CN114892199A - RuO 2 Preparation method and application of loaded Ni-MOF electrode material - Google Patents
RuO 2 Preparation method and application of loaded Ni-MOF electrode material Download PDFInfo
- Publication number
- CN114892199A CN114892199A CN202210427970.4A CN202210427970A CN114892199A CN 114892199 A CN114892199 A CN 114892199A CN 202210427970 A CN202210427970 A CN 202210427970A CN 114892199 A CN114892199 A CN 114892199A
- Authority
- CN
- China
- Prior art keywords
- mof
- ruo
- electrode material
- loaded
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000013099 nickel-based metal-organic framework Substances 0.000 title claims abstract description 79
- 239000007772 electrode material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 82
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 39
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 32
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 18
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 92
- 238000001035 drying Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 235000019441 ethanol Nutrition 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 15
- 230000009467 reduction Effects 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 11
- ZTWIEIFKPFJRLV-UHFFFAOYSA-K trichlororuthenium;trihydrate Chemical compound O.O.O.Cl[Ru](Cl)Cl ZTWIEIFKPFJRLV-UHFFFAOYSA-K 0.000 claims description 11
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005520 cutting process Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 7
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 238000000840 electrochemical analysis Methods 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000010411 electrocatalyst Substances 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 18
- 229910052938 sodium sulfate Inorganic materials 0.000 description 18
- 235000011152 sodium sulphate Nutrition 0.000 description 18
- 239000003792 electrolyte Substances 0.000 description 16
- 238000006722 reduction reaction Methods 0.000 description 13
- 229910021607 Silver chloride Inorganic materials 0.000 description 11
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 11
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 10
- 235000010344 sodium nitrate Nutrition 0.000 description 9
- 239000004317 sodium nitrate Substances 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 239000012621 metal-organic framework Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003411 electrode reaction Methods 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000008240 homogeneous mixture Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000002798 spectrophotometry method Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000009620 Haber process Methods 0.000 description 1
- 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 1
- 229910019854 Ru—N Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000004172 nitrogen cycle Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- 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
- C25B1/27—Ammonia
-
- 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
- C25B11/055—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
-
- 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
- Y02E60/13—Energy storage using capacitors
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of environment functional materials, and provides RuO 2 A supported Ni-MOF electrode material is prepared by taking foamed nickel as a substrate and growing RuO in situ, and is a composite electrocatalyst which can improve the selectivity of converting nitrate into ammonia to 100% and does not generate nitrite aiming at the problem of low selectivity of a catalyst related to ammonia synthesis by electrocatalysis of nitrate 2 Supported Ni-MOF electrodes by construction of Ni-MOF with RuO 2 The interface structure between the ruthenium and the metal effectively improves the atom utilization rate of the ruthenium metal, thereby reducing the cost. The results of electrochemical tests carried out by adopting a three-electrode system show that the maximum synthetic ammonia yield reaches 1.37mg h ‑1 cm ‑2 After repeated use, the electrode produces NH 4 + Both rate and selectivityAnd keeping stable.
Description
Technical Field
The invention belongs to the technical field of environment functional materials, and relates to RuO 2 A preparation method and application of a loaded Ni-MOF electrode material.
Background
Ammonia (NH) 3 ) As one of the basic industrial chemicals, has played an increasingly important role in agriculture, new energy and textile industries, the Haber-Bosch processNow, large-scale production of ammonia is made possible to meet the needs of human life and production, however, due to the high stability of the N-N triple bond (941kJ/mol), the Haber-Bosch process requires high temperature and high pressure conditions (usually 400 ℃ and 200atm) to drive the reaction, which consumes a large amount of fossil fuel and releases greenhouse gases, causing a huge burden on the ecological environment, and thus, there is a great need to find a green and efficient ammonia synthesis process to reduce pollution to the ecological environment and reduce carbon emission.
In the natural nitrogen cycle, Nitrates (NO) 3 - ) Because the dissociation energy of N-O bond is low and the N-O bond is rich in natural water, the synthesis of ammonia by catalytic reduction of nitrate driven by electric energy is a green ammonia synthesis process with a great prospect. Due to NO 3 - Reduction to NH 4 + Multiple electron transfer reactions are required, the actual reduction potential of which is usually lower than the Hydrogen Evolution (HER) potential (0V versus the standard hydrogen electrode), inevitably producing hydrogen and other nitrogen oxides as by-products. In the existing research of electrocatalytic nitrate reduction, most of electrodes have the problem of low selectivity of synthetic ammonia, the main byproduct of the electrodes is nitrite, and the application of the electrodes is limited due to the toxicity of the nitrite.
