CN114703488A - Water electrolysis method adopting hydrogen evolution and oxygen evolution promoter - Google Patents
Water electrolysis method adopting hydrogen evolution and oxygen evolution promoter Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000001257 hydrogen Substances 0.000 title claims abstract description 46
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 46
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 43
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000001301 oxygen Substances 0.000 title claims abstract description 42
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 42
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 22
- 239000003792 electrolyte Substances 0.000 claims abstract description 50
- 239000012528 membrane Substances 0.000 claims abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 39
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical group OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- -1 15-crown ether-5 Chemical compound 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 229920001983 poloxamer Polymers 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 239000003115 supporting electrolyte Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920001400 block copolymer Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 description 39
- 238000012360 testing method Methods 0.000 description 37
- 230000000052 comparative effect Effects 0.000 description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 238000011056 performance test Methods 0.000 description 9
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 238000004502 linear sweep voltammetry Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 125000001033 ether group Chemical group 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 3
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- NLMDJJTUQPXZFG-UHFFFAOYSA-N 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane Chemical compound C1COCCOCCNCCOCCOCCN1 NLMDJJTUQPXZFG-UHFFFAOYSA-N 0.000 description 2
- DSFHXKRFDFROER-UHFFFAOYSA-N 2,5,8,11,14,17-hexaoxabicyclo[16.4.0]docosa-1(22),18,20-triene Chemical compound O1CCOCCOCCOCCOCCOC2=CC=CC=C21 DSFHXKRFDFROER-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000003776 cleavage reaction 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
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical compound C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- FXGFZZYDXMUETH-UHFFFAOYSA-L difluoroplatinum Chemical compound F[Pt]F FXGFZZYDXMUETH-UHFFFAOYSA-L 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical group OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical group NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical class [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical group [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a water electrolysis method adopting a hydrogen evolution and oxygen evolution promoter, which comprises the following steps: placing a cathode and an anode in a cathode chamber and an anode chamber containing electrolyte respectively, and separating by a diaphragm or an ion-conducting membrane; applying voltage on the cathode and the anode, electrolyzing water in the electrolyte, separating hydrogen out at the cathode, separating oxygen out at the anode, and adding a hydrogen-separating and oxygen-separating promoter into the electrolyte. The invention can effectively reduce the overpotential of HER and OER of the electrolyzed water, thereby improving the efficiency of the electrolyzed water.
Description
Technical Field
The invention belongs to the technical field of hydrogen production and oxygen production by water electrolysis, and particularly relates to a water electrolysis method adopting a hydrogen and oxygen evolution promoter.
Background
In the process of electrolyzing water, the actual electrolytic voltage is far away from the equilibrium voltage due to the influence of electrode polarization, solution resistance and wire resistance, namely, an overpotential exists. A higher overpotential means a lower efficiency. In order to improve the efficiency of water electrolysis, firstly, high-efficiency, low-cost and stable Hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER) electrocatalysts suitable for alkaline conditions are developed; second, optimizing electrolysisA trench structure to reduce internal resistance; thirdly, developing a new diaphragm material to improve OH-Mobility; furthermore, an electrolytic water accelerator is added.
