WO2019024146A1

WO2019024146A1 - Black phosphorus/precious metal composite material, preparation method and application thereof

Info

Publication number: WO2019024146A1
Application number: PCT/CN2017/098564
Authority: WO
Inventors: 喻学锋; 王欣; 白力诚
Original assignee: 深圳先进技术研究院
Priority date: 2017-08-04
Filing date: 2017-08-23
Publication date: 2019-02-07
Also published as: CN107469845B; CN107469845A

Abstract

Disclosed are a black phosphorus/precious metal composite material, a preparation method and the use thereof, wherein the black phosphorus/precious metal composite material is a product of precious metal nano-particles and/or precious metal alloy nano-particles with the black phosphorus formed by means of coordination bonds, and by means of the modification of the black phosphorus with a precious metal, the black phosphorus cannot be oxidized in water and air, thus increasing the stability of the structure and performance of black phosphorus materials. The physicochemical characteristic of the black phosphorus/precious metal composite material compared to that of the black phosphorus material and the precious metal/precious metal alloy nano-particles is even better, and the catalytic performance thereof compared to that of the black phosphorus is also better. The black phosphorus/precious metal composite material can be applied in the wider catalytic field, and can be used as high efficient photocatalysts, electro-catalysts and organic catalyst in the fields of photocatalysis, electrochemistry and organic reactions, etc.

Description

Black phosphorus/precious metal composite material, preparation method thereof and application thereof

Technical field

The invention relates to the technical field of black phosphorus materials, in particular to a black phosphorus/precious metal composite material, a preparation method thereof and application thereof.

Background technique

Two-dimensional black phosphorus (referred to as black phosphorus) is a new type of two-dimensional semiconductor material that has received widespread attention. As a member of the two-dimensional planar material, black phosphorus has a two-dimensional layered structure similar to graphene, and the phosphorus atoms in the same layer are connected by covalent bonds, and the layers are stacked together by van der Waals force. Through nearly three years of research, black phosphorus has shown many unique properties. First, black phosphorus is a direct bandgap semiconductor compared to the 0 band gap of graphene and the indirect band gap of transition metal sulfide (more than two layers), that is, the bottom of the conduction band and the top of the valence band are in the same position, which means Black phosphorus can be directly coupled to light. Moreover, the band gap of black phosphorus can be adjusted with the number of layers, and by adjusting the number of layers of black phosphorus, the response to light of different wavelengths can be realized. In addition, black phosphorus also has high electron mobility, unique anisotropy and other properties. These properties make black phosphorus have broad application potential in the fields of optics, electricity, biology and chemistry. The application of black phosphorus to a variety of catalytic fields has attracted a wide range of research interests from researchers all over the world. At the same time, precious metals have always been a hot spot and focus in scientific research due to their excellent electrocatalysis, photocatalysis and organic catalytic activity. In recent decades, research on precious metal nanomaterials has continuously promoted the continuous development of precious metal catalysis. Therefore, the combination of black phosphorus and precious metals to form a composite material with both excellent physical properties will broaden the potential application of black phosphorus and precious metal composites in various catalytic fields.

In the existing technical solutions, unmodified black phosphorus is mainly used as a catalyst for photocatalysis, electrocatalysis and the like. In 2015, Professor Xie Yi from the University of Science and Technology of China reported the application of black phosphorus nanosheets in photocatalytic preparation of singlet oxygen and photocatalytic degradation of methyl orange. The results show that the phosphorus atom on the surface of the black phosphorus nanosheet has a large number of active sites, and also exhibits low electron-hole recombination rate and high carrier mobility, thus exhibiting good photocatalytic activity. . Professor Yang Shangfeng from the Hefei National Laboratory for Physical Sciences at the Microscale reports the photohydrogen production performance of black phosphorus nanosheets. The results show that the black phosphorus nanosheets under visible light have excellent photocatalytic hydrogen production performance, and their hydrogen production rate is 512 umol• h ^-1 •g ^-1 , basically rivals or even surpasses the hydrogen production rate of graphene-like carbon nitride. In 2016, Professor Wang Shuangyin's research group supported black phosphorus nanosheets and black phosphorus nanoparticles on titanium substrates and carbon nanotubes, respectively, and tested the electrochemical oxygen evolution properties of these two materials, including black phosphorus nanoparticles and carbon nanotubes. Composite materials have good electrocatalytic properties.

