In-situ endogenous doped nano-porous composite powder material as well as preparation method and application thereof

Abstract

The invention relates to an in-situ endogenous doped nano-porous 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 nano-porous carrier of in-situ endogenous doped E1 element to form a nano-porous main body component of in-situ endogenous doped E1 element; and then carrying out secondary compounding on the in-situ ectogenesis doped E2 component and the in-situ endogenesis doped E1 element nano-porous main body component. The preparation method of the in-situ endogenous doped nano-porous composite powder material has the characteristics of simple process, easiness in operation, high efficiency and low cost, and has a good application prospect 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 nanoporous composite powder material and preparation method and use thereof Technical Field

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

[0002] Noble metal nanoparticles, due to their pronounced surface, volume, quantum, and small size effects, possess excellent optical, electronic, biological, and chemical properties, and hold broad application prospects in catalysis, chemistry, biology, medicine, food, and molecular engineering. Generally speaking, their application requires good dispersibility. To address this issue, they are typically combined with nanoscale carriers, which then disperse the particles for further application.

[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 surface, leading to instability and deterioration of the noble metal nanoparticles' performance. Therefore, the development of composite materials composed of in-situ generated noble metal nanoparticles and nanoscale supports is of great significance.

[0004] Summary of the Invention

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

[0006] On the one hand, an in-situ endogenously doped nanoporous composite powder material is characterized in that it is mainly composed of a nanoporous powder main component in-situ endogenously doped with E1 element and an in-situ exogenously doped E2 component; the nanoporous powder main component in-situ endogenously doped with E1 element is mainly composed of a nanoporous carrier and an in-situ endogenously doped E1 element, and the components of the nanoporous carrier include at least one of nanoporous titanate, nanoporous titanic acid, and nanoporous oxide M; in the nanoporous oxide M, M contains at least one of Ti, Zr, Hf, Cr, V, Nb, Ta, W, Mo, Mn, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; the oxide M, The nanoporous carrier mainly presents a "sponge-like" structure in terms of microstructure, and the solid part of the "sponge-like" structure is mainly composed of a three-dimensional continuous network of "laces"; the void part of the "sponge-like" structure is mainly composed of a three-dimensional continuous network of holes; the diameter of the "laces" ranges from 0.5nm to 250nm; the diameter of the holes ranges from 0.5nm to 300nm; the in-situ exogenously doped E2 component includes E2 nanoporous particles, At least one of the 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 exactly 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 nanoporous composite powder material is V e2 , and 0≤V e2 ≤40%; the total molar number of E1 element C in the main component of the nanoporous powder doped with E1 element in situ e1 The ratio C to the total molar number C0 of Ti and M in the nanoporous support e1 / C0 satisfies: 0 <C e1 / C0<0.25;

[0007] In the nanoporous powder main component in-situ endogenously doped with E1 elements, the in-situ endogenous doping method of the nanoporous carrier by E1 elements includes at least one of the following three methods:

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

[0009] 2) The E1 element is in situ embedded in the "lacing" of the nanoporous carrier, and the E1 element mainly dopes the "lacing" of the nanoporous carrier in the form of E1 nanoparticles; the size of the E1 nanoparticles is 2nm to 50nm;

[0010] 3) The E1 element mainly exists in the form of E1 nanoparticles, and the E1 nanoparticles are adsorbed on the surface of the "tie" of the nanoporous carrier by physical adsorption, and are simultaneously located in the pore space of the nanoporous carrier. The size of the E1 nanoparticles is 2nm-150nm; wherein the third doping method occurs simultaneously with the first or second doping method.

[0011] Furthermore, the average particle size of the in-situ endogenously doped nanoporous composite powder material is 201nm-500um;

[0012] Furthermore, the average particle size of the in-situ endogenously doped nanoporous composite powder material is 501nm-500um;

[0013] Furthermore, the average particle size of the in-situ endogenously doped nanoporous composite powder material is 201nm-100um;

[0014] Furthermore, the average particle size of the in-situ endogenously doped nanoporous composite powder material is 201nm-20um;

[0015] Furthermore, when the in-situ endogenously doped nanoporous composite powder material particles are refined, the lower limit of the average particle size will be greatly reduced, such as as low as 5 nm;

[0016] Furthermore, the refinement treatment method includes at least one of ultrasonic crushing, ball milling, and sand milling;

[0017] After refinement,

[0018] Furthermore, the average particle size of the in-situ endogenously doped nanoporous composite powder material particles is 5nm-50um;

[0019] Furthermore, the average particle size of the in-situ endogenously doped nanoporous composite powder material particles is 5nm-5um;

[0020] Furthermore, the average particle size of the in-situ endogenously doped nanoporous composite powder material particles is 5nm-500nm;

[0021] Furthermore, the average particle size of the in-situ endogenously doped nanoporous composite powder material particles is 5nm-250nm;

[0022] Furthermore, during the refinement process, the in-situ exogenously doped E2 component is also refined, and its average particle size is also reduced;

[0023] 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 its nanoporous bands is 2nm~200nm; in the in-situ exogenously doped E2 component, the average particle size of the E2 nanoparticles is 2nm~500nm; further, the average particle size of the E2 nanoparticles is 2nm~200nm.

[0024] Furthermore, the "sponge-like" structure refers to a structure that is the same as or similar to a strict sponge-like structure, and is mainly composed of "ligaments" in the solid part and holes in the void part, but the specific characteristics of the "ligaments" and holes may be different from those of the standard sponge-like structure.

[0025] Furthermore, the surface of the ultrafine nanoporous powder particles in situ endogenously doped with E1 elements has fracture marks caused by crushing; and the fracture marks are caused by at least one of ultrasonic crushing, ball milling, and sand milling; the fracture mark characteristics include the traces of typical "sponge body" fracture under the action of ultrasonic crushing, ball milling, and sand milling, such as the sharp angles of the fracture cross-section and the silk-like fracture morphology;

[0026] Further, the diameter of the "lace" ranges from 0.5nm to 150nm; further, the diameter of the "lace" ranges from 0.5nm to 100nm; further, the diameter of the "lace" ranges from 0.5nm to 50nm;

[0027] Further, the diameter of the hole is in the range of 0.5nm-200nm; further, the diameter of the hole is in the range of 0.5nm-100nm; further, the diameter of the hole is in the range of 0.5nm-50nm;

[0028] Furthermore, 0 <V e2 ≤40%; further, 0≤V e2 ≤20%

[0029] Furthermore, 0 <V e2 ≤25%; further, 0 <V e2 ≤20%;

[0030] Furthermore, 0 <C e1 / C0<0.20; further, 0 <C e1 / C0<0.15; further, 0 <C e1 / C0<0.10;

[0031] Further, the M mainly comprises Ti;

[0032] Furthermore, the M mainly comprises at least one of Zr and Hf;

[0033] Furthermore, the M mainly comprises at least one of Cr, V, Nb, Ta, W, Mo, Mn, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu;

[0034] Furthermore, the M mainly comprises at least one of Cr, V, Nb, Ta, W, and Mo;

[0035] Further, the M comprises Mn;

[0036] Furthermore, the M mainly comprises at least one of Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu;

[0037] Furthermore, the oxidation M comprises a mixture of one or more oxides of M with different valence states;

[0038] Furthermore, the oxidized M includes at least one of oxidized M and hydrated M, because the hydrated M is hydrated oxidized M.

[0039] Furthermore, the oxidized M includes oxidized M of different crystal forms, such as at least one of an amorphous state, a partially crystalline state, and a crystalline state;

[0040] Furthermore, the E element includes at least one of Cu, Ag, Fe, Ni, and Co;

[0041] Further, the E element mainly contains Ag; further, the E element mainly contains Cu; further, the E element mainly contains Fe;

[0042] Furthermore, the E1 element includes at least one of Au, Pt, Pd, Ru, Rh, Re, Os, Ir, Ag, Cu, Fe, Ni, and Co;

[0043] Furthermore, the E1 element includes at least one of Au, Pt, Pd, Ru, Rh, Os, Ir, and Re;

[0044] Furthermore, the E1 element includes at least one of Cu, Ag, Fe, Ni, and Co;

[0045] Furthermore, the E2 element includes at least one of Au, Pt, Pd, Ru, Rh, Re, Os, Ir, Ag, Cu, Fe, Ni, and Co;

[0046] Further, the E2 component comprises at least one of Au, Pt, Pd, Ru, Rh, Os, Ir, and Re;

[0047] Furthermore, the E2 element includes at least one of Cu, Ag, Fe, Ni, and Co;

[0048] Furthermore, the cations in the nanoporous titanate include at least one of Na, K, Li, Rb, Ba, Ca, and Sr;

[0049] Furthermore, the cations in the nanoporous 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;

[0050] Furthermore, the cations in the nanoporous titanate include at least one of Na and K; further, the titanate includes at least one of sodium titanate and potassium titanate;

[0051] Furthermore, the titanate, titanic acid, and M oxide include titanates, titanic acid, and M oxides of different crystal forms, such as at least one of amorphous, partially crystalline, and crystalline;

[0052] Furthermore, the crystalline oxide M includes oxides of different crystal forms. For example, when the oxide M is TiO2, it includes at least one of anatase TiO2 and rutile TiO2.