In recent years, ruthenium-based catalysts having hydrogen bond strength similar to Pt have received attention. Experiments and theoretical calculations show that the ruthenium-based catalyst is used for preparing NH under mild reaction conditions 3 Due to the equilibrium interaction between Ru-N and Ru-H, which contributes to NO 3 - The hydrogenation process of (1). However, in the application of the existing ruthenium-based catalyst in the electrocatalytic reduction of nitrate to generate ammonia, the atom utilization rate and metal activity of ruthenium metal are low, and the yield of the synthetic ammonia is still to be improved.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide the composite electrocatalyst which can improve the selectivity of converting nitrate into ammonia to 100% and does not generate nitrite.
The first aspect of the present invention provides a RuO 2 A method for preparing a supported Ni-MOF electrode material, comprising the steps of:
(1) dissolving terephthalic acid and nickel chloride hexahydrate in dimethylformamide to form a homogeneous mixed solution;
(2) and (2) putting the foamed nickel into the mixed solution, adding a sodium hydroxide solution, stirring uniformly, transferring into a high-pressure reaction kettle, reacting at a constant temperature of 90-100 ℃ for 10-15 h, cooling to room temperature, washing with absolute ethyl alcohol and deionized water, and drying to obtain the Ni-MOF material.
(3) Putting the Ni-MOF material into an ethanol solution containing ruthenium chloride trihydrate, reacting at the constant temperature of 80-90 ℃ for 10-15 h, cooling to room temperature, washing with absolute ethyl alcohol and deionized water, and drying to obtain RuO 2 A supported Ni-MOF electrode material.
Preferably, the concentration of the terephthalic acid in the mixed solution is 0.06-0.07 mol/L.
Preferably, the concentration of nickel chloride hexahydrate in the mixed solution is 0.06-0.07 mol/L.
Preferably, the preparation step of the foamed nickel in the step (2) comprises:
cutting the spare foamed nickel into the size of 2cm multiplied by 2 cm;
pretreating with ethanol for 30min to remove surface impurities;
treating with hydrochloric acid solution for 15min to remove the oxide layer on the surface;
rinsing with deionized water and ethanol, and drying to obtain the foamed nickel.
Preferably, the conditions of the isothermal reaction in the step (2) are that the heating temperature is 100 ℃ and the heating time is 15 h.
Preferably, the isothermal reaction condition in the step (3) is that the heating temperature is 80 ℃ and the heating time is 12 h.
Preferably, the placing of the Ni-MOF electrode material in an ethanol solution containing ruthenium chloride trihydrate comprises placing the Ni-MOF material in 20mL of ethanol followed by the addition of 50mg of ruthenium chloride trihydrate.
Preferably, said drying to obtain a Ni-MOF material and said drying to obtain RuO 2 In the loaded Ni-MOF electrode, the drying temperature is 60 ℃ and the drying time is 24 h.
Preferably, the RuO is obtained by reacting at a constant temperature of 80-90 ℃ for 10-15 h, cooling to room temperature, washing with absolute ethyl alcohol and deionized water, and drying 2 In the loaded Ni-MOF electrode material, the washing with absolute ethyl alcohol and deionized water is specifically carried out 5 times by using the absolute ethyl alcohol to centrifugally wash at 8000rpm, and then 5 times by using the deionized water to centrifugally wash at 8000 rpm.
In a second aspect, the invention provides a RuO prepared by the above preparation method 2 The application of the supported Ni-MOF electrode material in synthesizing ammonia by electrocatalytic reduction of nitrate.
Compared with the prior art, the invention has the beneficial effects that:
(1) the RuO in-situ growth method adopts a hydrothermal method to grow RuO in foam nickel with high specific surface area 2 The particle and the synthetic method are simple and can be produced in a quantitative way.
(2) The in-situ growth method deposits electrode materials on the foamed nickel with high specific surface area, provides more active area for electrocatalysis reaction, promotes the interaction between an electrode carrier and a catalyst, and improves the catalytic activity. By constructing Ni-MOF and RuO 2 The interface structure between the ruthenium and the metal effectively improves the atom utilization rate and the metal activity of the ruthenium metal, thereby reducing the cost.