Several electrolytic water promoters are known, such as vanadium salts (Long-term electrolytic hydrogen peroxide in aqueous and the effect of the calcium catalysts addition, R.M. Abouatallada et al, Electrochiam.Acta.2002, 47,2483-2494), cobalt salts (electrochemical effects of Mo-Pt interfacial metals single and with ionic reactants, D.L. basic et al, int.J. hydro.energy. 32,2314-2319), fluorides (reaction additives: platinum fluoride in aqueous solution, inorganic salts to organic reactants for the purpose of the electrolytic reaction of the calcium phosphates, chemical salts of inorganic salts, inorganic salts of inorganic salts, inorganic salts of inorganic salts, inorganic salts of inorganic salts, inorganic salts of inorganic salts, inorganic salts of inorganic salts, inorganic salts of inorganic salts, inorganic salts of inorganic salts, inorganic salts of inorganic salts, inorganic salts of inorganic salts, inorganic salts of inorganic salts, inorganic salts of inorganic salts, inorganic salts of inorganic salts, inorganic salts of inorganic salts, inorganic salts of inorganic salts, inorganic salts of inorganic salts, inorganic salts of inorganic salts, inorganic salts of inorganic salts, inorganic salts of inorganic salts, Carboxylates (Surface-adsorbed carboxylate ligands on layered double hydroxides/metal-organic framework products, C.Li et al, Angew. chem. int. Ed.2021,60, 18129-carboxylic acid reactions 18137) and the like. The deposition of vanadium and cobalt salts results in the decomposition of the electrolyzed water cathode (e.g., nickel) hydrogen compound, maintaining HER overpotential at the original level of the cathode. The addition of chloride ions to the alkaline or acidic electrolyte favors the OER of the manganese oxide electrode. In the acidic electrolyte, the phosphate increases the OER activity of the cobalt-based catalyst. The ionic liquid (comprising imidazolyl, amidosulfonic acid group, salicylic acid group ionic liquid and the like) can improve HER of the alkaline electrolyzed water. The addition of carboxylate to the alkaline electrolyte improves the OER performance of the nickel-iron based catalyst. However, each of these known electrolytic water promoters has its limitations, including single action, insufficient pronounced promoting action, high corrosivity, toxicity, and the like.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for electrolyzing water by using a hydrogen evolution and oxygen evolution promoter, so as to reduce overpotential and improve water electrolysis efficiency. In addition, the application of the hydrogen evolution and oxygen evolution promoter in the reaction of anode OER, cathode HER and total hydrolysis in alkaline (or acidic) electrolyte is provided.
The technical scheme of the invention is as follows:
a method of electrolyzing water using a hydrogen evolution and oxygen evolution promoter comprising applying a voltage across a cathode and an anode separated by an electrolyte and producing hydrogen at the cathode and oxygen at the anode, wherein: adding a hydrogen and oxygen evolution promoter into the electrolyte. The hydrogen evolution and oxygen evolution accelerant is added into the electrolyte, so that the overpotential can be effectively reduced, and the water electrolysis efficiency can be improved.
Preferably, the hydrogen evolution and oxygen evolution accelerator is at least one of 18-crown-6, 15-crown-5, benzo 18-crown-6, bicyclohexane 18-crown-6, monoaza 18-crown-6, diaza 18-crown-6, polypropylene oxide, polyethylene glycol and pluronic polyether series.
Preferably, the pluronic polyether series includes polyoxyethylene polyoxypropylene block copolymers.
Preferably, the mass concentration of the hydrogen evolution and oxygen evolution accelerant in the electrolyte is 6.0g/L to 39.6 g/L.
Preferably, the mass concentration of the hydrogen evolution and oxygen evolution accelerant in the electrolyte is 20.0 g/L-26.4 g/L.
Preferably, the electrolyte is an alkaline electrolyte or an acidic electrolyte.
Preferably, the alkaline electrolyte is potassium hydroxide or sodium hydroxide, and the acidic electrolyte is perchloric acid.
Preferably, the electrolyte further comprises an inert supporting electrolyte, which is optionally a sulfate, chloride, or the like.
The water electrolysis method of the hydrogen evolution and oxygen evolution accelerant is applied to the electrolyzed water.
The invention has the advantages and positive effects that:
the hydrogen evolution and oxygen evolution accelerator of the invention comprises a hydrocarbon chain group and an ether group which are connected with each other. The nonpolar hydrocarbon chain group enables the promoter molecules to have soft characteristics, and organic molecules can be adsorbed on the surface of the electrode; the ether group is easy to form hydrogen bond with HER and OER intermediates at the interface of the electrode and the electrolyte, accelerates the O-H cleavage and is beneficial to HER and OER. Can effectively reduce the overpotential of HER and OER of the electrolyzed water, thereby improving the efficiency of the electrolyzed water.
Drawings
Fig. 1 is a graph showing results of anode OER performance tests of example 1 and comparative example 1, in which the abscissa represents electrode potential with respect to a Reversible Hydrogen Electrode (RHE) and the ordinate represents current density.
Figure 2 is a graph of the results of the cathodic HER performance tests of example 1 and comparative example 1, wherein the abscissa represents electrode potential relative to RHE and the ordinate represents current density.
FIG. 3 is a graph of results of anode OER performance tests of example 2 and comparative example 2, wherein the abscissa represents electrode potential relative to RHE and the ordinate represents current density.
Figure 4 is a graph of the results of the cathodic HER performance tests of example 2 and comparative example 2, where the abscissa represents electrode potential relative to RHE and the ordinate represents current density.