[0053] 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;

[0054] Furthermore, the E1 element is in situ embedded in the nanoporous support, the E1 element is mainly doped into the nanoporous 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;

[0055] 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;

[0056] Furthermore, the nanoporous 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;

[0057] Furthermore, the nanoporous support endogenously doped with the in-situ E1 element and the in-situ exogenously doped E2 component are generated simultaneously;

[0058] Furthermore, in the in-situ endogenously doped nanoporous composite powder material, the E element is respectively compounded with the nanoporous carrier in a two-stage compounding manner: first, the in-situ endogenously doped E1 element is compounded with the nanoporous carrier in the first stage to form a nanoporous main component in-situ endogenously doped with the E1 element; then, the in-situ exogenously doped E2 component is compounded with the nanoporous main component in-situ endogenously doped with the E1 element in the second stage;

[0059] Furthermore, the in-situ exogenously doped E2 component is dispersed and softly agglomerated by the nanoporous carrier in-situ endogenously doped with the E1 element;

[0060] 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 nanoporous carrier through in-situ embedding; this in-situ embedding is the result of the simultaneous in-situ generation and in-situ recombination of the nanoporous carrier and the doped E1 element during the formation of the nanoporous 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 "ligaments" of the nanoporous carrier.

[0061] Furthermore, the size of the atoms or atomic clusters of the E1 element is 0.2 nm to 2 nm;

[0062] Furthermore, the size of the atoms or atomic clusters of the E1 element is 0.2nm-1.5nm.

[0063] Furthermore, when the E1 element is mainly composed of Ag, the E1 element is in situ embedded in the nanoporous support, and the E1 element mainly dopes the "ties" of the nanoporous support with E1 atoms or atomic clusters, and the size of the E1 atoms or atomic clusters is 0.2 nm to 2 nm;

[0064] Furthermore, the nanoporous carrier includes at least one of nanoporous titanate, nanoporous titanic acid, and nanoporous Cr oxide, and when the doping component E1 element is mainly composed of Ag, the E1 element mainly dopes the "ligaments" of the nanoporous carrier in the form of atoms or atomic clusters.

[0065] Furthermore, when the E1 element is mainly composed of Cu, the E1 element is in situ embedded in the nanoporous support, and the E1 element mainly dopes the nanoporous support with 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;

[0066] Further, the composition of the E1 metal oxide nanoparticles includes at least one of Cu2O and CuO;

[0067] Furthermore, when the E1 element is mainly composed of Au, the E1 element is in situ embedded in the nanoporous support, and the E1 element mainly dopes the nanoporous support with E1 metal nanoparticles, and the size of the E1 metal nanoparticles is 2 nm to 20 nm;

[0068] Furthermore, when the nanoporous support is mainly composed of titanate, the cations thereof are replaced with H ions by reacting the nanoporous support with a dilute acid, thereby converting the titanate into titanic acid, thereby obtaining a nanoporous support mainly composed of titanic acid.

[0069] Furthermore, in the dilute acid solution, the hydrogen ion concentration is lower than 0.1 mol / L;

[0070] Furthermore, when the E1 element dopes the nanoporous 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 nanoporous carrier.

[0071] Furthermore, due to the solid solution and pinning effect of E1 atoms or atomic clusters on the nanoporous support, when the nanoporous support is doped with the E1 element mainly in the form of atoms or atomic clusters, the phase transition thermal stability of the nanoporous support is significantly improved;

[0072] Furthermore, when the E1 element is doped into the nanoporous support mainly in the form of atoms or atomic clusters, the phase transition temperature of the doped nanoporous support is increased by more than 100° C. compared to the undoped nanoporous support;

[0073] Furthermore, the phase change of the nanoporous support is a phase change from titanic acid to TiO2;

[0074] Furthermore, when the main component of the nanoporous 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;

[0075] Furthermore, the diameter of the ligaments of the nanoporous support becomes thicker during the heat treatment, while the specific area decreases;

[0076] Furthermore, in the in-situ exogenously doped E2 component, the average particle size of the E2 nanoporous particles is 10 nm to 50 μm, and the average diameter of the nanoporous bands is 2 nm to 200 nm;

[0077] Furthermore, in the in-situ exogenously doped E2 component, the average particle size of the E2 nanoporous particles is 10 nm-20 μm;

[0078] Furthermore, in the in-situ exogenously doped E2 component, the average particle size of the E2 nanoporous particles is 10 nm-5 μm;

[0079] Furthermore, in the in-situ exogenously doped E2 component, the average particle size of the E2 nanoporous particles is 10 nm-1 μm;

[0080] Furthermore, in the in-situ exogenously doped E2 component, the average particle size of the E2 nanoparticles is 2 nm to 500 nm;

[0081] Furthermore, in the in-situ exogenously doped E2 component, the average particle size of the E2 nanoparticles is 2 nm to 250 nm;

[0082] Furthermore, in the in-situ exogenously doped E2 component, the average particle size of the E2 nanoparticles is 2 nm to 150 nm.

[0083] 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 nanoporous carrier main component in situ endogenously doped with the E1 element in an external manner, but the precursors of the two exist adjacent to each other at the same time (such as different phases in the solidified structure exist adjacent to each other) and are generated in situ adjacent to each other at the same time during a certain reaction process.

[0084] 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.

[0085] 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;

[0086] Furthermore, when the E2 element includes at least one of Cu, Ag, Fe, Ni, and Co, the components of the E2 nanoporous particles include at least one of E2 nanoporous metal particles and E2 nanoporous metal oxide particles;

[0087] 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;

[0088] 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.

[0089] In the first doping method,

[0090] When the size of E1 atoms or atomic clusters is smaller than 2nm, it is difficult to observe the difference in contrast and aggregation of E1 atoms or atomic clusters in the "bands" of the nanoporous support through observation methods such as transmission electron microscopy (TEM); in this case, it can be considered that the E1 element exists in the "bands" of the nanoporous support in solid solution;

[0091] In the second doping method,

[0092] The contrast differences and aggregation of E1 nanoparticles in the “lacing” of the nanoporous support can be observed by transmission electron microscopy (TEM) and other observation methods;

[0093] Furthermore, when the E1 element is mainly doped into the nanoporous carrier "band" in the form of atoms or atomic clusters, through heat treatment, the E1 element is further transformed into the form of E1 nanoparticles to dope the nanoporous carrier "band" through diffusion, agglomeration, nucleation and growth.

[0094] In the doping method in the third step,

[0095] Since the nanoporous powder has a certain size, it is like a "sponge" containing a large number of network-like "ties", and the E1 nanoparticles are also confined to the pore space inside the nanoporous powder; since the E1 nanoparticles and the nanoporous carrier are generated in situ at the same time, the E1 nanoparticles can be inside the three-dimensional continuous network of pores. Therefore, even if the E1 nanoparticles are generated in situ and adsorbed on the surface of the nanoporous carrier "ties" by physical adsorption, they cannot easily desorb from the pore space inside the nanoporous carrier; even if they desorb from the surface of a nanoporous carrier "ties", they will re-adsorb on the surface of another nanoporous carrier "ties" after moving a short distance in the nanoporous pore space.

[0096] In a second aspect, a method for preparing an in-situ endogenously doped nanoporous composite powder material is characterized by comprising the following steps:

[0097] Step 1: Prepare an initial alloy, which mainly includes T elements, M elements and E elements; wherein the T elements include at least one of Al and Zn, the M elements include at least one of Ti, Zr, Hf, Cr, V, Nb, Ta, W, Mo, Mn, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, and the E elements include Au, Pt, Pd, Ru, Rh, Re, Os, At least one of Ir, Ag, Cu, Fe, Co, and Ni; the solidified structure of the initial alloy is mainly composed of an MTE intermetallic compound or an MT(E) intermetallic compound having an E-type element dissolved therein, and a TE phase; wherein the molar percentage content of the TE phase in the initial alloy is V0, and 0≤V0≤40%; the atomic percentage content of the E element in the TE phase is higher than the atomic percentage content of the E element in the MTE intermetallic compound or the MT(E) intermetallic compound having an E-type element dissolved therein;

[0098] Step 2: The initial alloy is reacted with an alkaline solution of a certain temperature and concentration, and the temperature and concentration of the alkaline solution are controlled so that during the hydrogen evolution and T removal reaction between the initial alloy and the alkaline solution, the reaction interface advances inward from the surface of the initial alloy at an average rate of less than 5 μm / min; during the reaction, the T-type elements in the initial alloy MTE intermetallic compound or the MT(E) intermetallic compound having the E-type element dissolved therein are mainly removed by the reaction and dissolved in the solution, and the M-type elements are oxidized by the O element in the alkaline solution or combined with the O element in the alkaline solution to form a nanoporous support. , and at the same time, the E element is in situ endogenized in the ligaments of the nanoporous carrier to obtain a main component of the nanoporous powder in situ endogenously doped with the E1 element; at the same time, the TE phase in the initial alloy undergoes a traditional de-T reaction during the 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;

