CN111672514A - Bifunctional electrocatalytic material and preparation method and application thereof - Google Patents
Bifunctional electrocatalytic material and preparation method and application thereof Download PDFInfo
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- CN111672514A CN111672514A CN202010554643.6A CN202010554643A CN111672514A CN 111672514 A CN111672514 A CN 111672514A CN 202010554643 A CN202010554643 A CN 202010554643A CN 111672514 A CN111672514 A CN 111672514A
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- 239000000463 material Substances 0.000 title claims abstract description 61
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000000758 substrate Substances 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 19
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 239000000376 reactant Substances 0.000 claims abstract description 12
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 61
- 229910052759 nickel Inorganic materials 0.000 claims description 19
- 239000006260 foam Substances 0.000 claims description 15
- 239000004202 carbamide Substances 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000011221 initial treatment Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000012153 distilled water 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 230000008901 benefit Effects 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 13
- 238000005265 energy consumption Methods 0.000 abstract description 8
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 abstract description 8
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 239000007772 electrode material Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000001000 micrograph Methods 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000012467 final product Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000007605 air drying Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000010587 phase diagram Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000012716 precipitator Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 229910016719 Ni0.5Co0.5(OH)2 Inorganic materials 0.000 description 1
- 229910017062 Ni0.67Co0.33(OH)2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/33—
-
- 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
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- 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
-
- 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
The invention discloses a bifunctional electrocatalytic material and a preparation method and application thereof, wherein the method comprises the following steps: mixing nickel nitrate and cobalt nitrate according to a preset molar ratio, and adding an auxiliary reactant and water ionized water to prepare a mixed solution; and adding the pretreated conductive substrate and the mixed solution into a reaction kettle filled with polytetrafluoroethylene, heating, and growing nickel-cobalt double metal hydroxide on the surface of the pretreated conductive substrate to obtain the bifunctional electrocatalytic material. The invention adopts a one-step hydrothermal method to grow nickel-cobalt double metal hydroxide in situ on a conductive substrate to prepare the bifunctional electrocatalytic material. The bifunctional electrocatalytic material has the advantages of multiple surface activities and good electrochemical performance, can be applied to a methanol-water co-electrolysis reaction system, realizes value-added conversion of methanol and low energy consumption high-efficiency hydrogen production, and has wide application prospects.
Description
Technical Field
The invention relates to the field of electrochemical catalytic materials, in particular to a bifunctional electrocatalytic material and a preparation method and application thereof.
Background
With the gradual depletion of fossil energy and the gradual increase of environmental problems, the utilization of new energy sources such as hydrogen energy and the development of high-efficiency conversion devices have become hot spots of current research, and renewable hydrogen energy has many advantages of abundant resources, no pollution of combustion products and the like. In recent years, an electrolytic water system provides a green hydrogen production conversion approach, water electrolysis can be realized by two reactions of cathode hydrogen evolution and anode Oxygen evolution, but the slower anode Oxygen evolution reaction (abbreviated as OER) in the system has a higher kinetic reaction energy barrier, so that the energy utilization rate of the whole water electrolysis reaction system is lower, and the water electrolysis system is considered as a main problem of hindering the industrialization of the traditional electrolytic water hydrogen production.
Explosive H may be formed by gas diffusion in conventional electrolytic water systems2/O2The gas mixture causes potential safety hazard and shortens the service life of the traditional full-hydrolysis electrolytic cell. Meanwhile, methanol is used as a basic chemical, and can be industrially used for preparing important chemicals such as formaldehyde, formic acid, dimethyl ether, methyl formate and the like, but the traditional industry needs high-temperature rectification to realize value-added conversion. Therefore, the electrochemical catalytic oxidation of methanol at room temperature and the realization of the incremental conversion thereof have become very interesting research hotspots. Therefore, the Methanol Oxidation Reaction (MOR) which is more favorable in thermodynamics is adopted to replace the water oxidation Reaction (OER) in the traditional electrolytic water which has slow Reaction and low product value, the hydrogen production with low energy consumption and the methanol value-added conversion at room temperature can be realized simultaneously, and the methanol-water co-electrolysis system has great research prospect and economic benefit. In addition, conventional electrolytic water systems are typically strongly acidic electrolytes composed of strongly alkaline liquid electrolytes or Proton Exchange Membranes (PEM), with noble metal catalysts (e.g., Pt for high HER activity, and IrO for high OER activity)2、RuO2Or stainless steel, etc.). At the heart of the electrolysis process is the electrocatalyst required for the electrochemical reaction, which directly affects the electrolysis efficiency, the electrolysis energy consumption and the electrolysis cost.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a bifunctional electrocatalytic material which can electrolyze water to produce hydrogen and methanol value-added chemicals, has high electrochemical activity and low cost, and a preparation method and application thereof.
