CN109046408B - Composite hydrogen evolution electro-catalytic material and preparation method and application thereof - Google Patents
Composite hydrogen evolution electro-catalytic material and preparation method and application thereof Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 82
- 239000001257 hydrogen Substances 0.000 title claims abstract description 82
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 239000000463 material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000010941 cobalt Substances 0.000 claims abstract description 66
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 66
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000007833 carbon precursor Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 12
- 238000005868 electrolysis reaction Methods 0.000 abstract description 6
- 230000002378 acidificating effect Effects 0.000 abstract description 3
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- 230000007935 neutral effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000919 ceramic Substances 0.000 description 10
- 229910021389 graphene Inorganic materials 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 239000002041 carbon nanotube Substances 0.000 description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 description 6
- 239000002135 nanosheet Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- NZESGFPAWOEZLP-UHFFFAOYSA-N [N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[Co+2].[Co+2].[Co+2] Chemical group [N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[Co+2].[Co+2].[Co+2] NZESGFPAWOEZLP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910021404 metallic carbon Inorganic materials 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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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
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- 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
- B01J27/24—Nitrogen compounds
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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Abstract
The invention belongs to the field of hydrogen production by water electrolysis, and particularly relates to a preparation method and application of a composite hydrogen evolution electro-catalytic material. The method for preparing the composite hydrogen evolution electro-catalysis material specifically comprises the following steps: dispersing polyvinylpyrrolidone and cobalt nitrate hexahydrate in deionized water, and stirring to obtain a mixed solution; performing water bath reaction, calcining the product in a tubular furnace, naturally cooling to room temperature, and washing to obtain a cobalt simple substance @ three-dimensional nitrogen-doped porous carbon material; and mixing the prepared cobalt simple substance @ three-dimensional nitrogen-doped porous carbon material with a phosphorus source, calcining in a tubular furnace, washing and drying the obtained product to obtain the cobalt phosphide @ three-dimensional nitrogen-doped porous carbon composite hydrogen evolution electrocatalytic material. The invention adopts a two-step synthesis method, and the preparation method is easy to operate, simple and feasible; the used raw materials have rich reserves and low price. The composite hydrogen evolution electro-catalysis material prepared by the invention has a three-dimensional porous structure and has excellent electro-catalysis hydrogen evolution performance under acidic, neutral and alkaline conditions.
Description
Technical Field
The invention belongs to the field of hydrogen production by water electrolysis, and particularly relates to a preparation method and application of a composite hydrogen evolution electro-catalysis material, in particular to a cobalt phosphide @ three-dimensional nitrogen-doped porous carbon composite hydrogen evolution electro-catalysis material and a preparation method and application thereof.
Background
With the increasing energy crisis and environmental pollution, developing green energy and solving the problems of environmental pollution and energy crisis are the first choice for maintaining sustainable development. The main energy in China is non-renewable fossil fuel, the energy structure is single, and carbon dioxide released by the fossil fuel in the combustion process is also the culprit of the greenhouse effect. The current renewable energy sources mainly comprise wind energy, solar energy, biomass energy, hydrogen energy and the like. The hydrogen energy is a recognized ideal fuel, the combustion value of the hydrogen energy is 3 times that of petroleum, and most importantly, the combustion product of the hydrogen is only water, so that the hydrogen energy is an efficient and clean energy source. Therefore, development of hydrogen energy is the most effective method for solving the current problems.
At present, the most efficient electrocatalytic Hydrogen Evolution Reaction (HER) catalyst is still a noble metal Pt, and the noble metal has rare reserves and high price, so that the catalyst cannot be produced and applied on a large scale. Therefore, the development of non-noble metal HER catalysts capable of replacing the noble metal Pt is an effective way to solve this problem. Cobalt phosphide proved to be a highly active HER catalyst, and is suitable for large-scale production applications due to its abundant and inexpensive reserves, but the monomeric cobalt phosphide tends to agglomerate, which is not conducive to sufficient exposure of active sites, an effective strategy to prevent agglomeration when combined with a suitable carbon support. For example, graphene and carbon nanotubes are commonly used as the carbon support. Although the graphene and the carbon nano tube can anchor the cobalt phosphide nanoparticles to prevent the cobalt phosphide nanoparticles from agglomerating, the preparation process of the graphene needs to use strong oxidants such as concentrated sulfuric acid, potassium permanganate and the like, the time consumption is long, the preparation conditions are harsh and dangerous, the obtained graphene is difficult to disperse, and the defects limit the general application of the graphene; the preparation process of the carbon nanotube is complicated, and uniform carbon nanotubes are difficult to obtain. Therefore, the method for loading the nano particles with HER catalytic activity on the carbon carrier which is easy to prepare by adopting a proper method is an effective way for improving the easy agglomeration of the monomers and solving the defects in the preparation of the carbon carriers such as graphene and the like.