[0099] In 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 nanoporous composite powder material, the characteristics of which are as described in one aspect, including: it is mainly composed of a nanoporous powder main component in which the E1 element is endogenously doped in situ and an E2 component in which the E1 element is exogenously doped in situ; the main component of the nanoporous powder in which the E1 element is endogenously doped in situ is mainly composed of a nanoporous carrier and an in-situ endogenously doped E1 element, and the composition of the nanoporous carrier includes at least one of nanoporous titanate, nanoporous titanic acid, and nanoporous oxide M; in the nanoporous oxide M, M contains at least one of Ti, Zr, Hf, Cr, V, Nb, Ta, W, Mo, Mn, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; the oxidized M includes at least one of oxidized M and oxidized M; the nanoporous carrier is microscopically The structure is mainly "sponge-like", and the entity part of the "sponge-like" structure is mainly composed of a three-dimensional continuous network of "laces"; the void part of the "sponge-like" structure is mainly composed of a three-dimensional continuous network of holes; the diameter range of the "laces" is 0.5nm-250nm; the diameter range of the holes is 0.5nm-300nm; 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 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 exactly 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 nanoporous composite powder material is V e2 , and 0≤V e2 ≤40%; the total molar number of E1 element C in the main component of the nanoporous powder doped with E1 element in situ e1 The ratio C to the total molar number C0 of Ti and M in the nanoporous support e1 / C0 satisfies: 0 <C e1 / C0<0.25;

[0100] In the nanoporous powder main component in-situ endogenously doped with E1 elements, the in-situ endogenous doping method of the nanoporous carrier by E1 elements includes at least one of the following three methods:

[0101] 1) The E1 element is in situ embedded in the "laces" of the nanoporous support, and the E1 element mainly dopes the "laces" of the nanoporous support in the form of atoms or atomic clusters, and the size of the atoms or atomic clusters of the E1 element is 0.2nm-2nm;

[0102] 2) The E1 element is in situ embedded in the "lacing" of the nanoporous carrier, and the E1 element mainly dopes the "lacing" of the nanoporous carrier in the form of E1 nanoparticles; the size of the E1 nanoparticles is 2nm to 50nm;

[0103] 3) The E1 element mainly exists in the form of E1 nanoparticles, and the E1 nanoparticles are adsorbed on the surface of the "tie" of the nanoporous carrier by physical adsorption, and are simultaneously located in the pore space of the nanoporous carrier. The size of the E1 nanoparticles is 2nm-150nm; wherein the third doping method occurs simultaneously with the first or second doping method.

[0104] In the step 1,

[0105] Further, the T-type elements mainly include Al; further, the T-type elements mainly include Zn;

[0106] Furthermore, the M-type elements mainly include Ti;

[0107] Furthermore, the M-type element includes at least one of Zr and Hf;

[0108] Furthermore, the M-type element includes at least one of Cr, V, Nb, Ta, W, Mo, Mn, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu;

[0109] Furthermore, the M-type elements mainly include Mn;

[0110] Furthermore, the M-type element includes at least one of Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu;

[0111] Furthermore, the E-type element includes at least one of Au, Pt, Pd, Ru, Rh, Os, Ir, and Re;

[0112] Furthermore, the E-type elements mainly include Ag;

[0113] Furthermore, the E-type elements mainly include Cu;

[0114] Furthermore, the initial alloy is prepared by solidifying an alloy melt containing three types of elements: E, T, and M; the alloy solidification structure mainly consists of an MTE intermetallic compound or an MT(E) intermetallic compound containing an E type element in solid solution, and a TE phase;

[0115] Furthermore, the solidification rate of the initial alloy melt is 0.01K / s to 10 8 K / s;

[0116] Furthermore, when the content of the E-type element is low, the E-type element generally exists in the MT(E) intermetallic compound in a solid solution manner; wherein the MT(E) intermetallic compound and the MT intermetallic compound have almost the same crystal structure, except that the MT(E) intermetallic compound has the E-type element solid-solved therein, and the solid-solution manner includes at least one of interstitial solid solution and substitutional solid solution;

[0117] Furthermore, the main stoichiometric relationships of the MT(E) intermetallic compounds include MT4, MT3, M4T 11 , MT2, M5T8, M3T8, M2T3, MT.

[0118] Furthermore, the MT(E) intermetallic compound can be a single phase, such as a NbAl3 intermetallic compound with Au solid solution, or a (Nb-Ta)Al3 intermetallic compound with Au solid solution; or a multiphase intermetallic compound composed of different M-type sub-elements and T-type elements, such as a composite multiphase intermetallic compound composed of TaAl3 with Au solid solution, or YAl3 with Au solid solution;

[0119] When the content of E-type elements is moderate, in some cases, in addition to existing in the MT(E) intermetallic compound as a solid solution, the E-type elements can also form MTE intermetallic compounds, whose crystal structure is different from that of MT(E) intermetallic compounds;

[0120] Regardless of whether the E-type elements exist in solid solution in the MT(E) intermetallic compound or directly in the MTE intermetallic compound, the E-type element atoms are dispersed in the corresponding intermetallic compound, that is, the corresponding intermetallic compound does not contain a phase mainly composed of E-type elements or an E-type element agglomerate mainly composed of E-type elements.

[0121] 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;

[0122] Furthermore, in the initial alloy, the T(E) phase is composed of one or more sub-T(E) phases; for example, when T is Al and E contains Ag and Pt, the T(E) phase is composed of an Al3Pt phase and an Al(Ag) phase;

[0123] Furthermore, the T(E) phase may be a TE intermetallic compound phase or a T(E) phase of a solid-solution E element;

[0124] Furthermore, the shape of the initial alloy has an average size in any three-dimensional direction greater than 2 μm;

[0125] Furthermore, the shape of the initial alloy includes at least one of block, granular, filament, strip, ribbon, and sheet;

[0126] 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;

[0127] 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;

[0128] 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.

[0129] In the step 2,

[0130] Furthermore, the temperature of the alkaline solution is T1, and the concentration of the alkaline solution is C1; generally speaking, the higher the temperature of the alkaline solution and the higher the concentration of the alkaline solution, the higher the reaction rate of the alkaline solution and the initial alloy.

[0131] At this time, the temperature T1 of the alkaline solution and the concentration C1 of the alkaline solution do not need to be specifically limited. The combination of the two is sufficient as long as it can ensure that the reaction interface advances inward from the surface of the initial alloy at an average rate of less than 5 μm / min during the reaction between the initial alloy and the alkaline solution.

[0132] Furthermore, during the reaction between the initial alloy and the alkaline solution, the reaction interface advances inward from the initial alloy surface at an average rate of less than 2 μm / min;

[0133] Further, the alkaline solution comprises at least one of NaOH, KOH, LiOH, RbOH, Ba(OH)2, Ca(OH)2, and Sr(OH)2 solutions;

[0134] Furthermore, the solvent in the alkaline solution includes water; preferably, the solvent in the alkaline solution is water;

[0135] Further, the concentration C1 of the alkali in the alkaline solution is 0.25 to 30 mol / L; further, the concentration C1 of the alkali in the alkaline solution is 0.25 to 20 mol / L; further, the concentration C1 of the alkali in the alkaline solution is 0.25 to 10 mol / L;

[0136] Furthermore, the concentration of the base C1 refers to the OH - concentration;

[0137] Furthermore, the alkali in the alkali solution reacting with the initial alloy is in an excess dosage;

[0138] Furthermore, the temperature T1 of the alkaline solution is the reaction temperature of the initial alloy and the alkaline solution;

[0139] Further, T1<100°C; further, T1<85°C; further, T1<75°C; further, T1<60°C;

[0140] Further, when the alkali concentration C1 is high, the high value of T1 may be a smaller value; when the alkali concentration C1 is low, the high value of T1 may be a higher value;

[0141] Furthermore, when 5.1 mol / L≤C1≤30 mol / L, T1<60°C;

[0142] Furthermore, when 5.1 mol / L≤C1<10.1 mol / L, T1<75°C;

[0143] Furthermore, when 3 mol / L≤C1<5.1 mol / L, T1<85°C;

[0144] Furthermore, when 1mol / L≤C1<3mol / L, T1<100℃;

[0145] Furthermore, when 0.25mol / L≤C1<1mol / L, 100℃ <T1≤T f沸点 ; Among them, T f沸点 is the boiling point of the alkali solution at this alkali concentration;

[0146] Since T-type elements (Al, Zn) are amphoteric metals, they can react with OH in alkaline solution. - The reaction turns into a salt containing T-type elements and dissolves in the alkaline solution, while releasing hydrogen. Therefore, T in the MTE intermetallic compound in the initial alloy or the MT(E) intermetallic compound with E-type elements dissolved therein can be removed by the reaction of the T-type elements with the alkaline solution. At the same time, the remaining M-type elements and E-type elements further interact with the alkaline solution and undergo a series of changes at the same time, namely, the M-type elements are oxidized by the O element in the alkaline solution or combined with the O element in the alkaline solution, while the E-type elements are endogenously doped in situ, thereby obtaining the main component of the nanoporous powder in situ endogenously doped with the E1-type elements.