The technical scheme of the invention is as follows:
a method for preparing a bifunctional electrocatalytic material, comprising the steps of:
mixing nickel nitrate and cobalt nitrate according to a preset molar ratio, and adding an auxiliary reactant and water ionized water to prepare a mixed solution;
and adding the pretreated conductive substrate and the mixed solution into a reaction kettle filled with polytetrafluoroethylene, heating, and growing nickel-cobalt double metal hydroxide on the surface of the pretreated conductive substrate to obtain the bifunctional electrocatalytic material.
The preparation method of the bifunctional electrocatalytic material comprises the step of preparing the bifunctional electrocatalytic material, wherein the preset molar ratio of the nickel nitrate to the cobalt nitrate is 3:1-1: 3.
The preparation method of the bifunctional electrocatalytic material comprises the step of preparing an auxiliary reactant, wherein the auxiliary reactant is urea.
The preparation method of the bifunctional electrocatalytic material comprises the following steps of preparing an auxiliary reactant from urea and ammonium fluoride.
The preparation method of the bifunctional electrocatalytic material comprises the step of preparing the conductive substrate by using foamed nickel, foamed copper, carbon paper, carbon cloth, a stainless steel sheet or a titanium sheet.
The preparation method of the bifunctional electrocatalytic material comprises the following steps of:
carrying out ultrasonic treatment on the initial conductive substrate in distilled water, acetone and ethanol respectively to obtain a primary treatment conductive substrate;
and soaking the primary treatment conductive substrate in dilute hydrochloric acid and carrying out ultrasonic treatment to obtain the pretreatment conductive substrate.
The preparation method of the bifunctional electrocatalytic material comprises the step of adding the pretreated conductive substrate and the mixed solution into a reaction kettle filled with polytetrafluoroethylene and heating, wherein the heating temperature is 100-150 ℃.
The preparation method of the bifunctional electrocatalytic material comprises the step of adding the pretreated conductive substrate and the mixed solution into a reaction kettle filled with polytetrafluoroethylene and heating for 3-8 hours.
The invention relates to a bifunctional electrocatalytic material, which is prepared by the preparation method of the bifunctional electrocatalytic material.
The application of the bifunctional electrocatalytic material is to use the bifunctional electrocatalytic material in the hydrogen production by water electrolysis and methanol value-added chemicals.
Has the advantages that: the invention provides a preparation method of a bifunctional electrocatalytic material, which is characterized in that a nickel-cobalt bimetallic hydroxide is grown in situ on a conductive substrate by adopting a one-step hydrothermal method to prepare the bifunctional electrocatalytic material. The bifunctional electrocatalytic material has the advantages of multiple surface activities and good electrochemical performance, can be applied to a methanol-water co-electrolysis reaction system, realizes value-added conversion of methanol and low energy consumption high-efficiency hydrogen production, and has wide application prospects.
Drawings
FIG. 1 is a flow chart of a preferred embodiment of a method for preparing a bifunctional electrocatalytic material according to the present invention.
FIG. 2a is a scanning electron micrograph of nickel foam.
FIG. 2b shows Ni (OH) obtained in example 12Scanning electron microscope images of/NF electrode materials.
FIG. 2c shows Co (OH) obtained in example 22Scanning electron microscope images of/NF electrode materials.
FIG. 2d shows Ni prepared in example 30.33Co0.67(OH)2A scanning electron microscope image of the/NF-F electrode material.
FIG. 2e shows Ni prepared in example 40.5Co0.5(OH)2Scanning electron microscope images of/NF electrode materials.
