WO2024060821A1

WO2024060821A1 - In-situ endogenous doped nano-porous composite powder material and preparation method therefor and use thereof

Info

Publication number: WO2024060821A1
Application number: PCT/CN2023/108954
Authority: WO
Inventors: 赵远云
Original assignee: 赵远云
Priority date: 2022-09-23
Filing date: 2023-07-24
Publication date: 2024-03-28

Abstract

The present application relates to an in-situ endogenous doped nano-porous composite powder material and a preparation method therefor and a use thereof. The powder material has a two-stage compounding feature: first-stage compounding of a nano-porous carrier of an in-situ endogenous doped E1 element, which forms a nano-porous host component of the in-situ endogenous doped E1 element; and second-stage compounding of an in-situ exogenous doped E2 component and the nano-porous host component of the in-situ endogenous doped E1 element. The preparation method for the in-situ endogenous doped nano-porous composite powder material has the characteristics of simple process, easy operation, high efficiency and low cost, and has good application prospects in the fields of composite materials, ceramic materials, photocatalytic materials, hydrophobic materials, sewage degradation materials, sterilization materials, electronic materials, coatings and the like.

Description

In-situ endogenously doped nanoporous composite powder materials and preparation methods and uses thereof

Technical field

The invention relates to the technical field of nanomaterials, in particular an in-situ endogenously doped nanoporous composite powder material and its preparation method and use.

Background technique

Noble metal nanoparticles have obvious surface effects, volume effects, quantum effects, and small size effects, which lead to good optical, electronic, biological, and chemical properties. They have great application in the technical fields of catalysis, chemistry, biology, medicine, food, molecules, etc. Broad application prospects. Generally speaking, noble metal nanoparticles need to have good dispersion during application. In order to solve this problem, noble metal nanoparticles are generally compounded with nanoscale carriers, and the nanoscale carriers are used to disperse the noble metal nanoparticles for further applications.

At present, the method often used to composite noble metal nanoparticles and nanoscale carriers is the mixing method, that is, after preparing nanoscale carrier materials, the noble metal nanoparticles prepared by other methods are mixed with the above carrier materials to allow the noble metal nanoparticles to adsorb on the surface of the carrier material. This mechanical mixing-adsorption method is not only unfavorable to the physical-chemical interaction between the precious metal nanoparticles and the carrier material at the atomic scale, but also easily causes the precious metal nanoparticles to fall off on the surface of the carrier material, thereby causing the performance of the precious metal nanoparticles to deteriorate. Stability and deterioration. Therefore, it is of great significance to develop composite materials of noble metal nanoparticles and nanoscale carriers generated in situ.

Contents of the invention

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

On the one hand, an in-situ endogenously doped nanoporous composite powder material is characterized in that it mainly consists of a nanoporous powder main component with in-situ endogenous doping of the _E1 element and an in-situ exogenously doped nanoporous powder material. The main component of the nanoporous powder with in-situ endogenously doped _E1 element is mainly composed of a nanoporous carrier and an in _- situ endogenously doped _E1 element, and the composition of the nanoporous carrier The composition includes at least one of nanoporous titanate, nanoporous titanic acid, and nanoporous oxide M; in the nanoporous oxide M, M includes Ti, Zr, Hf, Cr, V, Nb, Ta, W, Mo , at least one of Mn, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; the oxidized M, Including at least one of oxidized M and hydroxidized M; the nanoporous carrier mainly has a "sponge-like" structure in its microstructure, and the physical part of its "sponge-like" structure is mainly composed of a three-dimensional continuous network-like "system". The void part of its "sponge-like" structure is mainly composed of a three-dimensional continuous network of holes; the diameter range of the "tie" is 0.5nm-250nm; the diameter range of the holes is 0.5nm-300nm ; The in-situ exogenously doped E ₂ component includes at least one of E ₂ nanoporous particles and E ₂ nanoparticles; both the E ₁ element and the E ₂ component are mainly composed of the E element, and E Elements include at least one of Au, Pt, Pd, Ru, Rh, Re, Os, Ir, Ag, Cu, Fe, Ni, and Co; when the E ₁ element or the E ₂ component includes two or more E element, the composition of E ₁ is not necessarily exactly the same as the composition of E ₂ ; the in-situ exogenously doped E ₂ component in the in-situ endogenously doped nanoporous composite powder material The molar percentage content is V _e2 , and 0 ≤ V _e2 ≤ 40%; in the main component of the nanoporous powder with in-situ endogenous doping of E ₁ element, the total number of moles of E ₁ element C _e1 and the nanoporous carrier The ratio C _e1 /C ₀ of the total moles of Ti and M in C ₀ satisfies: 0<C _e1 /C ₀ <0.25;

In the main component of the nanoporous powder in which the E ₁ element is endogenously doped in situ, the in situ endogenous doping method of the E ₁ element to the nanoporous carrier includes at least one of the following three methods:

1) The E ₁ element is embedded in-situ in the "tie" of the nanoporous carrier, and the E ₁ element mainly dopes the "tie" of the nanoporous carrier with atoms or atomic clusters, The size of the atoms or atomic clusters of the E ₁ element is 0.2nm-2nm;

2) The _E1 element is in-situ embedded in the "tie" of the nanoporous carrier, and the _E1 element is mainly doped with the "tie" of the nanoporous carrier in the form of _E1 nanoparticles; the size of the _E1 nanoparticles is 2nm to 50nm;

3) The E ₁ element mainly exists in the form of E ₁ nanoparticles, and the E ₁ nanoparticles are adsorbed on the surface of the nanoporous carrier "tie" by physical adsorption, and are located in the pores of the nanoporous carrier at the same time. In space, the size of the E ₁ nanoparticles is 2 nm-150 nm; wherein the 3) doping method appears simultaneously with the 1) or 2) doping method.

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

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

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

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

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

Further, the refining treatment method includes at least one of ultrasonic crushing, ball mill crushing, and sand grinding crushing;

After refinement,

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

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

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

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

Further, during the refining process, the in-situ exogenously doped E ₂ component is also refined at the same time, and its average particle size is also reduced at the same time;

Further, in the in-situ exogenous doped E ₂ component, the average particle size of the E ₂ nanoporous particles is 5 nm-50 μm, and the average diameter of the nano-porous belt is 2 nm-200 nm; the in-situ exogenous doped E 2 component In the doped E ₂ component, the average particle size of the E ₂ nanoparticles is 2 nm to 500 nm; further, the average particle size of the E ₂ nano particles is 2 nm to 200 nm.

Further, the "sponge-like" structure means that it is the same or similar to a strict sponge-like structure, which is mainly composed of "laces" in the solid part and holes in the void part, but the specific "laces" Characteristics of holes can be distinguished from standard sponge-like structures.

Further, the appearance of the ultrafine nanoporous powder particles doped with _E1 element endogenously in situ has fracture traces of crushing treatment; and the fracture traces are obtained by at least one of ultrasonic crushing, ball milling crushing, and sand grinding crushing. Caused by a variety of ways; the fracture trace characteristics include the traces of typical "sponge body" fractures under the action of ultrasonic crushing, ball milling, and sand grinding, such as fracture intersection edges and filament-like fracture morphology;

Further, the diameter range of the "frenulum" is 0.5nm-150nm; further, the diameter range of the "frenulum" is 0.5nm-100nm; further, the diameter range of the "frenulum" is 0.5 nm-50nm;

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

Further, 0<V _e2 ≤ 40%; further, 0 ≤ V _e2 ≤ 20%

Further, 0<V _e2 ≤25%; further, 0<V _e2 ≤20%;

Further, 0<C _e1 /C ₀ <0.20; further, 0<C _e1 /C ₀ <0.15; further, 0<C _e1 /C ₀ <0.10;

Further, the M mainly includes Ti;

Further, the M mainly includes at least one of Zr and Hf;

Further, the M mainly includes Cr, V, Nb, Ta, W, Mo, Mn, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, At least one of Yb and Lu;

Further, the M mainly includes at least one of Cr, V, Nb, Ta, W, and Mo;

Further, the M includes Mn;

Further, the M mainly includes at least one of Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu;

Further, the oxidation M comprises a mixture of one or more oxides of M with different valence states;

Further, the oxidation of M includes at least one of oxidation of M and hydration of M, because hydration of M is hydrated oxidation of M.