[0147] Furthermore, when the M-type elements in the original initial alloy mainly include Ti, the composition of the nanoporous support is mainly titanate, and the cations of the titanate are consistent with the cation types in the alkaline solution; that is, the initial alloy reacts with the alkaline solution to remove the T-type elements (the T-type elements enter the solution and are dissolved), and at the same time, the M-type elements combine with the O element in the alkaline solution, and the E-type elements are in-situ endogenously doped to generate a nanoporous titanate main component in-situ endogenously doped with the E1-type elements;

[0148] When the M-type elements in the original initial alloy do not mainly include Ti, the composition of the nanoporous support is mainly nano-oxidized M; that is, the initial alloy reacts with the alkaline solution to remove the T-type elements (the T-type elements enter the solution and are dissolved), and at the same time, the M-type elements are oxidized by the O element in the alkaline solution to generate the nanoporous oxidized M support, and the E-type elements are in situ endogenously doped in the nanoporous oxidized M support; wherein M includes at least one of Zr, Hf, Cr, V, Nb, Ta, W, Mo, Mn, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu;

[0149] Furthermore, the in-situ embedding in the in-situ endogenous doping method refers to the partial wrapping or complete embedding of E1 atoms or atomic clusters, or E1 nanoparticles in the "ribbons" of the nanoporous carrier by in-situ embedding; this in-situ embedding is the result of the simultaneous in-situ generation and in-situ recombination of the nanoporous carrier and the doped E1 element during the formation of the main components of the nanoporous carrier with the in-situ endogenous doped E1 element. It does not rely on and cannot rely on external addition or external mixing to embed the doped E1 element in the nanoporous carrier.

[0150] The partial encapsulation means that a portion of the volume of the E1 nanoparticles is embedded in the "tether" of the nanoporous carrier, and another portion of the volume of the E1 nanoparticles is outside the "tether" of the nanoporous carrier;

[0151] The origin of in-situ intrinsic doping lies in the fact that the E element is dissolved atomically in the MTE intermetallic compound or the MT(E) intermetallic compound in the precursor. When the MTE intermetallic compound or the MT(E) intermetallic compound undergoes reaction evolution, the E element remains in the reaction product, thereby in-situ doping the main component of the nanoporous support product as atoms or atomic clusters.

[0152] Furthermore, when the M-type elements in the original initial alloy mainly include at least one of Ti and Cr, and at the same time the E-type elements mainly include Ag, the E1 element in the nanoporous support in situ endogenously doped with the E1 element mainly dopes the nanoporous support "laces" in the form of atoms or atomic clusters; and the size of the atoms or atomic clusters of the E1 element is 0.2nm-2nm; further, the component of the nanoporous support is at least one of titanate, chromium oxide, and chromium hydroxide;

[0153] Furthermore, when the initial alloy reacts with the alkaline solution, the TE phase mainly undergoes the traditional de-T reaction;

[0154] Under the traditional de-T reaction, when the atomic percentage of the E element in the TE phase is high, such as higher than 20%, it mainly generates 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;

[0155] Under the traditional de-T reaction, when the content of the E element in the TE phase is relatively low, such as 5%-15% by atomic percentage, it mainly generates 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.

[0156] 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 stable E2 nanoporous particles, and its dealloyed product is easy to generate fragmented E2 nanoparticles.

[0157] Since the E2 nanoparticles are not embedded in the main components of the nanoporous support but are generated separately at the same time, they have a certain short-range mobility in the nanoporous support after their formation. Therefore, after their in situ generation, smaller E2 nanoparticles may aggregate and grow into larger E2 nanoparticles. This aggregation phenomenon is particularly obvious when the reaction temperature is maintained for a long time or after annealing treatment.

[0158] 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.

[0159] 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;

[0160] 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.

[0161] Furthermore, when the E2 element 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;

[0162] Furthermore, by adjusting the values ​​of T1 and C1, the reaction interface during the reaction between the initial alloy and the alkaline solution was pushed inward from the initial alloy surface at an average rate of less than 5 μm / min. At this reaction rate, the reaction products may undergo some initial fragmentation due to the slow generation of hydrogen, but it is difficult for them to undergo complete nano-fragmentation.

[0163] Furthermore, when the initial alloy is relatively large or thick, such as when the thickness or particle size exceeds 2 μm or even reaches the millimeter level, the initial alloy reacts with the alkaline solution layer by layer, the reaction interface expands inward, and the reaction product of the initial alloy forms a nanoporous structure. Under the expansion effect of hydrogen generated by the slow reaction and the convection of the solution, the generated nanoporous product undergoes a certain degree of initial fragmentation, generating nanoporous main component powder particles with an average particle size of no more than 500 μm. However, this degree of fragmentation is relatively weak, so that the average particle size of the nanoporous powder particles after initial fragmentation still exceeds 201 nm.

[0164] Therefore, when the reaction interface advances inward from the initial alloy surface at an average rate of less than 5 μm / min, in-situ endogenously doped nanoporous composite powder particles with an average particle size ranging from 201 nm to 500 um can be obtained.

[0165] Step 4: performing one or more of the following modification treatments 1) to 4) on the in-situ endogenously doped nanoporous composite powder material prepared in step 3 to obtain more in-situ endogenously doped nanoporous composite powder materials with different characteristics:

[0166] Modification treatment 1): When the nanoporous support is mainly composed of titanate, the cations thereof are replaced with H ions by reacting the nanoporous support with a dilute acid, thereby converting the titanate into titanic acid, thereby obtaining a titanyl support mainly composed of titanic acid;

[0167] Furthermore, in the dilute acid solution, the hydrogen ion concentration is lower than 0.1 mol / L;

[0168] The in-situ endogenously doped nanoporous composite powder material obtained at this time has basically the same characteristics as before the acid reaction, except that the titanate nanoporous support is changed into a titanate nanoporous support.

[0169] Modification treatment 2): When the E1 element is in situ embedded in the "bands" of the nanoporous support, and the E1 element mainly dopes the nanoporous support "bands" in the form of atoms or atomic clusters, a medium-low temperature heat treatment is performed to allow the E1 element to diffuse, agglomerate, nucleate and grow, and further transform into E1 nanoparticles to dope the nanoporous support "bands". At the same time, the diameter of the nanoporous support "bands" becomes thicker during the heat treatment, while the specific area is reduced.

[0170] Modification treatment 3): through medium-to-high temperature heat treatment, the titanate nanoporous support is transformed into a TiO2 nanoporous support, or the amorphous oxidized M nanoporous support is transformed into a crystalline oxidized M nanoporous support;

[0171] Furthermore, due to the solid solution and pinning effect of E1 atoms or atomic clusters on the "bands" of the nanoporous carrier, when the E1 element mainly dopes the "bands" of the nanoporous carrier in the form of atoms or atomic clusters, the phase change thermal stability of the "bands" of the nanoporous carrier is significantly improved; further, compared with the "bands" of the undoped nanoporous carrier, the phase change transition temperature of the "bands" of the doped nanoporous carrier is increased by more than 100°C; during the phase transition of the nanoporous carrier, the in-situ endogenous E1 atoms or atomic clusters diffuse, agglomerate, nucleate and grow, and further transform into E1 nanoparticles to dope the nanoporous carrier after the phase transition; further, the phase transition of the "bands" of the nanoporous carrier is a phase transition from titanate to TiO2;

[0172] Furthermore, when the main component of the nanoporous carrier is at least one of titanate and titanic acid, 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 titanic acid to anatase TiO2, and then further to rutile TiO2;

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

[0174] Modification treatment 4): After the in-situ endogenously doped nanoporous composite powder material is refined, its particle size will be greatly reduced;

[0175] Furthermore, the refinement treatment method includes at least one of sand milling, ball milling, and ultrasonic crushing;

[0176] Furthermore, the refinement treatment method includes sanding treatment;

[0177] Among all the refinement treatment methods, sand grinding has the best refinement effect, which can fully refine the in-situ endogenously doped nanoporous composite powder material.

[0178] After refinement,

[0179] Furthermore, the average particle size of the in-situ endogenously doped nanoporous composite powder material particles is 5nm-50um;

[0180] Furthermore, the average particle size of the in-situ endogenously doped nanoporous composite powder material particles is 5nm-5um;

[0181] Furthermore, the average particle size of the in-situ endogenously doped nanoporous composite powder material particles is 5nm-500nm;

[0182] Furthermore, the average particle size of the in-situ endogenously doped nanoporous composite powder material particles is 5nm-250nm;

[0183] Furthermore, during the refinement process, the in-situ exogenously doped E2 component is also refined, and its average particle size is also reduced;

[0184] 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 its nanoporous bands is 2nm~200nm; in the in-situ exogenously doped E2 component, the average particle size of the E2 nanoparticles is 2nm~500nm; in the in-situ exogenously doped E2 component, the average particle size of the E2 nanoparticles is 2nm~200nm.

