CN110314690B - Bimetallic sulfide Ni with heterogeneous interface coupling3S2/FeS composite material and preparation method and application thereof - Google Patents
Bimetallic sulfide Ni with heterogeneous interface coupling3S2/FeS composite material and preparation method and application thereof Download PDFInfo
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- CN110314690B CN110314690B CN201910644020.5A CN201910644020A CN110314690B CN 110314690 B CN110314690 B CN 110314690B CN 201910644020 A CN201910644020 A CN 201910644020A CN 110314690 B CN110314690 B CN 110314690B
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- 239000002131 composite material Substances 0.000 title claims abstract description 75
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims description 31
- 239000002243 precursor Substances 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 46
- 238000004073 vulcanization Methods 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000004070 electrodeposition Methods 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910052742 iron Inorganic materials 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 111
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 46
- 238000000151 deposition Methods 0.000 claims description 30
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 25
- 230000008021 deposition Effects 0.000 claims description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000003792 electrolyte Substances 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- -1 iron ions Chemical class 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000005868 electrolysis reaction Methods 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000002482 conductive additive Substances 0.000 claims description 7
- 229910001453 nickel ion Inorganic materials 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 229910052976 metal sulfide Inorganic materials 0.000 claims 1
- 238000000643 oven drying Methods 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 24
- 239000001257 hydrogen Substances 0.000 abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 abstract description 18
- 239000001301 oxygen Substances 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 9
- 238000010168 coupling process Methods 0.000 abstract description 6
- 238000005859 coupling reaction Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 230000007704 transition Effects 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 11
- 238000010586 diagram Methods 0.000 description 9
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 8
- 229910000510 noble metal Inorganic materials 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- 239000010411 electrocatalyst Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 150000004679 hydroxides Chemical class 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- YGHCWPXPAHSSNA-UHFFFAOYSA-N nickel subsulfide Chemical compound [Ni].[Ni]=S.[Ni]=S YGHCWPXPAHSSNA-UHFFFAOYSA-N 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000005486 sulfidation Methods 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001991 steam methane reforming Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 238000011426 transformation method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention belongs to the technical field of energy catalytic materials, and discloses a bimetallic sulfide Ni with heterogeneous interface coupling3S2the/FeS composite material is applied to electrocatalytic Hydrogen Evolution Reaction (HER), Oxygen Evolution Reaction (OER) and total water decomposition. The invention prepares the bimetal hydroxide precursor containing Ni and Fe by an electrodeposition method, and forms the dual-phase Ni and Fe sulfide composite material with a heterogeneous interface by in-situ vulcanization treatment. Wherein, the NiS and the FeS respectively have strong adsorption to transition state OH and H in the reaction process of OER and HER, and further synergistically improve the OER and HER performances of the material. Material source prepared by the inventionThe sites grow on the carrier and therefore have stronger electrocatalytic activity and better stability than other methods.
Description
Technical Field
The invention relates to the technical field of energy catalytic materials, in particular to a bimetallic sulfide Ni with heterogeneous interface coupling3S2a/FeS composite material, a preparation method and application thereof.
Background
In recent years, since excessive consumption of traditional fossil energy causes a series of global energy crisis and environmental pollution problems, development of new clean energy technology is considered as one of effective approaches to solve the two problems. Among the numerous new energy sources, hydrogen energy is considered as a very potential alternative energy source due to its high energy density and zero carbon emission. Currently, the methods for industrially producing hydrogen mainly include steam methane reforming and coal gasification. However, both of the above methods are based on consuming conventional fossil energy and facing a large amount of CO in the simultaneous production process2And (4) discharge problems. In addition, the hydrogen produced by the above industrial processes is not highly pure and requires further energy-consuming purification. The hydrogen production by water electrolysis is a green experimental method for preparing high-purity hydrogen and oxygen. Although the hydrogen production by water electrolysis has a long history (beginning in 1890 years), the hydrogen production by water electrolysis accounts for less than 5% of the market after more than one hundred years of development, mainly because of low energy conversion efficiency in the water electrolysis process. In the water electrolysis process, oxygen evolution reaction occurs at the anode for generating oxygen, and hydrogen evolution reaction occurs at the cathode for generating hydrogen. The cost of the water electrolysis process is greatly increased due to the existence of the overpotential. Thus, preparing suitable electrocatalysts to reduce the overpotential for hydrogen evolution reactions, oxygen evolution reactions and total water decomposition hasThe significance is important.
At present, the commercial electrocatalysts generally use noble metals Pt/C catalyst and RuO2、IrO2Respectively as hydrogen-producing and oxygen-producing catalysts. Although the noble metal-based catalyst has good electrocatalytic effect, the noble metal-based catalyst is expensive and is not beneficial to the practical popularization and application of the electrolyzed water. To solve such technical problems, non-noble metal based electrocatalysts are a good choice, such as: transition metal sulfides, phosphides, and the like. However, such catalysts, while having good intrinsic activity, are often limited to single-function electrocatalytic performance.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention provides a bimetallic sulfide Ni with heterogeneous interface coupling3S2the/FeS composite material is used for realizing the synergistic promotion of the single function to the dual-function activity of the electrocatalyst.
