CN113373475B - Platinum monatomic hydrogen oxidation reaction electrocatalyst based on reactant enrichment and preparation method thereof - Google Patents
Platinum monatomic hydrogen oxidation reaction electrocatalyst based on reactant enrichment and preparation method thereof Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 183
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 50
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- MBUJACWWYFPMDK-UHFFFAOYSA-N pentane-2,4-dione;platinum Chemical compound [Pt].CC(=O)CC(C)=O MBUJACWWYFPMDK-UHFFFAOYSA-N 0.000 claims description 2
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- C—CHEMISTRY; METALLURGY
- 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
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- 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
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Abstract
The invention belongs to the technical field of electrocatalysts, and discloses a platinum monatomic hydrogen oxidation reaction electrocatalyst based on reactant enrichment and a preparation method thereof, wherein the hollow core-shell structure electrocatalyst with the noble metal loading amount of 1-12 percent and composed of monatomic distributed noble metal serving as a catalytic active center and a porous nitrogen-doped hollow carbon shell is prepared by preparing Pt x+ /SiO 2 Intermediate and Pt 1 /SiO 2 @ PNC intermediate Final preparation of Pt 1 @ PNC catalyst. The preparation method of the invention has simple and convenient operation and low cost, and the prepared Pt 1 @ PNC catalyst in which metal platinum is in monoatomic state and uniformly distributed on inner surface of PNC to increase hydrogen content in Pt 1 Adsorption and oxidation rates on the active center surface, resulting in Pt 1 The @ PNC catalyst exhibits excellent activity and stability of the hydrogen oxidation reaction at lower potentials. The invention is suitable for being used as a catalyst for electrocatalytic hydrogen oxidation reaction and hydrogen evolution reaction.
Description
Technical Field
The invention belongs to the technical field of electrocatalysts, and relates to a hydrogen oxidation reaction electrocatalyst, in particular to a platinum monatomic hydrogen oxidation reaction electrocatalyst based on reactant enrichment and a preparation method thereof.
Background
A Proton Exchange Membrane Fuel Cell (PEMFC) is a high-efficiency energy conversion device that converts chemical energy stored in hydrogen fuel and an oxidant into electrical energy at a temperature of less than 100 ℃ by means of an electrocatalyst, using a high-energy substance hydrogen gas as a fuel. When the PEMFC operates, fuel does not pass through a combustion process and is not limited by Carnot cycle, the energy conversion efficiency reaches 40-60 percent, and the PEMFC is a clean, quiet and environment-friendly power generation device. Based on the advantages, the PEMFC has wide application prospect in the fields of unmanned aerial vehicle power supplies, standby power supplies and the like. However, in the process of large-scale application of PEMFCs, high catalyst cost, low activity and poor stability have been the core problems that plague their development, mainly expressed as:
at present, a commercialized catalyst of a PEMFC anode is a carbon-supported platinum catalyst, the production cost is high, the hydrogen oxidation reaction activity of a non-platinum catalyst is low, the output power of the PEMFC is greatly reduced, and the key for reducing the cost of the PEMFC is to improve the utilization rate of metal platinum (Pt); meanwhile, the anodic hydrogen oxidation reaction involves a series of adsorption and desorption processes and electron transfer reactions, the reaction process is complex, and the kinetic reaction rate is reduced; in addition, the currently used carbon-supported platinum catalyst has an unstable structure, a carrier is easily corroded under reaction conditions, and platinum nanoparticles are easily shed and agglomerated, so that the catalyst has poor stability.
In recent years, a great deal of research is carried out at home and abroad aiming at improving the dynamic reaction rate of the hydrogen oxidation reaction and the stability of the catalyst. An article entitled "high Selective Pt/TiOx Catalysts for the Hydrogen Oxidation Reaction" reports a porous coated Pt/TiOx/C catalyst in which Pt active sites are coated with porous TiO x Layer coating, tiO x The layer can effectively inhibit the oxidation and agglomeration of Pt and improve the HOR intrinsic activity and stability of the Pt catalyst, but TiO x The layer occupies part of the Pt active sites, and the utilization rate of Pt is reduced.
Therefore, the hydrogen oxidation reaction electrocatalyst with a stable structure is designed, the utilization rate of Pt, the dynamic reaction rate of hydrogen oxidation reaction and the stability of the catalyst are improved on the basis of reducing the platinum loading capacity of the catalyst, and the hydrogen oxidation reaction electrocatalyst has very important significance for promoting the scale application of the PEMFC.
