CN117089884A - Lewis acid metal doped cobaltosic oxide electrode and preparation method and application thereof - Google Patents
Lewis acid metal doped cobaltosic oxide electrode and preparation method and application thereof Download PDFInfo
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- CN117089884A CN117089884A CN202311058785.3A CN202311058785A CN117089884A CN 117089884 A CN117089884 A CN 117089884A CN 202311058785 A CN202311058785 A CN 202311058785A CN 117089884 A CN117089884 A CN 117089884A
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- lewis acid
- acid metal
- electrode
- seawater
- metal doped
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- 239000002841 Lewis acid Substances 0.000 title claims abstract description 54
- 150000007517 lewis acids Chemical class 0.000 title claims abstract description 54
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 48
- 239000002184 metal Substances 0.000 title claims abstract description 48
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000013535 sea water Substances 0.000 claims abstract description 58
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 239000010936 titanium Substances 0.000 claims abstract description 14
- 238000011065 in-situ storage Methods 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 239000011733 molybdenum Substances 0.000 claims abstract description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 239000011651 chromium Substances 0.000 claims abstract description 4
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 4
- 239000010955 niobium Substances 0.000 claims abstract description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 50
- 239000001301 oxygen Substances 0.000 claims description 50
- 229910052760 oxygen Inorganic materials 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 239000001257 hydrogen Substances 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- 239000002243 precursor Substances 0.000 claims description 16
- 238000000137 annealing Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- 150000001868 cobalt Chemical class 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 6
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 15
- 239000000460 chlorine Substances 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- -1 hydroxyl anions Chemical class 0.000 abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 abstract description 4
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 230000005764 inhibitory process Effects 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 229910000314 transition metal oxide Inorganic materials 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 35
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 24
- 238000001075 voltammogram Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 5
- 238000011010 flushing procedure Methods 0.000 description 5
- 239000013505 freshwater Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000002073 nanorod Substances 0.000 description 4
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 4
- 230000036961 partial effect Effects 0.000 description 4
- 229910003450 rhodium oxide Inorganic materials 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 229910001425 magnesium ion Inorganic materials 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 description 1
- 239000002090 nanochannel Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- KUJRRRAEVBRSIW-UHFFFAOYSA-N niobium(5+) pentanitrate Chemical compound [Nb+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUJRRRAEVBRSIW-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention belongs to the technical field of nano material preparation and clean energy, and particularly relates to a Lewis acid metal doped tricobalt tetraoxide electrode, a preparation method and application thereof. The Lewis acid metal doped cobaltosic oxide electrode comprises a three-dimensional conductive substrate and a Lewis acid metal doped cobaltosic oxide array which grows on the surface of the three-dimensional conductive substrate in situ, wherein the Lewis acid metal comprises one or more of niobium, zirconium, aluminum, molybdenum, titanium and chromium. By introducing a lewis acid on the transition metal oxide cobaltosic oxide catalyst, water molecules can be dynamically electrolyzed and hydroxyl anions can be captured, and the special structure has high intrinsic catalytic activity, high exposed active sites, rapid proton and gas mass transfer rate and inhibition of adsorption of chloride ions on the surface. The electrode provided by the invention is directly used for seawater electrolysis in natural seawater, has high current density and stability, and avoids the occurrence of chlorine evolution side reaction.
Description
Technical Field
The invention belongs to the technical field of nano material preparation and clean energy, and particularly relates to a Lewis acid metal doped tricobalt tetraoxide electrode, a preparation method and application thereof.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
Hydrogen (H) 2 ) As a sustainable and safe energy source, it has 142.351MJ kg -1 And does not discharge any pollution. Is important to solve the current urgent environmental crisis and insufficient supply of fossil energy. Electrolytic water hydrogen production must include an anodic half reaction, typically an Oxygen Evolution Reaction (OER), in addition to a cathodic hydrogen evolution half reaction (HER). However, the development of highly active and stable OER catalytic electrodes is critical for the electrolysis of aqueous hydrogen because of its slow, multi-step proton-coupled electron transfer process, which greatly impedes the overall efficiency of the electrolysis of aqueous hydrogen.