(3) Under higher current density, the selectivity of the synthetic ammonia reaches 100 percent, no nitrite is generated, and the maximum synthetic ammonia yield reaches 1.37mg h -1 cm -2 (0.352mol -1 s -1 cm -2 ) The maximum Faraday Efficiency (FE) is 72.56% at-1.3V vs. Ag/AgCl, and NH is produced by the electrode through continuous 24-hour repeated experiments 4 + Both the rate and the selectivity remained stable.
Drawings
FIG. 1 is RuO prepared according to the present invention 2 A schematic diagram of a process for preparing a supported Ni-MOF electrode (RuNi-MOF);
FIG. 2 shows Ni-MOF and RuO prepared by the present invention 2 Supported Ni-MOF electrodes (RuNi-MOF) with an X-ray diffraction pattern (XRD) with an abscissa of twice the diffraction angle (degree) and an ordinate of the intensity of the diffraction peak (a.u.);
FIG. 3 shows Ni-MOF and RuO prepared by the present invention 2 Scanning Electron Micrographs (SEM) and Transmission Electron Micrographs (TEM) of the supported Ni-MOF electrode (RuNi-MOF);
FIG. 4 shows Ni-MOF and RuO prepared by the present invention 2 XPS spectra of supported Ni-MOF electrodes (RuNi-MOF);
FIG. 5 shows Ni-MOF and RuO prepared by the present invention 2 Linear sweep voltammograms of a supported Ni-MOF electrode (RuNi-MOF) (linear sweep rate: 5mV/s, voltage range: 0.3 to-1.7V vs Ag/AgCl electrode, electrolyte: 0.1mol/L sodium sulfate +50mg/L nitrate nitrogen);
FIG. 6 is a graph of ammonia production performance of Ni-MOF prepared by the invention in electrocatalytic reduction of nitrate to ammonia in 0.1mol/L sodium sulfate +50mg/L nitrate nitrogen electrolyte;
FIG. 7 is RuO prepared according to the present invention 2 Faradaic efficiency and ammonia production performance plots for electrocatalytic reduction of nitrate to ammonia in nitrate nitrogen electrolyte and a repetitive performance plot for the electrical grade of RuNi-MOF with supported Ni-MOF electrodes (RuNi-MOF).
Detailed Description
The invention is further described below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby. The reagents used in the present invention were purchased from the national pharmaceutical group and the nickel foam was purchased from Anhui Zerise technologies, Inc.
Referring to FIG. 1, RuO prepared for the present invention 2 Schematic diagram of the preparation process of supported Ni-MOF electrode (RuNi-MOF). RuO provided by the invention 2 A method for preparing a supported Ni-MOF electrode material, comprising the steps of:
s1, dissolving the terephthalic acid and the nickel chloride hexahydrate in the dimethylformamide to form a homogeneous mixed solution.
According to the invention, the concentration of the terephthalic acid in the mixed solution is preferably 0.06-0.07 mol/L, the concentration of the nickel chloride hexahydrate in the mixed solution is preferably 0.06-0.07 mol/L, and the molar ratio of the terephthalic acid to the nickel chloride hexahydrate is preferably 1: 1.
s2, putting the foamed nickel into the mixed solution, adding a sodium hydroxide solution, stirring uniformly, transferring into a high-pressure reaction kettle, reacting at a constant temperature of 90-100 ℃ for 10-15 h, cooling to room temperature, washing with absolute ethyl alcohol and deionized water, and drying to obtain the Ni-MOF material.
Firstly, cutting the spare foamed nickel into a size of 2cm multiplied by 2cm, pretreating with ethanol for 30min to remove surface impurities, then treating with hydrochloric acid solution for 15min to remove an oxide layer on the surface, finally rinsing with deionized water and ethanol, and drying to obtain the foamed nickel.
According to the invention, the foamed nickel is added into a sodium hydroxide solution, stirred uniformly, transferred into a high-pressure reaction kettle, reacted at a constant temperature of 90-100 ℃ for 10-15 h, wherein the reaction temperature is preferably 100 ℃, the heating time is preferably 15h, cooled to room temperature, washed by absolute ethyl alcohol and deionized water, and dried at 60 ℃ for 24h to obtain the Ni-MOF material.
