CN110721749A - NiCo coated with metal organic framework structure derived carbon composite2S4Nanowire array-shaped electrocatalyst and preparation method thereof - Google Patents
NiCo coated with metal organic framework structure derived carbon composite2S4Nanowire array-shaped electrocatalyst and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 91
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 41
- 229910003266 NiCo Inorganic materials 0.000 title claims abstract description 40
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000004744 fabric Substances 0.000 claims abstract description 53
- 239000008367 deionised water Substances 0.000 claims abstract description 51
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 51
- 239000002131 composite material Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 238000005406 washing Methods 0.000 claims abstract description 19
- 238000005303 weighing Methods 0.000 claims abstract description 19
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 18
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims abstract description 14
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims abstract description 13
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004202 carbamide Substances 0.000 claims abstract description 12
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 claims abstract description 11
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 23
- 239000010935 stainless steel Substances 0.000 claims description 17
- 229910001220 stainless steel Inorganic materials 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 16
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 2
- 229940068911 chloride hexahydrate Drugs 0.000 claims 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims 1
- 238000000643 oven drying Methods 0.000 claims 1
- 239000002070 nanowire Substances 0.000 abstract description 51
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 31
- 239000001301 oxygen Substances 0.000 abstract description 31
- 229910052760 oxygen Inorganic materials 0.000 abstract description 31
- 239000001257 hydrogen Substances 0.000 abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 27
- 239000000463 material Substances 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 7
- 238000001354 calcination Methods 0.000 abstract 1
- 239000011363 dried mixture Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- 238000003491 array Methods 0.000 description 17
- 239000003054 catalyst Substances 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 229910017052 cobalt Inorganic materials 0.000 description 9
- 239000010941 cobalt Substances 0.000 description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 229910052596 spinel Inorganic materials 0.000 description 8
- 239000011029 spinel Substances 0.000 description 8
- 150000004770 chalcogenides Chemical class 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000001075 voltammogram Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000004502 linear sweep voltammetry Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- -1 Transition Metal Sulfides Chemical class 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B01J35/33—
-
- B01J35/40—
-
- 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
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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
Abstract
NiCo coated with metal organic framework structure derived carbon composite2S4The preparation method of the nanowire array-shaped electrocatalyst comprises the steps of respectively weighing 0.2-1.2 g of nickel chloride hexahydrate, 0.4-2.4 g of cobalt chloride hexahydrate, 0.2-1.2 g of urea and 0.2-1.2 g of hexadecyl trimethyl ammonium bromide, dissolving in 30-60 mL of deionized water, transferring into a 50mL reaction kettle, putting into a carbon cloth with the thickness of 2cm multiplied by 3cm, and reacting at 80-120 ℃ for 6-12 hours; then weighing 0.6-1.8 g of sodium sulfide nonahydrate, dissolving in 30-60 mL of deionized water, adding the obtained product, and reacting at 140-180 ℃ for 6-12 h; finally, putting the product into a dimethyl imidazole solution, and placing the product in a chamberPlacing the mixture at a warm temperature for 8-16 h, respectively washing the mixture for several times by using deionized water and ethanol, drying the washed mixture, and calcining the dried mixture in a tubular furnace at the temperature of 300-400 ℃ for 2-5 h to obtain the NiCo coated with the metal organic framework structure derived carbon composite2S4An electrocatalyst in the form of an array of nanowires. The preparation method is simple in preparation process, the reaction conditions are random, and the prepared material has excellent electrochemical oxygen evolution and hydrogen evolution performances.
Description
Technical Field
The invention relates to NiCo coated by a metal organic framework structure derived carbon composite2S4The catalyst can be used for the research of electrochemical oxygen evolution and hydrogen evolution reactions.