Disclosure of Invention
The invention aims to provide a reactant enrichment-based platinum monatomic hydrogen oxidation reaction electrocatalyst, which is a hollow core-shell structure electrocatalyst with the noble metal loading amount of 1-12% and consists of a catalytic active center and a porous nitrogen-doped hollow carbon shell, so as to achieve the purposes of improving the utilization rate of Pt, the dynamic reaction rate of hydrogen oxidation reaction and the stability of the catalyst on the basis of reducing the platinum loading amount of the catalyst;
it is another object of the present invention to provide a method for preparing the above electrocatalyst for a monatomic hydrogen oxidation reaction based on enriched platinum in the reactant.
In order to achieve the purpose, the invention adopts the technical scheme that:
a platinum monatomic hydrogen oxidation reaction electrocatalyst based on reactant enrichment is a hollow core-shell structure electrocatalyst composed of a catalytic activity center and a porous nitrogen-doped hollow carbon shell, wherein the catalytic activity center is noble metal distributed in a monatomic mode, and the noble metal loading amount is 1-12%.
As a limitation, the hollow core-shell structure electrocatalyst is Pt 1 @ PNC catalyst, wherein, pt 1 Is a catalytic active center and is platinum metal with monoatomic distribution; the diameter of the porous nitrogen-doped hollow carbon shell is 5nm-100nm.
The invention also provides a preparation method of the platinum monatomic hydrogen oxidation reaction electrocatalyst based on reactant enrichment, which comprises the following steps in sequence:
s1: preparation of Pt x+ /SiO 2 Intermediate:
soaking spherical nanometer silica carrier and platinum metal precursor solution in the same volume, mixing, and ultrafilteringPerforming acoustic and ball milling, drying in vacuum, cooling and drying to obtain Pt x+ /SiO 2 An intermediate.
S2: preparation of Pt 1 /SiO 2 @ PNC intermediate:
mixing Pt x+ /SiO 2 Uniformly mixing the intermediate, the nitrogen-containing organic matter, the carbon source organic matter and the structural assistant, anchoring platinum atoms through polymerization reaction, performing suction filtration to obtain a solid, drying, grinding, heating under the protection of inert gas, and cooling to obtain Pt 1 /SiO 2 @ PNC intermediate.
S3: preparation of Pt 1 @ PNC catalyst:
mixing Pt 1 /SiO 2 Mixing the @ PNC intermediate with alkaline aqueous solution, filtering to remove spherical nano-silica carrier, drying the filtrate to obtain solid, grinding, heating under inert gas protection to etch nitrogen-doped carbon shell with residual alkali to obtain Pt 1 @ PNC catalyst.
As a limitation, in step S1, the spherical nano-silica support is prepared by a chemical precipitation method.
The mass ratio of the platinum metal precursor to the deionized water in the platinum metal precursor solution is 1:1-50, and the platinum metal precursor is chloroplatinic acid, acetylacetone platinum or chloroplatinate;
the spherical nano silicon dioxide carrier and the platinum metal precursor are weighed according to the platinum carrying capacity of 1-12%.
As another limitation, in the step S1, the temperature of the vacuum drying is 50-200 ℃ and the time is 0.2-12h.
As a third limitation, the Pt x+ /SiO 2 The mass ratio of the intermediate, the nitrogen-containing organic matter, the carbon source organic matter and the structural assistant is 1:1-100;
the nitrogen-containing organic matter is at least one of dopamine, urea, thiourea, ethylenediamine, L-cysteine, cyanamide, dicyandiamide and melamine;
the carbon source organic matter is at least one of chitosan, glucose, resorcinol, carbon tetrachloride, ethylene diamine tetraacetic acid and formaldehyde;
the structural auxiliary agent is m-phenylenediamine, p-aminophenol or m-diphenol.
As a fourth limitation, in the step S2, the heating temperature is 200-800 ℃ and the time is 0.2-12h; the cooling is to 18-26 ℃.
As a fifth limitation, in step S3, the Pt 1 /SiO 2 The mass-volume ratio of the @ PHC intermediate to the alkaline aqueous solution is 1 g;
the heating temperature is 200-800 ℃, and the time is 0.2-12h.
