CN112928271A - In-situ delamination method of hydrotalcite nanosheet array for electrocatalytic small molecule oxidation coupling hydrogen production - Google Patents
In-situ delamination method of hydrotalcite nanosheet array for electrocatalytic small molecule oxidation coupling hydrogen production Download PDFInfo
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- CN112928271A CN112928271A CN202110099787.1A CN202110099787A CN112928271A CN 112928271 A CN112928271 A CN 112928271A CN 202110099787 A CN202110099787 A CN 202110099787A CN 112928271 A CN112928271 A CN 112928271A
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- nanosheet array
- electrocatalytic
- hydrogen production
- hydrotalcite
- small molecule
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 93
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 title claims abstract description 64
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 64
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 33
- 230000003647 oxidation Effects 0.000 title claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 230000032798 delamination Effects 0.000 title claims abstract description 26
- 239000001257 hydrogen Substances 0.000 title claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 26
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 26
- 150000003384 small molecules Chemical class 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 230000008878 coupling Effects 0.000 title abstract description 6
- 238000010168 coupling process Methods 0.000 title abstract description 6
- 238000005859 coupling reaction Methods 0.000 title abstract description 6
- 238000003491 array Methods 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 15
- 239000004202 carbamide Substances 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 14
- 239000004917 carbon fiber Substances 0.000 claims description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 11
- 239000004744 fabric Substances 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- 239000006260 foam Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 4
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 3
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 3
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229910015221 MoCl5 Inorganic materials 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 3
- 238000005137 deposition process Methods 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 229910001510 metal chloride Inorganic materials 0.000 claims description 3
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 claims description 3
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 3
- 229910013553 LiNO Inorganic materials 0.000 claims description 2
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000004146 energy storage Methods 0.000 abstract 1
- 238000007429 general method Methods 0.000 abstract 1
- 239000000454 talc Substances 0.000 abstract 1
- 229910052623 talc Inorganic materials 0.000 abstract 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 10
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 10
- BLJNPOIVYYWHMA-UHFFFAOYSA-N alumane;cobalt Chemical compound [AlH3].[Co] BLJNPOIVYYWHMA-UHFFFAOYSA-N 0.000 description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 4
- 239000010411 electrocatalyst Substances 0.000 description 4
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- 238000004832 voltammetry Methods 0.000 description 3
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Inorganic materials [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
本发明公开了一种用于电催化小分子氧化耦合制氢的水滑石纳米片阵列的原位剥层方法，所述方法包括：(Ⅰ)水滑石纳米片阵列的水热生长；(Ⅱ)滑石纳米片阵列的电化学原位剥层等步骤。本发明提供了一种采用简单快速的水滑石纳米片阵列电化学原位剥层的较为普适的方法，采用本发明方法制备的超薄水滑石纳米片阵列可用于电催化小分子氧化耦合制氢等多种清洁能源储存与转化领域；合成步骤快速温和，剥层方法条件温和，操作简便，剥层后的超薄LDHs纳米片活性高，稳定性好。
The invention discloses an in-situ stripping method of a hydrotalcite nanosheet array used for electrocatalytic small molecule oxidation coupled with hydrogen production. The method comprises: (I) hydrothermal growth of the hydrotalcite nanosheet array; (II) Electrochemical in-situ delamination of talc nanosheet arrays and other steps. The invention provides a relatively general method for electrochemical in-situ stripping of a simple and fast hydrotalcite nanosheet array, and the ultrathin hydrotalcite nanosheet array prepared by the method of the invention can be used for electrocatalytic small molecule oxidation coupling preparation Hydrogen and other clean energy storage and conversion fields; the synthesis steps are fast and mild, the stripping method is mild, the operation is simple, and the ultrathin LDHs nanosheets after stripping have high activity and good stability.
Description
Technical Field
The invention belongs to the field of inorganic nano material synthesis, and particularly relates to an in-situ delamination method of a hydrotalcite nanosheet array for hydrogen production through electrocatalysis small-molecule oxidation coupling.