Background
With the development of society, the problem of energy shortage is becoming more severe, and thus, it is imperative to find a clean and sustainable energy source, such as solar energy, tidal energy, wind energy and hydrogen energy. Among these renewable energy sources, hydrogen is highly likely to replace fossil fuels as an energy carrier. The use of electrolyzed water for large scale hydrogen production is a promising environmental protection method. However, in general, the water electrolysis process has a problem that the kinetics of the anodic oxygen evolution reaction is slow (acid: 2H)2O→4H++O2+4e-(ii) a Base: 4OH-→2H2O+O2+4e-) I.e. a reaction that results in significant efficiency loss and excessive overpotential. To overcome this critical problem in the electrolysis of water, a suitable electrocatalyst is needed to promote kinetics and reduce overpotential during the oxygen evolution reaction. Generally, some important characteristics of electrolyzed water (e.g., electrolysis rate, energy efficiency, and stability thereof) are largely dependent on the performance of the catalyst. Conventionally, noble metals platinum, ruthenium oxide and iridium oxide have high oxygen evolution reaction activity and are considered to be the most advanced oxygen evolution reaction electrocatalysts. However, the high cost and scarcity have hindered their practical application in commercial water electrolysis. Therefore, the development of the non-noble metal type oxygen evolution reaction electrocatalyst with low cost, high catalytic activity and high catalytic stability is significant.
Transition metal (e.g., nickel, cobalt, iron) materials are a promising electrocatalyst for oxygen evolution reactions due to their high stability in alkaline electrolytes and their environmentally benign nature. Wherein, the spinel cobalt-based oxide has high catalytic activity, convenient preparation and high priceThe price is low and the attention is paid. To further enhance the electrocatalytic activity, metal atoms are added to the spinel structure, such as nickel, zinc, iron, to enhance the electrochemical activity of the cobalt-based oxide. It is well known that nickel cobaltate (NiCo)2O4) Due to the special spinel structure, the catalytic active sites are increased, and the conductivity is enhanced (compared with Co)3 O 4100 times higher). In this structure, Co is distributed in tetrahedral and octahedral sites, and Ni occupies the octahedral sites, forming different valence states. Thus, due to the presence of these two pairs of redox pairs, significant electrocatalytic activity (i.e. co) can be obtained3+/Co2+And Ni3+/Ni2+). Although the nickel cobaltate catalyst has been developed, the catalytic performance of the nickel cobaltate catalyst is still further improved in practical application. In recent years, a great number of researchers have devised spinel cobalt-based chalcogenides through diligent efforts. It has been shown that Transition Metal Sulfides (TMS) have a lower band gap and higher conductivity, electrochemical activity, capacitance and mechanical stability than the corresponding oxides and hydroxides (y.zhang, w.sun, x.rui, b.li, h.t.tan, g.guo, q.yan, One-potsythesis of tunable crystalline Ni3S4@amorphous MoS2core/shell nanospheresfor high performance supercapacitors, Small 11(2015) 3694-3702.). Compared with oxides, the chalcogenide has richer redox active centers, more controllable structural characteristics and lower band gap energy, and has the synergistic electrochemical effect of bimetallic ions. (Y.Gao, L.Mi, W.Wei, S.Cui, Z.Zheng, H.Hou, W.Chen, Double metal ion mechanical effect in a hierarchical multiple subflow microfluiders for enhancing performance, ACS appl.Mater. interfaces 7(2015) 4311-4319.). To further improve the electrochemical performance of spinel chalcogenides, extensive research has shown that metal-organic frameworks (MOFs) are highly porous materials with ultra-high surface areas (up to 10000 m)2g-1) Large pore volume, good aperture and abundant metal centers, effectively enhances the ion exchange in the oxygen and hydrogen evolution process in the electrolyzed water, and greatly improves the efficiency of the electrolyzed water.Therefore, by considering the effective combination of the spinel chalcogenide and the metal organic framework, the composite material formed by the spinel chalcogenide and the metal organic framework is designed and prepared, so that the active surface area and the active sites of the electrocatalyst are greatly improved.
On the other hand, besides the composition of the catalyst, the structure and morphology of the electrode material also have a significant influence on its electrochemical performance. (X.Pan, Z.Fan, W.Chen, Y.Ding, H.Luo, X.Bao, Enhanced ethanol production reagents carbon-nanotube contacting catalytic composites, nat. Mater.6(2007) 507-511.). In recent years, many cobalt-based nanomaterials with different morphologies have been synthesized to improve their electrochemical performance. Such as needle, plate, cage, and tube, etc. Hollow nanostructures, a class of cavities of special materials and shells with chemical functions, have favorable physicochemical properties, such as low energy density, large effective area and good mass permeability, and the favorable dynamic open structure greatly improves the catalytic performance of the electrode material. Therefore, designing hollow structure nano materials with special chemical structures and morphologies is of great significance for basic research and practical application, but at the same time, the design also faces huge challenges.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides NiCo coated with a metal organic framework structure derived carbon composite2S4The nanowire array-shaped electrocatalyst and the preparation method thereof, and the research on the catalytic electrochemical oxygen evolution and hydrogen evolution reaction.