Further, the oxidized M includes different crystal forms of oxidized M, such as at least one of amorphous state, partially crystalline state, and crystalline state;

Further, the E element includes at least one of Cu, Ag, Fe, Ni, and Co;

Further, the E element mainly includes Ag; further, the E element mainly includes Cu; further, the E element mainly includes Fe;

Further, the E ₁ element includes at least one of Au, Pt, Pd, Ru, Rh, Re, Os, Ir, Ag, Cu, Fe, Ni, and Co;

Further, the E ₁ element includes at least one of Au, Pt, Pd, Ru, Rh, Os, Ir, and Re;

Further, the E ₁ element includes at least one of Cu, Ag, Fe, Ni, and Co;

Further, the _E2 element includes at least one of Au, Pt, Pd, Ru, Rh, Re, Os, Ir, Ag, Cu, Fe, Ni, and Co;

Further, the _E2 component comprises at least one of Au, Pt, Pd, Ru, Rh, Os, Ir, and Re;

Further, the _E2 element includes at least one of Cu, Ag, Fe, Ni, and Co;

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

Further, the cations in the nanoporous titanate include at least one of Na, K, Li, and Ba; further, the titanate includes sodium titanate, potassium titanate, lithium titanate, and titanate. At least one of barium;

Further, 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;

Further, the titanate, titanic acid, and oxidized M include titanate, titanic acid, and oxidized M in different crystal forms, such as at least one of amorphous state, partially crystalline state, and crystalline state;

Further, the crystalline oxidized M includes oxidized M of different crystal forms. For example, when the oxidized M is TiO ₂ , it includes at least one of anatase TiO ₂ and rutile TiO ₂ ;

Further, the size of the E ₁ nanoparticles is 2 nm to 20 nm; further, the size of the E ₁ nano particles is 2nm～15nm; further, the size of the E ₁ nanoparticles is 2nm～10nm;

Further, the E ₁ element is embedded in the nanoporous carrier in situ, the E ₁ element is mainly doped with E ₁ nanoparticles on the nanoporous carrier, and the E ₁ element includes Cu, Ag, When at least one of Fe, Ni, and Co is selected, the E ₁ nanoparticles include at least one of E ₁ metal nanoparticles and E ₁ metal oxide nanoparticles;

Further, the E ₁ metal oxide nanoparticles include CuO nanoparticles, Cu ₂ O nanoparticles, Ag ₂ O nanoparticles, FeO nanoparticles, Fe ₂ O ₃ nanoparticles, Fe ₃ O ₄ nanoparticles, and NiO nanoparticles. , at least one of CoO nanoparticles, Co ₂ O ₃ nanoparticles, and Co ₃ O ₄ nanoparticles;

Further, the in-situ endogenously doped nanoporous carrier of the E ₁ element and the in-situ exogenously doped E ₂ component are independently reacted and evolved from different precursor components through different reaction processes at the same time;

Further, the nanoporous carrier with in-situ endogenous doping of the E ₁ element is generated simultaneously with the in-situ exogenous doping of the E ₂ component;

Further, in the in-situ endogenously doped nanoporous composite powder material, the E element is compounded with the nanoporous carrier through a two-stage compounding method: first, the in-situ endogenously doped E ₁ element is compounded with the nanoporous carrier. The first level of recombination forms a nanoporous host component doped with in-situ endogenous E ₁ element; then the in-situ exogenously doped E ₂ component forms a nanoporous host component with in-situ endogenous doped E ₁ element. Secondary compounding of components;

Further, the in-situ exogenously doped E ₂ component is dispersed and softly agglomerated and wrapped by a nanoporous carrier in-situ endogenously doped with the E ₁ element;

Further, in-situ embedding in the in-situ endogenous doping method refers to E ₁ atoms or atomic clusters, or E ₁ nanoparticles being partially or fully embedded 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 nano-porous carrier and the doped E ₁ element during the formation process of the in-situ endogenous doped nano-porous carrier with E ₁ element. It does not It is impossible to rely on external addition or external mixing to embed the doped E ₁ element in the "tie" of the nanoporous carrier.

Further, the size of the atoms or atomic clusters of the E ₁ element is 0.2nm-2nm;

Further, the size of the atoms or atomic clusters of the E ₁ element is 0.2nm-1.5nm.

Further, when the E ₁ element is mainly composed of Ag, the E ₁ element is embedded in the nanoporous carrier in situ, and the E ₁ element mainly interacts with the nanoporous carrier in the form of E ₁ atoms or atomic clusters. The "tie" is doped, and the size of the E ₁ atom or atomic cluster is 0.2nm~2nm;

Further, the nanoporous carrier includes at least one of nanoporous titanate, nanoporous titanic acid, and nanoporous oxidized Cr, and when the doping component _E1 element is mainly composed of Ag, the _E1 element is mainly composed of atoms. Or atomic clusters are used to dope the "tie" of the nanoporous carrier.

Further, when the _E1 element is mainly composed of Cu, the _E1 element is in-situ embedded in the nanoporous carrier, and the _E1 element is mainly doped with the nanoporous carrier in the form of _E1 metal nanoparticles or (and) _E1 metal oxide nanoparticles, and the size of the _E1 metal nanoparticles or (and) _E1 metal oxide nanoparticles is 2nm to 20nm;

Further, the components of the E ₁ metal oxide nanoparticles include at least one of Cu ₂ O and CuO;

Further, when the E ₁ element is mainly composed of Au, the E ₁ element is embedded in the nanoporous carrier in situ, and the E ₁ element is mainly used to form E ₁ metal nanoparticles on the nanoporous carrier. Doping, the size of the E ₁ metal nanoparticles is 2nm ~ 20nm;

Further, when the nanoporous carrier is mainly composed of titanate, its cations are replaced by H ions by reacting with dilute acid, and the titanate is converted into titanic acid, thereby obtaining a nanoporous carrier mainly composed of titanic acid. Nanoporous carrier;

Further, in the dilute acid solution, the hydrogen ion concentration is lower than 0.1 mol/L;

Further, when the E ₁ element is mainly doped with the nanoporous carrier in the form of atoms or atomic clusters, the E ₁ element is allowed to grow through diffusion, agglomeration, and nucleation through heat treatment, and is further transformed into E ₁ nanometer Particles dope the nanoporous support.

Furthermore, because of the solid solution and pinning effect of E ₁ atoms or atomic clusters on the nanoporous carrier, when the E ₁ element mainly dopes the nanoporous carrier with atoms or atomic clusters, the nanoporous carrier will Phase change thermal stability is significantly improved;

Furthermore, when the _E1 element is doped with 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 with the undoped nanoporous support;

Further, the phase change of the nanoporous carrier is a phase change of titanic acid into TiO ₂ ;

Further, when the main component of the nanoporous carrier is at least one of titanate and titanic acid, its crystal form is mainly in a low crystalline state; when it is subjected to a certain degree of heat treatment, its crystallinity is further improved, There may even be a crystalline transformation, such as from titanic acid to anatase TiO ₂ , and then further to rutile TiO ₂ ;

Further, the strap diameter of the nanoporous carrier becomes thicker during the heat treatment process, and the specific area decreases at the same time;

Further, in the in-situ exogenously doped E ₂ component, the average particle diameter of the E ₂ nanoporous particles is 10 nm-50 μm, and the average diameter of the nanoporous belt is 2 nm-200 nm;

Further, in the in-situ exogenously doped E ₂ component, the average particle size of the E ₂ nanoporous particles is 10 nm-20 μm;

Further, in the in-situ exogenously doped E ₂ component, the average particle size of the E ₂ nanoporous particles is 10 nm-5 μm;

Further, in the in-situ exogenously doped E ₂ component, the average particle size of the E ₂ nanoporous particles is 10 nm-1 μm;

Further, in the in-situ exogenously doped E ₂ component, the average particle size of the E ₂ nanoparticles is 2 nm to 500 nm;

Further, in the in-situ exogenously doped _E2 component, the average particle size of the _E2 nanoparticles is 2nm to 250nm;

Furthermore, in the in-situ exogenously doped _E2 component, the average particle size of the _E2 nanoparticles is 2nm to 150nm.

Furthermore, the "in-situ" in the in-situ exogenously doped E ₂ component means that the exogenously doped E ₂ component is not related to the in-situ endogenously doped E ₁ element through external means. The main components of the nanoporous carrier are doped and mixed, but the two precursors exist adjacently at the same time (such as different phases in the solidified structure exist adjacently), and are generated adjacently in situ at the same time during a certain reaction process.

The E ₁ element and the E ₂ component are both mainly composed of the E element. When the E element includes only one element, the E ₁ element or the E ₂ component can only be this element. However, when the E ₁ element or E ₂ component includes two or more elements, the composition of E ₁ is not necessarily exactly the same as that of E ₂ ; for example, the E ₁ element or E ₂ component includes two single elements. elements, the ratio of two single elements in the E ₁ component is 1:4, and the ratio of the same two single elements in the E ₂ component may be 2:1.

Further, 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;

Further, when the _E2 element contains at least one of Cu, Ag, Fe, Ni, and Co, the components of the _E2 nanoporous particles include _E2 nanoporous metal particles and _E2 nanoporous metal oxide particles. at least one of;

Further, when the _E2 element contains 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. A sort of;

Further, the components of the E ₂ nanoporous metal oxide and E ₂ nanoporous metal oxide respectively include CuO, Cu ₂ O, Ag ₂ O, FeO, Fe ₂ O ₃ , Fe ₃ O ₄ , NiO, CoO, Co At least one of ₂ O ₃ and Co ₃ O ₄ .

In the 1) doping method,

When E ₁ atoms or atomic clusters are less than 2nm, it is difficult to observe the difference in contrast and aggregation of E ₁ atoms or atomic clusters in the nanoporous carrier "tie" through observation methods such as transmission electron microscopy (TEM); at this time, it can be considered The E ₁ element exists in solid solution in the nanoporous carrier "tie";

In the second) doping method,

The difference in contrast and aggregation of E ₁ nanoparticles in the nanoporous carrier "tether" can be observed through observation methods such as transmission electron microscopy (TEM);

Furthermore, when the E ₁ element is doped with the nanoporous carrier "tie" mainly in the form of atoms or atomic clusters, the E ₁ element is allowed to grow through diffusion, agglomeration, and nucleation through heat treatment, and is further transformed. In order to dope the nanoporous carrier "tie" in the presence of _E1 nanoparticles.