S3, placing the Ni-MOF material in an ethanol solution containing ruthenium chloride trihydrate, reacting at a constant temperature of 80-90 ℃ for 10-15 h, cooling to room temperature, washing with absolute ethanol and deionized water, and drying to obtain RuO 2 A supported Ni-MOF electrode material.
According to the invention, RuO is grown in situ on foamed nickel with high specific surface area by adopting a hydrothermal method 2 Particles, Ru in ruthenium chloride trihydrate 3+ With Ni in Ni-MOF 2+ Ion exchange takes place and RuO is formed under the reduction of ethanol 2 . Preferably, the Ni-MOF material is put into 20mL of ethanol, 50mg of ruthenium chloride trihydrate is added, the mixture reacts for 12 hours at a constant temperature of 80 ℃, after the mixture is cooled to the room temperature, absolute ethyl alcohol is used for centrifugal cleaning for 5 times at 8000rpm, deionized water is used for centrifugal cleaning for 5 times at 8000rpm, and RuO is obtained by drying 2 A supported Ni-MOF electrode material.
The following examples further illustrate the invention.
Example 1
1mmol of terephthalic acid and 1mmol of nickel chloride hexahydrate were dissolved in 15mL of dimethylformamide to form a homogeneous mixture.
Cutting the spare foamed nickel into 2cm multiplied by 2cm, pretreating with ethanol for 30min to remove surface impurities, then placing into 3.0M HCl solution for treating for 15min to remove an oxide layer on the surface, rinsing with deionized water and ethanol, and finally drying to obtain the foamed nickel.
And (2) putting the foamed nickel into the mixed solution, adding 1mL of 0.4mol/L sodium hydroxide solution, stirring for 10min, transferring the foamed nickel into a high-pressure reaction kettle, reacting at a constant temperature of 100 ℃ for 15h, cooling to room temperature, centrifugally cleaning with absolute ethyl alcohol at 8000rpm for 5 times, centrifugally cleaning with deionized water at 8000rpm for 5 times, and drying at 60 ℃ for 24h to obtain the nickel-loaded MOF electrode material.
Putting the nickel-loaded MOF electrode material into 20mL of ethanol, adding 50mg of ruthenium chloride trihydrate, stirring for 10min, transferring the mixture into a high-pressure reaction kettle, reacting at the constant temperature of 80 ℃ for 12h, cooling to room temperature, rinsing with deionized water and ethanol, and drying at the temperature of 60 ℃ for 24h to obtain RuO 2 Supported Ni-MOF electrodes (denoted as RuNi-MOF).
Application example 1
In a single reaction tank, a three-electrode reaction system is adopted: RuO prepared as in example 1 2 A loaded Ni-MOF electrode (RuNi-MOF) is used as a working electrode, a saturated silver/silver chloride electrode is used as a reference electrode, a platinum sheet electrode is used as a counter electrode, and a three-electrode system is formed for electrochemical test, wherein electrolyte respectively adopts 0.1mol/L sodium sulfate +50mg/L sodium nitrate (calculated by nitrogen), 0.1mol/L sodium sulfate +100mg/L sodium nitrate (calculated by nitrogen) and 0.1mol/L sodium sulfate +200mg/L sodium nitrate (calculated by nitrogen). Before testing, nitrogen is introduced into the electrolyte to remove oxygen in the water body so as to achieve an anaerobic condition, wherein the introduction amount of the nitrogen is 10-20 mL/min, and the purity of the nitrogen is more than 90%.
The reaction is tested by adopting constant voltage, the testing potential is set to be 0.3 to-1.7V relative to a saturated silver/silver chloride electrode, the reaction temperature is 25 ℃, and the tested product is quantitatively analyzed by adopting an ultraviolet spectrophotometry.
Example 2
1mmol of terephthalic acid and 1mmol of nickel chloride hexahydrate were dissolved in 15mL of dimethylformamide to form a homogeneous mixture.
Cutting the spare foamed nickel into 2cm multiplied by 2cm, pretreating with ethanol for 30min to remove surface impurities, then placing into 3.0M HCl solution for treating for 15min to remove an oxide layer on the surface, rinsing with deionized water and ethanol, and finally drying to obtain the foamed nickel.
