CN113416980B - Efficient full-hydrolysis water catalyst MoO 2 -CeO x /NF and preparation method thereof - Google Patents
Efficient full-hydrolysis water catalyst MoO 2 -CeO x /NF and preparation method thereof Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 54
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 45
- 239000001257 hydrogen Substances 0.000 claims abstract description 44
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000002243 precursor Substances 0.000 claims abstract description 27
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 25
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000009467 reduction Effects 0.000 claims abstract description 18
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 9
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 9
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 9
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 9
- 238000005516 engineering process Methods 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 95
- 229910052759 nickel Inorganic materials 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052573 porcelain Inorganic materials 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 abstract description 25
- 239000001301 oxygen Substances 0.000 abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 23
- 230000001276 controlling effect Effects 0.000 abstract description 6
- 230000001105 regulatory effect Effects 0.000 abstract description 5
- 230000006870 function Effects 0.000 abstract description 4
- -1 rare earth cerium oxide Chemical class 0.000 abstract description 3
- 239000011241 protective layer Substances 0.000 abstract description 2
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 2
- 239000002110 nanocone Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 90
- 230000000052 comparative effect Effects 0.000 description 18
- 239000006260 foam Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 238000006722 reduction reaction Methods 0.000 description 15
- 238000010586 diagram Methods 0.000 description 11
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 10
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 10
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 8
- 229910000510 noble metal Inorganic materials 0.000 description 8
- 238000011161 development Methods 0.000 description 7
- 230000001788 irregular Effects 0.000 description 6
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 6
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 2
- RQYSWULBRFINID-UHFFFAOYSA-N [Mo].[Ce] Chemical compound [Mo].[Ce] RQYSWULBRFINID-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- 229910017299 Mo—O Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
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- 238000012827 research and development Methods 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000009044 synergistic interaction Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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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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- Chemical Kinetics & Catalysis (AREA)
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Abstract
Efficient full-hydrolysis water catalyst MoO 2 ‑CeO x /NF and preparation method thereofThe method is carried out. The preparation method comprises the steps of synthesizing a nanocone precursor by a hydrothermal reaction of ammonium molybdate, cerium nitrate and acetamide in a certain proportion; then MoO is synthesized by hydrogen reduction technology 2 ‑CeO x An electrocatalyst material of/NF. The catalyst material realizes three functions of regulating and controlling the surface electronic structure of the material, regulating and controlling the concentration of surface oxygen vacancies and forming a protective layer on the surface to improve the circulation stability of the material simultaneously through the interface regulation and control function of rare earth cerium oxide, and the obtained electrocatalyst has excellent hydrogen evolution and oxygen evolution performances and good stability.
Description
Technical Field
The invention belongs to the field of new energy materials, and particularly relates to a high-efficiency full-hydrolysis water-power catalyst MoO 2 -CeO x /NF and its preparation method.
Background
With the development of society and the continuous advance of industrialization, the global energy demand is sharply increased. At present, the problem of environmental pollution and the shortage of energy are important factors for the urgent development of clean energy form, and the development of a clean, efficient and sustainable new energy system is a fundamental way to solve the increasingly severe energy crisis and environmental pollution in the world today. The hydrogen energy is used as a secondary energy with wide source, green and high efficiency, has the advantages of rich resources, cleanness, high efficiency, high energy density, environmental friendliness and the like, is an ideal renewable energy source, and will certainly become an important component of an energy system in the future. The production and utilization of hydrogen energy is critical to the mitigation of energy and environmental concerns and has attracted considerable attention by researchers. The electrolytic water and hydrogen-oxygen fuel cell is concerned because of having unique advantages and application prospects in the preparation and utilization of hydrogen, and the popularization and application of hydrogen production by electrolytic water to consume renewable energy sources such as water and electricity with excessive structural capacity, wind power and photovoltaic power generation are more important ways for optimizing energy consumption structures.