Another significant problem with hydrogen production from electrolyzed water is the lack of natural fresh water resources, and the use of fresh water as an electrolyte for the electrolysis of aqueous hydrogen will place a heavy pressure on the important water resources. The ocean occupies 96.5% of water reserves of the earth, provides infinite hydrogen resources without seriously affecting global fresh water resources, and is a promising electrolyte for preparing hydrogen by electrolyzing water in the future. However, the activity and stability of the OER electrocatalyst for producing hydrogen by seawater electrolysis are not ideal due to the interference of various metal ions in the seawater, and the industrial requirement cannot be met all the time. However, direct electrolysis of natural seawater is still in the onset stage due to the complexity of the natural seawater components. For this purpose, a seawater reverse osmosis system and a conventional electrolyte are coupled together, and the desalination treatment is carried out to obtain fresh water and then electrolyze the fresh water. Alternatively, the seawater is purified by acidification or alkalization and then electrolyzed. However, these require complicated pretreatment steps and are costlyAnd measuring manpower and material resources. Thus, direct seawater electrolysis without purification processes and chemical additives is very attractive and researchers have been devoted to this direction of research for up to 40 years, but the key challenges of this technology remain in terms of catalyst design and plant construction. Electrocatalytic materials are low in catalytic efficiency and poor in stability under near neutral (pH 8.0) conditions, and more importantly, a great deal of harmful chloride ions and cations including magnesium ions, calcium ions and the like exist in natural seawater. In particular, the chloride anions (Cl) present in natural seawater - 0.5M) will lead to chlorine evolution side reactions (ClER) at the anode, competing with OER. While OER has thermodynamic advantages, its complex four electron transfer reaction is more retarded than the ClER reaction kinetics of only two electrons. In this case, detrimental oxidation/corrosion of chlorine may result, further reducing the overall electrolysis efficiency and severely eroding the catalyst. In addition, chloride corrosion and poisoning by insoluble precipitates or microorganisms can also impair the stability and service life of the electrode material, which places higher demands on the structural stability and corrosion resistance of the electrode material. Thus, to meet the subsequent industrial seawater electrolysis applications, a current density (50-150 mAcm) was developed that could be driven at low potential (below 700 mV) in direct seawater -2 ) OER electrocatalysts that maintain good stability are very necessary and challenging.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a Lewis acid metal doped tricobalt tetraoxide electrode, a preparation method and application thereof. The invention electrolyzes water molecules by introducing a Lewis acid layer on the surface of the electrode catalyst and captures a large amount of hydroxyl anions (OH-) generated in situ around the catalyst, and the existence of the local alkalinity generated in situ leads OH to be - Is concentrated on the surface of the catalyst, thereby effectively inhibiting the chloric reaction on the surface of the catalyst to resist Cl - Enters the surface of the catalyst, and obviously reduces the ion pair OH of magnesium ions and calcium ions in the seawater electrolyte - Is a capture of (a). The Lewis acid layer effectively captures a large number of hydroxyl anions (OH) generated in situ around the catalyst - ) So that the local alkalinity is effectively resistedErosion of chloride ions with a substantial enrichment of OH on the catalyst surface - Effectively promotes OER.
In order to achieve the above object, the present invention is realized by the following technical scheme:
in a first aspect, the invention provides a lewis acid metal doped cobaltosic oxide electrode comprising a three-dimensional conductive substrate and a lewis acid metal doped cobaltosic oxide array grown in situ on the surface of the three-dimensional conductive substrate, wherein the lewis acid metal comprises one or more of niobium, zirconium, aluminum, molybdenum, titanium and chromium.
In a second aspect, the invention provides a method for preparing the Lewis acid metal doped cobaltosic oxide electrode according to the first aspect, which comprises the following steps:
s1, dissolving cobalt salt, lewis acid metal salt and urea in deionized water to form a reaction solution;
s2, placing the three-dimensional conductive substrate in a reaction solution for hydrothermal reaction to obtain a Lewis acid metal doped cobalt hydroxide precursor;
and S3, annealing the Lewis acid metal doped cobalt hydroxide precursor, and washing and drying after annealing to obtain the Lewis acid metal doped cobaltosic oxide electrode.
In a third aspect, the invention provides the use of a lewis acid metal doped tricobalt tetraoxide electrode according to the first aspect in electrocatalytic oxygen evolution and/or electrocatalytic total water splitting and/or electrocatalytic seawater splitting hydrogen production.