The technical scheme adopted by the invention is as follows:
NiCo coated with metal organic framework structure derived carbon composite2S4The nano-wire array-shaped electrocatalyst is prepared by the following method:
(1) respectively weighing 0.2-1.2 g of nickel chloride hexahydrate, 0.4-2.4 g of cobalt chloride hexahydrate, 0.2-1.2 g of urea and 0.3-1.4 g of cetyltrimethylammonium bromide (CTAB) and dissolving in 30-60 mL of deionized water, stirring for 5-20 minutes at room temperature, then transferring into a 50mL stainless steel autoclave, putting into treated carbon cloth (2cm multiplied by 3cm), keeping for 6-12 hours at 80-120 ℃, cooling to room temperature, washing with deionized water and ethanol for multiple times, and finally drying;
(2) weighing 0.6-1.8 g of sodium sulfide nonahydrate, dissolving in 30-60 mL of deionized water, stirring at room temperature for 5-20 minutes, transferring into a 50mL stainless steel autoclave, placing a carbon cloth with a grown nickel-cobalt precursor, keeping at 140-180 ℃ for 6-12 hours, cooling to room temperature, ultrasonically washing with deionized water and ethanol for three times, and finally drying;
(3) weighing 0-2.4 g of dimethyl imidazole, dissolving in 10-20 mL of mixed solution of deionized water and ethanol, carrying out ultrasonic treatment for 5-10 minutes, and putting into a growing NiCo2S4Placing the carbon cloth of the nanowire array at room temperature for reacting for 8-16 hours, then washing the carbon cloth with deionized water and ethanol for multiple times, putting the carbon cloth into an oven, and drying the carbon cloth at 70-90 ℃ for 10-16 hours; finally, in a tube furnace, in a nitrogen atmosphere, at 2 ℃ for min-1The temperature rise rate of (2) is kept for 2 to 5 hours at 300 to 400 ℃; obtaining NiCo coated by the metal organic framework structure derived carbon compound2S4An electrocatalyst in the form of an array of nanowires.
NiCo coated with metal organic framework structure derived carbon composite2S4A method for preparing a nanowire array-like electrocatalyst, the method comprising the steps of:
(1) 0.2 to 1.2g of nickel chloride hexahydrate and 0.4 to 2.4g of cobalt chloride hexahydrate are respectively weighed,
0.2 to 1.2g of urea and 0.3 to 1.4g of cetyltrimethylammonium bromide are dissolved in 30 to 60 g of ammonium bromide
Stirring for 5-20 minutes in mL deionized water at room temperature, then transferring into a 50mL stainless steel autoclave, putting into treated carbon cloth (2cm multiplied by 3cm), keeping for 6-12 hours at 80-120 ℃, cooling to room temperature, washing with deionized water and ethanol for multiple times, and finally drying;
(2) weighing 0.6-1.8 g of sodium sulfide nonahydrate, dissolving in 30-60 mL of deionized water, stirring at room temperature for 5-20 minutes, transferring into a 50mL stainless steel autoclave, placing a carbon cloth with a grown nickel-cobalt precursor, keeping at 140-180 ℃ for 6-12 hours, cooling to room temperature, ultrasonically washing with deionized water and ethanol for three times, and finally drying;
(3) weigh 1.Dissolving 2-2.4 g of dimethylimidazole in 10-20 mL of mixed solution of deionized water and ethanol, performing ultrasonic treatment for 5-10 minutes, and putting the NiCo grown in2S4Placing the carbon cloth of the nanowire array at room temperature for reacting for 8-16 hours, then washing the carbon cloth with deionized water and ethanol for multiple times, putting the carbon cloth into an oven, and drying the carbon cloth at 70-90 ℃ for 10-16 hours; finally, in a tube furnace, in a nitrogen atmosphere, at 2 ℃ for min-1The temperature rise rate of (2) is kept for 2 to 5 hours at 300 to 400 ℃; obtaining NiCo coated by the metal organic framework structure derived carbon compound2S4An electrocatalyst in the form of an array of nanowires.
