CN111389431A - 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 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 20
- 239000001257 hydrogen Substances 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 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
- 238000000034 method Methods 0.000 claims description 8
- 239000010949 copper Substances 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
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910002520 CoCu Inorganic materials 0.000 description 3
- 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
- 239000000047 product Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 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
- 239000002243 precursor Substances 0.000 description 2
- 230000001105 regulatory effect Effects 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
- 229910021536 Zeolite Inorganic materials 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
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 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
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 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
- 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
- 238000000634 powder X-ray diffraction Methods 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
- 239000010457 zeolite Substances 0.000 description 1
Images
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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
-
- B01J35/33—
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention belongs 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 CuPS3And CoPS two-phase mixed isomeric structures. The preparation method comprises the following steps: mixing Co (NO)3)2·6 H2O、Cu(NO3)2·3 H2O and CO (NH)2)2Dissolving in water, stirring for dissolving to clear, transferring into a reaction kettle, performing hydrothermal reaction at 150 deg.C for 3-9 h, cooling, centrifuging, washing, drying to obtain CoCu-L DH, placing CoCu-L DH at downstream of tubular furnace, and placing in P-shaped furnace2S5Placing the catalyst at the upstream of a tubular furnace, raising the temperature 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 is used for hydrogen production by electrolyzing waterHas high and stable catalytic activity.
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 global energy and environment crisis, 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 phosphide 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 catalyst structure to obtain good catalytic performance and stability. Therefore, the catalyst can be further improved, and the ideal catalytic material can be obtained by introducing elements of the second metal and regulating and controlling different proportions. 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, which is prepared byThe flake catalyst CoCuPS is CuPS3And CoPS two-phase mixed isomeric structures.
The preparation method comprises the following steps:
(1) mixing Co (NO)3)2·6 H2O、Cu(NO3)2·3 H2O and CO (NH)2)2Dissolving in water, stirring and dissolving until the solution is clear, transferring the solution into a reaction kettle, carrying out hydrothermal reaction at the temperature of 120-150 ℃ for 3-9 h, cooling, centrifuging, washing and drying to obtain cobalt-copper double hydroxide CoCu-L DH;
(2) placing CoCu-L DH at the downstream of the tube furnace, P2S5Placing the catalyst at the upstream of a tubular furnace, raising the temperature 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 H2O and Cu (NO)3)2·3 H2O is added in an equimolar ratio and every 2mmol of Co (NO)3)2·6 H2O，CO(NH2)2The dosage of the water is 1-10 mol, and the dosage of the water is 60-80 m L.
Preferably, in the step (1), the washing is carried out several times with water and ethanol, respectively, and the temperature during drying is 70-90 ℃.
Preferably, in step (2), the mass ratio of CoCu-L DH: P2S5=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 P2S5The CoCu bimetallic sulfide-phosphide flaky CoCuPS catalyst is obtained by molecular high-temperature sulfide-phosphide CoCu-L DH, and the prepared flaky CoCuPS catalyst has ultrahigh activity and catalytic stability when used for hydrogen production by water electrolysis.
Drawings
FIG. 1 is a field emission scanning electron microscope (a) of CoCu-L DH prepared in example 1, a field emission scanning electron microscope (b) and a transmission electron microscope (c) of CoCuPS catalyst.
FIG. 2: example 1 and comparative examples 1 to 3Catalysts CoCuPS, CoPS, Co2CuPS、CoCu2X-ray powder diffractogram of PS.
FIG. 3: example 1 and comparative examples 1-3 catalysts CoCuPS, CoPS, Co2CuPS、CoCu2A polarization curve (L SV) 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 shows the polarization curve (L SV) before and after 5000 CV cycles of the CoCuPS catalyst prepared in example 1, graph (a) and i-t stability graph (b).