FIG. 2f shows Ni prepared in example 40.33Co0.67(OH)2Scanning electron microscope images of/NF electrode materials.
FIG. 2g shows Ni prepared in example 40.25Co0.75(OH)2Scanning electron microscope images of/NF electrode materials.
FIG. 2h shows Ni prepared in example 40.67Co0.33(OH)2Scanning electron microscope images of/NF electrode materials.
FIG. 2i shows Ni obtained in example 40.75Co0.25(OH)2Scanning electron microscope images of/NF electrode materials.
FIG. 3 is an X-ray diffraction diagram of an electrode material prepared by NiCo-LDH/NF in different proportions.
FIG. 4a is a linear polarization plot of MOR for different electrode materials in different electrolytes of the present invention.
FIG. 4b is a graph showing the OER linear polarization curves of different electrode materials in different electrolytes according to the present invention.
Detailed Description
The invention provides a bifunctional electrocatalytic material, and a preparation method and application thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, fig. 1 is a flow chart of a preferred embodiment of a method for preparing a bifunctional electrocatalytic material according to the present invention, as shown in the figure, the method comprises the following steps:
s10, mixing nickel nitrate and cobalt nitrate according to a preset molar ratio, and adding an auxiliary reactant and water ionized water to prepare a mixed solution;
s20, adding the pretreated conductive substrate and the mixed solution into a reaction kettle filled with polytetrafluoroethylene, heating, and growing nickel-cobalt double metal hydroxide on the surface of the pretreated conductive substrate to obtain the bifunctional electrocatalytic material.
Specifically, Layered Double Hydroxides (LDHs) are also called hydrotalcite-like compounds, and their basic structure is a charge-balanced double-layer structure composed of positively charged metal ion layers and interlayer anions, and they have unique physicochemical properties due to their special structures and flexibly variable chemical compositions. Aiming at the problem of poor conductivity of LDHs powder materials, the invention prepares the bifunctional electrocatalytic electrode by introducing materials such as porous foam nickel (Ni foam, NF for short) and the like as a conductive substrate and constructing an LDHs nano array on the conductive substrate. As a typical LDHs compound, the nickel-cobalt double-metal hydroxide/foamed nickel (NiCo-LDH/NF) nano array structure has large specific surface area, the porous structure is favorable for mass transfer process and gas diffusion, and the material has the advantages of low cost, high electrochemical activity and the like. The bifunctional electrocatalytic material has the advantages of multiple surface activities and good electrochemical performance, can be applied to a methanol-water co-electrolysis reaction system, realizes value-added conversion of methanol and low energy consumption high-efficiency hydrogen production, and has wide application prospects. The one-step hydrothermal preparation method provided by the invention is simple to operate and low in cost, and the prepared bifunctional electrocatalytic material avoids the defects of high resistance and easy shedding of a powder catalyst caused by the addition of an organic adhesive; the prepared bifunctional electrocatalytic material presents different three-dimensional appearances, is beneficial to mass transfer and electron transmission in electrolytic reaction, and presents good electrocatalytic performance in a common electrolytic performance test.
In some embodiments, the predetermined molar ratio of the nickel nitrate to the cobalt nitrate is 3:1-1:3, and in this embodiment, by changing different proportions of the components, the morphology of the material is adjusted, so that the surface active sites of the material can be increased, and the electrochemical performance of the prepared bifunctional electrocatalytic material is further improved.
In some embodiments, the auxiliary reactant is urea. In other embodiments, the auxiliary reactants are urea and ammonium fluoride.
In some embodiments, the conductive substrate is nickel foam, copper foam, carbon paper, carbon cloth, stainless steel sheet, or titanium sheet, but is not limited thereto.
