CN111389431B - Flake catalyst CoCuPS for hydrogen production by water electrolysis and preparation method thereof - Google Patents
Flake catalyst CoCuPS for hydrogen production by water electrolysis and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 19
- 239000001257 hydrogen Substances 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- 239000010949 copper Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 229910002520 CoCu Inorganic materials 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000012467 final product Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 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
- 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
- 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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- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
- 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
- C25B11/095—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 at least one of the compounds being organic
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- 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
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- 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
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Abstract
The inventionBelongs to the technical field of hydrogen production by water electrolysis, and discloses a flaky catalyst CoCuPS for hydrogen production by water electrolysis and a preparation method thereof. The flaky catalyst CoCuPS is CuPS 3 And CoPS two-phase mixed isomeric structures. The preparation method comprises the following steps: mixing Co (NO) 3 ) 2 ·6 H 2 O、Cu(NO 3 ) 2 ·3 H 2 O and CO (NH) 2 ) 2 Dissolving in water, stirring to dissolve until the solution is clear, transferring the solution into a reaction kettle, carrying out hydrothermal reaction for 3-9 h at the temperature of 120-150 ℃, cooling, centrifuging, washing and drying to obtain CoCu-LDH; placing CoCu-LDH downstream of the tube furnace, P 2 S 5 Placing the catalyst at the upstream of a tubular furnace, heating to 450-550 ℃ in an inert atmosphere, keeping the temperature for 1-2 h, and cooling to obtain the flaky catalyst CoCuPS. The flaky CoCuPS catalyst prepared by the invention has high-efficiency and stable catalytic activity when being used for hydrogen production by electrolyzing water.
Description
Technical Field
The invention belongs to the technical field of hydrogen production by water electrolysis, and particularly relates to a flaky catalyst CoCuPS for hydrogen production by water electrolysis and a preparation method thereof.
Background
The rapid development of economy also leads to the crisis of global energy and environment, and the development of new energy is urgent. Compared with the traditional fuel energy, new energy sources such as wind energy, solar energy and the like are developed in large quantities in recent years. The discontinuity of energy and the high loss of long-distance transmission limit the application of the energy, and the energy is mainly converted into energy which is convenient to use, such as electric energy at present. HER can convert small electrical energy into hydrogen energy for convenient utilization and storage. The hydrogen energy is clean, pollution-free and sustainable and is a new energy expected to replace fossil energy in the future. Noble metal Pt is the best HER catalyst and is not widely used due to its scarce reserves and high prices, and it is required to develop a non-noble metal catalyst which is inexpensive and abundant in reserves. The metal sulfur phosphide achieves the activity close to that of noble metal and is a promising catalyst.
The metal cobalt-based sulfide has excellent HER catalytic performance but insufficient catalytic stability, so that the precursor structure of the stable and efficient catalyst needs to be regulated to obtain a stable structure. The current research shows that the bimetallic catalyst can obtain catalytic materials with various structures and excellent performance. The interaction between the two metals can regulate and control the structure of the catalyst to obtain good catalytic performance and stability. Therefore, the further improvement of the catalyst can adjust and control different proportions by introducing elements of the second metal to obtain the ideal catalytic material. The transition metal Cu has stable chemical property, is easy to combine with other transition metals to form a stable structure, and is widely applied to energy storage. Meanwhile, recent research on the pyramid of free hydrogen adsorption energy by metal shows that the catalyst has the necessary characteristic of moderate adsorption energy. The Cu element is introduced into the Co-based catalyst to construct non-noble metal CoCu sulfide phosphide for catalysis, and the stability of the catalyst is hopefully improved by utilizing the interaction between CoCu metals, so that the high-efficiency and stable HER catalyst is obtained.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention aims to provide a flaky catalyst CoCuPS for hydrogen production by water electrolysis and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a flaky catalyst CoCuPS for hydrogen production by water electrolysis is CuPS 3 And CoPS two-phase mixed isomeric structures.