Ni of the invention3S2The component of the/FeS composite material contains FeS and Ni3S2The interface composition is FeS (100) and Ni3S2(202) Interface coupling and heterogeneous interface coupling cause lattice disorder of the biphase material to a certain degree, and more active sites are added. Meanwhile, the density of the active center electron cloud is changed under the stress action generated between the bimetallic cations, so that the adsorption capacity of the material on transition state H and OH is further enhanced. Under the synergistic effect of the two, Ni3S2The dual-function catalytic activity of the/FeS composite material is obviously improved. The invention leads Ni to regulate the reaction kinetic process of transition states H and OH in the process of OER and HER by creatively introducing a two-phase active site so as to lead Ni to be3S2The OER, HER and total water decomposition performance of the/FeS composite material reach the level of commercial noble metal catalyst.
The invention also provides the bimetallic sulfide Ni3S2The preparation method of the/FeS composite material comprises the following steps:
(1) preparing a NiFe hydroxide precursor by an electrochemical deposition method;
(2) before the NiFe hydroxideCarrying out high-temperature vulcanization treatment on the precursor to obtain the bimetallic sulfide Ni3S2the/FeS composite catalytic material.
Preferably, the molar concentration ratio of nickel ions to iron ions in the electrolyte for electrochemical deposition is (1-4): 1. More preferably, the molar concentration ratio of nickel ions to iron ions is 3: 1. According to the invention, researches show that the electrochemical properties of the prepared NiFe hydroxide precursor can be obviously influenced due to different molar concentration ratios of nickel ions and iron ions. And nickel ion: when the molar concentration ratio of iron ions is (1-4): 1, the obtained NiFe hydroxide precursor has uniform sample size, small thickness and good electrochemical performance. Nickel ion: when the molar concentration ratio of iron ions is 3:1, the obtained NiFe hydroxide precursor sample has the most uniform size, the smallest thickness and the best electrochemical performance.
The nickel source and iron source for preparing the electrolyte according to the present invention are preferably inexpensive metal salts such as: nickel nitrate, nickel chloride, ferric nitrate, ferric chloride.
Preferably, the electrolyte for electrochemical deposition further contains a conductive additive. Preferably, the molar concentration ratio of the conductive additive to the iron ions in the electrolyte for electrochemical deposition is 1: 1. Preferably, the conductive additive includes at least one of lithium chloride and ammonium chloride.
Preferably, the preparation method of the electrolyte comprises the following steps: and completely dissolving the nickel source, the iron source and the conductive additive in deionized water.
Preferably, the working electrode of the electrochemical deposition is foamed nickel, carbon cloth or stainless steel mesh, and the counter electrode is a platinum sheet or a carbon rod. Preferably, the purity of the foamed nickel is 99.9%, and the purity of the platinum sheet is 99.9%. Preferably, the working electrode further comprises the following processing steps before use: ultrasonically cleaning with absolute ethyl alcohol and acetone for 30 minutes respectively, and drying for later use.
Preferably, the electrochemical deposition is a constant voltage deposition.
Preferably, the voltage of the electrochemical deposition is-0.8V to-2.0V, the deposition time is less than 10min, and the deposition temperature is room temperature. The invention discovers that: when the voltage of the electrochemical deposition is between-0.8V and-2.0V, the yield of the precursor is higher, and serious agglomeration cannot occur. When the voltage reaches or is lower than-0.8V, the yield of the precursor begins to be lower; when the voltage of the electrochemical deposition reaches or exceeds-2.0V, the precursor starts to agglomerate seriously. Meanwhile, the deposition time can also influence the product, the constant voltage is used for deposition, and when the deposition time is less than 10min, the flaky thickness of the precursor is controllable and the size is uniform; when the deposition time is more than or equal to 10min, the flaky thickness of the precursor is uncontrollable. In addition, the electrochemical deposition is carried out at room temperature, high and low temperature conditions are not needed, and the preparation cost is low.
Preferably, the voltage of the electrochemical deposition is-1.0V, the deposition time is 5min, and the deposition temperature is room temperature. The electrochemical deposition is carried out under the condition, the yield of the precursor is high, agglomeration is avoided, and the thickness is controllable.
Preferably, the NiFe hydroxide precursor further comprises the following processing steps before the high-temperature sulfidation treatment: and ultrasonically cleaning with deionized water.
Preferably, the high-temperature vulcanization treatment adopts a separated gas vulcanization reaction, specifically: the sulfur source and the sample to be vulcanized (i.e., the NiFe hydroxide precursor) are separately placed and placed in parallel in a tube furnace.
