oxide M matrix is ​​such that at least one dimension in the three-dimensional direction does not exceed 250 nm.

[0342] Furthermore, the shape of the above nano-oxide M matrix is ​​such that at least one dimension in the three-dimensional direction does not exceed 150 nm.

[0343] Furthermore, different valence states of M in the above nano-oxidized M correspond to different nano-oxidized M. For example, the oxidized Mn can be MnO or MnO2.

[0344] Furthermore, the shape of the nano-oxide M matrix includes at least one of the following: film-like, granular, plate-like, ribbon-like, tubular, and aggregate-like.

[0345] Furthermore, if the shape of the above nano-oxide M matrix is ​​mainly film-like, its thickness is 0.25 nm to 50 nm, and the average area of ​​the film is 50 nm. 2 Larger.

[0346] Furthermore, when the shape of the nano-oxide M matrix is ​​mainly granular, the particle size range is 1.5 nm to 500 nm, preferably 1.5 nm to 200 nm, and preferably 1.5 nm to 100 nm.

[0347] Furthermore, when the shape of the above nano-oxide M matrix is ​​mainly plate-like, its thickness is 1.5 nm to 200 nm, preferably 5 nm to 30 nm, more preferably 5 nm to 20 nm, and the average area of ​​the plate is 100 nm. 2 Larger.

[0348] Furthermore, if the shape of the above nano-oxide M matrix is ​​mainly tubular or rod-shaped, it includes tubular or rod-shaped forms, its diameter range is 2 nm to 200 nm, and its aspect ratio is greater than 2.

[0349] Furthermore, if the shape of the above-mentioned nano-oxide M matrix is ​​mainly aggregates, the size of the aggregate microstructure is 0.25 nm to 15 nm.

[0350] Furthermore, when the shape of the above nano-oxide M matrix is ​​mainly that of a sintered aggregate, its particle size increases significantly due to sintering and aggregation, and the particle size range is 5 nm to 1 mm.

[0351] Furthermore, the above-mentioned low-crystalline nanooxide M includes amorphous nanooxide M.

[0352] Since nanooxide M can be considered as a composite of nanooxide M and H2O, nanooxide M can be obtained by heating and dehydrating at a relatively low temperature. Therefore, the hydrated nanooxide M described in the present invention is nanooxide M.

[0353] Furthermore, the above nanooxide M may be a single nanooxide M, or it may be a composite nanooxide M composed of different M subelements, such as a composite nanometal oxide consisting of oxide Y and oxide Ta (both Y and Ta are subelements of element M).

[0354] Furthermore, if the element A in the A-containing nanoparticles is mainly composed of at least one of Ag and Cu, then the A-containing nanoparticles include at least one of Ag nanoparticles, silver oxide nanoparticles, Cu nanoparticles, and copper oxide nanoparticles.

[0355] When the element A in A-containing nanoparticles consists only of small amounts of Ag and Cu, the Ag and Cu are generally dissolved in the A nanoparticles made up of other inert elements A, and in this case, the dissolved Ag and Cu are not easily oxidized.

[0356] Furthermore, the method for doping the above-mentioned A-containing nanoparticles into a nano-oxidized M matrix includes at least one of an in-situ embedding method and a physicoadsorption method.

[0357] Furthermore, the method of doping the above-mentioned A-containing nanoparticles into a nano-oxidized M matrix includes in-situ embedding doping.

[0358] Furthermore, the method for doping the above A-containing nanoparticles into a nano-oxide M matrix is ​​primarily in-situ embedding doping, i.e., the A-containing nanoparticles are formed in situ by being partially or completely encapsulated by the nano-oxide M matrix. This in-situ embedding is achieved during the hydrogen deposition and de-T reaction process, while the A-containing nanoparticles and the nano-oxide M matrix are formed simultaneously.

[0359] The above-mentioned in-situ embedding means that A-containing nanoparticles are embedded and dispersed in a nano-oxide M matrix by in-situ embedding, that is, A-containing nanoparticles are formed in situ by being partially or completely encapsulated by the nano-oxide M matrix, and do not rely on external addition or external mixing to embed them within it. The A-containing nanoparticles produced by the above-mentioned in-situ embedding cannot move freely within the nano-oxide M matrix and are not easily detached. This in-situ embedding is achieved by simultaneously embedding the A-containing nanoparticles and simultaneously forming the nano-oxide M matrix during the reaction process. The above-mentioned in-situ means that the A-containing nanoparticles are produced simultaneously with the nano-oxide M matrix, and rather than transporting the A-containing nanoparticles from another location and then compound-doping them with the nano-oxide M matrix, the A-containing nanoparticles are produced while being directly compound-doped with the nano-oxide M matrix in situ. The above-mentioned partial encapsulation means that a portion of the A-containing nanoparticles is embedded in the nano-oxide M matrix, while the portion remains external.

[0360] Furthermore, the shape of the A-containing nanoparticles is mainly spherical, substantially spherical, and short rod-shaped, at least one of these.

[0361] Furthermore, the particle size range of the A-containing nanoparticles is 0.25 nm to 100 nm.

[0362] Furthermore, the particle size range of the A-containing nanoparticles is 0.25 nm to 50 nm.

[0363] Furthermore, when the A-containing nanoparticles have a particle size range of 0.25 nm to 2 nm and are embedded in a nano-oxide M matrix in situ, the A-containing nanoparticles within this particle size range are embedded in the nano-oxide M matrix in the form of atoms or atomic clusters. In this case, A-containing atoms or atomic clusters cannot be called A-containing nanoparticles, but for the sake of convenience, they will be referred to as A-containing nanoparticles of atomic or atomic cluster size.

[0364] Furthermore, when A mainly contains Ag and M mainly contains Cr, the A-containing nanoparticles are mainly embedded in-situ intrinsically in the nano-Cr oxide or nano-Cr hydroxide support in the form of atoms or atomic clusters, and the particle size range of the A-containing nanoparticles is 0.25 nm to 2 nm.

[0365] Furthermore, if the A-containing nanoparticles have a particle size range of 0.25 nm to 2 nm and are embedded in a nano-oxide M matrix in situ, it is difficult to observe the corresponding A-containing nanoparticles using observation methods. In this case, the corresponding A element is embedded in the nano-oxide M matrix in the form of atoms or atomic clusters, and the size of the corresponding atoms or atomic clusters corresponds to the size of the corresponding A-containing nanoparticles.

[0366] Furthermore, the thermal stability of the nanometal oxide doped with the above A nanoparticles is higher than that of the corresponding nanooxide matrix manufactured under similar conditions.

[0367] Furthermore, when the particle size range of the A-containing nanoparticles includes 0.25 nm to 2 nm, the thermal stability of the corresponding nano-oxide M matrix is ​​significantly improved. Specifically, when the corresponding nano-oxide M matrix is ​​low-crystallinity or amorphous, embedded A-containing nanoparticles (particle size range of 0.25 nm to 2 nm) existing in the form of atoms or atomic clusters significantly improve the thermal stability of the low-crystallinity or amorphous nano-oxide M matrix, and its crystallization temperature increases significantly (see Comparative Example 2). The clear increase in the thermal stability of the corresponding doped nano-oxide M matrix is ​​key to determining whether the doped A-containing nanoparticles are embedded as atoms or atomic clusters.

[0368] Furthermore, in-situ doping with the A-containing nanoparticles improves the thermal stability of the corresponding nano-oxide M matrix. Specifically, when the corresponding nano-oxide M matrix is ​​in a low-crystallinity or amorphous state, the in-situ doped A-containing nanoparticles significantly improve the thermal stability of the low-crystallinity or amorphous nano-oxide M matrix. In other words, compared to a low-crystallinity or amorphous nano-oxide M that is not doped with A-containing nanoparticles, a higher temperature is required for complete crystallization in the same heat treatment time (see Comparative Example 2).

[0369] Furthermore, the preferred particle size range for in-situ embedded doped A-containing nanoparticles to improve the thermal stability of the above nano-oxide M matrix is ​​0.25 nm to 10 nm.

[0370] Furthermore, in order to improve the thermal stability of the above nano-oxide M matrix, in-situ embedded doped A-containing nanoparticles are provided, having a preferred particle size range of 0.25 nm to 2 nm, and the A-containing nanoparticles exist in the form of atoms or atomic clusters.

[0371] Furthermore, the nanometal oxide doped with the above A nanoparticles is produced by a manufacturing method described in any one of the first to third embodiments thereof, where A includes at least one of Au, Pt, Pd, Ru, Rh, Os, Ir, Re, Ag, and Cu.

[0372] In a tenth aspect, the present invention also relates to applications of nanometal oxide composites doped with the A nanoparticles described in the ninth aspect, catalytic materials, ceramic materials, refractory materials, advanced electronic materials, battery materials, color-changing materials, wave-absorbing materials, wastewater decomposition materials, sterilizing materials, paints, pigments, thermal spray materials, and sensors.

[0373] In an eleventh aspect, the present invention also relates to the application of the A nanoparticles described in the ninth aspect to home decor paints, antibacterial sprays, and antifouling paints. Herein, the component composition of the noble metal nanoparticles comprises Cu and at least one of Ag.

[0374] For use in decorative residential paints, the invention is characterized by doping nanometal oxides containing Cu and / or Ag nanoparticles with A nanoparticles as a paint additive, mixing them with other components of the paint, and applying them together to the surfaces of furniture, fixtures, and walls to achieve an antibacterial effect.

[0375] For use as a disinfectant spray, the antibacterial effect is achieved by mixing nanometal oxides doped with A nanoparticles containing Cu and / or Ag with other liquid spray components and spraying them together onto furniture, fixtures, fabrics, and wall surfaces through a spray carrier.

[0376] The antifouling coating is characterized by using nanometal oxides doped with A nanoparticles containing Cu and / or Ag as an antifouling agent, replacing the antibacterial and antifouling components (e.g., cuprous oxide powder) in conventional antifouling coatings (e.g., antifouling paints) to achieve an antifouling effect.

[0377] Since Cu and Ag exist in the nanooxide M matrix at very small particle sizes, their utilization efficiency is extremely high, and therefore, only a very small amount of additive is needed to achieve the best antifouling effect.

[0378] Furthermore, the above Ag exists as at least one of Ag, Ag2O, and AgO, and the above Cu exists as at least one of Cu, Cu2O, and CuO.

[0379] In a twelfth aspect, the present invention also relates to the application of the A nanoparticle-doped nanometal oxide described in the ninth aspect to antimicrobial fabrics, wherein the component composition of the A nanoparticles comprises Cu and at least one of Ag.

[0380] Furthermore, the above application is characterized in that, after dispersing nanometal oxides doped with Cu and / or Ag-containing A nanoparticles, the material is attached to or coated on the surface of the fabric, or mixed with the fabric and knitted, thereby enabling the fabric to acquire antibacterial and germicidal effects and capabilities.

[0381] Furthermore, the above Ag exists as at least one of Ag, Ag2O, and AgO, and the above Cu exists as at least one of Cu, Cu2O, and CuO.

[0382] Specifically, the present invention has the following beneficial effects.

[0383] Firstly, using an MTA intermetallic compound or MT(A) intermetallic compound containing element A as a solid solution as a precursor, high-efficiency production of A nanoparticle-doped nanooxide M was achieved at atmospheric pressure by rapidly reacting the MTA intermetallic compound or MT(A) intermetallic compound with a base solution for a short period of time. By combining this with subsequent heat treatment or modification treatment, nanooxide M doped with A nanoparticles with increased crystallinity or nanooxide M doped with modified A nanoparticles was further produced. Furthermore, the production of inert A nanoparticles became possible by dissolving the nanooxide M matrix with an etching solution.

[0384] The strong base hydrothermal method is currently a relatively mature process for producing nanometal oxides. However, the reaction requires the use of a high-pressure reaction vessel, and generally involves using inexpensive metal oxides in different forms and a high concentration of a strong base (e.g., an aqueous NaOH solution) as raw materials, carrying out a hydrothermal synthesis reaction under high temperature conditions for a long period of time. The characteristics of conventional strong base hydrothermal methods for producing nanometal oxides are: 1) the use of inexpensive metal oxides in different forms as precursors (the precursors are already metal oxides), 2) the need for airtightness and high pressure conditions because it is carried out in a high-pressure reaction vessel, 3) the operation is carried out at high temperatures, and 4) the reaction time is very long, measured in units of several hours. In contrast, in the first aspect of the present invention, a strong base solution is also used to produce nanometal oxides doped with noble metal nanoparticles and their subsequent products, but it differs from the conventional strong base hydrothermal method in the following ways: 1) MTA intermetallic compounds or MT(A) intermetallic compounds in which element A is solid-dissolved are mainly used as precursors; 2) The reaction is carried out in an open container under atmospheric pressure, eliminating the need for a high-pressure sealed container; 3) The reaction is preferably carried out at or near the boiling point of the base solution, and does not need to be carried out at very high temperatures, and the upper limit of the temperature is the boiling point of the base solution, and is precise. The advantages include: 4) it is very easy to control; 5) the reaction can be completed in a few minutes to tens of seconds; and 6) the A-containing intermetallic compound in the initial alloy precursor undergoes nanofragmentation through vigorous hydrogen deposition and T-desorption reactions, and further undergoes reconstruction of shape and composition to generate nanoscale nanooxide M. At the same time, atoms of element A in the original MTA intermetallic compound and the MT(A) intermetallic compound in which element A is solid-solved evolve through diffusion dislocation to generate A-containing nanoparticles mainly composed of element A, thus enabling in-situ embedding doping of A-containing nanoparticles and nanooxide M.

[0385] The high-temperature base solution used in this invention serves three main purposes: 1) To remove the T element from the original MTA or MT(A) intermetallic compound by vigorous hydrogen deposition and T desorption reactions, thereby evolving the M element towards nano-oxidized M, and simultaneously evolving the A element towards A-containing nanoparticles. 2) To add OH to the high-temperature base solution. -The presence of dissolved O2 allows M element atoms left behind by hydrogen deposition and T removal to be rapidly liberated and rapidly bond with O, resulting in the rapid generation of nano-oxide M in as little as tens of seconds. Simultaneously, A element atoms left behind by hydrogen deposition and T removal do not form a nanoporous structure, but instead aggregate and bond, forming in-situ embedded and / or physically adsorbed A-containing nanoparticles. In contrast, the conventional high-pressure hydrothermal method uses highly stable oxide M as a precursor, requiring high pressure, high temperature, and several hours of reaction time to first break the MO bond structure in the oxide M precursor to liberate M, and then recombine it with O and other elements in a new and unique way to generate new nano-oxide M. 3) Provides a system environment of reaction equilibrium for obtaining specific forms of oxide M products with specific temperature, concentration, and type of high-temperature base solution. Changing the temperature, concentration, and type of high-temperature base solution may result in different morphologies of the resulting nano-oxide M matrix.