However, due to the presence of a lone pair of electrons on the surface of black phosphorus, it is easily oxidized by oxygen in water or air, thereby affecting its structure and function. This seriously affects the performance of black phosphorus in the catalytic system, especially for aqueous phase catalytic systems. Therefore, certain anti-oxidation measures must be taken for black phosphorus to ensure the long-term stable presence of black phosphorus in the catalytic system is the premise of using black phosphorus in various catalytic fields. At the same time, how to improve the catalytic activity of black phosphorus itself is a key issue affecting and expanding the application of black phosphorus.

Summary of the invention

The technical problem to be solved by the present invention is that black phosphorus is easily oxidized to cause problems in structure and function. To this end, the present invention provides a black phosphorus/precious metal composite material, a preparation method thereof and an application thereof.

The technical solution adopted by the present invention is:

A black phosphorus/noble metal composite material is a product in which noble metal nanoparticles and/or noble metal alloy nanoparticles are bonded to black phosphorus via a coordination bond.

In some preferred embodiments, the noble metal nanoparticles are nanoparticles of at least one of gold, silver, platinum, palladium, rhodium, ruthenium, osmium, and iridium, and the noble metal alloy nanoparticles are gold alloys and silver alloys. Nanoparticles of at least one of a platinum alloy, a palladium alloy, a ruthenium alloy, a ruthenium alloy, a ruthenium alloy, and a ruthenium alloy.

In some preferred embodiments, the black phosphorus is a black phosphorus nanosheet or a black phosphorus quantum dot.

The present invention also provides a method for preparing a black phosphorus/noble metal composite material as described above, comprising the steps of: mixing a precious metal nanoparticle and/or a noble metal alloy nanoparticle organic solution with black phosphorus, heating the reaction, and separating the solid in the reaction system, A black phosphorus/precious metal composite is obtained.

In some preferred embodiments, the temperature increasing reaction process is carried out by stirring at 20-100 ° C for 15-30 hours and then at 25-300 ° C for 1-40 hours under a protective gas atmosphere.

In some preferred embodiments, the temperature increasing reaction process is carried out under a protective gas atmosphere by stirring at 28-60 ° C for 23-25 hours and then at 40-200 ° C for 1-40 hours.

In some preferred embodiments, the black phosphorus is a modified black phosphorus.

In some further preferred embodiments, the modified black phosphorus is an amino-modified or thiol-modified black phosphorus.

In some further preferred embodiments, the amino-modified or sulfhydryl-modified black phosphorus is obtained by the following steps: mixing an organic substance having an amino group or a thiol group with black phosphorus in a solvent, and refluxing at 30-180 ° C under a protective gas atmosphere. The solid in the reaction system is separated by cooling to obtain an amino-modified or fluorenyl-modified black phosphorus.

In some preferred embodiments, the black phosphorus is mixed with an organic solution of the noble metal nanoparticles and/or noble metal alloy nanoparticles in the form of a black phosphorus dispersion.

In some further preferred embodiments, the black phosphorus dispersion is an alkaline dispersion.

In some further preferred embodiments, the black phosphorus dispersion contains a surfactant, and the surfactant includes at least one of a nonionic surfactant, an anionic surfactant, or a cationic surfactant.

In some further preferred embodiments, the nonionic surfactant comprises at least one of polyvinylpyrrolidone, polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer, and alkyloxyvinylphenol ether. The anionic surfactants include alkyl sulfonates, alkyl benzene sulfonates, fatty alcohol sulphates, fatty alcohol ether sulphates, oleamide methyl taurates, fatty alcohol phosphates At least one of the surfactants, the cationic surfactant comprising at least one of a fatty amine salt, a higher fatty amine salt, and a quaternary ammonium surfactant.

