Inorganic-organic hybrid metal super-particle and preparation method and application thereof
阅读说明：本技术 一种无机有机杂化金属超粒子及其制备方法和应用 (Inorganic-organic hybrid metal super-particle and preparation method and application thereof ) 是由 刘坚 孙源卿 罗佳庆 马婧文 于 2020-03-17 设计创作，主要内容包括：本发明提供了一种无机有机杂化金属超粒子及其制备方法和应用。该制备方法包括：向聚合物水溶液中加入金属离子溶液,加入还原剂,在60℃-100℃下搅拌30min-480min；加入沉淀剂,沉淀后离心,将离心得到的固体分散到水溶液中,得到无机有机杂化金属超粒子。本发明的无机有机杂化金属超粒子经过处理后可以用于催化电解水反应,并具有较好的催化活性和稳定性。(The invention provides an inorganic-organic hybrid metal super particle and a preparation method and application thereof. The preparation method comprises the following steps: adding a metal ion solution into the polymer aqueous solution, adding a reducing agent, and stirring at 60-100 ℃ for 30-480 min; adding a precipitator, precipitating, centrifuging, and dispersing the solid obtained by centrifuging into an aqueous solution to obtain the inorganic-organic hybrid metal super-particles. The inorganic-organic hybrid metal super-particles can be used for catalyzing water electrolysis reaction after being treated, and have better catalytic activity and stability.)
1. A preparation method of inorganic-organic hybrid metal super particles comprises the following steps:
adding a metal ion solution with the concentration of 0.01 mmol/L-50 mmol/L into a polymer aqueous solution with the concentration of 0.0045 mmol/L-150 mmol/L, adding a reducing agent, and stirring at 60-100 ℃ for 30-480 min to obtain a mixed solution, wherein the molar ratio of the polymer to the metal ion is 1:250-600000: 1;
and adding a precipitator into the mixed solution, precipitating, centrifuging, and dispersing the solid obtained by centrifuging into water to obtain the inorganic-organic hybrid metal super-particles.
2. The production method according to claim 1, wherein the polymer used in the aqueous polymer solution is polymethyl acrylate, polyacrylic acid, polyethyleneimine, polyethylene glycol, or polyallylamine hydrochloride;
preferably, the molecular weight of the polymer is 1800g/mol to 30000 g/mol.
3. The production method according to claim 1, wherein the metal ion used in the metal ion solution is Au3+、Pt4+、Ag+Or Cu2+。
4. The production method according to claim 3, wherein the metal ion solution is HAuCl4Aqueous solution, H2PtCl6Aqueous solution, AgNO3Aqueous solution, CH3COOAg aqueous solution, AgF aqueous solution, Ag2SO4Aqueous solution, AgClO4Aqueous solution, CuCl2Aqueous solution, CuNO3Aqueous solution, CuSO4Aqueous solution or CH3An aqueous solution of COOCu.
5. The production method according to claim 1, wherein the reducing agent is sodium borohydride, hydrazine hydrate, sodium citrate, or ascorbic acid;
preferably, the molar ratio of the reducing agent to the metal ion is 1 to 10: 1.
6. the production method according to claim 1, wherein the precipitating agent is acetone;
preferably, the addition volume of the precipitant is 2 to 10 times the volume of the mixed solution.
7. An inorganic-organic hybrid metal ultrafine particle produced by the method for producing an inorganic-organic hybrid metal ultrafine particle according to any one of claims 1 to 6.
8. The inorganic-organic hybrid metal ultrafine particle according to claim 7, which has a uniform particle diameter, and is formed by coating and bridging 20 to 50 metal nanoclusters having an average particle diameter of 2 to 5nm with an organic polymer layer, wherein the average particle diameter of the inorganic-organic hybrid metal ultrafine particle is 30 to 150 nm.
9. An electrocatalytic full-hydrolysis catalyst, which is prepared by the following steps:
immersing the foamed nickel subjected to acid washing treatment in the dispersion liquid containing the inorganic-organic hybrid metal super-particles of claim 7 or 8 for 24 to 48 hours;
drying at 60-80 ℃ for 4-8 h, and roasting at 300-600 ℃ for 2-3 h under the protection of argon to obtain an electrocatalytic full-hydrolysis catalyst;
the catalyst is formed by loading carbonized hybrid metal super particles on the surface of foamed nickel, wherein the average particle size of the carbonized super particles is 30-150 nm, and the carbonized hybrid metal super particles are formed by coating and bridging 20-50 metal nano clusters with the average particle size of 2-5 nm through an organic polymer layer.