As a sixth limitation, in step S3, OH in the basic aqueous solution - The concentration of (B) is 0.5-12mol/L.
Pt in the reactant enrichment based platinum monatomic hydrogen oxidation reaction electrocatalyst of the invention 1 The working principle of the @ PNC catalyst is as follows: pt 1 Is a platinum metal with monoatomic distribution and is a catalytic active center; the PNC is a porous nitrogen-doped hollow carbon shell and has the functions of enriching hydrogen, stabilizing a reaction center and providing an active surface area; the high concentration of hydrogen in the PNC cavity will increase the hydrogen and Pt 1 The collision frequency of the active center increases the adsorption and oxidation rate of hydrogen on the surface of the active site, thereby improving the dynamic reaction rate of the hydrogen oxidation reaction; meanwhile, the nitrogen atom in the PNC shell is reacted with Pt 1 Strong interaction between them can modulate Pt 1 The catalytic activity of the active center is improved; on the other hand, the nitrogen atom in the PNC shell layer and the Pt atom form stable coordination strong interaction to anchor the platinum atom, so that the Pt can be effectively inhibited 1 The stability of the catalyst is effectively improved by the falling, migration and agglomeration of the active center.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the technical progress that:
(1) In the catalyst, the catalytic activity center noble metal is uniformly distributed on the inner surface of the PNC in a monatomic state, the loading amount of the noble metal is 1-12%, and the catalyst shows excellent catalytic activity and stability in the catalytic hydrogen oxidation reaction process;
(2) The catalyst has a special pore structure, the PNC shell layer on the non-electrically neutral surface has a certain adsorption effect on hydrogen, and the reactant hydrogen can be enriched in the surface active area in the PNC cavity, so that the collision frequency of the hydrogen and the catalytic activity center is effectively increased, the adsorption and oxidation rate of the hydrogen on the surface of the catalytic activity center is promoted, and the dynamic reaction rate of the hydrogen oxidation reaction and the activity of the catalyst are improved;
(3) Pt prepared by the preparation method of the invention 1 The nitrogen atom in the PNC shell layer in the @ PNC catalyst and the Pt atom can form stable coordination strong interaction to anchor the platinum atom, so that the Pt can be effectively inhibited 1 The shedding, migration and agglomeration of the catalytic active center can be adjusted by the electronic interaction 1 The electronic structure effectively improves the reaction activity and stability of the catalyst;
the preparation method is simple and easy to operate, has low cost and is suitable for industrial production, and the prepared electro-catalyst based on the reactant enrichment for the platinum monatomic hydrogen oxidation reaction has low noble metal loading capacity and high utilization rate, and is suitable for being used as a catalyst for the electro-catalytic hydrogen oxidation reaction and the hydrogen precipitation reaction.
Drawings
FIG. 1 is a diagram of Pt prepared in example 1 of the present invention 1 Structure schematic of @ PNC catalyst J1;
FIG. 2 is a graph of Pt prepared in example 1 of the present invention 1 High power transmission electron micrograph of @ PNC catalyst J1;
FIG. 3 is a diagram showing Pt prepared in example 1 of the present invention 1 The extended X-ray absorption fine structure spectrogram of @ PNC catalyst J1;
FIG. 4 shows Pt in example 9 of the present invention 1 @ PNC catalyst J1 and H for comparative sample Pt/C 2 -striping profile;
FIG. 5 shows Pt in example 9 of the present invention 1 Comparative plots of catalytic activity for @ PNC catalyst J1 and comparative sample Pt/C;
FIG. 6 shows Pt in example 9 of the present invention 1 The Pt/C current-time plot for the @ PNC catalyst J1 and the comparative sample.
Detailed Description
The present invention is further illustrated by the following specific examples, which are to be construed as merely illustrative, and not limitative, of the remainder of the disclosure.
If the experimental conditions not specified in the examples are specified, the conditions are generally conventional or recommended by the reagent company; reagents, consumables and the like used in the following examples are commercially available unless otherwise specified, and all processes used therein are conventional in the art unless otherwise specified.