And (3) putting the foamed nickel into the mixed solution, adding 1mL of 0.4mol/L sodium hydroxide solution, stirring for 10min, transferring the foamed nickel into a high-pressure reaction kettle, reacting at a constant temperature of 100 ℃ for 15h, cooling to room temperature, carrying out centrifugal cleaning on the foamed nickel for 5 times at 8000rpm by using absolute ethyl alcohol, carrying out centrifugal cleaning on the foamed nickel for 5 times at 8000rpm by using deionized water, and drying at 60 ℃ for 24h to obtain the nickel-loaded MOF electrode material.
Putting the nickel-loaded MOF electrode material into 20mL of ethanol, adding 80mg of ruthenium chloride trihydrate, stirring for 10min, transferring the mixture into a high-pressure reaction kettle, reacting at the constant temperature of 80 ℃ for 12h, cooling to room temperature, rinsing with deionized water and ethanol, and drying at the temperature of 60 ℃ for 24h to obtain RuO 2 Supported Ni-MOF electrodes (denoted as RuNi-MOF).
Application example 2
In a single reaction tank, a three-electrode reaction system is adopted: RuO prepared as in example 2 2 A loaded Ni-MOF electrode (RuNi-MOF) is used as a working electrode, a saturated silver/silver chloride electrode is used as a reference electrode, a platinum sheet electrode is used as a counter electrode, and a three-electrode system is formed for electrochemical test, wherein electrolyte respectively adopts 0.1mol/L sodium sulfate +50mg/L sodium nitrate (calculated by nitrogen), 0.1mol/L sodium sulfate +100mg/L sodium nitrate (calculated by nitrogen) and 0.1mol/L sodium sulfate +200mg/L sodium nitrate (calculated by nitrogen). Before testing, nitrogen is introduced into the electrolyte to remove oxygen in the water body so as to achieve an anaerobic condition, wherein the introduction amount of the nitrogen is 10-20 mL/min, and the purity of the nitrogen is more than 90%.
The reaction is tested by adopting constant voltage, the testing potential is set to be 0.3 to-1.7V relative to a saturated silver/silver chloride electrode, the reaction temperature is 25 ℃, and the tested product is quantitatively analyzed by adopting an ultraviolet spectrophotometry.
Comparative example 1
1mmol of terephthalic acid and 1mmol of nickel chloride hexahydrate were dissolved in 15mL of dimethylformamide to form a homogeneous mixture.
Cutting the spare foamed nickel into 2cm multiplied by 2cm, pretreating with ethanol for 30min to remove surface impurities, then placing into 3.0M HCl solution for treating for 15min to remove an oxide layer on the surface, rinsing with deionized water and ethanol, and drying to obtain the foamed nickel.
And (2) putting the foamed nickel into the mixed solution, adding 1mL of 0.4mol/L sodium hydroxide solution, stirring for 10min, transferring the foamed nickel into a high-pressure reaction kettle, reacting at a constant temperature of 100 ℃ for 15h, cooling to room temperature, centrifugally cleaning with absolute ethyl alcohol at 8000rpm for 5 times, centrifugally cleaning with deionized water at 8000rpm for 5 times, and drying at 60 ℃ for 24h to obtain the nickel-loaded MOF (record as Ni-MOF).
Application comparative example 1
In a single reaction tank, a three-electrode reaction system is adopted: the electrochemical test was performed using the Ni-MOF electrode prepared in comparative example 1 as a working electrode, a saturated silver/silver chloride electrode as a reference electrode, and a platinum sheet electrode as a counter electrode, to form a three-electrode system, in which 0.1mol/L sodium sulfate +50mg/L sodium nitrate (in terms of nitrogen), 0.1mol/L sodium sulfate +100mg/L sodium nitrate (in terms of nitrogen), and 0.1mol/L sodium sulfate +200mg/L sodium nitrate (in terms of nitrogen) as electrolytes, respectively. Before testing, nitrogen is introduced into the electrolyte to remove oxygen in the water body so as to achieve an anaerobic condition, wherein the introduction amount of the nitrogen is 10-20 mL/min, and the purity of the nitrogen is more than 90%.
The reaction is tested by adopting constant voltage, the testing potential is set to be 0.3 to-1.7V relative to a saturated silver/silver chloride electrode, the reaction temperature is 25 ℃, and the tested product is quantitatively analyzed by adopting an ultraviolet spectrophotometry.