In a fourth aspect, the invention provides a method for producing hydrogen by electrolysis of seawater, wherein the Lewis acid metal doped tricobalt tetraoxide electrode as described in the first aspect is used as an anode for electrolysis of seawater.
In a fifth aspect, the present invention provides an electrocatalytic natural seawater electrolysis hydrogen generating apparatus, the anode of which is a lewis acid metal doped tricobalt tetraoxide electrode as described in the first aspect.
The beneficial effects obtained by one or more of the technical schemes of the invention are as follows:
(1) The preparation method provided by the invention is carried out at a lower temperature, and is easy to operate and prepare in batches; the method is suitable for different substrates, is a universal method for synthesizing the oxide material array, and is suitable for large-scale industrial production.
(2) The electrode material is provided with a hierarchical pore nano channel, so that the transfer and transportation of substances can be rapidly promoted; and meanwhile, the nano-array grown in situ is beneficial to the stability of the material catalysis process and the rapid transmission of electrons. The surface of the catalyst is introduced with a Lewis acid layer to electrolyze water molecules and capture a large amount of hydroxyl anions (OH-) generated in situ around the catalyst. The existence of the in-situ generated local alkalinity, the preferential enrichment of OH < - > on the catalyst surface effectively inhibits the chlorine chemical reaction on the catalyst surface so as to 'resist' Cl < - > from entering the catalyst surface, remarkably reduces the capture of magnesium ions and calcium ions cations in the seawater electrolyte on the OH < - >, and shows excellent stability in natural seawater.
(3) The local alkalinity generated in situ of the electrode prepared by the invention obviously improves OER activity and effectively solves the problem of low OER activity of natural seawater.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 shows an aluminum-doped tricobalt tetraoxide electrode (Al-Co) prepared in example 1 of the present invention 3 O 4 TM) is applied to the electrolytic schematic diagram of natural seawater;
FIG. 2 is a schematic diagram of an aluminum-doped tricobalt tetraoxide electrode (Al-Co) prepared in example 1 of the present invention 3 O 4 A field emission scanning electron microscope image of (TM), b is a partial enlarged image of a;
FIG. 3 is a niobium-doped tricobalt tetraoxide electrode (Nb-Co) prepared in example 2 of the present invention 3 O 4 A field emission scanning electron microscope image of (TM), b is a partial enlarged image of a;
FIG. 4 is a schematic diagram of a molybdenum-doped tricobalt tetraoxide electrode (Mo-Co) prepared in example 3 of the invention 3 O 4 Field emission scanning of/TM)An electron microscope image, b is a partial enlarged image of a;
FIG. 5 is a zirconium-doped tricobalt tetraoxide electrode (Zr-Co) prepared in example 4 of the present invention 3 O 4 A field emission scanning electron microscope image of (TM), b is a partial enlarged image of a;
FIG. 6 shows an aluminum-doped tricobalt tetraoxide electrode (Al-Co) prepared in example 1 of the present invention 3 O 4 X-ray diffraction pattern of/TM), and tricobalt tetraoxide electrode (Co) prepared in comparative example 1 3 O 4 TM), tricobalt tetraoxide (Co 3 O 4 ) Is compared with the standard card JCPDS No.05-6123 of titanium (Ti) and the standard card JCPDS No. 07-6265;
FIG. 7 shows a niobium-doped tricobalt tetraoxide electrode (Nb-Co) prepared in example 2 of the present invention 3 O 4 X-ray diffraction pattern of/TM), and tricobalt tetraoxide electrode (Co) prepared in comparative example 1 3 O 4 TM), tricobalt tetraoxide (Co 3 O 4 ) Is compared with the standard card JCPDS No.05-6123 of titanium (Ti) and the standard card JCPDS No. 07-6265;