However, the hysteresis of the electrocatalytic reactions such as the oxygen evolution reaction, the hydrogen evolution reaction, and the oxygen reduction reaction, which are involved in the conventional energy conversion devices such as electrolysis water and fuel cells, is one of the important bottlenecks that restrict the development thereof, and the cause of the hysteresis is mainly due to the hysteresis of the catalyst performance. Although the traditional noble metal catalyst has better electrocatalytic performance, the high price and limited reserves prevent the large-scale commercial production of the traditional noble metal catalyst and also limit the development of the traditional noble metal catalyst in the electrocatalytic field. Therefore, research and development of cheap, abundant and efficient non-noble metal catalysts to replace noble metal catalysts have become a hot area of research. Among them, a full hydrolysis catalyst capable of producing hydrogen and oxygen simultaneously is gaining wide attention.
In recent years, considerable research effort has been devoted to the development of low cost non-noble metal electrocatalysts, including transition metal carbides, sulfides, selenides, and oxide-substituted noble metal catalysts. Molybdenum dioxide (MoO), a potential molybdenum-based oxide to replace noble metal catalysts 2 ) It is a hot spot of research because of its good metal conductivity and chemical stability. The tetravalent molybdenum of the molybdenum dioxide can provide good metal indication characteristics in the catalytic reaction, and has good activity at the fermi level. In addition, moO 2 Has high electron transfer rate, and Mo-O bond can be well dissociated to effectively adsorb and desorb the catalytic intermediate, thereby being beneficial to catalysis. But MoO alone 2 HER activity exhibited in HER catalysis is not superior, and therefore, there is a need for an effective strategy to change the electronic environment on the surface of the catalyst, thereby exposing additional active sites during hydrogen evolution of the catalyst and further increasing the rate of electrocatalytic water decomposition.
The increase in charge transfer rate can accelerate the performance of the electrocatalyst due to strong interactions between the different domains at the interface. Interface engineering is considered to design high efficiency electricityAn efficient method of catalysis because electrocatalytic reactions typically occur at the interface. Research shows that heterojunction through interface engineering can promote electron transfer, influence adsorption/desorption energy of active substances in electrocatalysis reaction, and adjust catalytic capacity. Moreover, the synergistic interaction of the two components may also be beneficial to further improve catalytic activity and stability of the heterostructure. Heterogeneous nanostructures show synergistically enhanced kinetics at different active center and electron reconstitution interfaces, superior to their single component electrocatalysts. Due to MoO 2 It is difficult to exhibit better HER capacity and stability in acidic media, in order to solve MoO 2 Huihui Zhao et al provides Mo source by Mo Foil (MF), and obtains MoO by hydrothermal method with mixed solution of hydrogen peroxide and deionized water 2 The mixture is subjected to hydrothermal and low-temperature phosphorization in sequence to obtain CoP-MoO with a heterogeneous interface 2 a/MF nano-array. This "bottom-up" approach enables heterogeneous nanoarrays to grow on MF without being easily shed. CoP-MoO 2 the/MF heterojunction can not only maintain good HER performance and high stability in alkaline solution, but also in acidic. (H.ZHao, Z.Li, X.Dai, M.Cui, F.Nie, X.ZHang, Z.ren, Z.Yang, Y.gan, X.yin, Y.Wang, W.Song, heterogeneous structured CoP/MoO) 2 on Mo foam as high-efficiency electrolytes for the hydrogen evolution reaction in the boundary acid and alkali medium, journal of Materials Chemistry A, (2020) 6732-6739.). As another example, gancing Yang et al applied the synthesis of POMOF to a self-sacrificial template of FeOOH matrix by in situ growth of phosphomolybdic acid and iron-based complex (PMo12 @ Fe complex), followed by low temperature phosphating to form MoO 2 -FeP@C。MoO 2 Interfacial electron redistribution at FeP @ C occurs at the interface, where electron accumulation at FeP favors H 2 Optimization of O and H absorption energy, thereby improving HER activity, and MoO 2 The accumulation of the upper cavities is beneficial to the absorption of biomass organic matters. The stronger synergistic effect of the nano heterostructure is greatly improved in the aspect of hydrogen evolution performance. (G.Yang, Y.Jiano, H.Yan, Y.Xie, A.Wu, X.Dong, D.Guo, C.Tian, H.Fu, interfacial Engineeering of MoO 2 -FeP Heterojunction for Highly Efficient Hydrogen Evolution Coupled with Biomass Electrooxidation,Advanced Materials,32(2020)2000455.)。
The method is characterized in that the catalyst combines the excellent hydrogen evolution performance of molybdenum oxide and the excellent oxygen evolution performance of cerium oxide to obtain the electrocatalyst with the efficient full-hydrolysis performance, and simultaneously, the research of regulating and controlling the rearrangement of electrons at an interface, the concentration of oxygen vacancies and the formation of a surface protection layer through the synergistic action between heterojunction interfaces is very important, so that the method has important significance for the development of the efficient full-hydrolysis electrocatalyst.
