CN117904672A - Cerium-vanadium bimetal hollow nano-pillar array type electrocatalytic material and preparation method and application thereof - Google Patents
Cerium-vanadium bimetal hollow nano-pillar array type electrocatalytic material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 46
- 239000002061 nanopillar Substances 0.000 title claims abstract description 45
- SKAXWKNRKROCKK-UHFFFAOYSA-N [V].[Ce] Chemical compound [V].[Ce] SKAXWKNRKROCKK-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 51
- 239000000758 substrate Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000005530 etching Methods 0.000 claims abstract description 20
- 150000000703 Cerium Chemical class 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000003446 ligand Substances 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- 239000013130 vanadium-based metal-organic framework Substances 0.000 claims abstract description 3
- 239000002131 composite material Substances 0.000 claims abstract 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052720 vanadium Inorganic materials 0.000 claims description 9
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 9
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 6
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 6
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 4
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 3
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 claims description 3
- -1 cerium ions Chemical class 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims 1
- 239000011261 inert gas Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 230000009977 dual effect Effects 0.000 abstract description 4
- 238000010000 carbonizing Methods 0.000 abstract description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 22
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical group [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000010411 electrocatalyst Substances 0.000 description 11
- 238000001878 scanning electron micrograph Methods 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 229910021607 Silver chloride Inorganic materials 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000000840 electrochemical analysis Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
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- 235000019441 ethanol Nutrition 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
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- 238000011161 development Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
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- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910000863 Ferronickel Inorganic materials 0.000 description 2
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- 238000001816 cooling Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 239000013246 bimetallic metal–organic framework Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000000970 chrono-amperometry 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
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- 239000012921 cobalt-based metal-organic framework Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
Classifications
-
- 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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- Catalysts (AREA)
Abstract
The invention provides a cerium-vanadium bimetallic hollow nano-pillar array type electrocatalytic material, a preparation method and application thereof, comprising a substrate and a compound loaded on the substrate; the composite forms a hollow nano-pillar array structure on a substrate, and the composite comprises CeO 2、V8C7 and V 2O5. Obtaining a V-MOF nano-pillar array of the vanadium-based metal organic framework on a substrate by an in-situ growth method; then, based on the principle that the coordination and binding energy of cerium and a ligand is lower and the formed structure is more stable, cerium salt is utilized for etching to construct a cerium-vanadium MOF hollow nano-column array; finally carbonizing at high temperature in argon atmosphere to obtain the cerium-vanadium double-metal hollow nano-column array type electrocatalytic material. The cerium-vanadium bimetal hollow nano-pillar array type electrocatalytic material has the dual functions of catalyzing oxygen evolution reaction and hydrogen evolution reaction, and has high catalytic activity and good stability.
Description
Technical Field
The invention belongs to the technical field of hydrogen production by water electrolysis, and particularly relates to a cerium-vanadium bimetallic hollow nano-pillar array type electrocatalytic material and a preparation method and application thereof.
Background
Development of sustainable green energy is an important approach to alleviating increasingly serious global energy and environmental crisis. Hydrogen energy, which has the characteristics of high energy density and zero carbon emission, is considered to be one of the most promising alternative energy sources for traditional fossil fuels. Electrochemical decomposition of water is attractive for large-scale hydrogen production due to its reliability and sustainability compared to other technologies. Unfortunately, the large-scale commercial application of electrochemically decomposing water is limited by aspects such as the much greater overpotential required to drive the overall electrolyzed water than theoretical (1.23V), poor stability of electrode materials, etc., and the need to develop highly efficient and durable electrocatalysts to reduce the overpotential of the anodic Oxygen Evolution Reaction (OER) and the cathodic Hydrogen Evolution Reaction (HER) and to increase the electrolyzed water efficiency. Ruthenium/iridium-based and platinum-based noble metal materials have heretofore been recognized as excellent OER and HER catalysts, respectively. However, the scarcity and poor stability of these materials severely hamper their commercial use. Therefore, the design and preparation of the non-noble metal electrocatalyst for accelerating the hydrolysis have important practical significance.