In some preferred embodiments, the organic solution of the noble metal nanoparticles is obtained by reducing a noble metal salt in an aromatic phenolic solution by a reducing agent, and the organic solution of the noble metal alloy nanoparticles is a noble metal salt solution and other metal salts. The solution is reduced in an aromatic phenolic solution by a reducing agent.

In some further preferred embodiments, the noble metal salt is chloroplatinate, chloropalladium, tetrachloroauric acid, silver nitrate, chlorodecanoate, chlorodecanoate, chlorate, chlorodecanoate At least one of the salts.

In some further preferred embodiments, the reducing agent is at least one of formaldehyde, sodium borohydride, ethanol, and ascorbic acid.

The invention also provides the use of a black phosphorus/noble metal composite as described above in photocatalysis, organic catalysis, batteries, optoelectronic devices or electrocatalysis.

The beneficial effects of the invention are:

The invention provides a black phosphorus/precious metal composite material, which is a product of a noble metal nanoparticle and/or a noble metal alloy nanoparticle and a black phosphorus through a coordination bond, through a coordination method. The modification of black phosphorus by noble metal makes black phosphorus not oxidized in water and air, which enhances the stability of structure and performance of black phosphorus material; black phosphorus/precious metal composite material compared with black phosphorus material, precious metal/precious metal Alloy nanoparticles have better physicochemical properties, better catalytic performance than black phosphorus, and can be applied in a wider range of catalysis. They can be used as photocatalysts, electrocatalysts, and organic catalysts in the field of photocatalysis. Electrochemical field, organic catalytic reaction field, etc.

DRAWINGS

Figure 1 is a scanning transmission electron micrograph of a black phosphorus/ultra small platinum nanoparticle composite.

Figure 2 is a high resolution transmission electron micrograph of a black phosphorus/ultra small platinum nanoparticle composite.

Figure 3 is a graph showing the stability of black phosphorus/ultra-small platinum nanoparticle composites in water.

Figure 4 is a comparison of the stability of black phosphorus nanosheets and black phosphorus/ultra small platinum nanoparticle composites.

Figure 5 is a comparison of photocatalytic activity of black phosphorus nanosheets and black phosphorus/ultra small platinum nanoparticle composites.

Figure 6 is a comparison diagram of electrochemical hydrogen evolution performance of black phosphorus nanosheets and black phosphorus/ultra small platinum nanoparticle composites.

Figure 7 is a scanning transmission electron micrograph of a black phosphorus/ultra small platinum-palladium alloy nanoparticle composite.

Figure 8 is a high resolution transmission electron micrograph of a black phosphorus/ultra small platinum-palladium alloy nanoparticle composite.

Detailed ways

The present invention provides a black phosphorus/noble metal composite material which is a product of noble metal nanoparticles and/or noble metal alloy nanoparticles bonded to black phosphorus via a coordinate bond. The noble metal nanoparticles are nanoparticles of at least one of gold, silver, platinum, palladium, rhodium, ruthenium, osmium, and iridium, and the noble metal alloy nanoparticles are gold alloy, silver alloy, platinum alloy, palladium alloy, ruthenium. Nanoparticles of at least one of an alloy, a bismuth alloy, a bismuth alloy, and a bismuth alloy. The black phosphorus is a black phosphorus nanosheet or a black phosphorus quantum dot.

The present invention also provides a method for preparing a black phosphorus/noble metal composite material as described above, comprising the steps of: mixing a precious metal nanoparticle and/or a noble metal alloy nanoparticle organic solution with black phosphorus, heating the reaction, and separating the solid in the reaction system, A black phosphorus/precious metal composite is obtained. The temperature rising reaction process is carried out under a protective gas atmosphere by first stirring at 20-100 ° C for 15-30 hours and then at 25-300 ° C for 1-40 hours. The temperature rising reaction process is carried out under a protective gas atmosphere, and the reaction is stirred at 28-60 ° C for 23-25 hours, and then at 40-200 ° C for 1-40 hours.