Example 1 preparation of a platinum monatomic hydrogen oxidation reaction electrocatalyst based on reactant enrichment
The preparation of example 1 comprising the following steps carried out in sequence:
preparing a spherical nano silicon dioxide carrier by a chemical precipitation method:
taking 20L of ethanol and 40L of deionized water, uniformly mixing, adding 0.6L of tetramethyl silicate and 0.2kg of cetyltrimethylammonium chloride (CTAC) surfactant, stirring for 1h at room temperature, dropwise adding 0.8L of 25% ammonia water solution, stirring for 4h at room temperature, washing a product obtained by filtering by using the deionized water and the ethanol in sequence, drying at 60 ℃, heating for 6h at 600 ℃ in air, and preparing the spherical nano-silica carrier for later use.
Among them, spherical nano silica supports are also commercially available.
S1: preparation of Pt x+ /SiO 2 Intermediate:
weighing 2kg of spherical nano silicon dioxide carrier and 168g of chloroplatinic acid according to the platinum loading capacity of 4%, and dissolving to obtain a chloroplatinic acid solution according to the mass ratio (marked as: ratio 1) of the chloroplatinic acid to the deionized water of 1;
isovolumetrically impregnating a spherical nano silicon dioxide carrier and a chloroplatinic acid solution, uniformly mixing, ultrasonically dispersing for 1h, mechanically ball-milling for 1h, vacuum drying for 8h at the temperature of 80 ℃, naturally cooling and drying to obtain Pt loaded with metal platinum oxide x+ /SiO 2 An intermediate.
S2: preparation of Pt 1 /SiO 2 @ PNC intermediate:
0.5kg of Pt x+ /SiO 2 Intermediate addition to 10kg of m-phenylenediamine (structural auxiliary agent) is added with 1kg of ethylenediamine (nitrogen-containing organic matter) and 2kg of carbon tetrachloride (carbon source organic matter) in sequence, stirred and polymerized for 4 hours, platinum atoms are anchored by utilizing strong coordination interaction, solid is obtained by suction filtration, and the solid is dried and ground. Putting the obtained solid powder into a tube furnace, heating for 5h at 600 ℃ under the protection of nitrogen, cooling to 20 ℃ to obtain Pt 1 /SiO 2 @ PNC intermediate;
wherein, pt x+ /SiO 2 The mass ratio of the intermediate, the nitrogen-containing organic matter, the carbon source organic matter and the structural auxiliary agent is (1).
S3: preparation of Pt 1 @ PNC catalyst:
1kg of Pt 1 /SiO 2 Mixing the @ PNC intermediate with 2.5L and 6mol/L NaOH solution, filtering to remove spherical nano-silica carrier, drying the filtrate to obtain solid, grinding the solid, heating at 800 deg.C for 5h under the protection of argon gas to etch the nitrogen-doped carbon shell with residual NaOH to obtain Pt 1 The @ PNC catalyst is a platinum monatomic hydrogen oxidation reaction electrocatalyst based on reactant enrichment, labeled J1.
Wherein, pt 1 /SiO 2 The mass-to-volume ratio of the @ PHC intermediate to the basic aqueous solution was 1g.
FIG. 1 shows Pt 1 The structure of the @ PNC catalyst J1 is a schematic diagram, and the catalyst is a hollow core-shell structure electrocatalyst composed of a catalytic active center and a porous nitrogen-doped hollow carbon shell (PNC), wherein the catalytic active center is a platinum metal Pt distributed by single atoms 1 The platinum metal loading is 4%, and the cavity formed by PNC provides an active surface area, and has the functions of hydrogen enrichment and reaction center stabilization.
FIG. 2 shows Pt 1 The high power transmission electron micrograph of @ PNC catalyst J1 shows that the metal platinum is in a monoatomic state and is very uniformly distributed in the cavity of the PNC shell, and the thickness of the PNC shell is 8nm through measurement.
FIG. 3 is a diagram of an expanded X-ray absorption fine structure, and it can be seen that Pt exists in Pt as a single atom 1 @ PNC catalyst, no platinum clusters or particulate platinum.
Examples 2-8 preparation of a platinum monatomic hydrogen oxidation reaction electrocatalyst based on reactant enrichment
Examples 2-8 are processes for preparing a platinum monatomic hydrogen oxidation electrocatalyst based on reactant enrichment, which are substantially the same as in example 1, except for the selection of raw materials and the adjustment of other process parameters, which are identified in table 1 for the raw material reference codes and in table 2 for the process parameter adjustments.