Disclosure of Invention
In order to solve the technical problem, the invention provides an electrocatalyst MoO for efficient full water decomposition 2 -CeO x A method for the preparation of/NF, wherein x =1.5-2, said method comprising the steps of:
(1) Selecting a porous nickel carrier for pretreatment for later use;
(2) Weighing a certain amount of ammonium molybdate, cerium nitrate and acetamide, and adding water to mix uniformly to obtain a load solution;
(3) Placing the pretreated porous nickel carrier obtained in the step (1) in the loading solution to enable the porous nickel carrier to be completely immersed in the loading solution, obtaining a nano conical precursor compounded on the porous nickel carrier through hydrothermal reaction, and washing and drying the nano conical precursor for later use;
(4) Completely putting the dried porous nickel carrier compounded with the nano-cone-shaped precursor into a furnace, reacting at the temperature of 400-600 ℃ by using a hydrogen reduction technology, and cooling the furnace to room temperature to obtain the high-efficiency full-electrolysis hydro-electric catalyst MoO 2 -CeO x /NF。
Specifically, in the step (1), the porous nickel carrier is foamed nickel.
Specifically, in the step (1), the pretreatment step includes a step of sequentially placing the porous nickel carrier in a dilute hydrochloric acid solution, absolute ethyl alcohol and deionized water for ultrasonic treatment, and a step of vacuum drying at a low temperature.
Wherein the concentration of the dilute hydrochloric acid solution is preferably 3mol/L, and the ultrasonic treatment time in the dilute hydrochloric acid solution, the absolute ethyl alcohol and the deionized water is preferably controlled to be 15-25min (preferably 20 min) respectively.
Specifically, in the step (2):
controlling the molar ratio of molybdenum element to cerium element in the ammonium molybdate and the cerium nitrate to be 5:1-40;
the molar ratio of acetamide to ammonium molybdate is controlled to be 2-8:1.
And as for the amount of water in the supporting solution, it is preferable to use an amount sufficient to dissolve the above-mentioned substances for the purpose of dissolving ammonium molybdate, cerium nitrate and acetamide, and to use an amount sufficient to completely impregnate the porous nickel support.
Specifically, in the step (3), the temperature of the hydrothermal reaction is controlled to be 150-240 ℃, and the reaction time is 6-32h.
Specifically, in the step (4), the furnace tube furnace is a ceramic boat containing a porous nickel carrier and is placed in the center of the tube furnace.
Specifically, in the step (4), H is controlled during the hydrogen reduction treatment 2 The volume ratio of/Ar is 1:4-12.
Specifically, in the step (4), the reaction temperature is controlled to be 400-600 ℃ and the heat preservation time is 1-6h when the hydrogen reduction treatment is carried out.
Specifically, in the step (3), the washing step is washing with deionized water, and the drying step is drying at 30-70 ℃ for 6-15h.