In some specific embodiments, the initial conductive substrate is subjected to ultrasonic treatment in distilled water, acetone and ethanol for 10 minutes respectively to remove impurities stained on the surface, so as to obtain a primary treatment conductive substrate; then soaking the once-treated conductive substrate in dilute hydrochloric acid, carrying out ultrasonic treatment for 10 minutes, removing an oxide layer on the surface, finally cleaning the substrate for a plurality of times by using distilled water, and then air-drying the substrate for later use to obtain the pretreated conductive substrate; weighing nickel nitrate and cobalt nitrate in a beaker according to a certain proportion, adding an auxiliary reactant and deionized water, and magnetically stirring until the nickel nitrate and the cobalt nitrate are dissolved into clear solutions with different colors; adding the pretreated conductive substrate and the mixed solution into a reaction kettle filled with polytetrafluoroethylene, and heating at the temperature of 100 ℃ and 150 ℃ for 3-8 h; and after the reaction is finished, naturally cooling the reaction product to room temperature, taking out the reacted conductive substrate, carrying out ultrasonic treatment for 2 minutes, and washing the powder aggregated on the surface of the substrate to obtain the bifunctional electrocatalytic material.
In some embodiments, there is also provided a bifunctional electrocatalytic material, which is prepared by the above-mentioned preparation method of one bifunctional electrocatalytic material of the present invention. Specifically, the bifunctional electrocatalytic material comprises an electrically conductive substrate and a nickel-cobalt double metal hydroxide grown on the surface of the electrically conductive substrate. As a typical LDHs compound, the nickel-cobalt double-metal hydroxide nano array structure grown on the surface of the conductive substrate has large specific surface area, the porous structure of the nickel-cobalt double-metal hydroxide nano array structure is favorable for mass transfer process and gas diffusion, and the material has the advantages of low cost, high electrochemical activity and the like. The bifunctional electrocatalytic material provided by the embodiment has the advantages of multiple surface activities and good electrochemical performance, can be applied to a methanol-water co-electrolysis reaction system, realizes value-added conversion of methanol and low energy consumption high-efficiency hydrogen production, and has wide application prospects.
In some embodiments, the application of the bifunctional electrocatalytic material is provided, and the bifunctional electrocatalytic material is used for hydrogen production by water electrolysis and methanol value-added chemicals. The bifunctional electrocatalytic material provided by the embodiment has the advantages of multiple surface activities and good electrochemical performance, can be applied to a methanol-water co-electrolysis reaction system, realizes value-added conversion of methanol and low energy consumption high-efficiency hydrogen production, and has wide application prospects.
The following is a further explanation of the bifunctional electrocatalytic material of the present invention, its preparation method and properties by means of specific examples:
example 1
A method for preparing a single metal hydroxide electrode material, comprising the steps of:
dissolving nickel nitrate and precipitator urea in deionized water, stirring and mixing uniformly to prepare a solution A1N, wherein the final molar concentration of nickel nitrate is 0.085mol/L, and the final molar concentration of urea is 0.35 mol/L;
adding commercial foam nickel into the solution A1N, wherein the scanning electron microscope image of the foam nickel is shown in FIG. 2 a; then carrying out hydrothermal reaction for 6h at 120 ℃, washing and naturally air drying to obtain a final product Ni (OH)2and/NF. The appearance and phase diagram of the sample are respectively shown in fig. 2b and fig. 3, and it can be seen from the figure that the foam nickel after pretreatment has a smooth surface, and after hydrothermal reaction, the supported nickel hydroxide has a nano-sheet structure, which shows that the prepared Ni (OH)2The catalyst was successfully supported on foamed nickel and Ni (OH)2the/NF is a sheet structure.
Example 2
A method for preparing a single metal hydroxide electrode material, comprising the steps of:
dissolving cobalt nitrate and a precipitator urea in deionized water together, stirring and mixing uniformly to prepare a solution A7N, wherein the final molar concentration of the cobalt nitrate is 0.085mol/L, and the final molar concentration of the urea is 0.35 mol/L;
adding commercial foam nickel into the solution A7N, performing hydrothermal reaction for 6h at 120 ℃, washing, and naturally drying to obtain a final product Co (OH)2and/NF. The morphology and phase diagram of the sample are shown in FIG. 2c and FIG. 3, respectively, showing the Co (OH) produced2The catalyst was successfully supported on foamed nickel and Co (OH)2the/NF is a sea urchin-shaped radiation structure, exposes more active specific surface area and is beneficial to promoting the electrolytic reaction.