For many years, efforts have been made to develop transition metal compounds based on cobalt, nickel and iron-based materials as water electrolysis replacement catalysts. For example, transition metal-based oxides, hydroxides, phosphates and hydroxides exhibit excellent OER activity, whereas transition metal-based phosphides, selenides, sulfides and nitrides exhibit higher catalytic activity in HER. However, the catalytic performance and stability of the electrolyzed water of the materials can not meet the actual requirements, and development and exploration are required to be continued.
On the other hand, existing electrolyzed water catalysts are mainly powders, which require the application of a polymeric binder to coat the conductive substrate in electrochemical tests. This form can have some negative effects on the electrocatalytic reaction: the catalyst loading is reduced, resulting in limited active sites; the interface resistance between the catalyst layer and the conductive substrate is large, so that the electron transfer efficiency is affected; the adhesion between the catalyst layer and the substrate is weak, and the catalyst layer is easy to fall off in the electrochemical process. In contrast, the introduction of a catalytically active component onto a porous electrically conductive substrate, represented by Nickel Foam (NF) and carbon cloth, to construct a self-supporting electrocatalyst avoids the above-described problems. Another advantage of the self-supported electrocatalyst is that by controlling the morphology and microstructure of the porous substrate surface catalyst layer, the catalytic activity and stability thereof can be further improved. For example, the present subject group previously prepared two-dimensional ferronickel Metal Organic Frameworks (MOFs) nanoplatelets on carbon cloth by an in-situ hydrothermal method, and then constructed ferronickel phosphorous nanoplatelets self-supported electrocatalyst using a vapor deposition method, which exhibits excellent OER performance [Chai R Q,Zhou T Q,Sun D L,et al.Bimetallic-MOF derived nickel-iron phosphide nanosheets on carbon cloth for efficacious oxygen evolution reaction.International Journal of Hydrogen Energy,2022,47,36129-36138]. in alkaline solution, and in addition, the ideal electrocatalyst should have dual functions of catalyzing HER and OER in the same electrolyte solution, thereby improving the overall efficiency of electrolyzed water. Notably, existing electrolyzed water catalysts (including self-supporting electrocatalysts) are OER or HER mono-functional catalysts, with few OER and HER bi-functional electrocatalysts reported, which are mainly due to the large differences in OER and HER reaction mechanisms and processes. Based on the above discussion, the development of a bifunctional, self-supporting, non-noble metal catalyst with catalytic OER and HER is a critical issue that needs to be addressed by a vast number of scientific researchers.
Disclosure of Invention
In view of the above, the invention aims to solve the bottleneck problem in the related art at least to a certain extent, and provides a cerium-vanadium bimetal hollow nano-pillar array type electrocatalytic material, a preparation method and application thereof, so as to prepare the electrolyzed water catalytic material with high catalytic activity and good stability, and the catalytic material has the dual functions of catalyzing OER and HER.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
The cerium-vanadium bimetallic hollow nano-pillar array type electrocatalytic material comprises a substrate and a compound loaded on the substrate, wherein the compound forms a hollow nano-pillar array structure on the substrate, and the compound comprises cerium oxide (CeO 2), octavanadium heptacarbide (V 8C7) and vanadium pentoxide (V 2O5).
In some embodiments, the molar ratio of CeO 2、V8C7 to V 2O5 is (3-15): (10-40): (30-70), preferably (5-10): (20-30): (40-60).
In some embodiments, the substrate is nickel foam NF.
In some embodiments, the total loading of CeO 2、V8C7 and V 2O5 on the substrate is 1 to 5mg cm -2, preferably 2 to 3mg cm -2.
