CN111298815A - Platinum/phosphorus catalyst and preparation method and application thereof - Google Patents

Platinum/phosphorus catalyst and preparation method and application thereof Download PDF

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CN111298815A
CN111298815A CN201811517423.5A CN201811517423A CN111298815A CN 111298815 A CN111298815 A CN 111298815A CN 201811517423 A CN201811517423 A CN 201811517423A CN 111298815 A CN111298815 A CN 111298815A
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platinum
phosphorus
catalyst
solvent
carbon
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CN111298815B (en
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喻学锋
白力诚
王欣
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Hubei Xingfa Chemicals Group Co Ltd
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Shenzhen Institute of Advanced Technology of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/28—Phosphorising
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
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    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/94—Non-porous diffusion electrodes, e.g. palladium membranes, ion exchange membranes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

The invention discloses a platinum/phosphorus catalyst and a preparation method and application thereof. The platinum/phosphorus catalyst is prepared by the following preparation method: 1) synthesis of platinum-carbon catalyst: mixing a carbon carrier, a surfactant, alkali and a solvent to obtain a substrate mixed solution; then mixing the substrate mixed solution, a reducing agent and a platinum salt solution for reaction to obtain a solid product which is a platinum-carbon catalyst; 2) phosphating of platinum-carbon catalyst: mixing a platinum carbon catalyst, a phosphorus source and an organic solvent for reaction, and obtaining a solid product which is the platinum/phosphorus catalyst. The application of the platinum/phosphorus catalyst as an electrocatalyst in electrochemical hydrogen evolution is also disclosed. Compared with the prior art, the invention can achieve the function of regulating and controlling the electronic structure on the surface of the metal platinum at low temperature and low pressure, even normal temperature and normal pressure, thereby obtaining the high-efficiency electrocatalytic material with simple synthesis, convenient process and low cost.

Description

Platinum/phosphorus catalyst and preparation method and application thereof
Technical Field
The invention relates to the field of catalyst materials, in particular to a platinum/phosphorus catalyst and a preparation method and application thereof.
Background
Today, due to the overuse of fossil fuels and the pollution to the environment, there has been a great interest in renewable energy sources. Hydrogen is considered to be a promising chemical fuel in renewable energy applications due to its high energy density and zero environmental pollution advantages. Water electrolysis is a highly efficient method of producing hydrogen, but it relies primarily on a cathode catalyst. Noble metal platinum is the best hydrogen evolution catalyst to date. Due to the outstanding activity, selectivity and stability, the platinum-based catalyst occupies overwhelming technical advantages and unimaginable market share in a plurality of catalyst material systems, and has wide application in electrocatalysis reaction. However, the cost is high due to the problems of low content of the platinum in the earth crust, high mining difficulty and the like, and further application of the platinum-based catalyst is limited. Meanwhile, with the rapid development of economy and society, the demand of platinum-based electrocatalysts in the relevant electrocatalysis industries is increasing day by day. Therefore, in the face of the contradiction between the increasingly severe resource exhaustion and the increasing resource demand, there is an urgent need for a new approach to explore new technologies to improve the catalytic activity of platinum-based electrocatalysts.
Currently, the following three methods are adopted: (1) alloy nanocrystals with various morphologies are prepared by adopting a co-reduction method, expensive platinum with higher catalytic activity and base metal with lower electrocatalytic activity; (2) coating expensive platinum on non-noble metal particles to form a core-shell structure; (3) platinum alloy composite catalysts having a porous structure are prepared, as well as non-noble metal catalysts composed of nickel and cobalt compounds under development. A great deal of research proves that some platinum alloy catalysts with specific structures have improved surface electronic state density due to alloying in the electrocatalytic hydrogen evolution reaction, so that the electrocatalytic performance of the platinum alloy catalysts is far superior to that of the existing pure platinum catalyst with the best electrocatalytic activity, the electrocatalytic performance of the platinum alloy catalysts is enhanced, the use amount of noble metals is reduced, the platinum alloy catalysts become the most possible way, and the platinum alloy catalysts also provide possibility for large-scale commercial popularization of the platinum-based catalysts.