FIG. 8 is a molybdenum-doped tricobalt tetraoxide electrode (Mo-Co) prepared in example 3 of the invention 3 O 4 X-ray diffraction pattern of/TM), and tricobalt tetraoxide electrode (Co) prepared in comparative example 1 3 O 4 TM), tricobalt tetraoxide (Co 3 O 4 ) Is compared with the standard card JCPDS No.05-6123 of titanium (Ti) and the standard card JCPDS No. 07-6265;
FIG. 9 is a zirconium-doped tricobalt tetraoxide electrode (Zr-Co) prepared in example 4 of the present invention 3 O 4 X-ray diffraction pattern of/TM), and tricobalt tetraoxide electrode (Co) prepared in comparative example 1 3 O 4 TM), tricobalt tetraoxide (Co 3 O 4 ) Is compared with the standard card JCPDS No.05-6123 of titanium (Ti) and the standard card JCPDS No. 07-6265;
FIG. 10 is a schematic diagram of an aluminum-doped tricobalt tetraoxide electrode (Al-Co) prepared in example 1 of the present invention 3 O 4 (TM) electrochemical performance of anodic oxygen evolution, compared with the tricobalt tetraoxide electrode (Co) prepared in comparative example 1 3 O 4 TM) commercial rhodium oxide supported titanium mesh (RuO) 2 TM), wherein (a) is in 1M PBS electrolyteLinear sweep voltammogram for oxygen evolution reactions; (b) Tafel curves for oxygen evolution reactions in 1M PBS electrolyte; (c) A linear sweep voltammogram for an oxygen evolution reaction in a natural seawater electrolyte; (d) Tafel curves for oxygen evolution reactions in natural seawater electrolytes; rhe represents the current density as compared to a standard hydrogen electrode, j represents;
FIG. 11 is a drawing showing a niobium-doped tricobalt tetraoxide electrode (Nb-Co) prepared in example 2 of the present invention 3 O 4 (TM) electrochemical performance of anodic oxygen evolution, compared with the tricobalt tetraoxide electrode (Co) prepared in comparative example 1 3 O 4 TM) commercial rhodium oxide supported titanium mesh (RuO) 2 (TM) comparison, wherein (a) is a linear sweep voltammogram of oxygen evolution reaction in 1M PBS electrolyte; (b) Tafel curves for oxygen evolution reactions in 1M PBS electrolyte; (c) A linear sweep voltammogram for an oxygen evolution reaction in a natural seawater electrolyte; (d) Tafel curves for oxygen evolution reactions in natural seawater electrolytes; rhe represents the current density as compared to a standard hydrogen electrode, j represents;
FIG. 12A molybdenum-doped tricobalt tetraoxide electrode (Mo-Co) prepared in example 3 of the invention 3 O 4 (TM) electrochemical performance of anodic oxygen evolution, compared with the tricobalt tetraoxide electrode (Co) prepared in comparative example 1 3 O 4 TM) commercial rhodium oxide supported titanium mesh (RuO) 2 (TM) comparison, wherein (a) is a linear sweep voltammogram of oxygen evolution reaction in 1M PBS electrolyte; (b) Tafel curves for oxygen evolution reactions in 1M PBS electrolyte; (c) A linear sweep voltammogram for an oxygen evolution reaction in a natural seawater electrolyte; (d) Tafel curves for oxygen evolution reactions in natural seawater electrolytes; rhe represents the current density as compared to a standard hydrogen electrode, j represents;
FIG. 13A zirconium-doped tricobalt tetraoxide electrode (Zr-Co) prepared in example 4 of the present invention 3 O 4 (TM) electrochemical performance of anodic oxygen evolution, compared with the tricobalt tetraoxide electrode (Co) prepared in comparative example 1 3 O 4 TM) commercial rhodium oxide supported titanium mesh (RuO) 2 (TM) comparison, wherein (a) is a linear sweep voltammogram of oxygen evolution reaction in 1M PBS electrolyte; (b) To reverse oxygen evolution in 1M PBS electrolyteA corresponding Tafel curve; (c) A linear sweep voltammogram for an oxygen evolution reaction in a natural seawater electrolyte; (d) Tafel curves for oxygen evolution reactions in natural seawater electrolytes; rhe represents the current density as compared to a standard hydrogen electrode, j represents;
FIG. 14 shows an aluminum-doped tricobalt tetraoxide electrode (Al-Co) prepared in example 1 of the present invention 3 O 4 TM) and tricobalt tetraoxide electrode (Co) prepared in comparative example 1 3 O 4 TM) stability profile of oxygen evolution reaction current density in natural seawater electrolyte over time.
