In-situ endogenous doped titanium-oxygen-based composite powder material as well as preparation method and application thereof

Abstract

The invention relates to an in-situ endogenous doped titanium-oxygen-based composite powder material as well as a preparation method and application thereof. The powder material has two-stage composite characteristics, and comprises the following steps: firstly, carrying out first-stage composite on a titanium-oxygen-based carrier by in-situ endogenous doped E1 element to form a titanium-oxygen-based main component of the in-situ endogenous doped E1 element; and then carrying out secondary compounding on the in-situ exogenous doped E2 component and the in-situ endogenous doped E1 element titanoxyl main component. The preparation method of the in-situ endogenous doped titanium-oxygen-based composite powder material has the characteristics of simple process, easiness in operation, high efficiency and low cost, and can be used for preparing various in-situ endogenous doped titanium-oxygen-based composite powder materials of which the main components comprise a nano-film, a nano-sheet, a nano-tube / rod, nano-particles and other morphologies; the method has good application prospects in the fields of composite materials, ceramic materials, photocatalytic materials, hydrophobic materials, sewage degradation materials, sterilization materials, electronic materials, coatings and the like.

Description

In-situ endogenously doped titanium oxide composite powder material and its preparation method and use Technical Field

[0001] The present invention relates to the technical field of nanomaterials, and in particular to an in-situ endogenously doped titanium-based composite powder material, a preparation method thereof, and applications thereof. Background Art

[0002] Metal nanoparticles, especially precious metal nanoparticles, possess excellent optical, electronic, biological, and chemical properties due to their pronounced surface, volume, quantum, and small size effects. These properties hold broad application prospects in a variety of technical fields, including catalysis, chemistry, biology, medicine, food, and molecular biology. Generally speaking, precious metal nanoparticles require good dispersibility during their application. To address this issue, precious metal nanoparticles are typically combined with nanoscale carriers, which then disperse the particles for further application. Furthermore, the finer the precious metal nanoparticles, the higher their specific surface area and the better their performance. Therefore, preparing ultrafine precious metal nanoparticles and simultaneously loading them onto specific carriers is of great significance.

[0003] Currently, the most commonly used method for combining noble metal nanoparticles with nanoscale supports is a mixing process. This involves preparing a nanoscale support material and then mixing the noble metal nanoparticles, prepared by another method, with the support material to allow the noble metal nanoparticles to adsorb onto the support material's surface. This mechanical mixing-adsorption approach not only hinders the physical-chemical interaction between the noble metal nanoparticles and the support material at the atomic scale, but also easily causes the noble metal nanoparticles to fall off the support material's surface, leading to instability and deterioration in the performance of the noble metal nanoparticles. Therefore, it is of great significance to develop a composite technology for combining in-situ generated noble metal nanoparticles with nanoscale supports to prepare in-situ endogenously doped nanocomposite powder materials.

[0004] Summary of the Invention

[0005] Based on this, it is necessary to provide an in-situ endogenously doped titanium-based composite powder material and a preparation method thereof to address the above problems:

[0006] On the one hand, an in-situ endogenously doped titanium-based composite powder material is characterized in that it is mainly composed of a titanium-based main component in-situ endogenously doped with E1 element and an in-situ exogenously doped E2 component; the titanium-based main component in-situ endogenously doped with E1 element is mainly composed of a titanium-based carrier and an endogenously doped E1 element, and the components of the titanium-based carrier include at least one of titanate, titanic acid, and TiO2, and the shape of the titanium-based carrier includes at least one of nanofilm, nanosheet, nanotube / rod, and nanoparticle; the in-situ exogenously doped E2 component The invention comprises at least one of E2 nanoporous particles and E2 nanoparticles; the E1 element and the E2 component are mainly composed of E elements, and the E element includes at least one of Au, Pt, Pd, Ru, Rh, Re, Os, Ir, Ag, Cu, Fe, Ni, and Co; when the E1 element or the E2 component includes two or more E elements, the composition of E1 is not necessarily the same as the composition of E2; the molar percentage content of the in-situ exogenously doped E2 component in the in-situ endogenously doped titanium-based composite powder material is V e2 , and 0 <V e2 ≤25%; the total molar number of E1 element in the titanium-based main component doped with E1 element in situ, C e1 The ratio C to the total molar number C0 of Ti in the titanyl support e1 / C0 satisfies: 0 <C e1 / C0<0.20;

[0007] In the titanyl main component in-situ endogenously doped with E1 elements, the in-situ endogenous doping method of the E1 element on the titanyl support includes at least one of the following two methods:

[0008] 1) The E1 element is in situ embedded in the titanyl support, and the E1 element mainly dopes the titanyl support in the form of E1 atoms or atomic clusters, and the size of the E1 atoms or atomic clusters is 0.2 nm to 2 nm;

[0009] 2) The E1 element is in-situ embedded in the titanium-based carrier, and the E1 element is mainly doped into the titanium-based carrier in the form of E1 nanoparticles, and the size of the E1 nanoparticles is 2 nm to 50 nm.

[0010] Furthermore,

[0011] In the titanyl main component in situ endogenously doped with E1 element, when the shape of the titanyl carrier is mainly a nanofilm, its thickness is 0.25nm to 10nm;

[0012] In the titanyl main component in situ endogenously doped with E1 element, when the shape of the titanyl support is mainly nanosheet, its thickness is 3nm to 30nm;

[0013] In the titanyl main component in situ endogenously doped with E1 element, when the shape of the titanyl support is mainly nanotubes / rods, the outer diameter thereof is 2nm to 20nm;

[0014] In the titanyl main component in situ endogenously doped with E1 element, when the shape of the titanyl carrier is mainly nanoparticles, the average particle size is 2nm to 600nm; preferably, the average particle size is 2nm to 200nm; preferably, the average particle size is 2nm to 50nm; preferably, the average particle size is 2nm to 30nm;

[0015] Furthermore, in the in-situ exogenously doped E2 component, the average particle size of the E2 nanoporous particles is 5nm-50μm, and the average diameter of the nanoporous bands is 2nm~200nm; in the in-situ exogenously doped E2 component, the average particle size of the E2 nanoparticles is 2nm~500nm.

[0016] Furthermore, the E1 element is in situ embedded in the titanyl support, the E1 element is mainly doped with the titanyl support in the form of E1 nanoparticles, and when the E1 element comprises at least one of Cu, Ag, Fe, Ni, and Co, the E1 nanoparticles comprise at least one of E1 metal nanoparticles and E1 metal oxide nanoparticles;

[0017] Further, the E1 metal oxide nanoparticles include at least one of CuO nanoparticles, Cu2O nanoparticles, Ag2O nanoparticles, FeO nanoparticles, Fe2O3 nanoparticles, Fe3O4 nanoparticles, NiO nanoparticles, CoO nanoparticles, Co2O3 nanoparticles, and Co3O4 nanoparticles;

[0018] Furthermore, the titanium-based support in situ endogenously doped with the E1 element and the in situ exogenously doped E2 component are simultaneously and independently evolved from different precursor components through different reaction processes;

[0019] Furthermore, in the in-situ endogenously doped titanyl composite powder material, the E element is respectively compounded with the titanyl carrier in a two-stage compounding manner: first, the in-situ endogenously doped E1 element is compounded with the titanyl carrier in the first stage to form a titanyl main component in-situ endogenously doped E1 element; then, the in-situ exogenously doped E2 component is compounded with the titanyl main component in-situ endogenously doped E1 element in the second stage;

[0020] Furthermore, the titanyl support in situ endogenously doped with the E1 element and the in situ exogenously doped E2 component are generated simultaneously;

[0021] Furthermore, the in-situ exogenously doped E2 component is dispersed and softly agglomerated by the in-situ endogenously doped E1 element titanium-based support;

[0022] Furthermore, the titanium-based carrier in situ endogenously doped with the E1 element has a powder material morphology from a macroscopic perspective, but is microscopically composed of a large number of nanofilms, nanosheets, nanotubes / rods, and nanoparticles aggregated together through soft agglomeration and entanglement, and its structure is completely different from a three-dimensional network-like nanoporous structure.

[0023] Furthermore, 0 <V e2 ≤15%; further, 0 <V e2 ≤10%; further, 0 <V e2 ≤5%; further, 0 <V e2 ≤2%;

[0024] Furthermore, 0 <C e1 / C0<0.15; further, 0 <C e1 / C0<0.10; further, 0 <C e1 / C0<0.075; further, 0 <C e1 / C0<0.05;

[0025] Furthermore, the cations in the titanate include at least one of Na, K, Li, Rb, Ba, Ca, and Sr;

[0026] Furthermore, the cations in the titanate include at least one of Na, K, Li, and Ba; further, the titanate includes at least one of sodium titanate, potassium titanate, lithium titanate, and barium titanate;

[0027] Furthermore, the cations in the titanate include at least one of Na and K; further, the titanate includes at least one of sodium titanate and potassium titanate;

[0028] Furthermore, the titanate, titanic acid, and TiO2 include titanates, titanic acid, and TiO2 of different crystal forms, such as at least one of amorphous, partially crystalline, and crystalline;

[0029] Furthermore, the crystalline TiO2 includes TiO2 of different crystal forms, such as at least one of anatase and rutile forms;

[0030] Furthermore, when the shape of the titanium-based carrier is mainly a nanofilm, the average area of ​​the titanium-based nanofilm in situ doped with E1 element is greater than 200nm 2 Furthermore, the average area of ​​the in-situ endogenously doped titanium oxide nanofilm is greater than 1000nm 2Furthermore, the average area of ​​the in-situ endogenously doped titanium oxide nanofilm is greater than 10000nm 2 ;

[0031] Furthermore, when the shape of the titanium-based carrier is mainly a nanofilm, after the in-situ endogenously doped titanium-based composite powder material is refined, the average area of ​​the in-situ endogenously doped titanium-based nanofilm of the E1 element will be greatly reduced, such as as low as 10nm. 2 ;

[0032] Furthermore, the refinement treatment method includes at least one of ultrasonic crushing, ball milling, and sand milling;

[0033] After refinement:

[0034] Furthermore, the average area of ​​the titanium oxide nanofilm in situ doped with E1 element is 10nm 2 -1000nm 2 ;

[0035] Furthermore, the average area of ​​the titanium oxide nanofilm in situ doped with E1 element is 10nm 2 -400nm 2 ;

[0036] Furthermore, the in-situ endogenously doped titanium oxide nanofilm has traces of crushing treatment, such as the hole characteristics caused by ultrasonic crushing, ball milling, and sand milling. Even if the shape of the titanium oxide nanofilm after crushing is roughly intact, the film still contains one or more holes running through it.

[0037] Furthermore, during the refinement process, the in-situ exogenously doped E2 component is also refined, and its average particle size is also reduced;

[0038] Furthermore, when the main component of the titanium-based carrier is at least one of titanate and titanic acid, the thickness of the titanium-based nanofilm in situ endogenously doped with E1 element is 0.25 nm to 7.5 nm;

[0039] Furthermore, when the main component of the titanium-based carrier is at least one of titanate and titanic acid, the thickness of the titanium-based nanofilm in situ endogenously doped with E1 element is 0.25 nm to 5 nm;

[0040] Furthermore, when the main component of the titanium-based carrier is at least one of titanate and titanic acid, the thickness of the titanium-based nanofilm in situ endogenously doped with E1 element is 0.25 nm to 2.5 nm;

[0041] Furthermore, when the main component of the titanium-based support is TiO2, the thickness of the titanium-based nanosheets in situ endogenously doped with E1 elements is 3 nm to 25 nm;

[0042] Furthermore, the E element includes at least one of Cu, Ag, Fe, Ni, and Co;

[0043] Further, the E element mainly contains Ag; further, the E element mainly contains Cu; further, the E element mainly contains Fe;

[0044] Furthermore, the E1 element includes at least one of Au, Pt, Pd, Ru, Rh, Re, Os, Ir, Ag, Cu, Fe, Ni, and Co;

[0045] Furthermore, the E1 element includes at least one of Au, Pt, Pd, Ru, Rh, Os, Ir, and Re;

[0046] Furthermore, the E1 element includes at least one of Cu, Ag, Fe, Ni, and Co;

[0047] Furthermore, the E2 element includes at least one of Au, Pt, Pd, Ru, Rh, Re, Os, Ir, Ag, Cu, Fe, Ni, and Co;

[0048] Further, the E2 component comprises at least one of Au, Pt, Pd, Ru, Rh, Os, Ir, and Re;

[0049] Furthermore, the E2 element includes at least one of Cu, Ag, Fe, Ni, and Co;

[0050] Note: In this application, the term "mainly comprises" a component means that the atomic percentage or molar percentage content of the component exceeds 50%;

[0051] Furthermore, the E1 nanoparticles include at least one of E1 metal nanoparticles and E1 metal oxide nanoparticles;

[0052] Further, the size of the E1 nanoparticles is 2nm to 20nm; further, the size of the E1 nanoparticles is 2nm to 15nm; further, the size of the E1 nanoparticles is 2nm to 10nm;

[0053] Furthermore, the in-situ embedding in the in-situ endogenous doping method refers to the partial or complete embedding of E1 atoms or atomic clusters, or E1 nanoparticles in the titanium-based carrier by in-situ embedding; this in-situ embedding is the result of the simultaneous in-situ generation and in-situ recombination of the titanium-based carrier and the doped E1 element during the formation of the titanium-based carrier with the in-situ endogenous doping E1 element. It does not rely on and cannot rely on external addition or external mixing to embed the doped E1 element in the titanium-based carrier.