At present, the cobalt phosphide nano particle size of some catalysts compounded by cobalt phosphide and carbon carriers is larger, so that the exposure of active sites is insufficient, the overpotential for hydrogen evolution by water electrolysis is higher, and electric energy is wasted; poor stability, inability to operate stably for long periods of time, resulting in low HER efficiency; some catalysts can only obtain better hydrogen evolution activity under single conditions of acidity or alkalinity and the like, and cannot work in the environment of full-pH aqueous solution, so that the application range of the HER catalyst is limited. In addition, different carbon materials can have special effects, such as doping of nitrogen atoms can cause carbon material defects and generate more active sites, thereby enhancing the catalytic activity thereof.
Disclosure of Invention
The invention aims to overcome the technical defects in the prior art, such as: the cobalt phosphide monomer is easy to agglomerate and is not beneficial to fully exposing active sites; the adopted graphene is harsh and dangerous in preparation conditions and difficult to disperse; it is difficult to obtain uniform carbon nanotubes; the invention provides a preparation method of a composite hydrogen evolution electro-catalysis material, which solves the problems that the cobalt phosphide nano-particle size is larger, the exposure of an active site is insufficient, the overpotential of electrolysis water hydrogen evolution is higher, the electric energy is wasted, the stability is poor, the HER efficiency is low and the like in some catalysts compounded by cobalt phosphide and a carbon carrier.
Specifically, the technical scheme adopted by the invention is as follows:
(1) preparing a metal carbon precursor:
dispersing polyvinylpyrrolidone and cobalt nitrate hexahydrate in deionized water, and stirring to obtain a mixed solution; performing water bath reaction to obtain a product; placing the product in a tubular furnace for calcining, naturally cooling to room temperature, and washing to obtain a cobalt simple substance @ three-dimensional nitrogen-doped porous carbon material;
(2) phosphorization:
mixing the cobalt simple substance @ three-dimensional nitrogen-doped porous carbon material obtained in the step (1) with a phosphorus source, placing the mixture in a tubular furnace for calcination, and washing and drying the obtained product to obtain the cobalt phosphide @ three-dimensional nitrogen-doped porous carbon composite hydrogen evolution electrocatalytic material.
In the step (1), the mass ratio of the cobalt nitrate hexahydrate to the polyvinylpyrrolidone is 0.8-1.4; the stirring time is 10min-30 min; the water bath temperature is 65-75 ℃, and the water bath time is 5-7 h; the calcination temperature is 750-800 ℃, the calcination time is 40-50 min, and the heating rate is 5 ℃ min-1；
In the step (2), the phosphorus source is red phosphorus; the mass ratio of the cobalt simple substance @ three-dimensional nitrogen-doped porous carbon material to the phosphorus source is 0.5-0.7; the calcination temperature is 500-600 ℃, the calcination time is 1.5-2.5 h, and the heating rate is 5 ℃ min-1(ii) a The drying temperature was 80 ℃.
The invention also provides a composite hydrogen evolution electro-catalytic material which is in a three-dimensional porous carbon nanosheet network structure and has a large specific surface area; the cobalt phosphide nano-particles are uniformly embedded into the carbon nano-sheets, and the particle size of the cobalt phosphide is 5-10 nm.
The invention also provides the application of the composite hydrogen evolution electro-catalytic material, and the composite hydrogen evolution electro-catalytic material is used for electrolyzing water to evolve hydrogen.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention takes polyvinylpyrrolidone (PVP) as a carbon source and cobalt nitrate hexahydrate as a cobalt source, and the used raw materials have rich reserves and low price. The polyvinylpyrrolidone can be used as a dispersing agent to ensure that the cobalt nitrate is dispersed in the aqueous solution more uniformly, and the reduced cobalt simple substance has smaller size and uniform particle size. At high temperature, gas generated by decomposition of the cobalt hexa-nitrate causes formation of three-dimensional porous carbon, and cobalt ions are reduced into cobalt simple substances to be embedded into the nano carbon sheet, so that the process of firstly preparing carbon carriers in some researches is saved, the particle size of finally obtained cobalt phosphide is only 5-10nm, and more active sites are exposed.