Preferably, the vulcanizing temperature of the high-temperature vulcanizing treatment is 200-400 ℃, the heating rate is 1-10 ℃/min, and the heat preservation time is 1-4 h. During vulcanization treatment, insufficient vulcanization temperature, too short vulcanization time and too slow heating speed can cause insufficient vulcanization degree of the sample; too high a vulcanization temperature, too long a vulcanization time, and too fast a temperature rise rate all result in a loss of sulfur source and a change in product morphology. The vulcanization is carried out under the conditions of the invention, so that the vulcanization effect is better, and the obtained product has better hydrogen production and oxygen production performance.
Preferably, the vulcanization temperature of the high-temperature vulcanization treatment is 250 ℃, the heating rate is 2 ℃/min, and the heat preservation time is 2 h. The products obtained by vulcanization under the condition have the best hydrogen and oxygen production performance.
The sulfuration treatment of the invention can adopt sulfur powder, thiourea, thioacetamide and the like as sulfur sources, and preferably adopts the sulfur powder as the sulfur source because the sulfur powder has low price and can achieve better sulfuration effect.
Preferably, the high temperature sulfidation treatment is carried out in an inert gas. Preferably, the inert gas comprises nitrogen.
To facilitate Ni3S2The invention selects cheap metal salt and sulfur powder as raw materials, combines the electrodeposition and heat treatment methods to prepare the Ni with the nano structure3S2a/FeS composite material.
The invention prepares the NiFe bimetal oxide precursor by an electrodeposition method, and carries out in-situ vulcanization heat treatment on the precursor to generate the heterogeneous interface coupled two-phase Ni3S2a/FeS composite material. Wherein the NiS and the FeS have strong adsorption effects on transition state OH and H in the OER and HER reaction processes respectively, so that the OER and HER performances of the material are synergistically improved. Compared with other methods, the material prepared by the invention has better stability while enhancing the electrocatalytic activity because the material grows on the carrier in situ.
The invention also provides the bimetallic sulfide Ni3S2Use of/FeS composite material, in particular of the bimetallic sulfide Ni3S2The application of the/FeS composite material in the water electrolysis catalyst comprises the application in electrocatalytic Hydrogen Evolution Reaction (HER), electrocatalytic Oxygen Evolution Reaction (OER) and electrocatalytic total water decomposition.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention prepares the NiFe bimetal oxide precursor by an electrodeposition method and creatively uses an in-situ phase transformation method to generate the heterogeneous interface coupled two-phase Ni in situ3S2a/FeS composite material. The formed two-phase coupling interface is beneficial to increasing active sites and optimizing the dynamic process of catalytic reaction, and further the bifunctional electrocatalysis performance of the composite material is obviously improved.
2. Ni of the invention3S2the/FeS composite material shows excellent stability and is applied toThe electro-catalysis hydrogen evolution reaction and the oxygen evolution reaction can greatly reduce the overpotential of the reaction and reduce the cost of hydrogen and oxygen production by electrolyzing water, and simultaneously, the performance of catalyzing full-water decomposition is excellent and is equivalent to that of a noble metal-based catalyst.
3. The preparation method disclosed by the invention is green, economic and controllable in process and is suitable for large-area large-scale production.
Drawings
FIG. 1 is an XRD pattern of the NiFe hydroxide precursor of example 1;
FIG. 2 is an SEM image of a NiFe hydroxide precursor of example 1;
FIG. 3 shows the bimetallic sulfide Ni of example 13S2SEM image of/FeS composite material;
FIG. 4 shows the bimetallic sulfide Ni of example 13S2TEM image of/FeS composite;
FIG. 5 shows the bimetallic sulfide Ni of example 13S2XRD pattern of/FeS composite material;
FIG. 6 is an SEM image of a NiFe hydroxide precursor of example 2;
FIG. 7 is an SEM image of a NiFe hydroxide precursor of example 3;
FIG. 8 is an SEM image of a NiFe hydroxide precursor of example 4;
FIG. 9 is an SEM image of a NiFe hydroxide precursor of example 5;
FIG. 10 is an SEM image of a NiFe hydroxide precursor of example 6;
FIG. 11 is an SEM image of a NiFe hydroxide precursor of example 7;
FIG. 12 shows the bimetallic sulfide Ni of example 83S2SEM image of/FeS composite material;
FIG. 13 shows the bimetallic sulfide Ni of example 83S2An oxygen production performance diagram of the/FeS composite material;
FIG. 14 shows the bimetallic sulfide Ni of example 83S2The hydrogen production performance diagram of the/FeS composite material;
FIG. 15 shows the bimetallic sulfide Ni of example 93S2SEM image of/FeS composite material;
FIG. 16 shows the bimetallic sulfide Ni of example 93S2An oxygen production performance diagram of the/FeS composite material;
FIG. 17 shows the bimetallic sulfide Ni of example 93S2The hydrogen production performance diagram of the/FeS composite material;
FIG. 18 shows Ni of comparative example 13S2SEM picture of (1);