In the doping method mentioned in 3),

Since the nanoporous powder has a certain size, it is like a "sponge" containing a large number of network-like "tie-ups", and the E ₁ nanoparticles are also limited in the pore space inside the nanoporous powder; due to the E ₁ nano The particles and the nanoporous carrier are generated in situ at the same time. The E ₁ nanoparticles can be inside the three-dimensional continuous network of holes. Therefore, even after the E ₁ nanoparticles are generated in situ, they are adsorbed on the nanoporous carrier "tie" by physical adsorption. On the surface, it cannot easily detach from the pore space inside the nanoporous carrier; even if it detaches from the surface of a certain nanoporous carrier "tie", it will not detach after moving a short distance in the nanoporous pore space. It will be re-adsorbed on the surface of another nanoporous carrier "tie".

In its second aspect, a method for preparing an in-situ endogenously doped nanoporous composite powder material is characterized in that it is prepared by including the following steps:

Step 1, preparing an initial alloy, wherein the initial alloy mainly comprises T elements, M elements and E elements; wherein the T elements comprise at least one of Al and Zn, the M elements comprise 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 comprise at least one of Au, Pt, Pd, Ru, Rh, Re, Os, Ir, Ag, Cu, Fe, Co and Ni; the solidified structure of the initial alloy mainly consists of MTE intermetallic compounds or MT (E) intermetallic compounds containing E elements in solid solution, and TE phase; wherein the molar percentage content of TE phase in the initial alloy is V ₀ , and 0≤V ₀ ≤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 the E type element dissolved therein;

Step 2: react the initial alloy with an alkali solution of a certain temperature and concentration. By regulating the temperature and concentration of the alkali solution, during the hydrogen evolution and deT reaction between the initial alloy and the alkali solution, the reaction interface will be at an average value of less than 5 μm/min. The rate advances inward from the surface of the initial alloy; during the reaction process, the T elements in the initial alloy MTE intermetallic compounds or MT (E) intermetallic compounds with E elements in solid solution are mainly removed by the reaction and enter the solution to dissolve, M type The element is oxidized by the O element in the alkaline solution or combined with the O element in the alkaline solution to form a nanoporous carrier. At the same time, the E element is endogenized in situ in the straps of the nanoporous carrier, resulting in nanometers doped with in situ endogenous E ₁ element. The main component of porous powder; at the same time, the TE phase in the initial alloy undergoes a traditional de-T reaction during the reaction process to generate an in-situ exogenously doped E ₂ component; the E ₂ component includes E ₂ nanoporous particles , at least one of E ₂ nanoparticles; the E ₁ element and the E ₂ component are both mainly composed of the E element, and when the E ₁ element or the E ₂ component includes two or more elements, E ₁ The composition of ingredients is not necessarily exactly the same as that of E ₂ ;

Step 3: After the de-T reaction is completed, the solid reaction product in step 2 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-situ endogenously doped with _E1 element and an in-situ exogenously doped _E2 component; the nanoporous in-situ endogenously doped with _E1 element The main component of the powder 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 oxide M includes at least one of oxidized M and oxidized M; the nanoporous carrier is mainly "sponge-like" in microstructure, 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 three-dimensional continuous network 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 E _{The 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 completely the same as the composition of _E2 ; the molar percentage content of the in-situ exogenously doped _E2 component in the in-situ endogenously doped nanoporous composite powder material is _Ve2 , and _0≤Ve2≤40 %; in the main component of the nanoporous powder in-situ endogenously doped _E1 element, the ratio _Ce1/C0 of the total molar number Ce1 of the _E1 element to the total molar _number _C0 of _Ti and M in the nanoporous carrier satisfies: 0< _Ce1 / _C0 <0.25;

In the nanoporous powder main component in-situ endogenously doped with _E1 element, the in-situ endogenous doping method of _E1 element to the nanoporous carrier includes at least one of the following three methods:

2) The E ₁ element is embedded in-situ in the "tether" of the nanoporous carrier, and the E ₁ element is mainly doped with E ₁ nanoparticles to the "tether" of the nanoporous carrier; The size of the E ₁ nanoparticles is 2 nm to 50 nm;

3) The E ₁ element mainly exists in the form of E ₁ nanoparticles, and the E ₁ nanoparticles are adsorbed on the surface of the nanoporous carrier "tie" by physical adsorption, and are also located in the pores of the nanoporous carrier. In space, the size of the E ₁ nanoparticles is 2 nm-150 nm; wherein the 3) doping method appears simultaneously with the 1) or 2) doping method.

In step one,

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

Further, the M-type elements mainly include Ti;

Further, the M-type elements include at least one of Zr and Hf;

Further, 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;

Further, the M-type elements mainly include Mn;

Further, the M-type elements include at least one of Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu;

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

Further, the E-type elements mainly include Ag;

Further, the E-type elements mainly include Cu;

Further, the initial alloy is prepared by solidifying an alloy melt containing three types of elements: E, T, and M; the alloy solidification structure is mainly composed of M-T-E intermetallic compounds or M-T(E) intermetallic compounds with E-type elements dissolved in them. And T-E phase composition;

Further, the solidification rate of the initial alloy melt is 0.01K/s～10 ⁸ K/s;

Furthermore, when the content of E-type elements is low, generally E-type elements exist in solid solution in the M-T(E) intermetallic compound; among them, the M-T(E) intermetallic compound and the M-T intermetallic compound have almost the same properties. The crystal structure of the M-T(E) intermetallic compound is that E elements are solidly dissolved in it, and the solid solution method includes at least one of interstitial solid solution and substitutional solid solution;

Further, the main stoichiometric relationships of the MT (E) intermetallic compounds include MT ₄ , MT ₃ , M ₄ T ₁₁ , MT ₂ , M ₅ T ₈ , M ₃ T ₈ , M ₂ T ₃ , and MT in At least one.

Further, the MT (E) intermetallic compound can be a single phase, such as NbAl ₃ intermetallic compound with Au solid solution, (Nb-Ta) Al ₃ intermetallic compound with Au solid solution; it can also be different M Multiphase intermetallic compounds composed of sub-type elements and T-type elements, such as TaAl ₃ with Au in solid solution and YAl ₃ with Au in solid solution;

When the content of E-type elements is moderate, in some cases, in addition to existing in solid solution in M-T(E) intermetallic compounds, E-type elements can also form M-T-E intermetallic compounds, whose crystal structures are similar to those of M-T(E). ) The crystal structures of intermetallic compounds are different;

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

Further, the T-E phase includes at least one of a T-E intermetallic compound phase and a T(E) phase; wherein the T-E intermetallic compound is an intermetallic compound composed of T elements and E elements, and the T(E) phase is T(E) phase with E element in solid solution;

Further, in the initial alloy, the T(E) phase is composed of one or more sub-T(E) phases; for example: T is Al, E includes Ag, When Pt is used, the T(E) phase consists of Al ₃ Pt phase and Al(Ag) phase;

Further, the T(E) phase can be a T-E intermetallic compound phase, or it can be a T(E) phase of solid solution E element;

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

Further, the shape of the initial alloy includes at least one of block, granule, filament, strip, strip, and sheet;

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-dimensional directions;

Further, when the initial alloy is in the form of strips, it can be prepared by a method including a melt stripping method;

Further, 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.

In the second step,

Further, the temperature of the alkali solution is T ₁ and the concentration of the alkali solution is C ₁ ; generally speaking, the higher the temperature of the alkali solution and the higher the concentration of the alkali solution, the higher the reaction rate between the alkali solution and the initial alloy. .

At this time, the temperature T ₁ of the alkali solution and the concentration C ₁ of the alkali solution do not need to be specifically limited, as long as the combination of the two can ensure that the average rate of the reaction interface between the initial alloy and the alkali solution is less than 5 μm/min. Just push inward from the initial alloy surface.

Further, during the reaction between the initial alloy and the alkali solution, the reaction interface advances inward from the surface of the initial alloy at an average rate of less than 2 μm/min;

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

Further, the solvent in the alkaline solution contains water; preferably, the solvent in the alkaline solution is water;

Further, the concentration C ₁ of the alkali in the alkali solution is 0.25-30 mol/L; further, the concentration C ₁ of the alkali in the alkali solution is 0.25-20 mol/L; further, the alkali concentration C 1 in the alkali solution is 0.25-30 mol/L. Concentration C ₁ is 0.25~10mol/L;

Further, the concentration C ₁ of the base refers to the concentration of OH ^- in the base;

Further, the alkali in the alkali solution reacting with the initial alloy is an excessive dose;

Further, the temperature T ₁ of the alkali solution is the reaction temperature of the initial alloy and the alkali solution;

Further, T ₁ <100°C; further, T ₁ <85°C; further, T ₁ <75°C; further, T ₁ <60°C;

Further, when the alkali concentration C ₁ is higher, the high value of T ₁ can be a smaller value; when the alkali concentration C ₁ is lower, the high value of T ₁ can be a higher value;

Further, when 5.1mol/L≤C ₁ ≤30mol/L, T ₁ <60℃;

Further, when 5.1mol/L≤C ₁ <10.1mol/L, T ₁ <75°C;

Further, when 3mol/L≤C ₁ <5.1mol/L, T ₁ <85℃;

Further, when 1mol/L≤C ₁ <3mol/L, T ₁ <100℃;

Further, when 0.25mol/L≤C ₁ <1mol/L, 100℃<T ₁ ≤T _{f boiling point} ; where, T _{f boiling point} is the boiling point temperature of the alkali solution at the alkali concentration;

Since T-type elements (Al, Zn) are amphoteric metals, they can react with OH ^- in an alkaline solution to become salts containing T-type elements, and dissolve in the alkaline solution while releasing hydrogen; therefore, T-type elements can react with The alkaline solution reaction removes T from the MTE intermetallic compounds in the initial alloy or the MT(E) intermetallic compounds with E-type elements in solid solution. At the same time, the remaining M-type elements and E-type elements further interact with the alkaline solution and occur simultaneously. A series of changes, that is, the M-type elements are oxidized by the O element in the alkaline solution or combined with the O element in the alkaline solution, and the E-type elements are endogenously doped in situ, resulting in nanometers with in-situ endogenous doping of E _1- type elements. Porous powder main component.