Further, the concentration and volume of nickel chloride hexahydrate, cobalt chloride hexahydrate, sodium sulfide nonahydrate, dimethylimidazole, the amount of urea and CTAB, and the temperature and time of reaction were controlled to control the metal organic framework structure-derived carbon composite-coated NiCo2S4The morphology and structure of nanowire arrays.
The electrochemical hydrogen evolution and oxygen evolution reaction is carried out at normal temperature and normal pressure, and the specific performance test operation process is as follows:
(1) the electrochemical measurements were performed in a CHI 852D electrochemical workstation with a typical three electrode system. In the system, a carbon cloth with the size of 1cm multiplied by 1cm is taken as a working electrode, a carbon rod electrode is taken as a counter electrode, and a Saturated Calomel Electrode (SCE) is taken as a reference electrode to carry out electrochemical hydrogen and oxygen evolution performance tests.
(2) RHE calibration was performed for all potentials using the formula (e (RHE) ═ e (sce) +0.059pH + 0.098V). Obtaining a polarization curve by Linear Sweep Voltammetry (LSV) at a sweep rate of 5mv s-1. All electrochemical tests were carried out at 25 ℃ in 1MKOH solution. And finally, calculating the Tafel slope according to the measured data and a corresponding formula, and evaluating the hydrogen evolution performance and the oxygen evolution performance of the catalyst by the number of transferred electrons and the yields of hydrogen and oxygen.
The invention has the following beneficial effects:
(1) the preparation method can be amplified, the nanowire array can be directly obtained through multi-step hydrothermal reaction, and the nanowire array is easy to grow;
(2) nickel cobalt precursors with different shapes can be obtained by changing the dosage of the precursor and chemical reagents, and the electrochemical properties are different;
(3) NiCo coated with metal organic framework structure derived carbon composite2S4The nanowire array-shaped electrocatalyst shows outstanding activity and stability in hydrogen evolution and oxygen evolution reactions, and the spinel-based material has a very high application prospect as the electrocatalyst.
Drawings
FIG. 1 is a schematic representation of an embodiment of the present invention 1. NiCo coated with a carbon composite derived from a metal organic framework2S4SEM image of nanowire array.
FIG. 2 is a schematic representation of an embodiment of the present invention 1. NiCo coated with a carbon composite derived from a metal organic framework2S4TEM and HRTEM images of nanowire arrays.
FIG. 3 is a schematic representation of an embodiment of the present invention 1. NiCo coated with a metal organic framework structure derived carbon composite2S4XRD pattern of nanowire arrays.
FIG. 4 is a schematic representation of an embodiment of the present invention 1. NiCo coated with a metal organic framework structure derived carbon composite2S4XPS plot of nanowire arrays.
FIG. 5 is a schematic representation of an embodiment of the present invention 1. NiCo coated with a metal organic framework structure derived carbon composite2S4Graph of oxygen evolution reaction performance of nanowire arrays.
FIG. 6 is a schematic representation of an embodiment of the present invention 1. NiCo coated with a metal organic framework structure derived carbon composite2S4Double layer capacitance plots of nanowire arrays.
FIG. 7 is a schematic representation of an embodiment of the present invention 1. NiCo coated with a metal organic framework structure derived carbon composite2S4Hydrogen evolution reaction performance diagram of nanowire array.
FIG. 8 shows an embodiment 2NiCo of the present invention2S4SEM image of nanowire array.
FIG. 9 shows an embodiment 2NiCo of the present invention2S4Oxygen evolution and hydrogen evolution electrochemical performance diagrams of the nanowire arrays.
Fig. 10 is an SEM image of a nickel cobalt precursor nanowire array according to embodiment 3 of the invention.
