CN117344333A - Method for preparing nickel-based catalysts with different functions based on solution supersaturation degree regulation - Google Patents
Method for preparing nickel-based catalysts with different functions based on solution supersaturation degree regulation Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 173
- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 30
- 230000033228 biological regulation Effects 0.000 title claims abstract description 11
- 230000006870 function Effects 0.000 title claims abstract description 6
- 239000006260 foam Substances 0.000 claims abstract description 40
- 239000000243 solution Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004202 carbamide Substances 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 230000001276 controlling effect Effects 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 230000009467 reduction Effects 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 230000001105 regulatory effect Effects 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 230000008878 coupling Effects 0.000 claims abstract description 6
- 238000010168 coupling process Methods 0.000 claims abstract description 6
- 238000005859 coupling reaction Methods 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 239000002086 nanomaterial Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 150000001450 anions Chemical class 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 4
- 102000020897 Formins Human genes 0.000 claims description 4
- 108091022623 Formins Proteins 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000010405 anode material Substances 0.000 claims description 3
- 239000010406 cathode material Substances 0.000 claims description 3
- 229910019614 (NH4)6 Mo7 O24.4H2 O Inorganic materials 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 12
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 239000000047 product Substances 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 238000004146 energy storage Methods 0.000 abstract description 2
- 150000002431 hydrogen Chemical class 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 description 15
- 238000012360 testing method Methods 0.000 description 12
- 238000012512 characterization method Methods 0.000 description 8
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 7
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 3
- 229940010552 ammonium molybdate Drugs 0.000 description 3
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
- 239000011609 ammonium molybdate Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000012937 correction Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 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 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 1
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 1
- 229910018089 Al Ka Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910019887 RuMo Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000011217 control strategy Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- 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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/089—Alloys
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
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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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention relates to the field of electrocatalytic energy storage, and aims to provide a method for preparing nickel-based catalysts with different functions based on solution supersaturation degree regulation. The preparation method comprises the steps of preparing a precursor by utilizing a multi-element metal salt solution and foam nickel, and then obtaining a nickel-based catalyst through reduction treatment; when the precursor is prepared, the UOR catalyst or the HER catalyst is respectively obtained by controlling the molar ratio of each metal element and regulating and controlling the supersaturation degree of the solution. The method is simple and easy to implement, and the morphology and electronic structure of the Ni-based catalyst can be adjusted only by simply regulating and controlling the molar ratio of the reaction product and the supersaturation degree of the solution, so that the method is suitable for different catalytic reaction systems. The reaction equipment can be reused, and the configuration of the equipment is not required to be changed according to different catalyst products; the precursor has rich material reserve and low cost. The catalyst of the invention can be used for urea oxidation reaction and electrolytic water hydrogen separation reaction when being used independently, and can be used for urea coupling full water hydrogen production when being used in combination.
Description
Technical Field
The invention belongs to the field of electrocatalytic energy storage, and particularly relates to a method for preparing a bifunctional catalyst based on solution supersaturation degree regulation.
Background
The hydrogen energy is used as green secondary energy, has the advantages of high energy density, no pollution of combustion products and the like, and is an important carrier for realizing green low-carbon transformation by using energy terminals in China. Based on the electrolytic water green hydrogen preparation technology, the renewable energy source can provide green energy source to realize green zero-carbon circulation. The electrolytic hydrogen production principle involves two half reactions, namely Hydrogen Evolution (HER) at the cathode and Oxygen Evolution (OER) at the anode. However, since the OER kinetics of four electrons are slow, its theoretical driving water splitting requires 1.23V and theoretically generates 1Nm 3 H 2 The energy required is about 2.94kWh. In actual operation, 1Nm is generated due to anodic polarization, ohmic polarization and other factors 3 H 2 The energy required is greater than 4.00kWh. Thus, the electrolytic hydrogen production still faces energy consumption efficiencyA bottleneck with low rate.
Recent researchers have utilized more thermodynamically advantageous urea oxidation reactions (UOR (CO (NH) 2 ) 2 +H 2 O→3H 2 +N 2 +CO 2 ) Instead of the traditional kinetic slow oxygen evolution reaction (OER: 2H (H) 2 O→2H 2 +O 2 ). The UOR coupling electrolysis hydrogen production technology can reduce the thermodynamic potential from the traditional electrolysis potential of 1.23V to 0.37V, thereby improving the overall hydrogen production energy efficiency. Nickel (Ni) based catalysts are widely used in the field of electrocatalysis, including HER, OER and UOR reactions.