Furthermore, when the M elements in the original initial alloy mainly contain Ti, the composition of the nanoporous carrier is mainly titanate, and the cations of the titanate are consistent with the cations in the alkaline solution; that is, the initial alloy reacts with the alkaline solution to remove In addition to T-type elements (T-type elements enter the solution and are dissolved), M-type elements are combined with O elements in the alkaline solution, while E-type elements are endogenously doped in situ, generating in-situ endogenously doped E _1- type elements. Nanoporous titanate main component;

When the M-type elements in the original initial alloy mainly do not contain Ti, the composition of the nanoporous carrier is mainly nano-oxidized M; that is, the initial alloy reacts with the alkali 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 The elements are oxidized by the O element in the alkaline solution to generate a nanoporous oxidized M carrier, while the E elements are endogenously doped in-situ in the nanoporous oxidized M carrier; among them, M includes Zr, Hf, Cr, V, Nb, Ta, and W , at least one of Mo, Mn, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu;

Furthermore, in-situ embedding in the in-situ endogenous doping method refers to E ₁ atoms or atomic clusters, or E ₁ nanoparticles being partially wrapped or fully embedded in the nanoporous carrier through in-situ embedding. In the "tie"; this kind of in-situ embedding is the process of forming the main component of the nano-porous carrier doped with E ₁ element endogenously in situ. The nano-porous carrier and the doped E ₁ element are simultaneously generated in situ and The result of in-situ recombination does not rely on and cannot rely on external addition or external mixing to embed the doped E ₁ element in the nanoporous carrier.

The partial encapsulation means that part of the volume of _E1 nanoparticles is embedded in the nanoporous carrier "tie", and the other part of the volume of _E1 nanoparticles is outside the nanoporous carrier "tie";

The root cause of the in-situ endogenous doping is that in the precursor, the E element is solidly dissolved as atoms in the MTE intermetallic compound. Or solid solution in MT(E) intermetallic compounds. When the reaction evolution occurs in the MTE intermetallic compound or the MT(E) intermetallic compound, the E element still exists in the reaction product, and is thus endogenously doped in the form of atoms or atomic clusters in the main component of the nanoporous carrier product. middle.

Further, 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, E ₁ in the nanoporous carrier with in-situ endogenous doping of E ₁ element The elements mainly dope the nanoporous carrier "tie" with 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 carrier is titanium At least one of acid salt, chromium oxide, and chromium hydroxide;

Furthermore, when the initial alloy reacts with an alkali solution, the T-E phase mainly undergoes the traditional de-T reaction;

Under the traditional T removal reaction, when the atomic percentage content of the E element in the TE phase is high, such as higher than 20%, it mainly generates E ₂ nanoporous particles, and the shape of the E ₂ nanoporous particles is similar to the TE in the original initial alloy. The shapes of the phases are similar; when the E element is mainly at least one of Cu, Fe, Ni, and Co, the composition of the generated E ₂ nanoporous particles is mainly at least one of the metals and metal oxides of these elements. ;

Under the traditional de-T reaction, when the content of E element in 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 TE phase; when E element is mainly at least one of Cu, Fe, Ni, and Co, the components of the generated _E2 nanoparticles are mainly at least one of the metals and metal oxides of these elements;

It can be understood that when the content of E element in the TE phase is low, its dealloying product is difficult to maintain the shape and size of the TE phase and generate stable E ₂ nanoporous particles, and its dealloying product easily generates fragmented E ₂ nanoparticles .

Since the _E2 nanoparticles are not embedded in the main component of the nanoporous carrier, but are generated separately at the same time, after their formation, they have a certain short-range movement ability in the nanoporous carrier. Therefore, after their in-situ generation, they are smaller The E ₂ nanoparticles may aggregate and grow into larger E ₂ nanoparticles; especially when the reaction temperature is maintained for a long time, or after annealing, this aggregation phenomenon is more obvious;

Further, when the E ₂ element includes at least one of Cu, Ag, Fe, Ni, and Co, the composition of the E ₂ nanoparticles includes at least one of E ₂ nanometal particles and E ₂ nanometal oxide particles;

Further, the components of the E ₂ nanoporous metal oxide and E ₂ nanometal oxide respectively include CuO, Cu ₂ O, At least one of Ag ₂ O, FeO, Fe ₂ O ₃ , Fe ₃ O ₄ , NiO, CoO, Co ₂ O ₃ and Co ₃ O ₄ .

Further, when the E ₂ includes two or more elements, the E ₂ component may be mainly one component particle, or may include multiple sub-component particles; for example: when the E ₂ element includes Ag and Au, The E ₂ component is mainly AgCu nanoporous particles; when the E ₂ element contains Ag and Pt, the E ₂ component includes two sub-component particles, Ag nanoporous particles and Pt nanoporous particles;

Further, by adjusting the values of T ₁ and C ₁ , during the reaction between the initial alloy and the alkali solution, the reaction interface advances inward from the surface of the initial alloy at an average rate of less than 5 μm/min; at this reaction rate, because the reaction is slow The reason for the generation of hydrogen is that the reaction product may undergo some preliminary fragmentation, but it is difficult to achieve complete nano-fragmentation;

Furthermore, when the initial alloy is larger or thicker, such as the thickness and particle size exceed 2um, or even reaches the millimeter level, the initial alloy reacts with the alkali solution layer by layer, the reaction interface expands inward, and the reaction product of the initial alloy forms nanometer Porous structure; under the expansion of hydrogen generated by the slow reaction and the convection of the solution, the generated nanoporous product will undergo a certain degree of preliminary fragmentation, producing nanoporous main component powder particles with an average particle size of no more than 500 μm; however, this The degree of fragmentation is weak, so that the average particle size of the nanoporous powder particles after preliminary fragmentation still exceeds 201nm;

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 μm can be obtained.

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

Modification treatment 1): When the nanoporous carrier is mainly composed of titanate, its cations are replaced by H ions by reacting with dilute acid, and the titanate is converted into titanic acid, thereby obtaining a material mainly composed of titanic acid. A titanium-based carrier composed of;

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 carrier changes into a titanate nanoporous carrier;

Modification treatment 2): When the E ₁ element is embedded in the "tie" of the nanoporous carrier in situ, and the E ₁ element mainly "ties" the nanoporous carrier as atoms or atomic clusters "When doping, through medium and low temperature heat treatment, the E ₁ element grows up through diffusion, agglomeration, and nucleation, and is further transformed into E ₁ nanoparticles to dope the nanoporous carrier "tie"; at the same time, the The diameter of the nanoporous carrier "tie" becomes thicker during the heat treatment process, and the specific area decreases at the same time;

Modification treatment 3): Through medium-high temperature heat treatment, the titanate nanoporous carrier is transformed into a TiO ₂ nanoporous carrier, or the amorphous oxidized M nanoporous carrier is transformed into a crystalline oxidized M nanoporous carrier;

Furthermore, because of the solid solution and pinning effect of E ₁ atoms or atomic clusters on the "tethering" of the nanoporous carrier, when the E ₁ element mainly uses atoms or atomic clusters to "tether" the nanoporous carrier "When doping, the nanoporous carrier The phase transition thermal stability of the "tie" is significantly improved; furthermore, compared with the "tie" of the undoped nanoporous carrier, the phase transition temperature of the "tie" doped with the nanoporous carrier is increased by 100 °C or above; during the phase transformation process of the nanoporous carrier, the in-situ endogenous E ₁ atoms or atomic clusters grow up through diffusion, agglomeration, and nucleation, and are further transformed into E ₁ nanoparticles on the nanoporous carrier after the phase change. Doping; further, the phase change of the "tie" of the nanoporous carrier is a phase change of titanic acid into TiO ₂ ;

Furthermore, when the main component of the nanoporous carrier is at least one of titanate and titanic acid, its crystal form is in a low crystalline state. After a certain degree of heat treatment, its crystallinity is further improved, and even crystallization occurs. Type transformation, such as from titanic acid to anatase TiO ₂ , and then further to rutile TiO ₂ ;

During the above three modification processes, the in-situ exogenously doped E ₂ 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 tie becomes thicker and the specific surface area become smaller.

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

Further, the refining treatment method includes at least one of sand grinding treatment, ball milling treatment, and ultrasonic crushing treatment;

Furthermore, the refinement treatment method includes sanding treatment;

Among all the refining treatment methods, sanding treatment has the best refining effect, which can fully refine the in-situ endogenously doped nanoporous composite powder materials;

After refinement,

Further, in the in-situ exogenous doped E ₂ component, the average particle size of the E ₂ nanoporous particles is 5 nm-50 μm, and the average diameter of the nano-porous belt is 2 nm-200 nm; the in-situ exogenous doped E 2 component In the doped E ₂ component, the average particle size of the E ₂ nanoparticles is 2 nm to 500 nm; in the in-situ exogenously doped E ₂ component, the average particle size of the E ₂ nano particles is 2 nm to 200 nm.

In its third aspect, the present invention also relates to the in-situ endogenously doped nanoporous composite powder material described in any one of the first aspect to the second aspect or the in-situ endogenously doped nanoporous composite powder material prepared by the preparation method. Composite powder materials are used in composite materials, ceramic materials, photocatalytic materials, hydrophobic materials, sewage degradation materials, sterilization materials, electronic materials, and coatings.