[0386] Secondly, the present invention has found that when an MTA or MT(A) intermetallic compound is reacted with a base solution at a high temperature, particularly preferably at the boiling point of the base solution, the shape of the initial alloy is rapidly and completely destroyed, achieving nanofragmentation of the original initial alloy. Through the reconstruction of shape and composition, a nanoscale nano-oxide M matrix with particle dispersibility is generated, and the A element diffuses and rearranges, producing doped A-containing nanoparticles. For example, if the average particle size of the initial alloy powder is 10 μm, the product obtained by carrying out a conventional concentrated base de-alloying reaction at or near room temperature for a long time is usually a nanoporous metal oxide or nanoporous metal with an average particle size of 10 μm, where the original particle shape, such as angular, is maintained and contains a nanoporous secondary structure inside. As in Comparative Example 1, when an initial alloy powder mainly composed of an Al3Nb(Au) intermetallic compound in which Au is solid-dissolved was reacted with a 10 mol / L NaOH aqueous solution at 25°C for 2 hours under atmospheric pressure, the shape of the original initial alloy powder remained almost unchanged before and after the reaction, remaining as the original angular pulverized powder particles. Its microstructure also did not produce numerous dispersed products such as nanoparticles, nanosheets, or nanorods, but rather a nanoporous structure was formed. This nanoporous structure formed an appearance consistent with the shape of the original alloy powder through a three-dimensional continuous rigid network linkage method, and its particle size remained equivalent to that of the initial alloy powder, mainly ranging from a few microns to several tens of microns. In contrast, in the manufacturing process of the present invention, the average particle size of the initial alloy powder or the thickness of the initial alloy strip is generally greater than 10 μm, and after nanofragmentation occurs by high-temperature base solution reaction, the resulting product is an A-containing nanoparticle doped with a nanooxide M matrix that has particle dispersibility and an average particle diameter of 500 nm or less, and does not contain a nanoporous secondary structure inside. Furthermore, these individual nano-oxide M matrices are monodisperse and can be softly aggregated, but they cannot be firmly bonded by a three-dimensional continuous network structure to maintain the rigid shape of the original initial alloy (including the angular shape of the particles).Therefore, considering that the initial alloy strips are thick, or the powder particle size is generally large (for example, the strip thickness is usually 10 μm or more, and the average particle size is usually 5 μm or more), if the morphology of the products before and after the de-alloying reaction does not change much, reacting MTA or MT(A) intermetallic compounds with a base solution at room temperature or below generally yields nanoporous oxides or nanoporous metals of a micron size that are comparable to and still large to the initial alloy particle size. These products are unsuitable for many applications requiring fine particle size and dispersibility. Furthermore, even if small nanoscale fragments of such materials can be collected for TEM observation by, for example, ultrasonic dispersion, they belong to a three-dimensional network skeletal structure and therefore cannot be completely dispersed in a single dispersed particle that does not contain the nanoporous secondary structure. In contrast, the present invention cleverly utilizes the expansion effect of hydrogen gas generated by the vigorous reaction and water vapor generated by vaporization, as well as the shape reconstruction characteristics of the special hydrogen deposition / de-T reaction product of the present invention, to thoroughly nano-fragment the shape of the product (although the gas expansion effect is not necessarily the sole cause of nano-fragmentation, it undoubtedly greatly accelerates the nano-fragmentation process and is one of the important factors in the nano-fragmentation of the product) and reconstruct it. As a result, instead of conventional large nanoporous materials, nano-oxide M doped with highly dispersed A nanoparticles is obtained, greatly expanding the application fields of the manufactured material and clearly having positive significance.

[0387] Furthermore, shape reconstruction occurs in parallel with nanofragmentation. Shape reconstruction means that the nanoscale product obtained by the hydrogen precipitation-de-T reaction is not merely fragmentation of the nanoporous structure (ligament), but a complete reconstruction. If the nanoporous structure is obtained by the low-temperature hydrogen precipitation-de-T reaction, and the product obtained by the high-temperature hydrogen precipitation-de-T reaction is merely fragmentation of the nanoporous structure, then it can only be described as mere fragmentation, and the form of the product is a fragmented porous ligament. However, in reality, what occurs in the embodiments of the present invention is not just such simple fragmentation, but also shape reconstruction. Various different shapes of nano-oxidized M matrix, such as lath-like structures, aggregated structures, and especially film structures, cannot be simply obtained by fragmentation of the nanoporous structure ligament alone. Therefore, the present invention inventively realizes, by controlling the reaction conditions, that the nano-oxidized M matrix in the product is formed not by the nanoporous structure formation mechanism and further fragmented, but through a special fragmentation and complete reconstruction process, which has excellent theoretical and practical significance.

[0388] Thirdly, by precisely controlling the reaction conditions, the composition and morphology of the product can be precisely controlled. Specifically, once the concentration of the base in the solution is determined, the boiling point at which the base solution can be heated under atmospheric pressure is also determined, and the pressure and temperature in the reaction conditions are precisely determined. If the reaction temperature is preferably the boiling point of the base solution, and the concentration of the base solution is kept nearly constant by means of replenishing the solvent, the excess heat added to the base solution is converted into the heat of vaporization of water without raising the temperature of the base solution, so that the temperature of the base solution can be kept constant at the boiling point by continuous heating. Furthermore, even if a large amount of latent heat of reaction is generated during the reaction process, the temperature of the reacting base solution can be reliably maintained at the boiling point of the base solution. On the other hand, conventional high-pressure hydrothermal synthesis methods synthesize products at high temperature and high pressure. If it is necessary to terminate the reaction, it is difficult to quickly return to room temperature and atmospheric pressure and remove the sample, and it takes a certain amount of time to complete. In contrast, since the manufacturing process of the present invention is carried out under atmospheric pressure in an open vessel, if it is necessary to terminate the reaction, it is only necessary to rapidly add the solvent (cold water or room temperature water) to the reaction vessel within a few seconds, and the temperature and concentration of the reaction system can be reduced almost instantaneously to a temperature at which the reaction can no longer be continued, while maintaining the composition and form of the original reaction equilibrium product. Therefore, the technical solution provided by the present invention can yield a product with a very stable composition and form. Stable control of the composition and form of the product is one of the important elements for broad application and has positive significance.

[0389] Fourth, the simultaneous production of doped A-containing nanoparticles and nano-oxide M matrix can be achieved, and the doped A-containing nanoparticles and nano-oxide M matrix can be bonded by in-situ embedding. Doped elements and doped nanoparticles play a very important and active role in the functional applications of nanometal oxides, such as in the field of photocatalysis. Conventional strategies for producing nanometal oxides containing doped metal nanoparticles mainly involve producing nanometal oxides first, and then mixing them with doped metal nanoparticles produced by other methods. The metal nanoparticles produced in this two-step process are mainly attached to the nanometal oxide matrix by physical adsorption. Furthermore, this mechanical mixing and physical attachment is not only unfavorable for atomic-scale physicochemical interactions between the doped elements and the matrix, but also makes the doped metal nanoparticles prone to detaching from the nanometal oxide matrix, resulting in unstable and degraded material performance. This invention creatively solves the above problems: through the embedding distribution of doped A-containing nanoparticles embedded in a nanometal oxide matrix, the problem of doped metal nanoparticle detachment is effectively resolved, and the physicochemical interaction between the doped metal nanoparticles and the nanometal oxide matrix is ​​also significantly enhanced. Furthermore, the particle size of the in-situ embedded doped A-containing nanoparticles can be reduced to the atomic or atomic cluster level (0.25 nm to 2 nm), which is absolutely unattainable by conventional methods. This is because there are limitations to the particle size of metal nanoparticles that can be manufactured by conventional manufacturing methods; generally, the particle size of metal nanoparticles that can be manufactured is large, and it is difficult to first manufacture dispersed noble metal nanoparticles with a particle size of 10 nm or less and then physically mix them with nanometal oxides. Moreover, conventional manufacturing methods cannot obtain nanometal oxides doped with ultrafine noble metal nanoparticles or noble metal atoms / atomic clusters, and the doped elements affect the thermal stability of the nanometal oxide matrix.For example, in one embodiment of the present invention, it was found that when element A is doped into the nanochromium oxide matrix in the form of atoms or atomic clusters with extremely small particle sizes, the thermal stability and crystallization temperature of the low-crystallinity nanochromium oxide matrix are significantly improved. Furthermore, the element M in this invention includes Cr, V, Nb, Ta, W, Mo, Mn, and rare earth elements (Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), but all of them were not chosen randomly, but selected after extensive research. The applicant has found that when element M is replaced with elements such as Fe, Co, Ni, Zr, Hf, and Ti, the reaction process and products differ. For example, when element M is replaced with Fe, Co, or Ni, the resulting product is not a nanometal oxide matrix of Fe, Co, or Ni, but mainly consists of nanoporous metal (Fe, Co, Ni) powder such as Raney Ni (the temperature of the base solution is generally about 50°C, and the reaction time is generally several tens of minutes). When element M is replaced with Zr or Hf, no M-containing nanosolid product is obtained in step 2 of the first embodiment (Zr and Hf also dissolve in the base solution and do not exist as solid substances). When element M is replaced with Ti, the matrix obtained in step 3 of the first embodiment is not a nanometal oxide matrix containing M, but a nanotianate.

[0390] Fifth, in its fourth embodiment, the present invention provides a method for creatively producing inert noble metal nanoparticles by utilizing the inert properties of doped A nanoparticles and the property that nano-oxide M, which has an ultra-high specific surface area, can be dissolved by a specific etching solution, which is of great significance. This method first involves melting to obtain an initial alloy whose solidified structure mainly consists of MTA or MT(A) intermetallic compounds. At this time, the A element is uniformly dispersed, and the atoms of the A element are generally not bonded to each other. That is, the melting and solidification of the initial alloy first achieves a uniform dispersion distribution of A element atoms in the MTA or MT(A) intermetallic compound. Next, the MTA or MT(A) intermetallic compound is reacted with a high-temperature concentrated base solution, the T element is introduced into the solution and removed, and the M element is transformed into a nano-oxide M matrix by nano-fragmentation and reconstruction of composition and shape. Meanwhile, the A element atoms undergo diffusive dislocations simultaneously in the process, generating A-containing nanoparticles, which are composite-doped into the nano-oxide M matrix by embedding and / or physical adsorption. Finally, the nanooxide M matrix is ​​removed with a specific etching solution to obtain A nanoparticles, which are mainly composed of inert element A.

[0391] Sixth, large-scale industrial production of related product materials becomes possible. The reaction pressure in the key steps of this series of inventions is atmospheric pressure, eliminating the need for high-pressure sealed containers, and the reaction temperature is at or near the boiling point of the solution (depending on the concentration of base in the solution, the temperature is approximately 105°C to 150°C, which is relatively mild). The required precursors are mainly MTA or MT(A) intermetallic compounds, which can be manufactured on a large scale by methods such as "alloy melting + casting + grinding" or "alloy melting + melt stripping". Particularly important is that the critical reaction time is short, only a few seconds, making it extremely efficient, and that conditions such as reaction temperature and pressure can be precisely controlled to obtain the desired product. These features greatly simplify the manufacturing process, improve production efficiency, reduce manufacturing costs, and enable the large-scale production of corresponding products at low cost, atmospheric pressure, medium temperature, short time, and high efficiency.

[0392] Therefore, the most important originality of the present invention is to provide a rapid and simple method for producing nanometal oxides doped with highly dispersible noble metal nanoparticles by using an alloy as a raw material. The manufacturing method of the present invention has the characteristics of a simple process, easy operation, high efficiency and low cost, and can produce various products such as nanometal oxide powder doped with noble metal nanoparticles, highly crystalline nanometal oxide powder doped with noble metal nanoparticles, and noble metal nanopowder, which can be used in a wide range of applications such as composite materials, catalyst materials, ceramic materials, refractory materials, advanced electronic materials, battery materials, discoloration materials, wave absorbing materials, wastewater decomposition materials, sterilization materials, paints, pigments, thermal spray materials, and sensors. [Brief explanation of the drawing]

[0393] [Figure 1] Figure 1 shows the TEM image and diffraction spectrum of nanoniobium oxide doped with Au nanoparticles, which was produced in Example 1 of the present invention.

[0394] [Figure 2] Figure 2 shows the TEM image and diffraction spectrum of the nanoniobium oxide doped with Au nanoparticles, manufactured in Example 1 of the present invention, after heat treatment at 600°C.

[0395] [Figure 3] Figure 3 is a high-magnification TEM image of nanoniobium oxide doped with Au nanoparticles, manufactured in Example 1 of the present invention, after heat treatment at 600°C.

[0396] [Figure 4] Figure 4 shows a low-magnification TEM image and diffraction spectrum of nanotantalum oxide doped with Au nanoparticles, produced in Example 3 of the present invention.

[0397] [Figure 5] Figure 5 shows a high-magnification TEM image and diffraction spectrum of nanotantalum oxide doped with Au nanoparticles, manufactured in Example 3 of the present invention.

[0398] [Figure 6] Figure 6 shows a high-magnification TEM image and diffraction spectrum of nanotantalum oxide doped with Au nanoparticles, manufactured in Example 3 of the present invention.

[0399] [Figure 7] Figure 7 shows a low-magnification TEM image and diffraction spectrum of nanotantalum oxide doped with Au nanoparticles, manufactured in Example 3 of the present invention, after heat treatment at 600°C.

[0400] [Figure 8] Figure 8 is a high-magnification TEM image of nanotantalum oxide doped with Au nanoparticles, manufactured in Example 3 of the present invention, after heat treatment at 600°C.

[0401] [Figure 9] Figure 9 is a high-resolution TEM image of nanotantalum oxide doped with Au nanoparticles, manufactured in Example 3 of the present invention, after heat treatment at 600°C.

[0402] [Figure 10] Figure 10 is a TEM image of the Ag nanoparticle-doped nanovanadium oxide produced in Example 4 of the present invention.

[0403] [Figure 11] Figure 11 shows a low-magnification TEM image and diffraction spectrum of the Ag nanoparticle-doped nanotungsten oxide produced in Example 5 of the present invention after heat treatment at 600°C.

[0404] [Figure 12] Figure 12 is a high-magnification TEM image of the Ag nanoparticle-doped nanotungsten oxide produced in Example 5 of the present invention after heat treatment at 600°C.

[0405] [Figure 13]Figure 13 shows a low-magnification TEM image and diffraction spectrum of the Ag nanoparticle-doped nanomolybdenum oxide produced in Example 6 of the present invention.

[0406] [Figure 14] Figure 14 is a high-magnification TEM image of the Ag nanoparticle-doped nanomolybdenum oxide produced in Example 6 of the present invention.

[0407] [Figure 15] Figure 15 shows a low-magnification TEM image and diffraction spectrum of the Ag nanoparticle-doped nanoyttrium oxide produced in Example 7 of the present invention.

[0408] [Figure 16] Figure 16 is a high-magnification TEM image of the Ag nanoparticle-doped nanoyttrium oxide produced in Example 7 of the present invention.

[0409] [Figure 17] Figure 17 is a low-magnification TEM image of nanoyttrium oxide doped with Au nanoparticles, produced in Example 8 of the present invention.

[0410] [Figure 18] Figure 18 shows a high-magnification TEM image and diffraction spectrum of nanoyttrium oxide doped with Au nanoparticles, prepared in Example 8 of the present invention.

[0411] [Figure 19] Figure 19 shows a low-magnification TEM image and diffraction spectrum of nanoyttrium oxide doped with Au nanoparticles, prepared in Example 9 of the present invention.

[0412] [Figure 20] Figure 20 is a high-magnification TEM image of nanoyttrium oxide doped with Au nanoparticles, manufactured in Example 9 of the present invention.

[0413] [Figure 21]Figure 21 is a high-resolution TEM image of nanoyttrium oxide doped with Au nanoparticles, produced in Example 9 of the present invention.

[0414] [Figure 22] Figure 22 shows a low-magnification TEM image and diffraction spectrum of the Au nanoparticle-doped nanochromium oxide produced in Example 10 of the present invention.

[0415] [Figure 23] Figure 23 is a high-magnification TEM image of nanochromium oxide doped with Au nanoparticles, manufactured in Example 10 of the present invention.

[0416] [Figure 24] Figure 24 shows the TEM image and diffraction spectrum of the Au nanoparticles produced in Example 10 of the present invention.

[0417] [Figure 25] Figure 25 shows a low-magnification TEM image and diffraction spectrum of the Au nanoparticle-doped nanochromium oxide produced in Example 11 of the present invention.

[0418] [Figure 26] Figure 26 is a high-magnification TEM image of nanochromium oxide doped with Au nanoparticles, manufactured in Example 11 of the present invention.

[0419] [Figure 27] Figure 27 shows a high-magnification TEM image of nanochromium oxide doped with Au nanoparticles produced in Example 11 of the present invention, and a high-resolution TEM image of the embedded Au nanoparticles.

[0420] [Figure 28] Figure 28 is a backscatter SEM image of the solidification structure of the alloy ingot described in Example 12 of the present invention.

[0421] [Figure 29]Figure 29 is a low-magnification TEM image of the Ag nanoparticle-doped nanochromium oxide produced in Example 12 of the present invention.