However, different catalytic reactions depend on the morphology and electronic structure of different Ni-based catalysts. Numerous strategies have been applied to regulate morphology and electronic structures, including surface engineering, defect engineering, p-block doping, heterostructures, and the like. Among the numerous regulation strategies, adjusting the balance between the ionization degree (α) of the electrolyte and the supersaturation degree (S) of the solution can control the thermodynamic growth and adjust the morphology and electronic structure of the Ni-based catalyst. The morphology and electronic structure required for Ni-based catalysts based on different reactions can be achieved by adjusting the supersaturation of the solution. Under the condition of relatively low ionization degree, the preparation of one-dimensional and two-dimensional materials can be realized by adjusting the supersaturation degree of the solution, so that the production efficiency of the catalyst is improved, and the morphology structure and the electronic structure of the Ni-based catalyst are efficiently and flexibly regulated so as to adapt to the requirements of different catalytic reaction systems.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing a method for preparing nickel-based catalysts with different functions based on the regulation and control of the supersaturation degree of a solution.
In order to solve the technical problems, the invention adopts the following solutions:
providing a method for preparing nickel-based catalysts with different functions based on solution supersaturation regulation, preparing a precursor by using a multi-element metal salt solution and foam nickel, and then obtaining the nickel-based catalysts through reduction treatment; when preparing a precursor, controlling the molar ratio of each metal element and regulating and controlling the supersaturation degree of the solution to obtain a UOR catalyst or a HER catalyst respectively; the method specifically comprises the following steps:
(1) Uniformly mixing a nickel source, an iron source, a molybdenum source and deionized water under ultrasonic conditions, and controlling the atomic ratio of Ni to Fe to Mo in the mixed solution to be 8 to 1 to 0.1 and the anion concentration to be 0.00033M; at this time, the mixed solution is in high supersaturation degree, and a large amount of sediment is generated;
then the mixed solution is moved into a hydrothermal kettle, and the cleaned foam nickel is immersed below the liquid level to carry out hydrothermal reaction; cooling to room temperature after the reaction is finished, taking out the foam nickel, cleaning and drying the foam nickel, and forming a NiFeMo-based nano structure on the surface of the foam nickel;
in Ar/H 2 In the mixed reducing atmosphere of (2), heating the foam nickel after the hydrothermal reaction treatment to 500 ℃, preserving heat for 1h for reduction treatment, and cooling to obtain a nickel-based UOR catalyst; or,
(2) Mixing nickel source, iron source, molybdenum source, ruthenium source and deionized water under ultrasonic condition, controlling the atomic ratio of Ni, fe, mo, ru in the mixed solution to 8:1:2:0.01, and the anion concentration to 0.0066M; at the moment, the solution has low supersaturation, and the mixed solution is clear and transparent;
then the mixed solution is moved into a hydrothermal kettle, and the cleaned foam nickel is immersed below the liquid level to carry out hydrothermal reaction; cooling to room temperature after the reaction is finished, taking out foam nickel, cleaning and drying the foam nickel, and forming a RuNiFeMo-based nano structure on the surface of the foam nickel;
in Ar/H 2 In the mixed reducing atmosphere of (2), the foamed nickel after the hydrothermal reaction treatment is heated to 500 ℃, and is preserved for 1h for reduction treatment, and the nickel-based HER catalyst is obtained after cooling.
As a preferable scheme of the invention, the nickel source, the iron source, the molybdenum source and the ruthenium source are respectively: ni (NO) 3 ) 2 ·6H 2 O、Fe(NO 3 ) 3 ·9H 2 O、(NH 4 ) 6 Mo 7 O 24 .4H 2 O、RuCl 3 ·xH 2 O。
As a preferred embodiment of the present invention, the nickel foam is subjected to a cleaning treatment prior to its use: sequentially washing with acetone, 3M HCl solution, deionized water and ethanol under ultrasonic conditions for 5min.