Example 3
Flaky bimetal hydroxide Ni0.33Co0.67(OH)2The preparation method of the/NF-F electrode material comprises the following steps:
dissolving nickel nitrate and cobalt nitrate, ammonium fluoride and urea together according to the proportion of Ni/Co being 0.5 in deionized water, stirring and mixing uniformly to prepare a solution A5F, wherein the total molar concentration of the nickel nitrate and the cobalt nitrate is 0.085mol/L, the final molar concentration of ammonium fluoride is 0.17mol/L, and the final molar concentration of ammonium fluoride is 0.35 mol/L;
adding commercial foam nickel into the solution A5F, performing hydrothermal reaction for 3h at 120 ℃, washing, and naturally air-drying to obtain a final product Ni0.33Co0.67(OH)2/NF-F. The morphology of the sample is shown in FIG. 2d, which shows that the prepared catalyst is successfully loaded on the foamed nickel, and Ni0.33Co0.67(OH)2the/NF-F is a sheet structure.
Example 4
Needle-like double metal hydroxide NixCo1-x(OH)2The preparation method of the/NF electrode material comprises the following steps:
dissolving nickel nitrate and cobalt nitrate in deionized water together with a precipitator urea according to different proportions:
1) the molar ratio of the nickel nitrate to the cobalt nitrate is 3:1, and the solution is marked as A2N;
2) the molar ratio of the nickel nitrate to the cobalt nitrate is 2:1, and the solution is marked as A3N;
3) the molar ratio of the nickel nitrate to the cobalt nitrate is 1:1, and the solution is marked as A4N;
4) the molar ratio of the nickel nitrate to the cobalt nitrate is 1:2, and the solution is marked as A5N;
5) the molar ratio of the nickel nitrate to the cobalt nitrate is 1:3, and the solution is marked as A6N;
the total molar concentration of the metal salt is 0.085mol/L, the final molar concentration of the urea is 0.35mol/L, and the metal salt and the urea are stirred and mixed uniformly to prepare a solution;
adding commercial foam nickel into the solution A2N, A3N, A4N, A5N and A6N, performing hydrothermal reaction for 6 hours at 120 ℃, washing and naturally drying to obtain a final product Ni0.75Co0.25(OH)2/NF；Ni0.67Co0.33(OH)2/NF；Ni0.5Co0.5(OH)2/NF；Ni0.33Co0.67(OH)2/NF and Ni0.25Co0.75(OH)2The shape of a corresponding sample of the/NF is shown in figures 2e-2I, the phase diagram of the corresponding sample is shown in figure 3, and the figure shows that the surface of the foam nickel after pretreatment is smooth, the nickel hydroxide loaded after hydrothermal reaction is of a nano-sheet structure, the cobalt hydroxide is of a nano-sea urchin-like structure, and Ni is increased along with the increase of cobalt componentsxCo1-x(OH)2The larger the size of the nanoneedle structure of/NF, the more the nickel component increases, the agglomeration phenomenon of the nanoneedle structure gradually occurs. From this figure it can be seen that NiCo-LDH was successfully grown in situ on foam nickel. This indicates that the prepared catalyst was successfully grown in situ on foamed nickel and that the double metal hydroxide NixCo1-x(OH)2the/NF is of a nano needle-shaped structure, exposes more active specific surface area, promotes mass transfer and electron transfer processes, and is beneficial to the high-efficiency implementation of electrolytic reaction.
By comparing FIG. 2d (Ni)0.33Co0.67(OH)2SEM of/NF-F) and FIG. 2F (Ni)0.33Co0.67(OH)2/NF scanning electron microscope), different reaction times show different catalyst morphologies, the needle structure is the product after 6 hours of hydrothermal reaction, and the sheet structure is the product after 3 hours of hydrothermal reaction. The preparation of the electrocatalysts with different morphologies under different temperature and time conditions by a one-step hydrothermal method is illustrated, and in addition, the regulation and control of different morphologies and electrochemical properties are realized by changing the proportional relationship of the components.