[0422] [Figure 30] Figure 30 shows a high-magnification TEM image and diffraction spectrum of Ag nanoparticle-doped nanochromium oxide produced in Example 12 of the present invention.

[0423] [Figure 31] Figure 31 shows a low-magnification TEM image and diffraction spectrum of the Ag nanoparticle-doped nanochromium oxide produced in Example 12 of the present invention after heat treatment at 600°C.

[0424] [Figure 32] Figure 32 is a high-magnification TEM image of the Ag nanoparticle-doped nanochromium oxide produced in Example 12 of the present invention after heat treatment at 600°C.

[0425] [Figure 33] Figure 33 is a low-magnification TEM image of the Ag-Cu-Au nanoparticle-doped nanochromium oxide produced in Example 13 of the present invention.

[0426] [Figure 34] Figure 34 is a high-magnification TEM image of a nanochromium oxide doped with Ag-Cu-Au nanoparticles, manufactured in Example 13 of the present invention.

[0427] [Figure 35] Figure 35 shows a low-magnification TEM image and diffraction spectrum of the Au nanoparticle-doped nanomanganese oxide produced in Example 14 of the present invention.

[0428] [Figure 36] Figure 36 is a high-magnification TEM image of nanomanganese oxide doped with Au nanoparticles, manufactured in Example 14 of the present invention.

[0429] [Figure 37] Figure 37 shows a low-magnification TEM image and diffraction spectrum of the Au nanoparticle-doped nanomanganese oxide produced in Example 14 of the present invention after heat treatment at 600°C.

[0430] [Figure 38] Figure 38 is a high-magnification TEM photograph-1 of the nanomanganese oxide doped with Au nanoparticles produced in Example 14 of the present invention after heat treatment at 600°C.

[0431] [Figure 39] Figure 39 is a high-magnification TEM photograph-2 of the nanomanganese oxide doped with Au nanoparticles produced in Example 14 of the present invention after heat treatment at 600°C.

[0432] [Figure 40] Figure 40 is a high-magnification TEM photograph-3 of the nanomanganese oxide doped with Au nanoparticles produced in Example 14 of the present invention after heat treatment at 600°C.

[0433] [Figure 41] Figure 41 is a low-magnification TEM image of the Ag nanoparticle-doped nanomanganese oxide produced in Example 15 of the present invention.

[0434] [Figure 42] Figure 42 is a high-magnification TEM image of the Ag nanoparticle-doped nanomanganese oxide produced in Example 15 of the present invention.

[0435] [Figure 43] Figure 43 is a low-magnification TEM image of modified nanomanganese oxide doped with Ag nanoparticles, which was produced in Example 16 of the present invention.

[0436] [Figure 44] Figure 44 is a medium-magnification TEM image of modified nanomanganese oxide doped with Ag nanoparticles, which was produced in Example 16 of the present invention.

[0437] [Figure 45] Figure 45 is a high-magnification TEM image of modified nanomanganese oxide doped with Ag nanoparticles, which was produced in Example 16 of the present invention.

[0438] [Figure 46] Figure 46 is a high-resolution TEM image of modified nanomanganese oxide doped with Ag nanoparticles, produced in Example 16 of the present invention.

[0439] [Figure 47] Figure 47 is a low-magnification TEM image of nanochromium oxide doped with Pt-Pd-Au-Ru nanoparticles, manufactured in Example 17 of the present invention.

[0440] [Figure 48] Figure 48 is a high-magnification TEM image of nanochromium oxide doped with Pt-Pd-Au-Ru nanoparticles, manufactured in Example 17 of the present invention.

[0441] [Figure 49] Figure 49 is a low-magnification SEM image of nanochromium oxide doped with Au nanoparticles, manufactured in Example 18 of the present invention.

[0442] [Figure 50] Figure 50 is a high-magnification SEM image of nanochromium oxide doped with Au nanoparticles produced in Example 18 of the present invention.

[0443] [Figure 51] Figure 51 is an SEM image of nanoporous niobium oxide doped with Au nanoparticles, which was produced in Comparative Example 1 of the present invention.

[0444] [Figure 52] Figure 52 shows the TEM image and diffraction spectrum of the nanochromium oxide produced in Comparative Example 2 of the present invention.

[0445] [Figure 53]Figure 53 shows the TEM image and diffraction spectrum of the nanochromium oxide produced in Comparative Example 2 of the present invention after heat treatment at 600°C.

[0446] [Modes for carrying out the invention]

[0447] The present invention will be further described below with reference to specific examples.

[0448] [Example 1] This embodiment provides a nanoniobium oxide doped with Au nanoparticles and a method for producing Au nanoparticles, comprising the following steps.

[0449] Au 0.5 Al 74.5 Nb 25 (According to the nominal composition of (atomic percentage), Al, Nb and Au raw materials are melted and Au 0.5 Al 74.5 Nb 25 A molten alloy mainly composed of was obtained. The obtained molten alloy was cast by copper roller strip casting to a thickness of ~25 μm and a composition mainly of Au. 0.5 Al 74.5 Nb 25 The initial alloy ribbon was manufactured, and its solidified structure mainly consisted of an Al3Nb(Au) intermetallic compound in which Au was dissolved, with a solid solution amount of Au of approximately 0.5 at.%.

[0450] Under normal pressure, the Au manufactured above 0.5 Al 74.5 Nb 25 The initial alloy ribbon was reacted with a NaOH solution. The concentration of the NaOH solution was 10 mol / L, and the temperature was the boiling point at atmospheric pressure (approximately 119°C). The volume of the NaOH solution was Au 0.5 Al 74.5 Nb 25 The volume was approximately 50 times that of the initial alloy ribbon, and the hydrogen deposition reaction was completed within 1 minute. The initial alloy was nano-fragmented by the hydrogen deposition and de-Al reaction, and its shape and composition were simultaneously reconfigured, generating solid aggregate products.

[0451] After 2 minutes from the start of the hydrogen deposition and de-Al reaction, the solid aggregate product was separated from the solution, washed, and dried to obtain a low-crystallinity nano-Nb oxide doped with Au nanoparticles, mainly consisting of amorphous nano-Nb oxide or amorphous Nb hydroxide as the matrix. Its TEM morphology and diffraction spectrum are shown in Figure 1. Its morphology consists mainly of extremely fine aggregate microstructures ranging from 1.0 nm to 15 nm. Such aggregate microstructures are not rigid nanoporous structures, but rather non-rigid aggregate structures that can be dispersed flatly. Due to its low crystallinity (see diffraction spectrum), it is difficult to clearly observe the details of the aggregate microstructure by TEM. The Au nanoparticles doped therein have a particle size of 0.25 nm to 5 nm and are mainly embedded in the nano-Nb oxide matrix in the form of atoms or atomic clusters (the nano-niobium oxide mentioned above corresponds to the nano-Nb oxide).

[0452] The solid aggregate product recovered 2 minutes after the start of the hydrogen deposition and de-Al reaction described above was heat-treated at 600°C for 2 hours to obtain nano-Nb oxide doped with Au nanoparticles with slightly improved crystallinity. The low-magnification TEM morphology and diffraction spectrum are shown in Figure 2, and the high-magnification TEM morphology is shown in Figure 3. From the diffraction spectrum, it was found that the crystallinity of the nano-Nb oxide after heat treatment at this temperature was only slightly improved, and it was still mainly composed of low-crystallinity nano-Nb oxide. However, its morphology evolved from the aggregated structure before heat treatment to a partially thin-film structure, with a film thickness of 5 nm or less and an area of ​​100 nm. 2 In summary, after heat treatment, the Au nanoparticles underwent some degree of fusion and growth, resulting in particle sizes ranging from 0.25 nm to 10 nm, for example, the approximately 4 nm Au nanoparticles shown in the inset of Figure 3. The applicant found that simple low-crystallinity nanoniobium oxide Nb becomes essentially crystalline nanoniobium oxide Nb by heat treatment at 600°C for 2 hours. Therefore, the phenomenon of improved thermal stability (reduced crystallization) of the low-crystallinity nanoniobium oxide Nb matrix in this embodiment further suggests that elemental Au is embedded in the nano-Nb oxide matrix in-situ before heat treatment, mainly in the form of atoms or atomic clusters.

[0453] The above-mentioned Au nanoparticles with slightly improved crystallinity were doped with nano-oxidized Nb in a 2 mol / L hydrofluoric acid aqueous solution. By removing the nano-oxidized Nb matrix with slightly improved crystallinity, the originally embedded inactive Au nanoparticles separated freely and grew through a certain degree of free fusion, yielding Au nanoparticles with particle sizes ranging from 3 nm to 75 nm.

[0454] The solid aggregate product recovered 2 minutes after the start of the hydrogen deposition and de-Al reaction described above was directly heat-treated at 900°C for 2 hours to obtain crystalline nano-oxide Nb doped with Au nanoparticles. The crystalline nano-oxide Nb was mainly granular in shape, with a particle size of 3 nm to 150 nm. The Au nanoparticles were mainly partially or completely embedded within the crystalline nano-oxide Nb, with a particle size of 1 nm to 30 nm.

[0455] Au 0.5 Al 74.5 Nb 25 One minute after the start of the hydrogen deposition and de-Al reaction of the initial alloy ribbon, the base solution of the reaction system was sealed directly into the reaction vessel along with the solid product. The temperature of the reaction vessel and its interior was raised to 250°C and maintained for 20 minutes. Under sealed conditions, the pressure inside the reaction vessel was higher than atmospheric pressure. After 20 minutes of maintenance, the temperature and pressure were reduced, the product in the reaction vessel was separated into solid and liquid components, washed and dried to obtain nano-Nb oxide doped with modified Au nanoparticles. Here, the nano-Nb oxide matrix was mainly crystalline, and its morphology consisted mainly of tubular and short rod shapes. The diameter range of the tubular or short rod shapes was 2 nm to 30 nm, and the aspect ratio was 2 or greater. The Au nanoparticles were embedded and grown in the nano-Nb oxide matrix, and the particle size of the nanoparticles was 0.5 nm to 20 nm.

[0456] [Example 2] This embodiment provides a method for producing nanoniobium oxide doped with Au nanoparticles, and includes the following steps.

[0457] Au 10 Al 55 Nb 35According to the nominal composition ((atomic percentage)), the raw materials of Al, Nb, and Au were melted to obtain an alloy melt mainly composed of Au 10 Al 55 Nb 35 The obtained alloy melt was made into an initial alloy ribbon with a thickness of ~25 μm and a composition mainly of Au 10 Al 55 Nb 35 The solidification structure of the initial alloy ribbon was mainly composed of an Al-Nb-Au intermetallic compound with the above composition, and the atomic percentage content of Au was about 10 at.%.

[0458] Under normal pressure, the initial alloy ribbon of Au 10 Al 55 Nb 35 was reacted with a KOH solution while stirring. The concentration of the KOH solution was 15 mol / L, the temperature was the boiling point at normal pressure (about 150 °C), and the volume of the KOH solution was about 50 times the volume of the initial alloy ribbon of Au 0.5 Al 74.5 Nb 25 The hydrogen evolution reaction ended within 30 s. The initial alloy was nano-fragmented by the hydrogen evolution and de-Al reaction, and at the same time, the shape and composition were reorganized to form a solid agglomerated product.

[0459] One minute after the start of the hydrogen evolution and de-Al reaction, 10 times the amount of normal temperature water (20 °C) was added to the reaction system to rapidly lower the reaction temperature to 40 °C or below and reduce the base solution concentration to 1.5 mol / L or below. After dilution, the solid product was separated from the solution, washed, and dried to obtain a low-crystalline nano Nb oxide doped with Au nanoparticles with mainly amorphous nano Nb oxide or amorphous Nb hydroxide as the matrix. The shape of the nano Nb oxide matrix was mainly granular and film-like. The particle size of the granular particles was 2 nm to 100 nm, the thickness of the film was 1 nm to 15 nm, and the average area was 100 nm 2The above describes the size of the Au nanoparticles, ranging from 0.25 nm to 50 nm, which are doped into a nano-Nb oxide matrix by in-situ embedding and physioadsorption. In-situ embedded Au nanoparticles are fixed and embedded in the nano-Nb oxide matrix. On the other hand, physioadsorbed Au nanoparticles can undergo adsorption, desorption, and readsorption reactions with the nano-Nb oxide matrix under specific conditions.

[0460] [Example 3] This embodiment provides a nanotantalum oxide doped with Au nanoparticles and a method for producing Au nanoparticles, comprising the following steps.

[0461] Au 0.75 Al 74.25 Ta 25 According to the nominal composition (atomic percentage), Al, Ta, and Au raw materials are melted and Au 0.75 Al 74.25 Ta 25 A molten alloy mainly composed of was obtained. The obtained molten alloy was cast by copper roller strip casting to a thickness of 20 μm to 30 μm, with a composition mainly of Au. 0.75 Al 74.25 Ta 25 The initial alloy ribbon was manufactured, and its solidified structure mainly consisted of an Al3Ta(Au) intermetallic compound in which Au was dissolved, with a solid solution amount of Au of approximately 0.75 at.%.

[0462] Under normal pressure, Au 0.75 Al 74.25 Ta 25 The initial alloy ribbon was reacted with a NaOH solution. The concentration of the NaOH solution was 12 mol / L, the temperature was the boiling point at atmospheric pressure (approximately 128°C), and the volume of the NaOH solution was Au. 0.75 Al 74.25 Ta 25 The volume was approximately 100 times that of the initial alloy ribbon. The hydrogen deposition and de-algae reaction was completed within 1 minute, and the initial alloy was nano-fragmented by the reaction, simultaneously undergoing a reconfiguration of its shape and composition, and generating solid aggregate products.

[0463] After 2 minutes from the start of the hydrogen deposition and de-Al reaction, all solid products were separated from the solution, washed, and dried to obtain low-crystalline nano-Ta oxide doped with Au nanoparticles. Its TEM image and diffraction spectrum are shown in Figure 4. From the diffraction spectrum, it can be seen that the nano-Ta oxide matrix is ​​mainly amorphous nano-Ta oxide or amorphous Ta hydroxide. As can be seen from the figure, the morphology of the nano-Ta oxide matrix consists mainly of aggregated clusters (shown in the upper right inset of Figure 4) and spiral films (shown in Figure 4). Here, the size range of the aggregated cluster microstructure was 1.0 nm to 10 nm, and the film-like structure curled to enclose an incomplete hollow spherical shell, with a film thickness of 1.0 nm to 10 nm. The Au nanoparticles doped therein were composite-doped into the nano-Ta oxide matrix by two methods: in-situ embedding and physioadsorption. Some of the physioadsorbed Au nanoparticles can undergo adsorption, desorption, and re-adsorption reactions with the nano-Ta oxide matrix under specific conditions (see the particles at the top of Figure 5). The particle size range of in-situ embedded Au nanoparticles was 0.25 nm to 20 nm (see Figure 6), and the particle size range of physically adsorbed Au nanoparticles was 2 nm to 20 nm (see Figure 5). The applicant found that the solid product obtained from Al3Ta intermetallic compounds without solid solution of Au under similar reaction conditions was mainly crystalline nano-Ta oxide solid spherical particles (particle size 3 nm to 100 nm), and that solid solution of Au in Al3Ta(Au) intermetallic compounds completely changes the crystallinity and morphology of the nano-Ta oxide matrix doped with Au nanoparticles obtained by the hydrogen deposition and de-Al reaction of the Al3Ta(Au) intermetallic compound.

[0464] The solid product recovered 2 minutes after the start of the hydrogen deposition and de-Al reaction described above was heat-treated at 600°C for 2 hours to obtain clearly crystalline nano-Ta oxide doped with Au nanoparticles. Its low-magnification TEM morphology and diffraction spectrum are shown in Figure 7, and its high-magnification TEM morphology is shown in Figures 8 and 9. From the diffraction spectrum, it was found that the crystallinity of the nano-Ta oxide matrix after heat treatment at this temperature was significantly improved, and that it was mainly crystalline nano-Ta oxide. The morphology of the nano-Ta oxide matrix evolved from the original aggregated clusters and curled films to granular, with particle sizes ranging from 5 nm to 100 nm (see Figure 7). Simultaneously, in-situ embedded Au nanoparticles fused and grew, with particle sizes ranging from 3 nm to 50 nm (see Figures 8-9).