Figure 5 is a graph of the results of the cathodic HER performance tests of example 3 and comparative example 3, where the abscissa represents electrode potential relative to RHE and the ordinate represents current density.
FIG. 6 is a graph of results of anode OER performance tests of example 4 and comparative example 4, wherein the abscissa represents electrode potential relative to RHE and the ordinate represents current density.
Figure 7 is a graph of the results of the cathodic HER performance tests of example 4 and comparative example 4, where the abscissa represents electrode potential relative to RHE and the ordinate represents current density.
FIG. 8 is a graph of results of anode OER performance tests of example 5 and comparative example 5, wherein the abscissa represents electrode potential relative to RHE and the ordinate represents current density.
Figure 9 is a graph of the results of the cathodic HER performance tests of example 5 and comparative example 5, where the abscissa represents electrode potential relative to RHE and the ordinate represents current density.
FIG. 10 is a graph of chronopotentiometric test results for example 6 and comparative example 6, wherein the abscissa represents time and the ordinate represents electrode potential relative to a Saturated Calomel Electrode (SCE).
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the accompanying drawings. Although not all embodiments shown in the drawings should be considered as limiting the scope of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The lower electrolysis efficiency in the water electrolysis process is an important problem which troubles the industry of hydrogen production and oxygen production by water electrolysis. Various attempts have been made in the industry to improve the efficiency of water electrolysis, including electrode development, cell design and membrane modification. The main approach is also focused on the choice of materials for the electrodes and the design of the electrode structure.
The invention provides a strategy for introducing a hydrogen and oxygen evolution promoter into an electrolyte, so as to reduce the overpotential of electrolyzed water and improve the efficiency of electrolyzed water.
Specifically, the invention discloses a method for electrolyzing water by using a hydrogen evolution and oxygen evolution promoter, which comprises the steps of applying voltage to a cathode and an anode which are separated by an electrolyte, obtaining hydrogen at the cathode and obtaining oxygen at the anode. The electrolyte comprises water, an alkaline electrolyte (or an acidic electrolyte) and a hydrogen evolution and oxygen evolution promoter. The method can be applied to two half reactions of cathode HER and anode OER of water electrolysis to reduce overpotential.
The hydrogen evolution and oxygen evolution accelerator of the present invention comprises a hydrocarbon chain group and an ether group which are linked to each other. The nonpolar hydrocarbon chain group enables the promoter molecules to have soft characteristics, and organic molecules can be adsorbed on the surface of the electrode; the ether group is easy to form hydrogen bond with HER and OER intermediates at the interface of an electrode and an electrolyte, accelerates O-H fracture and is beneficial to HER and OER.
The water electrolysis method adopting the hydrogen evolution and oxygen evolution promoter disclosed by the invention can effectively reduce the overpotential of HER and OER of the electrolyzed water, thereby improving the water electrolysis efficiency.
In some embodiments, the hydrogen evolution oxygen evolution electrolytic water accelerator is selected from at least one of 18-crown-6, 15-crown-5, benzo 18-crown-6, bicyclohexane-18-crown-6, monoaza 18-crown-6, diaza 18-crown-6, polyoxypropylene, polyoxyethylene, polyethylene glycol, and pluronic polyether series (including all polyoxyethylene polyoxypropylene block copolymers).
In some embodiments, the mass concentration of the hydrogen evolution and oxygen evolution water electrolysis accelerant in the electrolyte is 6.0g/L to 39.6g/L, and the preferred mass concentration is 20.0g/L to 26.4 g/L.
In some embodiments, the electrolyte further comprises an optional inert supporting electrolyte. Inert electrolytes include, but are not limited to, sulfates or chlorides.
The following is further illustrated with reference to specific examples.
Example 1
Adding 18-crown ether-6 into a potassium hydroxide aqueous solution, wherein the concentration of potassium hydroxide is 0.1mol/L, and the mass concentration of 18-crown ether-6 is 26.4 g/L.
The test is carried out in a standard three-electrode test system, a commercial Ti/RuIr electrode is used as a working electrode when an OER test is carried out, a NiMo alloy electrode is used as the working electrode when an HER test is carried out, a Pt sheet electrode is used as a counter electrode, and a Saturated Calomel Electrode (SCE) with a Rujin capillary tube is used as a reference electrode. The linear sweep voltammetry test is carried out by using a Chenghua electrochemical workstation, the test potential range is set to be 1.2V-1.7V (vs RHE) for carrying out an OER test and 0V-0.25V (vs RHE) for carrying out an HER test.