[0054] Furthermore, when the E1 atoms or atomic clusters are smaller than 2 nm, it is difficult to observe the difference in contrast and aggregation of the E1 atoms or atomic clusters in the titanyl support by means of transmission electron microscopy (TEM) or the like; in this case, it can be considered that the E1 element exists in solid solution in the titanyl support;

[0055] Furthermore, when the E1 element is mainly composed of Ag, the E1 element is in situ embedded in the titanyl support, and the E1 element mainly dopes the titanyl support with E1 atoms or atomic clusters, and the size of the E1 atoms or atomic clusters is 0.2 nm to 2 nm;

[0056] Furthermore, when the E1 element is mainly composed of Cu, the E1 element is in situ embedded in the titanium-based support, and the E1 element mainly dopes the titanium-based support in the form of E1 metal nanoparticles or (and) E1 metal oxide nanoparticles, and the size of the E1 metal nanoparticles or (and) E1 metal oxide nanoparticles is 2 nm to 20 nm;

[0057] Further, the composition of the E1 metal oxide nanoparticles includes at least one of Cu2O and CuO;

[0058] Furthermore, when the E1 element is mainly composed of Au, the E1 element is in situ embedded in the titanium-based carrier, and the E1 element mainly dopes the titanium-based carrier with E1 metal nanoparticles, and the size of the E1 metal nanoparticles is 2 nm to 20 nm;

[0059] Furthermore, when the titanyl support is mainly composed of titanate, the cations thereof are replaced with H ions by reacting the titanate with a dilute acid, thereby converting the titanate into titanic acid, thereby obtaining a titanyl support mainly composed of titanic acid;

[0060] Furthermore, in the dilute acid solution, the hydrogen ion concentration is lower than 0.1 mol / L;

[0061] Furthermore, when the E1 element dopes the titanium-based carrier mainly in the form of atoms or atomic clusters, the E1 element is transformed into E1 nanoparticles through diffusion, aggregation, nucleation and growth through heat treatment to dope the titanium-based carrier.

[0062] Furthermore, due to the solid solution and pinning effect of E1 atoms or atomic clusters on the titanium-based support, when the titanium-based support is doped with the E1 element mainly in the form of atoms or atomic clusters, the phase change thermal stability of the titanium-based support is significantly improved;

[0063] Furthermore, when the E1 element is doped into the titanyl support mainly in the form of atoms or atomic clusters, the phase transition temperature of the doped titanyl support is increased by more than 100° C. compared to the undoped titanyl support;

[0064] Furthermore, the phase change of the titanium-based support is a phase change of titanic acid into TiO2;

[0065] Furthermore, when the main component of the titanium-based carrier is at least one of titanate and titanic acid, its crystal form is mainly low crystalline; after a certain degree of heat treatment, its crystallinity is further improved, and even a crystal form transformation occurs, such as from titanic acid to anatase TiO2, and then further to rutile TiO2;

[0066] Furthermore, the thickness of the titanyl support increases during the heat treatment while the area decreases;

[0067] Furthermore, in the in-situ exogenously doped E2 component, the average particle size of the E2 nanoporous particles is 10 nm-20 μm;

[0068] Furthermore, in the in-situ exogenously doped E2 component, the average particle size of the E2 nanoporous particles is 10 nm-5 μm;

[0069] Furthermore, in the in-situ exogenously doped E2 component, the average particle size of the E2 nanoporous particles is 10 nm-1 μm;

[0070] Furthermore, in the in-situ exogenously doped E2 component, the average particle size of the E2 nanoparticles is 2 nm to 250 nm;

[0071] Furthermore, in the in-situ exogenously doped E2 component, the average particle size of the E2 nanoparticles is 2 nm to 150 nm.

[0072] Furthermore, the "in situ" in the in situ exogenously doped E2 component means that the exogenously doped E2 component is not doped and mixed with the in situ endogenously doped titanium-based main component of the E1 element by external addition, but both are generated in situ simultaneously during a certain reaction process.

[0073] Both the E1 element and the E2 component are mainly composed of the E element. When the E element includes only one element, then either the E1 element or the E2 component can only be this element. However, when the E1 element or the E2 component includes two or more elements, the composition of E1 does not necessarily have to be exactly the same as the composition of E2; for example, when the E1 element or the E2 component includes two single elements, the ratio of the two single elements in the E1 element is 1:4, and the ratio of the same two single elements in the E2 component may be 2:1.

[0074] Furthermore, when the E2 includes two or more elements, the E2 component can mainly be one component particle or can include multiple sub-component particles; for example: when the E2 element contains Ag and Au, the E2 component is mainly AgCu nanoporous particles; when the E2 element contains Ag and Pt, the E2 component contains two sub-component particles, namely Ag nanoporous particles and Pt nanoporous particles;

[0075] Furthermore, when the E2 element contains at least one of Cu, Ag, Fe, Ni, and Co, the composition of the E2 nanoporous particles includes at least one of E2 nanoporous metal particles and E2 nanoporous metal oxide particles;

[0076] Furthermore, when the E2 element contains at least one of Cu, Ag, Fe, Ni, and Co, the composition of the E2 nanoparticles includes at least one of E2 nanometal particles and E2 nanometal oxide particles;

[0077] Furthermore, the compositions of the E2 nanoporous metal oxide and the E2 nanometal oxide respectively include at least one of CuO, Cu2O, Ag2O, FeO, Fe2O3, Fe3O4, NiO, CoO, Co2O3, and Co3O4.

[0078] On the second aspect, a preparation method of an in-situ endogenously doped titanium oxy-compound powder material, characterized by comprising the following steps of preparation:

[0079] Step 1, preparing an initial alloy, the initial alloy containing T-type elements, Ti, and the E element, and the phase composition of the initial alloy mainly consisting of a T-Ti(E) intermetallic compound in which the E element is dissolved and a T-E phase, wherein the molar percentage content of the T-E phase in the initial alloy is V0, and 0 < V0 ≤ 25%, and the atomic percentage content of the E element in the T-E phase is higher than the atomic percentage content of the E element in the T-Ti(E) intermetallic compound; wherein, the T-type elements include at least one of Al and Zn, and the E element includes at least one of Au, Pt, Pd, Ru, Rh, Re, Os, Ir, Ag, Cu, Fe, Ni, and Co;

[0080] Step 2: reacting the initial alloy with a hot alkaline solution, and by controlling the concentration and temperature of the alkaline solution, the reaction interface is advanced inward from the surface of the initial alloy at an average rate of greater than 7.5 μm / min during the reaction, and the T-Ti (E) intermetallic compound at the reaction interface is nano-fragmented by a violent hydrogen evolution de-T reaction, and simultaneously undergoes shape and composition reconstruction to generate a titanate main component in situ endogenously doped with the E1 element; at the same time, the TE phase at the reaction interface undergoes a traditional de-T reaction to generate an in situ exogenously doped E2 component; the E2 component includes at least one of E2 nanoporous particles and E2 nanoparticles; the E1 element and the E2 component are both mainly composed of the E element, and when the E1 element or the E2 component includes two or more elements, the composition of E1 is not necessarily exactly the same as the composition of E2;

[0081] Step three, after the de-T reaction is completed, the solid reaction product in step two is collected to obtain an in-situ endogenously doped titanium-based composite powder material, the characteristics of which are described in one aspect, and the specific characteristics also include: it is mainly composed of a titanate main component in-situ endogenously doped with E1 element and an in-situ exogenously doped E2 component; the titanate main component in-situ endogenously doped with E1 element is mainly composed of a titanate carrier and an endogenously doped E1 element; the component of the titanate carrier is mainly titanate, and the shape of the titanate carrier is mainly a nanofilm, and its thickness is 0.25nm to 25nm; the total molar number C of the E1 element e1 The ratio C to the total molar number C0 of Ti in the titanate support e1 / C0 satisfies: 0 <C e1 / C0<0.20.

[0082] In the step 1,

[0083] Further, the T-type element includes Al; further, the T-type element includes Zn;

[0084] Furthermore, the E element includes at least one of Cu, Ag, Fe, Ni, and Co;

[0085] Further, the E element mainly contains Ag; further, the E element mainly contains Cu; further, the E element mainly contains Fe;

[0086] Furthermore, the E1 element includes at least one of Au, Pt, Pd, Ru, Rh, Re, Os, Ir, Ag, Cu, Fe, Ni, and Co;

[0087] Furthermore, the E1 element includes at least one of Au, Pt, Pd, Ru, Rh, Os, Ir, and Re;

[0088] Furthermore, the E1 element includes at least one of Cu, Ag, Fe, Ni, and Co;

[0089] Furthermore, the E2 element includes at least one of Au, Pt, Pd, Ru, Rh, Re, Os, Ir, Ag, Cu, Fe, Ni, and Co;

[0090] Further, the E2 component comprises at least one of Au, Pt, Pd, Ru, Rh, Os, Ir, and Re;

[0091] Furthermore, the E2 element includes at least one of Cu, Ag, Fe, Ni, and Co;

[0092] Furthermore, the solid solution includes interstitial solid solution and substitutional solid solution;

[0093] Furthermore, the T-Ti(E) intermetallic compound having the E element solid-dissolved therein means that the E element exists in the lattice gap of the T-Ti(E) intermetallic compound in the form of an interstitial atom, or the E element replaces the T atom position or the Ti atom position in the lattice of the T-Ti(E) intermetallic compound in the form of a substitution atom; the T refers to a T-type element, and T represents any one of Al, Zn, and AlZn;

[0094] Furthermore, the T-Ti(E) intermetallic compound may be a single phase, such as a TiAl3 intermetallic compound with Au solid solution, or a multiphase intermetallic compound composed of Ti and T elements, such as a composite multiphase intermetallic compound composed of TiAl3 with Au solid solution and Ti Al2 with Au solid solution;

[0095] Furthermore, the atomic percentage content of the E element in the T-Ti(E) intermetallic compound is less than 5%;

[0096] Furthermore, the initial alloy is prepared by melting a melt containing T elements, Ti and E elements and then solidifying it, forming a solidification structure during the solidification process of the alloy, and the phase composition of the initial alloy solidification structure mainly consists of a T-Ti (E) intermetallic compound in which the E element is solid-dissolved and a TE phase;

[0097] Furthermore, the solidification rate of the initial alloy melt is 0.01K / s to 10 8 K / s;

[0098] Furthermore, by controlling the solidification rate of the initial alloy melt, the size, morphology, composition, and distribution characteristics of the T-Ti(E) intermetallic compound and TE phase in the initial alloy can be controlled. Generally speaking, the higher the cooling rate, the smaller the T-Ti(E) intermetallic compound and TE phase, and the higher the solid solubility of the E element in the T-Ti(E) intermetallic compound. When it is desired to obtain a smaller TE phase and the smallest possible in-situ exogenously doped E2 component, the lowest possible solidification rate is also desirable.