To date, there have been various approaches to improve the performance of electrocatalysts, such as changing the physical structure, chemical structure, and electronic structure of the catalyst. The catalyst is alloyed or doped with metal or nonmetal elements, so that the surface electronic structure of the material can be changed, and the purpose of improving the activity of the catalyst is achieved. There are many reports that the metal platinum is alloyed with other transition metals, the electronic state of the surface of the metal platinum is regulated in a micro-scale manner, and the catalyst shows excellent catalytic activity. The method for alloying the surface of the metal platinum comprises high-temperature annealing, ultrahigh vacuum or physical sputtering/evaporation procedures. However, these approaches can result in high costs and a severe dependence on equipment. Therefore, it is of great significance to develop a platinum-based catalyst with low cost, high catalytic activity and high cycle stability.
Disclosure of Invention
The prior art has the defects of high cost, harsh conditions and strong equipment dependence, and is difficult to realize large-scale application. In order to overcome the defects of the prior art, the invention aims to solve the technical problems of high preparation cost and low platinum utilization rate of the conventional platinum and platinum-based alloy catalyst in the prior art, thereby providing a platinum/phosphorus catalyst with good stability and higher catalytic activity, and a preparation method and application thereof.
The invention designs a platinum/phosphorus electrocatalyst based on the principle of regulating the electronic structure on the surface of platinum to regulate the catalytic activity of the platinum. Through the high adsorption energy of the phosphorus element and the platinum element, the platinum nano particles and the phosphorus element are subjected to surface alloying to form platinum-phosphorus bonds, so that the aim of regulating and controlling the surface electronic structure state of the platinum nano particles is fulfilled.
The technical scheme adopted by the invention is as follows:
a method of preparing a platinum/phosphorus catalyst comprising the steps of:
1) synthesis of platinum-carbon catalyst: mixing a carbon carrier, a surfactant, alkali and a solvent to obtain a substrate mixed solution; then mixing the substrate mixed solution, a reducing agent and a platinum salt solution for reaction to obtain a solid product which is a platinum-carbon catalyst;
2) phosphating of platinum-carbon catalyst: mixing a platinum carbon catalyst, a phosphorus source and an organic solvent for reaction, and obtaining a solid product which is the platinum/phosphorus catalyst.
Preferably, in the step 1) of the preparation method of the platinum/phosphorus catalyst, the platinum salt concentration of the platinum salt solution is 0.08-1 mol/L; further preferably, in the step 1), the platinum salt solution has a platinum salt concentration of 0.08 to 0.12 mol/L.
Preferably, in step 1) of the preparation method of the platinum/phosphorus catalyst, the platinum salt is at least one of platinum dichloride, platinum tetrachloride, chloroplatinate, chloroplatinite, hexachloroplatinate, tetranitro platinate, platinum tetraamine nitrate, platinum tetraamine chloride, dinitrosopropylamine and platinum acetylacetonate; further preferably, in step 1), the platinum salt is at least one of platinum dichloride, platinum tetrachloride, potassium chloroplatinate, sodium chloroplatinate, ammonium chloroplatinate, potassium hexachloroplatinate, sodium hexachloroplatinate, ammonium hexachloroplatinate, potassium tetranitroplatinate, sodium tetranitroplatinate, ammonium tetranitroplatinate, platinum tetraammine nitrate, platinum tetraammine chloride, platinum dinitrosoporide and platinum acetylacetonate.
Preferably, in the preparation method of the platinum/phosphorus catalyst, in step 1), the carbon carrier is at least one of carbon black, graphite, graphene, carbon fiber, carbon nanotube, activated carbon and carbon molecular sieve; more preferably, in step 1), the carbon support is at least one of graphite, graphene, and carbon fiber.
Preferably, in step 1) of the preparation method of the platinum/phosphorus catalyst, the surfactant is at least one of a nonionic surfactant, an anionic surfactant and a cationic surfactant; further preferably, in the surfactant of step 1), the nonionic surfactant is at least one selected from polyvinylpyrrolidone and polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer; the anionic surfactant is at least one selected from sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate and sodium dodecyl sulfate; the cationic surfactant is at least one selected from cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride and dodecyl dimethyl benzyl ammonium chloride.