Detailed Description
In a first exemplary embodiment of the present invention, a lewis acid metal doped tricobalt tetraoxide electrode comprises a three-dimensional conductive substrate and a lewis acid metal doped tricobalt tetraoxide array grown in situ on the surface of the three-dimensional conductive substrate, wherein the lewis acid metal comprises one or more of niobium, zirconium, aluminum, molybdenum, titanium, and chromium.
In one or more embodiments of this embodiment, the three-dimensional conductive substrate comprises one of carbon paper, carbon cloth, graphite felt, titanium sheet, titanium mesh.
In a second exemplary embodiment of the present invention, a method for preparing a lewis acid metal doped tricobalt tetraoxide electrode according to the first exemplary embodiment, comprises the following steps:
s1, dissolving cobalt salt, lewis acid metal salt and urea in deionized water to form a reaction solution;
s2, placing the three-dimensional conductive substrate in a reaction solution for hydrothermal reaction to obtain a Lewis acid metal doped cobalt hydroxide precursor;
and S3, annealing the Lewis acid metal doped cobalt hydroxide precursor, and washing and drying after annealing to obtain the Lewis acid metal doped cobaltosic oxide electrode.
In one or more examples of this embodiment, the cobalt salt and the lewis acid metal salt are soluble salts, the molar ratio of lewis acid metal salt to cobalt salt is 1:5-100, the total molar concentration of lewis acid metal salt to cobalt salt is 40-200mM, and the ratio of the total molar number of lewis acid metal salt and cobalt salt to urea molar number is 1:1-10.
In one or more embodiments of this embodiment, in step S2, the hydrothermal reaction is performed at a temperature of 100 to 200 ℃ for a time of 2 to 72 hours.
In one or more embodiments of this embodiment, in step S3, the annealing temperature is 350-550 ℃, the heating rate is 2-10 ℃/min, and the incubation time is 1-6h.
In one or more embodiments of this embodiment, in step S3, the drying temperature is 50-70 ℃ for 8-16 hours.
The third exemplary embodiment of the invention is the use of the lewis acid metal doped tricobalt tetraoxide electrode according to the first exemplary embodiment in electrocatalytic oxygen evolution and/or electrocatalytic total water decomposition and/or electrocatalytic seawater decomposition hydrogen production.
In a fourth exemplary embodiment of the invention, a method for producing hydrogen by electrolysis of seawater comprises using the lewis acid metal doped tricobalt tetraoxide electrode as described in the first exemplary embodiment as an anode to electrolyze seawater.
In a fifth exemplary embodiment of the present invention, an electrocatalytic natural seawater electrolysis hydrogen generating apparatus, the anode of which is a lewis acid metal doped tricobalt tetraoxide electrode as described in the first exemplary embodiment.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail below with reference to specific examples and comparative examples.
Comparative example 1
1.44mmol of cobalt nitrate and 7.5mmol of urea are weighed and added into 35mL of deionized water, and the mixture is stirred uniformly to form a reaction solution;
will be 3 x 3cm 2 The titanium mesh is placed in a reaction solution and reacts for 6 hours in a closed container at 120 ℃ to obtain a precursor;
annealing the precursor at 400 ℃ for 2 hours at a heating rate of 5 ℃/min, flushing with deionized water, and drying at 60 ℃ for 12 hours to obtain the cobaltosic oxide electrode (Co) 3 O 4 /TM)。
Comparative example 2
1.44mmol commercial RuO 2 Dissolving in Nafion/ethanol/water mixed solution to form ink, and dripping into 3 x 3cm 2 Is dried to obtain RuO 2 TM electrode.
Example 1
1.2mmol of cobalt nitrate, 0.24mmol of aluminum nitrate and 7.5mmol of urea are weighed and added into 35mL of deionized water, and the mixture is stirred uniformly to form a reaction solution;
will be 3 x 3cm 2 The titanium mesh is placed in a reaction solution and reacts for 6 hours in a closed container at 120 ℃ to obtain a precursor;
annealing the precursor at a heating rate of 5 ℃/min at 400 ℃ for 2 hours, flushing with deionized water, and drying at 60 ℃ for 12 hours to obtain the aluminum-doped cobaltosic oxide electrode (Al-Co) 3 O 4 /TM)。
The obtained Al-Co 3 O 4 The field emission scanning electron microscope of/TM is shown in FIG. 2, which shows that the electrode has the shape of an ordered nano rod array structure. The X-ray diffraction diagram is shown in figure 6, has good crystallinity, and is proved to be single Co by comparison with PDF card 3 O 4 And (3) phase (C).