[0099] Further, the T-Ti(E) intermetallic compound includes at least one of T3Ti(E), T2Ti(E), and TTi(E) intermetallic compounds;

[0100] Further, the T-Ti(E) intermetallic compound includes at least one of Al3Ti(E), Al2Ti(E), and AlTi(E) intermetallic compounds;

[0101] Furthermore, the T-Ti(E) intermetallic compound means that the phase composition of the intermetallic compound is a T-Ti intermetallic compound phase, that is, the XRD phase analysis result of the T-Ti(E) intermetallic compound is a T-Ti intermetallic compound;

[0102] Furthermore, the TE phase includes at least one of a TE intermetallic compound phase and a T(E) phase; wherein the TE intermetallic compound is an intermetallic compound composed of a T-type element and an E element, and the T(E) phase is a T(E) phase in which the E element is solid-dissolved;

[0103] Further, in the initial alloy, the T-Ti(E) intermetallic compound is composed of one or more daughter T-Ti(E) intermetallic compounds;

[0104] Furthermore, in the initial alloy, the T(E) phase is composed of one or more sub-T(E) phases; for example, when Ti is Al and E contains Ag and Pt, the T(E) phase is composed of an Al3Pt phase and an Al(Ag) phase;

[0105] Furthermore, the T(E) phase can be a TE intermetallic compound phase or a T(E) phase of a solid solution E element.

[0106] Furthermore, the atomic percentage of the E element in the TE phase is higher than 5%;

[0107] Furthermore, the shape of the initial alloy has an average size in any three-dimensional direction greater than 4 μm;

[0108] Furthermore, the shape of the initial alloy includes at least one of block, granular, filament, strip, ribbon, and sheet;

[0109] Furthermore, the initial alloy is in powder or strip form, and the powder particles or strips have at least one dimension smaller than 5 mm in three dimensions;

[0110] Further, when the initial alloy is in the form of a strip, it can be prepared by a method including a melt spinning strip method;

[0111] Furthermore, when the initial alloy is in powder form, a larger initial alloy ingot can be prepared by a casting method and then crushed into initial alloy powder.

[0112] In the step 2,

[0113] Further, the alkaline solution comprises at least one of NaOH, KOH, LiOH, RbOH, Ba(OH)2, Ca(OH)2, and Sr(OH)2 solutions;

[0114] Furthermore, the solvent in the alkaline solution includes water; preferably, the solvent in the alkaline solution is water;

[0115] Furthermore, the concentration of the alkali in the alkaline solution is 5.1 to 25 mol / L; preferably, the concentration of the alkali in the alkaline solution is 5.1 to 15 mol / L;

[0116] Furthermore, the concentration of the alkali solution refers to the OH - concentration;

[0117] Furthermore, the alkali in the alkali solution reacting with the initial alloy is in excess dosage, so that the reaction can be carried out at a higher alkali concentration.

[0118] Furthermore, the temperature of the alkaline solution is the reaction temperature of the initial alloy and the alkaline solution;

[0119] The temperature and concentration of the alkaline solution are not specifically limited; their combination is sufficient as long as the reaction interface between the T-Ti(E) intermetallic compound in the initial alloy and the alkaline solution advances inward from the initial alloy surface at an average rate of greater than 7.5 μm / min. At this reaction rate, the T-Ti(E) intermetallic compound can be nano-fragmented during the reaction via hydrogen evolution and de-Ti reaction.

[0120] Furthermore, the hydrogen evolution and de-T reaction refers to a reaction in which, when the initial alloy reacts with a hot alkaline solution, T is dissolved by the hot alkali and converted into salt that enters the solution, while simultaneously releasing hydrogen.

[0121] Furthermore, by controlling the concentration and temperature of the alkaline solution, the reaction interface was advanced inward from the initial alloy surface at an average rate greater than 17.5 μm / min during the reaction.

[0122] Furthermore, by controlling the concentration and temperature of the alkaline solution, the reaction interface is advanced inward from the initial alloy surface at an average rate greater than 35 μm / min during the reaction process;

[0123] Furthermore, by controlling the concentration and temperature of the alkaline solution, the reaction interface is advanced inward from the initial alloy surface at an average rate greater than 100 μm / min during the reaction process;

[0124] Further, the temperature of the hot alkaline solution is greater than 81°C; further, further, the temperature of the hot alkaline solution is greater than 91°C;

[0125] Further, the temperature of the hot alkaline solution is greater than 100°C; further, further, the temperature of the hot alkaline solution is the boiling point temperature of the hot alkaline solution under normal pressure;

[0126] Furthermore, the reaction is carried out under normal pressure, which generally refers to 1 standard atmosphere, at which the boiling point of water is 100°C. When alkali is dissolved in water, the boiling point of the aqueous solution of the alkali at 1 standard atmosphere is higher than 100°C, and the higher the concentration of the alkali, the higher its boiling point. For example, the molar concentration of 5.1 mol / L sodium hydroxide aqueous solution has a boiling point T f溶液 About 108℃; molar concentration 7mol / L sodium hydroxide aqueous solution, boiling point T f溶液 About 112℃; molar concentration of 10mol / L sodium hydroxide aqueous solution, boiling point T f溶液 About 119℃; molar concentration of 12mol / L sodium hydroxide aqueous solution, boiling point T f溶液 About 128℃; molar concentration of 15mol / L sodium hydroxide aqueous solution, boiling point T f溶液 About 140℃; molar concentration of 17mol / L sodium hydroxide aqueous solution, boiling point T f溶液 About 148℃; molar concentration of 20mol / L sodium hydroxide aqueous solution, boiling point T f溶液 About 160℃; molar concentration 25mol / L sodium hydroxide aqueous solution, boiling point T f溶液 About 180℃; molar concentration of 10mol / L potassium hydroxide aqueous solution, boiling point T f溶液 About 125℃; molar concentration of 12mol / L potassium hydroxide aqueous solution, boiling point T f溶液 About 136℃; molar concentration of 15mol / L potassium hydroxide aqueous solution, boiling point T f溶液 About 150℃;

[0127] Since the highest temperature to which the reaction solution can be heated under normal pressure is its boiling point (T f溶液), once the temperature reaches this point, further heating will not increase the solution temperature. Therefore, controlling the boiling point of an alkaline solution is the easiest, simplest, and most precise. Furthermore, under the same conditions, reactions at the boiling point require a shorter reaction time than reactions at temperatures below the boiling point, resulting in the highest product yield and efficiency.

[0128] Since T-type elements (Al, Zn) are amphoteric metals, they can react with hydroxide in hot concentrated alkaline solutions to become T salts, which dissolve in the solution and release hydrogen violently. Therefore, T in the initial alloy T-Ti(E) intermetallic compound can be removed by reacting T with hot alkaline solution. The remaining E elements and Ti in the T-Ti(E) intermetallic compound further interact with the alkaline solution and undergo a series of changes at the same time, including the diffusion and rearrangement of Ti atoms and their reactions with E elements, hydrogen, oxygen, and OH. - , and the interaction between cations in the base, and generating titanate films in situ endogenously doped with E1 elements through shape and composition reconstruction.

[0129] Furthermore, the type of cations of the titanate in the titanate film is consistent with the type of cations of the alkaline solution during the reaction process; for example, when the alkaline solution is NaOH, the titanate is sodium titanate;

[0130] The realization of the above process requires a more intense hydrogen evolution and de-Ti reaction during the reaction process, which ultimately leads to thorough nano-fragmentation of the product. In the present application, this is achieved by advancing the reaction interface from the initial alloy surface inward at an average rate of greater than 7.5 μm / min during the reaction process. When the reaction rate is low, such as less than 2 μm / min, the hydrogen evolution and de-Ti reaction of the T-Ti(E) intermetallic compound is slow, and it is difficult for the product to undergo thorough nano-fragmentation. The product generated at this time is generally not a film, but a nanoporous product, and the shape of the nanoporous product is similar to the shape of the T-Ti(E) intermetallic compound phase before the reaction, as shown in Comparative Example 2.

[0131] In particular, the nanoporous fragmentation effect is excellent from 100°C to the boiling point of the alkaline solution, especially at the boiling point. When the reaction occurs at atmospheric pressure and at the boiling point of the alkaline solution, the solution composition of the reaction system undergoes significant and unique changes. Specifically, in the temperature range below the boiling point of the alkaline solution, the solvent is primarily liquid water. However, at or near the boiling point of the alkaline solution, in addition to liquid water and vaporous water produced by boiling, the solvent also contains critical water undergoing a transition from liquid to vaporous water. This provides a very unique reaction environment, allowing the initial alloy to undergo efficient nanofragmentation and shape and composition reconstruction through the hydrogen evolution de-tantalum reaction. This makes it difficult to maintain the three-dimensional network-like continuous nanoporous structure typically formed by low-temperature or room-temperature dealloying reactions. Instead, a product primarily composed of a titanate thin film doped with the El element is produced through a unique nanofragmentation and shape and composition reconstruction process. Furthermore, due to the constant boiling point of the specific alkaline solution, temperature control can be extremely precise, making the control of product morphology and composition extremely accurate and simple.

[0132] Furthermore, since the "nano-fragmentation - product shape and composition reconstruction" process described in step 2 occurs almost simultaneously with the "hydrogen evolution and de-Ti" reaction of the T-Ti(E) intermetallic compound; therefore, the shortest time required for the generation of the titanate thin film carrier product in situ endogenously doped with E1 element in step 2 is the time required for the initial alloy reaction interface to advance inward from the surface to complete the hydrogen evolution and de-Ti reaction, which can be judged by whether the hydrogen evolution is completed.

[0133] Furthermore, ultrasound is applied during the hydrogen evolution and de-T reaction to further enhance the nano-fragmentation effect and reaction rate through ultrasound treatment;

[0134] Furthermore, the frequency of the ultrasound is 20kHz~10 6 kHz;

[0135] The minimum reaction time t required for the hydrogen evolution and dehydrogenation reaction to complete can be calculated based on the average propagation rate of the reaction interface and the size of the initial alloy. For example, if the initial alloy is in the form of a strip with a thickness of d and the average propagation rate of the reaction interface is v, then t = 0.5d / v, considering that the reaction interface propagates from both the upper and lower surfaces of the strip. Similarly, if the initial alloy is in the form of particles with a diameter of d and the average propagation rate of the reaction interface is v, then t = 0.5d / v.

[0136] In one embodiment, an initial alloy strip primarily composed of Pt-Ag-Ti-Al reacts with a 10 mol / L boiling-point NaOH solution (about 119° C.) at an average rate of advancement of the initial alloy strip reaction interface of about 120 μm / min. This means that a 40 μm thick initial alloy strip can complete the hydrogen evolution and de-Al reaction in 10 seconds. Even a 5 mm diameter initial alloy sphere can complete the hydrogen evolution and de-Al reaction in 21 minutes.

[0137] Obviously, when the temperature of the alkaline solution is higher, the thickness of the initial alloy is thinner or the particle size is smaller, the required reaction time is shorter; conversely, the reaction time is longer;

[0138] Furthermore, the nano-fragmentation refers to the fragmentation of the T-Ti(E) intermetallic compound at the reaction interface into nano-scale intermediate products or products through hydrogen evolution and de-T reaction, and at the same time, the shape and composition are reconstructed to form a two-dimensional nano-titanate film in situ endogenously doped with E1 elements;

[0139] Furthermore, the nano-fragmentation refers to the fragmentation of the T-Ti(E) intermetallic compound phase in the initial alloy into a single intermediate product or product with a size of less than 500 nm in at least one dimension in the three-dimensional direction through hydrogen evolution and T removal reaction;

[0140] Furthermore, the nano-fragmentation refers to the fragmentation of the T-Ti(E) intermetallic compound phase in the initial alloy into a single intermediate product or product with a size of less than 100 nm in at least one dimension in the three-dimensional direction through hydrogen evolution and T removal reaction;

[0141] Furthermore, the shape and composition reconstruction refers to the further changes in shape and composition of the products after hydrogen evolution and de-T reaction of the T-Ti(E) intermetallic compound phase in the initial alloy and nano-fragmentation, thereby generating nano-scale products with completely different composition and shape from the initial micron-scale or millimeter-scale alloy.

[0142] Furthermore, the generated two-dimensional nano-titanate film endogenously doped with E1 elements in situ does not contain a three-dimensional continuous network nano-porous structure or a porous skeleton structure;

[0143] Furthermore, while the initial alloy reacts with the alkaline solution, the TE phase at the reaction interface undergoes a traditional de-T reaction to generate an in-situ exogenously doped E2 component. Since the TE phase mainly contains T-type elements and E elements, after the T reaction is removed, only the E element remains. It does not have the complex evolution of the Ti element during the de-T process of the T-Ti(E) intermetallic compound phase, so the TE phase mainly undergoes a traditional de-T reaction.