[0465] The solid product prepared 2 minutes after the start of the hydrogen deposition and de-Al reaction described above was reacted with a 2 mol / L hydrofluoric acid aqueous solution to remove the nanooxide Ta matrix, which allowed the originally embedded inert Au nanoparticles to be freely separated and mixed with the originally physically adsorbed inert Au nanoparticles, resulting in Au nanoparticles with a particle size of 3 nm to 100 nm.

[0466] Au 0.75 Al 74.25 Ta 25 One minute after the start of the hydrogen deposition and de-Al reaction of the initial alloy ribbon, the base solution of the reaction system was sealed directly into the reaction vessel along with the solid product. The temperature of the reaction vessel and its interior was raised to 200°C and maintained for 30 minutes. Under sealed conditions, the pressure inside the reaction vessel was higher than atmospheric pressure. After 30 minutes of maintenance, the temperature and pressure were reduced, the product in the reaction vessel was separated into solid and liquid components, washed and dried to obtain nano-oxide Ta doped with modified Au nanoparticles. Here, the nano-Ta oxide matrix was mainly crystalline, and its morphology consisted mainly of particles with a particle size range of 2 nm to 150 nm. The Au nanoparticles were embedded and grown in the nano-Ta oxide matrix, with a particle size range of 0.5 nm to 15 nm.

[0467] [Example 4] This embodiment provides a method for producing a nanovanadium oxide doped with Ag nanoparticles, and includes the following steps.

[0468] Ag 0.3 Al 61.7 V 38 According to the nominal composition (atomic percentage), Al, V and Ag raw materials are melted and Ag 0.3 Al 61.7 V 38 A molten alloy mainly composed of was obtained. The obtained molten alloy was solidified into an ingot, and then the ingot was crushed to obtain an alloy with a particle size of approximately 50 μm and a composition mainly of Ag. 0.3 Al 61.7 V 38 The initial alloy powder was manufactured, and its solidified structure mainly consisted of an Al8V5(Ag) intermetallic compound in which Ag was dissolved, with a solid solution amount of Ag of approximately 0.3 at.%.

[0469] Under normal pressure, Ag 0.3 Al 61.7 V 38 The initial alloy powder was reacted with NaOH solution while stirring. The concentration of the NaOH solution was 10 mol / L, the temperature was the boiling point at atmospheric pressure (approximately 119°C), and the volume of the NaOH solution was Ag. 0.3 Al 61.7 V 38 The volume was approximately 50 times that of the initial alloy powder. The hydrogen deposition and de-algae reaction was completed within 2 minutes. The initial alloy powder was fragmented into nano-fragments by the hydrogen deposition and de-algae reaction, and its shape and composition were simultaneously reconfigured, producing a solid product.

[0470] After 2 minutes from the start of the hydrogen deposition and de-Al reaction, the solid product was separated from the solution, washed, and dried to obtain low-crystalline nano-V oxides doped with Ag nanoparticles, mainly consisting of amorphous nano-V oxide or amorphous V hydroxide as the matrix. A TEM image of this is shown in Figure 10. The morphology of the nano-oxide V matrix consists mainly of extremely fine aggregated microstructures ranging from 1.0 nm to 10 nm. Such aggregated microstructures are not rigid nanoporous structures, but rather non-rigid aggregated structures that can be dispersed flat (the contrast in Figure 10 is relatively uniform because the change in thickness after flat dispersion is small). The Ag nanoparticles doped therein are composite-doped mainly by in-situ embedding into the nano-oxide V matrix, as indicated by the arrows in Figure 10. The components of the Ag-containing nanoparticles included at least one of Ag or Ag oxide, and the size range of the Ag-containing nanoparticles was 0.25 nm to 15 nm.

[0471] The solid product prepared 2 minutes after the start of the hydrogen deposition and de-Al reaction was directly heat-treated at 900°C for 2 hours to obtain crystalline nano-oxide V doped with Ag nanoparticles. The crystalline nano-oxide V was mainly granular in shape, with a particle size of 3 nm to 150 nm, and the Ag nanoparticles were mainly embedded within the crystalline nano-oxide V, with a particle size of 1 nm to 30 nm.

[0472] Ag 0.3 Al 61.7 V 38 The initial alloy powder was mixed with 50 times its volume of 10 mol / L NaOH aqueous solution at a temperature of 30°C. The mixture was then sealed directly into a reaction vessel, and the temperature of the vessel and its interior was raised to 250°C. The temperature was maintained for 20 minutes. Under sealed conditions, the pressure inside the reaction vessel was higher than atmospheric pressure. After 20 minutes of maintenance, the temperature and pressure were reduced, the product in the reaction vessel was separated into solid and liquid components, washed and dried to obtain nano-V oxide doped with modified Ag nanoparticles. Here, the nano-V oxide matrix was mainly crystalline, and its morphology consisted mainly of particles with a particle size range of 2 nm to 150 nm. Ag nanoparticles were embedded and grown in the nano-V oxide matrix, with a particle size range of 0.5 nm to 15 nm.

[0473] [Example 5] This embodiment provides a method for producing a nanotungsten oxide doped with Ag nanoparticles, and includes the following steps.

[0474] Ag 0.2 Al 78.8 W 20 (According to the nominal composition of (atomic percentage), Al, W and Ag raw materials are melted and Ag 0.2 Al 78.8 W 20 A molten alloy mainly composed of was obtained. The obtained molten alloy was cast by copper roller strip casting to a thickness of 20 μm to 30 μm, with a composition mainly of Ag. 0.2 Al 78.8 W 20 The initial alloy ribbon was manufactured, and its solidified structure mainly consisted of an Al4W(Ag) intermetallic compound in which Ag was dissolved, with a solid solution amount of Ag of approximately 0.2 at.%.

[0475] Under normal pressure, Ag 0.2 Al 78.8 W 20 The initial alloy ribbon was reacted with a NaOH solution. The concentration of the NaOH solution was 10 mol / L, the temperature was the boiling point at atmospheric pressure (approximately 119°C), and the volume of the NaOH solution was Ag. 0.2 Al 78.8 W 20 The volume was approximately 30 times that of the initial alloy ribbon. The hydrogen deposition reaction was completed within 1 minute, and the initial alloy ribbon was nanofragmented by the hydrogen deposition and de-Al reaction, simultaneously reconstructing its shape and composition to produce a solid product.

[0476] After 2 minutes from the start of the above hydrogen deposition and de-Al reaction, the solid product was separated from the solution, washed, and dried to obtain low-crystallinity nano-W oxides doped with Ag nanoparticles, mainly consisting of amorphous nano-W oxide or amorphous W hydroxide as the matrix. Its TEM morphology and diffraction spectrum are shown in Figure 1. The morphology of the nano-oxide W matrix consisted mainly of extremely fine, low-crystallinity aggregated microstructures, with a size range of 1.0 nm to 10 nm. The Ag nanoparticles doped therein were mainly composite-doped by in-situ embedding into the nano-oxide W matrix. The components of the Ag-containing nanoparticles included at least one of Ag or Ag oxide, with a size range of 0.25 nm to 10 nm.

[0477] The solid product prepared 2 minutes after the start of the hydrogen deposition and de-Al reaction described above was heat-treated at 600°C for 2 hours to obtain partially crystalline nano-oxide W doped with Ag nanoparticles with improved crystallinity. Its TEM morphology and diffraction spectrum are shown in Figures 11-12. The shape of the partially crystalline nano-oxide W was mainly in the form of a fine film, with a film thickness range of 1 nm to 10 nm. The Ag nanoparticles were mainly embedded in the crystalline nano-oxide W, and their particle size was 0.25 nm to 10 nm, as shown by the arrows in Figure 12.

[0478] [Example 6] This embodiment provides a method for producing nanomolybdenum oxide doped with Ag nanoparticles, and includes the following steps.

[0479] Ag 1.5 Al 74 Mo 24.5 According to the nominal composition (atomic percentage), Al, Mo, and Ag raw materials are melted and Ag 1.5 Al 74 Mo 24.5 A molten alloy mainly composed of was obtained. The obtained molten alloy was cast by copper roller strip casting to a thickness of 20 μm to 30 μm, with a composition mainly of Ag. 1.5 Al 74 Mo 24.5The initial alloy ribbon was manufactured, and its solidified structure mainly consisted of an Al3Mo(Ag) intermetallic compound in which Ag was dissolved, with a solid solution amount of Ag of approximately 1.5 at.%.

[0480] Under normal pressure, Ag 1.5 Al 74 Mo 24.5 The initial alloy ribbon was reacted with a NaOH solution. The concentration of the NaOH solution was 12 mol / L, the temperature was the boiling point at atmospheric pressure (approximately 128°C), and the volume of the NaOH solution was Ag. 1.5 Al 74 Mo 24.5 The volume was approximately 50 times that of the initial alloy ribbon. The hydrogen deposition reaction was completed within 1 minute, and the initial alloy ribbon was nanofragmented by the hydrogen deposition and de-Al reaction, simultaneously undergoing a reconfiguration of its shape and composition, and generating solid aggregate products.

[0481] The hydrogen deposition and de-Al reaction was carried out by adding 10 times the volume of room temperature water (20°C) to the reaction system 2 minutes after the start of the reaction, rapidly lowering the reaction temperature to below 40°C and reducing the base solution concentration to below 1.2 mol / L. After dilution, the solid aggregate product was separated from the solution, washed, and dried to obtain low-crystallinity nanomo oxides doped with Ag nanoparticles, mainly consisting of amorphous nanomo oxide or amorphous mo hydroxide as the matrix. Its TEM morphology and diffraction spectra are shown in Figures 13-14. The shape of the above nanooxide Mo matrix consisted mainly of extremely fine aggregate microstructures, with a size range of 1.0 nm to 10 nm. Such aggregate microstructures were not rigid nanoporous structures, but rather non-rigid aggregate structures that could be dispersed flatly. The Ag nanoparticles doped therein contained at least one component of Ag or Ag oxide, and as indicated by the arrows in Figure 14, the Ag-containing nanoparticles were composite-doped mainly by in-situ embedding in the nanooxide Mo matrix.

[0482] The solid product prepared 3 minutes after the start of the hydrogen deposition and de-Al reaction described above was heat-treated at 900°C for 2 hours to obtain crystalline nano-mo oxide doped with Ag nanoparticles. The crystalline nano-mo oxide was mainly granular in shape, with a particle size range of 3 nm to 150 nm, and the Ag nanoparticles were mainly embedded within the crystalline nano-mo oxide, with a particle size range of 0.25 nm to 30 nm.

[0483] The above Ag 1.5 Al 74 Mo 24.5 One minute after the start of the hydrogen deposition and de-Al reaction of the initial alloy ribbon, the base solution of the reaction system was sealed directly into the reaction vessel along with the solid aggregate product. The temperature of the reaction vessel and its interior was raised to 250°C and maintained for 20 minutes. Under sealed conditions, the pressure inside the reaction vessel was higher than atmospheric pressure. After 20 minutes of maintenance, the temperature and pressure were reduced, the product in the reaction vessel was separated into solid and liquid components, washed and dried to obtain nano-Mo oxide doped with modified Ag nanoparticles. Here, the nano-Mo oxide matrix was mainly crystalline, and its morphology consisted mainly of particles with a particle size range of 3 nm to 150 nm. The Ag nanoparticles doped therein contained at least one component of Ag or Ag oxide. The Ag-containing nanoparticles were composite-doped into the modified nano-Mo oxide matrix mainly by in-situ embedding, with a particle size range of 0.5 nm to 15 nm.

[0484] [Example 7] This embodiment provides a method for producing nanoyttrium oxide doped with Ag nanoparticles, and includes the following steps.

[0485] Ag 10 Al 67 Y 23 (According to the nominal composition of (atomic percentage), Al, Y and Ag raw materials are melted and Ag 10 Al 67 Y 23 A molten alloy mainly composed of was obtained. The obtained molten alloy was cast by copper roller strip casting to a thickness of ~25 μm, with a composition mainly of Ag 10 Al 67 Y 23The initial alloy ribbon was manufactured, and its solidification structure consisted mainly of Al-Y-Ag intermetallic compounds with the above composition, with an atomic percentage content of Ag of approximately 10 at.%.

[0486] Under normal pressure, Ag 10 Al 67 Y 23 The initial alloy ribbon was reacted with NaOH solution while stirring. The concentration of the NaOH solution was 12 mol / L, the temperature was the boiling point at atmospheric pressure (approximately 128°C), and the volume of the NaOH solution was Ag. 10 Al 67 Y 23 The volume was approximately 50 times that of the initial alloy ribbon. The hydrogen deposition reaction was completed within 1 minute, and the initial alloy was nano-fragmented by the hydrogen deposition and de-Al reaction, simultaneously reconstructing its shape and composition to produce a solid product.

[0487] The hydrogen deposition and de-Al reaction was initiated, and 2 minutes later, 10 times the volume of room temperature water (20°C) was added to the reaction system to rapidly lower the reaction temperature to below 40°C, reducing the base solution concentration to below 1.2 mol / L. After dilution, the solid product was separated from the solution, washed, and dried to obtain partially crystalline nano-Y oxide doped with Ag nanoparticles. Its TEM morphology and diffraction spectra are shown in Figures 15 and 16. The shape of the above partially crystalline nano-oxide Y matrix was mainly an irregular aggregate structure, with the size of the aggregate microstructure ranging from 2 nm to 15 nm. Due to the high content of Ag nanoparticles, the diffraction spectrum in Figure 15 is mainly that of Ag nanoparticles, and the diffraction information of the partially crystalline nano-oxide Y matrix is ​​not very prominent because it is not completely crystallized itself and its content is not absolutely dominant. Figure 16 shows that the Ag nanoparticles were primarily composite-doped into a partially crystalline nanooxide Y matrix by in-situ embedding, and the particle size range of the Ag nanoparticles was 0.25 nm to 50 nm.

[0488] [Example 8] This embodiment provides a method for producing nanoyttrium oxide doped with Au nanoparticles, and includes the following steps.

[0489] Au7Al 70 Y 23 According to the nominal composition (atomic percentage), Al, Y, and Au raw materials are melted to form Au7Al 70 Y 23 A molten alloy mainly composed of was obtained. The obtained molten alloy was solidified into an ingot, and then the ingot was crushed to obtain an alloy with an average particle size of 2 mm and a composition mainly of Au7Al. 70 Y 23 The initial alloy was manufactured as a crude powder, and its solidification structure consisted mainly of Al-Y-Au intermetallic compounds with the above composition, with an atomic percentage content of Au of approximately 7 at.%.

[0490] Under normal pressure, Au7Al 70 Y 23 The initial crude alloy powder was reacted with NaOH solution while stirring. The concentration of the NaOH solution was 12 mol / L, the temperature was the boiling point at atmospheric pressure (approximately 128°C), and the volume of the NaOH solution was Au7Al 70 Y 23 The volume was approximately 100 times that of the initial crude alloy powder. The hydrogen deposition and de-algae reaction was completed within 8 minutes, and the initial alloy was nano-fragmented by the reaction, simultaneously undergoing a reconfiguration of its shape and composition to produce a solid product.

[0491] After 10 minutes from the start of the hydrogen deposition and de-Al reaction, the solid product was separated from the solution, washed, and dried to obtain low-crystallinity nano-Y oxide doped with Au nanoparticles. Its TEM morphology and diffraction spectra are shown in Figures 17 and 18. The shape of the low-crystallinity nano-oxide Y matrix was mainly an irregular aggregate structure, with the size of the aggregate microstructure ranging from 1 nm to 20 nm. The Au nanoparticles were composite-doped into the low-crystallinity nano-oxide Y matrix by two methods: in-situ embedding and physioadsorption. As shown in Figure 18, some of the Au nanoparticles detached from the nano-oxide Y matrix to become free Au nanoparticles, with a particle size range of 0.25 nm to 30 nm.