Background
The consumption of fossil fuel and the pollution problem caused by the fossil fuel are serious problems facing all people, and the search for renewable green clean energy is one of the important directions of current scientific research. Hydrogen as a clean energy has the advantages of high heat value, no greenhouse gas emission during combustion and the like, and the hydrogen production method with great potential is realized by electrically catalyzing and decomposing water. How to design a low-cost high-activity electrocatalyst is the key. In addition, the overpotential required for the oxygen evolution reaction (one of the half reactions for electrocatalytic decomposition of water) is large, the generated oxygen is not very valuable, and there is a risk of explosion when mixed with the generated hydrogen. Therefore, the development of thermodynamically more powerful small molecule oxidation reaction to replace the oxygen evolution reaction for coupled hydrogen production has received more and more attention. The small-molecule oxidation reaction can accelerate the hydrogen production efficiency and prepare chemicals with high added values. However, the products of small molecule oxidation are more and the competition of oxygen evolution reaction leads to a decrease in its efficiency. Therefore, the small-molecule electrocatalyst with low development cost, good selectivity and high efficiency is a hot spot of current scientific research.
Layered double hydroxides (LDHs, also known as hydrotalcite) are a typical host-guest layered material, and are widely researched in the field of electrocatalysts due to the characteristics of adjustable structure and performance. However, its large thickness and size become one of the factors limiting its activity. Therefore, how to prepare the LDHs with the ultrathin structure is the key for improving the catalytic performance of the LDHs. The traditional method for preparing the ultrathin LDHs is mainly a layer stripping method, namely, a large block of synthesized LDHs is stripped, so that an ultrathin structure is obtained. The liquid phase stripping method needs to add an organic solvent, and LDHs stripped are easy to re-stack; the gas phase stripping method has high requirements on equipment, and simultaneously, the stripping efficiency is low. Therefore, how to realize the high-efficiency delamination of the LDHs and obtain the ultrathin LDHs electrocatalyst with high activity and good stability still remains a problem.
Disclosure of Invention
The invention is provided for overcoming the defects in the prior art, and aims to provide an in-situ delamination method of a hydrotalcite nanosheet array for electrocatalysis small-molecule oxidation coupling hydrogen production.
The invention is realized by the following technical scheme:
an in-situ delamination method of a hydrotalcite nanosheet array for electrocatalytic small-molecule oxidation coupled hydrogen production comprises the following steps:
hydrothermal growth of hydrotalcite nanosheet arrays
Preparing a mixed solution of metal salt and urea with a certain concentration and ultrasonically dispersing;
(ii) putting the cleaned conductive substrate into a hydrothermal kettle containing the mixed solution in the step (i) for hydrothermal growth, and after the growth is finished, washing and drying the obtained nanosheet array;
(II) electrochemical in-situ delamination of hydrotalcite nanosheet array
Using the nanosheet array obtained in the step (I) as a battery anode, and using a metal lithium sheet as a battery cathode to assemble a battery;
(ii) subjecting the assembled battery to deposition of metallic lithium in a battery test system;
(iii) after the deposition process is finished, disassembling the battery, taking out the deposited positive electrode nanosheet array, placing the positive electrode nanosheet array into a solvent for standing and stripping, and cleaning and drying the nanosheet array after stripping to obtain the stripped ultrathin hydrotalcite nanosheet array.
In the technical scheme, the metal salt is metal nitrate or metal chloride; the mixed solution of the metal salt and the urea adopts deionized water as a solvent.
In the above technical scheme, the metal salt is Fe (NO)3)3、FeCl2、FeCl3、FeSO4、Fe2(SO4)3、Co(NO3)2、CoCl2、CoSO4、Ni(NO3)2、NiCl2、NiSO4、Cu(NO3)2、CuCl2、CuSO4、Zn(NO3)2、V(NO3)4、TiCl4、VCl4、MoCl5、H8MoN2O4Any one or more of them.
In the technical scheme, the concentration of the metal salt is 0.1 mM-5 mM; the concentration of the urea is 0.5 mM-25 mM.
In the above technical scheme, the conductive substrate is any one of carbon fiber cloth, carbon fiber paper, copper foam, copper mesh, nickel foam, nickel sheet, titanium sheet or FTO.