(2) In addition, the invention adopts a two-step synthesis method, the cobalt simple substance @ three-dimensional nitrogen-doped porous carbon material is prepared in the first step, and the cobalt phosphide @ three-dimensional nitrogen-doped porous carbon composite hydrogen evolution electrocatalytic material is prepared in the second step. In the preparation process, the specific surface area of the compound is increased and the conductivity of the compound is improved due to the introduction of the three-dimensional porous carbon, so that the transmission rate of electrons is increased while more active sites are exposed, and the electro-catalytic hydrogen evolution performance of the compound is greatly enhanced.
(3) Compared with a catalyst material taking graphene and carbon nano tubes as carriers, the catalyst material can be prepared only in small batches, the catalyst material is easy for mass production, cobalt phosphide ions embedded into carbon nano sheets are wrapped by surrounding carbon, direct contact with an electrolyte solution is avoided, and the catalyst material is more stable than a catalyst exposed on the surface of a carbon carrier. The conductivity of the carbon material doped with nitrogen atoms is further improved, thereby improving the hydrogen evolution efficiency.
(4) The cobalt phosphide @ three-dimensional nitrogen-doped porous carbon composite hydrogen evolution electrocatalytic material prepared by the invention has small cobalt phosphide nano particles which are about 10nm and are uniformly dispersed on a carbon nano sheet; the carbon material has a three-dimensional porous structure, so that multi-channel transmission of electrons and ions in an electrolyte solution is guaranteed, the electronic structure of the carbon material can be optimized by doping nitrogen, and the electro-catalytic activity is further enhanced; has excellent catalytic performance under acidic, neutral and alkaline conditions. The composite hydrogen evolution electro-catalysis material prepared by the invention has good electro-catalysis hydrogen evolution performance within the full pH range, and the electro-catalysis hydrogen evolution performance is 0.5M H2SO41.0M PBS and 1.0M KOH, when the current density reached 10mA cm-2When in use, the required hydrogen evolution overpotential is 131mV, 300mV and 180mV in sequence, and the corresponding tafel slopes are 58 mV dec in sequence-1、71 mV dec-1And 65 mV dec-1。
Drawings
FIG. 1 is an XRD diffraction spectrum of the cobalt phosphide @ three-dimensional nitrogen-doped porous carbon composite hydrogen evolution electrocatalytic material;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the cobalt phosphide @ three-dimensional nitrogen-doped porous carbon composite hydrogen evolution electrocatalytic material;
FIG. 3 is a Transmission Electron Microscope (TEM) of the cobalt phosphide @ three-dimensional nitrogen-doped porous carbon composite hydrogen evolution electrocatalytic material of the present invention;
FIG. 4 is a graph at 0.5M H2SO4In the electrocatalytic hydrogen evolution curve diagram of the cobalt phosphide @ three-dimensional nitrogen-doped porous carbon composite hydrogen evolution electrocatalytic material;
FIG. 5 is a graph at 0.5M H2SO4In the method, a Tafel slope diagram of the cobalt phosphide @ three-dimensional nitrogen-doped porous carbon composite hydrogen evolution electro-catalytic material is shown;
FIG. 6 is a graph of electrocatalytic hydrogen evolution curves for cobalt phosphide @ three-dimensional nitrogen doped porous carbon composite hydrogen evolution electrocatalytic material in 1.0M KOH;
FIG. 7 is a Tafel slope diagram of cobalt phosphide @ three-dimensional nitrogen-doped porous carbon composite hydrogen evolution electrocatalytic material in 1.0M KOH;
FIG. 8 is a graph of electrocatalytic hydrogen evolution curves for cobalt phosphide @ three-dimensional nitrogen-doped porous carbon composite hydrogen evolution electrocatalytic material in 1.0M PBS;
fig. 9 is a tafel slope diagram of cobalt phosphide @ three-dimensional nitrogen-doped porous carbon composite hydrogen evolution electrocatalytic material in 1.0M PBS.