Al-Co 3 O 4 The schematic of the application of/TM to natural seawater electrolysis is shown in FIG. 1. The linear sweep voltammogram of oxygen evolution in 1MPBS electrolyte is shown as a in FIG. 10, al-Co 3 O 4 TM at 10 and 100mA cm -2 Is 491.43mV and 624.12mV, respectively. Al-Co 3 O 4 The Tafel curve of the oxygen evolution of TM in 1M PBS electrolyte is shown in FIG. 10 b, al-Co 3 O 4 Tafel slope of/TM is only 100.86mV dec -1 Below commercial RuO 2 (126.95mV dec -1 )。Al-Co 3 O 4 Linear sweep voltammograms of oxygen evolution of TM in Natural seawater are shown in FIG. 10 c, at 10 and 100mA cm -2 Is 536.15mV and 635.sup.82 mV, respectively. Al-Co 3 O 4 The Tafel curve of the oxygen evolution of TM in the natural seawater electrolyte is shown as d in FIG. 10, al-Co 3 O 4 Tafel slope of/TM is only 100.41mV dec -1 Below commercial RuO 2 (102.23mV dec -1 ) Indicating Al-Co 3 O 4 Has excellent oxygen evolution kinetics.
Further, the Al-Co is comprehensively compared 3 O 4 Oxygen evolution performance of TM in 1M PBS, natural seawater. As shown in a and c of FIG. 10, al-Co 3 O 4 The performance in natural seawater is better than 1MPBS. However, the difference between the two is not large, indicating that Al-Co 3 O 4 TM is resistant to interference such as Cl-. And Tafel slope 100.86mV dec in 1M PBS and natural seawater, respectively - And 100.41mV dec -1 With less kinetic differences. As shown in FIG. 14, al-Co 3 O 4 There was no significant decrease in current density after 30h of operation of/TM in natural seawater, indicating Al-Co 3 O 4 Has excellent stability of oxygen evolution by seawater electrolysis.
Example 2
1.2mmol of cobalt nitrate, 0.24mmol of niobium nitrate and 7.5mmol of urea are weighed and added into 35mL of deionized water, and the mixture is stirred uniformly to form a reaction solution;
will be 3 x 3cm 2 The titanium mesh is placed in a reaction solution and reacts for 6 hours in a closed container at 120 ℃ to obtain a precursor;
annealing the precursor at a heating rate of 5 ℃/min at 400 ℃ for 2 hours, flushing with deionized water, and drying at 60 ℃ for 12 hours to obtain the niobium-doped cobaltosic oxide electrode (Nb-Co) 3 O 4 /TM)。
The obtained Nb-Co 3 O 4 The field emission scanning electron microscope of/TM is shown in FIG. 3, which shows that the appearance of the catalytic electrode is an ordered nano rod array structure. The X-ray diffraction pattern is shown in figure 7, has good crystallinity, and compared with PDF card, it proves that its single Co 3 O 4 And (3) phase (C).
Nb-Co 3 O 4 Linear sweep voltammograms of oxygen evolution of TM in 1M PBS electrolyte are shown in FIG. 11 as a, at 10 and 100mA cm -2 Is 460.15mV and 590.01mV, respectively. Tafel curves for oxygen evolution in 1M PBS electrolyte are shown in FIG. 11 b, nb-Co 3 O 4 Tafel slope of/TM is only 116.99mV dec -1 Far below commercial RuO 2 (128.46mV dec -1 )。Nb-Co 3 O 4 Linear sweep voltammogram of oxygen evolution of TM in Natural seawater electrolyte as shown in FIG. 11 c at 10 and 100mA cm -2 Is 571.03mV and 693.12mV, respectively. Tafel curves of oxygen evolution in Natural electrolytes are shown as d in FIG. 11, nb-Co 3 O 4 Tafel slope of/TM is only 117.11mV dec -1 Far below commercial RuO 2 (141.83mV dec -1 ) Indicating Nb-Co 3 O 4 Has excellent oxygen evolution kinetics.