Example 2
Adding 15-crown ether-5 into the sodium hydroxide aqueous solution, wherein the concentration of the sodium hydroxide is 0.1mol/L, and the mass concentration of the 15-crown ether-5 is 22.0 g/L.
The test was performed in a standard three-electrode test system with a nickel foam electrode as the working electrode, a platinum sheet electrode as the counter electrode, and a Saturated Calomel Electrode (SCE) with a luggin capillary as the reference electrode. The linear sweep voltammetry test is carried out by using a Chenghua electrochemical workstation, the test potential range is set to be 1.2V-1.7V (vs RHE) for carrying out an OER test and 0V-0.25V (vs RHE) for carrying out an HER test.
Example 3
18-crown-6 was added to an aqueous solution of perchloric acid, wherein the concentration of perchloric acid was 0.1mol/L and the mass concentration of 18-crown-6 was 26.4 g/L.
The test was performed in a standard three-electrode test system, with a platinum sheet electrode for the working electrode, a platinum sheet electrode for the counter electrode, and a Saturated Calomel Electrode (SCE) with a luggin capillary as the reference electrode. The linear sweep voltammetry test is carried out by using a Chenghua electrochemical workstation, and the test potential is set to be 0.1V to-0.1V (vs RHE) for HER test.
Example 4
Adding 18-crown ether-6 into a potassium hydroxide aqueous solution, wherein the concentration of potassium hydroxide is 0.1mol/L, and the mass concentration of 18-crown ether-6 is 26.4 g/L.
And testing in a standard three-electrode testing system, wherein a working electrode adopts a foamed nickel electrode, a counter electrode adopts a platinum sheet electrode, and a reference electrode is a Saturated Calomel Electrode (SCE) with a Rujin capillary tube. The linear sweep voltammetry test is carried out by using a Chenghua electrochemical workstation, the test potential range is set to be 1.0V-1.7V (vs RHE) for carrying out an OER test and 0V-0.35V (vs RHE) for carrying out an HER test.
Example 5
Adding polyethylene oxide polypropylene oxide monobutyl ether into a potassium hydroxide aqueous solution, wherein the concentration of potassium hydroxide is 0.1mol/L, and the mass concentration of the polyethylene oxide polypropylene oxide monobutyl ether is 13.2 g/L.
The test is carried out in a standard three-electrode test system, a foamed nickel electrode is used as a working electrode when an OER test is carried out, a platinum sheet electrode is used as the working electrode when an HER test is carried out, a platinum sheet electrode is used as a counter electrode, and a reference electrode is a Saturated Calomel Electrode (SCE) with a luggin capillary tube. The linear sweep voltammetry test is carried out by using a Chenghua electrochemical workstation, the test potential range is set to be 1.0V-1.7V (vs RHE) for carrying out an OER test and 0V-0.3V (vs RHE) for carrying out an HER test.
Example 6
The same as example 4, except that the test system was an H-type electrolytic cell, two nickel foam electrodes were fixed in the two electrolytic cells by electrode clamps, and the middle nafion membrane was used as a separator, and one side was connected to the working electrode of the electrochemical workstation, and the other side was connected to the counter electrode and the reference electrode of the electrochemical workstation. The electrolyte is 0.1mol/L potassium hydroxide aqueous solution, and 26.4 g/L18-crown ether-6 is added as an electrolytic water accelerator. The chronopotentiometric test was performed using a Chenghua electrochemical workstation at a constant current of 0.1A.
Comparative example 1
Unlike example 1, the electrolyte was an aqueous solution of potassium hydroxide having a concentration of 0.1 mol/L.
Comparative example 2
Unlike example 2, the electrolyte was an aqueous solution of sodium hydroxide having a concentration of 0.1 mol/L.
Comparative example 3
Unlike example 3, the electrolyte was a perchloric acid aqueous solution having a concentration of 0.1 mol/L.
Comparative example 4
Unlike example 4, the electrolyte was an aqueous solution of potassium hydroxide having a concentration of 0.1 mol/L.
Comparative example 5
Unlike example 5, the electrolyte was an aqueous solution of potassium hydroxide having a concentration of 0.1 mol/L.