Detailed Description
The invention is further illustrated below with reference to specific examples:
example 1:
(1) preparing a metal carbon precursor:
5g polyvinylpyrrolidone was dissolved in 150 ml solution containing 4 g Co (NO)3)2·6H2Stirring for 10 minutes in deionized water containing O to obtain a mixed solution; then transferring the mixed solution into a water bath and carrying out water bath for 5 hours at 65 ℃ to obtain a product; then the product is put into a porcelain crucible and calcined in a tube furnace at 750 ℃ for 40min, and the heating rate is 5 ℃ min-1Naturally cooling to room temperature, collecting the obtained product, and washing with deionized water and ethanol for 3 times respectivelyAnd obtaining the cobalt simple substance @ three-dimensional nitrogen-doped porous carbon material (Co @3D-NPC composite material).
(2) Phosphorization:
placing 0.5g of the Co @3D-NPC composite material obtained in the step (1) and 1g of red phosphorus powder in a ceramic boat, and placing the red phosphorus powder on the upstream side; then heating the ceramic boat in a quartz tube at 500 ℃ for 1.5h, protecting the ceramic boat under nitrogen flow, and raising the temperature at the rate of 5 ℃ min-1(ii) a And finally, cooling the furnace to room temperature, washing the obtained black product with deionized water and ethanol for 3 times respectively, and drying at 80 ℃ to obtain the cobalt phosphide @ three-dimensional nitrogen-doped porous carbon composite hydrogen evolution electro-catalytic material (CoP @3D-NPC composite material).
Example 2:
(1) preparation of metallic carbon precursor
5g polyvinylpyrrolidone was dissolved in 150 ml solution containing 6g Co (NO)3)2·6H2Stirring for 20 minutes in deionized water containing O to obtain a mixed solution; then transferring the mixed solution into a water bath and carrying out water bath for 6 hours at 70 ℃ to obtain a product; then the product is put into a ceramic crucible and calcined for 45min in a tube furnace at 775 ℃, and the heating rate is 5 ℃ per min-1And naturally cooling to room temperature, collecting the obtained product, and washing the product for 3 times by using deionized water and ethanol respectively to obtain the cobalt simple substance @ three-dimensional nitrogen-doped porous carbon material (Co @3D-NPC composite material).
(2) Phosphorization:
placing 0.6g of the Co @3D-NPC composite material obtained in the step (1) and 1g of red phosphorus powder in a ceramic boat, and placing the red phosphorus powder on the upstream side; then heating the ceramic boat in a quartz tube at 550 ℃ for 2h, protecting the ceramic boat under nitrogen flow, and raising the temperature at the rate of 5 ℃ min-1(ii) a And finally, cooling the furnace to room temperature, washing the obtained black product with deionized water and ethanol for 3 times respectively, and drying at 80 ℃ to obtain the cobalt phosphide @ three-dimensional nitrogen-doped porous carbon composite hydrogen evolution electro-catalytic material (CoP @3D-NPC composite material).
Example 3:
(1) preparing a metal carbon precursor:
5g of polyvinyl pyridinePyrrolidinone was dissolved in 150 ml of a solution containing 7g of Co (NO)3)2·6H2Stirring for 30 minutes in deionized water containing O to obtain a mixed solution; then transferring the mixed solution into a water bath and carrying out water bath for 7 hours at the temperature of 75 ℃ to obtain a product; then the product is put into a porcelain crucible and calcined for 50min in a tube furnace at 800 ℃, and the heating rate is 5 ℃ min-1And naturally cooling to room temperature, collecting the obtained product, and washing the product for 3 times by using deionized water and ethanol respectively to obtain the cobalt simple substance @ three-dimensional nitrogen-doped porous carbon material (Co @3D-NPC composite material).
(2) Phosphorization:
placing 0.7g of the Co @3D-NPC composite material obtained in the step (1) and 1g of red phosphorus powder in a ceramic boat, and placing the red phosphorus powder on the upstream side; then heating the ceramic boat in a quartz tube at 600 ℃ for 2.5h, protecting the ceramic boat under nitrogen flow, and raising the temperature at the rate of 5 ℃ min-1(ii) a And finally, cooling the furnace to room temperature, washing the obtained black product with deionized water and ethanol for 3 times, and drying at 80 ℃ to obtain the cobalt phosphide @ three-dimensional nitrogen-doped porous carbon composite hydrogen evolution electrocatalytic material (CoP @3D-NPC composite material).