In the above technical solution, the method for cleaning the conductive substrate specifically comprises: and sequentially performing ultrasonic treatment on the conductive substrate for 15min by using dilute hydrochloric acid, acetone, absolute ethyl alcohol and deionized water respectively.
In the technical scheme, the temperature of the hydrothermal growth is 90-120 ℃, and the growth time is determined according to the type of the metal salt; the temperature of the drying was 60 ℃.
In the technical scheme, the electrolyte of the battery is LiNO-containing electrolyte3An ether electrolyte added; the diameter of the nanosheet array serving as the battery anode is 10-16 mm.
In the technical scheme, the discharge current is 0.1 mA-1 mA during the deposition of the metal lithium, the discharge time is 2 h-24 h, and the deposition time is determined according to the anode material.
In the technical scheme, the standing time for standing and stripping is 2-12 h; the solvent for standing and stripping is any one or more of water, methanol or ethanol.
The invention has the beneficial effects that:
according to the invention, in-situ delamination of the LDHs nanosheets is realized by using a simple and rapid electrochemical method, no organic delamination solvent is required to be added in the delamination process, the delamination efficiency is high, and the delaminated ultrathin structure can be kept stable on a substrate; the invention not only creates a brand-new LDHs stripping method, but also the nanosheet prepared by the method has excellent performance and application prospect, and is expected to be applied to various fields such as electro-catalytic Oxygen Evolution Reaction (OER), electro-catalytic Hydrogen Evolution Reaction (HER), electro-catalytic biomass oxidation, lithium battery anode materials, fuel cells and the like.
Drawings
FIG. 1 is a scanning electron micrograph of an ultrathin cobalt aluminum hydrotalcite nanosheet array prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope photograph of an ultra-thin nickel aluminum hydrotalcite nanosheet array prepared in example 2 of the present invention;
FIG. 3 is a scanning electron microscope photograph of a nickel iron ultrathin hydrotalcite nanosheet array prepared in example 3 of the present invention;
FIG. 4 is a characterization of 5-hydroxymethylfurfural oxidation performance of cobalt-aluminum ultrathin hydrotalcite nanosheet arrays prepared in example 1 of the present invention;
FIG. 5 is a characteristic of benzyl alcohol oxidation performance of nickel aluminum ultrathin hydrotalcite nanosheet array prepared in example 2 of the present invention;
fig. 6 is an aniline oxidation performance characterization of the nickel iron ultrathin hydrotalcite nanosheet array prepared in example 3 of the present invention.
Detailed Description
In order to make the technical scheme of the present invention better understood by those skilled in the art, the technical scheme of the in-situ delamination method of a hydrotalcite nanosheet array for hydrogen production through electrocatalytic small molecule oxidation coupling according to the present invention is further described below by referring to the drawings of the specification and through specific embodiments.
An in-situ delamination method of a hydrotalcite nanosheet array for electrocatalytic small-molecule oxidation coupled hydrogen production comprises the following steps:
hydrothermal growth of hydrotalcite nanosheet arrays
Dissolving metal salt and urea by deionized water and ultrasonically dispersing to obtain a mixed solution of the metal salt and the urea;
the metal salt is metal nitrate or metal chloride, and is Fe (NO)3)3、FeCl2、FeCl3、FeSO4、Fe2(SO4)3、Co(NO3)2、CoCl2、CoSO4、Ni(NO3)2、NiCl2、NiSO4、Cu(NO3)2、CuCl2、CuSO4、Zn(NO3)2、V(NO3)4、TiCl4、VCl4、MoCl5Or H8MoN2O4Any one or more of;
the concentration of the metal salt is 0.1 mM-5 mM; the concentration of the urea is 0.5 mM-25 mM; the volume of the deionized water is 25 mL-100 mL;
(ii) putting the cleaned conductive substrate into a hydrothermal kettle containing the mixed solution in the step (i) for hydrothermal growth, and after the growth is finished, washing and drying the obtained nanosheet array;
cleaning a conductive substrate, then placing the conductive substrate into a polytetrafluoroethylene hydrothermal kettle, adding the dispersed mixed solution obtained in the step (i), and carrying out reaction growth at the temperature of 90-120 ℃, wherein the growth time and temperature are properly adjusted according to the type of the selected salt; after the growth is finished, washing the obtained nanosheet array, and drying the nanosheet array in a 60 ℃ drying oven;
the conductive substrate is any one of carbon fiber cloth, carbon fiber paper, copper foam, copper mesh, nickel foam, nickel sheet, titanium sheet or FTO;
the cleaning method of the conductive substrate specifically comprises the following steps: sequentially performing ultrasonic treatment on the conductive substrate for about 15min by using dilute hydrochloric acid, acetone, absolute ethyl alcohol and deionized water respectively to remove impurities on the surface;
(II) electrochemical in-situ delamination of hydrotalcite nanosheet array
Cutting the hydrotalcite nanosheet array obtained in the step (I) into a proper size (the diameter is 10-16mm), using the hydrotalcite nanosheet array as a battery anode, and using a metal lithium sheet as a cathode to assemble the battery, wherein the electrolyte contains LiNO3And an ether electrolyte is added.