In a preferred embodiment, the black phosphorus is a modified black phosphorus, and further, the modified black phosphorus is an amino-modified or sulfhydryl-modified black phosphorus. The amino-modified or sulfhydryl-modified black phosphorus is obtained by the following steps: mixing an organic substance having an amino group or a thiol group with black phosphorus in a solvent, refluxing at 30-180 ° C under a protective gas atmosphere, cooling, and separating the solid in the reaction system. Amino-modified or thiol-modified black phosphorus is obtained. The amino-modified black phosphorus can be prepared by the following method: in A Add B g black phosphorus and C mL to mL isopropanol 3-amino-4-hydroxybenzenesulfonic acid, followed by reflux under nitrogen for 30-12 ° C for 5-12 hours, reflux is complete, the system is naturally cooled down to room temperature, the solid in the reaction system is separated and anhydrous Wash the ethanol several times. Then, it is dispersed in absolute ethanol for use to obtain an amino-modified black phosphorus dispersion; wherein A: B: C = (50-100): (0.1-10): (0.01-10).

In some specific embodiments, the black phosphorus/precious metal composite is prepared by the following steps: adding J to the I mL black phosphorus dispersion mL absolute ethanol, K mL deionized water, D mL aqueous ammonia solution and E g surfactant and stirred uniformly at normal temperature to obtain a base mixture, the content of black phosphorus in the black phosphorus dispersion is 0.25-50 g / L, the mass fraction of aqueous ammonia solution is 25%-28%; The mL resorcinol solution, the G mL precious metal salt solution and the H mL formaldehyde solution are uniformly mixed and added to the above substrate mixture, wherein the concentration of the resorcin solution is 22-28 g/L, the mass fraction of the formaldehyde solution is 35-40%, the concentration of the precious metal in the precious metal salt solution is 0.08-0.12 mol/L, and the surfactant includes a nonionic surfactant, an anionic surfactant or a cationic surfactant. At least one of them; under a nitrogen atmosphere, the above mixed solution is stirred in a water bath at 28-60 ° C for 23-25 hours, then heated to 40-200 ° C and refluxed for 1-40 hours; after the reflux is completed, separated The solid in the reaction system is washed several times with anhydrous ethanol, and then dried, that is, a noble metal nanoparticle layer is prepared on the surface of black phosphorus to obtain a black phosphorus/precious metal composite material; wherein D: E: F: G: H = (1-5): (1-200): (1-200): (0.1-50): (0.1-30), I: J: K = (1-100): (0.1-50): (0.1-150).

In some preferred embodiments, the organic solution of the noble metal nanoparticles is obtained by reducing a noble metal salt in an aromatic phenolic solution by a reducing agent, and the organic solution of the noble metal alloy nanoparticles is a noble metal salt solution and other metal salts. The solution is obtained by reducing a reducing agent in an aromatic phenolic solution, which is a chloroplatinate, a chloropalladium salt, a tetrachloroauric acid, a silver nitrate, a chloromethane salt, a chlorate, a chlorate. And at least one of chloromethane salts, wherein the reducing agent is at least one of formaldehyde, sodium borohydride, ethanol, and ascorbic acid.

In some preferred embodiments, the black phosphorus dispersion contains a surfactant, and the surfactant includes at least one of a nonionic surfactant, an anionic surfactant, or a cationic surfactant. The nonionic surfactant includes at least one of polyvinylpyrrolidone, polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer, and alkyloxyvinylphenol ether, and the anionic surfactant includes an alkyl group. At least one of a sulfonate, an alkylbenzenesulfonate, a fatty alcohol sulfate, a fatty alcohol ether sulfate, an oleamide methyl taurate, and a fatty alcohol phosphate surfactant The cationic surfactant includes at least one of a fatty amine salt, a higher fatty amine salt, and a quaternary ammonium surfactant.