FIG. 19 is an SEM image of FeS of comparative example 2;
FIG. 20 shows the bimetallic sulfide Ni of example 13S2/FeS composite material and Ni3S2Comparison of oxygen evolution reaction performance of FeS and NiFe hydroxides;
FIG. 21 shows the bimetallic sulfide Ni of example 13S2/FeS composite material and Ni3S2Comparison of the oxygen evolution reaction kinetics of FeS and NiFe hydroxides;
FIG. 22 shows the bimetallic sulfide Ni of example 13S2A test chart of the stability of the oxygen evolution reaction of the/FeS composite material;
FIG. 23 shows the bimetallic sulfide Ni of example 13S2/FeS composite material and Ni3S2A comparison graph of hydrogen evolution reaction performance of FeS and NiFe hydroxides;
FIG. 24 shows the bimetallic sulfide Ni of example 13S2/FeS composite material and Ni3S2Comparison of hydrogen evolution reaction kinetics of FeS and NiFe hydroxides;
FIG. 25 shows the bimetallic sulfide Ni of example 13S2A hydrogen evolution reaction stability test chart of the/FeS composite material;
FIG. 26 shows the bimetallic sulfide Ni of example 13S2A real object diagram of the water electrolysis process of the/FeS composite material;
FIG. 27 is the bimetallic sulfide Ni of example 13S2FeS composite and commercial noble metals Pt/C and IrO2A comparative plot of electrolyzed water performance of (a);
FIG. 28 is the bimetallic sulfide Ni of example 13S2FeS complexThe electrolytic water performance stability test chart of the composite material;
FIG. 29 shows the bimetallic sulfide Ni of example 13S2The molecular structure of the/FeS composite material is shown schematically.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention is further illustrated by the following examples. It is apparent that the following examples are only a part of the embodiments of the present invention, and not all of them. It should be understood that the embodiments of the present invention are only for illustrating the technical effects of the present invention, and are not intended to limit the scope of the present invention.
Example 1
Example 1 provides a bimetallic sulfide Ni3S2The preparation method of the/FeS composite material comprises the following steps:
(1) dissolving 0.03mol of nickel nitrate, 0.01mol of ferric nitrate and 0.01mol of lithium chloride in 1L of deionized water, and ultrasonically dissolving at normal temperature to prepare electrolyte;
(2) putting 25mL of the electrolyte prepared in the step (1) into a beaker, and preparing a NiFe hydroxide precursor by a constant voltage deposition method, wherein the voltage is-1.0V, the deposition time is 5 minutes, the deposition temperature is room temperature (25 ℃), the working electrode is a foamed nickel electrode, and the counter electrode is a platinum sheet electrode;
the purity of the foamed nickel electrode is 99.9 percent, the purity of the platinum sheet electrode is 99.9 percent, and the foamed nickel electrode is ultrasonically cleaned for 30 minutes by absolute ethyl alcohol and acetone respectively before use and is dried for standby;
ultrasonically cleaning the prepared NiFe hydroxide precursor for 20 minutes by using deionized water, and drying for later use;
(3) under the protection of nitrogen, taking sulfur powder as a sulfur source, and carrying out vulcanization treatment on the NiFe hydroxide precursor prepared in the step (2) by adopting a separated gas vulcanization reaction, wherein the vulcanization temperature is 250 ℃, the heating rate is 2 ℃/min, and the heat treatment heat preservation time is 2 hours to prepare the bimetallic sulfide Ni3S2a/FeS composite material.
Fig. 1 and 2 are XRD and SEM images of the NiFe hydroxide precursor prepared in this example, respectively. As can be seen from FIGS. 1 and 2, the NiFe hydroxide precursor is an amorphous nanosheet material, and has high yield and no agglomeration phenomenon.
FIG. 3, FIG. 4 and FIG. 5 are the bimetallic sulfide Ni prepared by the present example respectively3S2SEM, TEM and XRD patterns of/FeS composite materials.
Example 2
This example 2 provides a bimetallic sulfide Ni3S2The preparation method of the/FeS composite material comprises the following steps:
(1) dissolving 0.01mol of nickel chloride, 0.01mol of ferric chloride and 0.01mol of ammonium chloride in 1L of deionized water, and ultrasonically dissolving at normal temperature to prepare electrolyte;
(2) placing 25mL of the electrolyte prepared in the step (1) in a beaker, and preparing a NiFe hydroxide precursor by a constant voltage deposition method, wherein the voltage is-1.0V, the deposition time is 5 minutes, the deposition temperature is room temperature (25 ℃), the working electrode is a stainless steel mesh, and the counter electrode is a carbon rod electrode;
before use, the stainless steel mesh is respectively ultrasonically cleaned for 30 minutes by absolute ethyl alcohol and acetone and dried for later use;
ultrasonically cleaning the prepared NiFe hydroxide precursor for 20 minutes by using deionized water, and drying for later use;
(3) under the protection of nitrogen, taking sulfur powder as a sulfur source, and carrying out vulcanization treatment on the NiFe hydroxide precursor prepared in the step (2) by adopting a separated gas vulcanization reaction, wherein the vulcanization temperature is 250 ℃, the heating rate is 2 ℃/min, and the heat treatment heat preservation time is 2 hours to prepare the bimetallic sulfide Ni3S2a/FeS composite material.