The electrode structure and application analysis prepared by the embodiment of the invention are as follows:
referring to FIG. 2, RuO prepared for example 1 of the present invention 2 X-ray of supported Ni-MOF electrode (RuNi-MOF) and Ni-MOF electrode prepared in comparative example 1Diffraction Pattern (XRD), with the abscissa being twice the diffraction angle (degree) and the ordinate being the intensity of the diffraction peak (a.u.), it can be seen from FIG. 2 that at 8.9 °, 14.1 °, 15.7 ° and 17.8 °, the (200), (001), (201) (-201) facets of Ni-MOF prepared in comparative example 1, when loaded with a certain amount of RuO 2 While still maintaining the Ni-MOF crystal structure.
Referring to FIG. 3, (a) in FIG. 3 is RuO 2 Scanning electron microscope images of supported Ni-MOF electrode (RuNi-MOF), and (b) and (c) are RuO 2 High-resolution transmission electron microscope picture of supported Ni-MOF electrode (RuNi-MOF), and (d) RuO 2 Elemental mapping of the supported Ni-MOF electrode (RuNi-MOF), as can be seen in FIG. 3, the synthesized RuO 2 The loaded Ni-MOF electrode is a leaf-shaped nano-sheet vertically arranged, and hundreds of nano-sheets are mutually linked like a nano-flower. High resolution Transmission Electron microscopy (HR-TEM) images showed ultrathin structures of Ni-MOF with a lattice spacing of about 1nm, corresponding to the Ni-MOF (200) lattice plane, RuO 2 The cluster diameter is about 3nm and is uniformly distributed on the surface of the Ni-MOF.
Referring to FIG. 4, in FIG. 4, (a) is XPS spectrum of Ni-MOF electric grade prepared in comparative example 1 of the present invention, (b) is RuO prepared in example 1 of the present invention 2 XPS spectra of supported Ni-MOF electrodes (RuNi-MOF), it can be seen from FIG. 4 that both Ni-MOF and RuNi-MOF have two Ni 2+ Characteristic peak of oxidation state. The binding energy of Ni 2p3/2 and Ni 2p1/2 in RuNi-MOF was shifted positively compared to Ni-MOF, indicating the dissipation of electrons on Ni, which is due to the electronic coupling of Ru and Ni atoms. In addition, the peaks at 463.28eV and 485.52eV belong to Ru 3p3/2 and Ru 3p 1/2.
Referring to fig. 5, the rate of current density increase is greater in the presence of nitrate, indicating that the RuNi-MOF electrode has nitrate catalytic activity.
Referring to FIG. 6, the ammonia production performance of the Ni-MOF prepared in comparative example 1 of the present invention in the synthesis of ammonia by electrocatalytic reduction of nitrate in 0.1mol/L sodium sulfate +50mg/L nitrate nitrogen electrolyte is shown. As can be seen from FIG. 6, the synthetic NH of the Ni-MOF electrode scale 4 + Maximum yield of-N, 0.076mg h only at-1.7V vs. Ag/AgCl -1 cm -2 。
See alsoFIG. 7 is a graph showing Faraday efficiency and ammonia production performance of RuNi-MOF electrode in 0.1mol/L sodium sulfate +50mg/L nitrate nitrogen electrolyte for electrocatalytic reduction of nitrate to synthesize ammonia, (b) a graph showing Faraday efficiency and ammonia production performance of RuNi-MOF electrode in 0.1mol/L sodium sulfate +100mg/L nitrate nitrogen electrolyte for electrocatalytic reduction of nitrate to synthesize ammonia, (c) a graph showing Faraday efficiency and ammonia production performance of RuNi-MOF electrode in 0.1mol/L sodium sulfate +200mg/L nitrate nitrogen electrolyte for electrocatalytic reduction of nitrate to synthesize ammonia, and (d) a graph showing repetition performance of RuNi-MOF electrode in 0.1mol/L sodium sulfate +50mg/L nitrate nitrogen electrolyte for electrocatalytic reduction of nitrate to synthesize ammonia. As can be seen from FIG. 7, the RuNi-MOF electrode has high ammonia synthesis performance under different nitrate concentrations and different voltages. Wherein, in 0.1mol/L sodium sulfate +100mg/L nitrate nitrogen electrolyte, NH is synthesized when-1.7V vs. Ag/AgCl 4 + The maximum yield of-N reaches 1.37mg h -1 cm -2 (0.352mol -1 s -1 cm -2 ) (ii) a In 0.1mol/L sodium sulfate +50mg/L nitrate nitrogen electrolyte, the maximum Faraday efficiency was 72.56% at-1.3V vs. Ag/AgCl. Through continuous 24h repeatability experiments, the electrode produces NH 4 + Both the rate and the selectivity remained stable.