Example 1:

The black phosphorus/ultra-small platinum nanoparticle composite was prepared using the following procedure:

1) Black phosphorus nanosheet amino modification: Disperse 0.1 g of black phosphorus nanosheet into 50 mL of isopropanol (HPLC grade), then add 0.1 mL 3-amino-4-hydroxybenzenesulfonic acid (APS), refluxed at 70 ° C for 10 hours, then centrifuged, the solid portion was washed with a mixture of absolute ethanol and water, and redispersed in 150 In the absolute ethanol of mL, an amino-modified black phosphorus nanosheet dispersion was obtained.

2) Preparation of ultra-small platinum nanoparticles on the surface of black phosphorus nanosheets. Take 3 mL of the amino-modified black phosphorus nanosheet dispersion prepared in step 1), and add it to a mixture of 20 mL of absolute ethanol, 125 mL of deionized water and 0.2 mL of aqueous ammonia solution (28 wt%). Add 0.3 g of sodium dodecylbenzene sulfonate (SDBS) and mix well. Resorcin was formulated into a 25 g/L solution, and potassium tetrachloroplatinate was formulated into a 0.1 mol/L solution. 10 mL of the prepared resorcinol solution and 2 mL of K ₂ PtCl ₄ solution and 0.42 mL of formaldehyde solution (37 wt%) were uniformly mixed and added to the above-mentioned base mixture, and stirred in a water bath at 28 ° C for 25 hours. After that, it was refluxed at 70 ° C for 10 hours, then centrifuged, and the solid portion was washed several times with a mixture of ethanol and water, and then dried in an oven at 60 ° C to prepare a noble metal nanoparticle layer on the surface of the substrate to obtain black phosphorus. / Ultra-small platinum nanoparticle composite.

The amino modification of black phosphorus is to make the subsequent noble metal nanoparticles more evenly distributed on the surface of the black phosphorus nanosheet. It is not a necessary step to prepare the black phosphorus/precious metal composite material, and the sulfhydryl modification of the black phosphorus can also be performed first. The noble metal nanoparticles can be more evenly distributed on the surface of the black phosphorus nanosheet.

The prepared black phosphorus/ultra-fine platinum nanoparticle composites were analyzed by transmission electron microscopy. The results are shown in Fig. 1 and Fig. 2. It can be seen from Fig. 1 that the white bright spots are platinum nanoparticles, which are evenly distributed throughout the black phosphorus nanometer. Sheet surface. The dark part in Figure 2 is ultra-small platinum nanoparticles, and it can be seen that the platinum particle size is 1 Around nm, the particle size is uniform and evenly distributed.

The stability of black phosphorus can be characterized by whether the absorption of its solution in the ultraviolet-visible-near-infrared region is stable, if its absorption intensity decreases with time, indicating that it is being slowly oxidized, and if its absorption intensity is with time The change remains basically unchanged, indicating that its structure is stable. Black phosphorus is the most unstable in aqueous solution. We studied the stability of black phosphorus/ultra-fine platinum nanoparticle composites in water using ordinary black phosphorus nanosheets. The results are shown in Figure 3. The results in Figure 3 show The absorption of the black phosphorus/ultra-fine platinum nanoparticle composite in aqueous solution is very stable, and the stability in aqueous solution is maintained for at least seven days.

Comparing the stability of the conventional black phosphorus nanosheet with the prepared black phosphorus/ultra small platinum nanoparticle composite, the results are shown in Fig. 4. The absorption intensity of the ordinary black phosphorus nanosheet in aqueous solution (A/A ₀ ) decreases with time, and its absorption intensity is only 50% of the original solution after one day, while the absorption intensity of the black phosphorus/ultra small platinum nanoparticle composite hardly decreases within seven days, indicating that black phosphorus is modified by noble metal nanoparticles. The antioxidant capacity is greatly enhanced.

The photocatalytic activity of the conventional black phosphorus nanosheets and the prepared black phosphorus/ultra-fine platinum nanoparticle composites were compared. The results are shown in Fig. 5. As can be seen from Fig. 5, the black phosphorus after modification with noble metals The photocatalytic degradation time of the organic dye is reduced by about 25%, and the catalytic efficiency is improved.