(ii) subjecting the assembled cell to deposition of metallic lithium in a battery test system: the discharge current is: 0.1-1mA, the discharge time is 2-24 h, and the specific deposition time is properly adjusted according to different anode materials;
(iii) after the deposition process is finished, disassembling the battery, taking out the deposited positive electrode nanosheet array, and then putting the positive electrode nanosheet array into a solvent for standing and stripping, wherein the standing time is 2-12 h. And (3) after stripping, cleaning the nanosheet array and drying the nanosheet array in an oven to obtain the ultrathin LDHs nanosheet array after stripping.
The stripping solvent is any one of deionized water, methanol or ethanol.
Example 1
The method for synthesizing the cobalt-aluminum ultrathin hydrotalcite nanosheet array comprises the following specific steps of:
growing a cobalt-aluminum hydrotalcite nanosheet array on the surface of a foamed nickel substrate by using a hydrothermal method;
mixing Co (NO)3)2、Al(NO3)3Dissolving urea with deionized water, and performing ultrasonic dispersion to obtain a mixed solution of the urea and the deionized water;
sequentially performing ultrasonic treatment on the foamed nickel substrate for about 15min by using dilute hydrochloric acid, acetone, absolute ethyl alcohol and deionized water respectively to remove impurities on the surface;
cleaning a foamed nickel substrate, putting the cleaned foamed nickel substrate into a polytetrafluoroethylene hydrothermal kettle, adding the dispersed mixed solution, and carrying out reaction growth for 6 hours at 90 ℃; after the growth is finished, washing the obtained nanosheet array, and drying the nanosheet array in a 60 ℃ drying oven;
(ii) taking the cobalt-aluminum hydrotalcite nanosheet array obtained in the previous step as a positive electrode to carry out lithium battery assembly and discharge for 12 hours;
and (iii) after the discharging is finished, disassembling the battery, removing the positive electrode, placing the positive electrode into an absolute ethyl alcohol solution, standing for 6 hours, and drying to obtain the cobalt-aluminum ultrathin hydrotalcite nanosheet array.
Fig. 1 is a scanning electron microscope photograph of the cobalt-aluminum ultrathin hydrotalcite nanosheet array obtained by preparation.
Fig. 4 shows that the prepared cobalt-aluminum ultrathin hydrotalcite nanosheet has a linear voltammetry scanning curve for electrocatalysis of 5-hydroxymethylfurfural oxidation in an alkaline solution (1 mol/l of potassium hydroxide solution), and shows a larger current in an electrolyte containing 10 mmol/l of 5-hydroxymethylfurfural, which indicates that the prepared cobalt-aluminum ultrathin hydrotalcite nanosheet has good electrocatalytic oxidation performance of 5-hydroxymethylfurfural.