As a preferable scheme of the invention, the temperature of the hydrothermal reaction is 150 ℃ and the time is 6 hours.
As a preferable scheme of the invention, washing foam nickel after hydrothermal reaction with absolute ethyl alcohol and deionized water for multiple times; the drying treatment is to put the foam nickel into a vacuum drying oven and dry the foam nickel for 6 hours at 30 ℃.
As a preferable mode of the invention, ar/H in a volume ratio of 95%/5% is used in the reduction treatment 2 In a mixed reducing atmosphere at 5 ℃ for min -1 Heating to 500 ℃ and preserving heat for 1h, and cooling to room temperature along with a furnace after the reaction is completed.
The invention also provides a combined use method of the nickel-based UOR catalyst and the HER catalyst prepared by the method, wherein the UOR catalyst and the HER catalyst are respectively used for preparing anode materials and cathode materials, and are used for urea coupling full water splitting hydrogen production after being assembled into an electrolytic tank.
Description of the inventive principles:
the low cost transition metal Ni is widely used in HER catalysts because of its excellent dissociation capability for water molecules. In addition, the Ni-based catalyst also exhibits excellent catalytic performance in the anode UOR system. On the basis, the morphology and the electronic structure of the Ni-based catalyst are regulated and controlled by a simple and efficient method, so that the Ni-based catalyst can be applied to different catalytic reaction systems.
(1) The invention regulates and controls crystal growth dynamics through oversaturation of the solution, thereby affecting nucleation and growth of the nano material. At relatively low ammonium molybdate concentrations, the solution is highly supersaturated and there is a significant amount of precipitation in the solution. Under the condition, the two-dimensional NiFeMo catalyst is prepared, the surface area and the number of active sites of the catalyst are increased, and meanwhile, strong electronic interaction and synergistic effect exist between Mo, ni and Fe, so that the catalyst shows excellent UOR catalytic activity.
(2) Based on a solution supersaturation degree regulation strategy, when the concentration of ammonium molybdate is relatively high, the solution is low in supersaturation degree, the solute is completely dissolved, and the mixed solution is clear and transparent. Under the condition, preparing a one-dimensional RuNiFeMo catalyst, and adjusting the electronic structures of Ni and Mo by utilizing the electronegativity difference of Ru, ni and Mo to change the adsorption/analysis energy of H; on the other hand, the strong water dissociation capability and high catalytic activity of Ru are utilized to improve the integral intrinsic activity of the Ni-based catalyst, and finally RuNiFeMo shows excellent HER catalytic activity.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention adopts a one-step hydrothermal method, has no complicated steps of pretreatment, post-treatment pickling and the like, has rich raw material reserves of the used precursor and low cost, and is suitable for large-scale industrialized production.
2. The preparation method is simple and feasible, and the morphology and the electronic structure of the Ni-based catalyst can be adjusted only by simply regulating and controlling the molar ratio of the reaction product and the supersaturation degree of the solution, so that the preparation method is suitable for different catalytic reaction systems. Thus, the reaction apparatus in the present invention can be reused without changing the configuration of the apparatus according to the difference of catalyst products.
3. The catalyst product of the present invention has excellent properties. Based on anion concentration regulation, the two-dimensional NiFeMo-based UOR catalyst can be obtained under the condition of high supersaturation degree, and 100mA cm is realized at 1.36V vs. RHE -2 Is a current density of (a); under the condition of low supersaturation degree, a one-dimensional RuNiFeMo-based HER catalyst is obtained, ruNiFeMo is obtained through the atomic-level doping of the subordinated metal Ru, and 10 mAcm is realized at 19mV vs. RHE -2 Is used for the current density of the battery.
4. The UOR catalyst and HER catalyst prepared by the invention are used for preparing anode material and cathode material respectively, and can be used for assembling an electrolytic cell singly or in combination. Can be used for urea oxidation reaction and electrolytic water hydrogen separation reaction when being singly used, and can be used for urea coupling full water separation hydrogen production when being combined.
Taking urea coupling full water-splitting hydrogen production after the assembled electrolytic tank is used in combination as an example, 10mA cm can be obtained by applying a tank pressure of 1.32V due to the improvement of the catalytic activity of the anode and the cathode -2 And can be stabilizedThe operation is more than 60 hours, and the current density is higher under the same tank pressure compared with the traditional electrolytic water hydrogen production.