[0185] In its third aspect, the present invention also relates to the use of the in situ endogenously doped nanoporous composite powder material described in any one of the first to second aspects or the in situ endogenously doped nanoporous 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.

[0186] Furthermore, the coating includes antibacterial coating, anticorrosive coating, marine coating, and marine engineering coating;

[0187] Furthermore, the composite material includes polymer-based nanocomposite materials and resin-based composite materials;

[0188] The specific application method includes: mixing the nanoporous composite powder material in situ endogenously doped with E1 element with a polymer to prepare a composite coating of the nanoporous composite powder material in situ endogenously doped with E1 element and the polymer;

[0189] Furthermore, the polymer includes at least one of a polymer material, a resin material, and a coating;

[0190] 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;

[0191] In its fourth aspect, the present invention also relates to the use of the in-situ endogenously doped nanoporous composite powder material described in any one of the first to second aspects or the in-situ endogenously doped nanoporous composite powder material obtained by the preparation method in home decoration coatings, bactericidal sprays, and antifouling coatings.

[0192] As an application of home decoration coating, it is characterized in that the nanoporous composite powder material in situ endogenously doped with E1 element is applied on the surface of furniture, utensils, and walls as a coating additive and mixed with other components of the coating to achieve an antibacterial effect;

[0193] The application as a bactericidal spray is characterized in that the nanoporous composite powder material in situ endogenously doped with E1 elements is mixed with other liquid spray components and sprayed onto the surface of furniture, utensils, fabrics, and walls through a spray carrier to achieve an antibacterial effect;

[0194] The application of the antifouling coating is characterized in that the above-mentioned nanoporous composite powder material endogenously doped with E1 elements in situ replaces the bactericidal and antifouling components (such as cuprous oxide powder) in traditional antifouling coatings (such as antifouling paints) to achieve an antifouling effect;

[0195] Furthermore, 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.

[0196] In a fifth aspect, the present invention further relates to the use of the in-situ endogenously doped nanoporous composite powder material or the in-situ endogenously doped nanoporous composite powder material prepared by the preparation method described in any one of the first to second aspects in antibacterial fabrics;

[0197] Furthermore, it is characterized in that the nanoporous 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;

[0198] Furthermore, 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.

[0199] The beneficial effects of the in-situ endogenously doped nanoporous composite powder material of the present invention are mainly reflected in the following aspects:

[0200] First, a nanoporous composite powder material with an in-situ endogenous doping and a porous structure was prepared. Generally speaking, for ordinary solid solid powder materials, it is difficult to crush them to an average particle size of less than 500nm even through sand milling. However, through a special and ingenious design, the present application not only can obtain an ultrafine nanoporous powder with an average particle size of less than 500nm that is in-situ endogenously doped with E1 elements, but the obtained powder is not a solid powder, but a three-dimensional network-like "sponge-like" nanoporous ultrafine powder whose main component is mainly composed of nanoporous carrier "ties" and pores. To achieve this goal, first, through the ingenious alloy design in step one and the ingenious reaction condition design in step two, a nanoporous composite coarse powder with in-situ endogenous doping of E1 elements is prepared, the interior of which is mainly composed of nanoporous carrier "ties" and doped E1 elements. Specifically, by controlling the concentration of the alkaline solution and the reaction temperature, the reaction rate is made lower than 5μm / min, so that only limited initial fragmentation of the product occurs and a nanoporous microstructure is generated. Then, through refinement processing technology, such as sand milling, an ultrafine nanoporous composite powder material in situ endogenously doped with E1 elements with an average particle size of less than 250 nm or even an average particle size of less than 150 nm can be obtained.

[0201] This combination of a nanoporous structure and in-situ endogenous doping with an E1 element offers numerous advantages. For example, if the composite powder carrier is a nanoporous powder with a three-dimensional network of porous pores, even if physically adsorbed E1 nanoparticles desorb from the surface of one nanoporous carrier "tether," they will re-adsorb onto the surface of another nanoporous carrier "tether," as if trapped in a "maze" of porous pores, thus remaining confined within the three-dimensional network of porous pores. However, when the E1 element or E1 nanoparticle is in situ endogenously embedded within the nanoporous three-dimensional network of "tethers," the E1 element or E1 nanoparticle and its carrier are in an optimal composite state, and the E1 element atoms / atomic clusters or E1 nanoparticles cannot move freely.

[0202] Furthermore, the porous structure of the nanoporous composite powder material in situ doped with the E1 element can also utilize the channels formed by the three-dimensional network of pores to produce even more excellent properties. For example, it can allow other nanoscale powders, or liquids / gases that can enter the three-dimensional network of pores to enter, thereby further combining or reacting with the nanoporous carrier "tethers" and the E1 element (or E1 nanoparticles), thereby achieving even more excellent properties.

[0203] Second, the in-situ endogenous doping of the E1 element in the "laces" of the nanoporous powder carrier is achieved. The in-situ embedding in the in-situ endogenous doping method refers to the partial or complete embedding of E1 atoms / atomic clusters, or E1 nanoparticles in the "laces" of the nanoporous carrier through in-situ embedding. This in-situ embedding is the result of the simultaneous in-situ generation and in-situ recombination of the nanoporous carrier and the in-situ endogenously doped E1 element during the formation of the nanoporous powder carrier with the in-situ endogenously doped E1 element. It does not rely on, and cannot rely on, external addition or external mixing to embed the doped E1 element in the "laces" of the nanoporous carrier. This in-situ endogenous doping solves the problem that the traditional mechanical mixing-adsorption method is not only not conducive to the physical-chemical interaction between the doped nanoparticles and the carrier material at the atomic scale, but also easily causes the doped nanoparticles to fall off the surface of the carrier material, thereby causing instability and deterioration of the performance of the doped nanoparticles. It is of great significance. Furthermore, the nanoporous carrier serves as a carrier, matrix, and dispersion, and the doped E1 element serves as a key functional element. When the E1 element is "solid-dissolved" in the nanoporous carrier as E1 atoms or atomic clusters, nearly all of the doped E1 atoms can fully exert their functional applications, thereby significantly reducing the amount of doped E1 element used. For example, Ag nanoparticles are currently commonly used in the industry as bactericidal materials, and nano-titanates, nano-titanic acids, and nano-oxides mechanically mixed with them generally serve as their carriers. Because the Ag that exerts the bactericidal effect is primarily Ag atoms on the surface of the Ag nanoparticles, this results in a certain waste of the Ag atoms within the Ag nanoparticles in terms of performance, increasing costs. Furthermore, physically adsorbed Ag nanoparticles are easily detached from the carrier, resulting in unstable performance and poor performance durability. The present invention creatively achieves the in-situ endogenous embedding of Ag in the nanoporous carrier as atoms or atomic clusters. This eliminates the need to worry about Ag shedding and maximizes Ag utilization, which is of great benefit.

[0204] Third, a nanoporous composite powder material with in-situ endogenous doping and two-level composite characteristics was creatively invented. Doping elements or doped nanoparticles have a very important positive effect on the functional applications of nano-titanates, nano-titanic acids, and nano-oxides M. By regulating the solidification rate of the initial alloy melt, when the cooling rate is extremely high, a nano-scale TE phase can be obtained. By reacting with an alkaline solution, the nano-scale TE phase can be converted into nano-scale E2 nanoporous particles or E2 nanoparticles. The nanoporous composite powder material formed by mixing the nano-porous carrier main component with the in-situ endogenous doping of the E1 element can simultaneously have different composite physical and chemical properties. For example, the nanoporous titanate composite powder material with in-situ endogenous doping of Ag (Pt) elements prepared in Example 2 can not only utilize the in-situ endogenous doping of Ag (Pt) elements as a bactericidal component, but the in-situ exogenously doped nanoporous Pt also has formaldehyde catalytic-oxidation properties. When the two components are combined, they will have extremely excellent composite physical and chemical properties.

[0205] Fourth, when the E1 element is mainly doped into the "ribbons" of the nanoporous carrier in the form of atoms or atomic clusters, the pinning effect of the E1 element also greatly improves the phase change thermal stability of the nanoporous carrier, which increases the phase change thermal stability of the nanoporous carrier by more than 100°C, which has great application significance.