Fig. 6 is an SEM image of the NiFe hydroxide precursor prepared in this example.
Example 3
Example 3 provides a bimetallic sulfide Ni3S2The preparation method of the/FeS composite material comprises the following steps:
(1) dissolving 0.02mol of nickel nitrate, 0.01mol of ferric nitrate and 0.01mol of lithium chloride in 1L of deionized water, and ultrasonically dissolving at normal temperature to prepare electrolyte;
(2) putting 25mL of the electrolyte prepared in the step (1) into a beaker, and preparing a NiFe hydroxide precursor by a constant voltage deposition method, wherein the voltage is-1.0V, the deposition time is 5 minutes, the deposition temperature is room temperature (25 ℃), the working electrode is a foamed nickel electrode, and the counter electrode is a platinum sheet electrode;
the purity of the foamed nickel electrode is 99.9 percent, the purity of the platinum sheet electrode is 99.9 percent, and the foamed nickel electrode is ultrasonically cleaned for 30 minutes by absolute ethyl alcohol and acetone respectively before use and is dried for standby;
ultrasonically cleaning the prepared NiFe hydroxide precursor for 20 minutes by using deionized water, and drying for later use;
(3) under the protection of nitrogen, taking sulfur powder as a sulfur source, and carrying out vulcanization treatment on the NiFe hydroxide precursor prepared in the step (2) by adopting a separated gas vulcanization reaction, wherein the vulcanization temperature is 250 ℃, the heating rate is 2 ℃/min, and the heat treatment heat preservation time is 2 hours to prepare the bimetallic sulfide Ni3S2a/FeS composite material.
Fig. 7 is an SEM image of the NiFe hydroxide precursor prepared in this example.
Example 4
Example 4 provides a bimetallic sulfide Ni3S2The preparation method of the/FeS composite material comprises the following steps:
(1) dissolving 0.04mol of nickel nitrate, 0.01mol of ferric nitrate and 0.01mol of lithium chloride in 1L of deionized water, and ultrasonically dissolving at normal temperature to prepare electrolyte;
(2) putting 25mL of the electrolyte prepared in the step (1) into a beaker, and preparing a NiFe hydroxide precursor by a constant voltage deposition method, wherein the voltage is-1.0V, the deposition time is 5 minutes, the deposition temperature is room temperature (25 ℃), the working electrode is a carbon cloth electrode, and the counter electrode is a platinum sheet electrode;
the purity of the platinum sheet electrode is 99.9%, and the carbon cloth electrode is ultrasonically cleaned for 30 minutes by absolute ethyl alcohol and acetone respectively before use and is dried for standby;
ultrasonically cleaning the prepared NiFe hydroxide precursor for 20 minutes by using deionized water, and drying for later use;
(3) under the protection of nitrogen, taking sulfur powder as a sulfur source, and carrying out vulcanization treatment on the NiFe hydroxide precursor prepared in the step (2) by adopting a separated gas vulcanization reaction, wherein the vulcanization temperature is 250 ℃, the heating rate is 2 ℃/min, and the heat treatment heat preservation time is 2 hours to prepare the bimetallic sulfide Ni3S2a/FeS composite material.
Fig. 8 is an SEM image of the NiFe hydroxide precursor prepared in this example.
Example 5
Example 5 provides a bimetallic sulfide Ni3S2The preparation method of the/FeS composite material is different from the example 1 only in that: the electrochemical deposition of example 5 was carried out at a constant voltage of-0.8V, and the other preparation conditions were the same as in example 1.
FIG. 9 is an SEM image of the NiFe hydroxide precursor prepared in this example, and it can be seen that the yield of the precursor prepared in example 5 was lower than that of example 1, indicating that the yield of the precursor started to be lower at a constant voltage of-0.8V for electrochemical deposition.
The invention also selects the voltage lower than-0.8V to carry out the experiment, the yield of the precursor is still lower, which shows that when the constant voltage of the electrochemical deposition is lower than-0.8V, the yield of the precursor is also lower.
Example 6
Example 6 provides a bimetallic sulfide Ni3S2The preparation method of the/FeS composite material is different from the example 1 only in that: the electrochemical deposition of example 6 was carried out at a constant voltage of-2.0V, and the other preparation conditions were the same as in example 1.