[0144] Under the traditional de-T reaction, when the atomic percentage content of the E element in the TE phase is high, such as higher than 20%, and the E element is mainly an inert precious metal element (such as Au, Pt, Pd, Ru, Rh, Re, Os, Ir, Ag), it mainly generates precious metal E2 nanoporous particles, and the shape of the E2 nanoporous particles is similar to the shape of the TE phase in the original initial alloy; when the E element is mainly at least one of Cu, Fe, Ni, and Co, the composition of the generated E2 nanoporous particles is mainly at least one of the metals and metal oxides of these elements;

[0145] Under the traditional de-T reaction, when the content of the E element in the TE phase is low, such as 5%-20% by atomic percentage, and the E element is mainly an inert precious metal element (such as Au, Pt, Pd, Ru, Rh, Re, Os, Ir, Ag), it mainly generates precious metal E2 nanoparticles, and the E2 nanoparticles are smaller than the size of the TE phase; when the E element is mainly at least one of Cu, Fe, Ni, and Co, the composition of the generated E2 nanoparticles is mainly at least one of the metals and metal oxides of these elements;

[0146] It can be understood that when the content of E element in TE phase is low, its dealloyed product is difficult to maintain the shape and size of TE phase and generate a stable nanoporous structure, and its dealloyed product easily generates fragmented E2 nanoparticles.

[0147] Since the E2 nanoparticles are not embedded in the titanyl main component, they have a certain short-range mobility in the powder material after formation. Therefore, after in-situ generation, they may aggregate and grow into larger E2 nanoparticles. This aggregation phenomenon is more obvious when the reaction temperature is maintained for a long time or after annealing treatment.

[0148] Both the E1 element and the E2 component are primarily composed of the E element. When the E element comprises only one element, the E1 element or E2 component can only be that element. However, when the E1 element or E2 component comprises two or more elements, the composition of E1 is not necessarily identical to the composition of E2. For example, when the E1 element or E2 component comprises two single elements, the ratio of the two single elements in the E1 element is 1:4, while the ratio of the same two single elements in the E2 component may be 2:1.

[0149] Furthermore, when the E2 element includes at least one of Cu, Ag, Fe, Ni, and Co, the components of the E2 nanoparticles include at least one of E2 nanometal particles and E2 nanometal oxide particles;

[0150] Furthermore, the components of the E2 nanoporous metal oxide and the E2 nanometal oxide respectively include at least one of CuO, Cu2O, Ag2O, FeO, Fe2O3, Fe3O4, NiO, CoO, Co2O3, and Co3O4.

[0151] Furthermore, when the E2 includes two or more elements, the E2 component may be mainly one component particle, or may include multiple sub-component particles; for example, when the E2 element includes Ag and Au, the E2 component is mainly AgCu nanoporous particles; when the E2 element includes Ag and Pt, the E2 component includes two sub-component particles, namely Ag nanoporous particles and Pt nanoporous particles;

[0152] In the step three, the solid reaction product of the step two is collected to obtain an in-situ endogenously doped titanium-based composite powder material, the characteristics of which are described in the first aspect.

[0153] Furthermore, the obtained in-situ endogenously doped titanyl composite powder material is mainly composed of a titanate main component in-situ endogenously doped with E1 element and an in-situ exogenously doped E2 component; the in-situ endogenously doped titanate main component is mainly composed of a titanate carrier and an endogenously doped E1 element; the titanate carrier is mainly composed of titanate, and the shape of the titanate carrier is mainly a nanofilm with a thickness of 0.25nm to 25nm; the total molar number of the E1 element C e1 The ratio C to the total molar number C0 of Ti in the titanate support e1 / C0 satisfies: 0 <C e1 / C0<0.20;

[0154] Furthermore, when the E1 element is mainly composed of Ag, the E1 element is in situ embedded in the titanate carrier, and the E1 element mainly dopes the titanate carrier with E1 atoms or atomic clusters, and the size of the E1 atoms or atomic clusters is 0.2 nm to 2 nm;

[0155] Furthermore, when the atomic percentage of Ag in the E1 element is lower than 50%, the E1 element is in-situ embedded in the titanate carrier, and the E1 element mainly dopes the titanate carrier in the form of E1 nanoparticles, and the size of the E1 nanoparticles is 2 nm to 25 nm.

[0156] Furthermore, when the E1 element is mainly composed of Cu, the E1 element is in situ embedded in the titanium-based support, and the E1 element mainly dopes the titanium-based support in the form of E1 metal nanoparticles or (and) E1 metal oxide nanoparticles, and the size of the E1 metal nanoparticles or (and) E1 metal oxide nanoparticles is 2 nm to 20 nm;

[0157] Further, the composition of the E1 metal oxide nanoparticles includes at least one of Cu2O and CuO;

[0158] Furthermore, when the E1 element is mainly composed of Au, the E1 element is in situ embedded in the titanium-based carrier, and the E1 element mainly dopes the titanium-based carrier with E1 metal nanoparticles, and the size of the E1 metal nanoparticles is 2 nm to 20 nm;

[0159] Furthermore, in the in-situ exogenously doped E2 component, the average particle size of the E2 nanoporous particles is 5nm-50μm, and the average diameter of the nanoporous bands is 2nm~200nm; in the in-situ exogenously doped E2 component, the average particle size of the E2 nanoparticles is 2nm~500nm.

[0160] Furthermore, the thickness of the main component of the titanate nanofilm in situ endogenously doped with E1 element is 0.25nm to 10nm;

[0161] Furthermore, the thickness of the main component of the titanate nanofilm in situ endogenously doped with E1 element is 0.25nm to 5nm;

[0162] Step 4: The in-situ endogenously doped titanium-based composite powder material prepared in step 3 is subjected to the following modification treatments 1) to 5) to obtain more in-situ endogenously doped titanium-based composite powder materials with different characteristics:

[0163] Modification treatment 1): When the titanyl support is mainly composed of titanate, the cations thereof are replaced with H ions by reacting the titanate with a dilute acid, thereby converting the titanate into titanic acid, thereby obtaining a titanyl support mainly composed of titanic acid;

[0164] Furthermore, in the dilute acid solution, the hydrogen ion concentration is lower than 0.1 mol / L;

[0165] The in-situ endogenously doped titanyl composite powder material obtained at this time has the same characteristics as before the acid reaction, except that the titanate film carrier is changed into a titanate acid film carrier;

[0166] Modification treatment 2): When the titanyl support is mainly composed of at least one of titanate and titanic acid, and the in-situ endogenous E1 element mainly dopes the titanate or (and) titanic acid thin film support in the form of atoms or atomic clusters, the E1 element is further transformed into E1 nanoparticles through diffusion, agglomeration, nucleation and growth through medium and low temperature heat treatment to dope the titanate or (and) titanic acid thin film support; at the same time, the thickness of the titanate or (and) titanic acid thin film support is slightly thickened and the area is slightly reduced during the heat treatment;

[0167] Modification treatment 3): Through medium-to-high temperature heat treatment, the titanate thin film carrier can be shrunk in area and thickened to become a TiO2 nanosheet carrier. At the same time, the in-situ endogenous E1 atoms or atomic clusters grow through diffusion, agglomeration, nucleation, and further transform into E1 nanoparticles to dope the TiO2 sheet carrier.

[0168] When the E1 nanoparticles grow to a certain size, there is no more E1 element to replenish them, and the E1 nanoparticles are dispersed by the TiO2 flake carrier, so the E1 nanoparticles no longer grow.

[0169] Furthermore, when the main component of the titanium-based carrier is at least one of a titanate film and a titanate film, its crystal form is low crystalline. After a certain degree of heat treatment, its crystallinity is further improved, and even a crystal form transformation occurs, such as from titanate to anatase TiO2, and then further to rutile TiO2;

[0170] Furthermore, due to the solid solution and pinning effect of E1 atoms or atomic clusters on the titanium-based support, when the titanium-based support is doped with the E1 element mainly in the form of atoms or atomic clusters, the phase change thermal stability of the titanium-based support is significantly improved;

[0171] Furthermore, when the E1 element is doped into the titanyl support mainly in the form of atoms or atomic clusters, the phase transition temperature of the doped titanyl support is increased by more than 100° C. compared to the undoped titanyl support;

[0172] Furthermore, the phase change of the titanium-based support is a phase change of titanic acid into TiO2;

[0173] During the three modification treatments mentioned above, the in-situ exogenously doped E2 component also undergoes corresponding changes based on its own material physical and chemical properties; for example, during the heat treatment process, the specific surface area becomes smaller.

[0174] Modification treatment 4): When the above step 2 is not carried out under normal pressure, but is treated at high temperature and high pressure in a closed container, the shape of the titanyl support in the in-situ endogenously doped titanyl composite powder material product is mainly nanotubes / rods; this is achieved by changing the pressure and temperature of the reaction to modify the morphology of the titanyl support in the product;

[0175] Furthermore, in a closed container, when the type and concentration of the alkaline solution are determined, a certain temperature value must correspond to a certain pressure value, that is, the pressure value is a function of the temperature value; the higher the temperature, the higher the pressure.

[0176] If the high temperature is T2, the boiling point of the alkaline solution at normal pressure is T f溶液 ,but:

[0177] Furthermore, T f溶液 <T2 < 300 °C; Furthermore, T f溶液 <T2 < 250 °C; Furthermore, T f溶液 <T2 < 200 °C;

[0178] Furthermore, T f溶液 <120 °C < T2 < 200 °C; Furthermore, T f溶液 <140 °C < T2 < 200 °C;

[0179] Modification treatment 5): When the shape of the titanate-based carrier is mainly a nanofilm, after the in-situ endogenously doped titanate-based composite powder material is refined, the average area of the titanate-based nanofilm in-situ endogenously doped with element E1 will be greatly reduced;

[0180] Furthermore, the refining treatment method includes at least one of ultrasonic crushing, ball milling, and sand milling;

[0181] After refining treatment:

[0182] Furthermore, the average area of the titanate-based nanofilm in-situ endogenously doped with element E1 is 10 nm 2 -1000 nm 2 ;

[0183] Furthermore, the average area of the titanate-based nanofilm in-situ endogenously doped with element E1 is 10 nm 2 -400 nm 2 ;

[0184] Furthermore, the titanate-based nanofilm in-situ endogenously doped with element E1 has traces of crushing treatment; such as the hole characteristics of the titanate-based nanofilm caused by ultrasonic crushing, ball milling, or sand milling; even when the shape of the fragmented titanate-based nanofilm is roughly intact, the film contains one or more holes that penetrate up and down;

[0185] Due to the large area and ultra-thin thickness of the titanate-based carrier nanofilm, its average area can be easily reduced by methods such as ultrasonic crushing, ball milling, and sand milling. After its average area is reduced, it will have extremely excellent dispersibility.

[0186] In addition, for the refined titanate-based carrier nanofilm with a low average area, further medium and high temperature heat treatment can greatly reduce the particle size of the obtained TiO2 carrier nanosheets or TiO2 carrier nanoparticles, and even the average particle size can be as low as below 10 nm; Therefore, medium and high temperature heat treatment after refining treatment can prepare ultra-fine in-situ endogenously doped TiO2-based composite powder materials.

[0187] When the titanate carrier nanofilm is refined and then heat-treated, when the film area is refined to a small enough size, the obtained TiO2 carrier may have a nearly spherical feature. At this time, the shape of the TiO2 carrier is nano-granular.

[0188] When the shape of the titanyl support is mainly nanotubes / rods, the thinning treatment can also break or shorten the length of the nanotubes / rods;

[0189] Furthermore, during the refinement process, the in-situ exogenously doped E2 component is also refined, and its average particle size is also reduced;

[0190] Furthermore, after the refinement treatment, the average particle size of the E2 nanoporous particles in the in-situ exogenously doped E2 component is 5 nm-1 μm; the average particle size of the E2 nanoparticles in the in-situ exogenously doped E2 component is 2 nm to 400 nm.

[0191] In its third aspect, the present invention also relates to the use of the in situ endogenously doped titanium-based composite powder material described in any one of its first to second aspects or the in situ endogenously doped titanium-based composite powder material obtained by the preparation method in composite materials, ceramic materials, photocatalytic materials, hydrophobic materials, sewage degradation materials, sterilization materials, electronic materials, and coatings.