[0206] 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 nanoporous composite powder materials, 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

[0207] FIG1 is a SEM backscattered image of the solidified structure of the initial alloy described in Example 1;

[0208] FIG2 is a low-magnification secondary electron SEM image of the nanoporous composite powder material in situ endogenously doped with CuAu nanoparticles according to Example 1;

[0209] FIG3 is a low-magnification backscattered SEM image of the nanoporous composite powder material in situ endogenously doped with CuAu nanoparticles according to Example 1;

[0210] FIG4 is a SEM image of nanoporous Au in the nanoporous composite powder material in situ endogenously doped with CuAu nanoparticles as described in Example 1;

[0211] FIG5 is a medium magnification SEM backscattered image of the nanoporous composite powder material in situ endogenously doped with CuAu nanoparticles according to Example 1;

[0212] FIG6 is a high-magnification SEM backscattered image of the nanoporous composite powder material in situ endogenously doped with CuAu nanoparticles according to Example 1;

[0213] FIG7 is a low-magnification SEM image of the solidified structure of the initial alloy described in Example 2;

[0214] FIG8 is a high-magnification SEM image of the solidified structure of the initial alloy described in Example 2;

[0215] FIG9 is an SEM backscattered image of the nanoporous titanate composite powder material in situ endogenously doped with Cu / Cu2O nanoparticles as described in Example 3;

[0216] FIG10 is a high-magnification SEM image of the main components of the nanoporous titanate composite powder material in situ endogenously doped with Cu / Cu2O nanoparticles described in Example 3;

[0217] FIG11 is a low-magnification SEM image of the solidified structure of the initial alloy described in Example 4;

[0218] FIG12 is a TEM morphology of the main components of the nanoporous Cr oxide composite powder material in situ endogenously doped with Ag element after the heat treatment described in Example 4;

[0219] FIG13 is a low-magnification SEM image of the solidified structure of the initial alloy described in Example 5;

[0220] FIG14 is a TEM morphology of the main component of the nanoporous Nb oxide composite powder material in situ endogenously doped with Au nanoparticles as described in Example 5;

[0221] FIG15 is a low-magnification SEM image of the solidified structure of the initial alloy described in Example 6. DETAILED DESCRIPTION

[0222] The technical solution will be further described below through the following specific embodiments:

[0223] Example 1:

[0224] According to the ratio of Au, Cu and Ti atomic percentages of about 2.5%, 2.5% and 23.5% respectively (the balance is mainly Al), an Al-Ti-Au-Cu alloy melt is smelted; the alloy melt is solidified into an Al-Ti-Au-Cu alloy plate with a thickness of 5 mm at a cooling rate of about 100 K / s. The solidified structure is mainly composed of an average composition of about Al 74 Ti 25 Cu 0.5 Au 0.5 、Al 72.5 Ti 24 Cu2Au 1.5 、Al 71.5Ti 23 Cu3Au 2.5 Three Al3Ti(CuAu) intermetallic compounds with different Cu and Au solid solubility and Al 70 Au 30 The SEM backscattered image is shown in Figure 1, where the three gray and black phases indicated by arrows are Al3Ti (CuAu) intermetallic compounds.

[0225] The Al-Ti-Au-Cu alloy plate obtained above was crushed into a powder with an average particle size of 100 μm. This powder was then dealloyed with a 10 mol / L NaOH aqueous solution at room temperature. After a 40-minute reaction, the solid product was collected, cleaned, and dried to obtain a nanoporous composite powder material in situ endogenously doped with CuAu nanoparticles. The in situ endogenously doped CuAu nanoparticles provided the primary doping of the nanoporous sodium titanate support, which served as the primary component, while the in situ exogenously doped nanoporous Au particles provided the secondary doping of the nanoporous sodium titanate support, which was in situ endogenously doped with CuAu nanoparticles. The molar percentage of nanoporous Au particles in the composite powder product is less than 20%. The low-magnification secondary electron SEM image and backscattered SEM image of the nanoporous sodium titanate composite powder material in situ endogenously doped with CuAu nanoparticles are shown in Figures 2 and 3, and the high-magnification backscattered SEM images are shown in Figures 5 and 6. The morphology of nanoporous Au is shown in Figure 4. The white spots in Figures 2, 3, and 5 are nanoporous Au particles. Figure 6 shows the morphology of the nanoporous sodium titanate support and the CuAu nanoparticles in situ endogenously doped in the nanoporous sodium titanate support. The particle size of the in situ endogenously doped CuAu nanoparticles is 2nm-20nm, and the nanoporous sodium titanate support has a "sponge-like" structure.

[0226] The nanoporous sodium titanate composite powder material in situ endogenously doped with CuAu nanoparticles is reacted with a 0.015 mol / L HCl solution to convert the nanoporous sodium titanate carrier into a nanoporous titanate carrier. The nanoporous titanate composite powder material in situ endogenously doped with CuAu nanoparticles is obtained through solid-liquid separation, washing and drying. The particle size of the in situ endogenously doped CuAu nanoparticles is 2 nm-20 nm.

[0227] The nanoporous titanate composite powder material in situ endogenously doped with CuAu nanoparticles was sand-milled for 2 hours. Because the nanoporous titanate support and the nanoporous Au particles are loose and porous, the sand-milling process easily yielded a refined, ultrafine nanoporous titanate composite powder material in situ endogenously doped with CuAu nanoparticles. After refinement, the average particle size of the nanoporous titanate support was less than 300 nm, and the average particle size of the exogenously doped nanoporous Au particles was less than 200 nm. The particle size of the in situ endogenously doped CuAu nanoparticles ranged from 2 nm to 20 nm.

[0228] The ultrafine nanoporous titanate composite powder material in situ endogenously doped with CuAu nanoparticles was heat treated at 700°C for 2 hours to obtain a composite powder primarily composed of nanoporous anatase TiO2 in situ endogenously doped with CuAu nanoparticles and nanoporous Au particles in situ exogenously doped. The nanoporous carrier had a significantly increased band size and a significantly reduced specific surface area. The in situ endogenously doped CuAu nanoparticles had a particle size of 2nm to 50nm.

[0229] Example 2:

[0230] 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 Al3Ti(AgPt) intermetallic compound phase is composed of Ag-rich Al(Ag) phase and Pt-rich Al-Pt intermetallic compound phase. Its SEM secondary electron image is shown in Figures 7-8, where the matrix phase is the Al3Ti(AgPt) intermetallic compound phase, and the nanoscale (10nm-250nm) bright white particle phase is the Ag-rich Al(Ag) phase and Pt-rich Al-Pt intermetallic compound phase.

[0231] The Al-Ti-Au-Cu initial alloy ribbons prepared above were dealloyed with an 8 mol / L NaOH aqueous solution at room temperature. After a 25-minute reaction, the solid product was collected, washed, and dried to obtain a nanoporous sodium titanate composite powder material in situ endogenously doped with Ag(Pt). The in-situ endogenously doped Ag(Pt) element provided the primary doping of the nanoporous sodium titanate support, with a molar ratio of Ag to Pt of approximately 10:1. The Ag(Pt) element was primarily endogenously doped into the nanoporous sodium titanate support ribbons in the form of atoms or atomic clusters. The in-situ exogenously doped nanoporous Pt particles and nanoporous Ag particles provided the secondary doping of the nanoporous sodium titanate support. Since the sizes of the nanoporous Pt particles and the nanoporous Ag particles are comparable to those of the Al(Ag) phase and the Al-Pt intermetallic compound phase in the initial alloy strips, the nanoporous Pt particles and the nanoporous Ag particles are also nanoscale (10 nm-250 nm).

[0232] The nanoporous sodium titanate composite powder material in situ endogenously doped with Ag (Pt) element is reacted with a 0.015 mol / L HCl solution to convert the nanoporous sodium titanate support into a nanoporous titanate support. After solid-liquid separation, washing and drying, the nanoporous titanate composite powder material in situ endogenously doped with Ag (Pt) element is obtained.

[0233] The nanoporous titanate composite powder material in situ doped with Ag (Pt) was sand-milled for 2 hours. Because the nanoporous titanate support and the in situ exogenously doped nanoporous Pt and nanoporous Ag particles are loose and porous, the sand-milling process easily yielded a refined nanoporous titanate composite powder material in situ doped with Ag (Pt). The average particle size of the nanoporous titanate support was less than 300 nm, and the particle sizes of the nanoporous Pt and nanoporous Ag particles were in the range of 10 nm to 200 nm.

[0234] After the sanding treatment, the refined nanoporous titanate composite powder material, which is in situ endogenously doped with Ag(Pt) elements, is mixed with PDMS (polydimethylsiloxane), and then a nanoporous titanate-PDMS composite coating containing Ag(Pt) is obtained according to the coating preparation method. In this coating, the Ag(Pt) element is dispersed in the ultrafine nanoporous titanate carrier as atoms or atomic clusters, and the ultrafine nanoporous titanate carrier is dispersed in the PDMS, which can maximize the bactericidal properties of the Ag(Pt) element, resulting in an Ag(Pt)-PDMS composite coating with excellent mechanical properties, hydrophobic properties, and bactericidal properties.

[0235] 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.