Preferably, in the preparation method of the platinum/phosphorus catalyst, in the step 1), the base is at least one of alkali metal hydroxide, alkali metal carbonate, alkali metal bicarbonate and ammonia water; further preferably, in the step 1), the alkali is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate and ammonia water; still more preferably, in the step 1), the alkali is ammonia water; in some preferred embodiments of the present invention, the mass content of the ammonia water used in step 1) is 25% to 30%.
Preferably, in step 1) of the preparation method of the platinum/phosphorus catalyst, the reducing agent is at least one of alkali metal hydride, alkali metal borohydride and aldehyde solution; further preferably, in step 1), at least one of reducing agents of sodium borohydride, potassium borohydride and formaldehyde solution; still further preferably, in the step 1), the reducing agent is formaldehyde solution; in some preferred embodiments of the present invention, the mass content of the formaldehyde solution used in step 1) is 35% to 40%.
Preferably, in the preparation method of the platinum/phosphorus catalyst, in step 1), the solvent is one or more of water, an alcohol solvent, an ether solvent, an alcohol ether solvent, a ketone solvent, an ester solvent and an amide solvent; further preferably, in the step 1), the solvent is at least one of water, methanol, ethanol, propanol, isopropanol, diethyl ether, acetone and N, N-dimethylformamide; still more preferably, in the step 1), the solvent is a mixed solvent composed of ethanol and water; in some preferred embodiments of the present invention, the alcohol-water solvent used in step 1) has a volume ratio of ethanol to water of 1: (2-3).
Preferably, in step 1) of the preparation method of the platinum/phosphorus catalyst, the mass ratio of the carbon carrier, the surfactant, the alkali, the solvent, the reducing agent and the platinum salt is 1: (0.1-10): (0.05-1): (100-500): (0.05-1): (0.1-10).
Preferably, in the preparation method of the platinum/phosphorus catalyst, in the step 1), the temperature of the mixing reaction is 20-80 ℃, and the time of the mixing reaction is 24-48 h; more preferably, in the step 1), the mixing reaction is carried out for 20 to 30 hours at 25 to 30 ℃, and then the temperature is increased to 65 to 75 ℃ for 10 to 15 hours.
Preferably, in the step 1) of the preparation method of the platinum/phosphorus catalyst, after the mixing reaction, the solid product is obtained through centrifugal separation, and then the solid product is washed to obtain the platinum carbon catalyst.
Preferably, in step 2) of the preparation method of the platinum/phosphorus catalyst, the phosphorus source in the phosphorus source solution is at least one of phosphorus simple substance, phosphorus trioxide, phosphorus pentoxide, inorganic phosphate, trioctylphosphine, triphenylphosphine, ethyldiphenylphosphine, 1, 2-bis (diphenylphosphino) benzene, 1, 2-bis (dimethylphosphino) ethane and chlorodiisopropylphosphine; further preferably, in the step 2), the phosphorus source is at least one of red phosphorus, black phosphorus, phosphorus pentoxide, trioctylphosphine and triphenylphosphine.
Preferably, in the step 2) of the preparation method of the platinum/phosphorus catalyst, the organic solvent is one or more of an alcohol solvent, an ether solvent, an alcohol ether solvent, a ketone solvent, an ester solvent and an amide solvent; further preferably, in the step 2), the organic solvent is at least one of methanol, ethanol, propanol, isopropanol, diethyl ether, acetone and N, N-dimethylformamide; still more preferably, in the step 2), the organic solvent is at least one of methanol, ethanol, propanol and isopropanol.
Preferably, in step 2) of the preparation method of the platinum/phosphorus catalyst, the mass ratio of platinum in the platinum carbon catalyst, phosphorus in the phosphorus source and the organic solvent is 1: (0.01-0.1): (500-2000).
Preferably, in the step 2) of the preparation method of the platinum/phosphorus catalyst, the mixing reaction is specifically ultrasonic treatment at normal temperature for 1min to 10 min.