[0492] The solid product prepared 10 minutes after the start of the hydrogen deposition and de-Al reaction was heat-treated at 900°C for 2 hours to obtain crystalline nano-oxide Y doped with Au nanoparticles. The shape of the above crystalline nano-oxide Y was mainly granular, with a particle size range of 3 nm to 150 nm. The Au nanoparticles were composite-doped into the low-crystallinity nano-oxide Y matrix by two methods: in-situ embedding and physioadsorption, with particle sizes ranging from 0.5 nm to 50 nm.

[0493] Au7Al 70 Y 23 Eight minutes after the start of the hydrogen deposition and de-Al reaction of the initial crude alloy powder, the base solution of the reaction system was sealed directly into the reaction vessel along with the solid aggregate product. The temperature of the reaction vessel and its interior was raised to 250°C and maintained for 1 hour. Under sealed conditions, the pressure inside the reaction vessel was higher than atmospheric pressure. After 1 hour of maintenance, the temperature and pressure were reduced, the product in the reaction vessel was separated into solid and liquid components, washed and dried to obtain nano-oxide Y doped with modified Au nanoparticles. Here, the nano-Y oxide matrix was mainly crystalline, and its morphology consisted mainly of particles with a particle size range of 3 nm to 250 nm. For the Au nanoparticles doped therein, the Au-containing nanoparticles were composite-doped into the mainly crystalline nano-oxide Y matrix by two methods: in-situ embedding and physicoadsorption, with a particle size range of 0.5 nm to 50 nm.

[0494] [Example 9] This embodiment provides a nanoyttrium oxide doped with Au nanoparticles and a method for producing Au nanoparticles, comprising the following steps.

[0495] Au1Al 74 Y 25 According to the nominal composition (atomic percentage), Al, Y, and Au raw materials are melted to form Au1Al 74 Y 25 A molten alloy mainly composed of was obtained. The obtained molten alloy was cast by copper roller strip casting to a thickness of ~25 μm and a composition mainly of Au1Al. 74 Y 25The initial alloy ribbon was manufactured, and its solidified structure mainly consisted of an Al3Y(Au) intermetallic compound in which Au was dissolved, with a solid solution amount of Au of approximately 1 at.%.

[0496] Under normal pressure, Au1Al 74 Y 25 The initial alloy ribbon was reacted with a NaOH solution. The concentration of the NaOH solution was 12 mol / L, the temperature was the boiling point at atmospheric pressure (approximately 128°C), and the volume of the NaOH solution was Al 74 Y 25 The volume was approximately 50 times that of the initial Au1 alloy ribbon. The hydrogen deposition and de-algae reaction was completed within 1 minute, and the initial alloy was nano-fragmented by the hydrogen deposition and de-algae reaction, simultaneously reconstructing its shape and composition and generating solid aggregate products.

[0497] Two minutes after the start of the hydrogen deposition and de-Al reaction, the solid product was separated from the solution, washed, and dried to obtain low-crystalline nano-Y oxide doped with Au nanoparticles. Its TEM morphology and diffraction spectra are shown in Figures 19-21. As can be seen from the figures, the nano-Y oxide matrix was mainly crystalline, with plate-like or short rod-like shapes, a diameter range of 3 nm to 150 nm, and an aspect ratio of 1.5 to 5. The Au nanoparticles doped therein were mainly composite-doped by in-situ embedding into the nano-Y oxide matrix, with a particle size range of 0.25 nm to 50 nm (as shown by the black contrast particles in Figure 20).

[0498] Two minutes after the start of the hydrogen deposition and de-Al reaction described above, the solid aggregate product was reacted with a 2 mol / L hydrochloric acid solution to remove the nanooxide Y matrix. The originally embedded inert Au nanoparticles were then freely separated and grew through a certain degree of free fusion, yielding Au nanoparticles with a particle size range of 3 nm to 150 nm.

[0499] [Example 10] This embodiment provides a nanochromium oxide doped with Au nanoparticles and a method for producing Au nanoparticles, comprising the following steps.

[0500] Au 1.5 Al 79 Cr 19.5 According to the nominal composition (atomic percentage), Al, Cr, and Au raw materials are melted and Au 1.5 Al 79 Cr 19.5 A molten alloy mainly composed of Al was obtained. The obtained molten alloy was cast by copper roller strip casting to a thickness of ~25 μm, with a composition mainly of Al 79 Cr 19.5 Au 1.5 The initial alloy ribbon was manufactured, and its solidification structure mainly consisted of an Al4Cr(Au) intermetallic compound in which Au was dissolved, with a solid solution amount of Au of approximately 1.5 at.%.

[0501] Under normal pressure, Au 1.5 Al 79 Cr 19.5 The initial alloy ribbon was reacted with NaOH solution while stirring. The concentration of the NaOH solution was 12 mol / L, the temperature was the boiling point at atmospheric pressure (approximately 128°C), and the volume of the NaOH solution was Au. 1.5 Al 79 Cr 19.5 The volume was approximately 50 times that of the initial alloy ribbon. The hydrogen deposition and de-algae reaction was completed within 1 minute, and the initial alloy was fragmented into nano-fragments by the hydrogen deposition and de-algae reaction, simultaneously reconstructing its shape and composition and generating solid aggregate products.

[0502] After 2 minutes from the start of the hydrogen deposition and de-Al reaction, the solid aggregated product was separated from the solution, washed, and dried to obtain low-crystallinity nano-Cr oxides doped with Au nanoparticles, mainly consisting of amorphous nano-Cr oxide or amorphous Cr hydroxide as the matrix. Its TEM morphology and diffraction spectra are shown in Figures 22 and 23. The morphology of the nano-Cr oxide matrix consisted mainly of extremely fine aggregated microstructures, with a size range of 1.0 nm to 10 nm. Such aggregated microstructures were not rigid nanoporous structures, but rather loosely dispersed structures that could be dispersed flatly. Due to the low crystallinity (see diffraction spectrum), it was difficult to clearly observe the details of the aggregated microstructures by TEM. The doped Au nanoparticles were composite-doped into the low-crystallinity nanooxide Cr matrix by two methods: in-situ embedding and physicoadsorption. As shown in Figure 23, some of the physicoadsorbed Au nanoparticles detached from the nanooxide Cr matrix to become free Au nanoparticles. The particle size range of the in-situ embedded and physicoadsorbed Au nanoparticles was 0.25 nm to 30 nm.

[0503] The solid aggregate product prepared 2 minutes after the start of the hydrogen deposition and Al de-algae reaction was reacted with a 2 mol / L hydrochloric acid solution to remove the low-crystallinity nanooxide Cr matrix, allowing the originally embedded inert Au nanoparticles to freely separate. These then grew through a certain degree of free fusion with the originally physically adsorbed Au nanoparticles, resulting in Au nanoparticles with a particle size range of 3 nm to 100 nm, as shown in Figure 24.

[0504] The solid aggregate product prepared 2 minutes after the start of the hydrogen deposition and de-Al reaction described above was directly heat-treated at 900°C for 2 hours to obtain crystalline nano-chromium oxide doped with Au nanoparticles. The crystalline nano-chromium oxide was mainly granular in shape, with a particle size of 3 nm to 150 nm. The Au nanoparticles were mainly present in the crystalline nano-chromium oxide by partial or complete in-situ embedding (partial embedding means that a portion of the volume of the Au nanoparticles is exposed outside the nano-chromium oxide matrix), with a particle size of 1 nm to 50 nm. In addition, some of the Au nanoparticles that were originally physically adsorbed were composite-doped into the crystalline nano-chromium oxide by physical adsorption after heat treatment, with a particle size of 1 nm to 50 nm.

[0505] Au 1.5 Al 79 Cr 19.5 One minute after the start of the hydrogen deposition and de-Al reaction of the initial alloy ribbon, the base solution of the reaction system was sealed directly into the reaction vessel along with the solid product. The temperature of the reaction vessel and its interior was raised to 300°C and maintained for 10 minutes. Under sealed conditions, the pressure inside the reaction vessel was higher than atmospheric pressure. After 10 minutes of maintenance, the temperature and pressure were reduced, the product in the reaction vessel was separated into solid and liquid components, washed and dried to obtain nano-chromium oxide doped with modified Au nanoparticles. The modified nano-chromium oxide matrix was mainly crystalline, and its morphology consisted mainly of granular or short rod-shaped particles. The granular particle size ranged from 2 nm to 100 nm, the short rod-shaped diameter ranged from 2 nm to 50 nm, and the aspect ratio was 1.5 to 5. Au nanoparticles were composite-doped into a modified nano-Cr oxide matrix by two methods: in-situ embedding and physicoadsorption. Some of the physicoadsorbed Au nanoparticles detached from the modified nano-Cr oxide matrix to become free Au nanoparticles. The particle size range of the in-situ embedded and physicoadsorbed Au nanoparticles was 0.25 nm to 50 nm.

[0506] [Example 11] This embodiment provides a nanochromium oxide doped with Au nanoparticles and a method for producing Au nanoparticles, comprising the following steps.

[0507] Au5Al77 Cr 18 According to the nominal composition (atomic percentage), Al, Cr, and Au raw materials are melted to form Au5Al 77 Cr 18 A molten alloy mainly composed of was obtained. The obtained molten alloy was solidified into an ingot, and then the ingot was crushed to obtain a material with an average particle size of 100 μm and a composition mainly of Au5Al. 77 Cr 18 The initial alloy powder was manufactured as follows. The solidification structure of the above initial alloy powder mainly consisted of an Al4Cr(Au) intermetallic compound in which Au was dissolved, or an Al-Cr-Au intermetallic compound of the above composition, with an Au content of approximately 5 at.%. In both the Al4Cr(Au) intermetallic compound and the Al-Cr-Au intermetallic compound, Au was in the form of Au atoms in the Al4Cr(Au) phase or Au5Al 77 Cr 18 They are dispersed throughout the phase.

[0508] Under normal pressure, Au5Al 77 Cr 18 The initial alloy powder was reacted with NaOH solution while stirring. The concentration of the NaOH solution was 12 mol / L, the temperature was the boiling point at atmospheric pressure (approximately 128°C), and the volume of the NaOH solution was Al 77 Cr 18 The volume was approximately 100 times that of the initial Au5 alloy powder. The hydrogen deposition and de-algae reaction was completed within 1.5 minutes, and the initial alloy powder was nano-fragmented by the hydrogen deposition and de-algae reaction, simultaneously undergoing a reconfiguration of its shape and composition, and generating solid aggregate products.

[0509] After 2 minutes from the start of the hydrogen deposition and de-Al reaction, the solid aggregate product was separated from the solution, washed, and dried to obtain low-crystallinity nano-Cr oxides doped with Au nanoparticles, mainly consisting of amorphous nano-Cr oxide or amorphous Cr hydroxide as the matrix. Here, the morphology of the nano-Oxide Cr matrix consisted mainly of extremely fine aggregated microstructures, with a size range of 1.0 nm to 10 nm. The Au nanoparticles doped therein were mainly composite-doped into the low-crystallinity nano-Oxide Cr matrix by in-situ embedding, with a particle size range of 0.25 nm to 30 nm. When the particle size was less than 2 nm, the Au nanoparticles were mainly composite-doped into the low-crystallinity nano-Oxide Cr matrix in the form of atoms or atomic clusters.

[0510] The solid aggregate product, generated and recovered 2 minutes after the start of the hydrogen deposition and de-Al reaction, was heat-treated at 600°C for 2 hours to obtain low-crystalline nano-chromium oxide doped with Au nanoparticles. Its morphology and diffraction spectrum are shown in Figures 25-27. As can be seen from the figures, even after heat treatment at 600°C for 2 hours, the nano-chromium oxide matrix still maintains a low-crystalline aggregated microstructure. The diffraction spectrum in Figure 25 is a typical crystalline diffraction spectrum, but it mainly contains diffraction information from Au nanoparticles (because the Au nanoparticle content is relatively high in this embodiment), and there is almost no diffraction information from chromium oxide. When combined with the aggregated morphology of the nano-chromium oxide matrix, it can be concluded that the nano-chromium oxide matrix still maintains a low-crystalline state (according to Comparative Example 2, if simple nano-chromium oxide is changed to a crystalline state by heat treatment at 600°C for 2 hours, the morphology should be granular). Because numerous minute Au nanoparticles in the form of atoms or atomic clusters were embedded in-situ into the low-crystallinity nano-chromium oxide matrix before heat treatment, the thermal stability of the low-crystallinity nano-chromium oxide matrix was significantly improved, and the low-crystallinity nano-chromium oxide matrix did not undergo any significant crystallization or morphological changes after heat treatment at 600°C. Even after heat treatment, the in-situ embedded doped Au-containing nanoparticles remained compositely doped into the low-crystallinity nano-chromium oxide matrix, mainly through in-situ embedding. After heat treatment, the morphology and crystal shape of the nano-chromium oxide matrix did not change much, but the in-situ embedded Au nanoparticles embedded therein underwent significant fusion and growth, as shown in Figure 27 and its inset, with a particle size range of 1 nm to 200 nm.

[0511] The product obtained by heat treatment at 600°C for 2 hours was reacted with a 2 mol / L hydrochloric acid solution to remove the low-crystallinity, acid-reactive nanooxide Cr matrix, allowing the originally embedded inert Au nanoparticles to freely separate and grow through a certain degree of free fusion, resulting in Au nanoparticles with a particle size range of 3 nm to 300 nm.

[0512] [Example 12] This embodiment provides a method for producing nanochromium oxide doped with Ag nanoparticles, and includes the following steps.

[0513] Ag3Al 78 Cr 19 According to the nominal composition (atomic percentage), Al, Cr, and Ag raw materials are melted to form Ag3Al 78 Cr 19 A molten alloy mainly composed of was obtained. The obtained molten alloy was solidified into an ingot, and then the ingot was crushed to obtain a material with an average particle size of 100 μm and a composition mainly of Ag3Al. 78 Cr 19 The initial alloy powder was manufactured as follows. The solidification structure of the above alloy ingot or initial alloy powder is mainly composed of Al4Cr(Ag) intermetallic compounds in which Ag is dissolved (shown in Figure 28), and the Al4Cr(Ag) intermetallic compounds are Ag3Al 78 Cr 19 and Ag1Al 79 Cr 20 It consists of two types of Ag solid solutions, Ag3Al 78 Cr 19 The two substances were predominantly present, and the solid solubility of Ag was approximately 3 at.% and 1 at.% respectively.

[0514] Under normal pressure, Ag3Al 78 Cr 19 The initial alloy powder was reacted with NaOH solution while stirring. The concentration of the NaOH solution was 12 mol / L, the temperature was the boiling point at atmospheric pressure (approximately 128°C), and the volume of the NaOH solution was Ag3Al 78 Cr 19 The volume was approximately 100 times that of the initial alloy powder. The hydrogen deposition and de-algae reaction was completed within 1.5 minutes. The initial alloy powder was nano-fragmented by the hydrogen deposition and de-algae reaction, and its shape and composition were simultaneously reconfigured, generating solid aggregate products.

[0515] After 2 minutes from the start of the hydrogen deposition and de-Al reaction, the solid aggregate product was separated from the solution, washed, and dried to obtain low-crystallinity nano-chromium oxide doped with Ag nanoparticles. Its TEM morphology and diffraction spectra are shown in Figures 29 and 30. The nano-chromium oxide matrix was mainly amorphous nano-chromium oxide or amorphous chromium hydroxide, and its morphology consisted mainly of extremely fine aggregated microstructures, with a size range of 1.0 nm to 15 nm. The Ag nanoparticles doped therein included at least one of Ag nanoparticles and Ag oxide nanoparticles, and were composite-doped into the low-crystallinity nano-chromium oxide matrix mainly by in-situ embedding. The particle size range of the in-situ embedded Ag-containing nanoparticles was 0.25 nm to 10 nm, and most of the Ag-containing nanoparticles were small in size, making TEM observation difficult. When the particle size of the in-situ embedded Ag-containing nanoparticles was less than 2 nm, the Ag-containing nanoparticles were composite-doped into the low-crystallinity nano-chromium oxide matrix mainly in the form of atoms or atomic clusters. The low-crystalline nano-chromium oxide doped with the above-mentioned Ag-containing nanoparticles can be applied to sterilizing materials such as sterilizing paints, sterilizing pigments, sterilizing glazes, and sterilizing slurries.