[0192] Furthermore, the coating includes antibacterial coating, anticorrosive coating, marine coating, and marine engineering coating;

[0193] Furthermore, the composite material includes polymer-based nanocomposite materials and resin-based composite materials;

[0194] The specific application method includes: mixing the titanium-based composite powder material in situ endogenously doped with E1 element with a polymer to prepare a composite coating of the titanium-based composite powder material in situ endogenously doped with E1 element and the polymer;

[0195] Furthermore, the polymer includes at least one of a polymer material, a resin material, and a coating;

[0196] Further, the E1 element includes at least one of Au, Pt, Pd, Ru, Rh, Re, Os, Ir, Ag, Cu, Fe, Ni, and Co; further, the E1 element includes at least one of Cu, Ag, and Fe;

[0197] Furthermore, the in-situ Ag-doped titanium oxide composite powder was mixed with PDMS (also known as polydimethylsiloxane) to create a composite coating of the Ag-doped titanium oxide carrier and PDMS. This coating, in which Ag atoms or atomic clusters are embedded and dispersed within the nano-titanium oxide carrier, maximizes the bactericidal properties of the Ag and nano-titanate film while enhancing the hydrophobicity of the PDMS coating.

[0198] In its fourth aspect, the present invention also relates to the use of the in-situ endogenously doped titanium-based composite powder material described in any one of the first to second aspects or the in-situ endogenously doped titanium-based composite powder material obtained by the preparation method in home decoration coatings, bactericidal sprays, and antifouling coatings.

[0199] As an application of home decoration coating, it is characterized in that the above-mentioned titanium-based composite powder material endogenously doped with E1 element is applied as a coating additive to the surface of furniture, utensils, and walls, and then mixed with other components of the coating to achieve an antibacterial effect;

[0200] The application of the antibacterial spray is characterized in that the titanium-based composite powder material in situ endogenously doped with E1 elements is mixed with other liquid spray components and sprayed onto the surfaces of furniture, utensils, fabrics, and walls through a spray carrier to achieve an antibacterial effect;

[0201] The application of the antifouling coating is characterized in that the above-mentioned titanium-based composite powder material endogenously doped with E1 element in situ replaces the bactericidal and antifouling component (such as cuprous oxide powder) in traditional antifouling coatings (such as antifouling paint) to achieve an antifouling effect;

[0202] Further, the E1 element includes at least one of Au, Pt, Pd, Ru, Rh, Re, Os, Ir, Ag, Cu, Fe, Ni, and Co; further, the E1 element includes at least one of Cu, Ag, and Fe;

[0203] In its fifth aspect, the present invention further relates to the use of the in-situ endogenously doped titanium-based composite powder material described in any one of the first to second aspects or the in-situ endogenously doped titanium-based composite powder material prepared by the preparation method in antibacterial fabrics;

[0204] Furthermore, it is characterized in that the titanium-based composite powder material in situ endogenously doped with E1 element is dispersed and then attached to or coated on the surface of the fabric, or mixed with the fabric, so that the fabric has antibacterial and bactericidal effects and capabilities;

[0205] Further, the E1 element includes at least one of Au, Pt, Pd, Ru, Rh, Re, Os, Ir, Ag, Cu, Fe, Ni, and Co; further, the E1 element includes at least one of Cu, Ag, and Fe;

[0206] The beneficial effects of the present invention are mainly reflected in the following aspects:

[0207] First, through creative alloy design and reaction design, a cheap and easily available composite initial alloy consisting of T-Ti(E) intermetallic compound with E element solid solution and TE phase was used as the titanium source. Through its violent hydrogen evolution and T-desorption reaction with hot alkaline solution at a certain temperature, combined with different modification treatments, the preparation of a variety of in-situ endogenously doped titanium-based composite powder materials was achieved.

[0208] Thanks to the ingenious alloy design, the resulting material achieves a two-stage complexation of the E element with the titanyl support: first, a first-stage complexation of the in-situ endogenously doped E1 element with the titanyl support, forming a titanyl main component endogenously doped with the E1 element; then, a second-stage complexation of the in-situ exogenously doped E2 component with the in-situ endogenously doped E1 titanyl main component. Furthermore, through a vigorous hydrogen evolution-T-removal reaction, the large-scale T-Ti(E) intermetallic compound phase in the initial alloy is directly transformed into an ultrathin titanate nanofilm (less than 5 nm thick) through a shape and composition reconstruction reaction, with its composition and shape undergoing a profound change and refinement. This reaction and formation mechanism provides a novel approach for the simple preparation of nanoscale titanate or oxide powder materials. In contrast, in Comparative Example 2, when an Al-Ti-Au-Cu alloy sheet containing an Al3Ti(AuCu) intermetallic compound phase reacted with a 10 mol / L NaOH solution at 35°C for 2 hours, the original initial alloy sheet before and after the reaction was fragmented, but still in a state of relatively large fragments, and its microstructure did not generate a large number of monolithic two-dimensional thin film products, but rather a large fragment product composed of a nanoporous network structure. In particular, through the modification treatments 1) to 5), the state of the E1 element and the E2 element doped in the in-situ endogenously doped titanium-based composite powder material, the composition, morphology, and crystal form of the titanium-based carrier were further regulated, and a variety of different in-situ endogenously doped titanium-based composite powder materials were obtained.

[0209] Secondly, the researchers creatively invented an in-situ endogenously doped titanyl composite powder material with two-stage composite characteristics. Doping elements or doping nanoparticles have a significant positive impact on the functional applications of nano-titanates, nano-titanic acids, and nano-TiO2. Currently, conventional preparation methods struggle to achieve in-situ doping of nano-titanates and nano-titanic acids with doping elements via atoms or atomic clusters; they generally only achieve simple doping via externally added nanoparticles. These conventional preparation methods primarily employ a strategy: after preparing a carrier, doping nanoparticles prepared by another method are mixed with the carrier to produce a nano-titanate, nano-titanic acid, or nano-TiO2 composite material mixed with doped nanoparticles. The nanoparticles are primarily attached to the carrier via physical adsorption. This mechanical mixing and attachment method not only hinders the physical-chemical interaction between the doping element and the carrier at the atomic scale, but also easily causes the doping nanoparticles to fall off the carrier, resulting in instability and deterioration in the performance of the composite powder material. In the present application, not only can the effect of traditional doping be achieved by doping with in-situ exogenously doped E2 components, but the doping of titanium-based carrier films, tubes / rods with in-situ endogenously doped E1 elements is also creatively achieved. Moreover, for certain doping elements, such as Ag, it can not only be used to dope the titanium-based carrier in the form of atoms or atomic clusters, but also can be used to dope the titanium-based carrier films, tubes / rods in the form of in-situ endogenous Ag nanoparticles through heat treatment. It not only solves the problem of shedding of doped E1 elements, but also greatly enhances the physical-chemical interaction between the doped E1 elements and the carrier, greatly improving the phase change thermal stability of the titanium-based carrier. Moreover, the titanium-based carrier acts as a carrier, matrix, and dispersion, and the doped E1 element acts as a key functional element. When it is "solid-dissolved" in the titanium-based film carrier in the form of E1 atoms or atomic clusters, almost all of the doped E1 atoms can fully exert their functional applications, thereby greatly reducing the amount of doped E1 elements used. For example, Ag nanoparticles in the industry are generally used as sterilizing materials, and nano-titanates, nano-titanic acid, and nano-TiO2 mechanically mixed therewith can generally be used as their carriers. Since the Ag that has a sterilizing effect is mainly the Ag atoms on the surface of the Ag nanoparticles, this causes a certain waste of the Ag atoms inside the Ag nanoparticles in terms of performance, which increases the cost. Moreover, the physically adsorbed Ag nanoparticles are also easy to fall off from the carrier, resulting in unstable performance and poor performance durability. The present invention creatively realizes that Ag is distributed in the nano-titanium-based carrier in the form of atoms or atomic clusters, which not only does not require worrying about the problem of Ag falling off, but also maximizes the utilization of Ag and greatly improves the phase transition thermal stability of the nano-titanium-based carrier simultaneously, which is of great benefit.

[0210] Third, it provides the possibility for the preparation of in-situ endogenously doped ultrafine titanium-based composite powder materials. This is because the shape of the initially prepared titanium-based carrier is mainly a two-dimensional film with a thickness of less than 5nm and an area of ​​even more than 10,000nm. 2 Therefore, it can be easily crushed into an ultrafine titanium-based composite powder material with an in-situ endogenous doping and a sharply reduced average area through refining treatments such as ultrasonic crushing, ball milling, and sand milling. When its average area is reduced, it will have extremely excellent dispersibility, which is beneficial to its application. In addition, if the refined titanium-based carrier nanofilm with a low average area is further subjected to medium- and high-temperature heat treatment, the particle size of the TiO2 nanosheets or TiO2 nanoparticles that can be obtained will be greatly reduced, and the average particle size may even be as low as below 10nm; therefore, the medium- and high-temperature heat treatment after the refinement treatment can also prepare ultrafine in-situ endogenous doped TiO2-based composite powder materials. Even for the case where the titanium-based carrier is in the shape of nanotubes / rods, the refinement treatment can also break and shorten the length of the titanium-based nanotubes / rods, making them more dispersible and having better performance;

[0211] Fourth, large-scale industrial production of many of the products involved is possible. The reaction temperature in this series of inventions is relatively mild, at or near the boiling point of the solution. The required initial alloys can be produced on a large scale through methods such as "alloy smelting + casting + crushing" or "alloy smelting + melt stripping." Most importantly, the critical reaction time can be shortened to just a few seconds, making it extremely efficient and enabling low-cost, short-term, and efficient large-scale production of the corresponding products.

[0212] Therefore, the preparation method of the present invention has the characteristics of simple process, easy operation, high efficiency and low cost. It can prepare a variety of in-situ endogenously doped titanium-based composite powder materials with main components including nanofilms, nanosheets, nanotubes / rods and other morphologies, and has good application prospects in the fields of polymer-based nanocomposites, resin-based composite materials, ceramic materials, photocatalytic materials, hydrophobic materials, sewage degradation materials, bactericidal coatings, anti-corrosion coatings, marine engineering coatings, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0213] FIG1 is a SEM backscattered image of the solidified structure of the initial alloy described in Example 1;

[0214] FIG2 is a TEM photograph of the main components of the sodium titanate composite powder material in situ endogenously doped with Ag (Pt) elements described in Example 1;

[0215] FIG3 is a low-magnification SEM photograph of the solidified structure of the initial alloy described in Example 2;

[0216] FIG4 is a high-magnification SEM photograph of the solidified structure of the initial alloy described in Example 2;

[0217] FIG5 is a TEM image of the potassium titanate composite powder material in situ endogenously doped with Ag (Pt) element as described in Example 2;

[0218] FIG6 is a TEM image of the potassium titanate composite powder material in situ endogenously doped with Ag (Pt) elements as described in Example 2;

[0219] FIG7 is a TEM photograph of the titanate composite powder material containing in-situ embedded Ag (Pt) nanoparticles described in Example 2;

[0220] FIG8 is a TEM photograph of the TiO2 composite powder material containing in-situ embedded Ag (Pt) nanoparticles described in Example 2;

[0221] FIG9 is a SEM photograph of the solidified structure of the initial alloy described in Example 5;

[0222] FIG10 is a TEM image of the sodium titanate composite powder material in situ doped with AuCu nanoparticles as described in Example 5;

[0223] FIG11 is a TEM image of the product of the nano titanate film without doping elements described in Comparative Example 1 after heat treatment at 475° C. for 2 h;

[0224] FIG11 is a TEM diffraction photograph of the product of the nano titanate film without doping elements described in Comparative Example 1 after heat treatment at 475° C. for 2 h;

[0225] FIG13 is a SEM photograph of the reaction product of Comparative Example 2. DETAILED DESCRIPTION

[0226] The technical solution will be further described below through the following specific embodiments:

[0227] Example 1:

[0228] According to the ratio of Ag, Pt, and Ti atomic percentages of approximately 1.5%, 0.25%, and 24.5% respectively (the balance is mainly Al), an Al-Ti-Ag-Pt alloy melt is smelted; the alloy melt is solidified at a cooling rate of about 100K / s into an Al-Ti-Ag-Pt alloy plate with a thickness of 5mm. The solidified structure is mainly composed of an average composition of about Al 74 Ti 24.5 Ag 1.4 Pt 0.1 The Al3Ti(AgPt) intermetallic compound phase has an average composition of about Al 75 Pt 25 Al-Pt intermetallic compound phase, with an average composition of approximately Al 85 Ag 15The SEM backscattered image is shown in Figure 1, where the black phase is the Al3Ti(AgPt) intermetallic compound.