Fig. 11 is an electrochemical performance diagram of oxygen evolution and hydrogen evolution of the nickel-cobalt precursor nanowire array in accordance with an embodiment of the present invention.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
referring to fig. 1 to 11, in this embodiment, the oxygen evolution and hydrogen evolution electrochemical performance test on the grown nanowire array material is performed on a CHI 852D electrochemical workstation, and the operation process is as follows:
firstly, shearing a piece of carbon cloth (1cm multiplied by 1cm) in size as a working electrode, taking a carbon rod electrode as a counter electrode, taking a Saturated Calomel Electrode (SCE) as a reference electrode, and carrying out electrochemical hydrogen evolution and oxygen evolution performance tests;
and secondly, before testing, adding 1M potassium hydroxide solution into the electrolytic cell, selecting a test program of cyclic voltammetry and linear sweep voltammetry, and monitoring the current conditions of the working electrode at different sweep rates by using a computer. And finally, calculating the Tafel slope according to the measured data and a corresponding formula, and evaluating the oxygen evolution performance and the hydrogen evolution performance of the catalyst by the number of transferred electrons and the yields of oxygen and hydrogen.
Example 1
NiCo coated with metal organic framework structure derived carbon composite2S4A method for preparing a nanowire array-like electrocatalyst, the method comprising the steps of:
1) 0.595g of nickel chloride hexahydrate, 1.189g of cobalt chloride hexahydrate, 0.54 g of urea and 0.729g of cetyltrimethylammonium bromide (CTAB) were each weighed out and dissolved in 50mL of deionized water, stirred at room temperature for 10 minutes, then transferred to a 50mL stainless steel autoclave, placed in a treated carbon cloth (2 cm. times.3 cm), kept at 100 ℃ for 8 hours, cooled to room temperature, washed with deionized water and ethanol several times, and finally dried.
2) Weighing 1.2g of sodium sulfide nonahydrate, dissolving in 50mL of deionized water, stirring at room temperature for 10 minutes, transferring into a 50mL stainless steel autoclave, placing a carbon cloth with a precursor of nickel and cobalt, keeping at 160 ℃ for 8 hours, cooling to room temperature, ultrasonically washing with deionized water and ethanol for three times, and finally drying.
3) Weighing 1.64g of dimethylimidazole, dissolving in 5mL of deionized water and 5mL of ethanol, carrying out ultrasonic treatment for 5 minutes, and putting the mixture into a reactor in which NiCo grows2S4Placing the carbon cloth of the nanowire array at room temperature for reaction for 12 hours, then washing the carbon cloth with deionized water and ethanol for multiple times, putting the carbon cloth into an oven, and drying the carbon cloth for 12 hours at 85 ℃; finally, in a tube furnace, in a nitrogen atmosphere, at 2 ℃ for min-1The temperature rising rate of (2) was maintained at 350 ℃ for 3 hours.
The obtained NiCo coated with the metal organic framework structure derived carbon composite2S4SEM images of nanowire arrays are shown in figure 1. The obtained NiCo coated with the metal organic framework structure derived carbon composite2S4TEM and HRTEM images of the nanowire arrays are shown in fig. 2. The obtained NiCo coated with the metal organic framework structure derived carbon composite2S4The XRD pattern of the nanowire array is shown in figure 3. The obtained NiCo coated with the metal organic framework structure derived carbon composite2S4XPS plots of nanowire arrays are seen in figure 4. The obtained NiCo coated with the metal organic framework structure derived carbon composite2S4A graph of the oxygen evolution reaction performance of the nanowire array is shown in fig. 5. The obtained NiCo coated with the metal organic framework structure derived carbon composite2S4See figure 6 for a diagram of double layer capacitance for nanowire arrays. The obtained NiCo coated with the metal organic framework structure derived carbon composite2S4A graph of the hydrogen evolution reaction performance of the nanowire arrays is shown in fig. 7.