Drawings
FIG. 1 is a schematic diagram of a morphology control strategy of the present invention;
FIG. 2 is a flow chart of the preparation of the material of the present invention;
FIG. 3 is an SEM image of NiFeMo-811 of example 1 of the present invention;
FIG. 4 is a high resolution spectrum of Ni 2p (a) and Mo 3d (b) in XPS of NiFeMo-811 in example 1 of this invention;
FIG. 5 is a graph (a) and EIS graph (b) of the electrochemical performance of urea oxidation in example 1 of the present invention;
FIG. 6 is a graph comparing urea oxidation performance of different catalysts reported in example 1 of the present invention;
FIG. 7 is an SEM image of RuNiFeMo in example 1 of the present invention;
FIG. 8 is a high resolution spectrum of Mo 3d XPS in RuNiFeMo and NiFeMo in example 2 of the present invention;
FIG. 9 is a graph of hydrogen evolution electrochemical performance of example 2 of the present invention (a) versus overpotential for different materials at different current densities (b);
FIG. 10 is a graph comparing hydrogen evolution performance of example 2 of the present invention with reported catalysts;
FIG. 11 shows the results of the full water splitting stability test of example 2 of the present invention.
Detailed Description
The present invention will be described in detail with reference to the following examples, but the scope of the present invention is not limited to these examples.
Ammonium molybdate tetrahydrate ((NH) employed in the following examples 4 ) 6 Mo 7 O 24 .4H 2 O), nickel nitrate hexahydrate (Ni (NO) 3 ) 2 ·6H 2 O), ferric nitrate nonahydrate (Fe (NO) 3 ) 3 ·9H 2 O), ruthenium chloride (RuCl) 3 ) All purchased from sigma aldrich limited, analytically pure.
First part two-dimensional flake NiFeMo-based urea catalyst structure and electrochemical performance characterization
EXAMPLE 1 preparation of high supersaturated solution NiFeMo-based catalyst
The preparation method of the NiFeMo-based nano material comprises the following steps:
(1) Foam nickel pretreatment:
foam Ni with the thickness of 1.6mm is cut into 20mm multiplied by 30mm, and then is sequentially treated by ultrasonic for 5 minutes by acetone, 3M HCl solution, deionized water and ethanol, wherein the acetone is used for washing off organic matters on the surface, the dilute hydrochloric acid is used for washing off nickel oxide on the surface, and the deionized water and ethanol are used for washing off residual acetone and dilute hydrochloric acid.
(2) Preparation of nifemeo-based precursor:
according to the mass relation of the raw materials in the table 1, a proper amount of ammonium molybdate tetrahydrate ((NH) is weighed 4 ) 6 Mo 7 O 24 .4H 2 O), nickel nitrate hexahydrate (Ni (NO) 3 ) 2 ·6H 2 O), ferric nitrate nonahydrate (Fe (NO) 3 ) 3 ·9H 2 O) was added to deionized water and stirred for 10 minutes to mix well. The mixed solution has an atomic ratio of Ni/Fe/Mo of 8:1:0.1, and anion concentration of 0.00033M, and has high supersaturation degree, and a large amount of yellow flocculent precipitate.
Then adding the mixed solution and the treated foam nickel into a 50mL high-pressure reaction kettle, reacting for 6 hours at 150 ℃, and cooling along with a furnace after the reaction is finished. Washing the foam nickel after the reaction treatment with absolute ethyl alcohol and deionized water for a plurality of times, and then placing the foam nickel into a vacuum drying oven for vacuum drying at 30 ℃ for 6 hours.
As shown in Table 1, example NiFeMo-811 was prepared according to the difference in the molar ratio of Ni to Fe to Mo; and comparative example 1 was NiFe-810.5, comparative example 2 was NiFeMo-815, and comparative example 3 was NiFeMo-8110.
(3) Reduction of nifemeo-based precursor:
the foam nickel after the hydrothermal reaction treatment is put into a horizontal tube furnace for heating and reduction, and is heated and reduced in argon hydrogen (Ar/H) 2 ) Mixing at 5 deg.C for min under a mixed atmosphere (95%/5%) -1 Heating to 500 ℃ and preserving heat for 1h, cooling to room temperature along with a furnace after the reaction is completed, and taking out to obtain the NiFeMo-based sample.