Comparing the electrochemical hydrogen evolution performance of the conventional black phosphorus nanosheet with the prepared black phosphorus/ultra-fine platinum nanoparticle composite, the results are shown in Fig. 6. As can be seen from Fig. 6, the black phosphorus after modification by the noble metal In the electrolysis hydrogen evolution catalysis, the catalytic performance of the sheet is greatly improved compared with the unmodified black phosphorus sheet. Similarly, it can be applied to electrolysis of oxygen, oxygen oxidation, electrocatalytic oxidation reduction, carbon dioxide electrocatalytic reduction, carbon monoxide electrocatalytic oxidation and other electrocatalytic reactions.

Based on the two-dimensional planar structure of black phosphorus itself, direct band gap, high electron mobility, unique anisotropy and other characteristics. When combined with precious metal particles, the performance of noble metal nanoparticles in organic catalysis, batteries, optoelectronic devices or electrocatalysis can also be improved.

Example 2:

The black phosphorus/ultra-small platinum-palladium alloy nanoparticle composite was prepared by the following procedure:

1) Black phosphorus nanosheet amino modification: Disperse 10g black phosphorus nanosheet into 100mL isopropanol (HPLC grade), then add 10mL 3-amino-4-hydroxybenzenesulfonic acid (APS), refluxed at 180 ° C for 8 hours, then centrifuged, the solid portion was washed with absolute ethanol, and redispersed at 150 In the absolute ethanol of mL, an amino-modified black phosphorus nanosheet dispersion was obtained.

2) Preparation of ultra-small platinum-palladium alloy nanoparticles on the surface of black phosphorus nanosheets. 10 mL of the amino-modified black phosphorus nanosheet dispersion prepared in the step 1) was added to a mixture of 1 mL of absolute ethanol, 1 mL of deionized water and 10 mL of an aqueous ammonia solution (25 wt%). Add 10 g of sodium dodecylbenzene sulfonate (SDBS) and mix well. Resorcin was formulated into a 22 g/L solution, and K ₂ PtCl ₄ and Na ₂ PdCl _{4 were} formulated into a 0.12 mol/L solution. Take 10 mL of the prepared resorcinol solution and mix 0.5 mL of potassium tetrachloroplatinate solution, 0.5 mL of sodium tetrachloropalladate solution and 1 mL of formaldehyde solution (35 wt%) and add to the above substrate mixture. After stirring for 23 hours in a water bath of 60 ° C, refluxing at 40 ° C for 40 hours, and then centrifuging, the solid portion was washed several times with a mixture of absolute ethanol and water, and then dried in an oven at 60 ° C, that is, A noble metal nanoparticle layer is prepared on the surface of the substrate to obtain a black phosphorus/ultra-small platinum-palladium alloy nanoparticle composite.

The prepared black phosphorus/ultra-small platinum-palladium alloy nanoparticle composites were analyzed by transmission electron microscopy. The results are shown in Fig. 7 and Fig. 8. As can be seen from Fig. 7, the white bright spots are platinum-palladium alloy nanoparticles, which are evenly distributed. The entire black phosphorus nanosheet surface. The dark part in Figure 8 is a platinum-palladium alloy nanoparticle, and it can be seen that the platinum-palladium alloy nanoparticle size is 1.2. Around nm, the particle size is uniform and evenly distributed.

Example 3:

A black phosphorus/ultra-small silver nanoparticle composite was prepared in a manner similar to that of Example 1:

1) Black phosphorus quantum dot amino modification: Disperse 0.1g of black phosphorus quantum dots into 50 mL of isopropanol (HPLC grade), then add 0.01 mL 3-amino-4-hydroxybenzenesulfonic acid (APS), refluxed at 30 ° C for 20 hours, then centrifuged, the solid portion was washed with absolute ethanol, and redispersed at 150 In the absolute ethanol of mL, an amino-modified black phosphorus quantum dot dispersion was obtained.