Further, the Nb-Co is comprehensively compared 3 O 4 Oxygen evolution performance of TM in 1M PBS, natural seawater. As shown in a and c of FIG. 11, nb-Co 3 O 4 The performance of/TM in natural seawater is better than 1M PBS. However, the difference between the two is not large overall, indicating that Nb-Co 3 O 4 TM is resistant to Cl - And the like. And Tafel slope was 116.99mV dec in 1M PBS and natural seawater, respectively -1 And 117.11mV dec -1 With less kinetic differences.
Example 3
1.2mmol of cobalt nitrate, 0.24mmol of molybdenum nitrate and 7.5mmol of urea are weighed and added into 35mL of deionized water, and the mixture is stirred uniformly to form a reaction solution;
will be 3 x 3cm 2 The titanium mesh is placed in a reaction solution and reacts for 6 hours in a closed container at 120 ℃ to obtain a precursor;
annealing the precursor at a heating rate of 5 ℃/min at 400 ℃ for 2 hours, flushing with deionized water, and drying at 60 ℃ for 12 hours to obtain the molybdenum doped cobaltosic oxide electrode (Mo-Co) 3 O 4 /TM)。
The obtained Mo-Co 3 O 4 The field emission scanning electron microscope of/TM is shown as 4, which shows that the appearance of the catalytic electrode is an ordered nano rod array structure. The X-ray diffraction diagram is shown in figure 8, has good crystallinity, and compared with PDF card, it proves that its single Co 3 O 4 And (3) phase (C).
The linear sweep voltammogram of oxygen evolution in 1M PBS electrolyte is shown as a in FIG. 12, mo-Co 3 O 4 TM at 10 and 100mA cm -2 Is 416.19mV and 520.05mV, respectively. At 1MTafel curve of oxygen precipitation in PBS electrolyte is shown as b in FIG. 12, mo-Co 3 O 4 Tafel slope of/TM is only 80.85mV dec -1 Far below commercial RuO 2 (100.86mV dec -1 )。Mo-Co 3 O 4 Linear sweep voltammogram of oxygen evolution of TM in Natural electrolyte As shown in FIG. 12 c, mo-Co 3 O 4 TM at 10 and 100mA cm -2 Is 539.15mV and 616.61mV, respectively. Tafel curves of oxygen evolution in Natural electrolytes as shown in d in 12, mo-Co 3 O 4 Tafel slope of/TM is only 72.01mV dec -1 Far below commercial RuO 2 (98.83mV dec -1 ) Indicating Mo-Co 3 O 4 Has excellent oxygen evolution kinetics.
Further, comprehensively compare Mo-Co 3 O 4 Oxygen evolution performance of TM in 1M PBS, natural seawater. As shown in a and c of FIG. 12, mo-Co 3 O 4 The performance of/TM in natural seawater is better than 1M PBS. However, the three are not very different in general, indicating Mo-Co 3 O 4 TM is resistant to Cl - And the like. And Tafel slope of 80.85mV dec in 1M PBS and natural seawater, respectively -1 And 72.01mV dec -1 With less kinetic differences.
Example 4
1.2mmol of cobalt nitrate, 0.24mmol of zirconium nitrate and 7.5mmol of urea are weighed and added into 35mL of deionized water, and the mixture is stirred uniformly to form a reaction solution;
will be 3 x 3cm 2 The titanium mesh is placed in a reaction solution and reacts for 6 hours in a closed container at 120 ℃ to obtain a precursor;
annealing the precursor at a heating rate of 5 ℃/min at 400 ℃ for 2 hours, flushing with deionized water, and drying at 60 ℃ for 12 hours to obtain a zirconium-doped cobaltosic oxide electrode (Zr-Co) 3 O 4 /TM)。
The Zr-Co obtained 3 O 4 The field emission scanning electron microscope of/TM is shown in FIG. 5, which shows that the appearance of the catalytic electrode is an ordered nano rod array structure. The X-ray diffraction pattern is shown in figure 9, has good crystallinity, and compared with PDF card, it proves that its single Co 3 O 4 And (3) phase (C).