[0229] Under normal pressure, 0.25g of the Al-Ti-Ag-Pt alloy plate prepared above was crushed into a powder with an average particle size of 100μm, and then added to 50ml of a 10mol / L NaOH aqueous solution at its boiling point (about 119°C) with continuous stirring. During the reaction with the concentrated alkali solution, the Al3Ti(AgPt) in the initial Al-Ti-Ag-Pt alloy powder was nano-fragmented by a violent hydrogen evolution and de-Al reaction, and at the same time, the shape and composition were reconstructed to form a solid flocculent product. At the same time, the Al-Pt intermetallic compound phase and the Al(Ag) phase underwent a traditional dealloying reaction to obtain in-situ exogenously doped coarse nanoporous Ag and nanoporous Pt particles, whose porous band size ranged from 2nm to 50nm.

[0230] The hydrogen evolution de-Al reaction was completed within 2 minutes, and the temperature was kept at this temperature for another 2 minutes to ensure that the traditional dealloying reaction was also completely completed. Then, water was added to reduce the alkali concentration in the solution to 1 mol / L and the temperature to below 45°C.

[0231] All solid products are separated from the alkaline solution, washed, and dried to obtain a sodium titanate composite powder material in situ endogenously doped with Ag (Pt) elements. The main component is a two-dimensional sodium titanate nanofilm in situ endogenously doped with Ag (Pt) elements. The thickness of a single film is 0.25nm to 3nm, and the average area of ​​the film is greater than 1000nm. 2 , exhibiting distinct characteristics of a two-dimensional material. Ag (Pt) elements are in situ endogenously doped into the two-dimensional sodium titanate nanofilm primarily in the form of atoms or atomic clusters. The molar ratio of Ag to Pt in the Ag (Pt) is approximately 14:1. The TEM morphology of the main components of the resulting product is shown in Figure 2. Although the Ag (Pt)-doped sodium titanate nanofilms aggregate together, their shape is completely different from the Al3Ti (AgPt) intermetallic compound phase in the initial alloy, having undergone a complete nano-fragmentation with a reconstruction of both shape and composition. Furthermore, because the doped atoms or atomic clusters are too small, no contrast change in the Ag (Pt)-doped sodium titanate nanofilms can be observed. Since the size of the nanoporous Ag particles and the nanoporous Pt particles in the sodium titanate composite powder material in situ endogenously doped with Ag (Pt) elements is comparable to the size of the Al-Pt intermetallic compound phase and the Al (Ag) phase in the initial alloy powder, and their average particle size is 0.5 μm-15 μm, the nanoporous Ag and nanoporous Pt particles are not displayed simultaneously in the TEM morphology photograph.

[0232] The sodium titanate composite powder material in situ doped with Ag (Pt) element is heat treated at 550°C for 2 hours to obtain a sodium titanate composite powder material containing in situ embedded Ag (Pt) nanoparticles. The main component of the sodium titanate composite powder material is a sodium titanate film in situ embedded with Ag (Pt) nanoparticles. The thickness of the single film ranges from about 0.5nm to 4nm, and the average area of ​​the film is greater than 750nm. 2 The size of the Ag (Pt) nanoparticles ranges from 2 nm to 7 nm. Due to the pinning effect of Ag (Pt) atoms or atomic clusters, the thermal stability of the nano-sodium titanate film substrate is significantly improved, as shown in Comparative Example 1. The composition and morphology of the in-situ exogenously doped nanoporous Ag and Pt particles undergo corresponding changes before and after heat treatment, such as the coarsening of the porous ligaments.

[0233] The sodium titanate composite powder material in situ endogenously doped with Ag (Pt) elements is dispersed in water, and then 0.025 mol / L HCl solution is gradually added thereto to continuously decrease the pH value of the mixed solution, and finally the pH value of the mixed solution is controlled between 2 and 5. After 5 minutes, solid-liquid separation is performed, and the mixture is washed and dried to obtain a titanate composite powder material in situ endogenously doped with Ag (Pt) elements. Except that the sodium titanate carrier in the main component is replaced by titanic acid, the other characteristics of the composite powder material remain essentially unchanged, as described above in this embodiment. The composition and morphology of the in situ exogenously doped nanoporous Ag and nanoporous Pt particles remain essentially unchanged before and after acid treatment.

[0234] The prepared in-situ Ag (Pt) element-doped titanate composite powder material was heat-treated at 550°C for 2 hours to obtain a titanate composite powder material containing in-situ embedded Ag (Pt) nanoparticles. The main component of the material is a titanate film with in-situ embedded Ag (Pt) nanoparticles. The thickness of a single film ranges from about 0.5nm to 4nm, and the average area of ​​the film is greater than 750nm. 2 The size of the Ag (Pt) nanoparticles ranges from 2 nm to 7 nm. Due to the pinning effect of Ag (Pt) atoms or atomic clusters, the thermal stability of the nano-sodium titanate film substrate is significantly improved, as shown in Comparative Example 1. The composition and morphology of the in-situ exogenously doped nanoporous Ag and Pt particles undergo corresponding changes before and after heat treatment, such as the coarsening of the porous ligaments.

[0235] The prepared in-situ endogenously doped Ag (Pt) element titanate composite powder material is heat treated at 650°C for 3 hours to obtain a TiO2 composite powder material containing in-situ embedded Ag (Pt) nanoparticles, the main component of which is TiO2 nanosheets with in-situ embedded Ag (Pt) nanoparticles. During the heat treatment at this temperature, not only the Ag (Pt) elements distributed in the form of atoms or atomic clusters diffuse, agglomerate, and grow to generate in-situ embedded Ag (Pt) nanoparticles, but also the titanate film carrier undergoes a transformation to anatase TiO2, and the morphology also undergoes a transformation from a film to a sheet; the thickness of the anatase nano-TiO2 sheet carrier ranges from 1nm to 15nm, and the average area is greater than 500nm. 2 The size of the Ag (Pt) nanoparticles in situ embedded in the anatase nano-TiO2 sheets ranges from 2 nm to 7 nm. The composition and morphology of the in situ exogenously doped nanoporous Ag and Pt particles undergo corresponding changes before and after heat treatment, such as the coarsening of the porous ligaments.

[0236] The above-mentioned sodium titanate or titanate composite powder material in situ doped with Ag (Pt) element is sand-milled to reduce the average area of ​​the two-dimensional nano-sodium titanate or titanate film in situ doped with Ag (Pt) element in the main component to 200nm. 2 The following is a graph of the structure of the nanoporous Ag particles and the nanoporous Pt particles. The average particle size of the nanoporous Ag particles and the nanoporous Pt particles, which are in-situ exogenously doped components, is reduced to 0.1 μm-1 μm after sand milling. Except for the changes in the morphology and particle size of the main component and the exogenously doped component, other characteristics remain roughly unchanged.

[0237] The sand-milled in-situ Ag (Pt)-doped titanate composite powder material was heat-treated at 700°C for 2 hours to obtain a composite powder consisting mainly of anatase TiO2 sheets in-situ doped with Ag (Pt) nanoparticles and in-situ exogenously doped nanoporous Ag and nanoporous Pt particles. The thickness of the TiO2 sheet as the main component carrier is 3nm-10nm, and the average area is 10nm. 2 -200nm 2 The average particle size of the in-situ endogenously doped Ag (Pt) nanoparticles is 2 nm to 7 nm; the average particle size of the nanoporous Ag particles and nanoporous Pt particles as the in-situ exogenously doped components is 0.1 μm to 1 μm.

[0238] Example 2:

[0239] According to the ratio of Ag, Pt and Ti atomic percentages of about 0.55%, 0.20% and 24.5% respectively (the balance is mainly Al), Al-Ti-Ag-Pt alloy melt is smelted; the alloy melt is heated to about 10 6 K / s~107 K / s cooling rate solidified into an Al-Ti-Ag-Pt alloy strip with a thickness of 25 μm. Its solidification structure is mainly composed of an average composition of about Al 74 Ti 24.5 Ag 0.5 Pt 0.05 The SEM secondary electron images of the composite are shown in Figures 3-4, where the matrix phase is the Al3Ti(AgPt) intermetallic compound phase. Combined with the SEM results of Example 1, the bright white nanoscale (50nm-250nm) particles in the images are the Ag-rich Al(Ag) phase and the Pt-rich Al-Pt intermetallic compound phase. Due to the small size of the particles, the SEM energy spectrum cannot accurately determine their specific composition.

[0240] Under normal pressure, the Al-Ti-Ag-Pt alloy strip prepared above is added to 50 ml of a KOH aqueous solution with a concentration of 10 mol / L and a temperature of its boiling point (about 125°C) and stirred. The Al3Ti(AgPt) phase in the initial Al-Ti-Ag-Pt alloy strip is nano-fragmented by a violent hydrogen evolution and de-Al reaction during the reaction with the concentrated alkali solution, and at the same time, the shape and composition are reconstructed to form a solid flocculent product. At the same time, the Al-Pt intermetallic compound phase and the Al(Ag) phase undergo a traditional dealloying reaction to obtain in-situ exogenously doped fine nanoporous Pt particles and nano-Ag particles. The porous band size of the nanoporous Pt particles ranges from 2 nm to 25 nm.

[0241] The hydrogen evolution and Al removal reaction was completed within 1 minute. After the temperature was kept at room temperature for 10 minutes, the alkali concentration in the solution was reduced to 1 mol / L by adding water and the temperature was reduced to below 45°C.

[0242] All solid products are separated from the alkaline solution, washed, and dried to obtain a potassium titanate composite powder material in situ endogenously doped with Ag (Pt) elements. The main component is a two-dimensional nano-potassium titanate film in situ endogenously doped with Ag (Pt) elements. The thickness of a single film is 0.25nm to 4nm, and the average area of ​​the film is greater than 1000nm. 2, exhibiting distinct characteristics of a two-dimensional material. Ag (Pt) is in situ doped into the two-dimensional potassium titanate nanofilm primarily as atoms or atomic clusters. The molar ratio of Ag to Pt in the Ag (Pt) nanofilm is approximately 10:1. The TEM morphology of the resulting product is shown in Figures 5-6. Due to the small size of the doped atoms or atomic clusters, no contrast change in the potassium titanate nanofilm due to the doping of Ag (Pt) is observed. Since the size of the nanoporous Pt particles in the potassium titanate composite powder material with in-situ endogenous doping of Ag (Pt) elements is comparable to the size of the Al-Pt intermetallic compound phase in the initial alloy powder, they are also nanoscale, such as the nanoporous Pt particles shown by the arrows in Figure 5, whose porous band diameter is 10nm-20nm; and after the Al (Ag) phase undergoes a traditional dealloying reaction to generate nanoporous Ag particles, it may further undergo the collapse and spheroidization of the nanoporous structure due to the low Ag content in the original Al (Ag) phase, and partially evolves into nano-Ag particles with a particle size of 25nm-150nm, as shown in Figure 6.

[0243] The potassium titanate composite powder material in situ doped with Ag (Pt) was dispersed in water, and 0.025 mol / L HCl solution was gradually added to the solution, causing the pH of the mixed solution to continuously decrease until the pH was controlled between 2 and 5. After 5 minutes, solid-liquid separation, washing, and drying were performed to obtain the in situ doped titanate composite powder material. Aside from the potassium titanate support being replaced with titanic acid in the main component, the other characteristics of the composite powder material remained essentially unchanged. The composition and morphology of the in situ doped nanoporous Pt and nano-Ag particles remained essentially unchanged before and after the acid treatment.

[0244] The prepared in-situ endogenously doped Ag (Pt) element titanate composite powder material was heat treated at 550°C for 2 hours to obtain a titanate composite powder material containing in-situ embedded Ag (Pt) nanoparticles, as shown in FIG7 . The main component of the material is a titanate film with in-situ embedded Ag (Pt) nanoparticles. The thickness of a single film ranges from about 0.5 nm to 5 nm, and the average area of ​​the film is greater than 750 nm. 2 Dark contrast Ag (Pt) nanoparticles range in size from 2nm to 7nm. Due to the pinning effect of Ag (Pt) atoms or atomic clusters, the thermal stability of the nano-titanate thin film carrier is significantly improved, as shown in Comparative Example 1. The composition and morphology of the in-situ exogenously doped nanoporous Pt particles undergo corresponding changes before and after heat treatment, such as the coarsening of the porous ligaments. The composition and morphology of the in-situ exogenously doped nano-Ag particles remain essentially unchanged before and after heat treatment.