A preparation method of a cerium-vanadium bimetallic hollow nano-pillar array type electrocatalytic material comprises the following steps:
(1) Placing the substrate foam nickel NF in vanadium-based synthetic solution for in-situ growth, and reacting for 45-75 hours at 150-170 ℃ to form a vanadium-based metal organic framework V-MOF nano-column array on the substrate;
(2) Placing the substrate loaded with the V-MOF nano-pillar array in a cerium salt aqueous solution, standing for reaction for 6-18 h, and etching to obtain a CeV-MOF hollow nano-pillar array supported by the substrate;
(3) Placing the substrate loaded with the CeV-MOF hollow nano-pillar array in a muffle furnace, and roasting for 2-5 hours at 550-650 ℃ in an argon atmosphere to obtain a cerium-vanadium bimetallic hollow nano-pillar array electrocatalytic material;
The vanadium-based synthetic solution comprises vanadyl sulfate, a ligand and deionized water;
the ligand is terephthalic acid or amino terephthalic acid;
The cerium salt is any one of ammonium cerium nitrate, cerium chloride and cerium sulfate.
In some embodiments, the molar ratio of vanadyl sulfate, ligand, and deionized water is 1:1 (3500-4500).
In some embodiments, the concentration of cerium ions in the aqueous solution of cerium salt is greater than 0.3mol L -1 and less than 0.7mol L -1, preferably 0.5 to 0.6mol L -1.
In some embodiments, the cerium salt is ceric ammonium nitrate.
In some embodiments, the substrate has a size of (0.5-10) ×0.5-10 cm and a thickness of 0.1-10 mm.
In some embodiments, the roasting process of step (3) is temperature programmed, and the temperature rising rate is 2 ℃ min -1.
The cerium-vanadium bimetal hollow nano-pillar array type electrocatalytic material has double functions of catalyzing OER and HER, and can be used as an OER and HER catalyst when water is electrolyzed under alkaline conditions.
The raw materials to which the invention relates are all commercially available and the equipment used is well known to those skilled in the art.
The vanadium-based synthetic solution adopts reactants of vanadyl sulfate, ligand (terephthalic acid or amino terephthalic acid) and deionized water, and a V-MOF nano-column array is obtained on a substrate NF by an in-situ growth method; then, based on the principle that the coordination binding energy of cerium and a ligand is lower and the formed structure is more stable, a CeV-MOF hollow nano-column array is constructed on a substrate by etching cerium salt; finally, carbonizing at high temperature in argon atmosphere to obtain the cerium-vanadium bimetallic hollow nano-pillar array type electrocatalytic material. The characteristics of the electrocatalytic material enable the electrocatalytic material to have dual functions of catalyzing OER and HER.
Compared with the prior art, the cerium-vanadium bimetal hollow nano-pillar array type electrocatalytic material and the preparation method and application thereof have the following advantages:
(1) The cerium-vanadium bimetallic hollow nano-pillar array type electrocatalytic material prepared by the invention has a three-dimensional porous substrate with good conductivity, and can ensure high-efficiency transmission of electrons and substances; the hollow nano-column array structure can ensure the full exposure of the active site and the release and transportation of the gas product; the bimetal synergistic effect and etching bring a large number of oxygen vacancies, which can promote the improvement of the catalytic activity. Thus, it can significantly improve the efficiency and stability of electrolyzed water as OER and HER electrocatalysts.
(2) The cerium-vanadium bimetallic hollow nano-pillar array type electrocatalytic material prepared by the invention can obviously reduce the overpotential of electrocatalytic decomposition water when being used as an OER and HER bifunctional catalyst, and has good stability.