The preparation method comprises the following steps:
(1) Mixing Co (NO) 3 ) 2 ·6 H 2 O、Cu(NO 3 ) 2 ·3 H 2 O and CO (NH) 2 ) 2 Dissolving in water, stirring for dissolving until the solution is clear, transferring into a reaction kettle, carrying out hydrothermal reaction at 120-150 ℃ for 3-9 h, cooling, centrifuging, washing and drying to obtain cobalt-copper double hydroxide (CoCu-LDH);
(2) Placing the CoCu-LDH at the downstream of the tube furnace, P 2 S 5 Placing the catalyst at the upstream of a tubular furnace, heating to 450-550 ℃ in an inert atmosphere, keeping the temperature for 1-2 h, and cooling to obtain the flaky catalyst CoCuPS.
Preferably, in step (1), co (NO) 3 ) 2 ·6 H 2 O and Cu (NO) 3 ) 2 ·3 H 2 O is added in an equimolar ratio and every 2 mmol of Co (NO) 3 ) 2 ·6 H 2 O，CO(NH 2 ) 2 The dosage of the compound is 1 to 10 mol, and the dosage of the water is 60 to 80 mL.
Preferably, in step (1), washing is carried out several times with water and ethanol, respectively, and drying is carried out at a temperature of 70-90 ℃.
Preferably, in step (2), the mass ratio of CoCu-LDH: P 2 S 5 =1∶（5–10）。
Preferably, in step (2), the temperature is raised at a rate of 5 to 10 ℃/min.
Compared with the prior art, the invention adopts P 2 S 5 The CoCu bimetallic sulfide phosphide flaky CoCuPS catalyst is obtained by molecular high-temperature sulfide phosphorization CoCu-LDH, and the prepared flaky CoCuPS catalyst has ultrahigh activity and catalytic stability when used for hydrogen production by water electrolysis.
Drawings
FIG. 1: a field emission scanning electron micrograph (a) of the CoCu-LDH prepared in example 1, a field emission scanning electron micrograph (b) and a transmission electron micrograph (c) of the catalyst cocusps.
FIG. 2: example 1 and comparative examples 1-3 catalysts CoCuPS, coPS, co 2 CuPS、CoCu 2 X-ray powder diffractogram of PS.
FIG. 3: example 1 and catalysts CoCuPS, coPS, co prepared in comparative examples 1-3 2 CuPS、CoCu 2 A polarization curve (LSV) graph (a), a tafel slope graph (b), and an Electrochemical Impedance (EIS) graph (c) of an X-ray powder diffraction pattern of PS.
FIG. 4 is a schematic view of: FIG. (a) of the polarization curve (LSV) before and after 5000 CV cycles of the catalyst CoCuPS prepared in example 1 and FIG. b of the i-t stability plot.
Detailed Description
In order to make the invention clearer and clearer, the invention is further described in detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The preparation method of the catalyst CoCuPS comprises the following steps:
(1) Mixing Co (NO) 3 ) 2 ·6 H 2 O (2 mmol)、Cu(NO 3 ) 2 ·3 H 2 O (2 mmol) and CO (NH) 2 ) 2 (10 mol) dissolving in 70 mL of redistilled water, stirring and dissolving until the solution is clear, transferring the solution into a 100 mL reaction kettle, carrying out hydrothermal treatment at 150 ℃ for 6 h, cooling and centrifuging, washing with water and absolute ethyl alcohol respectively for three times, and drying at 70 ℃ to obtain flower-like cobalt-copper double hydroxide CoCu-LDH formed by nanosheets;
(2) 50 mg of CoCu-LDH is poured into a magnetic boat and placed at the downstream of the tube furnace, 0.5 g of P is taken 2 S 5 Pouring the mixture into magnetic boats, placing the magnetic boats at the upstream of a tube furnace, keeping the distance between the centers of the two magnetic boats at about 5 cm, heating the mixture to 500 ℃ at a speed of 5 ℃/min under the Ar atmosphere, keeping the temperature at 500 ℃ for 1 h, and cooling the mixture to obtain the catalyst CoCuPS.
Comparative example 1
A method for preparing a catalyst CoPS, which is different from example 1 in that: co (NO) 3 ) 2 ·6 H 2 The amount of O is 4 mmol, cu (NO) 3 ) 2 ·3 H 2 The amount of O is 0 mmol, namely no addition is carried out, and correspondingly, the product obtained in the step (1) is cobalt hydroxide which is used for replacing 'CoCu-LDH' in the step (2); the other steps are the same as in example 1.