TABLE 1 materials Mark code
Table 2 examples 2-8 process parameters
The prepared electro-catalyst for the hydrogen oxidation reaction of the platinum monatomic based on the enrichment of the reactant is Pt 1 The catalyst is a hollow core-shell structure electrocatalyst consisting of a catalytic active center and a porous nitrogen-doped hollow carbon shell (PNC), wherein the catalytic active center is a platinum metal Pt distributed in a single atom 1 The platinum metal loading is 1-12%, and a cavity formed by PNC provides an active surface area, and has the functions of enriching hydrogen and stabilizing a reaction center; the diameter of the porous nitrogen-doped hollow carbon shell is 5nm-100nm.
Example 9 detection of the Performance of an electrocatalyst for a platinum monatomic Hydrogen oxidation reaction based on enrichment of the reactants
One) Pt 1 @ PNC catalyst J1 and H of Pt/C 2 -striping curve
The experimental method comprises the following steps: 5mg of Pt 1 Mixing the @ PNC with 970 mu L of isopropanol and 30 mu L of Nafion membrane solution (mass fraction is 5 percent, duPont), absorbing 5 mu L of the mixture after the mixture is uniformly dispersed by ultrasonic oscillation for 40min, uniformly coating the mixture on a glassy carbon rotating ring plate electrode, and drying the mixture in the air for 10min to obtain a catalyst working electrode JJ1;
the catalyst working electrode was placed in 0.1M HClO saturated with hydrogen 4 After the electrolyte is dissolved for 20min, the hydrogen is switched to nitrogen to dissolve out the hydrogen dissolved in the electrolyte, a linear scanning polarization curve is recorded on an electrochemical workstation (CHI 650E, shanghai Chenghua instruments Co.), the scanning range is 0.075-1.0V (relative to a standard hydrogen electrode), the scanning speed is 10mV/s, the result is recorded, and H is drawn 2 -striping curve;
repeating the above operation on Pt/C to obtain a catalyst working electrode JJ2, and drawing a corresponding H 2 -striping curve. Wherein Pt/C is commercially available Alfa Pt/C (20 wt.%).
The experimental results are as follows: the results are shown in FIG. 4, which shows that Pt is compared to Pt/C 1 The surface of the @ PNC catalyst J1 can adsorb more hydrogen in a chemical adsorption state, and the surface active area in the cavity of the PNC is enriched with reactant hydrogen, so that the collision frequency of the hydrogen and a catalytic activity center is effectively increased, the adsorption and oxidation rate of the hydrogen on the surface of the catalytic activity center is promoted, and the Pt is improved 1 @ PNC catalyst J1 kinetic reaction rate in the hydrogen oxidation reaction.
Di) Pt 1 Test of catalytic Performance of the Hydrogen Oxidation reaction of @ PNC catalyst J1 and Pt/C
The detection method comprises the following steps: adopting a three-electrode system, taking JJ1 prepared in the step I) as a working electrode, an Ag/AgCl electrode as a reference electrode, a Pt wire as an auxiliary electrode, taking a hydrogen saturated 0.1mol/L perchloric acid aqueous solution as an electrolyte solution, recording a linear scanning polarization curve on an electrochemical workstation (CHI 660d, shanghai Chenghua apparatus company), wherein the rotating speed of a rotating electrode is 1600rpm, the scanning range is-0.02-0.1V (relative to a standard hydrogen electrode), the scanning speed is 10mV/s, recording results, drawing a curve chart, and obtaining the result as shown in figure 5;
the current-time curve of the catalyst is detected under the condition of a scanning range of 0.1V, and the result is shown in figure 6;
two) detection method in the middle was taken with the catalyst working electrode JJ2 instead of the catalyst working electrode JJ1, and the results are shown in fig. 5, 6.
And (3) detection results: FIG. 5 and FIG. 6 show Pt 1 The hydrogen oxidation reaction activity curve and current density-time curve of the @ PNC catalyst, and it can be seen from FIGS. 5 and 6 that Pt prepared by the method of the present invention 1 @ PNC catalyst Pt at platinum loadings much lower than commercial Pt/C (20 wt.%) 1 The catalytic activity and stability of @ PNC are obviously improved compared with those of a comparison sample Pt/C, which shows that the high-concentration hydrogen in the PNC shell increases the collision frequency of reactants and a catalytic activity center and increases the effective chemical adsorption and oxidation reaction of the hydrogen in the activity center; on the other hand, the strong coordination of the nitrogen atoms in the PNC shell and Pt can effectively inhibit the dissolution, aggregation and migration of the monoatomic Pt, and the overall stability of the catalyst is greatly improved.