An electrocatalyst is a platinum/phosphorus catalyst prepared by the foregoing preparation method.
The application of the electrocatalyst in electrochemical hydrogen evolution.
Preferably, in the application, the electrocatalyst is prepared into a catalyst solution, added into a working substrate electrode to prepare a working electrode, and then formed into a three-electrode system for electrochemical hydrogen evolution treatment.
Preferably, in this application, the platinum concentration in the catalyst solution is from 0.1mg/mL to 1 mg/mL.
Preferably, in this application, the working substrate electrode is a rotating disk electrode.
Preferably, in this application, the counter electrode of the three-electrode system is graphite and the reference electrode is a saturated calomel electrode.
The invention has the beneficial effects that:
the invention starts from the phenomenon of strong adsorption energy of the metal platinum and the phosphorus element, realizes the alloying of the phosphorus element on the surface of the metal platinum at low temperature and low pressure even at normal temperature and normal pressure, and achieves the regulation and control of the surface electronic state and the catalytic activity of the metal platinum-based catalyst. Compared with the prior art, the invention can achieve the function of regulating and controlling the electronic structure on the surface of the metal platinum at low temperature and low pressure, even normal temperature and normal pressure, thereby obtaining the high-efficiency electrocatalytic material with simple synthesis, convenient process and low cost.
Drawings
FIG. 1 is a transmission electron (a) and scanning transmission electron (b) images of a platinum/phosphorus catalyst;
FIG. 2 is a graph comparing X-ray photoelectron spectroscopy analysis of a platinum carbon catalyst with a platinum phosphorus catalyst;
FIG. 3 is a graph comparing X-ray diffraction spectroscopy analyses of a platinum-carbon catalyst and a platinum-phosphorus catalyst;
FIG. 4 is a high resolution valence band X-ray photoelectron spectrum of a platinum carbon catalyst and a platinum phosphorus catalyst;
fig. 5 is a graph comparing the electrochemical hydrogen evolution performance of a platinum carbon catalyst and a platinum phosphorus catalyst.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials used in the examples are, unless otherwise specified, commercially available from conventional sources. The aqueous ammonia solution, the formaldehyde solution and the potassium tetrachloroplatinate solution mentioned in the examples are each an aqueous solution.
Preparation example
First, a graphene-supported platinum composite material (platinum-carbon catalyst) was synthesized, and 50mg of sodium dodecylbenzenesulfonate was dissolved in a solution containing 12.5mL of water, 5mL of ethanol, 50mg of graphene nanoplatelets and 0.02mL of ammonia water (28 wt%) at 28 ℃. To this solution were added 0.03mL of a formaldehyde (37 wt%) solution and 0.4mL of a potassium tetrachloroplatinate (0.1mol/L) solution with vigorous stirring. After 24 hours, the temperature was raised to 70 ℃ and maintained at this temperature for a further 12 hours. The solid product was collected by centrifugation and washed three times with water/ethanol to give a platinum-carbon catalyst.
The obtained platinum-carbon catalyst was dispersed in ethanol so that the content of platinum was 0.5 mg/mL. And adding 0.3mL of black phosphorus nanosheet ethanol solution (0.1mg/mL) into 1mL of platinum-carbon catalyst solution, and then carrying out ultrasonic treatment for 3 minutes at normal temperature and normal pressure to obtain a solid product which is a platinum/phosphorus catalyst.
Characterization analysis
The structure of the prepared platinum/phosphorus catalyst is characterized by a transmission electron microscope. FIG. 1 is a transmission electron micrograph and a scanning transmission electron micrograph of a platinum/phosphorus catalyst; in FIG. 1, FIG. 1(a) is a transmission electron microscope image, and FIG. 1(b) is a scanning transmission electron microscope image. As can be seen from fig. 1, the platinum/phosphorus particles are distributed uniformly over the substrate surface.
The platinum-carbon catalyst before phosphating and the platinum/phosphorus catalyst after phosphating in the preparation examples were respectively characterized and analyzed as follows.