Further, the coatings include antibacterial coatings, anticorrosive coatings, ship coatings, and marine coatings;

Further, the composite materials include polymer-based nanocomposites and resin-based composite materials;

The specific application method includes: mixing the nanoporous composite powder material with in-situ endogenous doping of _E1 element and a polymer to prepare a nanoporous composite powder material with in-situ endogenous doping of _E1 element and polymer. composite coating;

Further, the polymer includes at least one of polymer materials, resin materials, and coatings;

Further, the E ₁ element includes at least one of Au, Pt, Pd, Ru, Rh, Re, Os, Ir, Ag, Cu, Fe, Ni, and Co; further, the E ₁ element includes Cu, Ag , at least one of Fe;

In its fourth aspect, the present invention also relates to the in-situ endogenously doped nanoporous composite powder material described in any one of the first aspect to the second aspect or the in-situ endogenously doped nanoporous composite powder material prepared by the preparation method. Composite powder materials are used in home decoration coatings, germicidal sprays, and antifouling coatings.

As an application for home decoration paint, it is characterized in that the above-mentioned nanoporous composite powder material doped with _E1 element endogenously in situ is used as a paint additive on the surface of furniture, utensils, and walls after being mixed with other components of the paint. Coating to achieve antibacterial effect;

The application as a sterilizing spray is characterized in that the above-mentioned nanoporous composite powder material doped with _E1 element endogenously in situ is mixed with other liquid spray components and sprayed together on furniture and utensils through a spray carrier , fabrics, and wall surfaces to achieve antibacterial effects;

As an application of antifouling paint, it is characterized by replacing the _bactericidal antifouling component ( Such as cuprous oxide powder) to achieve antifouling effect;

Further, the E ₁ element includes at least one of Au, Pt, Pd, Ru, Rh, Re, Os, Ir, Ag, Cu, Fe, Ni, and Co; further, the E ₁ element includes Cu, Ag , at least one of Fe.

In its fifth aspect, the present invention also relates to the in-situ endogenously doped nanoporous composite powder material described in any one of the first aspect to the second aspect or the in-situ endogenously doped nanoporous composite powder material prepared by the preparation method. Composite powder materials, application in antibacterial fabrics;

Further, it is characterized in that after the above-mentioned nanoporous composite powder material with in-situ endogenous doping of _E1 element is dispersed, it is attached or coated on the surface of the fabric, or mixed with the fabric, so that Fabrics have antibacterial and sterilizing effects and capabilities;

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

First, a nanoporous composite powder material with in-situ endogenous doping having a porous structure is 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, the present application, through a special and ingenious design, can not only obtain an ultrafine nanoporous powder with an average particle size of less than 500nm of in-situ endogenous doping _E1 element, but also the obtained powder is not a solid powder, but a three-dimensional network-like "sponge-like" nanoporous ultrafine powder mainly composed of nanoporous carrier "tie" and holes inside the main component. In order to achieve this goal, first, through the ingenious alloy design of step one and the ingenious reaction condition design of step two, a nanoporous composite coarse powder with in-situ endogenous doping _E1 element is prepared, and its interior is mainly composed of nanoporous carrier "tie" and doped _E1 element. Specifically, by controlling the concentration of the alkaline solution and the reaction temperature, the reaction rate is lower than 5μm/min, so that only a limited initial fragmentation of the product occurs, and a nanoporous microstructure is generated. Then, through refinement treatment technology, such as sand milling, an ultrafine nanoporous composite powder material with an average particle size of less than 250nm or even less than 150nm in situ endogenously doped with _E1 elements can be obtained.

The combination of this nanoporous structure and in-situ endogenous doping of _E1 elements has many advantages. For example, if the composite powder carrier is a nanoporous powder with three-dimensional network porous holes, even if the physically adsorbed _E1 nanoparticles are detached from the surface of a certain nanoporous carrier "tie", they will appear to be trapped in the porous The "maze" composed of holes is generally re-adsorbed on the surface of another nanoporous carrier "tie", so that the _E1 nanoparticles are always confined in the three-dimensional network of porous holes. When the E ₁ element or E ₁ nanoparticle is in-situ embedded in the nanoporous three-dimensional network-like "tie", the E ₁ element or E ₁ nanoparticle and its carrier are in the best composite state, and E ₁ Elemental atoms/atom clusters or _E1 nanoparticles cannot move freely.

In addition, the porous structure of the nanoporous composite powder material with in-situ endogenous doping of the E ₁ element can also utilize the channels formed by the three-dimensional network of porous holes to produce more excellent properties. For example, other nanoscale powders, or liquids/gases that can enter the three-dimensional network porous holes are allowed to enter, thereby further compounding with the nanoporous carrier "tie" and E ₁ elements (or E ₁ nanoparticles) or reaction to obtain more excellent properties.

Second, the in-situ endogenous doping of the E ₁ element in the nanoporous powder carrier "tie" is achieved. In-situ embedding in the in-situ endogenous doping method refers to E ₁ atoms/atom clusters, or E ₁ nanoparticles being partially or fully embedded in the "tie" of the nanoporous carrier through in-situ embedding. Medium; This kind of in-situ embedding is the process of forming the nano-porous powder carrier with in-situ endogenous doping of E ₁ element. The nano-porous carrier and the in-situ endogenous doped E ₁ element are simultaneously generated in situ. The result of in-situ compounding is that it does not and cannot rely on external addition or external mixing to embed the doped E ₁ element in the "tie" of the nanoporous carrier. This kind of in-situ endogenous doping solves the problem in one fell swoop that the traditional mechanical mixing-adsorption method is not only unfavorable for the physical-chemical interaction between the doped nanoparticles and the carrier material at the atomic scale, but also easily causes the doped nanoparticles to form in the carrier material. The problem of surface shedding, which causes instability and deterioration of the performance of doped nanoparticles, is of great significance. Moreover, the nanoporous carrier serves as a carrier, matrix, and dispersion, and the E ₁ element is doped as a key functional element. When it exists in "solid solution" in the nanoporous carrier in the form of E ₁ atoms or atomic clusters, almost all doping _E1 atoms can fully exert their functional applications, thus greatly reducing the amount of doped _E1 elements. For example, Ag nanoparticles in the current industry can generally be used as sterilization materials, and nano titanate, nano titanic acid, and nano oxide M that are mechanically mixed with them can generally be used as their carriers. Since the Ag that plays a bactericidal role is mainly Ag atoms on the surface of Ag nanoparticles, it causes a certain waste of performance of Ag atoms inside the Ag nanoparticles and increases the cost. Moreover, physically adsorbed Ag nanoparticles are easy to fall off from the carrier, resulting in unstable performance and poor performance durability. The present invention creatively realizes the in-situ endogenous incorporation of Ag into the nanoporous carrier in the form of atoms or atomic clusters. Not only does it not have to worry about the shedding of Ag, but it can also maximize the utilization of Ag, which is extremely beneficial. significance.

Third, a nanoporous composite powder material with in-situ endogenous doping with two-level composite characteristics was creatively invented. Doping elements or doping nanoparticles play a very important and positive role in the functional applications of nano-titanate, nano-titanate, and nano-oxide M. By controlling the solidification rate of the initial alloy melt, nanoscale TE phases can be obtained when the cooling rate is extremely high. By reacting with an alkali solution, the nanoscale TE phase can become nanoscale _E2 nanoporous particles or _E2 nanoparticles, which are formed by mixing with the main component of the nanoporous carrier endogenously doped with the _E1 element in situ. Porous composite powder materials can have different composite physical and chemical properties at the same time. For example, the nanoporous titanate composite powder material prepared in Example 2 with in-situ endogenous doping of Ag(Pt) element can not only utilize in-situ endogenous doping of Ag(Pt) element as a sterilization component. Application, at the same time, the in-situ exogenously doped nanoporous Pt also has formaldehyde catalytic-oxidation performance. When the two components are combined, they will have extremely excellent composite physical-chemical properties.

Fourth, when the E ₁ element is mainly used to dope the nanoporous carrier "tie" with atoms or atomic clusters, the phase change of the nanoporous carrier is also greatly improved due to the pinning effect of the E ₁ element. Thermal stability, which improves the phase transition thermal stability of nanoporous carriers by more than 100°C, has great application significance.

Therefore, the preparation method of the present invention has the characteristics of simple process, easy operation, high efficiency and low cost, and can prepare a variety of in-situ endogenously doped nanoporous composite powder materials. Materials, ceramic materials, photocatalytic materials, hydrophobic materials, sewage degradation materials, sterilizing coatings, anti-corrosion coatings, marine coatings and other fields have good application prospects.