The invention also discloses the high-efficiency full-hydrolysis water catalyst MoO prepared by the method 2 -CeO x /NF，Wherein x =1.5-2, and the catalyst is a heterojunction material of molybdenum oxide and cerium oxide.
The invention has the following beneficial technical effects:
the invention relates to a high-efficiency full-hydrolysis water catalyst MoO 2 -CeO x /NF is prepared by mixingThe ammonium molybdate, the cerous nitrate and the acetamide are synthesized into a nanometer conical precursor through a hydrothermal reaction; and then the heterojunction material of cerium oxide and molybdenum oxide with rich oxygen vacancies is obtained through hydrogen reduction treatment.
The catalyst is prepared by in-situ growing molybdenum-cerium-based precursor nanosheets on a porous nickel carrier, so that the intrinsic activity of the material is improved, and meanwhile, the active sites of the material are further increased; reducing the molybdenum-cerium-based precursor generated in situ into CeO by hydrogen reduction x And MoO 2 。
Formation of CeO x And MoO 2 The heterojunction of (2) realizes three functions of regulating and controlling the electronic structure on the surface of the material, regulating and controlling the concentration of oxygen vacancies on the surface and forming a protective layer on the surface to improve the circulation stability of the material simultaneously through the interface regulation and control function of the rare earth cerium oxide, and the obtained electrocatalyst has excellent hydrogen evolution and oxygen evolution performances and good stability.
Meanwhile, the preparation method of the whole catalyst is simple and feasible, and is suitable for industrial popularization.
Drawings
FIG. 1 is an SEM topography of pretreated nickel foam of example 1;
FIG. 2 is an SEM topography of a precursor prepared by hydrothermal reaction in example 1;
FIG. 3 shows the MoO production by reduction of hydrogen in example 1 2 -CeO x SEM topography of/NF;
FIG. 4 shows MoO obtained in example 1 2 -CeO x /NF MoO obtained in comparative example 1 2 CeO prepared in/NF and comparative example 2 x XRD pattern of/NF;
FIG. 5 shows MoO obtained in example 1 2 -CeO x LSV, tafel slope diagram and potential versus time diagram of/NF material;
FIG. 6 shows MoO obtained in example 1 2 -CeO x The LSV curve of the total water splitting of the NF material;
FIG. 7 shows MoO obtained in example 1 2 -CeO x The hydrogen evolution performance and the oxygen evolution performance of the/NF material are compared with those of other materials.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The full hydrolysis water catalyst MoO described in this example 2 -CeO x The preparation method of the/NF comprises the following steps:
(1) Cutting commercial foam nickel into the size of 10mm-20mm, sequentially performing ultrasonic treatment in 3M dilute hydrochloric acid, absolute ethyl alcohol and deionized water for 25min respectively, and then performing vacuum drying at 60 ℃ for 8h for later use, wherein an SEM (scanning electron microscope) morphology diagram is shown in FIG. 1;
(2) Weighing 1mmol of ammonium molybdate tetrahydrate, 0.4mmol of cerium nitrate hexahydrate and 4mmol of acetamide, adding 60ml of deionized water, and stirring for 30min to obtain a loading solution;
(3) Transferring the obtained load solution into a reaction kettle, adding the foamed nickel treated in the step (1), sealing, and then putting into a 200 ℃ drying oven for reaction for 14 hours; when the reaction kettle is cooled to room temperature, taking out the foamed nickel, washing with deionized water for 3 times, putting into a 45 ℃ oven, and drying for 8 hours to obtain a precursor, wherein an SEM appearance diagram of the precursor is shown in FIG. 2;
(4) Putting the dried foam nickel compounded with the nanometer cone-shaped precursor into a tube furnace, reacting at 500 ℃ by a hydrogen reduction technology, preserving the temperature for 2 hours, and cooling the tube furnace to room temperature to obtain the high-efficiency full-electrolysis water electro-catalyst MoO 2 -CeO x The SEM topography is shown in figure 3, and the XRD pattern is shown in figure 4.