Example 2
The method for synthesizing the nickel-aluminum ultrathin hydrotalcite nanosheet array comprises the following specific steps of:
growing a nickel-aluminum hydrotalcite nanosheet array on the surface of the carbon fiber cloth substrate by using a hydrothermal method;
mixing Ni (NO)3)2、Al(NO3)3Dissolving urea with deionized water, and performing ultrasonic dispersion to obtain a mixed solution of the urea and the deionized water;
sequentially performing ultrasonic treatment on the carbon fiber cloth substrate for about 15min by using dilute hydrochloric acid, acetone, absolute ethyl alcohol and deionized water respectively to remove impurities on the surface;
cleaning a carbon fiber cloth substrate, putting the cleaned carbon fiber cloth substrate into a polytetrafluoroethylene hydrothermal kettle, adding the dispersed mixed solution, and carrying out reaction growth for 8 hours at 110 ℃; after the growth is finished, washing the obtained nanosheet array, and drying the nanosheet array in a 60 ℃ drying oven;
(ii) taking the nickel-aluminum hydrotalcite nanosheet array obtained in the previous step as a positive electrode to carry out lithium battery assembly and discharge for 18 hours;
and (iii) after the discharging is finished, disassembling the battery, removing the positive electrode, placing the battery into an absolute ethyl alcohol solution, standing for 10 hours, and drying to obtain the nickel-aluminum ultrathin hydrotalcite nanosheet array.
Fig. 2 is a scanning electron microscope photograph of the prepared nickel-aluminum ultrathin hydrotalcite nanosheet array.
Fig. 5 shows a linear voltammetry scanning curve of the prepared nickel-aluminum ultrathin hydrotalcite nanosheet in an alkaline solution (1 mol/l of potassium hydroxide solution) for electrocatalytic oxidation of benzaldehyde, and the nickel-aluminum ultrathin hydrotalcite nanosheet shows a larger current in an electrolyte containing 10 mmol/l of benzaldehyde, which indicates that the prepared nickel-aluminum ultrathin hydrotalcite nanosheet has good electrocatalytic oxidation performance of benzaldehyde.
Example 3
The method for synthesizing the nickel iron ultrathin hydrotalcite nanosheet array comprises the following specific steps:
growing a nickel iron hydrotalcite nanosheet array on the surface of the carbon fiber cloth substrate by using a hydrothermal method;
mixing Ni (NO)3)2、Fe(NO3)3Dissolving urea with deionized water, and performing ultrasonic dispersion to obtain a mixed solution of the urea and the deionized water;
sequentially performing ultrasonic treatment on the carbon fiber cloth substrate for about 15min by using dilute hydrochloric acid, acetone, absolute ethyl alcohol and deionized water respectively to remove impurities on the surface;
cleaning a carbon fiber cloth substrate, putting the cleaned carbon fiber cloth substrate into a polytetrafluoroethylene hydrothermal kettle, adding the dispersed mixed solution, and carrying out reaction growth for 12 hours at 120 ℃; after the growth is finished, washing the obtained nanosheet array, and drying the nanosheet array in a 60 ℃ drying oven;
(ii) taking the nickel-iron hydrotalcite nanosheet array obtained in the last step as a positive electrode to carry out lithium battery assembly and discharge for 12 hours;
and (iii) after the discharging is finished, disassembling the battery, removing the positive electrode, placing the battery into an anhydrous methanol solution, standing for 12 hours, and drying to obtain the nickel iron ultrathin hydrotalcite nanosheet array.
Fig. 2 is a scanning electron microscope photograph of the prepared nickel iron ultrathin hydrotalcite nanosheet array.
Fig. 5 shows a linear voltammetry scan curve of the prepared nickel-iron ultrathin hydrotalcite nanosheet in an alkaline solution (1 mol/l potassium hydroxide solution) for electrocatalytic aniline oxidation, and the nickel-iron ultrathin hydrotalcite nanosheet shows a larger current in an electrolyte containing 10 mmol/l aniline, which indicates that the prepared nickel-iron ultrathin hydrotalcite nanosheet has good aniline electrocatalytic oxidation performance.