Example 5
Electrochemical tests such as methanol oxidation reaction (MOR for short) and oxygen evolution reaction (OER for short) were performed on the electrode materials obtained in examples 1 to 4:
under the condition of room temperature, a traditional three-electrode system is adopted to perform oxygen evolution performance test on a CHI 760E electrochemical workstation, a Hg/HgO electrode and a Pt sheet are respectively used as a reference electrode and a counter electrode, and electrolytes are respectively as follows:
1)1.0M potassium hydroxide, test OER performance;
2)1.0M potassium hydroxide and 0.5M methanol, MOR performance,
comparing the test curves as shown in fig. 4a-4b, the electrode material exhibited good OER and MOR catalytic performance. And in 1.0M potassium hydroxide, significant oxidation reactions occurred on the surface of the electrode material. After 0.5M of methanol is added into the electrolyte, the oxidation reaction potential of the methanol is far lower than the traditional oxygen evolution reaction potential, the MOR reaction preferentially occurs on the surface of the electrode material, the reaction rate is obviously accelerated, and the corresponding oxidation current is rapidly increased.
The above experimental results show that: the simple one-step hydrothermal method for preparing the bimetallic hydroxide electrode material provided by the invention has the advantages of low cost, high electrochemical activity and good stability. The electrode material is used for a methanol-water co-electrolysis strategy, so that the input voltage can be reduced, the reaction overpotential can be reduced, meanwhile, a high-efficiency co-electrolysis system which can realize the value increase of basic chemicals on an anode and drive a cathode to carry out low-energy hydrogen evolution can be constructed, and the benefit of energy investment can be improved to the maximum extent.
In summary, the invention provides a preparation method of a bifunctional electrocatalytic material, wherein a nickel-cobalt bimetallic hydroxide is grown in situ on a conductive substrate by a one-step hydrothermal method to prepare the bifunctional electrocatalytic material. The bifunctional electrocatalytic material has the advantages of multiple surface activities and good electrochemical performance, can be applied to a methanol-water co-electrolysis reaction system, realizes value-added conversion of methanol and low energy consumption high-efficiency hydrogen production, and has wide application prospects.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a bifunctional electrocatalytic material is characterized by comprising the following steps:
mixing nickel nitrate and cobalt nitrate according to a preset molar ratio, and adding an auxiliary reactant and water ionized water to prepare a mixed solution;
and adding the pretreated conductive substrate and the mixed solution into a reaction kettle filled with polytetrafluoroethylene, heating, and growing nickel-cobalt double metal hydroxide on the surface of the pretreated conductive substrate to obtain the bifunctional electrocatalytic material.
2. The method of preparing a bifunctional electrocatalytic material as set forth in claim 1, wherein the predetermined molar ratio of the nickel nitrate to the cobalt nitrate is 3:1 to 1: 3.
3. The method of claim 1, wherein the auxiliary reactant is urea.
4. The method of claim 1, wherein the auxiliary reactants are urea and ammonium fluoride.
5. The method of claim 1, wherein the conductive substrate is nickel foam, copper foam, carbon paper, carbon cloth, stainless steel sheet or titanium sheet.
6. The method of preparing a bifunctional electrocatalytic material as set forth in claim 1, wherein the preparing of the pretreated electrically conductive substrate comprises the steps of:
carrying out ultrasonic treatment on the initial conductive substrate in distilled water, acetone and ethanol respectively to obtain a primary treatment conductive substrate;
and soaking the primary treatment conductive substrate in dilute hydrochloric acid and carrying out ultrasonic treatment to obtain the pretreatment conductive substrate.
7. The method for preparing the bifunctional electrocatalytic material as set forth in claim 1, wherein the step of adding the pretreated conductive substrate and the mixed solution into a reaction vessel containing polytetrafluoroethylene and heating the mixture is performed at a temperature of 100 ℃ to 150 ℃.
8. The method for preparing a bifunctional electrocatalytic material as set forth in claim 7, wherein the step of adding the pretreated conductive substrate and the mixed solution into a reaction vessel containing polytetrafluoroethylene and heating for 3-8 hours.
9. A bifunctional electrocatalytic material, characterized by being obtained by the process for the preparation of a bifunctional electrocatalytic material according to any one of claims 1 to 8.
10. Use of a bifunctional electrocatalytic material as claimed in claim 9 for the production of hydrogen by electrolysis of water and for methanol value-added chemicals.
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