Description of the drawings

Figure 1 is an SEM backscattered image of the initial alloy solidification structure described in Example 1;

Figure 2 is a low-magnification secondary electron SEM image of the nanoporous composite powder material in-situ endogenously doped with CuAu nanoparticles described in Example 1;

Figure 3 is a low-magnification backscattered SEM image of the nanoporous composite powder material in-situ endogenously doped with CuAu nanoparticles described in Example 1;

Figure 4 is an SEM image of nanoporous Au in the nanoporous composite powder material with in-situ endogenous doping of CuAu nanoparticles as described in Example 1;

Figure 5 is a medium magnification SEM backscattered image of the nanoporous composite powder material in-situ endogenously doped with CuAu nanoparticles described in Example 1;

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

Figure 7 is a low-magnification SEM image of the initial alloy solidification structure described in Example 2;

Figure 8 is a high-magnification SEM image of the initial alloy solidification structure described in Example 2;

Figure 9 is an SEM backscattered image of the nanoporous titanate composite powder material in-situ endogenously doped with Cu/Cu ₂ O nanoparticles as described in Example 3;

Figure 10 is a high-magnification SEM image of the main component of the nanoporous titanate composite powder material in-situ endogenously doped with Cu/Cu ₂ O nanoparticles as described in Example 3;

FIG11 is a low-magnification SEM image of the initial alloy solidification structure described in Example 4;

Figure 12 is a TEM morphology of the main component of the nanoporous oxidized Cr composite powder material in-situ endogenously doped with Ag element after heat treatment as described in Example 4;

Figure 13 is a low-magnification SEM image of the initial alloy solidification structure described in Example 5;

Figure 14 is the TEM morphology of the main component of the nanoporous oxidized Nb composite powder material with in-situ endogenous doping of Au nanoparticles described in Example 5;

Figure 15 is a low-magnification SEM image of the solidification structure of the initial alloy described in Example 6.

Detailed ways

Below, the technical solution will be further explained through the following specific examples:

Embodiment 1:

The Al-Ti-Au-Cu alloy melt is melted according to the ratio of Au, Cu, and Ti atomic percentages of approximately 2.5%, 2.5%, and 23.5% respectively (the balance is mainly Al); The cooling speed of 100K/s solidifies into a thickness of 5mm. The solidification structure of the Al-Ti-Au-Cu alloy plate is mainly composed of three types with different average compositions: Al ₇₄ Ti ₂₅ Cu _0.5 Au _0.5 , Al _72.5 Ti ₂₄ Cu ₂ Au _1.5 , and Al _71.5 Ti ₂₃ Cu ₃ Au _2.5. The Al ₃ Ti (CuAu) intermetallic compound with solid solubility of Cu and Au is composed of an Al ₂ Au phase with a composition of approximately Al ₇₀ Au _30. Its SEM backscattered image is shown in Figure 1, in which the three gray colors indicated by the arrows , the black phase is Al ₃ Ti (CuAu) intermetallic compound.

The Al-Ti-Au-Cu initial alloy plate prepared above was crushed into powder with an average particle size of 100 μm, and then it was dealloyed with a NaOH aqueous solution with a concentration of 10 mol/L and a temperature of room temperature. After reacting for 40 minutes, the solid product was collected, washed and dried to obtain a nanoporous composite powder material with in-situ endogenous doping of CuAu nanoparticles. Among them, the in-situ endogenous doping of CuAu nanoparticles has a negative impact on the nanoparticles as the main component. The porous sodium titanate carrier is doped in the first level, while the in-situ exogenously doped nanoporous Au particles perform the second-level doping of the nanoporous sodium titanate carrier 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 of the nanoporous sodium titanate composite powder material doped with CuAu nanoparticles endogenously in situ is consistent with The backscattered SEM images are shown in Figures 2 and 3. The high-magnification and high-magnification backscattered SEM images are shown in Figures 5 and 6. The morphology of nanoporous Au is shown in Figure 4; Figure 2, Figure 3, Figure 5 The white appearance in the center is the nanoporous Au particles. Figure 6 shows the morphology of the nanoporous sodium titanate carrier and the CuAu nanoparticles in-situ endogenously doped in the nanoporous sodium titanate carrier. The particle size of the in-situ endogenously doped CuAu nanoparticles is 2nm-20nm, and the nanoporous sodium titanate carrier has a "sponge-like" structure.

The above-mentioned nanoporous sodium titanate composite powder material endogenously doped with CuAu nanoparticles is reacted with a 0.015 mol/L HCl solution, so that the nanoporous sodium titanate carrier is transformed into a nanoporous titanate carrier, and the solid-liquid separation is carried out. , clean and dry to obtain a nanoporous titanate composite powder material with in-situ endogenous doping of CuAu nanoparticles, and the particle size of the in-situ endogenous doped CuAu nanoparticles is 2 nm-20 nm.

The nanoporous titanate composite powder material of the in-situ endogenously doped CuAu nanoparticles is sand-milled for 2 hours. Since the nanoporous titanate carrier and the nanoporous Au particles are loose and porous, it is easy to obtain the refined ultrafine nanoporous titanate composite powder material of the in-situ endogenously doped CuAu nanoparticles by sand-milling. After refinement, the average particle size of the nanoporous titanate carrier is less than 300nm, and the average particle size of the exogenously doped nanoporous Au particles is less than 200nm. The particle size of the in-situ endogenously doped CuAu nanoparticles is 2nm-20nm.

The above-mentioned ultra-fine nanoporous titanate composite powder material doped with CuAu nanoparticles endogenously in situ is heat-treated at 700°C for 2 hours to obtain nanoporous anatase TiO ₂ mainly composed of endogenously doped CuAu nanoparticles in situ. In the composite powder composed of in-situ exogenously doped nanoporous Au particles, the band size of the nanoporous carrier is significantly increased and the specific surface area is significantly reduced. The particle size of the in-situ endogenously doped CuAu nanoparticles is 2 nm-50 nm.

Example 2:

Melt the Al-Ti-Ag-Pt alloy melt according to the ratio of Ag, Pt, and Ti atomic percentages of approximately 0.55%, 0.20%, and 24.5% respectively (the balance is mainly Al); The cooling rate is 10 ⁶ K/s ~ 10 ⁷ K/s and solidifies into a layer with a thickness of 25 μm. The solidification structure of the Al-Ti-Ag-Pt alloy strip is mainly composed of an Al ₃ Ti (AgPt) intermetallic compound phase with an average composition of approximately Al ₇₄ Ti _24.5 Ag _0.5 Pt _0.05 and an Ag-rich Al (Ag) phase. Pt is composed of Al-Pt intermetallic compound phase. Its SEM secondary electron image is shown in Figure 7-8. The matrix phase is Al ₃ Ti (AgPt) intermetallic compound phase, and the nanoscale (10nm-250nm) bright white The particle phases are Ag-rich Al(Ag) phase and Pt-rich Al-Pt intermetallic compound phase.

The Al-Ti-Au-Cu initial alloy strip prepared above was subjected to a dealloying reaction with a NaOH aqueous solution with a concentration of 8 mol/L and a temperature of room temperature. After reacting for 25 minutes, the solid product was collected, washed and dried to obtain a nanoporous sodium titanate composite powder material in-situ endogenously doped with Ag (Pt) element. Among them, the in-situ endogenously doped Ag(Pt) element performs the first-level doping of the nanoporous sodium titanate carrier. The molar ratio of Ag to Pt in Ag(Pt) is about 10:1, and the Ag(Pt) element It is mainly endogenously doped in the nanoporous sodium titanate carrier system in the form of atoms or atomic clusters; while the in-situ exogenous doped nanoporous Pt particles and nanoporous Ag particles are doped in the nanoporous sodium titanate carrier system. Perform second level doping. Since the sizes of nanoporous Pt particles and nanoporous Ag particles are similar to the sizes of the Al(Ag) phase and Al-Pt intermetallic compound phase in the initial alloy strips, the nanoporous Pt particles and nanoporous Ag particles are also nanosized. level (10nm-250nm).

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

The above-mentioned nanoporous titanate composite powder material in-situ endogenously doped with Ag (Pt) element was sanded for 2 hours. Since the nanoporous titanate carrier and the in-situ exogenously doped nanoporous Pt particles and nanoporous Ag particles It is loose and porous, so the refined nanoporous titanate composite powder material in-situ endogenously doped with Ag (Pt) element can be easily obtained by sanding. Among them, the average particle size of the nanoporous titanate carrier is less than 300 nm, and the particle size range of the nanoporous Pt particles and the nanoporous Ag particles is 10 nm-200 nm.

After the above-mentioned sand grinding treatment, the refined in-situ endogenously doped nanoporous titanate composite powder material with Ag (Pt) element is mixed with PDMS (polydimethylsiloxane), and then is obtained according to the coating preparation method. Nanoporous titanate-PDMS composite coating containing doped Ag(Pt). In this coating, the Ag (Pt) element is dispersed in an ultra-fine nanoporous titanate carrier in the form of atoms or atomic clusters, and the ultra-fine nanoporous titanate carrier is dispersed in PDMS, which can maximize utilization The bactericidal properties of the Ag(Pt) element resulted in an Ag(Pt)-PDMS composite coating with excellent mechanical properties, hydrophobic properties and bactericidal properties.

The Ag(Pt)-PDMS composite coating material can be used in fields including hydrophobic materials, wood antisepsis and sterilization materials, photocatalytic materials, sterilization coating materials, marine equipment and ship coatings.

The refined in-situ endogenously doped nanoporous titanate composite powder material with Ag (Pt) element,

Application as home decoration coating: The above-mentioned refined nanoporous titanate composite powder material doped with Ag (Pt) element endogenously in situ is used as a coating additive on the surface of furniture, utensils, and walls, mixed with other components of the coating. Then paint them together. Achieve antibacterial effect; at the same time, the exogenously doped nanoporous Pt particles in the composite powder material also have excellent catalytic properties, which are also of great significance for the catalytic-oxidative removal of formaldehyde.