(3) The preparation method is simple and feasible; the price of the used materials is low; the solvent is deionized water, so that the use of an organic solvent is reduced, and the method is environment-friendly and suitable for industrial production.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of V-MOF/NF obtained in example 1 of the present invention;
FIG. 2 is an SEM image of CeV-MOF/NF of example 1 of the present invention;
FIG. 3 is an SEM image of CeV-HNA/NF obtained in example 1 of the present invention;
FIG. 4 is an X-ray diffraction (XRD) pattern of CeV-HNA/NF obtained in example 1 of the present invention;
FIG. 5 is a graph showing the OER polarization curves of CeV-HNA/NF, ceV-MOF/NF, V-NA/NF, ceO 2/NF and IrO 2 obtained in example 1 of the present invention;
FIG. 6 is a graph showing the HER polarization curves of CeV-HNA/NF, and CeV-MOF/NF, V-NA/NF, ceO 2/NF, and PtC obtained in example 1 of the present invention;
FIG. 7 is a HER i-t graph of CeV-HNA/NF obtained in example 1 of the present invention;
FIG. 8 is a graph of the full water splitting voltammogram of CeV-HNA/NF and Pt/C IrO 2 prepared in example 1 of the present invention;
FIG. 9 is a graph of the total water dissolution i-t of CeV-HNA/NF prepared in example 1 of the present invention;
FIG. 10 is an SEM image of CeV-MOF/NF obtained in comparative example 1;
FIG. 11 is an SEM image of CeV-MOF/NF obtained in comparative example 2;
FIG. 12 is a graph showing the OER polarization of the CeV-HNA/NF obtained in example 1 of the present invention and the CeNiFe/NF, ceCo/NF and VCo/NF catalysts obtained in comparative examples 3 to 5;
FIG. 13 is a graph showing the HER polarization curves of the CeV-HNA/NF obtained in example 1 of the present invention and the CeNiFe/NF, ceCo/NF and VCo/NF catalysts obtained in comparative examples 3 to 5.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention pertains. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to the following examples and drawings.
Example 1
A preparation method of cerium-vanadium double-metal hollow nano-pillar array type electrocatalytic material. The cerium-vanadium bimetallic hollow nano-pillar array type electrocatalytic material prepared in example 1 is referred to as CeV-HNA/NF.
1. Preparation of materials:
The method comprises the following steps:
(1) 0.122g of vanadyl sulfate (0.75 mmol) and 0.125g of terephthalic acid (0.75 mmol) are dissolved in 54mL (3 mol) of deionized water (the molar ratio of the three is 1:1:4000), and ultrasonic treatment is carried out for 30min at normal temperature, thus obtaining a light green transparent vanadium-based synthetic liquid.
Transferring the vanadium-based synthetic solution into a stainless steel water thermal reaction kettle with a polytetrafluoroethylene lining, vertically immersing a substrate NF (thickness is 0.5mm, size is 1 x2 cm) into the vanadium-based synthetic solution, heating at 160 ℃ for 48h, and naturally cooling to room temperature. After the materials are taken out, deionized water and absolute ethyl alcohol are used for washing for a plurality of times, specifically: after soaking in deionized water in a beaker for 12 hours, replacing new deionized water, continuously soaking for 12 hours, and repeating the above operation twice again, wherein the purpose is to wash out unreacted substances; then, the mixture is soaked in ethanol for 12 hours, then new ethanol is replaced for further soaking for 12 hours, and the operation is repeated twice, so that deionized water in the previous step is removed. And finally, drying at 60 ℃ for 12 hours to obtain the V-MOF nano-pillar array supported by the substrate NF, namely V-MOF/NF.
(2) 4.122G of ceric ammonium nitrate is dissolved in 15mL of deionized water (molar concentration is 0.5mol L -1), then V-MOF/NF is vertically immersed in the ceric ammonium nitrate solution, and the mixture is stood for reaction for 12 hours; after cleaning with deionized water, drying for 12 hours at 60 ℃, and forming a CeV-MOF hollow nano-pillar array, namely CeV-MOF/NF, on the substrate NF.
(3) Finally, the CeV-MOF/NF is put into a ceramic boat, put into a muffle furnace, then purged for 1h by argon to remove air, and heated to 600 ℃ at a heating rate of 2 ℃ min -1 and kept for 2h, thus obtaining the cerium-vanadium bimetallic hollow nano-column array type electrocatalytic material, namely the CeV-HNA/NF.