10. Use of the electrocatalytic full hydrolysis catalyst as set forth in claim 9 for electrocatalytic full hydrolysis.
Technical Field
The invention relates to a catalyst, in particular to a catalyst for water electrocatalytic decomposition, and belongs to the technical field of catalyst preparation.
Background
The hydrogen production by water electrolysis is a clean, efficient and sustainable new energy technology, and is an effective way for solving the current energy problems and environmental problems. However, the water splitting reaction is difficult to perform kinetically, which greatly limits the industrial application thereof. The catalyst is used for promoting the water electrolysis reaction, so that the hydrogen production efficiency can be effectively improved, and the voltage required by water electrolysis is reduced. Therefore, the development of an efficient and stable water electrolysis catalyst has been one of the focuses of current scientific research.
At present, reported full-electrolysis water electric catalysts can be classified as noble metal-based catalysts, such as β -Ni2P2O7Pt (ACSAppl. Mater. interfaces 2019,11,4969-4982), Pt @ DNA-GC (ACS Catal.2016,67, 4660-4672); and non-noble metal catalysts, such as 3D-OMNiSA (ACS Catal.2016,6,1446-3N-VN/NF (adv. Mater.2019,1901174), etc. These catalysts have made great progress in reducing the overpotential of electrolyzed water, but their synthesis methods are complicated and difficult, and the reaction stability is still to be improved.
Therefore, the development of an electrolytic water catalyst with simple synthesis method and stable reaction process still has a problem to be solved in the field.
Disclosure of Invention
The invention aims to provide an electrocatalytic full-hydrolysis catalyst with high catalytic activity and good stability.
The invention also aims to provide a preparation method of the electrocatalytic full-hydrolysis catalyst.
In order to achieve the above object, the present invention provides a method for preparing inorganic-organic hybrid metal super particles, comprising the steps of:
adding a metal ion solution with the concentration of 0.01 mmol/L-50 mmol/L into a polymer aqueous solution with the concentration of 0.0045 mmol/L-150 mmol/L, adding a reducing agent, and stirring at 60-100 ℃ for 30-480 min to obtain a mixed solution, wherein the molar ratio of the polymer to the metal ion is 1:250-600000: 1;
and adding a precipitator into the mixed solution, precipitating, centrifuging, and dispersing the solid obtained by centrifuging into water to obtain the inorganic-organic hybrid metal super-particles.
The preparation method of the inorganic-organic hybrid metal super-particles prepares the inorganic-organic hybrid metal super-particles with controllable sizes by controlling the adding proportion of metal ions and polymers, wherein the more the polymer is added, the smaller the particle size of the inorganic-organic hybrid metal super-particles is, and the fewer nano-clusters forming a single super-particle is; the electronic structure of the carbonized super-particles is adjusted by adjusting the types of polymers containing different heteroatoms, so that better electrocatalytic water decomposition performance is obtained.
The preparation method of the inorganic-organic hybrid metal super-particles comprises the step of preparing the super-particles. Adding metal ions with a certain concentration into a water-soluble polymer aqueous solution as a precursor, adding a reducing agent into the solution after uniform dispersion, heating for a certain time, and preparing the super-particles in one step.
In the preparation method of the present invention, a water-soluble polymer is used as a stabilizer to make the particle size of the super particle uniform. In one embodiment of the present invention, the polymer used in the aqueous polymer solution may be polymethyl acrylate, polyacrylic acid, polyethyleneimine, polyethylene glycol, or polyallylamine hydrochloride.
In one embodiment of the invention, the molecular weight of the polymer is 1800g/mol to 30000 g/mol.
In one embodiment of the present invention, the concentration of the aqueous polymer solution may be 0.05 mmol/L to 50 mmol/L, and more preferably 0.1 mmol/L to 10 mmol/L.
In one embodiment of the present invention, the metal ion used in the metal ion solution may be Au3+、Pt4 +、Ag+Or Cu2+。
In one embodiment of the present invention, the metal ion solution may be HAuCl4Aqueous solution, H2PtCl6Aqueous solution, AgNO3Aqueous solution, CH3COOAg aqueous solution, AgF aqueous solution, Ag2SO4Aqueous solution, AgClO4Aqueous solution, CuCl2Aqueous solution, CuNO3Aqueous solution, CuSO4Aqueous solution or CH3An aqueous solution of COOCu.