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 H2O (2 mmol)、Cu(NO3)2·3 H2O (2 mmol) and CO (NH)2)2(10 mol) dissolving in 70 m L redistilled water, stirring and dissolving until the solution is clear, transferring the solution into a 100 m L reaction kettle, carrying out hydrothermal treatment at 150 ℃ for 6 h, cooling and centrifuging, washing with water and absolute ethyl alcohol for three times respectively, and drying at 70 ℃ to obtain flower-shaped cobalt-copper double hydroxide CoCu-L DH consisting of nanosheets;
(2) 50 mg of CoCu-L DH is poured into a magnetic boat and placed at the downstream of a tube furnace, and 0.5 g P is taken2S5Pouring 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 H2The amount of O is 4 mmol, Cu (NO)3)2·3 H2The amount of O is 0 mmol, i.e. no addition is made, correspondingly, in step (1)The product was cobalt hydroxide, which was used in place of "CoCu-L DH" in step (2), and the other steps were the same as in example 1.
The final product from this control example was the catalyst CoPS.
Comparative example 2
Catalyst Co2A process for the preparation of CuPS, which differs from example 1 in that: co (NO)3)2·6 H2The amount of O is 2.67mmol, Cu (NO)3)2·3 H2The amount of O used was 1.33mmol, and correspondingly, the product obtained in step (1) was Co2Cu-L DH, which was used in place of "CoCu-L DH" in step (2), and the other steps were the same as in example 1.
The final product obtained in this comparative example is catalyst Co2CuPS。
Comparative example 3
Catalyst CoCu2A method for preparing PS, which is different from example 1 in that: co (NO)3)2·6 H2The amount of O is 1.33mmol, Cu (NO)3)2·3 H2The amount of O used was 2.67mmol, and correspondingly, the product obtained in step (1) was CoCu2L DH, which was used in place of "CoCu-L DH" in step (2), and the other steps were the same as in example 1.
The final product obtained in this control example is the catalyst CoCu2PS。
Catalyst structural characterization
FIG. 1 is a field emission scanning electron microscope (a) of CoCu-L DH prepared in example 1, a field emission scanning electron microscope (b) and a transmission electron microscope (c) of catalyst CoCuPS, wherein the CoCu-L DH is in a flower shape formed by nanosheets with uniform thickness, and from the graphs (b) and (c), it is clear that the structure of the nanometer flower of the CoCu-L DH precursor is partially collapsed, but the catalyst CoCuPS still presents a stable nanosheet structure, and the flaky structure promotes mass transfer and charge transfer, has 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 32CuPS、CoCu2X-ray of PSPowder diffraction pattern. In FIG. 2, diamonds represent CuPS3The crystal diffraction peak of the (JCPDF number 48-1236) phase and the plum blossom represents the crystal diffraction peak of the CoPS (JCPDF number 27-0139) phase, which shows that the CoPS only contains the CoPS phase, while the CoCuPS and Co have the same structure2CuPS、CoCu2PS are all CuPS3And CoPS two-phase mixed isomeric structure, and it can be seen that: CoCuPS has moderate crystalline diffraction peaks and can provide a suitable catalytic structure.
Testing of catalyst Performance
The catalysts CoCuPS, CoPS and Co prepared in example 1 and comparative examples 1-32CuPS、CoCu2PS is respectively used for hydrogen production by electrolyzing water, the temperature is 25 ℃, after a catalyst of 3 mg, redistilled water of 330 mu L, N-dimethylformamide of 170 mu L and Nafion solution (5 wt%) of 50 mu L are ultrasonically formed into uniform mixed liquid, 183 mu L mixed liquid drops are sucked and prepared into a working electrode on 1 cm of 1 cm hydrophilic carbon fiber paper (CP), and the loading capacity of the catalyst on the CP is about 1 mg/cm2. Then a calomel electrode is used as a reference electrode, a graphite rod is used as an auxiliary electrode to form a three-electrode system, 0.5M H2SO4As an electrolyte, the CHI660E electrochemical workstation detects the catalytic performance of the catalyst, and comprises a polarization curve (L SV) graph and a corresponding Tafel slope graph and an Electrochemical Impedance (EIS) graph, wherein the test conditions are that the linear scanning sweep rate is 5 mV/s, the frequency range of constant voltage test electrochemical impedance of 0.15V vs RHE is 100000-0.1 Hz., and Pt/C (the mass percentage of Pt is 20%) is used as a control working electrode.