2. CeV-HNA/NF as OER and HER bifunctional catalyst:
The electrocatalytic performance test was carried out at a CHI760E electrochemical workstation, the electrolyte was 1mol L -1 potassium hydroxide solution, and the effective electrode area was 1cm 2. The OER and HER tests employ a three electrode system with reference, counter and working electrodes of Ag/AgCl, carbon rod and CeV-HNA/NF, respectively. The scanning rate of the linear sweep voltammetry was 10mV s -1. The electrode potential was converted to a reversible hydrogen electrode potential (RHE) according to the following formula:
ERHE＝E(Ag/AgCl)+0.0591*pH+0.197V
E (Ag/AgCl) is the voltage actually measured by using the Ag/AgCl electrode as a reference electrode, 0.197V is the standard potential of the used Ag/AgCl reference electrode, and the pH value of the electrolyte is the pH value of the electrolyte.
Commercial IrO 2 and PtC were used as control samples in OER and HER tests, respectively, and CeV-MOF/NF, V-NA/NF and CeO 2/NF were used simultaneously for comparison.
The preparation method of V-NA/NF comprises the following steps:
First, V-MOF/NF:
the preparation process is the same as in the step (1) of example 1;
Then, V-NA/NF was prepared:
the preparation process is the same as in step (3) of example 1, namely, the V-MOF/NF is put into a ceramic boat, put into a muffle furnace, then purged with argon for 1h to remove air, and heated to 600 ℃ at a heating rate of -1 min at 2 ℃ and kept for 2h to obtain the V-NA/NF.
The preparation method of CeO 2/NF comprises the following steps:
4.112g of ceric ammonium nitrate is dissolved in 15mL of deionized water (molar concentration is 0.5mol L -1), then a substrate NF (thickness is 0.5mm, size is 1 x 2 cm) is vertically immersed in the ceric ammonium nitrate solution, and the substrate NF is left stand for 12h; after cleaning with deionized water, the mixture was dried in a drying oven at 60℃for 12 hours.
Then, the obtained sample was subjected to high temperature calcination in the same manner as in step (3) of example 1, i.e., the sample was put into a ceramic boat, put into a muffle furnace, then purged with argon for 1h to remove air, and heated to 600℃at a heating rate of 2℃min -1 and kept for 2h to obtain CeO 2/NF.
The full water-splitting performance investigation adopts a double-electrode system, and CeV-HNA/NF is used as an anode and a cathode at the same time. And using commercial PtC and IrO 2 as anode and cathode cells as a control, testing was performed at 10mV s -1 and using chronoamperometry to investigate the full water stability of the catalyst.
FIG. 1 is an SEM image of V-MOF/NF produced in example 1. It can be seen that MOF grains with cubic columns are deposited on NF, covering the substrate NF.
FIG. 2 is an SEM image of CeV-MOF/NF of the sample of example 1. It can be seen that the CeV-MOF nanopillar array has become hollow after etching treatment with cerium salt solution.
FIG. 3 is an SEM image of CeV-HNA/NF obtained in example 1. It can be seen that the morphology of the CeV-HNA/NF obtained after roasting is similar to that of the CeV-MOF/NF, but the wall thickness of the hollow nano-column of the CeV-HNA/NF can be reduced.
FIG. 4 is an XRD pattern of CeV-HNA/NF obtained in example 1. From the figure, it can be seen that there are distinct peaks characteristic of CeO 2、V8C7 and V 2O5, which indicate that the material prepared is a complex of CeO 2、V8C7 and V 2O5.
FIG. 5 shows OER test results of CeV-HNA/NF, ceV-MOF/NF, V-NA/NF and CeO 2/NF、IrO2 obtained in example 1. As can be seen from FIG. 5, the overpotential of CeV-HNA/NF was smaller (220 mV) at 50mA cm -2 compared to CeV-MOF/NF, V-NA/NF, ceO 2/NF and the commercial IrO 2 catalyst, indicating that the OER performance of CeV-HNA/NF was optimal.