The final product from this control example was the catalyst CoPS.
Comparative example 2
Catalyst Co 2 A process for the preparation of CuPS, which differs from example 1 in that: co (NO) 3 ) 2 ·6 H 2 The amount of O used was 2.67 mmol, cu (NO) 3 ) 2 ·3 H 2 The amount of O used was 1.33 mmol, and correspondingly, the product obtained in step (1) was Co 2 Replacing the Cu-LDH in the step (2) with the Cu-LDH; the other steps are the same as in example 1.
The final product obtained in this comparative example is catalyst Co 2 CuPS。
Comparative example 3
Catalyst CoCu 2 A method for producing PS, which is different from example 1 in that: co (NO) 3 ) 2 ·6 H 2 The amount of O used was 1.33 mmol, cu (NO) 3 ) 2 ·3 H 2 The amount of O used was 2.67 mmol, corresponding,the product obtained in the step (1) is CoCu 2 -LDH, replacing it with "CoCu-LDH" in step (2); the other steps are the same as in example 1.
The final product obtained in this comparative example is the catalyst CoCu 2 PS。
Catalyst structural characterization
FIG. 1 is a field emission scanning electron micrograph (a), a field emission scanning electron micrograph (b), and a transmission electron micrograph (c) of CoCu-LDH prepared in example 1, and of the catalyst CoCuPS. As can be seen in fig. 1 (a): the CoCu-LDH is flower-shaped and is composed of nanosheets with uniform thickness. As is clear from fig. (b) and (c): the structure of the CoCu-LDH precursor nanoflower is partially collapsed, but the catalyst CoCuPS still presents a stable nanosheet structure, the flaky structure promotes mass transfer and charge transfer, the catalyst has a high catalytic surface area, and the catalytic activity is improved accordingly.
FIG. 2 shows CoCuPS, coPS, co catalysts prepared in example 1 and comparative examples 1 to 3 2 CuPS、CoCu 2 X-ray powder diffraction pattern of PS. In FIG. 2, diamonds represent CuPS 3 The (JCPDF No. 48-1236) phase and the plum blossom represents the CoPS (JCPDF No. 27-0139) phase, indicating that CoPS only contains the CoPS phase, and CoCuPS and Co 2 CuPS、CoCu 2 PS are both CuPS 3 And CoPS two-phase mixed isomeric structure, and it can be seen that: coCuPS has moderate crystalline diffraction peaks that provide a suitable catalytic structure.
Testing of catalyst Performance
The catalysts CoCuPS, coPS and Co prepared in example 1 and comparative examples 1-3 2 CuPS、CoCu 2 PS are respectively used for producing hydrogen by electrolyzing water, and the conditions are as follows: the temperature was 25 ℃. After a catalyst of 3 mg, redistilled water of 330 muL, N-dimethylformamide of 170 muL and Nafion solution (5 wt%) of 50 muL are ultrasonically formed into uniform mixed liquid, 183 muL mixed liquid drops are sucked on 1 cm x 1 cm hydrophilic carbon fiber paper (CP) to prepare a working electrode, and the loading capacity of the catalyst on the CP is about 1 mg/cm 2 . Then taking the calomel electrode as a reference electrode and the graphite rod as an auxiliary electrode to form a three-electrode system of 0.5M H 2 SO 4 As an electrolyte, the CHI660E electrochemical workstation detects the catalytic performance of the catalyst, including a polarization curve (LSV) graph and a corresponding tafel slope graph and an Electrochemical Impedance (EIS) graph, wherein each test condition is as follows: the linear scanning sweep rate is 5 mV/s, and the frequency range of constant voltage test electrochemical impedance of RHE is 100000-0.1 Hz at-0.15V vs. Meanwhile, pt/C (the mass percentage of Pt is 20%) is used as a reference working electrode.