The performance tests of example 9 were performed on all of J2-J8 prepared in examples 2-8, and the test results were consistent, which indicates that the platinum monatomic hydrogen oxidation electrocatalyst based on reactant enrichment of the invention has high kinetic reaction rate in the hydrogen oxidation reaction, good overall stability of the catalyst, low noble metal loading, and high utilization rate, and is suitable for being used as a catalyst for electrocatalytic hydrogen oxidation reaction and hydrogen evolution reaction.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in other forms, and any person skilled in the art may use the above-mentioned technical content as a teaching to make changes or modifications to the equivalent embodiments with equivalent changes, but all those simple changes, equivalent changes and modifications made to the above-mentioned embodiments without departing from the technical spirit of the present invention, and still all those embodiments are within the scope of the present invention as claimed in the claims.
Claims (7)
1. A preparation method of a platinum monatomic hydrogen oxidation reaction electrocatalyst based on reactant enrichment is characterized in that,
comprises the following steps which are carried out in sequence:
s1, preparing Pt x+ /SiO 2 Intermediates
Soaking spherical nano silicon dioxide carrier and platinum metal precursor solution in equal volume, mixing, performing ultrasonic treatment, ball milling, vacuum drying, cooling and drying to obtain Pt x+ /SiO 2 An intermediate;
s2, preparing Pt 1 /SiO 2 Intermediates of @ PNC
Mixing Pt x+ /SiO 2 Uniformly mixing the intermediate, the nitrogen-containing organic matter, the carbon source organic matter and the structural assistant, anchoring platinum atoms through polymerization reaction, performing suction filtration to obtain a solid, drying, grinding, heating under the protection of inert gas, and cooling to obtain Pt 1 /SiO 2 @ PNC intermediate;
wherein the nitrogen-containing organic matter is at least one of dopamine, urea, thiourea, ethylenediamine, L-cysteine, cyanamide, dicyandiamide and melamine;
the carbon source organic matter is at least one of dopamine, chitosan, glucose, resorcinol, carbon tetrachloride, ethylene diamine tetraacetic acid and formaldehyde;
the structural auxiliary agent is m-phenylenediamine, p-aminophenol or m-diphenol;
s3, preparing Pt 1 @ PNC catalyst
Mixing Pt 1 /SiO 2 Mixing the @ PNC intermediate with alkaline aqueous solution, filtering, drying the filtrate to obtain solid, grinding, heating under the protection of inert gas, etching to obtain Pt 1 @ PNC catalyst.
2. The method for preparing a reactant-enriched platinum monatomic hydrogen oxidation reaction electrocatalyst according to claim 1,
in the step S1, the spherical nano silicon dioxide carrier is prepared by a chemical precipitation method;
the mass ratio of the platinum metal precursor to the deionized water in the platinum metal precursor solution is 1:1-50, and the platinum metal precursor is chloroplatinic acid, acetylacetone platinum or chloroplatinate.
3. The method for preparing an electrocatalyst for a monatomic hydrogen oxidation reaction based on enriched platinum for a reactant according to claim 1 or 2,
in the step S1, the temperature of the vacuum drying is 50-200 ℃, and the time is 0.2-12h.
4. The method for preparing an electrocatalyst for a monatomic hydrogen oxidation reaction based on enriched platinum for a reactant according to claim 1 or 2,
in step S2, the Pt x+ /SiO 2 The mass ratio of the intermediate, the nitrogen-containing organic matter, the carbon source organic matter and the structural assistant is 1:1-100.
5. The method for preparing an electrocatalyst for a monatomic hydrogen oxidation reaction based on enriched platinum for a reactant according to claim 1 or 2,
in the step S2, the heating temperature is 200-800 ℃, and the time is 0.2-12h; the cooling is to 18-26 ℃.
6. The method for preparing a reactant-enriched platinum monatomic hydrogen oxidation reaction electrocatalyst according to claim 1,
in the step S3, the process is carried out,
the Pt is 1 /SiO 2 The mass-volume ratio of the @ PNC intermediate to the alkaline aqueous solution is 1 g;
the heating temperature is 200-800 ℃, and the time is 0.2-12h.