FIG. 6 shows the HER test results of CeV-HNA/NF, ceV-MOF/NF, V-NA/NF, ceO 2/NF and PtC obtained in example 1. As can be seen from FIG. 6, the overpotential of CeV-HNA/NF at 50mA cm -2 was smaller (125 mV) compared to CeV-MOF/NF, V-NA/NF, ceO 2/NF and commercial Pt/C catalysts, indicating that the HER performance of CeV-HNA/NF was optimal.
FIG. 7 is a graph showing i-t at a high current density of 100mA cm -2 for CeV-HNA/NF obtained in example 1. As can be seen from fig. 7, the CeV-HNA/NF can maintain the current density stable for 300 hours, exhibiting excellent stability.
FIGS. 8 and 9 are graphs showing the overall water splitting performance of CeV-HNA/NF obtained in example 1 as both anode and cathode of the water splitting cell. As can be seen from FIG. 8, ceV-HNA/NF was able to drive electrolyzed water to 10mA cm -2 at 1.52V, which is superior to the commercial Pt/C IrO 2 performance; as can be seen from FIG. 9, the CeV-HNA/NF can maintain the stability of the electrolyzed water for 150 hours at a high current density of 100mA cm -2, and has potential in practical application.
The CeV-HNA/NF obtained in the embodiment 1 has a three-dimensional porous substrate with good conductivity, and can ensure the efficient transmission of electrons and substances; the hollow nano-column array structure can ensure the full exposure of the active site and the release and transportation of the gas product; the synergistic effect of the bimetal and the large number of oxygen vacancies brought by etching can promote the further improvement of the catalytic activity. Thus, it was confirmed that it can significantly improve the efficiency and stability of electrolyzed water as OER and HER electrocatalysts, which are shown in the electrochemical properties shown in fig. 5 to 9. When CeV-HNA/NF was used as both the anode and cathode of the cell, the electrolyzed water was driven to 10mA cm -2 at 1.52V, which was superior to the commercial Pt/C IrO 2 performance, and the electrolyzed water stability was maintained for 150h at a high current density of 100mA cm -2.
Example 2:
The CeV-HNA/NF was prepared in the same manner as in example 1 except that the molar concentration of the ceric ammonium nitrate solution was adjusted to 0.4mol L -1 during the etching process, i.e., 3.302g of ceric ammonium nitrate was dissolved in 15mL of deionized water, and the other steps were the same as in example 1. The electrochemical test procedure of the prepared electrocatalytic material is the same as in example 1. The results show that when CeV-HNA/NF was used as both the anode and cathode of the electrolyzer, the electrolyzed water was driven to 10mA cm -2 at 1.65V, which is superior to the commercial Pt/C IrO 2 performance, and the electrolyzed water stability of 150h was maintained at a high current density of 100mA cm -2.
Example 3:
The CeV-HNA/NF was prepared in the same manner as in example 1 except that the molar concentration of the ceric ammonium nitrate solution was adjusted to 0.6mol L -1 during the etching process, i.e., 4.932g of ceric ammonium nitrate was dissolved in 15mL of deionized water, and the other steps were the same as in example 1. The electrochemical test procedure of the prepared electrocatalyst was the same as example 1. The results show that when CeV-HNA/NF was used as both the anode and cathode of the electrolyzer, the electrolyzed water was driven to 10mA cm -2 at 1.58V, which is superior to the commercial Pt/C IrO 2 performance, and the electrolyzed water stability of 150h was maintained at a high current density of 100mA cm -2.
Comparative example 1:
preparation of CeV-MOF/NF:
The CeV-MOF/NF was prepared in the same manner as in example 1 except that the molar concentration of the ammonium cerium nitrate solution during etching was 0.3mol L -1.
FIG. 10 is an SEM image of CeV-MOF/NF produced in comparative example 1. As can be seen from FIG. 10, the morphology of the obtained CeV-MOF/NF was the same as that of the Ce-MOF/NF, and no hollow structure was formed.