As can be seen, the obtained catalyst is NiCo coated by a metal organic framework structure derived carbon composite2S4And (3) forming a nanowire structure. Uniformly distributed on each carbon cloth, just like the carbon cloth is grown by dislocation, the carbon cloth extends to the periphery from the surface of the carbon cloth, and each carbon cloth is firmly wrapped. Through HRTEM, XRD and XPS analysis, the alloying degree of the material is good, and a nickel-cobalt alloy structure is formed. The structure not only can provide more active sites, but also can accelerate electron transfer in the reaction process, and can greatly improve the performance of the catalystAnd (4) performance. As is obvious from the curve of the electric double layer capacitance, the material has higher active specific surface area. As can be seen from the linear sweep voltammetry curve, the carbon composite coated NiCo derived from the metal-organic framework structure2S4The nanowire array had a very positive onset potential (1.52V vs. rhe) for catalyzing oxygen evolution and a very negative onset point for hydrogen evolution (-0.1V vs. rhe). The tafel slopes are calculated according to the linear sweep voltammograms and are 81.92mV dec respectively-1And 100.68mV dec-1The transfer of the first electron during oxygen evolution and hydrogen evolution proved to be the rate controlling step. From the linear sweep voltammetry curve before and after 10000 circles and the polarographic voltage time curve, the NiCo coated by the metal organic framework structure derived carbon composite can be seen2S4The nanowire array has good stability.
Example 2
NiCo2S4A method of preparing a nanowire-shaped electrocatalyst, the method comprising the steps of:
1) 0.595g of nickel chloride hexahydrate, 1.189g of cobalt chloride hexahydrate, 0.54 g of urea and 0.729g of cetyltrimethylammonium bromide (CTAB) were each weighed out and dissolved in 50mL of deionized water, stirred at room temperature for 10 minutes, then transferred to a 50mL stainless steel autoclave, placed in a treated carbon cloth (2 cm. times.3 cm), kept at 100 ℃ for 8 hours, cooled to room temperature, washed with deionized water and ethanol several times, and finally dried.
2) Weighing 1.2g of sodium sulfide nonahydrate, dissolving in 50mL of deionized water, stirring at room temperature for 10 minutes, transferring into a 50mL stainless steel autoclave, placing a carbon cloth with a precursor of nickel and cobalt, keeping at 160 ℃ for 8 hours, cooling to room temperature, ultrasonically washing with deionized water and ethanol for three times, and finally drying.
Obtaining NiCo2S4SEM images of nanowire-like arrays are seen in fig. 8. Obtaining NiCo2S4The graph of the oxygen evolution and hydrogen evolution reaction performance of the nanowire array is shown in fig. 9.
As can be seen from the SEM image, the resulting catalyst consisted of nanowire structures. NiCo can be seen by linear sweep voltammograms2S4The nanowire array-shaped electrocatalyst has an initial potential (1.54V vs. rhe) for more positive catalytic oxygen evolution and an initial point (-0.17V vs. rhe) for more negative hydrogen evolution. The tafel slopes are calculated according to the linear sweep voltammograms and are 83.74mV dec respectively-1And 100.68mV dec-1The transfer of the first electron during oxygen evolution and hydrogen evolution proved to be the rate controlling step.
Example 3
A method for preparing a nickel-cobalt precursor nanowire-shaped electrocatalyst, the method comprising the steps of:
1) 0.595g of nickel chloride hexahydrate, 1.189g of cobalt chloride hexahydrate, 0.54 g of urea and 0.729g of cetyltrimethylammonium bromide (CTAB) were each weighed out and dissolved in 50mL of deionized water, stirred at room temperature for 10 minutes, then transferred to a 50mL stainless steel autoclave, placed in a treated carbon cloth (2 cm. times.3 cm), kept at 100 ℃ for 8 hours, cooled to room temperature, washed with deionized water and ethanol several times, and finally dried.
The SEM image of the obtained nickel cobalt precursor nanowire-like array is shown in fig. 10. The oxygen evolution and hydrogen evolution reaction performance diagram of the nickel-cobalt precursor nanowire array is shown in fig. 11.
As can be seen from the SEM image, the resulting catalyst consisted of nanowire structures. It can be seen from the linear sweep voltammogram that the nickel-cobalt precursor nanowire array electrocatalyst has an initial potential (1.58V vs. rhe) for the precipitation of oxygen and a more negative initial point position (-0.18V vs. rhe) for the precipitation of hydrogen. The tafel slopes are calculated according to the linear sweep voltammograms and are 90.36mV dec respectively-1And 221.68mV dec-1The transfer of the first electron during oxygen evolution and hydrogen evolution proved to be the rate controlling step.