In one embodiment of the present invention, the concentration of the metal ion solution is 0.01 mmol/L-30 mmol/L, and more preferably 0.1 mmol/L-30 mmol/L.
In one embodiment of the present invention, the reducing agent used may be sodium borohydride, hydrazine hydrate, sodium citrate or ascorbic acid; preferably, the molar ratio of reducing agent to metal ion may be 1 to 10: 1.
the preparation method of the inorganic-organic hybrid metal super-particle comprises the step of preparing the polymer-coated metal super-particle. Which is obtained by precipitating the above-mentioned ultra-particles with a precipitating agent.
In one embodiment of the present invention, the precipitating agent used is acetone; preferably, the addition volume of the precipitant is 2 to 10 times the volume of the mixed solution.
The invention also provides an inorganic-organic hybrid metal super particle, which is prepared by the preparation method of the inorganic-organic hybrid metal super particle. The inorganic-organic hybrid metal super-particles have uniform particle size, the average particle size of the inorganic-organic hybrid metal super-particles is 30nm-150nm (55nm), and the inorganic-organic hybrid metal super-particles are formed by coating and bridging 20-50 metal nano-clusters with the average particle size of 2nm-5nm (4nm) through an organic polymer layer.
The invention also provides an electrocatalytic full-hydrolysis catalyst, which is prepared by the following steps:
soaking the foamed nickel subjected to acid cleaning treatment in the dispersion liquid of the inorganic-organic hybrid metal super particles for 24-48 h;
taking out the foamed nickel soaked in the super-particle dispersion liquid, drying at 60-80 ℃ for 4-8 h, and roasting at 300-600 ℃ for 2-3 h under the protection of argon to obtain an electrocatalytic full-hydrolysis catalyst; the catalyst is formed by loading carbonized hybrid metal super particles on the surface of foamed nickel, wherein the average particle size of the carbonized super particles is 30-150 nm, and the carbonized hybrid metal super particles are formed by coating and bridging 20-50 metal nano clusters with the average particle size of 2-5 nm through an organic polymer layer.
The electrocatalyst full-hydrolysis catalyst can be used for full-hydrolysis by electrocatalysis.
The inorganic-organic hybrid metal super-particles can be used for electrocatalytic full-hydrolysis after being treated. The prepared super-particles have pomegranate-shaped structures, and after high-temperature treatment, the polymer which plays a role in stabilizing the surfaces of the metal nano-clusters forming the super-particles is carbonized, so that the metal nano-clusters are coated by the carbon material, the metal nano-clusters can be highly dispersed in the carbon material, and the utilization efficiency of metal elements is improved. In addition, the heteroatom (sulfur, nitrogen, phosphorus) in the carbon material can modulate the electronic structure of the metal element, optimize the hydrogen adsorption energy of the material, and meanwhile, the heteroatom in the carbon material is also a good water adsorption site. In addition, the carbon material wrapping the metal nanoclusters can also effectively prevent the metal nanoclusters from being agglomerated and poisoned, and effectively improve the electrocatalytic activity and stability of the material.
The preparation method of the inorganic-organic hybrid metal super-particles has the advantages of small environmental pollution, high product purity, simple method, easy operation and good repeatability, and is suitable for mass production.
The inorganic-organic hybrid metal super-particles obtained by the preparation method have excellent electrocatalytic hydrogen evolution reaction activity and oxygen evolution reverse activity after being treated, have excellent stability and are an electrocatalytic full-hydrolysis catalyst with excellent performance.
The electrocatalytic full-hydrolysis catalyst has excellent catalytic performance when electrocatalytic full-hydrolysis is carried out.
Drawings
FIG. 1 is a transmission electron microscope photograph of the Au nanoparticles of example 1.
FIG. 2 is a plot of the electrocatalytic hydrogen evolution linear sweep voltammetry for the electrocatalytic total hydrolysis catalyst of example 2.
FIG. 3 is an electrocatalytic oxygen evolution cyclic voltammetry curve for the electrocatalytic total hydrolysis catalyst of example 2.
FIG. 4 is an i-t curve of the electrocatalytic stability of the electrocatalytic total hydrolysis catalyst of example 3.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.