The surface electron structures of platinum elements in the platinum carbon catalyst and the platinum phosphorus catalyst are measured by adopting X-ray photoelectron spectroscopy, and an X-ray photoelectron spectroscopy analysis contrast chart shown in the attached figure 2 can be seen. In FIG. 2, the platinum carbon catalyst shows two peaks of a Pt4f core-order photoelectron spectrum with a binding energy of 71.1eV of Pt4f7/2 and a binding energy of 72.2eV of front 4f 5/2. The peaks at Pt4f7/2 and Pt4f 5/2 were assigned to Pt0 and PtII, respectively. In addition, for the platinum phosphorus catalyst, in addition to the same Pt0 and PtII peaks as the platinum carbon catalyst, another set of Pt4f7/2 appeared at 72.9eV, which could be attributed to the formation of Pt-P bonds.
FIG. 3 is a graph showing the comparison of X-ray diffraction spectra of a platinum carbon catalyst and a platinum phosphorus catalyst. By comparison with the non-phosphatized platinum-carbon catalyst, the phosphatized platinum-carbon catalyst was found to have a new diffraction peak at 34 ° in the X-ray diffraction pattern, which indicates the formation of a platinum-phosphorus bond. At the same time, the Pt diffraction peak at 40 ° in the Pt-pd catalyst broadened and decreased, nearly disappeared. This indicates that the formation of a large number of platinum-phosphorus bonds results in a change in the platinum lattice of the metal.
A table of d-band electronic structures of the photoelectron spectra of the platinum carbon catalyst and the platinum phosphorus catalyst is obtained by using high-resolution valence band X-ray photoelectron spectra, and the attached figure 4 can be seen. It was found that the d-charge electron centre of the catalyst decreased from-4.28 eV to-5.12 eV after phosphating. According to the d band theory, the downward movement of the Pt d band center pulls down more of the anti-bond state below the fermi level, so that Pt has the best guest molecule adsorption and thus its electrochemical hydrogen evolution activity is increased.
Electrocatalytic application
The platinum carbon catalyst and the platinum phosphorus catalyst prepared in the preparation examples were analyzed to perform an electrochemical hydrogen evolution application test.
The electrochemical hydrogen evolution was measured using Shanghai Chenghua electrochemical workstation CHI 660D. The measurement system is a standard three-electrode system. The working electrode adopts a rotating disk electrode (0.07 cm)2). The graphite rod and the Saturated Calomel Electrode (SCE) are respectively a counter electrode and a reference electrode. In all measurements, the saturated calomel electrode was calibrated against the Reversible Hydrogen Electrode (RHE). In 1.0mol/L KOH, e (rhe) ═ e (sce) +0.0592 × 14+ 0.242V. Samples of platinum phosphorus catalyst and platinum carbon catalyst were working electrodes. The catalyst was ultrasonically mixed with ethanol and 5% Nafion (volume ratio, 5:0.02) for 1h, with a platinum concentration of 0.5mg/mL of catalyst ink. Then, 2. mu.L of the above mixed solution was dropped onto the working electrode, and dried in the air. Measurement of KOH saturation (1.0mol/L) at 5 mV. multidot.s in nitrogen by linear sweep voltammetry-1HER activity in the potential range of-0.3-0.1V at a (25 ℃) scan rate. Scanning with Cyclic Voltammetry (CV) in saturated KOH (1.0mol/L) at-0.6V to 0.1V at 20 mV. multidot.s-1Scan rate 1000 cycles of electrochemical stability test were performed. The rotating disk electrode was rotated at 1600 rpm to avoid accumulation of hydrogen gas bubbles. iR drop compensation was performed for all polarization curves.
The comparison of the electrochemical hydrogen evolution performance of the platinum phosphorus catalyst and the platinum carbon catalyst is shown in figure 5. In fig. 5 are two linear sweep voltammograms, respectively, in which the current density is normalized by the geometric area of the working electrode (disk) and the mass of Pt, respectively. The current density of the platinum-phosphorus catalyst is 125.43mA cm at the overpotential of 150mV and 70mV respectively-2And 42.28mA · cm-2Is a platinum-carbon catalyst (61.07mA · cm)-2And 19mA · cm-2) Twice as much. The Pt electronic structure is regulated and controlled after phosphorization, and the electrochemical hydrogen evolution performance is greatly improved.