And (3) testing the electrocatalytic hydrogen evolution performance:
the electrocatalytic hydrogen evolution performance of the Co @3D-NPC composite materials prepared in examples 1-3 was tested by using a three-electrode system. The working electrode is prepared by adopting a dripping coating method, and the specific process is as follows: weighing 5 mg of sample in a 2 mL centrifuge tube, adding 0.98 mL of ethanol and 0.02 mL of Nafion solution with the mass fraction of 5%, and carrying out ultrasonic treatment for 30min to form a catalyst solution. Polishing a 5 mm-diameter glassy carbon electrode serving as a working electrode to form a mirror surface, dripping 0.01 ml of catalyst solution on the working electrode, naturally airing, and performing electrochemical test, wherein the test solutions are respectively 0.5M H2SO4，1.0 M KOH，1.0 MPBS。
At 0.5MH2SO41.0MPBS and 1.0MKOH, when the current density reaches 10mAcm-2When in use, the required hydrogen evolution overpotential is 131mV, 300mV and 180mV in sequence, and the corresponding tafel slopes are respectively only 58 mV dec-1、71 mV dec-1And 65 mV dec-1。
Fig. 1 is an XRD diffraction spectrum of the cobalt phosphide @ three-dimensional nitrogen-doped porous carbon composite hydrogen evolution electrocatalytic material (cobalt phosphide @3D nitrogen-doped porous carbon) of the present invention, specifically, the XRD diffraction spectrum of the cobalt phosphide @3D nitrogen-doped porous carbon obtained in example 2, wherein a main diffraction peak of the XRD diffraction spectrum coincides with a CoP phase standard card JCPDS:29-0497, which indicates successful preparation of the cobalt phosphide @3D nitrogen-doped porous carbon.
FIG. 2 is a scanning electron microscope image of the cobalt phosphide @ three-dimensional nitrogen-doped porous carbon composite hydrogen evolution electrocatalytic material; as can be seen from fig. 2, it can be seen that the cobalt phosphide @3D nitrogen-doped porous carbon sample has a three-dimensional porous carbon nanosheet network structure and has a large specific surface area.
Fig. 3 is a transmission electron microscope image of the cobalt phosphide @ three-dimensional nitrogen-doped porous carbon composite hydrogen evolution electrocatalytic material, and it can be seen that CoP nanoparticles are uniformly embedded into carbon nanosheets, the particle size of the cobalt phosphide is 5-10nm, and the smaller particle size is beneficial to full exposure of active sites, so that the electrocatalytic activity is improved.
FIG. 4 is a graph at 0.5M H2SO4In the graph, a cobalt phosphide @ three-dimensional nitrogen-doped porous carbon composite hydrogen evolution electro-catalytic material (cobalt phosphide @3D nitrogen-doped porous carbon) electro-catalytic hydrogen evolution graph is shown; as can be seen from FIG. 4, when the current density reached 10mA cm-2The hydrogen evolution overpotential required is only 131mV, respectively.
FIG. 5 is a graph at 0.5M H2SO4In the method, a tafel slope diagram of the cobalt phosphide @ three-dimensional nitrogen-doped porous carbon composite hydrogen evolution electro-catalytic material (cobalt phosphide @3D nitrogen-doped porous carbon); as can be seen from FIG. 5, the corresponding Tafel slope is 58 mV dec-1。
FIG. 6 is the electrolytic water hydrogen evolution curve diagram of cobalt phosphide @ three-dimensional nitrogen-doped porous carbon composite hydrogen evolution electro-catalytic material (cobalt phosphide @3D nitrogen-doped porous carbon) in 1.0MKOH, when the current density reaches 10mA cm-2The hydrogen evolution overpotentials required are only 180mV, respectively.
FIG. 7 is a Tafel slope plot of cobalt phosphide @ three-dimensional nitrogen-doped porous carbon composite hydrogen evolution electrocatalytic material (cobalt phosphide @3D nitrogen-doped porous carbon) in 1.0M KOH; as can be seen from fig. 7, forThe Tafel slope should be 65 mV dec-1。
FIG. 8 is a graph of the hydrogen evolution by electrolysis water of the cobalt phosphide @ three-dimensional nitrogen-doped porous carbon composite hydrogen evolution electro-catalytic material (cobalt phosphide @3D nitrogen-doped porous carbon) in 1.0MPBS, when the current density reaches 10mA cm-2The hydrogen evolution overpotential required is only 300mV, respectively.