TABLE 1 raw material formulation table for different NiFeMo-based catalysts
Material structure morphology and electronic structure characterization example:
(1) Scanning electron microscope and spectroscopy (sem+eds): SEM analysis is used to characterize the microstructure morphology and features of the sample surface, and component and element distribution characterization is performed on SEM photographed areas by EDS.
(2) Transmission Electron Microscope (TEM): characterization of atomic scale morphology and structure was performed using a Talos F200X-type field emission transmission electron microscope of Thermo Scientific, which more accurately revealed the microstructure of the sample, and in addition, lattice fringes and crystal orientation of the material could be observed by High Resolution Transmission Electron Microscopy (HRTEM) and selective electron diffraction (SAED), which can more accurately reflect the microstructure information of the material.
(3) X-ray photoelectron spectroscopy (XPS): the element valence state analysis is carried out by adopting an Escalab 250Xi type X-ray photoelectron spectrometer of U.S. Thermo Fisher Scientific, the test light source is Al Ka ray (1486.6 eV), the test area is 500 mu m, and the test pressure is lower than 10 -7 Pa, after obtaining the map, requires charge correction, based on the C1s peak at 284.80 eV.
Application method example:
the NiFeMo prepared in example 1 can be used for urea oxidation UOR, and an exemplary application method includes:
(1) Electrochemical performance evaluation of urea oxidation was performed by the CHI660E electrochemical workstation at room temperature using the three electrode method. Hg/HgO, graphite rod and NiFeMo based catalyst are used as reference electrode, counter electrode and working electrode. The electrolyte was 0.5M urea and 1.0M KOH solution. The Hg/HgO electrode was scaled to a standard reversible hydrogen electrode (vs. RHE). Solution ph=13.8, standard electrode potential for hg/HgO electrode was 0.098V.
E(vs.RHE)＝E(vs.Hg/HgO)+0.0591pH+0.098
(2) Electrochemical impedance spectroscopy EIS test: the EIS of the different electrocatalysts was measured at an overpotential of 20mV, with a sweep frequency in the range 0.1Hz to 100000Hz and an amplitude of 5mV.
(3) And (3) iR compensation: ar was introduced into the electrolytic cell for 30 minutes to remove O from the solution before the test 2 Ensuring that the reference electrode and the working electrode remain at the same distance. And secondly, measuring electrochemical impedance EIS to obtain solution resistance, and performing manual iR compensation, so as to ensure that the catalytic performances of different catalyst materials are fairly compared.
(4) Urea oxidation performance comparison: at 100mV s in the interval of 1.3V-1.4V (vs. RHE) before testing -1 Cyclic Voltammetry (CV) scans for 20 cycles until stable. The scanning voltage of the Linear Scanning Voltammetry (LSV) test is from 1.2V to 1.5V (vs. RHE), and the scanning speed is 5mV s -1 The response current is recorded.
Second part one-dimensional columnar RuNiFeMo-based hydrogen evolution catalyst structure and electrochemical performance characterization
Example 2 preparation of one-dimensional RuNiFeMo-based Hydrogen evolution catalyst
With reference to the preparation method of NiMoFe in example 1, a proper amount of Ni (NO 3 ) 2 ·6H 2 O、Fe(NO 3 ) 3 ·9H 2 O、(NH 4 ) 6 Mo 7 O 24 ·4H 2 O、RuCl 3 Added to 30mL deionized water and stirred for 10 minutes to mix well. The mixed solution has an atomic ratio of Ni, fe, mo, ru of 8:1:2:0.01, and the anion concentration of 0.0066M solution is low supersaturation, and the solution is clear and transparent.