The beneficial effects of the invention are that compared with the prior art:
(1) the RuO in-situ growth method adopts a hydrothermal method to grow RuO in foam nickel with high specific surface area 2 The particle and the synthetic method are simple and can be produced in a quantitative way.
(2) The in-situ growth method deposits the electrode material on the foamed nickel with high specific surface area, provides more active area for electrocatalysis reaction, promotes the interaction between the electrode carrier and the catalyst, and improves the catalytic activity. By constructing Ni-MOF and RuO 2 The interface structure between the ruthenium and the metal effectively improves the atom utilization rate and the metal activity of the ruthenium metal, thereby reducing the cost.
(3) Under higher current density, the selectivity of the synthetic ammonia reaches 100 percent, no nitrite is generated, and the maximum synthetic ammonia yield reaches 1.37mg h -1 cm -2 (0.352mol -1 s -1 cm -2 ) Has the highest performance at-1.3V vs. Ag/AgClThe large Faraday Efficiency (FE) is 72.56%, and the electrode produces NH after continuous 24-hour repeated experiments 4 + Both the rate and the selectivity remained stable.
The present applicant has described and illustrated embodiments of the present invention in detail with reference to the accompanying drawings, but it should be understood by those skilled in the art that the above embodiments are merely preferred embodiments of the present invention, and the detailed description is only for the purpose of helping the reader to better understand the spirit of the present invention, and not for limiting the scope of the present invention, and on the contrary, any improvement or modification made based on the spirit of the present invention should fall within the scope of the present invention.
Claims (10)
1. RuO 2 The preparation method of the loaded Ni-MOF electrode material is characterized by comprising the following steps of:
(1) dissolving terephthalic acid and nickel chloride hexahydrate in dimethylformamide to form a homogeneous mixed solution;
(2) putting foamed nickel into the mixed solution, adding a sodium hydroxide solution, stirring uniformly, transferring into a high-pressure reaction kettle, reacting at a constant temperature of 90-100 ℃ for 10-15 h, cooling to room temperature, washing with absolute ethyl alcohol and deionized water, and drying to obtain a Ni-MOF material;
(3) putting the Ni-MOF material into an ethanol solution containing ruthenium chloride trihydrate, reacting at the constant temperature of 80-90 ℃ for 10-15 h, cooling to room temperature, washing with absolute ethyl alcohol and deionized water, and drying to obtain RuO 2 A supported Ni-MOF electrode material.
2. The RuO of claim 1 2 The preparation method of the loaded Ni-MOF electrode material is characterized in that the concentration of terephthalic acid in the mixed solution is 0.06-0.07 mol/L.
3. The RuO of claim 1 2 The preparation method of the loaded Ni-MOF electrode material is characterized in that the concentration of nickel chloride hexahydrate in the mixed solution is 0.06-0.07 mol/L.
4. The RuO of claim 1 2 The preparation method of the loaded Ni-MOF electrode material is characterized in that the preparation step of the foamed nickel in the step (2) comprises the following steps:
cutting the spare foamed nickel into the size of 2cm multiplied by 2 cm;
pretreating with ethanol for 30min to remove surface impurities;
treating with hydrochloric acid solution for 15min to remove the oxide layer on the surface;
rinsing with deionized water and ethanol, and drying to obtain the foamed nickel.
5. The RuO of claim 1 2 The preparation method of the loaded Ni-MOF electrode material is characterized in that the conditions of the constant-temperature reaction in the step (2) are that the heating temperature is 100 ℃ and the heating time is 15 h.
6. The RuO of claim 1 2 The preparation method of the loaded Ni-MOF electrode material is characterized in that the conditions of the constant-temperature reaction in the step (3) are that the heating temperature is 80 ℃ and the heating time is 12 h.
7. The RuO of claim 1 2 A preparation method of a supported Ni-MOF electrode material is characterized in that the Ni-MOF electrode material is placed in an ethanol solution containing ruthenium chloride trihydrate, and comprises the steps of placing the Ni-MOF electrode material in 20mL of ethanol, and adding 50mg of ruthenium chloride trihydrate.