FIG. 9 is a Tafel slope diagram of CoP @ three-dimensional N-doped porous carbon composite hydrogen evolution electrocatalytic material (CoP @3D N-doped porous carbon) in 1.0MPBS, and the corresponding Tafel slope is 71 mV dec-1。
The composite hydrogen evolution electro-catalysis material prepared by the invention has good electro-catalysis hydrogen evolution performance within the full pH range, namely under the acidic, neutral and alkaline conditions, and the electro-catalysis hydrogen evolution performance is 0.5M H2SO41.0M PBS and 1.0M KOH, when the current density reached 10mA cm-2When in use, the required hydrogen evolution overpotential is 131mV, 300mV and 180mV in sequence, and the corresponding tafel slopes are 58 mV dec in sequence-1、71 mV dec-1And 65 mV dec-1. In conclusion, the preparation method greatly reduces the hydrogen evolution overpotential of the prepared cobalt phosphide @ three-dimensional nitrogen-doped porous carbon, improves the stability and the electrolysis efficiency, and solves the problem that some catalysts can only work in a single aqueous solution environment.
Claims (8)
1. The preparation method of the composite hydrogen evolution electrocatalytic material is characterized by comprising the following steps of:
(1) preparing a metal carbon precursor:
dispersing polyvinylpyrrolidone and cobalt nitrate hexahydrate in deionized water, and stirring to obtain a mixed solution; performing water bath reaction to obtain a product; placing the product in a tubular furnace for calcining, naturally cooling to room temperature, and washing to obtain a cobalt simple substance @ three-dimensional nitrogen-doped porous carbon material;
(2) phosphorization:
mixing the cobalt simple substance @ three-dimensional nitrogen-doped porous carbon material obtained in the step (1) with a phosphorus source, placing the mixture in a tubular furnace for calcination, and washing and drying the obtained product to obtain the cobalt phosphide @ three-dimensional nitrogen-doped porous carbon composite hydrogen evolution electrocatalytic material.
2. The method for preparing the composite hydrogen evolution electrocatalytic material as set forth in claim 1, wherein in the step (1), the mass ratio of the cobalt nitrate hexahydrate to the polyvinylpyrrolidone is 0.8-1.4.
3. The method for preparing the composite hydrogen evolution electrocatalytic material as set forth in claim 1, wherein in the step (1), the stirring time is 10-30 min; the temperature of the water bath is 65-75 ℃, and the time of the water bath is 5-7 h.
4. The method for preparing the composite hydrogen evolution electro-catalytic material according to claim 1, wherein in the step (1), the calcination temperature is 750-800 ℃, the calcination time is 40-50 min, and the temperature rise rate is 5 ℃ min-1。
5. The method for preparing the composite hydrogen evolution electrocatalytic material as set forth in claim 1, wherein in the step (2), the phosphorus source is red phosphorus.
6. The preparation method of the composite hydrogen evolution electrocatalytic material as claimed in claim 1, wherein in the step (2), the mass ratio of the cobalt simple substance @ three-dimensional nitrogen-doped porous carbon material to the phosphorus source is 0.5-0.7.
7. The method for preparing the composite hydrogen evolution electro-catalytic material according to claim 1, wherein in the step (2), the calcination temperature is 500-600 ℃, the calcination time is 1.5-2.5 h, and the temperature rise rate is 5 ℃ min-1。
8. The method for preparing a composite hydrogen evolution electrocatalytic material as set forth in claim 1, wherein the drying temperature in the step (2) is 80 ℃.
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| CN112695343A (en) * | 2020-12-15 | 2021-04-23 | 桐乡市吉曼尔信息技术有限公司 | Preparation method and application of hydrogen evolution electrocatalyst of biomass-based graphitized porous carbon |
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| CN113668008B (en) * | 2021-08-25 | 2023-01-17 | 常州大学 | Molybdenum disulfide/cobalt carbon nanotube electrocatalyst and preparation method and application thereof |
| CN113707861A (en) * | 2021-08-26 | 2021-11-26 | 合肥工业大学 | Nitrogen-doped carbon layer-coated cobalt oxide nanosheet and preparation method and energy storage application thereof |
| CN114717572B (en) * | 2022-03-30 | 2023-09-05 | 上海工程技术大学 | Cobalt-iron bimetal phosphorization nanoparticle taking nitrogen doped carbon as substrate, and preparation method and application thereof |
| CN116791140B (en) * | 2023-06-30 | 2024-05-10 | 江西师范大学 | Preparation method and application of Mn-doped CoP/MXene heterostructure composite material |
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