Then adding the mixed solution and the dried foam nickel into a 50mL high-pressure reaction kettle, sealing, putting the reaction kettle into a blast oven for heating and preserving heat, reacting for 6 hours at 150 ℃, and cooling along with the furnace after the reaction is finished. And opening the sealing cover, taking out the reacted nickel sheet from the reaction kettle, washing the nickel sheet for a plurality of times by using absolute ethyl alcohol and deionized water, and then placing the nickel sheet into a vacuum drying oven for vacuum drying at 60 ℃ for 6 hours. The foam nickel after reaction and drying is put into a horizontal tube furnace for heating and reduction, and the foam nickel is heated and reduced in an argon-hydrogen mixed atmosphere (95%/5%) at 5 ℃ for min -1 Heating to 500 ℃ and preserving heat for 1h, cooling to room temperature along with a furnace after the reaction is completed, and taking out to obtain RuNiFeMo catalyst.
Referring to the preparation procedure of example 2 without addition of Ru, niFeMo catalyst was prepared as comparative example 5.
TABLE 2 raw material formulation table for one-dimensional different NiFeMo-based hydrogen evolution catalysts
Material structure morphology and electronic structure characterization example:
with reference to the exemplary steps of material structure morphology and electronic structure characterization in the application example of example 1, morphology and electronic structure characterization was performed on RuNiFeMo prepared in example 2 and nifemeo prepared in comparative example 5 by SEM, TEM, XPS.
Application method example:
referring to the application method example of example 1, electrochemical performance evaluation was performed in 1M KOH using a classical three-electrode system.
3. Analysis and conclusion
FIG. 1 reveals the mechanism of morphology of Ni-based catalysts regulated by solution supersaturation. Based on a weak electrolyte system, the pH value can be adjusted by adding the content of ammonium molybdate to realize the regulation and control of the supersaturation degree of the solution, a one-dimensional nano structure is generated under the condition of low supersaturation degree, and a two-dimensional nano sheet structure is generated under the condition of high supersaturation degree. FIG. 2 depicts a material synthesis process, where (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O、Ni(NO 3 ) 2 ·6H 2 O、Fe(NO 3 ) 3 ·9H 2 O is hydrothermal with foam nickel according to different proportions under different 150 DEG hydrothermal conditions for 6 hours, and further under Ar/H 2 In this case by a high temperature heat treatment at 500 ℃.
Based on the SEM image of the nifeme-811 sample (fig. 3 a), it can be seen that nifeme is a two-dimensional nano-sheet layered growing on the surface of the nickel foam and distributed with some nano-flower-like agglomerates, and it can be obviously observed that many fine nano-particles are also attached to the two-dimensional nano-sheet (fig. 3 b), and the two-dimensional folded sheet-like nano-structure can provide a relatively large accessible surface area, so that the distribution of active sites on the surface of the catalyst can be increased, which is beneficial to the promotion of catalytic activity.
To further investigate the effect of Mo incorporation on Ni, fe, mo electronic structure, niFeMo-811 was compared with the high resolution XPS spectrum of the control sample, as shown in FIG. 4a, ni in NiFeMo-811 compared with NiFe 2+ The peak ratio is obviously increased, indicating that more 2-valent Ni exists in the material, and Ni 0 Shift to high binding energy by 0.5eV indicates an increase in the valence state of Ni, which on the one hand enables Ni to be 2+ Is easier to Ni 3+ Transition, thereby hopefully lowering the charge transfer energy barrier, and on the other hand, improving Ni 3+ Thereby increasing the number of UOR catalytic active sites. And compared with other NiFeMo with different Mo contents, the Ni peak position is not changed obviously, which shows that the content of Mo has less influence on the electronic structure of Ni. In addition, as shown in fig. 4b, as the Mo content increases, the peak position of Mo in NiFeMo tends to shift toward high binding energy, indicating that the difference in Mo content has a certain effect on its own electronic structure. In conclusion, the strong electron interaction exists between Mo and Ni and Fe, so that XPS peaks of Ni and Fe can shift to a position with high binding energy, the valence state of Ni and Fe active substances can be improved, and finally the catalytic performance of UOR is expected to be improved.