2) Preparation of ultra-small gold nanoparticles on the surface of black phosphorus quantum dots. Take 100 mL of the black phosphorus quantum dot dispersion prepared in step 1, and add to 40 In a mixture of mL absolute ethanol, 150 mL of deionized water and 5 mL of aqueous ammonia solution (28 wt%), 200 g of sodium dodecylbenzenesulfonate (SDBS) was added and stirred well. Resorcinol is formulated into 28 A solution of g/L was prepared by formulating silver nitrate into a solution of 0.08 mol/L. Take 200 mL of resorcinol solution with 50 mL of silver nitrate solution and 30 mL of formaldehyde solution (40 The mixture was uniformly mixed and added to the above-mentioned base mixture, stirred in a water bath at 100 ° C for 15 hours, refluxed at 25 ° C for 40 hours, and then centrifuged, and the solid portion was washed several times with a mixture of absolute ethanol and water. Thereafter, it was dried in an oven at 60 ° C, that is, a noble metal nanoparticle layer was formed on the surface of the substrate to obtain a black phosphorus/ultra-small silver nanoparticle composite.

Example 4:

A black phosphorus/ultra-gold colloidal nanoparticle composite was prepared in a manner similar to that of Example 1:

1) fluorenyl modification of black phosphorus nanosheets and dispersion of thiol-modified black phosphorus quantum dots at 150 In the absolute ethanol of mL, a black phosphorus nanosheet dispersion after thiol modification was obtained.

2) Preparation of ultra-small gold nanoparticles on the surface of black phosphorus nanosheets. Take 3 mL of the thiol-modified black phosphorus nanosheet dispersion prepared in step 1), and add to 20 To a mixture of mL absolute ethanol, 125 mL of deionized water and 0.2 mL of aqueous ammonia solution (28 wt%), 0.3 g of sodium dodecylbenzenesulfonate (SDBS) was added and stirred well. Resorcinol is formulated into 25 A solution of g/L was prepared by formulating tetrachloroauric acid into a 0.1 mol/L solution. Take 10 mL of resorcinol solution and 2 mL of tetrachloroauric acid and 0.42 mL of formaldehyde solution (37). Gt%) uniformly mixed and added to the above substrate mixture, stirred in a water bath at 20 ° C for 30 hours, refluxed at 300 ° C for 1 hour, then centrifuged, and the solid portion was washed several times with a mixture of absolute ethanol and water. Thereafter, it was dried in an oven at 60 ° C to prepare a noble metal nanoparticle layer on the surface of the substrate to obtain a black phosphorus/ultra-gold nanoparticle composite.

The invention can load a plurality of kinds of noble metal nanoparticles of different sizes on the black phosphorus substrate. The above two examples are only illustrated by platinum nanoparticles and platinum-palladium alloy nanoparticles, and the applicable precious metal nanoparticles are not limited to the above three types. Also included are other various precious metals and related alloy nanoparticles, such as nanoparticles of at least one of gold, silver, platinum, palladium, rhodium, which are gold alloys, silver alloys, platinum alloys, palladium alloys, Nanoparticles of at least one of bismuth alloys. The composite material of the present invention may be a noble metal nanoparticle or a precious metal alloy supported on the surface of a black phosphorus material having different morphologies. Since precious metals such as platinum, palladium, and the like have higher adsorption energy with black phosphorus, and phosphorus atoms in black phosphorus can form ionic bonds or covalent bonds, which can effectively prevent black phosphorus oxidation. The loading of black phosphorus can provide a large specific surface area, high carrier mobility, and high light absorption rate for noble metal nanoparticles, thereby effectively improving precious metal nanoparticles in photocatalysis, electrocatalysis, organic catalysis, etc. Performance.