FIG. 3 shows the catalysts CoCuPS, CoPS, Co2CuPS、CoCu2PS polarization curve (L SV) graph (a), Tafel slope graph (b) and Electrochemical Impedance (EIS) graph (c). The L SV polarization curve shown in FIG. 3 (a) shows that at 10 mA/cm2Zeolite CoCuPS, CoPS, Co2CuPS and CoCu2The 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/cm2CoCuPS 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、Co2CuPS and CoCu2The 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 diagram of fig. 3 (c) shows: CoCuPS, CoPS, Co2CuPS and CoCu2The 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 (a) of the polarization curve (L SV) before and after 5000 CV cycles of the catalyst CoCuPS and a plot (b) of the i-t stability curve FIG. 4 (a) shows that the L SV curves of the catalyst before and after 5000 CV cycles almost completely coincide and exhibit high stability, and the i-t curve of FIG. 4 (b) shows that at 20 mA/cm2At 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 (6)
1. A flaky catalyst CoCuPS for hydrogen production by water electrolysis is characterized in that: the flaky catalyst CoCuPS is CuPS3And CoPS two-phase mixed isomeric structures.
2. The preparation method of the flake catalyst CoCuPS for hydrogen production by water electrolysis according to claim 1, characterized by comprising the following steps:
(1) mixing Co (NO)3)2·6 H2O、Cu(NO3)2·3 H2O and CO (NH)2)2Dissolving in water, stirring and dissolving until the solution is clear, transferring the solution into a reaction kettle, carrying out hydrothermal reaction at the temperature of 120-150 ℃ for 3-9 h, cooling, centrifuging, washing and drying to obtain cobalt-copper double hydroxide CoCu-L DH;
(2) placing CoCu-L DH at the downstream of the tube furnace, P2S5Placing the catalyst at the upstream of a tubular furnace, raising the temperature to 450-550 ℃ in an inert atmosphere, keeping the temperature for 1-2 h, and cooling to obtain the flaky catalyst CoCuPS.
3. The method for preparing the sheet catalyst CoCuPS for hydrogen production by electrolyzing water according to claim 2, characterized in that: in step (1), Co (NO)3)2·6 H2O and Cu (NO)3)2·3 H2O is added in an equimolar ratio and every 2mmol of Co (NO)3)2·6 H2O，CO(NH2)2The dosage of the water is 1-10 mol, and the dosage of the water is 60-80 m L.
4. The method for preparing CoCu-L DH, a catalyst for hydrogen production by electrolysis of water, according to claim 2, wherein in step (1), the catalyst is washed several times with water and ethanol respectively, and dried at 70-90 ℃.
5. The method for preparing CoCu-L DH as catalyst for hydrogen production by electrolyzing water as claimed in claim 2, wherein in step (2), CoCu-L DH: P is added in mass ratio2S5=1∶（5–10）。
6. The method for preparing CoCu-L DH, a catalyst for hydrogen production by electrolysis of water, according to claim 2, wherein in step (2), the temperature is raised at a rate of 5-10 ℃/min.
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| CN104971744A (en) * | 2015-06-02 | 2015-10-14 | 浙江理工大学 | Electrolyzed-water catalytic material with nanometer core-shell structure of cobalt sulfide and molybdenum disulfide |
| CN105688941A (en) * | 2016-01-13 | 2016-06-22 | 北京化工大学 | Cu7S4@MoS2 heterogeneous nanometer framework material and application thereof in producing hydrogen by catalytically electrolysing water |
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