FIG. 10 is an SEM image of the NiFe hydroxide precursor prepared in this example, from which it can be seen that the precursor prepared in example 6 is strongly agglomerated, indicating that the precursor starts to agglomerate seriously at a constant voltage of-2.0V for electrochemical deposition.
The invention also selects the voltage higher than-2.0V to carry out the experiment, the precursor still agglomerates seriously, which shows that the precursor also agglomerates seriously when the constant voltage of the electrochemical deposition is higher than-2.0V.
Example 7
Example 7 provides a bimetallic sulfide Ni3S2The preparation method of the/FeS composite material is different from the example 1 only in that: the electrochemical deposition time of example 7 was 10min, and the other preparation conditions were the same as in example 1.
Fig. 11 is an SEM image of the NiFe hydroxide precursor prepared in this example, and it can be seen that the lamellar thickness of the precursor is not controllable.
Example 8
Example 8 provides a bimetallic sulfide Ni3S2The preparation method of the/FeS composite material is different from the example 1 only in that: the vulcanization temperature of example 8 was 200 ℃, the temperature increase rate was 1 ℃/min, the heat treatment keeping time was 1 hour, and the other preparation conditions were the same as example 1.
FIG. 12 shows the bimetallic sulfide Ni prepared in this example3S2SEM image of/FeS composite material.
FIG. 13 shows the bimetallic sulfide Ni prepared in this example3S2The oxygen production performance diagram of the/FeS composite material.
FIG. 14 shows the bimetallic sulfide Ni prepared in this example3S2The hydrogen production performance diagram of the/FeS composite material.
Example 9
Example 9 provides a bimetallic sulfide Ni3S2The preparation method of the/FeS composite material is different from the example 1 only in that: the vulcanization temperature in example 9 was 400 ℃, the temperature increase rate was 10 ℃/min, the heat treatment keeping time was 4 hours, and the other preparation conditions were the same as in example 1.
FIG. 15 shows the bimetallic sulfide Ni prepared in this example3S2SEM image of/FeS composite material.
FIG. 16 shows the bimetallic sulfide Ni prepared in this example3S2The oxygen production performance diagram of the/FeS composite material.
FIG. 17 shows the bimetallic sulfide Ni prepared in this example3S2/FeS composite materialThe hydrogen production performance diagram.
Comparative example 1
Comparative example 1 provides an electrocatalytic material Ni3S2The preparation method specifically comprises the following steps:
(1) dissolving 0.03mol of nickel nitrate and 0.01mol of lithium chloride in 1L of deionized water, and ultrasonically dissolving at normal temperature;
(2) putting 25mL of the electrolyte prepared in the step (1) into a beaker, and preparing a Ni hydroxide precursor by adopting a constant voltage deposition method, wherein the constant voltage deposition condition parameters are the same as those of the embodiment 1;
ultrasonically cleaning the prepared Ni hydroxide precursor for 20 minutes by using deionized water, and drying for later use;
(3) under the protection of nitrogen, taking sulfur powder as a sulfur source, adopting a separated gas vulcanization reaction, and carrying out vulcanization treatment on the Ni hydroxide precursor prepared in the step (2), wherein the vulcanization temperature is 250 ℃, the heating rate is 2 ℃/min, and the heat treatment heat preservation time is 2 hours to obtain Ni3S2。
FIG. 18 shows Ni obtained in comparative example 13S2SEM image of (d).
Comparative example 2
Comparative example 2 provides a preparation method of an electrocatalytic material FeS, which specifically comprises the following steps:
(1) dissolving 0.01mol of iron molybdate and 0.01mol of lithium chloride in 1L of deionized water, and ultrasonically dissolving at normal temperature;
(2) putting 25mL of the electrolyte prepared in the step (1) into a beaker, and preparing a Fe hydroxide precursor by adopting a constant voltage deposition method, wherein the constant voltage deposition condition parameters are the same as those of the embodiment 1;
ultrasonically cleaning the prepared Fe hydroxide precursor by using deionized water, and drying for later use;
(3) under the protection of nitrogen, taking sulfur powder as a sulfur source, and carrying out a separated gas vulcanization reaction to carry out vulcanization treatment on the Fe hydroxide precursor prepared in the step (2), wherein the vulcanization temperature is 250 ℃, the heating rate is 2 ℃/min, and the heat treatment holding time is 2 hours, so as to obtain FeS.
Fig. 19 is an SEM image of FeS prepared in comparative example 2.
Examples of the experiments
Respectively using the NiFe hydroxide and the bimetallic sulfide Ni of example 13S2/FeS composite, Ni of comparative example 13S2Materials, and FeS material of comparative example 2 as test samples, OER and HER tests were performed. The test method comprises the following steps: a beaker, a three-port electrode tank and the like are selected as containers, a test sample is used as a working electrode, a platinum sheet electrode (for OER measurement) or a graphite carbon rod (for HER measurement) is selected as a counter electrode, a saturated calomel electrode is selected as the counter electrode, and the electrolyte is 1mol/L potassium hydroxide solution.