The invention provides a preparation method of an ultrathin hydrotalcite nanosheet array for small-molecule oxidation coupled hydrogen production, which is realized by an in-situ stripping strategy, and the ultrathin hydrotalcite nanosheet array with the thickness of below 5nm is obtained by in-situ stripping of the hydrotalcite nanosheets on a conductive substrate.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. An in-situ delamination method of a hydrotalcite nanosheet array for electrocatalytic small-molecule oxidation coupled hydrogen production is characterized by comprising the following steps of: the method comprises the following steps:
hydrothermal growth of hydrotalcite nanosheet arrays
Preparing a mixed solution of metal salt and urea with a certain concentration and ultrasonically dispersing;
(ii) putting the cleaned conductive substrate into a hydrothermal kettle containing the mixed solution in the step (i) for hydrothermal growth, and after the growth is finished, washing and drying the obtained nanosheet array;
(II) electrochemical in-situ delamination of hydrotalcite nanosheet array
Using the nanosheet array obtained in the step (I) as a battery anode, and using a metal lithium sheet as a battery cathode to assemble a battery;
(ii) subjecting the assembled battery to deposition of metallic lithium in a battery test system;
(iii) after the deposition process is finished, disassembling the battery, taking out the deposited positive electrode nanosheet array, placing the positive electrode nanosheet array into a solvent for standing and stripping, and cleaning and drying the nanosheet array after stripping to obtain the stripped ultrathin hydrotalcite nanosheet array.
2. The in-situ delamination method of the hydrotalcite nanosheet array for electrocatalytic small molecule oxidation-coupled hydrogen production according to claim 1, wherein: the metal salt is metal nitrate or metal chloride; the mixed solution of the metal salt and the urea adopts deionized water as a solvent.
3. The in-situ delamination method of the hydrotalcite nanosheet array for electrocatalytic small molecule oxidation-coupled hydrogen production according to claim 2, wherein: the metal salt is Fe (NO)3)3、FeCl2、FeCl3、FeSO4、Fe2(SO4)3、Co(NO3)2、CoCl2、CoSO4、Ni(NO3)2、NiCl2、NiSO4、Cu(NO3)2、CuCl2、CuSO4、Zn(NO3)2、V(NO3)4、TiCl4、VCl4、MoCl5、H8MoN2O4Any one or more of them.
4. The in-situ delamination method of the hydrotalcite nanosheet array for electrocatalytic small molecule oxidation-coupled hydrogen production according to claim 1, wherein: the concentration of the metal salt is 0.1 mM-5 mM; the concentration of the urea is 0.5 mM-25 mM.
5. The in-situ delamination method of the hydrotalcite nanosheet array for electrocatalytic small molecule oxidation-coupled hydrogen production according to claim 1, wherein: the conductive substrate is any one of carbon fiber cloth, carbon fiber paper, copper foam, copper mesh, nickel foam, nickel sheet, titanium sheet or FTO.
6. The in-situ delamination method of the hydrotalcite nanosheet array for electrocatalytic small molecule oxidation-coupled hydrogen production according to claim 1, wherein: the cleaning method of the conductive substrate specifically comprises the following steps: and sequentially performing ultrasonic treatment on the conductive substrate for 15min by using dilute hydrochloric acid, acetone, absolute ethyl alcohol and deionized water respectively.
7. The in-situ delamination method of the hydrotalcite nanosheet array for electrocatalytic small molecule oxidation-coupled hydrogen production according to claim 1, wherein: the temperature of the hydrothermal growth is 90-120 ℃, and the growth time is determined according to the type of the metal salt; the temperature of the drying was 60 ℃.
8. The in-situ delamination method of the hydrotalcite nanosheet array for electrocatalytic small molecule oxidation-coupled hydrogen production according to claim 1, wherein: the electrolyte of the battery is LiNO-containing electrolyte3An ether electrolyte added; the diameter of the nanosheet array serving as the battery anode is 10-16 mm.
9. The in-situ delamination method of the hydrotalcite nanosheet array for electrocatalytic small molecule oxidation-coupled hydrogen production according to claim 1, wherein: the discharge current is 0.1 mA-1 mA during the deposition of the metal lithium, the discharge time is 2 h-24 h, and the deposition time is determined according to the anode material.
10. The in-situ delamination method of the hydrotalcite nanosheet array for electrocatalytic small molecule oxidation-coupled hydrogen production according to claim 1, wherein: the standing time for the standing stripping is 2-12 h; the solvent for standing and stripping is any one or more of water, methanol or ethanol.
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