Comparative example 6
Unlike example 6, the electrolyte was an aqueous solution of potassium hydroxide having a concentration of 0.1 mol/L.
As can be seen from FIGS. 1 and 2, under the same overpotential, the absolute value of current density is increased and the initial overpotential is reduced under the same potentials of OER and HER of example 1 compared with comparative example 1, which shows that the addition of 18-crown-6 in alkaline electrolyte can reduce the overpotential of anode and cathode reactions and improve the efficiency of water electrolysis. This promoting effect on the electrolyzed water has general applicability to a variety of electrocatalysts, as compared with fig. 6 and 7.
As can be seen from FIGS. 3 and 4, the addition of 15-crown-5 to the alkaline electrolyte can reduce the overpotential of the anode and cathode reactions and improve the efficiency of water electrolysis.
As can be seen from FIG. 5, the addition of 18-crown-6 to the acid electrolyte can reduce the overpotential of the anode and cathode reactions and improve the efficiency of water electrolysis.
As can be seen from FIGS. 8 and 9, the addition of polyethylene oxide and polypropylene oxide monobutyl ether in the alkaline electrolyte can reduce the overpotential of the anode and cathode reactions and improve the efficiency of water electrolysis.
As can be seen from fig. 10, when the constant current I was 0.1A, the cell pressure decreased after the addition of 18-crown-6.
In conclusion, the hydrogen evolution and oxygen evolution promoter for the electrolyzed water provided by the invention can effectively reduce the overpotential of the cathode and the anode, improve the efficiency of the electrolyzed water and is verified in a plurality of tests.
Although the embodiments of the present invention and the accompanying drawings are disclosed for illustrative purposes, those skilled in the art will appreciate that: various substitutions, changes and modifications are possible without departing from the spirit and scope of the invention and appended claims, and therefore, the scope of the invention is not limited to the disclosure of the embodiments and drawings.
Claims (10)
1. A method for electrolyzing water by using a hydrogen evolution and oxygen evolution promoter comprises the following steps:
placing a cathode and an anode in a cathode chamber and an anode chamber containing electrolyte respectively, and separating by a diaphragm or an ion-conducting membrane; applying voltage on the cathode and the anode, electrolyzing water in the electrolyte, and separating out hydrogen at the cathode and oxygen at the anode, characterized in that: adding a hydrogen and oxygen evolution promoter into the electrolyte.
2. The method of electrolyzing water using a hydrogen evolution and oxygen evolution promoter as claimed in claim 1 wherein: the hydrogen evolution and oxygen evolution accelerator is at least one of 18-crown ether-6, 15-crown ether-5, benzo 18-crown ether-6, bicyclohexane-18-crown ether-6, mono aza 18-crown ether-6, diaza 18-crown ether-6, polypropylene oxide, polyethylene glycol and pluronic polyether series.
3. The method of electrolyzing water using a hydrogen evolution and oxygen evolution promoter as claimed in claim 1 wherein: the pluronic polyether series is polyoxyethylene polyoxypropylene block copolymer.
4. The method of electrolyzing water using a hydrogen evolution and oxygen evolution promoter as claimed in claim 1 wherein: the electrolyte is alkaline electrolyte or acidic electrolyte.
5. The method of electrolyzing water using a hydrogen evolution and oxygen evolution promoter as claimed in claim 4 wherein: the alkaline electrolyte is potassium hydroxide and sodium hydroxide, and the acidic electrolyte is perchloric acid.
6. The method of electrolyzing water using a hydrogen evolution and oxygen evolution promoter as claimed in claim 1 wherein: the mass concentration of the hydrogen evolution and oxygen evolution accelerant in the electrolyte is 6.0 g/L-39.6 g/L.
7. The method of electrolyzing water using a hydrogen evolution and oxygen evolution promoter as claimed in claim 1 wherein: the mass concentration of the hydrogen evolution and oxygen evolution accelerant in the electrolyte is 20.0 g/L-26.4 g/L.
8. The method of electrolyzing water using a hydrogen evolution and oxygen evolution promoter as claimed in claim 1 wherein: the electrolyte also includes an inert supporting electrolyte.
9. The method of electrolyzing water using a hydrogen evolution and oxygen evolution promoter as claimed in claim 8 wherein: the inert supporting electrolyte is sulfate and chloride.
10. Use of a method according to any one of claims 1 to 9 for the electrolysis of water.
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