The test results are shown in detail in fig. 20-28, and the test results show that: bimetallic sulfide Ni of example 13S2The OER and HER catalytic activities of the/FeS composite material are obviously higher than those of the NiFe hydroxide precursor and single-phase Ni3S2And a FeS catalyst. Meanwhile, bimetallic sulfide Ni of example 13S2the/FeS composite material shows excellent stability. Bimetallic sulfide Ni of example 1 as a bifunctional catalyst for direct application to electrolyzed water3S2the/FeS composite material is noble metal Pt/C-IrO2Is lower.
In conclusion, the bimetallic sulfide Ni of the invention3S2The self-growing structure and the interface coupling effect of the/FeS composite material endow the composite material with the electrolytic water catalysis dual-function active site and the structural stability, and have good application prospect.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. Bimetallic sulfide Ni3S2The preparation method of the/FeS composite material is characterized by comprising the following steps:
(1) preparing a NiFe hydroxide precursor by an electrochemical deposition method; in the electrolyte for electrochemical deposition, the molar concentration ratio of nickel ions to iron ions is (1-4): 1; the electrolyte for electrochemical deposition also contains a conductive additive; the electrochemical deposition is constant voltage deposition; the voltage of the electrochemical deposition is-0.8V to-2.0V, the deposition time is less than 10min, and the deposition temperature is room temperature;
(2) carrying out high-temperature vulcanization treatment on the NiFe hydroxide precursor to obtain the double-metal sulfide Ni3S2a/FeS composite; the high-temperature vulcanization treatment adopts a separated gas vulcanization reaction; the vulcanizing temperature of the high-temperature vulcanizing treatment is 200-400 ℃, the heating rate is 1-10 ℃/min, and the heat preservation time is 1-4 h.
2. The bimetallic sulfide Ni of claim 13S2The preparation method of the/FeS composite material is characterized in that the molar concentration ratio of nickel ions to iron ions in the electrolyte for electrochemical deposition is 3: 1.
3. The bimetallic sulfide Ni of claim 13S2The preparation method of the/FeS composite material is characterized in that in the electrolyte of electrochemical deposition, the molar concentration ratio of the conductive additive to iron ions is 1: 1; the conductive additive includes at least one of lithium chloride and ammonium chloride.
4. The bimetallic sulfide Ni of claim 13S2The preparation method of the/FeS composite material is characterized in that the working electrode of electrochemical deposition is foamed nickel, carbon cloth or stainless steel mesh, and the counter electrode is a platinum sheet or a carbon rod; the purity of the foamed nickel is 99.9 percent, and the purity of the platinum sheet is 99.9 percent; the working electrode further comprises the following processing steps before use: ultrasonically cleaning with anhydrous ethanol and acetone for 30min, and oven drying.
5. The bimetallic sulfide Ni of claim 13S2Method for producing FeS composite materialCharacterized in that the voltage of the electrochemical deposition is-1.0V, the deposition time is 5min, and the deposition temperature is room temperature.
6. The bimetallic sulfide Ni of claim 13S2The preparation method of the/FeS composite material is characterized in that the NiFe hydroxide precursor further comprises the following processing steps before high-temperature vulcanization processing: and ultrasonically cleaning with deionized water.
7. The bimetallic sulfide Ni of claim 13S2The preparation method of the/FeS composite material is characterized in that the vulcanization temperature of the high-temperature vulcanization treatment is 250 ℃, the heating rate is 2 ℃/min, and the heat preservation time is 2 h; the sulfur source for the high-temperature vulcanization treatment comprises sulfur powder.
8. The bimetallic sulfide Ni of claim 13S2The preparation method of the/FeS composite material is characterized in that the high-temperature vulcanization treatment is carried out in an inert atmosphere; the inert atmosphere comprises nitrogen.
9. Bimetallic sulfide Ni3S2A/FeS composite material characterized by comprising the bimetallic sulfide Ni as defined in any one of claims 1 to 83S2The preparation method of the/FeS composite material.
10. The bimetallic sulfide Ni of claim 93S2The application of the/FeS composite material in the water electrolysis catalyst.