[0236] The refined nanoporous titanate composite powder material in situ endogenously doped with Ag (Pt) elements,

[0237] As a home decoration coating application: the above-mentioned refined in-situ endogenously doped Ag (Pt) element nanoporous titanate composite powder material is mixed with other coating components as a coating additive and applied together on the surface of furniture, utensils, and walls to achieve an antibacterial effect; at the same time, the exogenously doped nanoporous Pt particles in the composite powder material also have excellent catalytic properties, which is also of great significance for the catalytic-oxidative removal of formaldehyde.

[0238] Application as a bactericidal spray: the refined in-situ endogenously doped Ag (Pt) nanoporous titanate composite powder material 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;

[0239] Application as antifouling coating: The above-mentioned refined in-situ endogenously doped Ag (Pt) element nanoporous titanate composite powder material replaces the bactericidal and antifouling components in traditional antifouling coatings to achieve antifouling effect;

[0240] Application as antibacterial fabric: After the above-mentioned refined in-situ endogenously doped Ag (Pt) element nanoporous titanate composite powder 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.

[0241] Example 3:

[0242] According to the ratio of Cu and Ti atomic percentages of about 4% and 24.5% respectively (the balance is mainly Al), Al-Ti-Cu alloy melt is smelted; the alloy melt is heated to about 10 2 K / s~10 3 K / s cooling rate solidified into an Al-Ti-Cu alloy plate with a thickness of about 2mm. Its solidification structure is mainly composed of an average composition of about Al 73 Ti 24 Cu3 Al3Ti(Cu) intermetallic compound phase and Cu-rich Al2Cu phase.

[0243] The Al-Ti-Cu alloy plate obtained above was crushed into a powder with an average particle size of 200 μm. This Al-Ti-Cu alloy powder was then dealloyed with an 8 mol / L aqueous NaOH solution at 40°C. After a 45-minute reaction, the solid product was collected, washed, and dried to obtain a nanoporous sodium titanate composite powder material in situ endogenously doped with Cu / Cu₂O nanoparticles. The in situ endogenously doped Cu / Cu₂O nanoparticles provided the primary doping of the nanoporous sodium titanate support, while the in situ exogenously doped nanoporous Cu / Cu₂O particles provided the secondary doping of the nanoporous sodium titanate support. A portion of the Cu in both the in situ endogenously doped Cu / Cu₂O nanoparticles and the in situ exogenously doped nanoporous Cu / Cu₂O particles was oxidized to Cu₂O. The particle size of the in-situ endogenously doped Cu / Cu2O nanoparticles is 2nm-25nm; the particle size of the in-situ exogenously doped nanoporous Cu / Cu2O particles is 5nm-1μm.

[0244] The nanoporous sodium titanate composite powder material in situ endogenously doped with Cu / Cu2O nanoparticles was reacted with a 0.015 mol / L HCl solution to convert the nanoporous sodium titanate support into a nanoporous titanate support. After solid-liquid separation, washing, and drying, a nanoporous titanate composite powder material in situ endogenously doped with Cu / Cu2O nanoparticles was obtained. A backscattered SEM image of the material is shown in Figure 9, and a high-magnification SEM image of the nanoporous titanate support is shown in Figure 10. The nanoporous titanate support exhibits a sponge-like structure, with faintly visible, white-bright doped, dot-like Cu / Cu2O nanoparticles.

[0245] Example 4:

[0246] According to the ratio of Ag and Cr atomic percentages of about 1.5% and 20% respectively (the balance is mainly Al), Al-Cr-Ag alloy melt is smelted; the alloy melt is heated to about 10 2 K / s~10 3 K / s cooling rate solidified into an Al-Cr-Ag alloy plate with a thickness of about 2mm. Its solidification structure is mainly composed of an average composition of about Al 77 Cr 22 Ag1 (gray-black phase), Al 78 Cr 19 The Al4Cr(Ag) intermetallic compound phase of Ag3 (gray-white phase) is composed of the Ag-rich Al(Ag) phase. Its SEM image is shown in Figure 11, where the matrix phase is two Al4Cr(Ag) intermetallic compound phases, and a small amount of bright white particle phase is the Ag-rich Al(Ag) phase, as indicated by the arrow.

[0247] The Al-Cr-Ag initial alloy plate prepared above was crushed into a powder with an average particle size of 300 μm. The alloy powder was then added to a 10 mol / L NaOH aqueous solution at 40°C for a dealloying reaction. After a 2-hour reaction, the solid product was collected, cleaned, and dried to obtain a nanoporous Cr oxide composite powder material in situ endogenously doped with Ag. The in situ endogenously doped Ag nanoporous Cr oxide support performed the primary doping step, with the Ag element primarily being endogenously doped in the nanoporous Cr oxide support system as atoms or atomic clusters. The in situ exogenously doped nanoporous Ag particles performed the secondary doping step. The nanoporous Cr oxide was in a low-crystalline state.

[0248] The nanoporous Cr oxide composite powder material in situ endogenously doped with Ag was sand-milled for 2 hours. Because the nanoporous Cr oxide support and the in situ exogenously doped nanoporous Ag particles are loose and porous, the sand-milling process easily yielded a refined nanoporous Cr oxide composite powder material in situ endogenously doped with Ag. The nanoporous Cr oxide support had an average particle size of less than 300 nm, and the nanoporous Ag had an average particle size of less than 200 nm.

[0249] The nanoporous Cr oxide composite powder material in situ endogenously doped with Ag was heat treated at 650°C for 2 hours to obtain a nanoporous Cr oxide composite powder material primarily composed of in situ endogenously doped Ag nanoparticles. During the heat treatment, the Ag elements, present as atoms or atomic clusters, aggregated into Ag nanoparticles with an average particle size of 2nm-15nm. Simultaneously, the nanoporous ligaments coarsened to a thickness of approximately 50nm. The TEM morphology of the main component of the nanoporous Cr oxide composite powder material in situ endogenously doped with Ag nanoparticles after heat treatment is shown in Figure 12, where the dark granular material is the in situ endogenously doped Ag nanoparticles.

[0250] Example 5:

[0251] According to the ratio of Au and Nb atomic percentages of about 0.5% and 25% respectively (the balance is mainly Al), Al-Nb-Au alloy melt is melted; the alloy melt is heated to about 10 2 K / s~10 3 K / s cooling rate solidified into an Al-Nb-Au alloy plate with a thickness of about 2 mm. Its solidification structure is mainly composed of an average composition of about Al 74.7 Nb 25 Au 0.3 The intermetallic compound phase and the Au-rich Al2Au phase are composed, and the SEM image is shown in Figure 13, wherein the matrix phase is the Al3Nb(Au) intermetallic compound phase and the bright white phase is the Al2Au phase.

[0252] The Al-Cr-Au initial alloy plate prepared above was crushed into a powder with an average particle size of 100 μm. The alloy powder was then added to a 10 mol / L NaOH aqueous solution at room temperature for a dealloying reaction. After a 45-minute reaction, the solid product was collected, washed, and dried to obtain a nanoporous Nb oxide composite powder material in situ endogenously doped with Au nanoparticles. The in situ endogenously doped Au nanoparticles provided the primary doping of the nanoporous Nb oxide support, while the in situ exogenously doped nanoporous Au particles provided the secondary doping of the nanoporous Nb oxide support. The nanoporous Nb oxide was in a low-crystalline state. The TEM morphology of the main component of the nanoporous Nb oxide composite powder material in situ endogenously doped with Au nanoparticles is shown in Figure 14, where the dark granular material represents the in situ endogenously doped Au nanoparticles.

[0253] Example 6:

[0254] According to the ratio of Au and Mn atomic percentages of about 1.2% and 30% respectively (the balance is mainly Al), Al-Mn-Au alloy melt is melted; the alloy melt is heated to about 10 6 K / s~10 7 K / s cooling rate solidified into an Al-Mn-Au alloy strip with a thickness of 25 μm. Its solidification structure is mainly composed of an average composition of about Al 69 Mn 30 The intermetallic compound phase of Au1 is composed of the Au-rich Al2Au phase. Its SEM backscattered image is shown in Figure 15, in which the matrix phase is Al 69 Mn 30 Au1 intermetallic compound phase, and the bright white phase is Al2Au phase.

[0255] The Al-Mn-Au alloy ribbons prepared above were dealloyed with a 10 mol / L NaOH aqueous solution at room temperature. After a 30-minute reaction, the solid product was collected, washed, and dried to obtain a nanoporous Mn oxide composite powder material in situ endogenously doped with Au nanoparticles. The in situ endogenously doped Au nanoparticles provided the primary doping of the nanoporous Mn oxide support, with the Au nanoparticles having a particle size range of 2 nm to 20 nm and the nanoporous ribbons having a diameter range of 10 nm to 200 nm. The in situ exogenously doped nanoporous Au particles provided the secondary doping of the nanoporous Mn oxide support, with the in situ exogenously doped nanoporous Au particles having a particle size range of 200 nm to 100 μm and the nanoporous Au ribbons having a diameter range of 20 nm to 100 nm.