To test the prepared electrode material for electrocatalytic performance, the apparent electrochemical UOR performance of nifeme-811 catalyst was evaluated by Linear Sweep Voltammetry (LSV) in a 1m koh+0.5m urea solution using a classical three electrode system (test area 1cm 2 Scanning speed is 5mV s -1 ) Comparison was made with NiFe and NiFeMo with different Mo additions, and UOR performance tests were performed under the same conditions. The LSV polarization curve after manual iR correction is shown in fig. 5 a. It can be seen that NiFeMo doped with Mo shows better UOR activity, wherein the performance is optimal with NiFeMo-811, reaching 10mA cm -2 And 100mA cm -2 Only potentials of 1.34V and 1.36V (vs. rhe), respectively, are required, much lower than those required for NiFe at the same current density (1.41V and 1.44V). Electricity for different catalysts at the same current densityAs can be seen from the bit comparison, the potential shows a tendency to decrease and then increase with increasing Mo content, but is superior to that of NiFe catalyst as a whole, and NiFeMo-811 shows excellent UOR catalytic performance at high current density up to 200mA cm -2 Only 1.37V is needed for NiFeMo-811 at current density, and the results show that the introduction of Mo can effectively improve the UOR catalytic activity of the NiFe catalyst. The EIS test results are shown in FIG. 5b, and the results show that the solution resistances of the several catalysts are similar, and the stable test environment is shown, and the curve curvature radius can be used for judging that the NiFeMo catalyst has lower charge transfer resistance compared with the NiFe catalyst, and the performance of the NiFeMo-811 is optimal, so that the doping of Mo can effectively reduce the impedance of the electron transfer process, and the charge transfer resistance is increased along with the increase of the Mo content, which is probably caused by the transition of Mo to a higher valence state. In conclusion, the proper amount of Mo is introduced to accelerate the UOR reaction kinetics of the NiFe catalyst and obviously improve the UOR catalytic activity. In addition, niMoFe-811 was measured at 100mA cm -2 The results of comparing the UOR performance with the performance of the UOR catalyst reported previously are shown in FIG. 6, which shows that the NiMoFe-811 catalyst was found to reach 100mA cm in 1M KOH+0.5M urea -2 The current densities of the catalyst are relatively low, the UOR performance of the catalyst is superior to that of most UOR catalysts reported at present, and the catalyst has good UOR application potential.
As can be seen from fig. 7, a one-dimensional rod-shaped nickel-based catalyst can be prepared after the low supersaturation degree. Furthermore, doping a small amount of the next-noble metal Ru further optimizes the electronic structure of the three-way catalyst Mo (fig. 8). Comparing the high resolution XPS spectra of RuNiFeMo and NiFeMo, compared with NiFeMo, the introduction of Ru leads the 0 valence peak of Mo to be 0.3eV towards the low binding energy (as shown in figure 8), and the valence state of Mo is reduced, which shows that the doping of Ru can change the electronic structure of Mo and adjust the whole electronic energy state of the catalyst, which is caused by electronegativity difference between RuMo, and shows that partial electrons are transferred from Ru to Mo, and the valence state change can adjust d-electron filling, thereby being beneficial to accelerating the adsorption/desorption process of H and further improving the HER catalytic efficiency.
Apparent electrochemical HER performance of RuNiFeMo catalysts was evaluated by Linear Sweep Voltammetry (LSV) (test area 1cm 2 Scanning speed is 5mV s -1 ) For comparison, the electrocatalysis performance test was performed under the same conditions using NiFeMo without Ru doping and Pt with hydrophilic treatment, and the LSV polarization curve after manual iR correction is shown in FIG. 9a, it can be seen that the Ru doped RuNiFeMo catalyst shows the best HER activity at 100mA cm -2 The hydrogen evolution overpotential was only 19mV, slightly lower than 22.3mV of NiFeMo and much lower than 68.5mV of Pt, and it can be seen from the comparison of FIG. 9b of hydrogen evolution overpotential of different catalysts at different current densities, at 10mA cm -2 The overpotential difference between RuNiFeMo and NiFeMo and Pt is 3.3mV and 49.5mV respectively, to 250mA cm -2 The difference in time overpotential becomes 26.4mV and 181.2mV, indicating that the RuNiFeMo catalyst also possesses excellent HER catalytic activity at high current densities. At 100mA cm -2 The overpotential is only 61.9mV, and the result shows that the doping of Ru can effectively improve the catalytic activity of HER.