As shown in fig. 1, it can be seen from (1) in fig. 1 that the three-dimensional net-like NF scaffold has a smooth surface, and it can be seen from (2) in fig. 1 that it has small protrusions thereon, which facilitates the adhesion of materials.
As shown in fig. 2, it can be seen from (1) in fig. 2 that irregular precursor cone structures grow on the surface of the precursor, and it can be seen from (2) in fig. 2 that these irregular precursor cone structures are formed by aggregation of nanospheres and particles, and the length of the precursor cone structures is about 1.1 μm.
As shown in fig. 3, it can be seen from (1) in fig. 3 that the morphology and size of the irregular vertebral structure after hydrogen reduction substantially correspond to those of the prepared precursor. Such irregular vertebral structures have extremely high stability and large specific surface area, and therefore can increase the material-electrolyte contact area, and can also expose additional edge active sites, which can lead to enhanced catalytic activity; as can be seen from comparison of fig. 3 (2) and fig. 2 (2), irregular tapered nanospheres formed due to aggregation of particles disappear after the thermal annealing process after hydrogen reduction. This observation may be attributed to the tendency of the particles to amorphize and the rearrangement of electrons, which results in close packing of the nanoparticles to form a protective film.
As shown in FIG. 4, it can be seen that the material prepared in example 1 contains CeO x 、MoO 2 And Ni. Wherein, moO 2 And CeO x From the product after hydrogen reduction, ni is the substrate foam nickel, the MoO 2 And CeO x Mainly the irregular vertebral structure.
MoO obtained in this example 2 -CeO x The LSV, tafel slope diagram and current density versus time diagram of the/NF material under alkaline conditions are shown in FIG. 5; wherein,
FIG. 5 (1) is a LSV graph of hydrogen evolution of the material, from which it can be seen that the hydrogen evolution performance of the material is 26mV at 10 mA/cm;
FIG. 5 (2) is a Tafel slope diagram converted from the LSV diagram of hydrogen evolution of the material, from which it can be seen that the Tafel slope of hydrogen evolution of the material is 52mA/dec;
FIG. 5 (3) shows the hydrogen evolution cycle of the material, which is 10mA/cm 2 The current density can be kept for 95h without obvious change, so that the hydrogen evolution catalyst has good hydrogen evolution cycle performance;
FIG. 5 (4) is the LSV diagram of oxygen evolution of the material, from which it can be seen that the oxygen evolution performance of the material is 100mA/cm 2 272mV at the time of (1);
FIG. 5 (5) is a Tafel slope diagram converted from the LSV diagram of oxygen evolution of the material, from which it can be seen that the Tafel slope of oxygen evolution of the material is 33.92mA/dec;
FIG. 5 (6) shows the oxygen evolution cycle of the material, which is shown to be at 100mA/cm 2 The current density can be kept for 58h without obvious change, so that the oxygen evolution cycle performance is good.
FIG. 6 shows MoO 2 -CeO x The full water splitting curve of the/NF material can be seen from the figure, at 10mA cm -2 And 20mA cm -2 In the presence of oxygen, moO 2 -CeO x /NF//MoO 2 -CeO x The electrolysis voltage of/NF is as low as 1.397V and 1.47V respectively.