Comparative example 2:
preparation of CeV-MOF/NF:
the CeV-MOF/NF synthesis procedure was the same as in example 1, except that the molar concentration of ceric ammonium nitrate during etching was 0.7mol L -1.
FIG. 11 is an SEM image of CeV-MOF/NF produced in comparative example 2. As can be seen from fig. 11, the morphology of the obtained CeV-MOF nanopillars was destroyed, and no regular hollow nanopillar array structure was formed.
Comparative example 3:
0.568g of ferric chloride hexahydrate, 0.61g of nickel nitrate hexahydrate, 0.135g of potassium hydroxide and 0.498g of terephthalic acid were dissolved in 60mL of N, N-Dimethylformamide (DMF), and magnetically stirred to obtain a homogeneous solution. Introducing the substrate NF into the solution, reacting for 2 hours at 150 ℃, cooling, washing the product with ethanol, and vacuum drying to obtain the NiFe-MOF/NF. Then, etching treatment was performed using cerium salt, and the etching step was the same as step (2) of example 1; finally, the treatment was carried out according to the calcination procedure of example 1, giving CeNiFe/NF.
OER and HER performance tests were performed at CeNiFe/NF following the electrochemical test procedure of example 1. As shown in FIGS. 12 and 13, the overpotential of CeNiFe/NF at 50mA cm -2 was 310mV and 252mV, respectively, and both were greater than the corresponding overpotential of CeV-HNA/NF of 220mV and 125mV, respectively, indicating that the catalytic activity was inferior to that of the electrocatalytic material prepared in example 1.
Comparative example 4:
3.6g of dimethyl imidazole and 0.126g of cetyltrimethylammonium bromide were dissolved in 30mL of water, and then 3mL of a solution containing 0.372g of cobalt acetate tetrahydrate was mixed with the above solution to obtain a synthetic solution; immersing a substrate NF into the solution, reacting for 10 hours at 120 ℃, washing with deionized water, and drying to obtain Co-MOF/NF; then, etching treatment was performed using cerium salt, and the etching step was the same as step (2) of example 1; finally, the treatment was carried out according to the calcination procedure of example 1, giving CeCo/NF.
OER and HER performance tests were performed at CeCo/NF following the electrochemical test procedure of example 1. As shown in FIGS. 12 and 13, the overpotential of CeCo/NF at 50mA cm -2 was 420 mV and 313mV, respectively, which were greater than the corresponding overpotential of CeV-HNA/NF of 220mV and 125mV, respectively, indicating that the catalytic activity was inferior to that of the electrocatalytic material prepared in example 1.
Comparative example 5:
Under magnetic stirring, 0.233g of ammonium metavanadate, 0.580g of cobalt nitrate hexahydrate and 0.466g of terephthalic acid were dissolved in 50mL of a mixed solution of DMF and H 2 O (volume ratio: 1:1); then, introducing the substrate NF into the synthesis solution, and heating at 180 ℃ for 6 hours; washing the product with ionized water and ethanol, and vacuum drying at 60deg.C for 12 hr to obtain VCo-MOF/NF; finally, the treatment was carried out according to the calcination procedure of example 1, obtaining VCo/NF.
OER and HER performance testing of VCo/NF was performed following the procedure of example 1. As shown in FIGS. 12 and 13, the overpotential of VCo/NF at 50mA cm -2 was 380 mV and 397mV, respectively, and both were greater than the corresponding overpotential of CeV-HNA/NF of 220mV and 125mV, indicating that the catalytic activity was inferior to that of the electrocatalytic material prepared in example 1.