Example 4
NiCo coated with metal organic framework structure derived carbon composite2S4A method for preparing a nanowire array-like electrocatalyst, the method comprising the steps of:
1) 0.2g of nickel chloride hexahydrate, 0.4g of cobalt chloride hexahydrate, 0.2g of urea and 0.3g of cetyltrimethylammonium bromide (CTAB) were each weighed out and dissolved in 30mL of deionized water, stirred at room temperature for 5 minutes, then transferred to a 50mL stainless steel autoclave, put into a treated carbon cloth (2 cm. times.3 cm), held at 80 ℃ for 6 hours, cooled to room temperature, washed with deionized water and ethanol several times, and finally dried.
2) Weighing 0.6g of sodium sulfide nonahydrate, dissolving in 30mL of deionized water, stirring at room temperature for 5 minutes, transferring into a 50mL stainless steel autoclave, placing a carbon cloth with a precursor of nickel and cobalt, keeping at 140 ℃ for 6 hours, cooling to room temperature, ultrasonically washing with deionized water and ethanol for three times, and finally drying.
3) Weighing 1.2g of dimethylimidazole, dissolving in 10mL of deionized water and 10mL of ethanol, carrying out ultrasonic treatment for 10 minutes, and putting the mixture into a reactor in which NiCo grows2S4Placing the carbon cloth of the nanowire array at room temperature for reaction for 5 hours, then washing the carbon cloth with deionized water and ethanol for multiple times, placing the carbon cloth into an oven, and drying the carbon cloth for 10 hours at 70 ℃; finally, in a tube furnace, in a nitrogen atmosphere, at 2 ℃ for min-1The temperature rise rate of (2) was maintained at 300 ℃ for 2 hours.
In the synthesis process, the concentrations of nickel chloride hexahydrate and cobalt chloride hexahydrate are too low, the reaction temperature is too low, the reaction time is too short, uniform nanowire arrays cannot grow on the carbon cloth, and the nanowire arrays are too thin and too sparse and have no good electrocatalysis performance.
Example 5
NiCo coated with metal organic framework structure derived carbon composite2S4A method for preparing a nanowire array-like electrocatalyst, the method comprising the steps of:
1) 1.2g of nickel chloride hexahydrate, 2.4g of cobalt chloride hexahydrate, 1.2g of urea and 1.4g of cetyltrimethylammonium bromide (CTAB) were each weighed and dissolved in 60mL of deionized water, stirred at room temperature for 20 minutes, then transferred to a 50mL stainless steel autoclave, put into a treated carbon cloth (2 cm. times.3 cm), held at 120 ℃ for 12 hours, cooled to room temperature, washed with deionized water and ethanol several times, and finally dried.
2) Weighing 1.8g of sodium sulfide nonahydrate, dissolving in 50mL of deionized water, stirring at room temperature for 10 minutes, transferring into a 50mL stainless steel autoclave, placing a carbon cloth with a precursor of nickel and cobalt, keeping at 180 ℃ for 12 hours, cooling to room temperature, ultrasonically washing with deionized water and ethanol for three times, and finally drying.
3) Weighing 2.4g of dimethylimidazole, dissolving in 10mL of deionized water and 10mL of ethanol, carrying out ultrasonic treatment for 10 minutes, and putting the mixture into a reactor in which NiCo grows2S4The carbon cloth of the nanowire array is placed at room temperature for reaction for 16 hours, then is washed with deionized water and ethanol for multiple times, is placed into an oven, and is dried for 16 hours at 90 ℃. Finally, in a tube furnace, in a nitrogen atmosphere, at 2 ℃ for min-1The temperature rising rate of (2) was maintained at 400 ℃ for 5 hours.
In the synthesis process, the concentrations of nickel chloride hexahydrate and cobalt chloride hexahydrate are too high, the reaction temperature is too high, the reaction time is too long, uniform nanowire arrays cannot grow on the carbon cloth, and the nanowire arrays are too thick and dense and have no good electrocatalysis performance.