[0256] Example 7:

[0257] 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 Al3Ti(CuFe) intermetallic compound phase is composed of a Cu-rich Al(Cu) phase and an Fe-rich Al-Fe intermetallic compound phase, with the matrix phase being the Al3Ti(CuFe) intermetallic compound phase. Due to the rapid cooling rate of the melt, the Cu-rich Al(Cu) phase and the Fe-rich Al-Fe intermetallic compound phase are both nanoscale (20nm-500nm).

[0258] Under normal pressure, the Al-Ti-Cu-Fe alloy ribbons prepared above were added to 50 ml of a 10 mol / L, room-temperature KOH aqueous solution. After 30 minutes, the solid product was separated from the alkaline solution, washed, and dried to obtain a nanoporous potassium titanate composite powder material in situ endogenously doped with CuFe elements. The composite powder consists primarily of nanoporous potassium titanate in situ doped with Cu2O nanoparticles and Fe atoms, with the Cu2O nanoparticles ranging in size from 2 nm to 10 nm. Simultaneously, the Al(Cu) phase and the Al-Fe intermetallic compound phase undergo a conventional dealloying reaction, generating fine, in situ exogenously doped nanoporous Cu / Cu2O particles and nanoporous Fe / iron oxide particles. The porous ribbons range in size from 2 nm to 50 nm, and the in situ exogenously doped nanoporous Cu / Cu2O particles and nanoporous Fe / iron oxide particles range in size from 20 nm to 500 nm.

[0259] The technical features of the above-mentioned embodiments can be combined arbitrarily. 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.

[0260] 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 nanoporous composite powder material, characterized in that: It mainly consists of a nanoporous powder main component in situ endogenously doped with E1 element and an in situ exogenously doped E2 component; the nanoporous powder main component in situ endogenously doped with E1 element mainly consists of a nanoporous carrier and an in situ endogenously doped E1 element, and the components of the nanoporous carrier include at least one of nanoporous titanate, nanoporous titanic acid, and nanoporous oxide M; in the nanoporous oxide M, M contains at least one of Ti, Zr, Hf, Cr, V, Nb, Ta, W, Mo, Mn, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; the oxide M includes at least one of oxide M and hydroxide M; the nanoporous carrier mainly presents a "sponge-like" structure in terms of microstructure, and the solid part of the "sponge-like" structure is mainly composed of a three-dimensional continuous network of "ligaments"; The hollow part of its "sponge-like" structure is mainly composed of three-dimensional continuous network-like holes; the diameter range of the "lace" is 0.5nm-250nm; the diameter range of the hole is 0.5nm-300nm; 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 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 exactly 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 nanoporous composite powder material is V e2 , and 0≤V e2 ≤40%; the total molar number of E1 element C in the main component of the nanoporous powder doped with E1 element in situ e1 The ratio C to the total molar number C0 of Ti and M in the nanoporous support e1 / C0 satisfies: 0 <C e1 / C0<0.25; In the nanoporous powder main component in-situ endogenously doped with E1 elements, the in-situ endogenous doping method of the nanoporous carrier by E1 elements includes at least one of the following three methods: 1) The E1 element is in situ embedded in the "laces" of the nanoporous support, and the E1 element mainly dopes the "laces" of the nanoporous support in the form of atoms or atomic clusters, and the size of the atoms or atomic clusters of the E1 element is 0.2nm-2nm; 2) The E1 element is in situ embedded in the "laces" of the nanoporous carrier, and the E1 element mainly dopes the "laces" of the nanoporous carrier in the form of E1 nanoparticles; the size of the E1 nanoparticles is 2nm to 50nm; 3) The E1 element mainly exists in the form of E1 nanoparticles, and the E1 nanoparticles are adsorbed on the surface of the "tether" of the nanoporous carrier by physical adsorption and are simultaneously located in the pore space of the nanoporous carrier. The size of the E1 nanoparticles is 2nm-150nm; wherein the third doping method occurs simultaneously with the first or second doping method.

2. The in-situ endogenously doped nanoporous composite powder material according to claim 1, characterized in that: The average particle size of the in-situ endogenously doped nanoporous powder particles ranges from 201 nm to 500 um.

3. The in-situ endogenously doped nanoporous composite powder material according to claim 1, characterized in that: The average particle size of the in-situ endogenously doped nanoporous powder particles ranges from 5 nm to 200 μm.

4. The in-situ endogenously doped nanoporous composite powder material according to claim 1, characterized in that: 0<V e2 ≤40％。 5. The in-situ endogenously doped nanoporous composite powder material according to claim 1, characterized in that: The cations in the nanoporous titanate include at least one of Na, K, Li, Rb, Ba, Ca, and Sr.

6. The in-situ endogenously doped nanoporous composite powder material according to claim 1, characterized in that: The E1 element is in situ embedded in the nanoporous carrier. The E1 element is mainly used to dope the nanoporous 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 metal oxide nanoparticles.

7. The in-situ endogenously doped nanoporous composite powder material according to claim 1, characterized in that: The nanoporous carrier includes at least one of nanoporous titanate, nanoporous titanic acid, and nanoporous Cr oxide, and when the doping component E1 element is mainly composed of Ag, the E1 element mainly dopes the "ties" of the nanoporous carrier in the form of atoms or atomic clusters.

8. The in-situ endogenously doped nanoporous 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 10nm-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.

9. The in-situ endogenously doped nanoporous composite powder material according to claim 1, characterized in that: Prepared by the steps of: Step 1: Prepare an initial alloy, which mainly includes T elements, M elements and E elements; wherein the T elements include at least one of Al and Zn, the M elements include at least one of Ti, Zr, Hf, Cr, V, Nb, Ta, W, Mo, Mn, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, and the E elements include Au, Pt, Pd, Ru, Rh, Re, Os, At least one of Ir, Ag, Cu, Fe, Co, and Ni; the solidified structure of the initial alloy is mainly composed of an MTE intermetallic compound or an MT(E) intermetallic compound having an E-type element dissolved therein, and a TE phase; wherein the molar percentage content of the TE phase in the initial alloy is V0, and 0≤V0≤40%; the atomic percentage content of the E element in the TE phase is higher than the atomic percentage content of the E element in the MTE intermetallic compound or the MT(E) intermetallic compound having an E-type element dissolved therein; Step 2: reacting the initial alloy with an alkaline solution of a certain temperature and concentration, and adjusting the temperature and concentration of the alkaline solution. degree, so that during the hydrogen evolution and de-T reaction of the initial alloy and the alkaline solution, the reaction interface advances inward from the surface of the initial alloy at an average rate of less than 5 μm / min; during the reaction, the T-type elements in the initial alloy MTE intermetallic compound or the MT(E) intermetallic compound with the E-type element dissolved therein are mainly removed by the reaction and dissolved in the solution, the M-type elements are oxidized by the O element in the alkaline solution or combined with the O element in the alkaline solution to form a nanoporous support, and the E element is in situ endogenously generated in the ligaments of the nanoporous support to obtain a main component of the nanoporous powder in situ endogenously doped with the E1 element; at the same time, the TE phase in the initial alloy undergoes a traditional de-T reaction during the 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; Step 3: After the de-T reaction is completed, the solid reaction product in step 2 is collected to obtain the in-situ endogenously doped nanoporous composite powder material as described in claim 1, and its characteristics are as described in claim 1.

10. The method for preparing the in-situ endogenously doped nanoporous composite powder material according to claim 9, characterized in that: The in-situ endogenously doped nanoporous composite powder material prepared in step 3 is subjected to one or more modification treatments in 1) to 4) below to obtain more in-situ endogenously doped nanoporous composite powder materials with different characteristics: Modification treatment 1): When the nanoporous support is mainly composed of titanate, the cations thereof are replaced with H ions by reacting the nanoporous support with a dilute acid, thereby converting the titanate into titanic acid, thereby obtaining a titanyl support mainly composed of titanic acid; Modification treatment 2): When the E1 element is in situ embedded in the "bands" of the nanoporous support, and the E1 element mainly dopes the nanoporous support "bands" in the form of atoms or atomic clusters, a medium-low temperature heat treatment is performed to allow the E1 element to diffuse, agglomerate, nucleate and grow, and further transform into E1 nanoparticles to dope the nanoporous support "bands". At the same time, the diameter of the nanoporous support "bands" becomes thicker during the heat treatment, while the specific area decreases. Modification treatment 3): through medium-to-high temperature heat treatment, the titanate nanoporous support is transformed into a TiO2 nanoporous support, or the amorphous oxidized M nanoporous support is transformed into a crystalline oxidized M nanoporous support; Modification treatment 4): After the in-situ endogenously doped nanoporous composite powder material is refined, its particle size will be greatly reduced; the refinement treatment method includes at least one of sand milling, ball milling, and ultrasonic crushing.

11. Use of the in-situ endogenously doped nanoporous 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.

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

13. Use of the in-situ endogenously doped nanoporous composite powder material according to claim 1 in antibacterial fabrics.

Images