Application as a sterilizing spray: Mix the above-mentioned refined in-situ nanoporous titanate composite powder material doped with Ag (Pt) element with other liquid spray components, and spray them together on the furniture through a spray carrier , utensils, fabrics, and wall surfaces to achieve antibacterial effects;

Application as antifouling coating: The above-mentioned refined nanoporous titanate composite powder material in-situ endogenously doped with Ag (Pt) element is used to replace the bactericidal and antifouling components in traditional antifouling coatings to achieve antifouling. Effect;

Application as an antibacterial fabric: After the above-mentioned refined in-situ nanoporous titanate composite powder material doped with Ag (Pt) element is dispersed, it can be attached to or coated on the surface of the fabric, or mixed with the fabric. Together, the fabric has antibacterial and bactericidal effects and capabilities.

Embodiment 3:

Melt the Al-Ti-Cu alloy melt according to a ratio of Cu and Ti atomic percentages of approximately 4% and ^24.5 % respectively (the balance is mainly Al); An Al-Ti-Cu alloy plate with a thickness of about 2 mm is solidified at a cooling rate of ³ K/s. Its solidified structure is mainly composed of an Al ₃ Ti (Cu) intermetallic compound phase with an average composition of about Al ₇₃ Ti ₂₄ Cu ₃ and a rich The Al ₂ Cu phase composition of Cu.

The Al-Ti-Cu initial alloy plate prepared above was crushed into powder with an average particle size of 200 μm, and the Al-Ti-Cu initial alloy powder prepared above was mixed with a NaOH aqueous solution with a concentration of 8 mol/L and a temperature of 40°C. Carry out dealloying reaction. After reacting for 45 minutes, the solid product was collected, washed and dried to obtain a nanoporous sodium titanate composite powder material in-situ endogenously doped with Cu/Cu ₂ O nanoparticles. Among them, the in-situ endogenously doped Cu/Cu ₂ O nanoparticles perform the first-level doping of the nanoporous sodium titanate carrier; while the in-situ exogenously doped nanoporous Cu/Cu ₂ O particles perform the first-level doping of the nanoporous titanium carrier. Sodium acid carrier is used for second-level doping. In the in-situ endogenously doped Cu/Cu ₂ O nanoparticles and the in-situ exogenously doped nanoporous Cu/Cu ₂ O particles, part of the Cu is oxidized to Cu ₂ O. The particle size of the in-situ endogenously doped Cu/Cu ₂ O nanoparticles is 2 nm-25 nm; the particle size of the in-situ exogenously doped nanoporous Cu/Cu ₂ O particles is 5 nm-1 μm.

The above-mentioned nanoporous sodium titanate composite powder material endogenously doped with Cu/Cu ₂ O nanoparticles is reacted with a 0.015 mol/L HCl solution to convert the nanoporous sodium titanate carrier into a nanoporous titanate carrier. After solid-liquid separation, cleaning and drying, a nanoporous titanate composite powder material with in-situ endogenous doping of Cu/Cu ₂ O nanoparticles is obtained. The backscattered SEM photo is shown in Figure 9, and the high-magnification SEM photo of the nanoporous titanate carrier is shown in Figure 10. The nanoporous titanate carrier has a "sponge-like" structure, and dot-like white bright contrast is vaguely visible. In situ endogenously doped Cu/Cu ₂ O nanoparticles.

Example 4:

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 is smelted. alloy melt; the alloy melt is solidified at a cooling rate of about 10 ² K/s to 10 ³ K/s into an Al-Cr-Ag alloy plate with a thickness of about 2 mm, and its solidification structure is mainly composed of Al ₄ Cr(Ag) intermetallic compound phase with an average composition of about Al ₇₇ Cr ₂₂ Ag ₁ (gray-black phase) and Al ₇₈ Cr ₁₉ Ag ₃ (gray-white phase) and Ag-rich Al(Ag) phase, and its SEM image is shown in Figure 11, wherein the matrix phase is two Al ₄ Cr(Ag) intermetallic compound phases, and a small amount of bright white particle phase is Ag-rich Al(Ag) phase, as indicated by the arrow.

The Al-Cr-Ag initial alloy plate prepared above was crushed into powder with an average particle size of 300 μm, and then the alloy powder was added to a NaOH aqueous solution with a concentration of 10 mol/L and a temperature of 40°C to perform a dealloying reaction. After reacting for 2 hours, the solid product was collected, washed and dried to obtain a nanoporous oxidized Cr composite powder material doped with Ag element in situ. Among them, the nanoporous oxide Cr carrier with in-situ endogenously doped Ag element is doped in the first level, and the Ag element is mainly in-situ endogenously doped in the nanoporous oxide Cr carrier system in the form of atoms or atomic clusters. ; The in-situ exogenously doped nanoporous Ag particles perform second-level doping on the nanoporous oxide Cr carrier. Among them, nanoporous oxidized Cr is in a low crystalline state.

The above-mentioned nanoporous oxidized Cr composite powder material in-situ endogenously doped with Ag element was sanded for 2 hours. Since the nanoporous oxidized Cr carrier and the in-situ exogenously doped nanoporous Ag particles are loose and porous, they can be easily The refined in-situ nanoporous oxidized Cr composite powder material doped with Ag element can be easily obtained through sanding treatment. The average particle size of the nanoporous oxidized Cr carrier is less than 300 nm, and the average particle size of the nanoporous Ag is less than 200 nm.

Heat the above-mentioned nanoporous oxidized Cr composite powder material in-situ endogenously doped with Ag element at 650°C for 2 hours to obtain a nanoporous oxidized Cr composite powder material mainly composed of in-situ endogenously doped Ag nanoparticles. Heat treatment During the process, Ag elements existing in the form of atoms or atomic clusters aggregate into Ag nanoparticles with an average particle size of 2nm-15nm. At the same time, the nanoporous belts are coarsened, and the thickness of the coarsened nanoporous belts is about 50nm. The TEM morphology of the main component of the nanoporous Cr oxide composite powder material doped with Ag nanoparticles endogenously in situ after heat treatment is shown in Figure 12, in which the dark granular material is endogenously doped in situ. Ag nanoparticles.

Example 5:

Melt the Al-Nb-Au alloy melt according to a ratio of Au and Nb atomic percentages of approximately 0.5% and ²⁵ % respectively (the balance is mainly Al); The cooling rate of ³ K/s is solidified into an Al-Nb-Au alloy plate with a thickness of about 2 mm. The solidified structure is mainly composed of an intermetallic compound phase with an average composition of about Al _74.7 Nb ₂₅ Au _0.3 and an Au-rich Al ₂ Au phase. The composition, its SEM image is shown in Figure 13, in which the matrix phase is the Al ₃ Nb (Au) intermetallic compound phase, and the bright white phase is the Al ₂ Au phase.

The Al-Cr-Au initial alloy plate prepared above was crushed into powder with an average particle size of 100 μm, and then the alloy powder was added to a NaOH aqueous solution with a concentration of 10 mol/L and a temperature of room temperature to perform a dealloying reaction. After reacting for 45 minutes, the solid product was collected, washed and dried to obtain a nanoporous oxidized Nb composite powder material in-situ endogenously doped with Au nanoparticles. Among them, the in-situ endogenously doped Au nanoparticles perform the first-level doping of the nanoporous oxidized Nb carrier, while the in-situ exogenously doped nanoporous Au nanoparticles perform the second-level doping of the nanoporous oxidized Nb carrier. . Nanoporous oxidized Nb is in a low crystalline state. TEM morphology of the main component of the nanoporous oxidized Nb composite powder material doped with in-situ Au nanoparticles As shown in Figure 14, the dark granular material is the in-situ endogenously doped Au nanoparticles.

Example 6:

The Al-Mn-Au alloy melt is melted according to a ratio of Au and Mn atomic percentages of approximately 1.2% and 30% respectively (the balance is mainly Al); the alloy melt is heated at approximately 10 ⁶ K/s ~ 10 The cooling rate of ⁷ K/s solidifies into an Al-Mn-Au alloy strip with a thickness of 25 μm. Its solidification structure is mainly composed of an intermetallic compound phase with an average composition of approximately Al ₆₉ Mn ₃₀ Au ₁ and an Au-rich Al ₂ Au phase. The composition, its SEM backscattered image is shown in Figure 15, in which the matrix phase is the Al ₆₉ Mn ₃₀ Au ₁ intermetallic compound phase, and the bright white phase is the Al ₂ Au phase.

The Al-Mn-Au alloy strip prepared above was subjected to a dealloying reaction in a 10 mol/L NaOH aqueous solution at room temperature. After reacting for 30 minutes, the solid product was collected, washed and dried to obtain a nanoporous oxidized Mn composite powder material doped with Au nanoparticles in situ. Among them, the in-situ endogenously doped Au nanoparticles perform the first-level doping of the nanoporous Mn oxide carrier. The particle size range of the Au nanoparticles is 2nm-20nm, and the diameter range of the nanoporous tie is 10nm-200nm. ; In-situ exogenously doped nanoporous Au particles perform second-level doping of the nanoporous oxide Mn carrier; the particle size range of the in-situ exogenously doped nanoporous Au particles is 200nm-100μm, and the nanoporous Au system The diameter of the ribbon ranges from 20nm-100nm.

Example 7:

Melt the Al-Ti-Cu-Fe alloy melt according to the ratio of Cu, Fe, and Ti atomic percentages of approximately 1.1%, 0.25%, and 24.5% respectively (the balance is mainly Al); The cooling rate of 10 ⁶ K/s ~ 10 ⁷ K/s solidifies into an Al-Ti-Cu-Fe alloy strip with a thickness of 25 μm. Its solidified structure is mainly composed of Al with an average composition of approximately Al _74.4 Ti _24.5 Cu ₁ Fe _0.1 _{The 3} Ti(CuFe) intermetallic compound phase is composed of a Cu-rich Al(Cu) phase and a Fe-rich Al-Fe intermetallic compound phase, in which the matrix phase is the Al ₃ Ti(CuFe) intermetallic compound phase. Due to the fast 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).