[0516] The solid aggregate product, recovered 2 minutes after the start of the hydrogen deposition and de-Al reaction, was heat-treated at 600°C for 2 hours to obtain low-crystallinity nano-chromium oxide doped with Ag nanoparticles. Its morphology and diffraction spectrum are shown in Figures 31-32. As can be seen from the figures, even after heat treatment at 600°C for 2 hours, the nano-chromium oxide matrix still maintains a low-crystallinity aggregated microstructure. Because numerous minute Ag nanoparticles in the form of atoms or atomic clusters were embedded in the low-crystallinity nano-chromium oxide in situ before heat treatment, the thermal stability of the low-crystallinity nano-chromium oxide matrix was greatly improved, and the low-crystallinity nano-chromium oxide matrix did not undergo any obvious crystallization or morphological changes after heat treatment at 600°C (according to Comparative Example 2, simple nano-chromium oxide changed to a granular crystalline state after heat treatment at 600°C for 2 hours). After heat treatment, the Ag nanoparticles doped therein remain composite-doped with the low-crystallinity nano-chromium oxide matrix, mainly by in-situ embedded growth, as shown in the embedded-grown particles in Figures 31-32. After heat treatment, the morphology and crystal shape of the nano-chromium oxide matrix did not change significantly, but as shown in Figures 31-32, the in-situ embedded Ag nanoparticles underwent clear fusion and growth, with a particle size range of 0.5 nm to 15 nm. The low-crystallinity nano-chromium oxide doped with the heat-treated Ag nanoparticles described above can be applied to sterilizing materials such as sterilizing paints, sterilizing pigments, sterilizing glazes, and sterilizing slurries.

[0517] The solid aggregate product recovered 2 minutes after the start of the hydrogen precipitation and de-Al reaction described above was directly heat-treated at 900°C for 2 hours to obtain crystalline nano-chromium oxide doped with Ag nanoparticles. The crystalline nano-chromium oxide was mainly granular in shape, with particle sizes ranging from 3 nm to 150 nm. The Ag nanoparticles were mainly embedded in the crystalline nano-chromium oxide by in-situ embedding, with particle sizes ranging from 2 nm to 50 nm. The heat-treated crystalline nano-chromium oxide doped with Ag nanoparticles can be applied to sterilizing materials such as sterilizing paints, sterilizing pigments, sterilizing glazes, and sterilizing slurries.

[0518] [Example 13] This example provides a nanochromium oxide doped with Ag-Cu-Au nanoparticles and a method for producing Ag-Cu-Au nanoparticles, comprising the following steps.

[0519] Ag 0.5 Cu 0.5 Au 0.5 Al 79 Cr 19.5 According to the nominal composition (atomic percentage), Al, Cr, Ag, Cu and Au raw materials are melted and Ag 0.5 Cu 0.5 Au 0.5 Al 79 Cr 19.5 A molten alloy mainly composed of was obtained. The obtained molten alloy was cast by copper roller strip casting to a thickness of ~200 μm and a composition mainly of Ag 0.5 Cu 0.5 Au 0.5 Al 79 Cr 19.5 The initial alloy was produced as a rapid settling fragment, and its solidification structure mainly consisted of an Al4Cr(Ag-Cu-Au) intermetallic compound in which Ag-Cu-Au were dissolved, with the solid solution amounts of Ag, Cu, and Au being approximately 0.5 at.%, 0.5 at.%, and 0.5 at.%, respectively.

[0520] Under normal pressure, Ag 0.5 Cu 0.5 Au 0.5 Al 79 Cr 19.5 The initial alloy rapid-setting fragments are reacted with a mixed aqueous solution of NaOH and KOH in a molar ratio of 1:1 while stirring, and OH - The concentration is 7 mol / L, the temperature is 105°C to 112°C, and the volume of the base solution is Ag 0.5 Cu 0.5 Au 0.5 Al 79 Cr 19.5 The volume was approximately 100 times that of the initial alloy agglomerate. The hydrogen deposition and de-algae reaction was completed within 4 minutes, and the initial alloy powder was nano-fragmented by the hydrogen deposition and de-algae reaction, simultaneously undergoing a reconfiguration of its shape and composition, and generating solid aggregate products.

[0521] After 5 minutes from the start of the hydrogen deposition and de-Al reaction, the solid aggregated product was separated from the solution, washed, and dried to obtain low-crystallinity nano-chromium oxide doped with Ag-Cu-Au nanoparticles. Its TEM morphology and diffraction spectra are shown in Figures 33 and 34. The nano-chromium oxide matrix consisted mainly of amorphous nano-chromium oxide or amorphous chromium hydroxide, and its morphology was mainly composed of extremely fine aggregated microstructures, with a size range of 1.0 nm to 10 nm. The Ag-Cu-Au nanoparticles doped therein are composite-doped into the low-crystallinity nanooxide Cr matrix by two methods: in-situ embedding and physicoadsorption. As shown in Figure 34, some of the physicoadsorbed Ag-Cu-Au nanoparticles can be freely detached. The particle size range of the Ag-Cu-Au nanoparticles is 0.25 nm to 10 nm. When the particle size is less than 2 nm, the Ag-Cu-Au nanoparticles are composite-doped into the low-crystallinity nanooxide Cr matrix mainly by in-situ embedding in the form of atoms or atomic clusters.

[0522] The solid aggregate product obtained above was reacted with a 2 mol / L hydrochloric acid solution to remove the nano-oxide Cr matrix, which has low crystallinity and is highly reactive with acid. The originally embedded inert Ag-Cu-Au nanoparticles were then freely separated and grew together with the originally physically adsorbed inert Ag-Cu-Au nanoparticles through a certain degree of free fusion, resulting in Ag-Cu-Au nanoparticles with a particle size range of 3 nm to 100 nm.

[0523] [Example 14] This embodiment provides a nanomanganese oxide doped with Au nanoparticles and a method for producing Au nanoparticles, comprising the following steps.

[0524] Au1Al 72 Mn 27 According to the nominal composition (atomic percentage), Al, Mn, and Au raw materials are melted to form Au1Al 72 Mn 27 A molten alloy mainly composed of was obtained. The obtained molten alloy was cast by copper roller strip casting to a thickness of ~100 μm and a composition mainly of Au1Al. 72Mn 27 It is manufactured as an initial alloy ribbon, and its solidification structure is mainly composed of Al with Au in solid solution. 11 The main component was an Mn4(Au) intermetallic compound, with an Au content of approximately 1 at.%.

[0525] Under normal pressure, Au1Al 72 Mn 27 The initial alloy ribbon was reacted with NaOH solution while stirring. The concentration of the NaOH solution was 12 mol / L, the temperature was the boiling point at atmospheric pressure (approximately 128°C), and the volume of the NaOH solution was Au1Al 72 Mn 27 The volume was approximately 100 times that of the initial alloy ribbon. The hydrogen deposition and de-algae reaction was completed within 2 minutes, and the initial alloy ribbon was nano-fragmented by the reaction, simultaneously undergoing a reconfiguration of its shape and composition to produce a solid product.

[0526] After 2 minutes from the start of the hydrogen deposition and de-Al reaction, the solid product was separated from the solution, washed, and dried to obtain partially crystalline nano-mcodium oxide with Au nanoparticles. Its TEM morphology and diffraction spectrum are shown in Figures 35 and 36. The nano-mcodium oxide matrix was mainly partially crystalline, with a particle size range of 2 nm to 400 nm. Some nano-mcodium oxide particles had a hexagonal shape (Figure 35), which indicated a more pronounced crystallization state. However, some parts of the nano-mcodium oxide matrix lacked clear particle boundaries, indicating insufficient crystallization. The Mn in the above oxide Mn matrix contained low-valence Mn, and the Au nanoparticles had a particle size range of 0.25 nm to 50 nm. They were mainly embedded in the nano-mcodium oxide matrix by in-situ embedding, with only a small portion of the Au nanoparticles being doped by physical adsorption.

[0527] The solid product, recovered 2 minutes after the start of the hydrogen deposition and de-Al reaction, was heat-treated at 600°C for 2 hours to obtain crystalline nano-mn oxide doped with Au nanoparticles. Its TEM morphology and diffraction spectra are shown in Figures 37-40. The nano-mn oxide matrix was found to be mainly partially crystalline, containing high-valence Mn, and its shape mainly consisted of plate-like particles and ordinary particles, with the plate-like particles including hexagonal plate-like particles (Figure 38). The particle size range of the nano-mn oxide was 2 nm to 500 nm, the particle size of the plate-like particles was 10 nm to 500 nm, and the thickness was 2 nm to 100 nm. The presence of Au nanoparticles is clearly shown in Figures 38-40. As indicated by the dark contrast in the figures, they are spherical or nearly spherical particles with a particle size of 0.25 nm to 100 nm. They are mainly embedded in a crystalline nano-mn oxide matrix by in-situ embedding doping, with only a small portion of the Au nanoparticles being doped by physical adsorption.

[0528] The solid aggregate product obtained by heat treatment at 600°C for 2 hours was reacted with a 2 mol / L hydrochloric acid solution to remove the acid-reactive crystalline nanooxide Mn matrix, allowing the originally embedded inert Au nanoparticles to freely separate and grow through a certain degree of free fusion, resulting in Au nanoparticles with a particle size range of 3 nm to 300 nm.

[0529] [Example 15] This embodiment provides a method for producing nanomanganese oxide doped with Ag-containing nanoparticles, and includes the following steps.

[0530] Ag 0.3 Al 72.7 Mn 27 According to the nominal composition (atomic percentage), Al, Mn and Ag raw materials are melted and Ag 0.3 Al 72.7 Mn 27 A molten alloy mainly composed of was obtained. The obtained molten alloy was cast by copper roller strip casting to a thickness of ~100 μm and a composition mainly of Ag 0.3 Al 72.7 Mn 27It is manufactured as an initial alloy ribbon, and its solidification structure is mainly composed of Al with Ag in solid solution. 11 The main component was an Mn4(Ag) intermetallic compound, with an Ag content of approximately 0.3 at.%.

[0531] Under normal pressure, Ag 0.3 Al 72.7 Mn 27 The initial alloy ribbon was reacted with NaOH solution while stirring. The concentration of the NaOH solution was 12 mol / L, the temperature was the boiling point at atmospheric pressure (approximately 128°C), and the volume of the NaOH solution was Ag. 0.3 Al 72.7 Mn 27 The volume was approximately 100 times that of the initial alloy ribbon. The hydrogen deposition and de-algae reaction was completed within 2 minutes, and the initial alloy powder was nano-fragmented by the hydrogen deposition and de-algae reaction, simultaneously reconstructing its shape and composition to produce a solid product.

[0532] After 2 minutes from the start of the hydrogen deposition and de-Al reaction, the solid product was separated from the solution, washed, and dried to obtain partially crystalline nano-mn oxide with Ag-containing nanoparticles, the TEM morphology and diffraction spectra of which are shown in Figures 41 and 42. The nano-mn oxide matrix was found to be mainly crystalline, with a plate-like shape, a diameter range of 5 nm to 400 nm, and a thickness of 3 nm to 100 nm. The Ag-containing nanoparticles consisted of at least one Ag nanoparticle and Ag oxide nanoparticles, with a particle size range of 0.25 nm to 100 nm, and were mainly embedded in the nano-mn oxide matrix by in-situ embedding, with only a small portion of the Ag-containing nanoparticles being doped by physical adsorption.

[0533] [Example 16] This embodiment provides a method for producing a nanomanganese oxide doped with Ag nanoparticles, and includes the following steps.

[0534] Ag 0.3 Al 72.7 Mn 27 According to the nominal composition (atomic percentage), Al, Mn and Ag raw materials are melted and Ag 0.3Al 72.7 Mn 27 A molten alloy mainly composed of was obtained. The obtained molten alloy was cast by copper roller strip casting to a thickness of ~100 μm and a composition mainly of Ag 0.3 Al 72.7 Mn 27 It is manufactured as an initial alloy ribbon, and its solidification structure is mainly composed of Al with Ag in solid solution. 11 The main component was an Mn4(Ag) intermetallic compound, with an Ag content of approximately 0.3 at.%.

[0535] Under normal pressure, Ag 0.3 Al 72.7 Mn 27 The initial alloy ribbon was reacted with NaOH solution while stirring. The concentration of the NaOH solution was 10 mol / L, the temperature was 105°C to 115°C, and the volume of the NaOH solution was Ag. 0.3 Al 72.7 Mn 27 The volume was approximately 100 times that of the initial alloy ribbon. The hydrogen deposition and de-algae reaction was completed within 2 minutes, and the initial alloy powder was nano-fragmented by the hydrogen deposition and de-algae reaction, simultaneously reconstructing its shape and composition to produce a solid product.

[0536] Two minutes after the start of the hydrogen deposition and de-Al reaction described above, the base solution of the reaction system was sealed directly into the reaction vessel along with the solid product. The temperature of the reaction vessel and its interior was raised to 175°C and maintained for 2 hours. Under sealed conditions, the pressure inside the reaction vessel was higher than atmospheric pressure. After 2 hours of maintenance, the temperature and pressure were reduced, the product in the reaction vessel was separated into solid and liquid components, washed, and dried to obtain nano-mn oxide doped with modified Ag-containing nanoparticles. Its TEM morphology and diffraction spectra are shown in Figures 43-46. Here, the modified nano-mn oxide matrix mainly consisted of low-crystallinity film-like structures (shown in Figures 43-44) and high-crystallinity tubular structures (shown in Figures 45-46). The thickness of the film-like structures was 1 nm to 20 nm, and the diameter of the tubular structures was 3 nm to 40 nm. The Ag-containing nanoparticles were mainly embedded and distributed in-situ within the modified nano-mn oxide, and their morphology is shown in the dark-contrast granular products in Figures 44 and 45. The composition of the Ag-containing nanoparticles included at least one of Ag nanoparticles and Ag oxide nanoparticles, and the size of the Ag-containing nanoparticles ranged from 2 nm to 30 nm.

[0537] [Example 17] This embodiment provides a method for producing nanochromium oxide doped with Pt-Pd-Au-Ru nanoparticles and Pt-Pd-Au-Ru nanoparticles, comprising the following steps.

[0538] Pt 0.5 Pd 0.5 Au 0.5 Ru 0.5 Al 79 Cr 19 According to the nominal composition (atomic percentage), Al, Cr, Pt, Pd, Au, and Ru raw materials are melted to form Pt 0.5 Pd 0.5 Au 0.5 Ru 0.5 Al 79 Cr 19 A molten alloy mainly composed of was obtained. The obtained molten alloy was solidified into an ingot, and then the ingot was crushed to obtain an alloy with an average particle size of 100 μm and a composition mainly of Pt. 0.5 Pd 0.5 Au 0.5 Ru 0.5 Al 79 Cr19 The initial alloy powder was manufactured as follows. The solidification structure of the above initial alloy powder consisted mainly of an Al4Cr(Pt-Pd-Au-Ru) intermetallic compound in which Pt-Pd-Au-Ru were dissolved, and the amounts of Al, Cr, Pt, Pd, Au, and Ru dissolved were approximately 0.5 at.%, 0.5 at.%, 0.5 at.%, and 0.5 at.%, respectively.

[0539] Under normal pressure, Pt 0.5 Pd 0.5 Au 0.5 Ru 0.5 Al 79 Cr 19 The initial alloy powder was reacted with a KOH solution while stirring. The KOH solution concentration was 12 mol / L, the temperature was 101°C to 115°C, and the volume of the KOH solution was Pt 0.5 Pd 0.5 Au 0.5 Ru 0.5 Al 79 Cr 19 The volume was approximately 50 times that of the initial alloy powder. The hydrogen deposition and de-algae reaction was completed within 1.5 minutes. The initial alloy powder was fragmented into nano-fragments by the hydrogen deposition and de-algae reaction, and its shape and composition were simultaneously reconfigured, generating solid aggregate products.