Claims

A black phosphorus/noble metal composite material characterized in that the black phosphorus/noble metal composite material is a product in which noble metal nanoparticles and/or noble metal alloy nanoparticles are bonded to black phosphorus via a coordination bond.
The black phosphorus/noble metal composite according to claim 1, wherein the noble metal nanoparticles are nanoparticles of at least one of gold, silver, platinum, palladium, rhodium, ruthenium, osmium, and iridium. The noble metal alloy nanoparticles are nanoparticles of at least one of a gold alloy, a silver alloy, a platinum alloy, a palladium alloy, a ruthenium alloy, a ruthenium alloy, a ruthenium alloy, and a ruthenium alloy.
The black phosphorus/noble metal composite according to claim 1 or 2, wherein the black phosphorus is a black phosphorus nanosheet or a black phosphorus quantum dot.
The method for preparing a black phosphorus/precious metal composite according to any one of claims 1 to 3, comprising the steps of: mixing a precious metal nanoparticle and/or a noble metal alloy nanoparticle organic solution with black phosphorus, heating the temperature, and separating The solid in the reaction system is obtained to obtain a black phosphorus/precious metal composite.
The method for preparing a black phosphorus/precious metal composite material according to claim 4, wherein the temperature increasing reaction process is carried out under a protective gas atmosphere, and the reaction is stirred at 20-100 ° C for 15-30 hours, and then at 25-300 ° C. Reflux for 1-40 hours.
The method for preparing a black phosphorus/precious metal composite material according to claim 4, wherein the temperature increasing reaction process is carried out under a protective gas atmosphere, and the reaction is stirred at 28-60 ° C for 23-25 hours, and then at 40-200 ° C. Reflux for 1-40 hours.
The method for producing a black phosphorus/precious metal composite according to any one of claims 4 to 6, wherein the black phosphorus is modified black phosphorus.
The method for preparing a black phosphorus/precious metal composite according to claim 7, wherein the modified black phosphorus is an amino-modified or fluoren-modified black phosphorus.
The method for preparing a black phosphorus/precious metal composite according to claim 7, wherein the amino-modified or sulfhydryl-modified black phosphorus is obtained by the following steps: an organic substance having an amino group or a thiol group is mixed with black phosphorus in a solvent, The reaction is refluxed at 30-180 ° C under a protective gas atmosphere, cooled, and the solid in the reaction system is separated to obtain an amino-modified or thiol-modified black phosphorus.
The method for preparing a black phosphorus/precious metal composite according to any one of claims 4-6, wherein the black phosphorus is in the form of a black phosphorus dispersion and the noble metal nanoparticles and/or precious metal alloy nanometers. The organic solution of the granules is mixed.
The method for producing a black phosphorus/precious metal composite according to claim 10, wherein the black phosphorus dispersion is an alkaline dispersion.
The method for preparing a black phosphorus/precious metal composite according to claim 10, wherein the black phosphorus dispersion contains a surfactant, and the surfactant comprises a nonionic surfactant, an anionic surfactant or At least one of cationic surfactants.
The method for preparing a black phosphorus/precious metal composite according to claim 12, wherein the nonionic surfactant comprises polyvinylpyrrolidone, polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer, At least one of an alkyl oxyethylene phenol ether, the anionic surfactant comprising an alkyl sulfonate, an alkyl benzene sulfonate, a fatty alcohol sulphate, a fatty alcohol ether sulphate, an oleamide At least one of a base taurate salt and a fatty alcohol phosphate salt surfactant, the cationic surfactant comprising at least at least one of a fatty amine salt, a higher fatty amine salt, and a quaternary ammonium salt surfactant. One.
The method for preparing a black phosphorus/precious metal composite according to any one of claims 4-6, wherein the organic solution of the noble metal nanoparticles is obtained by reducing a precious metal salt in an aromatic phenolic solution by a reducing agent. The organic solution of the noble metal alloy nanoparticles is obtained by reducing a precious metal salt solution and other metal salt solutions in an aromatic phenolic solution by a reducing agent.
The method for preparing a black phosphorus/precious metal composite according to claim 14, wherein the noble metal salt is chloroplatinate, chloropalladium, tetrachloroauric acid, silver nitrate, chloromethane, chlorine At least one of citrate, chlorate, and chlorate.
The method for producing a black phosphorus/precious metal composite according to claim 14, wherein the reducing agent is at least one of formaldehyde, sodium borohydride, ethanol, and ascorbic acid.
Use of the black phosphorus/precious metal composite according to any one of claims 1 to 3 in photocatalysis, organic catalysis, batteries, photovoltaic devices or electrocatalysis.