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| CN111569907A (en) * | 2020-04-29 | 2020-08-25 | 国电新能源技术研究院有限公司 | Bimetal composite material and preparation method and application thereof |
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| CN114561655B (en) * | 2022-03-28 | 2024-07-02 | 河北工业大学 | Preparation method and application of rare earth cerium doped nickel sulfide/iron sulfide heterojunction material |
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105334251A (en) * | 2015-11-16 | 2016-02-17 | 安徽师范大学 | Tremella-like Fe-Ni layered double hydroxides, oxygen evolution electrode as well as preparation methods and applications thereof |
| CN106011911A (en) * | 2016-05-26 | 2016-10-12 | 重庆大学 | Method of partial vulcanization to improve oxygen evolution electrode performance of metal hydroxide |
| CN108097270A (en) * | 2017-12-20 | 2018-06-01 | 青岛大学 | A kind of elctro-catalyst for being catalyzed water decomposition production hydrogen and its preparation method and application |
| CN108220997A (en) * | 2018-01-31 | 2018-06-29 | 中国科学院福建物质结构研究所 | A kind of carbon containing nickel coat single-walled carbon nanotube composite material and its preparation method and application |
| CN108212194A (en) * | 2018-01-31 | 2018-06-29 | 中国科学院福建物质结构研究所 | A kind of nitrogen-doped carbon nickel coat composite Nano carbon electrolysis water catalyst and preparation method thereof |
| CN108396329A (en) * | 2018-03-08 | 2018-08-14 | 北京化工大学 | A kind of two-phase nanometer nickel sulfide array material, the preparation method and the usage of Fe2O3 doping |
| CN109112566A (en) * | 2018-09-25 | 2019-01-01 | 陕西师范大学 | Three Raney nickel of curing of trace iron (III) ion doping for electrolysis water oxygen evolution reaction |
| CN109423660A (en) * | 2017-09-01 | 2019-03-05 | 中国科学院大连化学物理研究所 | A kind of water oxygen elctro-catalyst and preparation method thereof for electrocatalytic decomposition water |
| CN109530714A (en) * | 2018-11-19 | 2019-03-29 | 广州大学 | A kind of combination electrode material and its preparation method and application |
| CN109671571A (en) * | 2018-06-08 | 2019-04-23 | 天津大学 | A kind of preparation method of fabricated in situ multicomponent metal sulfide composite material |
-
2019
- 2019-07-16 CN CN201910644020.5A patent/CN110314690B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105334251A (en) * | 2015-11-16 | 2016-02-17 | 安徽师范大学 | Tremella-like Fe-Ni layered double hydroxides, oxygen evolution electrode as well as preparation methods and applications thereof |
| CN106011911A (en) * | 2016-05-26 | 2016-10-12 | 重庆大学 | Method of partial vulcanization to improve oxygen evolution electrode performance of metal hydroxide |
| CN109423660A (en) * | 2017-09-01 | 2019-03-05 | 中国科学院大连化学物理研究所 | A kind of water oxygen elctro-catalyst and preparation method thereof for electrocatalytic decomposition water |
| CN108097270A (en) * | 2017-12-20 | 2018-06-01 | 青岛大学 | A kind of elctro-catalyst for being catalyzed water decomposition production hydrogen and its preparation method and application |
| CN108220997A (en) * | 2018-01-31 | 2018-06-29 | 中国科学院福建物质结构研究所 | A kind of carbon containing nickel coat single-walled carbon nanotube composite material and its preparation method and application |
| CN108212194A (en) * | 2018-01-31 | 2018-06-29 | 中国科学院福建物质结构研究所 | A kind of nitrogen-doped carbon nickel coat composite Nano carbon electrolysis water catalyst and preparation method thereof |
| CN108396329A (en) * | 2018-03-08 | 2018-08-14 | 北京化工大学 | A kind of two-phase nanometer nickel sulfide array material, the preparation method and the usage of Fe2O3 doping |
| CN109671571A (en) * | 2018-06-08 | 2019-04-23 | 天津大学 | A kind of preparation method of fabricated in situ multicomponent metal sulfide composite material |
| CN109112566A (en) * | 2018-09-25 | 2019-01-01 | 陕西师范大学 | Three Raney nickel of curing of trace iron (III) ion doping for electrolysis water oxygen evolution reaction |
| CN109530714A (en) * | 2018-11-19 | 2019-03-29 | 广州大学 | A kind of combination electrode material and its preparation method and application |
Non-Patent Citations (5)
| Title |
|---|
| "Asymmetric 3d Electronic Structure for Enhanced Oxygen Evolution Catalysis";Yang Liu et al.;《ACS Appl. Mater. Interfaces》;20180619;第10卷(第27期);第23131-23139页 * |
| "Cross-linked trimetallic nanopetals for electrocatalytic water splitting";Shanqing Qu et al.;《Journal of Power Sources》;20180424;第390卷;第224-233页 * |
| "Ni-Fe 基析氧阳极材料的研究进展";何杨华;《化工进展》;20160705;第35卷(第7期);第2057-2062页 * |
| "Ternary nickel-iron sulfide microflowers as a robust electrocatalyst for bifunctional water splitting";Jiahao Yu et al.;《Journal of Materials Chemistry A》;20170711;第5卷;第15838-15844页 * |
| "Two-step synthesis of binary Ni–Fe sulfides supported on nickel foam as highly efficient electrocatalysts for the oxygen evolution reaction";Bin Dong et al.;《Journal of Materials Chemistry A》;20160730;第4卷;第13499-13508页 * |
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