Example 2
The full hydrolysis water catalyst MoO described in this example 2 -CeO x -0.2/NF preparation process comprising the steps of:
(1) Cutting commercial foam nickel into the size of 10mm-20mm, sequentially performing ultrasonic treatment in 3M dilute hydrochloric acid, absolute ethyl alcohol and deionized water for 25min respectively, and then performing vacuum drying at 60 ℃ for 8h for later use;
(2) Weighing 1mmol of ammonium molybdate tetrahydrate, 0.2mmol of cerous nitrate hexahydrate and 4mmol of acetamide, adding 60ml of deionized water, and stirring for 30min to obtain a load solution;
(3) Transferring the obtained load solution into a reaction kettle, adding the previously treated foamed nickel, sealing, and placing into a 200 ℃ drying oven for reaction for 14 hours; when the reaction kettle is cooled to room temperature, taking out the foamed nickel, washing with deionized water for 3 times, and putting into a 45 ℃ oven for drying for 8 hours to obtain a precursor;
(4) Putting the dried foam nickel compounded with the nanometer cone-shaped precursor into a tube furnace, reacting at 500 ℃ by using a hydrogen reduction technology, preserving the temperature for 2 hours, and cooling the tube furnace to room temperature to obtain the high-efficiency full-hydrolysis hydro-electric catalyst MoO 2 -CeO x -0.2/NF。
Through measurement, the electrocatalytic material obtained in the embodiment has the current density of 10mA/cm 2 When the hydrogen evolution overpotential was measured under alkaline conditions, it was 35mV, the Tafel slope was 55.75mV/dec, while at the same time, the constant was 10mA/cm 2 At current density, voltage after 95hCan still keep stable; measuring that the oxygen evolution overpotential is 296mV and the Tafel slope is 39.87mV/dec; at the same time, the constant current is 10mA/cm 2 Under the current density, the voltage can still keep stable after 58 h;
example 3
The full hydrolysis water catalyst MoO described in this example 2 -CeO x -0.6/NF preparation method, comprising the following steps:
(1) Cutting commercial foam nickel into the size of 10mm-20mm, sequentially performing ultrasonic treatment in 3M dilute hydrochloric acid, absolute ethyl alcohol and deionized water for 25min respectively, and then performing vacuum drying at 60 ℃ for 8h for later use;
(2) Weighing 1mmol of ammonium molybdate tetrahydrate, 0.6mmol of cerium nitrate hexahydrate and 4mmol of acetamide, adding 60ml of deionized water, and stirring for 30min to obtain a loading solution;
(3) Transferring the obtained load solution into a reaction kettle, adding the previously treated foamed nickel, sealing, and placing into a 200 ℃ drying oven for reaction for 14 hours; when the reaction kettle is cooled to room temperature, taking out the foamed nickel, washing with deionized water for 3 times, and putting into a 45 ℃ oven for drying for 8 hours to obtain a precursor;
(4) Putting the dried foam nickel compounded with the nanometer cone-shaped precursor into a tube furnace, reacting at 500 ℃ by using a hydrogen reduction technology, preserving the temperature for 2 hours, and cooling the tube furnace to room temperature to obtain the high-efficiency full-hydrolysis hydro-electric catalyst MoO 2 -CeO x -0.6/NF。
The electrocatalytic material obtained in the example was determined to have a current density of 10mA/cm 2 When the hydrogen evolution overpotential is measured under alkaline conditions, it is 46mV, the Tafel slope is 75.32mV/dec, while at the same time at a constant 10mA/cm 2 Under the current density, the voltage can still keep stable after 95 hours; the measured oxygen evolution overpotential is 320mV, and the Tafel slope is 69.47mV/dec; at the same time, the constant current is 10mA/cm 2 Under the current density, the voltage can still keep stable after 58 h;
comparative example 1
The material of the comparative example was a material without cerium nitrate (noted as MoO) 2 /NF) and the specific preparation process comprises the following steps:
(1) Cutting commercial foam nickel into the size of 10mm to 2mm, sequentially performing ultrasonic treatment in 3M dilute hydrochloric acid, absolute ethyl alcohol and deionized water for 25min, and then performing vacuum drying at 60 ℃ for 8h for later use;
(2) Weighing 1mmol of ammonium molybdate tetrahydrate and 4mmol of acetamide, adding 60ml of deionized water, and stirring for 30min to obtain a loading solution;
(3) Transferring the obtained load solution into a reaction kettle, adding the previously treated foamed nickel, sealing, and placing into a 200 ℃ drying oven for reaction for 14 hours; when the reaction kettle is cooled to room temperature, taking out the foamed nickel, washing with deionized water for 3 times, and putting into a 45 ℃ oven for drying for 8 hours to obtain a precursor;
(4) Putting the dried foam nickel compounded with the nanometer cone-shaped precursor into a tube furnace, reacting at 500 ℃ by a hydrogen reduction technology, preserving the temperature for 2 hours, cooling the tube furnace to room temperature, and finally obtaining the MoO of the comparative example 1 2 /NF electrocatalytic material.