FIG. 3 shows the catalysts CoCuPS, coPS, co 2 CuPS、CoCu 2 A polarization curve (LSV) graph (a), a tafel slope graph (b), and an Electrochemical Impedance (EIS) graph (c) of PS. As can be seen from the LSV polarization curve shown in fig. 3 (a): at 10 mA/cm 2 CoCuPS, coPS, co 2 CuPS and CoCu 2 The overpotential of PS is respectively 154 mV, 182 mV, 315 mV and 475 mV, the overpotential of CoCuPS is minimum, is close to 65 mV of Pt/C, and is at 100 mA/cm 2 CoCuPS has an ultra-small overpotential of 345 mV at high current density, 49 mV lower than commercial Pt/C (394 mV). The tafel slope plot of fig. 3 (b) shows: coCuPS, coPS, co 2 CuPS and CoCu 2 The Tafel slopes of PS are 71 mV/dec, 74 mV/dec, 139 mV/dec and 175 mV/dec, respectively, the Tafel slope of CoCuPS is the smallest and less than 76 mV/dec of Pt/C, and a small Tafel slope indicates a fast kinetic process. The impedance plot of fig. 3 (c) shows: coCuPS, coPS, co 2 CuPS and CoCu 2 The impedance values of the PS are respectively 15 omega, 20 omega, 40 omega and 72 omega, and the impedance value of the CoCuPS is the smallest, which shows that the material has small electron transmission resistance, can accelerate the electron transfer rate in the reaction process and reduce the reaction energy consumption.
FIG. 4 is a plot of the polarization curve (LSV) before and after 5000 CV cycles of the catalyst CoCuPS (a) and the i-t stability plot (b). Fig. 4 (a) shows: the LSV curves of the catalyst before and after 5000 CV cycles are almost completely overlapped, and high stability is shown. The i-t curve of FIG. 4 (b) shows: at 20 mA/cm 2 At the current density, the operation can be stably carried out for 12 h, and the current density is hardly attenuated. It is fully shown that: the catalyst CoCuPS shows high catalytic activity and stability.
Claims (5)
1. A preparation method of a flaky catalyst CoCuPS for hydrogen production by water electrolysis is characterized by comprising the following steps: the flaky catalyst CoCuPS is CuPS 3 And a CoPS two-phase mixed isomeric structure, the preparation steps are as follows:
(1) Mixing Co (NO) 3 ) 2 ·6 H 2 O、Cu(NO 3 ) 2 ·3 H 2 O and CO (NH) 2 ) 2 Dissolving in water, stirring for dissolving until the solution is clear, transferring into a reaction kettle, carrying out hydrothermal reaction at 120-150 ℃ for 3-9 h, cooling, centrifuging, washing and drying to obtain cobalt-copper double hydroxide (CoCu-LDH);
(2) Placing the CoCu-LDH at the downstream of the tube furnace, P 2 S 5 And (3) placing the catalyst at the upstream of a tubular furnace, heating to 450-550 ℃ in an inert atmosphere, keeping for 1-2 h, and cooling to obtain the flaky catalyst CoCuPS.
2. The method for preparing the sheet catalyst CoCuPS for hydrogen production by electrolyzing water as claimed in claim 1, wherein: in step (1), co (NO) 3 ) 2 ·6 H 2 O and Cu (NO) 3 ) 2 ·3 H 2 O is added in an equimolar ratio and every 2 mmol of Co (NO) 3 ) 2 ·6 H 2 O，CO(NH 2 ) 2 The dosage of the compound is 1 to 10 mol, and the dosage of the water is 60 to 80 mL.
3. The method for preparing the sheet catalyst CoCuPS for hydrogen production by electrolyzing water as claimed in claim 1, wherein: in the step (1), washing is carried out for a plurality of times by respectively using water and ethanol during washing, and the temperature during drying is 70-90 ℃.
4. The method for preparing the sheet catalyst CoCuPS for hydrogen production by electrolyzing water as claimed in claim 1, wherein: in the step (2), the mass ratio of CoCu-LDH to P is 2 S 5 =1∶（5–10）。
5. The method for preparing the sheet catalyst CoCuPS for hydrogen production by electrolyzing water according to claim 1, which is characterized in that: in the step (2), the temperature is increased at a rate of 5-10 ℃/min.
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