[0245] The prepared in-situ endogenously doped Ag (Pt) element titanate composite powder material was heat treated at 650°C for 3 hours to obtain a TiO2 sheet composite powder material containing in-situ embedded Ag (Pt) nanoparticles, as shown in Figure 8; its main component is TiO2 nanosheets with in-situ embedded Ag (Pt) nanoparticles. During the heat treatment at this temperature, not only the Ag (Pt) elements distributed in the form of atoms or atomic clusters diffuse, agglomerate, and grow to generate in-situ embedded dark contrast Ag (Pt) nanoparticles, but also the titanate film matrix undergoes a transformation to anatase TiO2, and the morphology also undergoes a transformation from a film to a sheet; the thickness of the anatase nano-TiO2 sheet carrier ranges from 1nm to 15nm, and the average area is greater than 500nm. 2 The size of the Ag (Pt) nanoparticles in situ embedded in the anatase nano-TiO2 sheets ranged from 2 nm to 7 nm. The composition and morphology of the in situ exogenously doped nanoporous Pt particles changed accordingly before and after heat treatment, such as the coarsening of the porous bands. The composition and morphology of the in situ exogenously doped nano-Ag particles remained essentially unchanged before and after heat treatment.

[0246] The above-mentioned potassium titanate or titanate composite powder material in situ doped with Ag (Pt) element is sand-milled to reduce the average area of ​​the two-dimensional potassium titanate or titanate film in situ doped with Ag (Pt) element in the main component to 200nm. 2 the following;

[0247] After the sanding process, the ultrafine nano-titanate composite powder material in situ endogenously doped with Ag(Pt) is mixed with PDMS (polydimethylsiloxane), and then a PDMS composite coating containing a nano-titanate thin film doped with Ag(Pt) is obtained according to the coating preparation method. In this coating, the Ag(Pt) element is dispersed in the ultrafine nano-titanate thin film as atoms or atomic clusters, and the nano-titanate thin film is dispersed in the PDMS. This maximizes the bactericidal properties of the Ag(Pt) element and the mechanical strengthening and strong hydrophobic properties of the nano-titanate thin film, resulting in an Ag(Pt)-PDMS composite coating with excellent mechanical, hydrophobic, and bactericidal properties.

[0248] The Ag(Pt)-PDMS composite coating material can be applied to fields including hydrophobic materials, wood antiseptic and sterilization materials, photocatalytic materials, sterilization coating materials, marine engineering equipment and ship coatings.

[0249] The ultrafine nano titanate composite powder material in situ endogenously doped with Ag (Pt) elements,

[0250] Application as home decoration coating: The above-mentioned ultrafine nano-titanate thin film material with in-situ endogenous doping of Ag (Pt) is applied on the surface of furniture, utensils, and walls as a coating additive and mixed with other coating components to achieve an antibacterial effect; at the same time, the Pt nanoparticles in the composite powder material also have excellent catalytic properties, which is also of great significance for the catalytic oxidation and removal of formaldehyde.

[0251] Application as a bactericidal spray: the ultrafine nano-titanate thin film material in situ endogenously doped with Ag (Pt) is mixed with other liquid spray components and sprayed onto the surfaces of furniture, utensils, fabrics, and walls through a spray carrier to achieve an antibacterial effect;

[0252] Application as antifouling coating: The ultrafine nano-titanate thin film material in situ endogenously doped with Ag (Pt) is used to replace the bactericidal and antifouling components in traditional antifouling coatings to achieve an antifouling effect;

[0253] Application as antibacterial fabric: After the above-mentioned in-situ endogenously doped Ag (Pt) ultrafine nano titanate film material is dispersed, it is attached to or coated on the surface of the fabric, or mixed with the fabric, so that the fabric has antibacterial and bactericidal effects and capabilities.

[0254] Example 3:

[0255] According to the ratio of Ag, Pt and Ti atomic percentages of about 0.55%, 0.20% and 24.5% respectively (the balance is mainly Al), Al-Ti-Ag-Pt alloy melt is smelted; the alloy melt is heated to about 10 6 K / s~10 7 K / s cooling rate solidified into an Al-Ti-Ag-Pt alloy strip with a thickness of 25 μm. Its solidification structure is mainly composed of an average composition of about Al 74 Ti 24.5 Ag 0.5 Pt 0.05 The SEM secondary electron images of the Al3Ti(AgPt) intermetallic compound phase are shown in Figures 3-4, where the matrix phase is the Al3Ti(AgPt) intermetallic compound phase. Combined with the SEM results of Example 1, the nanoscale (50nm-250nm) bright white particles are composed of the Ag-rich Al(Ag) phase and the Pt-rich Al-Pt intermetallic compound phase.

[0256] 0.25 g of Al-Ti-Ag-Pt alloy ribbon and 50 mL of 10 mol / L NaOH aqueous solution were placed in a sealed reactor lined with polytetrafluoroethylene. The reactor was then immediately sealed and heated to a temperature of 250°C, which was then maintained under high pressure for 25 minutes.

[0257] After 25 minutes, the reaction is terminated, and all solid matter in the reactor is separated from the solution, cleaned, and dried to obtain a sodium titanate composite powder material endogenously doped with Ag (Pt) elements in situ. The main component of the composite powder material is a nano-sodium titanate tube / rod endogenously doped with Ag (Pt) elements in situ, and the outer diameter of the tube / rod is 3nm-10nm. The Ag (Pt) elements are endogenously doped in the nano-sodium titanate tube / rod in situ mainly in the form of atoms or atomic clusters. The molar ratio of Ag to Pt in the Ag (Pt) is about 10:1.

[0258] Since the size of the in-situ exogenously doped nanoporous Pt particles in the sodium titanate composite powder material with in-situ endogenous doping of Ag (Pt) elements is comparable to that of the Al-Pt intermetallic compound phase in the initial alloy powder, they are also nanoscale, with a porous band diameter of 10nm-20nm; and after the Al (Ag) phase undergoes a traditional dealloying reaction to generate nanoporous Ag particles, the nanoporous structure further collapses and spheroidizes, and some evolve into nano-Ag particles with a particle size of 25nm-150nm.

[0259] Example 4:

[0260] According to the ratio of Cu, Fe and Ti atomic percentages of about 1.1%, 0.25% and 24.5% respectively (the balance is mainly Al), Al-Ti-Cu-Fe alloy melt is smelted; the alloy melt is heated to about 10 6 K / s~10 7 K / s cooling rate solidified into an Al-Ti-Cu-Fe alloy strip with a thickness of 25 μm. Its solidification structure is mainly composed of an average composition of about Al 74.4 Ti 24.5 Cu1Fe 0.1 The material is composed of an Al3Ti(CuFe) intermetallic phase, a Cu-rich Al(Cu) phase, and an Fe-rich Al-Fe intermetallic phase. The matrix phase is the Al3Ti(CuFe) intermetallic phase with a Cu:Fe ratio of 10:1. Due to the rapid cooling rate of the melt, the Cu-rich Al(Cu) phase and the Fe-rich Al-Fe intermetallic phase are both nanoscale (50nm-500nm).

[0261] Under normal pressure, the Al-Ti-Cu-Fe alloy strips prepared above were added to 50 ml of a 10 mol / L NaOH aqueous solution at its boiling point (about 119°C) and stirred. The Al3Ti(CuFe) intermetallic compound phase in the Al-Ti-Cu-Fe alloy strips was nano-fragmented by a violent hydrogen evolution and de-Al reaction during the reaction with the concentrated alkali solution, and simultaneously the shape and composition were reconstructed to form a solid flocculent product. At the same time, the Cu-rich Al(Cu) phase and the Fe-rich Al-Fe intermetallic compound phase underwent a traditional dealloying reaction to generate fine nanoporous Cu / Cu2O particles and nanoporous Fe / FeO particles, and the porous band size ranged from 2 nm to 50 nm.

[0262] The hydrogen evolution and Al removal reaction was completed within 2 minutes. After the temperature was kept at room temperature for another 2 minutes, the alkali concentration in the solution was reduced to 1 mol / L by adding water, and the temperature was reduced to below 45°C.

[0263] All solid products are separated from the alkaline solution, washed, and dried to obtain a sodium titanate composite powder material endogenously doped with CuFe elements. The main component is a two-dimensional nano-sodium titanate film doped with Cu2O nanoparticles and Fe atoms. The thickness of a single film is 0.25nm to 7nm, and the average area of ​​the film is greater than 1000nm. 2 , showing obvious characteristics of two-dimensional materials; and the particle size of Cu2O nanoparticles ranges from 2nm to 10nm;

[0264] Since the size of the in-situ exogenously doped nanoporous Cu / Cu2O particles and nanoporous Fe / FeO particles in the in-situ endogenously doped CuFe elements sodium titanate composite powder material is less than or equal to the size of the Cu-rich Al(Cu) phase and the Fe-rich Al-Fe intermetallic compound phase in the solidification structure of the original initial alloy strip, they are also nanoscale (50nm-500nm).

[0265] Example 5:

[0266] According to the ratio of Au, Cu and Ti atomic percentages of about 1.2%, 0.6% and 24.5% respectively (the balance is mainly Al), Al-Ti-Au-Cu alloy melt is smelted; the alloy melt is heated to about 10 3 K / s cooling rate solidified into a 1mm thick Al-Ti-Au-Cu alloy sheet, whose solidification structure is mainly composed of an average composition of about Al 74 Ti 24.5 Au1Cu 0.5The Al3Ti(AuCu) intermetallic compound phase and the AuCu-rich Al-AuCu intermetallic compound phase are composed of the matrix phase and the white phase is the Al-AuCu intermetallic compound phase, the SEM morphology of which is shown in Figure 9. Due to the slow cooling rate of the melt, the AuCu-rich Al-AuCu intermetallic compound phase is micron-sized (1μm-20μm).

[0267] The Al-Ti-Au-Cu alloy sheet prepared above was added to 50 ml of a 10 mol / L NaOH aqueous solution at its boiling point (approximately 119°C) under atmospheric pressure and stirred. During the reaction with the concentrated alkaline solution, the Al3Ti(AuCu) intermetallic compound phase in the Al-Ti-Au-Cu alloy sheet undergoes nanofragmentation through a vigorous hydrogen evolution de-Al reaction, and simultaneously undergoes shape and composition reconstruction to form a solid flocculent product. Simultaneously, the AuCu-rich Al-AuCu intermetallic compound undergoes a traditional dealloying reaction to form micron-sized nanoporous AuCu particles.

[0268] The hydrogen evolution and Al removal reaction was completed within 5 minutes. After the reaction was continued for 2 minutes, the alkali concentration in the solution was reduced to 1 mol / L by adding water and the temperature was reduced to below 45°C.

[0269] All solid products are separated from the alkaline solution, washed, and dried to obtain a sodium titanate composite powder material with in-situ endogenous doping of AuCu nanoparticles. The main component is a two-dimensional sodium titanate film with in-situ endogenous doping of AuCu nanoparticles. The thickness of a single film is 2nm to 10nm, and the average area of ​​the film is greater than 1000nm. 2 Among them, Au and Cu elements are mainly in situ doped into the nano-sodium titanate film in the form of AuCu nanoparticles, as shown in Figure 10. The Au:Cu ratio in the AuCu nanoparticles is about 2:1. Because the Au content is high and Cu is solid-dissolved in Au, the Cu in the AuCu nanoparticles is not easily oxidized. The particle size of the AuCu nanoparticles ranges from 2nm to 10nm.

[0270] Since the nanoporous AuCu particles in the in-situ AuCu-doped sodium titanate composite powder material are comparable in size to the AuCu-rich Al-AuCu intermetallic compound phase in the solidified structure of the original initial alloy strip, their particle size is also micron-level (1 μm-20 μm).

[0271] Comparative Example 1

[0272] Under normal pressure, 0.25g of 25μm thick Ti 25 Al 75The initial alloy strip was added to 50 ml of a 10 mol / L NaOH aqueous solution at its boiling point (approximately 119°C) and stirred. The hydrogen evolution and de-Al reaction was completed within 15 seconds. The solid flocculent product, separated from the alkaline solution, was then dispersed in water and an appropriate amount of dilute acid solution was added to convert the titanate into titanic acid, yielding a nano-titanate film product free of doping elements. The product was subjected to solid-liquid separation, cleaned, and heat-treated at 475°C for 2 hours to yield anatase-type nano-TiO2 flake powder, the TEM morphology and diffraction spectrum of which are shown in Figures 11-12. This comparative example demonstrates that nano-titanate films without doping by foreign atoms or atomic clusters undergo a significant phase transition at 475°C, accompanied by a significant morphological change from film to flake.