Comparative example 2
The material of this comparative example was the material without ammonium molybdate tetrahydrate (noted CeO x /NF) and the specific preparation process comprises the following steps:
cutting commercial foam nickel into the size of 10mm-20mm, sequentially performing ultrasonic treatment in 3M dilute hydrochloric acid, absolute ethyl alcohol and deionized water for 25min respectively, and then performing vacuum drying at 60 ℃ for 8h for later use;
(2) Weighing 0.4mmol of cerium nitrate hexahydrate and 4mmol of acetamide, adding 60ml of deionized water, and stirring for 30min to obtain a loading solution;
(3) Transferring the obtained load solution into a reaction kettle, adding the previously treated foamed nickel, sealing, and reacting in an oven at 200 ℃ for 14 hours; when the reaction kettle is cooled to room temperature, taking out the foamed nickel, washing with deionized water for 3 times, and putting into a 45 ℃ oven for drying for 8 hours to obtain a precursor;
(4) Putting the dried foam nickel compounded with the nanometer cone-shaped precursor into a tube furnace, reacting at 500 ℃ by using a hydrogen reduction technology, preserving the temperature for 2 hours, cooling the tube furnace to room temperature, and finally obtaining CeO x /NF comparative scheme electrocatalysisA material.
Catalytic materials (noted as MoO) from example 1, respectively 2 -CeO x NF), material prepared in comparative example 1 without cerium nitrate (noted as MoO) 2 /NF), comparative example 2 material prepared without ammonium molybdate tetrahydrate (noted CeO x /NF), and pure nickel foam (noted NF), commercial platinum carbon (noted Pt/C)/commercial ruthenium oxide (noted RuO) 2 ) The performance difference comparison was performed and the results are shown in FIG. 7.
FIG. 7 (1) is a comparison between the hydrogen evolution performance of the materials, and it can be seen that pure Nickel Foam (NF) has the worst performance because it is the matrix material and its hydrogen evolution performance is negligible; comparative example 1 preparation of a material without added cerium nitrate (noted as MoO) 2 NF), comparative example 2, the material prepared without ammonium molybdate tetrahydrate (noted CeO x NF) and commercial Pt-C (Pt/C) at 10mA/cm 2 The values of the time intervals are 52mV, 196mV and 27mV respectively.
FIG. 7 (2) shows the Tafel slope corresponding to the data in FIG. 7 (1), and it can be seen that the material prepared in comparative example 1 without cerium nitrate (denoted as MoO) 2 NF), comparative example 2, the material prepared without ammonium molybdate tetrahydrate (noted CeO x NF) and commercial platinum carbon (Pt/C) have Tafel slopes of 64.84mV/dec, 208.04mV/dec and 52.95mV/dec, respectively.
FIG. 7 (3) is a comparison between the oxygen evolution performance of the materials, and it can be seen that the pure Nickel Foam (NF) has the worst performance, because the nickel foam is the matrix material, and the oxygen evolution performance of the nickel foam is negligible; comparative example 1 preparation of a material without added cerium nitrate (noted as MoO) 2 NF), comparative example 2, the material prepared without ammonium molybdate tetrahydrate (noted CeO x /NF) and commercial ruthenium oxide (RuO) 2 ) At 100mA/cm 2 At times 428mV, 474mV and 393mV respectively.