7. The method for preparing an electrocatalyst for a monatomic hydrogen oxidation reaction based on enriched platinum for a reactant according to claim 1 or 2,
in step S3, OH in the alkaline aqueous solution - The concentration of (B) is 0.5-12mol/L.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105529475A (en) * | 2015-12-30 | 2016-04-27 | 中国科学院长春应用化学研究所 | A kind of platinum single atom dispersed catalyst and preparation method thereof |
| CN106654307A (en) * | 2017-01-10 | 2017-05-10 | 大连理工大学 | Preparation method and application of noble metal@graphite layer core-shell structured electro-catalyst |
| CN108906113A (en) * | 2018-08-17 | 2018-11-30 | 北京化工大学 | A kind of monatomic catalyst of noble metal of high load amount and its preparation method and application |
| CN109103473A (en) * | 2018-08-01 | 2018-12-28 | 大连理工大学 | Nitrogen-doped carbon for alkaline hydroxide reaction supports the preparation method and application of the metal nanoparticle elctro-catalyst of uniform particle diameter |
| CN109126857A (en) * | 2018-10-22 | 2019-01-04 | 南京大学 | Monatomic catalyst of a kind of metal based on nano cages carrier and preparation method thereof |
| CN109248712A (en) * | 2017-07-14 | 2019-01-22 | 中国科学院苏州纳米技术与纳米仿生研究所 | Monatomic dopen Nano carbon material catalytic carrier of metal and its preparation method and application |
| CN109950566A (en) * | 2019-04-15 | 2019-06-28 | 南京大学 | A high-performance oxygen reduction catalyst based on enhanced surface function and its preparation method |
| CN111841600A (en) * | 2020-07-03 | 2020-10-30 | 南方科技大学 | Platinum-based catalyst and its preparation method and application |
| CN112387295A (en) * | 2020-12-08 | 2021-02-23 | 中国科学院过程工程研究所 | Nitrogen-doped carbon-supported ruthenium monatomic catalyst and preparation method and application thereof |
-
2021
- 2021-05-31 CN CN202110600317.9A patent/CN113373475B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105529475A (en) * | 2015-12-30 | 2016-04-27 | 中国科学院长春应用化学研究所 | A kind of platinum single atom dispersed catalyst and preparation method thereof |
| CN106654307A (en) * | 2017-01-10 | 2017-05-10 | 大连理工大学 | Preparation method and application of noble metal@graphite layer core-shell structured electro-catalyst |
| CN109248712A (en) * | 2017-07-14 | 2019-01-22 | 中国科学院苏州纳米技术与纳米仿生研究所 | Monatomic dopen Nano carbon material catalytic carrier of metal and its preparation method and application |
| CN109103473A (en) * | 2018-08-01 | 2018-12-28 | 大连理工大学 | Nitrogen-doped carbon for alkaline hydroxide reaction supports the preparation method and application of the metal nanoparticle elctro-catalyst of uniform particle diameter |
| CN108906113A (en) * | 2018-08-17 | 2018-11-30 | 北京化工大学 | A kind of monatomic catalyst of noble metal of high load amount and its preparation method and application |
| CN109126857A (en) * | 2018-10-22 | 2019-01-04 | 南京大学 | Monatomic catalyst of a kind of metal based on nano cages carrier and preparation method thereof |
| CN109950566A (en) * | 2019-04-15 | 2019-06-28 | 南京大学 | A high-performance oxygen reduction catalyst based on enhanced surface function and its preparation method |
| CN111841600A (en) * | 2020-07-03 | 2020-10-30 | 南方科技大学 | Platinum-based catalyst and its preparation method and application |
| CN112387295A (en) * | 2020-12-08 | 2021-02-23 | 中国科学院过程工程研究所 | Nitrogen-doped carbon-supported ruthenium monatomic catalyst and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Mesoporous Nitrogen-Doped Carbon-Nanosphere-Supported Isolated Single-Atom Pd Catalyst for Highly Efficient Semihydrogenation of Acetylene;Quanchen Feng等;《Adv. Mater.》;20190725;第31卷;第1901024-1—1901024-7页及支持信息 * |
| Pt Single Atoms Supported on N-Doped Mesoporous Hollow Carbon Spheres with Enhanced Electrocatalytic H2-Evolution Activity;Panyong Kuang等;《Adv. Mater.》;20210401;第33卷;第2008599-1—2008599-9页 * |
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