The linear sweep voltammogram of oxygen evolution in 1M PBS electrolyte is shown as a in FIG. 13, zr-Co 3 O 4 TM at 10 and 100mA cm -2 Is 430.20mV and 570.14mV, respectively. Tafel curves for oxygen evolution in 1M PBS electrolyte are shown in FIG. 13 b, zr-Co 3 O 4 Tafel slope of/TM is only 112.59mV dec -1 Far below commercial RuO 2 (128.46mV dec -1 )。Zr-Co 3 O 4 Linear sweep voltammogram of oxygen evolution of TM in Natural electrolyte As shown in FIG. 13 c, at 10 and 100mA cm -2 Is 564.03mV and 709.21mV, respectively. Tafel curves of oxygen precipitation in Natural electrolyte are shown as d in FIG. 13, zr-Co 3 O 4 Tafel slope of/TM is only 139.32mV dec -1 Below commercial RuO 2 (141.83mV dec -1 ) Indicating Zr-Co 3 O 4 Has excellent oxygen evolution kinetics.
Further, the Zr-Co was comprehensively compared 3 O 4 Oxygen evolution performance of TM in 1M PBS, natural seawater. As shown in a and c of FIG. 13, zr-Co 3 O 4 The performance of/TM in natural seawater is better than 1M PBS. However, the three are not greatly different in general, indicating Zr-Co 3 O 4 TM is resistant to Cl - And the like. And Tafel slope was 112.59mV dec in 1M PBS and natural seawater, respectively -1 And 139.32mV dec -1 With less kinetic differences.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The Lewis acid metal doped cobaltosic oxide electrode is characterized by comprising a three-dimensional conductive substrate and a Lewis acid metal doped cobaltosic oxide array which grows on the surface of the three-dimensional conductive substrate in situ, wherein the Lewis acid metal comprises one or more of niobium, zirconium, aluminum, molybdenum, titanium and chromium.
2. The lewis acid metal-doped tricobalt tetraoxide electrode of claim 1, wherein said three-dimensional conductive substrate comprises one of carbon paper, carbon cloth, graphite felt, titanium sheet, titanium mesh.
3. A method for preparing a lewis acid metal doped tricobalt tetraoxide electrode as claimed in claim 1 or 2, comprising the steps of:
s1, dissolving cobalt salt, lewis acid metal salt and urea in deionized water to form a reaction solution;
s2, placing the three-dimensional conductive substrate in a reaction solution for hydrothermal reaction to obtain a Lewis acid metal doped cobalt hydroxide precursor;
and S3, annealing the Lewis acid metal doped cobalt hydroxide precursor, and washing and drying after annealing to obtain the Lewis acid metal doped cobaltosic oxide electrode.
4. The method of claim 3, wherein the cobalt salt and the lewis acid metal salt are soluble salts, the molar ratio of lewis acid metal salt to cobalt salt is 1:5-100, the total molar concentration of lewis acid metal salt to cobalt salt is 40-200mM, and the ratio of the total molar number of lewis acid metal salt and cobalt salt to urea molar number is 1:1-10.
5. The method according to claim 3, wherein in the step S2, the hydrothermal reaction is carried out at a temperature of 100 to 200℃for a time of 2 to 72 hours.
6. The method according to claim 3, wherein in the step S3, the annealing temperature is 350-550 ℃, the heating rate is 2-10 ℃/min, and the heat preservation time is 1-6h.
7. The method of claim 3, wherein in step S3, the drying is performed at a temperature of 50 to 70℃for a period of 8 to 16 hours.
8. Use of a lewis acid metal doped tricobalt tetraoxide electrode according to claim 1 or 2 for electrocatalytic oxygen evolution and/or electrocatalytic total water decomposition and/or electrocatalytic seawater decomposition for hydrogen production.
9. A method for producing hydrogen by electrolysis of seawater, characterized in that the lewis acid metal-doped tricobalt tetraoxide electrode as claimed in claim 1 or 2 is used as anode for electrolysis of seawater.
10. An electrocatalytic natural seawater electrolysis hydrogen production device, characterized in that the anode of the electrocatalytic natural seawater electrolysis hydrogen production device is the lewis acid metal doped tricobalt tetraoxide electrode as claimed in claim 1 or 2.
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