FIG. 7 (4) shows the Tafel slope corresponding to the data in FIG. 7 (3), and it can be seen that the material without cerium nitrate (denoted as MoO) prepared in comparative example 1 2 NF), comparative example 2, the material prepared without ammonium molybdate tetrahydrate (noted CeO x /NF) and quotientWith ruthenium oxide (RuO) 2 ) The Tafel slopes of 146.34mV/dec, 160.98mV/dec and 90.97mV/dec, respectively.
Therefore, the catalyst material has excellent hydrogen evolution performance and oxygen evolution performance and has electrocatalysis performance of high-efficiency full water decomposition performance.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. Efficient full-hydrolysis water catalyst MoO 2 -CeO x A method for the preparation of/NF, wherein x =1.5-2, said method comprising the steps of:
(1) Pretreating the porous nickel carrier for later use;
(2) Weighing a certain amount of ammonium molybdate, cerium nitrate and acetamide, and adding water to mix uniformly to obtain a load solution;
(3) Placing the pretreated porous nickel carrier obtained in the step (1) in the loading solution to enable the porous nickel carrier to be completely immersed in the loading solution, obtaining a nano conical precursor compounded on the porous nickel carrier through hydrothermal reaction, and washing and drying the nano conical precursor for later use;
(4) Putting the dried porous nickel carrier compounded with the nano-cone-shaped precursor into a furnace, reacting at a certain temperature by a hydrogen reduction technology, and cooling to room temperature to obtain the high-efficiency full-hydrolysis hydro-electric catalyst MoO 2 -CeO x /NF；
Wherein in the step (2):
controlling the molar ratio of molybdenum element to cerium element in the ammonium molybdate and the cerium nitrate to be 5:1-40.
2. The high-efficiency full-hydrolysis hydro-electrocatalyst MoO according to claim 1 2 -CeO x The preparation method of/NF is characterized in that in the step (1), the porous nickel carrier is foamed nickel.
3. The high efficiency fully hydrolyzed hydro-electric catalyst MoO according to claim 1 or 2 2 -CeO x The preparation method of/NF comprises the step (1) of sequentially placing the porous nickel carrier in dilute hydrochloric acid solution, absolute ethyl alcohol and deionized water for ultrasonic treatment and vacuum drying.
4. The high efficiency fully hydrolyzed hydro-electric catalyst MoO according to claim 1 or 2 2 -CeO x The preparation method of/NF, wherein, in the step (2):
the molar ratio of acetamide to ammonium molybdate is controlled to be 2-8:1.
5. The high efficiency fully hydrolyzed hydro-electric catalyst MoO according to claim 1 or 2 2 -CeO x The preparation method of/NF comprises the step (3), wherein the temperature of the hydrothermal reaction is controlled to be 150-240 ℃, and the reaction time is 6-32h.
6. The high efficiency fully hydrolyzed hydro-electric catalyst MoO according to claim 1 or 2 2 -CeO x The preparation method of/NF, wherein, in the step (4), the furnace is a tube furnace, and a porcelain boat containing a porous nickel carrier is placed in the center of the tube furnace.
7. The high efficiency fully hydrolyzed hydro-electric catalyst MoO according to claim 1 or 2 2 -CeO x The method for producing NF, wherein in the step (4), H is controlled during the hydrogen reduction treatment 2 The volume ratio of/Ar is 1:4-12.
8. The high efficiency fully hydrolyzed hydro-electric catalyst MoO according to claim 1 or 2 2 -CeO x The preparation method of/NF comprises the step (4), wherein the reaction temperature is 400-600 ℃ during the hydrogen reduction treatment, and the temperature is keptThe time is 1-6h.
9. The high-efficiency full-hydrolysis hydro-electrocatalyst MoO according to claim 1 2 -CeO x The preparation method of/NF comprises the steps of washing with deionized water and drying at 30-70 ℃ for 6-15h.
10. High-efficiency full-hydrolysis hydro-electric catalyst MoO prepared by the method of any one of claims 1 to 9 2 -CeO x /NF, wherein x =1.5-2, characterized in that the catalyst is a heterojunction material of molybdenum oxide and cerium oxide.
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