Under normal pressure, add the Al-Ti-Cu-Fe alloy strip prepared above into 50 ml of KOH aqueous solution with a concentration of 10 mol/L and a temperature of normal temperature. After 30 minutes, all the solid products were separated from the alkali solution, washed and dried to obtain a nanoporous potassium titanate composite powder material endogenously doped with CuFe element in situ. Its main component is nanoporous potassium titanate with in-situ endogenous doping of Cu ₂ O nanoparticles and in-situ doping of Fe atoms. The particle size range of the Cu ₂ O nanoparticles is 2nm-10nm; at the same time, Al( The Cu) phase and the Al-Fe intermetallic compound phase undergo a traditional dealloying reaction to generate small in-situ exogenously doped nanoporous Cu/Cu ₂ O particles and nanoporous Fe/iron oxide particles, with porous band sizes The range is 2nm-50nm; the particle size range of the in-situ exogenously doped nanoporous Cu/Cu ₂ O particles and nanoporous Fe/iron oxide particles is 20nm-500nm.

The technical features of the above-described embodiments can be combined in any way. To simplify the description, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, All should be considered to be within the scope of this manual.

The above-mentioned embodiments only express several implementation modes of the present invention. The descriptions are relatively specific and detailed, but they should not be construed as limiting the scope of the invention. It should be noted that, for those of ordinary skill in the art, several modifications and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the scope of protection of the patent of the present invention should be determined by the appended claims.

Claims

An in-situ endogenously doped nanoporous composite powder material, which is characterized in that it mainly consists of a nanoporous powder main component with in-situ endogenous doping of E1 element and in-situ exogenously doped E2 Component composition; the main component of the nanoporous powder with in-situ endogenous doping of E1 element is mainly composed of nanoporous carrier and in-situ endogenous doping of E1 element, and the composition of the nanoporous carrier includes nanoporous carrier At least one of titanate, nanoporous titanic acid, and nanoporous oxide M; in the nanoporous oxide M, M includes Ti, Zr, Hf, Cr, V, Nb, Ta, W, Mo, Mn, Y , at least one of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; the oxidation of M includes oxidation of M and hydration of M. At least one; the nanoporous carrier mainly has a "sponge-like" structure in its microstructure, and the physical part of its "sponge-like" structure is mainly composed of three-dimensional continuous network-like "laces"; its "sponge-like" structure "The void part of the structure is mainly composed of a three-dimensional continuous network of holes; the diameter range of the "tie" is 0.5nm-250nm; the diameter range of the holes is 0.5nm-300nm; the in-situ exogenous doping The E 2 component includes at least one of E 2 nanoporous particles and E 2 nanoparticles; the E 1 element and the E 2 component are both mainly composed of the E element, and the E element includes Au, Pt, Pd, Ru , Rh, Re, Os, Ir, Ag, Cu, Fe, Ni, Co; when the E 1 element or the E 2 component includes two or more E elements, the composition of E 1 does not It must be exactly the same as E 2 in composition; the molar percentage content of the in-situ exogenously doped E 2 component in the in-situ endogenously doped nanoporous composite powder material is V e2 , and 0 ≤V e2 ≤40%; in the main component of the nanoporous powder with in-situ endogenous doping of E 1 element, the total number of moles of E 1 element C e1 and the total number of moles of Ti and M in the nanoporous carrier C The ratio C e1 /C 0 of 0 satisfies: 0<C e1 /C 0 <0.25;

In the nanoporous powder main component in-situ endogenously doped with E1 element, the in-situ endogenous doping method of E1 element to the nanoporous carrier includes at least one of the following three methods:

1) The E 1 element is embedded in-situ in the "tie" of the nanoporous carrier, and the E 1 element mainly dopes the "tie" of the nanoporous carrier with atoms or atomic clusters, The size of the atoms or atomic clusters of the E 1 element is 0.2nm-2nm;

2) The E 1 element is embedded in-situ in the "tether" of the nanoporous carrier, and the E 1 element is mainly doped with E 1 nanoparticles to the "tether" of the nanoporous carrier; The size of the E 1 nanoparticles is 2 nm to 50 nm;

3) The E 1 element mainly exists in the form of E 1 nanoparticles, and the E 1 nanoparticles are adsorbed on the surface of the nanoporous carrier "tie" by physical adsorption, and are also located in the pores of the nanoporous carrier. In space, the size of the E 1 nanoparticles is 2 nm-150 nm; wherein the 3) doping method appears simultaneously with the 1) or 2) doping method.
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 500um.
The in-situ endogenously doped nanoporous composite powder material according to claim 1, wherein the average particle size of the in-situ endogenously doped nanoporous powder particles ranges from 5 nm to 200um.
The in-situ endogenously doped nanoporous composite powder material according to claim 1, wherein 0<V e2 ≤ 40%.
The in-situ endogenously doped nanoporous composite powder material according to claim 1, wherein the cations in the nanoporous titanate include Na, K, Li, Rb, Ba, Ca, and Sr. of at least one.
The in-situ endogenously doped nanoporous composite powder material according to claim 1, characterized in that the E 1 element is embedded in the nanoporous carrier in situ, and the E 1 element is mainly E 1 nanoparticles dope the nanoporous carrier, and the E 1 element includes at least one of Cu, Ag, Fe, Ni, and Co, the E 1 nanoparticles include E 1 metal nanoparticles, E 1 metal at least one type of oxide nanoparticles.
The in-situ endogenously doped nanoporous composite powder material according to claim 1, wherein the nanoporous carrier includes at least one of nanoporous titanate, nanoporous titanic acid, and nanoporous oxidized Cr. species, and when the doping component E1 element is mainly composed of Ag, the E1 element mainly dopes the "tie" of the nanoporous carrier with atoms or atomic clusters.
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 tie is 2nm-200nm; in the in-situ exogenously doped E2 component, the average particle size of the E2 nanoparticles is 2nm-500nm.
The in-situ endogenously doped nanoporous composite powder material according to claim 1, characterized in that it is prepared by including the following steps:

Step 1: Prepare an initial alloy. The initial alloy mainly includes T-type elements, M-type elements and E-type elements; wherein, the T-type elements include at least one of Al and Zn, and the M-type elements include Ti, Zr, Hf, 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, Lu , E-type elements include at least one of Au, Pt, Pd, Ru, Rh, Re, Os, Ir, Ag, Cu, Fe, Co, and Ni; the solidification structure of the initial alloy is mainly composed of MTE intermetallic compounds or It consists of MT (E) intermetallic compounds with E elements in solid solution and TE phase; among them, the molar percentage content of TE phase in the initial alloy is V 0 , and 0 ≤ V 0 ≤ 40%; E element in TE phase The atomic percentage content in is higher than the atomic percentage content of the E element in the MTE intermetallic compound or the MT(E) intermetallic compound with E elements in solid solution;

Step two: react the initial alloy with an alkali solution of a certain temperature and concentration, and adjust the temperature and concentration of the alkali solution. degree, so that during the hydrogen evolution and deT reaction between the initial alloy and the alkali 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 process, the initial alloy MTE intermetallic compounds or solid solution E-type elements The T elements in the MT(E) intermetallic compound are mainly removed by reaction and dissolved into the solution. The M 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 carrier. At the same time, the E element The main component of the nanoporous powder with in-situ endogenous doping of E 1 element is obtained by in-situ endogenization in the tether of the nanoporous carrier. At the same time, the TE phase in the initial alloy undergoes a traditional de-T reaction during the reaction process. Generate an in-situ exogenously doped E 2 component; the E 2 component includes at least one of E 2 nanoporous particles and E 2 nanoparticles; both the E 1 element and the E 2 component are mainly composed of E Elemental composition, and when the element E 1 or the component E 2 includes two or more elements, the composition of E 1 is not necessarily exactly the same as the composition of E 2 ;

Step three, after the T removal reaction is completed, the solid reaction product in step two 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.
The method for preparing an 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 three is performed as follows: 1) One or more modification treatments in -4) to obtain more in-situ endogenously doped nanoporous composite powder materials with different characteristics:

Modification treatment 1): When the nanoporous carrier is mainly composed of titanate, its cations are replaced by H ions by reacting with dilute acid, and the titanate is converted into titanic acid, thereby obtaining a material mainly composed of titanic acid. A titanium-based carrier composed of;

Modification treatment 2): When the E 1 element is embedded in the "tie" of the nanoporous carrier in situ, and the E 1 element mainly "ties" the nanoporous carrier as atoms or atomic clusters "When doping, through medium and low temperature heat treatment, the E 1 element grows up through diffusion, agglomeration, and nucleation, and is further transformed into E 1 nanoparticles to dope the nanoporous carrier "tie"; at the same time, the The diameter of the nanoporous carrier "tie" becomes thicker during the heat treatment process, and the specific area decreases at the same time;

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

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 methods include sand grinding, ball milling, and ultrasonic treatment. At least one of the crushing processes.
The in-situ endogenously doped nanoporous composite powder material according to claim 1 is used in composite materials, ceramic materials, photocatalytic materials, hydrophobic materials, sewage degradation materials, sterilization materials, electronic materials, and coatings.
Use of the in-situ endogenously doped nanoporous composite powder material according to claim 1 in home decoration coatings, bactericidal sprays, and antifouling coatings.
Application of the in-situ endogenously doped nanoporous composite powder material in antibacterial fabrics according to claim 1.