Claims (3)
1. NiCo coated with metal organic framework structure derived carbon composite2S4A nano-arrayed electrocatalyst prepared by the method comprising:
(1) respectively weighing 0.2-1.2 g of nickel chloride hexahydrate, 0.4-2.4 g of cobalt chloride hexahydrate, 0.2-1.2 g of urea and 0.3-1.4 g of hexadecyl trimethyl ammonium bromide, dissolving in 30-60 mL of deionized water, stirring for 5-20 minutes at room temperature, then transferring into a 50mL stainless steel autoclave, putting into treated carbon cloth (2cm multiplied by 3cm), keeping for 6-12 hours at 80-120 ℃, cooling to room temperature, washing with deionized water and ethanol for multiple times, and finally drying;
(2) weighing 0.6-1.8 g of sodium sulfide nonahydrate, dissolving in 30-60 mL of deionized water, stirring at room temperature for 5-20 minutes, then transferring into a 50mL stainless steel autoclave, placing carbon cloth with grown nickel-cobalt precursor, keeping at 140-180 ℃ for 6-12 hours, cooling to room temperature, ultrasonically washing with deionized water and ethanol for three times, and finally drying;
(3) weighing 1.2-2.4 g of dimethylimidazole, dissolving the dimethylimidazole in 10-20 mL of mixed solution of deionized water and ethanol, carrying out ultrasonic treatment for 5-10 minutes, putting carbon cloth with a cobaltosic sulfide nano-array growing therein, standing the carbon cloth at room temperature for reaction for 8-16 hours, washing the carbon cloth with the deionized water and the ethanol for multiple times, putting the carbon cloth into an ovenDrying at 70-90 ℃ for 10-16 hours; finally, in a tube furnace, in a nitrogen atmosphere, at 2 ℃ for min-1The temperature rise rate of (2) is kept for 2 to 5 hours at 300 to 400 ℃; obtaining NiCo coated by the metal organic framework structure derived carbon compound2S4A nano-arrayed electrocatalyst.
2. NiCo coated with metal organic framework structure derived carbon composite2S4A method for preparing a nano-arrayed electrocatalyst, comprising the steps of:
(1) respectively weighing 0.2-1.2 g of nickel chloride hexahydrate, 0.4-2.4 g of cobalt chloride hexahydrate, 0.2-1.2 g of urea and 0.3-1.4 g of hexadecyl trimethyl ammonium bromide, dissolving in 30-60 mL of deionized water, stirring for 5-20 minutes at room temperature, then transferring into a 50mL stainless steel autoclave, putting into treated carbon cloth (2cm multiplied by 3cm), keeping for 6-12 hours at 80-120 ℃, cooling to room temperature, washing with deionized water and ethanol for multiple times, and finally drying;
(2) weighing 0.6-1.8 g of sodium sulfide nonahydrate, dissolving in 30-60 mL of deionized water, stirring at room temperature for 5-20 minutes, then transferring into a 50mL stainless steel autoclave, placing carbon cloth with grown nickel-cobalt precursor, keeping at 140-180 ℃ for 6-12 hours, cooling to room temperature, ultrasonically washing with deionized water and ethanol for three times, and finally drying;
(3) weighing 1.2-2.4 g of dimethylimidazole, dissolving the dimethylimidazole in 10-20 mL of mixed solution of deionized water and ethanol, carrying out ultrasonic treatment for 5-10 minutes, putting a carbon cloth with a cobaltosic sulfide nano-array growing therein, standing the carbon cloth at room temperature for reaction for 8-16 hours, washing the carbon cloth with deionized water and ethanol for many times, putting the carbon cloth into an oven, and drying the carbon cloth at 70-90 ℃ for 10-16 hours; finally, in a tube furnace, in a nitrogen atmosphere, at 2 ℃ for min-1The temperature rise rate of (2) is kept for 2 to 5 hours at 300 to 400 ℃; obtaining NiCo coated by the metal organic framework structure derived carbon compound2S4A nano-arrayed electrocatalyst.
3. The method of claim 2, wherein the nickel chloride hexahydrate, cobalt chloride hexahydrate,sodium sulfide nonahydrate, concentration and volume of dimethylimidazole, amount of urea and CTAB, and temperature and time of reaction to control the metal organic framework-derived carbon composite coated NiCo2S4Morphology and structure of nanoarrays.
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