In summary, in comparative example 1, the concentration of cerium salt during etching was low, and the etching was not performed to an extent sufficient; in comparative example 2, cerium salt concentration was high during etching, and excessive etching caused damage to the MOF nanopillar array structure; in the above cases, a CeV-MOF hollow nano-pillar array with complete structure cannot be obtained, and a CeV-HNA/NF catalyst cannot be obtained. In comparative examples 3 to 5, the catalyst performance obtained by compounding Ce or V with Co, ni and Fe-based materials was comparable to that of the electrocatalytic material obtained in example 1 of the present invention. As can be seen from the SEM image of fig. 3, the structure of the hollow nano-pillar array obtained in example 1 is most complete. Exhibits excellent performance as HER and OER self-supported catalysts alone; when used as both anode and cathode of the electrolyzer, the electrolytic water can be driven to 10mA cm -2 at 1.52V, which is superior to the commercial Pt/C IrO 2 performance, and can maintain the electrolytic water stability for 150h at a high current density of 100mA cm -2.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. A cerium vanadium double-metal hollow nano-pillar array type electrocatalytic material is characterized in that: the composite comprises a substrate and a composite loaded on the substrate, wherein the composite forms a hollow nano-pillar array structure on the substrate, and the composite comprises CeO 2、V8C7 and V 2O5.
2. The cerium-vanadium bimetallic hollow nano-pillar array type electrocatalytic material as set forth in claim 1, wherein: the molar ratio of CeO 2、V8C7 to V 2O5 is (3-15): (10-40): (30-70).
3. The cerium-vanadium bimetallic hollow nano-pillar array type electrocatalytic material as set forth in claim 1, wherein: the substrate is foam nickel.
4. The cerium-vanadium bimetallic hollow nano-pillar array type electrocatalytic material as set forth in claim 1, wherein: the total load of CeO 2、V8C7 and V 2O5 on the substrate is 1-5 mg cm -2.
5. A method for preparing the cerium-vanadium bimetallic hollow nano-pillar array type electrocatalytic material as set forth in any one of claims 1 to 4, comprising the steps of:
(1) Placing a substrate in vanadium-based synthetic solution for in-situ growth, and forming a V-MOF nano-column array of the vanadium-based metal organic framework on the substrate;
(2) Placing the substrate loaded with the V-MOF nano-pillar array in a cerium salt aqueous solution for etching to obtain a CeV-MOF hollow nano-pillar array supported by the substrate;
(3) Roasting the substrate loaded with the CeV-MOF hollow nano-pillar array in an inert gas atmosphere to obtain a cerium-vanadium bimetallic hollow nano-pillar array type electrocatalytic material;
The vanadium-based synthetic solution comprises vanadyl sulfate, a ligand and deionized water;
the ligand is terephthalic acid or amino terephthalic acid.
6. The method for preparing the cerium-vanadium bimetallic hollow nano-pillar array type electrocatalytic material as set forth in claim 5, wherein the method comprises the following steps: the mol ratio of the vanadyl sulfate, the ligand and the deionized water is 1:1 (3500-4500).
7. The method for preparing the cerium-vanadium bimetallic hollow nano-pillar array type electrocatalytic material as set forth in claim 5, wherein the method comprises the following steps: the molar concentration of cerium ions in the aqueous solution of cerium salt is greater than 0.3mol L -1 and less than 0.7mol L -1.
8. The method for preparing the cerium-vanadium bimetallic hollow nano-pillar array type electrocatalytic material as set forth in claim 5, wherein the method comprises the following steps: the cerium salt is any one of ammonium cerium nitrate, cerium chloride and cerium sulfate.
9. The method for preparing the cerium-vanadium bimetallic hollow nano-pillar array type electrocatalytic material as set forth in claim 5, wherein the method comprises the following steps: the in-situ growth in the step (1) is carried out for 45-75 hours at the temperature of 150-170 ℃; the etching reaction in the step (2) needs 6-18 h; and (3) roasting in the step (3) is carried out for 2-5 hours in an argon atmosphere at 550-650 ℃.
10. The use of the cerium-vanadium bimetallic hollow nano-pillar array type electrocatalytic material according to any one of claims 1-4 in electrocatalytic decomposition of water for oxygen evolution and hydrogen evolution reactions under alkaline conditions.
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