Further, a NiFeMo RuNiFeMo electrolytic cell is formed by a cathode HER catalyst RuNiFeMo and an anode UOR catalyst NiFeMo, and an electrolyte is formed by using 1.0M KOH and 0.5M urea, and 40mA cm can be obtained by only applying a cell pressure of 1.5V -2 And can be stably operated for more than 60 hours without a significant decrease in activity. Therefore, the invention provides a new feasible scheme for preparing the low-cost and high-efficiency urea-coupled anode catalyst and cathode catalyst for producing hydrogen by electrolyzing water.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (7)
1. A method for preparing nickel-based catalysts with different functions based on solution supersaturation degree regulation, which comprises the steps of preparing a precursor by using a multi-element metal salt solution and foam nickel, and then obtaining the nickel-based catalysts through reduction treatment; the preparation method is characterized in that when a precursor is prepared, a UOR catalyst or a HER catalyst is respectively obtained by controlling the molar ratio of each metal element and regulating and controlling the supersaturation degree of the solution;
the method specifically comprises the following steps:
(1) Uniformly mixing a nickel source, an iron source, a molybdenum source and deionized water under ultrasonic conditions, and controlling the atomic ratio of Ni to Fe to Mo in the mixed solution to be 8 to 1 to 0.1 and the anion concentration to be 0.00033M; at this time, the mixed solution is in high supersaturation degree, and a large amount of sediment is generated;
then the mixed solution is moved into a hydrothermal kettle, and the cleaned foam nickel is immersed below the liquid level to carry out hydrothermal reaction; cooling to room temperature after the reaction is finished, taking out the foam nickel, cleaning and drying the foam nickel, and forming a NiFeMo-based nano structure on the surface of the foam nickel;
in Ar/H 2 In the mixed reducing atmosphere of (2), heating the foam nickel after the hydrothermal reaction treatment to 500 ℃, preserving heat for 1h for reduction treatment, and cooling to obtain a nickel-based UOR catalyst; or,
(2) Mixing nickel source, iron source, molybdenum source, ruthenium source and deionized water under ultrasonic condition, controlling the atomic ratio of Ni, fe, mo, ru in the mixed solution to 8:1:2:0.01, and the anion concentration to 0.0066M; at the moment, the solution has low supersaturation, and the mixed solution is clear and transparent;
then the mixed solution is moved into a hydrothermal kettle, and the cleaned foam nickel is immersed below the liquid level to carry out hydrothermal reaction; cooling to room temperature after the reaction is finished, taking out foam nickel, cleaning and drying the foam nickel, and forming a RuNiFeMo-based nano structure on the surface of the foam nickel;
in Ar/H 2 In the mixed reducing atmosphere of (2), the foamed nickel after the hydrothermal reaction treatment is heated to 500 ℃, and is preserved for 1h for reduction treatment, and the nickel-based HER catalyst is obtained after cooling.
2. The method of claim 1, wherein the nickel source, iron source, molybdenum source, ruthenium source are each: ni (NO) 3 ) 2 ·6H 2 O、Fe(NO 3 ) 3 ·9H 2 O、(NH 4 ) 6 Mo 7 O 24 .4H 2 O、RuCl 3 ·xH 2 O。
3. The method according to claim 1, characterized in that the nickel foam is subjected to a cleaning treatment before it is used: sequentially washing with acetone, 3M HCl solution, deionized water and ethanol under ultrasonic conditions for 5min.
4. The method of claim 1, wherein the hydrothermal reaction is performed at a temperature of 150 ℃ for a period of 6 hours.
5. The method according to claim 1, wherein the foam nickel after the hydrothermal reaction is washed with absolute ethanol and deionized water respectively for a plurality of times in sequence; the drying treatment is to put the foam nickel into a vacuum drying oven and dry the foam nickel for 6 hours at 30 ℃.
6. The method according to claim 1, wherein the reduction treatment is performed with a volume ratio of Ar/H of 95%/5% 2 In a mixed reducing atmosphere at 5 ℃ for min -1 Heating to 500 ℃ and preserving heat for 1h, and cooling to room temperature along with a furnace after the reaction is completed.
7. The method for using the nickel-based UOR catalyst and the HER catalyst in combination, which are prepared by the method as claimed in claim 1, is characterized in that the UOR catalyst and the HER catalyst are respectively used for preparing anode materials and cathode materials, and are used for urea coupling full water splitting hydrogen production after being assembled into an electrolytic tank.
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