[0273] Comparative Example 2

[0274] According to the ratio of Au, Cu and Ti atomic percentages of about 1.2%, 0.6% and 24.5% respectively (the balance is mainly Al), Al-Ti-Au-Cu alloy melt is smelted; the alloy melt is heated to about 10 3 K / s cooling rate solidified into a 1mm thick Al-Ti-Au-Cu alloy sheet, whose solidification structure is mainly composed of an average composition of about Al 74 Ti 24.5 Au1Cu 0.5 The matrix phase is composed of an Al3Ti(AuCu) intermetallic compound phase and an AuCu-rich Al-AuCu intermetallic compound phase, of which the matrix phase is the Al3Ti(AuCu) intermetallic compound phase, and its SEM morphology is shown in Figure 9. Due to the slow cooling rate of the melt, the AuCu-rich Al-AuCu intermetallic compound phase is micron-sized (1μm-20μm).

[0275] The initial alloy sheet was reacted with a 10 mol / L NaOH solution at 35°C for 2 hours under atmospheric pressure. The typical SEM morphology of the resulting product is shown in Figure 13. As can be seen, under these reaction conditions, although the initial alloy sheet fragmented somewhat before and after the reaction, it remained in a relatively large fragmented state. Furthermore, its microstructure did not produce a large number of monolithic two-dimensional thin films, but rather large fragments composed of a nanoporous network structure. Therefore, the reaction between the initial alloy and the alkaline solution at a lower temperature is completely different from the reaction at a higher temperature of the alkaline solution of the present invention, and the product morphology is also completely different. At higher temperatures, the T-Ti(E) intermetallic compound phase in the initial alloy undergoes a vigorous hydrogen evolution and de-T reaction with the alkaline solution, resulting in thorough nano-fragmentation through compositional and shape reconstruction.

[0276] The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above-mentioned embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0277] The above-described embodiments merely illustrate several implementations of the present invention, and while their descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be determined by the appended claims.

Claims

1. An in-situ endogenously doped titanium-based composite powder material, characterized in that: The invention mainly consists of a titanium-based main component endogenously doped with an E1 element in situ and an E2 component exogenously doped in situ; the titanium-based main component endogenously doped with an E1 element in situ mainly consists of a titanium-based carrier and an endogenously doped E1 element, and the components of the titanium-based carrier include at least one of titanate, titanic acid, and TiO2, and the shape of the titanium-based carrier includes at least one of a nanofilm, a nanosheet, a nanotube / rod, and a nanoparticle; the in-situ exogenously doped E2 component includes at least one of E2 nanoporous particles and E2 nanoparticles; the E1 element and the E2 component are mainly composed of E elements, and the E elements include at least one of Au, Pt, Pd, Ru, Rh, Re, Os, Ir, Ag, Cu, Fe, Ni, and Co; when the E1 element or the E2 component includes two or more E elements, the composition of E1 is not necessarily completely the same as the composition of E2; the molar percentage content of the in-situ exogenously doped E2 component in the in-situ endogenously doped titanium-based composite powder material is V e2 , and 0 <V e2 ≤25%; the total molar number of E1 element in the titanium-based main component doped with E1 element in situ, C e1 The ratio C to the total molar number C0 of Ti in the titanyl support e1 / C0 satisfies: 0 <C e1 / C0<0.20; In the titanyl main component in-situ endogenously doped with E1 elements, the in-situ endogenous doping method of the E1 element on the titanyl support includes at least one of the following two methods: 1) The E1 element is in situ embedded in the titanyl support, and the E1 element mainly dopes the titanyl support in the form of E1 atoms or atomic clusters, and the size of the E1 atoms or atomic clusters is 0.2 nm to 2 nm; 2) The E1 element is in-situ embedded in the titanium-based carrier, and the E1 element is mainly doped into the titanium-based carrier in the form of E1 nanoparticles, and the size of the E1 nanoparticles is 2 nm to 50 nm.

2. The in-situ endogenously doped titanium-based composite powder material according to claim 1, characterized in that: The cations in the titanate include at least one of Na, K, Li, Rb, Ba, Ca, and Sr.

3. The in-situ endogenously doped titanium-based composite powder material according to claim 1, characterized in that: In the titanium-based main component in situ endogenously doped with E1 element, when the shape of the titanium-based carrier is mainly a nanofilm, its thickness is 0.25nm to 10nm; in the titanium-based main component in situ endogenously doped with E1 element, when the shape of the titanium-based carrier is mainly a nanosheet, its thickness is 3nm to 30nm; in the titanium-based main component in situ endogenously doped with E1 element, when the shape of the titanium-based carrier is mainly a nanotube / rod, its outer diameter is 2nm to 20nm; in the titanium-based main component in situ endogenously doped with E1 element, when the shape of the titanium-based carrier is mainly a nanoparticle, its average particle size is 2nm to 600nm.

4. The in-situ endogenously doped titanium-based composite powder material according to claim 1, characterized in that: In the in-situ exogenously doped E2 component, the average particle size of the E2 nanoporous particles is 5nm-50μm, and the average diameter of the nanoporous bands is 2nm-200nm; in the in-situ exogenously doped E2 component, the average particle size of the E2 nanoparticles is 2nm-500nm.

5. The in-situ endogenously doped titanium-based composite powder material according to claim 1, characterized in that: The E1 element is in situ embedded in the titanium-based carrier. The E1 element mainly dopes the titanium-based carrier in the form of E1 nanoparticles. When the E1 element includes at least one of Cu, Ag, Fe, Ni, and Co, the E1 nanoparticles include at least one of E1 metal nanoparticles and E1 oxide nanoparticles.

6. The in-situ endogenously doped titanium-based composite powder material according to claim 1, characterized in that: When the E1 element is mainly composed of Ag, the E1 element is in-situ embedded in the titanyl carrier, and the E1 element mainly dopes the titanyl carrier with E1 atoms or atomic clusters, and the size of the E1 atoms or atomic clusters is 0.2 nm to 2 nm.

7. The in-situ endogenously doped titanium-based composite powder material according to claim 1, characterized in that: When the E1 element is mainly composed of Cu, the E1 element is in situ embedded in the titanium-based carrier, and the E1 element mainly dopes the titanium-based carrier in the form of E1 metal nanoparticles or (and) E1 metal oxide nanoparticles, and the size of the E1 metal nanoparticles or (and) E1 metal oxide nanoparticles is 2nm to 20nm.

8. The in-situ endogenously doped titanium-based composite powder material according to claim 1, characterized in that: When the titanyl support is doped with the E1 element mainly in the form of atoms or atomic clusters, the phase transition temperature of the doped titanyl support is increased by more than 100° C. compared with the undoped titanyl support.

9. The in-situ endogenously doped titanium-based composite powder material according to claim 1, characterized in that: When the main component of the titanyl carrier is at least one of titanate and titanic acid, its crystal form is mainly low crystalline.

10. The in-situ endogenously doped titanium-based composite powder material according to claim 1, characterized in that: The method comprises the following steps: Step 1: Prepare an initial alloy. The initial alloy contains T-type elements, Ti, and E elements. The phase composition of the initial alloy mainly consists of a T-Ti(E) intermetallic compound with dissolved E elements and a T-E phase. Among them, the molar percentage content of the T-E phase in the initial alloy is V0, and 0 < V0 ≤ 25%. The atomic percentage content of the E element in the T-E phase is higher than that in the T-Ti(E) intermetallic compound. Among them, the T-type elements include at least one of Al and Zn, and the E elements include at least one of Au, Pt, Pd, Ru, Rh, Re, Os, Ir, Ag, Cu, Fe, Ni, and Co. Step 2: React the initial alloy with a hot alkali solution. By controlling the concentration and temperature of the alkali solution, the reaction interface advances inward from the surface of the initial alloy at an average rate greater than 7.5 μm / min during the reaction process. The T-Ti(E) intermetallic compound at the reaction interface undergoes nano-fragmentation through a violent hydrogen evolution and T removal reaction, and at the same time, through shape and composition reconstruction, a titanate matrix component doped with E1 elements in-situ and endogenously is generated. At the same time, the T-E phase at the reaction interface undergoes a traditional T removal reaction to generate an in-situ and exogenously doped E2 component. The E2 component includes at least one of E2 nanoporous particles and E2 nanoparticles. The E1 element and the E2 component are both mainly composed of the E element. When the E1 element or the E2 component includes two or more elements, the composition of E1 does not necessarily be exactly the same as that of E2. Step three, after the de-T reaction is completed, the solid reaction product in step two is collected to obtain an in-situ endogenously doped titanium-based composite powder material, the characteristics of which are described in claim 1, and the specific characteristics also include: it is mainly composed of a titanate main component in-situ endogenously doped with E1 element and an in-situ exogenously doped E2 component; the titanate main component in-situ endogenously doped with E1 element is mainly composed of a titanate carrier and an endogenously doped E1 element; the component of the titanate carrier is mainly titanate, and the shape of the titanate carrier is mainly a nanofilm, and its thickness is 0.25nm to 25nm; the total molar number C of the E1 element e1 The ratio C to the total molar number C0 of Ti in the titanate support e1 / C0 satisfies: 0 <C e1 / C0<0.

20.

11. The preparation method of the in-situ and endogenously doped titanium oxy-compound powder material according to claim 10, wherein when the E1 element is mainly composed of Ag, the E1 element is in-situ embedded in the titanate carrier, and the E1 element mainly dopes the titanate carrier with E1 atoms or atomic clusters. The size of the E1 atoms or atomic clusters is  0.2 nm to 2 nm. when the atomic percentage content of Ag atoms in the E1 element is less than 50%, the E1 element is in-situ embedded in the titanate carrier, and the E1 element mainly dopes the titanate carrier with E1 nanoparticles. The size of the E1 nanoparticles is 2 nm to 25 nm.

12. The method for preparing the in-situ endogenously doped titanyl composite powder material according to claim 10, characterized in that: Perform the following 1)-5) modification treatments on the in-situ and endogenously doped titanium oxy-compound powder material prepared in Step 3 to obtain more in-situ and endogenously doped titanium oxy-compound powder materials with different characteristics: Modification treatment 1): When the titanium oxy carrier is mainly composed of titanate, react it with dilute acid to replace its cations with H ions, and convert the titanate into titanic acid, thereby obtaining a titanium oxy carrier mainly composed of titanic acid. Modification treatment 2): When the titanyl support is mainly composed of at least one of titanate and titanic acid, and the in-situ endogenous E1 element mainly dopes the titanate or (and) titanic acid thin film support in the form of atoms or atomic clusters, the E1 element is further transformed into E1 nanoparticles through diffusion, agglomeration, nucleation and growth through medium and low temperature heat treatment to dope the titanate or (and) titanic acid thin film support; at the same time, the thickness of the titanate or (and) titanic acid thin film support is slightly thickened and the area is slightly reduced during the heat treatment; Modification treatment 3): Through medium-to-high temperature heat treatment, the titanate thin film carrier can be shrunk in area and thickened to become a TiO2 nanosheet carrier. At the same time, the in-situ endogenous E1 atoms or atomic clusters grow through diffusion, agglomeration, nucleation, and further transform into E1 nanoparticles to dope the TiO2 sheet carrier. Modification treatment 4): When the above step 2 is not carried out under normal pressure, but is carried out under high temperature and high pressure in a closed container, In the in-situ endogenously doped titanium-based composite powder material product, the shape of the titanium-based carrier is mainly nanotubes / rods; Modification treatment 5): When the shape of the titanium-based carrier is mainly a nanofilm, after the in-situ endogenously doped titanium-based composite powder material is refined, the average area of ​​the titanium-based nanofilm in-situ endogenously doped with E1 elements will be greatly reduced; when the shape of the titanium-based carrier is mainly nanotubes / rods, the refinement treatment can also break and shorten the length of the nanotubes / rods; the refinement treatment method includes at least one of ultrasonic crushing, ball milling crushing, and sand milling crushing.

13. Use of the in-situ endogenously doped titanyl composite powder material according to claim 1 in composite materials, ceramic materials, photocatalytic materials, hydrophobic materials, sewage degradation materials, bactericidal materials, electronic materials, and coatings.

14. Use of the in-situ endogenously doped titanyl composite powder material according to claim 1 in home decoration coatings, fungicidal sprays, and antifouling coatings.

15. Use of the in-situ endogenously doped titanium-based composite powder material according to claim 1 in antibacterial fabrics.

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