[0540] After 2 minutes from the start of the hydrogen deposition and de-Al reaction, the solid aggregated product was separated from the solution, washed, and dried to obtain low-crystallinity nano-chromium oxide doped with Pt-Pd-Au-Ru nanoparticles, the TEM morphology of which is shown in Figures 47-48. Here, the nano-chromium oxide matrix is ​​mainly amorphous nano-chromium oxide or amorphous chromium hydroxide, and its morphology consists mainly of extremely fine aggregated microstructures (shown in Figure 47), with the size range of the aggregated microstructures being 1.0 nm to 10 nm. The doped Pt-Pd-Au-Ru nanoparticles are composite-doped into the low-crystallinity nanooxide Cr matrix mainly by two methods: in-situ embedding and physicoadsorption. As shown in Figure 48, some of the physicoadsorbed Pt-Pd-Au-Ru nanoparticles can be freely detached. The particle size range of the above Pt-Pd-Au-Ru nanoparticles is 0.25 nm to 15 nm. When the particle size is less than 2 nm, the Pt-Pd-Au-Ru nanoparticles are composite-doped into the low-crystallinity nanooxide Cr matrix mainly by in-situ embedding in the form of atoms or atomic clusters.

[0541] The solid aggregate product obtained above was reacted with a 1 mol / L nitric acid solution to remove the crystalline nanooxide Cr matrix, which has low crystallinity and is highly reactive with acid. The originally embedded inert Pt-Pd-Au-Ru nanoparticles were then freely separated and grew together with the originally physically adsorbed inert Pt-Pd-Au-Ru nanoparticles through a certain degree of free fusion, resulting in Pt-Pd-Au-Ru nanoparticles with a particle size range of 3 nm to 100 nm.

[0542] [Example 18] This embodiment provides a method for producing nanochromium oxide doped with Au nanoparticles, and includes the following steps.

[0543] Au 0.25 Al 61 Cr 38.75 According to the nominal composition (atomic percentage), Al, Cr, and Au raw materials are melted and Au 0.25 Al 61 Cr 38.75A molten alloy mainly composed of was obtained. The obtained molten alloy was cast by copper roller strip casting to a thickness of ~25 μm and a composition mainly of Au. 0.25 Al 61 Cr 38.75 The initial alloy ribbon was manufactured, and its solidification structure mainly consisted of an Al8Cr5(Au) intermetallic compound in which Au was dissolved, with a solid solution amount of Au of approximately 0.25 at.%.

[0544] Under normal pressure, Au 0.25 Al 61 Cr 38.75 The initial alloy ribbon was reacted with NaOH solution, and 40kHz ultrasound was applied. The concentration of the NaOH solution was 15 mol / L, the temperature was 60°C, and the volume of the NaOH solution was Au. 0.25 Al 61 Cr 38.75 The volume was approximately 100 times that of the initial alloy ribbon. The hydrogen deposition and de-algae reaction was completed within 1.7 minutes, and the initial alloy was nano-fragmented by the hydrogen deposition and de-algae reaction, simultaneously undergoing a reconstruction of its shape and composition, and generating solid aggregate products.

[0545] After 8 minutes from the start of the hydrogen deposition and de-Al reaction, the solid aggregate product was separated from the solution, washed, and dried to obtain low-crystallinity nano-chromium oxide doped with Au nanoparticles, the TEM morphology of which is shown in Figures 47-48. It mainly consisted of amorphous nano-chromium oxide or amorphous chromium hydroxide, and the morphology was low-crystallinity nano-chromium oxide doped with Au nanoparticles, with amorphous nano-chromium oxide or amorphous chromium hydroxide as the matrix. Here, the morphology of the nano-chromium oxide matrix mainly consisted of extremely fine aggregated microstructures, and the size range of the aggregated microstructures was 1.0 nm to 15 nm, as shown in Figures 49-50. The Au nanoparticles doped therein were mainly composite-doped into the low-crystallinity nano-chromium oxide matrix by in-situ embedding, and the particle size range of the in-situ embedded Au nanoparticles was 0.25 nm to 10 nm.

[0546] [Example 19] This embodiment provides a method for producing nanoyttrium oxide doped with Au nanoparticles, and includes the following steps.

[0547] Au 0.3 Zn 50 Y 49.7 It melts according to the chemical formula (atomic percentage) and Au 0.3 Zn 50 Y 49.7 A molten alloy mainly composed of was obtained, the molten alloy was solidified into an ingot, and then the ingot was crushed to produce an initial alloy powder with an average particle size of 50 μm, consisting mainly of a ZnY(Au) intermetallic compound phase in which Au is solid-solved.

[0548] Under normal pressure, Au 0.3 Zn 50 Y 49.7 The initial alloy powder was reacted with a KOH solution while stirring. The KOH solution concentration was 15 mol / L, the temperature was the boiling point at atmospheric pressure (approximately 150°C), and the volume of the KOH solution was Au. 0.3 Zn 50 Y 49.7 The volume was approximately 50 times that of the initial alloy powder. The hydrogen deposition reaction was completed within 5 minutes, and the initial alloy was nano-fragmented by the hydrogen deposition and de-Zn reaction, simultaneously reconstructing its shape and composition to produce a solid product.

[0549] After 5 minutes from the start of the reaction, the resulting solid product was separated from the solution, washed, and dried to obtain crystalline nanoyttrium oxide doped with Au nanoparticles. Here, the nano-oxide Y matrix was mainly granular and plate-like, with a particle size range of 3 nm to 300 nm, and the Au nanoparticles were mainly embedded in the low-crystalline nano-oxide Y matrix by in-situ embedding, with a particle size of 0.25 nm to 30 nm.

[0550] [Example 20] This embodiment provides a method for producing nanochromium oxide doped with Cu-containing nanoparticles, and includes the following steps.

[0551] Cu 1.5 Al 79 Cr19.5 According to the nominal composition (atomic percentage), Al, Cr, and Cu raw materials are melted to form Cu 1.5 Al 79 Cr 19.5 A molten alloy mainly composed of Al was obtained. The obtained molten alloy was cast by copper roller strip casting to a thickness of ~25 μm, with a composition mainly of Al 79 Cr 19.5 Cu 1.5 The initial alloy ribbon was manufactured, and its solidification structure consisted mainly of Al4Cr(Cu) intermetallic compounds with dissolved Cu, with a Cu solid solution content of approximately 1.5 at.%.

[0552] Under normal pressure, Cu 1.5 Al 79 Cr 19.5 The initial alloy ribbon was reacted with NaOH solution while stirring. The concentration of the NaOH solution was 10 mol / L, the temperature was the boiling point at atmospheric pressure (approximately 119°C), and the volume of the NaOH solution was Cu. 1.5 Al 79 Cr 19.5 The volume was approximately 100 times that of the initial alloy ribbon. The hydrogen deposition and de-algae reaction was completed within 1 minute, and the initial alloy was nano-fragmented by the reaction, simultaneously undergoing a reconfiguration of its shape and composition, and generating solid aggregate products.

[0553] After 2 minutes from the start of the hydrogen deposition and de-Al reaction, the solid aggregate product was separated from the solution, washed, and dried to obtain low-crystallinity nano-Cr oxides doped with Cu-containing nanoparticles, mainly consisting of amorphous nano-Cr oxide or amorphous Cr hydroxide as the matrix. Here, the morphology of the nano-Cr oxide matrix consisted mainly of extremely fine aggregated microstructures, with a size range of 1.0 nm to 10 nm. The Cu-containing nanoparticles doped therein were mainly composed of Cu oxide, which was composite-doped into the low-crystallinity nano-Cr oxide matrix mainly by in-situ embedding. The particle size range of the in-situ embedded Cu oxide nanoparticles was 0.25 nm to 30 nm, and their composition included at least one of Cu2O and CuO.

[0554] [Example 21] This example provides a method for producing nanochromium oxide doped with PtCu nanoparticles and Pt nanoparticles, and includes the following steps.

[0555] Cu 0.5 Pt1Al 79 Cr 19.5 According to the nominal composition (atomic percentage), Al, Cr, Pt and Cu raw materials are melted to form Cu 0.5 Pt1Al 79 Cr 19.5 A molten alloy mainly composed of was obtained. The obtained molten alloy was cast by copper roller strip casting to a thickness of ~25 μm and a composition mainly of Cu 0.5 Pt1Al 79 Cr 19.5 The initial alloy ribbon was manufactured, and its solidification structure consisted mainly of an Al4Cr(CuPt) intermetallic compound in which CuPt was dissolved, with a solid solution amount of Cu of approximately 1.5 at.% and a solid solution amount of Pt of approximately 1 at.%.

[0556] Under normal pressure, Cu 0.5 Pt1Al 79 Cr 19.5 The initial alloy ribbon was reacted with NaOH solution while stirring. The concentration of the NaOH solution was 10 mol / L, the temperature was the boiling point at atmospheric pressure (approximately 119°C), and the volume of the NaOH solution was Cu. 0.5 Pt1Al 79 Cr 19.5 The volume was approximately 100 times that of the initial alloy ribbon. The hydrogen deposition and de-algae reaction was completed within 1 minute, and the initial alloy was nano-fragmented by the reaction, simultaneously undergoing a reconfiguration of its shape and composition, and generating solid aggregate products.

[0557] After 2 minutes from the start of the hydrogen deposition and de-Al reaction, the solid aggregated product was separated from the solution, washed, and dried to obtain low-crystallinity nano-Cr oxides doped with Pt-Cu nanoparticles, mainly consisting of amorphous nano-Cr oxide or amorphous Cr hydroxide as the matrix. Here, the morphology of the nano-Oxide Cr matrix consisted mainly of extremely fine aggregated microstructures, with a size range of 1.0 nm to 10 nm. The Pt-Cu nanoparticles doped therein were mainly composite-doped into the low-crystallinity nano-Oxide Cr matrix by in-situ embedding, and the particle size range of the in-situ embedded Pt-Cu nanoparticles was 0.25 nm to 30 nm.

[0558] In the above hydrogen precipitation and de-Al reaction, the solid aggregate product obtained 2 minutes after the start was reacted with a 1 mol / L hydrochloric acid solution for 10 minutes. This removed the nano-oxide Cr matrix, which has low crystallinity and is highly reactive with acid, allowing the originally embedded inert Pt-Cu nanoparticles to freely separate and grow through a certain degree of free fusion, resulting in Pt-Cu nanoparticles with a particle size range of 3 nm to 100 nm. Due to the short reaction time and the higher Pt content in the Pt-Cu nanoparticles compared to the Cu content, the Cu in the Pt-Cu nanoparticles can be retained.

[0559] The above hydrogen deposition and Al removal reaction involved reacting the solid aggregate product obtained 2 minutes after the start of the reaction with a 0.5 mol / L hydrochloric acid solution for 5 days. This removed the nano-oxide Cr matrix, which had low crystallinity and was highly reactive with acid. Simultaneously, the long reaction time removed the Cu elements contained in the original Pt-Cu nanoparticles. Through a certain degree of free fusion, the nanoparticles grew, yielding Pt nanoparticles with a particle size range of 3 nm to 200 nm.

[0560] [Example 22] This embodiment provides a method for producing nanochromium oxide doped with Au nanoparticles, and includes the following steps.

[0561] Au 1.5 Al 79 Cr 19.5 According to the nominal composition (atomic percentage), Al, Cr, and Au raw materials are melted and Au1.5 Al 79 Cr 19.5 A molten alloy mainly composed of Al was obtained. The obtained molten alloy was cast by copper roller strip casting to a thickness of ~25 μm, with a composition mainly of Al 79 Cr 19.5 Au 1.5 The initial alloy ribbon was manufactured, and its solidification structure consisted mainly of Al4Cr(Au) intermetallic compounds with Au in solid solution, with a solid solution amount of Au of approximately 1.5 at.%.

[0562] Under normal pressure, Au 1.5 Al 79 Cr 19.5 0.25 g of initial alloy ribbon and 50 ml of NaOH aqueous solution at 30°C were placed in a reaction vessel, mixed, and sealed. During sealing, the hydrogen precipitation and de-algae reaction proceeded slowly.

[0563] After sealing, the temperature of the reaction vessel and its interior was raised to 250°C and maintained for 20 minutes. Under sealed conditions, the pressure inside the reaction vessel was higher than atmospheric pressure, and this pressure was due in part to the high temperature sealed environment and the pressure from hydrogen generated by the reaction. After 20 minutes of maintenance, the temperature and pressure were reduced, the product in the reaction vessel was separated into solid and liquid components, washed and dried to obtain nano-chromium oxide doped with modified Au nanoparticles. The modified nano-chromium oxide matrix had a crystallinity of 50% or more, and its morphology consisted mainly of granular or short rod-shaped particles. The particle size range of the granular particles was 2 nm to 50 nm, the diameter range of the short rod-shaped particles was 2 nm to 30 nm, and the aspect ratio was 1.5 to 5. Au nanoparticles were composite-doped into a modified nano-Cr oxide matrix by two methods: in-situ embedding and physicoadsorption. Some of the physicoadsorbed Au nanoparticles detached from the modified nano-Cr oxide matrix to become free Au nanoparticles. The particle size range of the in-situ embedded and physicoadsorbed Au nanoparticles was 0.5 nm to 30 nm.

[0564] After sealing the above reaction system, it is clear that the hydrogen precipitation and de-T reaction will be completely completed while the temperature of the reaction vessel and its interior is raised from 30°C to 250°C. The solid intermediate product obtained at this point will undoubtedly undergo changes in morphology and / or composition compared to the final product after subsequent incubation at 250°C for 20 minutes; this process is called morphological and / or compositional modification.

[0565] [Example 23] This embodiment provides a method for producing nanochromium oxide doped with Au nanoparticles, and includes the following steps.

[0566] Au 1.5 Al 79 Cr 19.5 According to the nominal composition (atomic percentage), Al, Cr, and Au raw materials are melted and Au 1.5 Al 79 Cr 19.5 A molten alloy mainly composed of Al was obtained. The obtained molten alloy was cast by copper roller strip casting to a thickness of ~25 μm, with a composition mainly of Al 79 Cr 19.5 Au 1.5 The initial alloy ribbon was manufactured, and its solidification structure consisted mainly of Al4Cr(Au) intermetallic compounds with Au in solid solution, with a solid solution amount of Au of approximately 1.5 at.%.

[0567] Under normal pressure, the Al produced as described above 79 Cr 19.5 Au 1.5 Initially, 0.5 g of the initial alloy ribbon and 50 ml of a 10 mol / L NaOH aqueous solution were placed in a sealed container, and the initial alloy ribbon was not in contact with the base solution.

[0568] The temperature inside the sealed container, as well as the temperature of the initial alloy ribbon and base solution, are raised to 150°C. At this time, the inside of the sealed container becomes under high pressure, and the Al inside the sealed container 79 Cr 19.5 Au 1.5 When the initial alloy ribbon is mixed with a base solution at this temperature, a vigorous hydrogen deposition and de-T reaction occurs, resulting in Al 79 Cr 19.5 Au1.5 The initial alloy was fragmented into nano-fragments through a vigorous hydrogen deposition and de-Al reaction during the high-temperature, high-pressure reaction process, simultaneously reconstructing its shape and composition and generating solid aggregate products.

[0569] The hydrogen deposition and de-algae reaction was completed within 10 seconds. After 10 seconds, the sealed container and reaction system were rapidly cooled to near room temperature in cooling water, and the pressure inside the sealed container was reduced to atmospheric pressure.

[0570] After the reaction system temperature decreased to room temperature and atmospheric pressure, the solid aggregate product was separated from the solution, washed, and dried to obtain low-crystallinity nano-Cr oxides doped with Au nanoparticles, mainly consisting of amorphous nano-Cr oxide or amorphous Cr hydroxide as the matrix. Here, the nano-Oxide Cr matrix was mainly composed of extremely fine aggregate microstructures, with a size range of 1.0 nm to 10 nm. The Au nanoparticles doped therein were mainly composite-doped into the low-crystallinity nano-Oxide Cr matrix by in-situ embedding, with a particle size range of 0.25 nm to 25 nm. When the particle size was less than 2 nm, the Au nanoparticles were mainly composite-doped into the low-crystallinity nano-Oxide Cr matrix in the form of atoms or atomic clusters.