Claims (10)

1. A method for preparing a platinum/phosphorus catalyst, which is characterized by comprising the following steps: the method comprises the following steps:
1) synthesis of platinum-carbon catalyst: mixing a carbon carrier, a surfactant, alkali and a solvent to obtain a substrate mixed solution; then mixing the substrate mixed solution, a reducing agent and a platinum salt solution for reaction to obtain a solid product which is a platinum-carbon catalyst;
2) phosphating of platinum-carbon catalyst: mixing a platinum carbon catalyst, a phosphorus source and an organic solvent for reaction, and obtaining a solid product which is the platinum/phosphorus catalyst.
2. The method of claim 1, wherein the platinum/phosphorus catalyst is prepared by: in the step 1), the platinum salt concentration of the platinum salt solution is 0.08-1 mol/L; the platinum salt is at least one of platinum dichloride, platinum tetrachloride, chloroplatinate, chloroplatinic acid salt, hexachloroplatinate, tetranitro platinate, platinum tetraammine nitrate, platinum tetraammine chloride, dinitrosopropylamine platinum and acetylacetone platinum.
3. The method of claim 1, wherein the platinum/phosphorus catalyst is prepared by: in the step 1), the carbon carrier is at least one of carbon black, graphite, graphene, carbon fiber, carbon nano tube, activated carbon and carbon molecular sieve; the surfactant is at least one of nonionic surfactant, anionic surfactant and cationic surfactant; the alkali is at least one of alkali metal hydroxide, alkali metal carbonate, alkali metal bicarbonate and ammonia water; the reducing agent is at least one of alkali metal hydride, alkali metal borohydride and aldehyde solution; the solvent is one or more of water, alcohol solvent, ether solvent, alcohol ether solvent, ketone solvent, ester solvent and amide solvent.
4. The method for preparing a platinum/phosphorus catalyst according to claim 2 or 3, wherein: in the step 1), the mass ratio of the carbon carrier, the surfactant, the alkali, the solvent, the reducing agent and the platinum salt is 1: (0.1-10): (0.05-1): (100-500):
(0.05～1)：(0.1～10)。
5. the method for preparing a platinum/phosphorus catalyst according to claim 4, wherein: in the step 1), the temperature of the mixing reaction is 20-80 ℃, and the time of the mixing reaction is 24-48 h.
6. The method of claim 1, wherein the platinum/phosphorus catalyst is prepared by: in the step 2), the phosphorus source of the phosphorus source solution is at least one of phosphorus simple substance, phosphorus trioxide, phosphorus pentoxide, inorganic phosphate, trioctylphosphine, triphenylphosphine, ethyldiphenylphosphine, 1, 2-bis (diphenylphosphino) benzene, 1, 2-bis (dimethylphosphino) ethane and chlorodiisopropylphosphine; the organic solvent is one or more of alcohol solvent, ether solvent, alcohol ether solvent, ketone solvent, ester solvent and amide solvent.
7. The method for preparing a platinum/phosphorus catalyst according to claim 1 or 6, wherein: in the step 2), the mass ratio of platinum in the platinum-carbon catalyst, phosphorus in the phosphorus source and the organic solvent is 1: (0.01-0.1): (500-2000).
8. The method of claim 7, wherein the platinum/phosphorus catalyst is prepared by: in the step 2), the mixing reaction is specifically ultrasonic treatment at normal temperature for 1min to 10 min.
9. An electrocatalyst, characterized by: is a platinum/phosphorus catalyst prepared by the preparation method of any one of claims 1 to 8.
10. Use of an electrocatalyst according to claim 9 for electrochemical hydrogen evolution.
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CN114628692A (en) * 2020-12-10 2022-06-14 深圳先进技术研究院 Phosphorus-activated platinum-based catalyst and preparation method and application thereof
CN115172775A (en) * 2022-07-04 2022-10-11 郑州大学 Black phosphorus nanodot modified Pt/C composite material and preparation method and application thereof
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