[0571] [Comparative Example 1] Au 0.25 Nb 25 Al 74.75 According to the (atomic percentage) composition, Au, Nb, and Al raw materials are melted, and Au 0.25 Nb 25 Al 74.75 A molten alloy mainly composed of was obtained. The molten alloy was solidified into an ingot, and then the ingot was crushed to produce an initial alloy powder with an average particle size of 25 μm, consisting mainly of an Al3Nb(Au) intermetallic compound phase in which the element Au is solid-dissolved.

[0572] Under atmospheric pressure, 0.5 g of the initial alloy powder prepared as described above was reacted with 50 mL of a 10 mol / L NaOH aqueous solution at 25°C for 2 hours (average propulsion speed at the reaction interface was 0.5 μm / min or less), and the resulting solid product was collected. The obtained product was mainly Au-containing nanoporous oxide Nb or nanoporous Nb, and its SEM morphology is shown in Figure 51.

[0573] Under these reaction conditions, the shape of the initial alloy powder before and after the reaction remained almost unchanged, still consisting of the original crushed, angular powder particles. Its microstructure did not undergo nanofragmentation, and instead of producing a large amount of dispersed nanooxide powder, coarse powder particles consisting of a nanoporous network structure that retained its original angular state were produced. Its particle size remained comparable to that of the initial alloy powder, being several microns or tens of microns. Therefore, the reaction of the initial alloy with the base solution at lower temperatures is completely different from the reaction at higher temperatures, particularly preferably near the boiling point, according to the present invention, and the morphology of the products is also completely different.

[0574] [Comparative Example 2] This embodiment provides a method for producing nanochromium oxide, and includes the following steps.

[0575] Al 80 Cr 20 According to the nominal formula (atomic percentage), commercially available Al and Cr raw materials are melted, and Al 80 Cr 20 A molten alloy mainly composed of was obtained. The above molten alloy was solidified into an ingot, and then the ingot was crushed to obtain an alloy with an average particle size of 100 μm and a solidified structure mainly composed of CrAl4 intermetallic compounds. 80 Cr 20 It was manufactured as an initial alloy powder with [the specified component] as the main component.

[0576] Under normal pressure, Al 80 Cr 20 The initial alloy powder was reacted with NaOH solution while stirring. The concentration of the NaOH solution was 12 mol / L, the temperature was the boiling point at atmospheric pressure (approximately 128°C), and the volume of the NaOH solution was Al 80 Cr 20The volume was approximately 100 times that of the initial alloy powder. The hydrogen deposition and de-algae reaction was completed within 1 minute, and the initial alloy was nano-fragmented by the reaction, simultaneously undergoing a reconfiguration of its shape and composition, and generating solid aggregate products.

[0577] Two minutes after the start of the reaction, the solid aggregate product was separated from the solution, washed, and dried to obtain a low-crystallinity nano-Cr oxide powder composed of amorphous nano-Cr oxide or amorphous Cr hydroxide. Its TEM morphology and diffraction spectrum are shown in Figure 52. Its morphology consisted mainly of extremely fine aggregate microstructures, with a particle size range of 1.0 nm to 10 nm. Such aggregate microstructures were not rigid nanoporous structures, but rather flat, dispersible gel aggregate structures.

[0578] The above powder, mainly composed of low-crystallinity nanoCr oxide, was heat-treated at 600°C for 2 hours to obtain crystalline nanoCr oxide particles with a particle size of 3 nm to 100 nm. The TEM morphology and diffraction spectrum are shown in Figure 53. After heat treatment, it was found that the aggregate structure of the original low-crystallinity nanoCr oxide crystallized, and granular nanoCr oxide with very good particle dispersion was obtained.

[0579] The technical features of the embodiments described above may be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the embodiments described above have been described, but any combination of these technical features should be considered to fall within the scope described herein, as long as it is inconsistent.

[0580] The embodiments described above merely illustrate some of the embodiments of the present invention, and although the description is relatively specific and detailed, it should not be understood as limiting the scope of protection of the invention. Furthermore, those skilled in the art can make several modifications and improvements as long as they do not depart from the concept of the present invention, and all of these fall within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be in accordance with the attached claims.

Claims

1. A method for producing nanometal oxides doped with precious metal nanoparticles, An initial alloy is provided, the initial alloy comprising M, T and A component elements, where the M element comprises at least one of Cr, V, Nb, Ta, W, Mo, Mn, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; the T element comprises at least one of Al and Zn; and the A element mainly consists of noble metal elements comprising at least one of Au, Pt, Pd, Ru, Rh, Os, Ir, Re, Ag, and Cu; the solidification structure of the initial alloy mainly comprises an M-T-A intermetallic compound, or / or an M-T(A) intermetallic compound in which the A component element is in solid solution; and the composition of the initial alloy is mainly A ｘ T ｙ M ｚ Step 1 is the process in which, where x, y, and z are the atomic percentage content of the corresponding elements, and 0 < x ≤ 15%, 40% ≤ y < 95%, and 5% ≤ z < 60%. Step 2 involves subjecting the initial alloy to a hydrogen deposition and de-T reaction with a base solution, controlling the temperature and concentration of the base solution so that the reaction interface moves inward from the surface of the initial alloy at an average rate exceeding 2 μm / min, during the reaction process the initial alloy undergoes nanofragmentation by the hydrogen deposition and de-T reaction, and through the reconstruction of its shape and composition, M-containing solid products having at least one dimension of 500 nm or less in the three-dimensional direction are generated, and simultaneously with the hydrogen deposition and de-T reaction, A element atoms in the original initial alloy intermetallic compound are rearranged by diffusion to form A-containing nanoparticles. After the hydrogen deposition and de-T reaction is completed, the solid product in the reaction system is recovered to obtain nanooxide M doped with A-containing nanoparticles, and this nanooxide M consists of A-containing nanoparticles and a nanooxide M matrix, where the A-containing nanoparticles include at least one of A nanoparticles and nanooxide A particles, and the particle size range of the A-containing nanoparticles is 0.25 nm to 100 nm, and the nanooxide M matrix includes at least one of low-crystalline nanooxide M, crystalline nanooxide M, and hydrated nanooxide M, where hydrated nanooxide M specifically refers to nanohydroxylated M, and the nanooxide M matrix has a shape in which the scale of at least one dimension in the three-dimensional direction is 500 nm or less, and A method for producing nanometal oxides doped with precious metal nanoparticles, characterized by containing the following:

2. A method for producing a nanometal oxide doped with noble metal nanoparticles according to claim 1, wherein the temperature of the base solution is T １ And, T １ A method for producing nanometal oxides doped with noble metal nanoparticles, characterized by a temperature of ≥60°C.

3. A method for producing a nanometal oxide doped with noble metal nanoparticles as described in claim 1, characterized in that the method for doping the A-containing nanoparticles into the nanometal oxide M matrix includes in-situ embedding doping.

4. A method for producing a nanometal oxide doped with noble metal nanoparticles as described in claim 1, wherein when the A-containing nanoparticles have a particle size range of 0.25 nm to 2 nm and are embedded in a nanooxide M matrix in situ, the A-containing nanoparticles of this particle size range are embedded in the nanooxide M matrix in the form of atoms or atomic clusters.

5. A method for producing nanometal oxides doped with noble metal nanoparticles, characterized in that a nanometal oxide M doped with A-containing nanoparticles produced by the production method described in claim 1 is heat-treated to obtain a nanometal oxide M doped with A-containing nanoparticles with increased crystallinity.

6. A method for producing nanometal oxides doped with precious metal nanoparticles, An initial alloy is provided, the initial alloy comprising M, T and A component elements, where the M element comprises at least one of Cr, V, Nb, Ta, W, Mo, Mn, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; the T element comprises at least one of Al and Zn; and the A element mainly consists of noble metal elements comprising at least one of Au, Pt, Pd, Ru, Rh, Os, Ir, Re, Ag, and Cu; the solidification structure of the initial alloy mainly comprises an M-T-A intermetallic compound, or / or an M-T(A) intermetallic compound in which the A component element is in solid solution; and the composition of the initial alloy is mainly A ｘ T ｙ M ｚ Step 1 is the process in which, where x, y, and z are the atomic percentage content of the corresponding elements, and 0 < x ≤ 15%, 40% ≤ y < 95%, and 5% ≤ z < 60%. Mix the initial alloy with a base solution at a temperature of T １ , where T ｓ溶液 < T １ ≤ T ｆ溶液 , and T ｆ溶液 is the boiling point temperature of the base solution involved in the reaction at normal pressure, and T ｓ溶液 is the freezing point temperature of the base solution involved in the reaction at normal pressure, and Step 2 The mixture of the initial alloy and the base solution is placed in a sealed container and heated to a temperature higher than atmospheric pressure T ２ The mixture is treated for a certain period of time, and the product is collected to obtain a nanooxide M doped with A-containing nanoparticles whose morphology and / or composition has changed compared to before high-pressure treatment, wherein the nanooxide M comprises A-containing nanoparticles and a nanooxide M matrix, where T ２ >T ｆ溶液 The A-containing nanoparticles comprise at least one of A nanoparticles and nanooxide A particles, the particle size range of the A-containing nanoparticles is 0.25 nm to 100 nm, the nanooxide M matrix comprises at least one of low-crystalline nanooxide M, crystalline nanooxide M, and hydrated nanooxide M, where hydrated nanooxide M specifically refers to nanohydroxyoxide M, and the modified nanooxide M matrix has a shape in which the scale of at least one dimension in the three-dimensional direction is 500 nm or less, and the process 3 is as follows: A method for producing nanometal oxides doped with precious metal nanoparticles, characterized by containing the following:

7. A method for producing precious metal nanoparticles, A method for producing noble metal nanoparticles, characterized in that the nanooxide M matrix in a solid product produced by the manufacturing method described in any one of claims 1 to 6 is dissolved by an etching solution reaction, and the inert noble metal elements in the A nanoparticles are retained in the solid product without dissolving, thereby obtaining A nanoparticles mainly composed of inert noble metal elements, wherein the composition of the A nanoparticles includes at least one of Au, Pt, Pd, Ru, Rh, Os, Ir, Re, and Ag, and the particle size range of the A nanoparticles is 2 nm to 300 nm.

8. Nanometal oxides doped with precious metal nanoparticles, A metal oxide doped with noble metal nanoparticles, manufactured by the manufacturing method described in any one of claims 1 to 6, comprises noble metal nanoparticles and a nanometal oxide matrix, wherein the molar percentage content of noble metal nanoparticles is lower than the molar percentage content of the nanometal oxide matrix, the noble metal nanoparticles are A-containing nanoparticles, mainly composed of noble metal element A, and containing at least one of Au, Pt, Pd, Ru, Rh, Os, Ir, Re, Ag, Cu, the A-containing nanoparticles comprise at least one of A nanoparticles and nano-oxidized A particles, the nanometal oxide matrix is ​​nano-oxidized M, and the element M is Cr, V, Nb, Ta, W, Mo, Mn, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, E Nanometal oxide doped with noble metal nanoparticles, comprising at least one of r, Tm, Yb, and Lu, wherein the nanooxide M comprises at least one of low-crystalline nanooxide M, crystalline nanooxide M, and hydrated nanooxide M, where the hydrated nanooxide M specifically refers to nanohydroxyoxide M, and the method of doping the nanooxide M matrix with A-containing nanoparticles comprises in-situ embedding doping, i.e., the A-containing nanoparticles are formed in-situ by being partially or completely encapsulated by the nanooxide M matrix, the particle size range of the A-containing nanoparticles is 0.25 nm to 200 nm, and the nanooxide M matrix has a shape in which the scale of at least one dimension in the three-dimensional direction is 500 nm or less.

9. A nanometal oxide doped with noble metal nanoparticles according to claim 8, characterized in that the thermal stability of the nanometal oxide doped with noble metal nanoparticles is higher than that of a corresponding nanooxide matrix manufactured under similar conditions.

10. Applications of nanometal oxide composite materials, catalyst materials, ceramic materials, refractory materials, advanced electronic materials, battery materials, color-changing materials, wave-absorbing materials, wastewater decomposition materials, sterilizing materials, paints, pigments, thermal spray materials, and sensors, all of which are doped with noble metal nanoparticles produced by the manufacturing method described in any one of claims 1 to 6.

11. For use in decorative paints for homes, nanometal oxides doped with noble metal nanoparticles containing Cu and / or Ag are mixed with other components of the paint as a paint additive and applied together to the surfaces of furniture, fixtures, and walls to achieve an antibacterial effect. For use as a disinfectant spray, the nanometal oxide doped with noble metal nanoparticles containing Cu and / or Ag is mixed with other liquid spray components and sprayed together onto furniture, utensils, fabrics, and wall surfaces through a spray carrier to achieve an antibacterial effect. The application of nanometal oxides doped with noble metal nanoparticles containing Cu and / or Ag, manufactured by the manufacturing method described in any one of claims 1 to 6, to home decor paints, antibacterial sprays, and antifouling paints, characterized in that the antifouling effect is achieved by using nanometal oxides doped with noble metal nanoparticles containing Cu and / or Ag in place of antibacterial and antifouling components in conventional antifouling paints. Herein, the component composition of the noble metal nanoparticles includes at least one of Cu and Ag.

12. Application of nanometal oxides doped with noble metal nanoparticles, produced by the manufacturing method described in any one of claims 1 to 6, to antibacterial fabrics, characterized in that the nanometal oxides doped with noble metal nanoparticles containing Cu and / or Ag are dispersed, then attached to or coated on the surface of a fabric, or mixed with the fabric and knitted, thereby giving the fabric antibacterial and germicidal effects and capabilities. Herein, the component composition of the noble metal nanoparticles includes at least one of Cu and Ag.

13. A nanometal oxide doped with nanoparticles, The metal oxide doped with A nanoparticles comprises A nanoparticles and a nanometal oxide matrix, wherein the molar percentage content of A nanoparticles is lower than the molar percentage content of the nanometal oxide matrix, the A nanoparticles are A-containing nanoparticles, mainly composed of element A, and containing at least one of Au, Pt, Pd, Ru, Rh, Os, Ir, Re, Ag, Cu, Fe, Ni, and Co, the A-containing nanoparticles comprise at least one of A nanoparticles and nano-oxidized A particles, the nanometal oxide matrix is ​​nano-oxidized M, and the element M is at least of Cr, V, Nb, Ta, W, Mo, Mn, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu A nanometal oxide doped with A nanoparticles, wherein the nano-oxide M comprises at least one of low-crystalline nano-oxide M, crystalline nano-oxide M, and hydrated nano-oxide M, where the hydrated nano-oxide M specifically refers to nano-hydroxylated M, and the method of doping the nano-oxide M matrix with A-containing nanoparticles comprises in-situ embedding doping, i.e., the A-containing nanoparticles are formed in-situ by being partially or completely encapsulated by the nano-oxide M matrix, the particle size range of the A-containing nanoparticles is 0.25 nm to 200 nm, and the nano-oxide M matrix has a shape in which the scale of at least one dimension in the three-dimensional direction is 500 nm or less.

14. The nanometal oxide doped with A nanoparticles according to claim 13 is characterized in that the A-containing nanoparticles have a particle size range of 0.25 nm to 2 nm, and when embedded in a nano-oxide M matrix in situ, the A-containing nanoparticles within this particle size range are embedded in the nano-oxide M matrix in the form of atoms or atomic clusters.

15. The nanometal oxide doped with A nanoparticles as described in claim 13 is characterized by its application to composite materials, catalytic materials, ceramic materials, refractory materials, advanced electronic materials, battery materials, color-changing materials, wave-absorbing materials, wastewater decomposition materials, sterilization materials, paints, pigments, thermal spray materials, and sensors.

Images