8. The RuO of claim 1 2 A method for preparing a supported Ni-MOF electrode material, characterized in that the drying provides a Ni-MOF material and the drying provides RuO 2 In the loaded Ni-MOF electrode, the drying temperature is 60 ℃ and the drying time is 24 h.
9. The RuO of claim 1 2 The preparation method of the loaded Ni-MOF electrode material is characterized by reacting at a constant temperature of 80-90 ℃ for 10-15 h, cooling to room temperature, and then passing through anhydrous ethyl acetateAfter washing with alcohol and deionized water, drying to obtain RuO 2 In the loaded Ni-MOF electrode material, the washing with absolute ethyl alcohol and deionized water is specifically carried out 5 times by using the absolute ethyl alcohol to centrifugally wash at 8000rpm, and then 5 times by using the deionized water to centrifugally wash at 8000 rpm.
10. RuO produced by the production method according to any one of claims 1 to 9 2 The application of the supported Ni-MOF electrode material in synthesizing ammonia by electrocatalytic reduction of nitrate.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210427970.4A CN114892199A (en) | 2022-04-22 | 2022-04-22 | RuO 2 Preparation method and application of loaded Ni-MOF electrode material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210427970.4A CN114892199A (en) | 2022-04-22 | 2022-04-22 | RuO 2 Preparation method and application of loaded Ni-MOF electrode material |
Publications (1)
Publication Number | Publication Date |
---|---|
CN114892199A true CN114892199A (en) | 2022-08-12 |
Family
ID=82718264
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210427970.4A Withdrawn CN114892199A (en) | 2022-04-22 | 2022-04-22 | RuO 2 Preparation method and application of loaded Ni-MOF electrode material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114892199A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115957822A (en) * | 2023-03-16 | 2023-04-14 | 四川大学 | Ruthenium cluster-loaded metal organic framework artificial enzyme and preparation and application thereof |
-
2022
- 2022-04-22 CN CN202210427970.4A patent/CN114892199A/en not_active Withdrawn
Non-Patent Citations (1)
Title |
---|
JIANGZHOU QIN ET. AL.: "Achieving high selectivity for nitrate electrochemical reduction to ammonia over MOFsupported RuxOy clusters", 《J. MATER. CHEM. A》, vol. 10, pages 3963 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115957822A (en) * | 2023-03-16 | 2023-04-14 | 四川大学 | Ruthenium cluster-loaded metal organic framework artificial enzyme and preparation and application thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN113828300B (en) | Preparation method of metal doped bismuth layered oxide and electrocatalytic reduction of CO 2 Application in (a) | |
CN113437314B (en) | Nitrogen-doped carbon-supported low-content ruthenium and Co 2 Three-function electrocatalyst of P nano particle and preparation method and application thereof | |
CN113403633B (en) | Preparation method of Cu-C-N metal organic framework electrocatalyst for reducing nitrate into ammonia | |
CN111229267B (en) | Supported phosphorus-doped metal oxyhydroxide nanosheet material and preparation method and application thereof | |
CN113529122B (en) | Nickel-organic framework nano-sheet array material and preparation method and application thereof | |
CN114892199A (en) | RuO 2 Preparation method and application of loaded Ni-MOF electrode material | |
CN110629248A (en) | Fe-doped Ni (OH)2Preparation method of/Ni-BDC electrocatalyst | |
CN113699549A (en) | Ruthenium and tin bimetallic oxide electrocatalytic material and preparation method and application thereof | |
CN109267095B (en) | Novel nickel phosphide catalyst and preparation method thereof | |
CN111905819A (en) | Preparation method of two-dimensional NiCoFe-MOF electrocatalyst | |
CN114774983B (en) | Ultra-small Ru nanocluster supported on MoO 3-x Double-function composite material of nano belt and preparation method and application thereof | |
CN114622227B (en) | Nanometer flake nickel-based electrocatalyst, preparation method and application | |
CN112864402B (en) | Preparation and application of oxygen reduction catalyst of Fe-N co-doped mesoporous carbon | |
CN114807981A (en) | High-efficiency synthesis of H 2 O 2 Preparation method and application of Zn-N-C electrocatalyst | |
CN112941542A (en) | Nitrogen-doped porous nanosphere loaded nanoflower-shaped Mo2C composite material and preparation method thereof | |
CN116534920B (en) | Preparation method of sheet SrRuO3 nano catalyst for electrocatalytic hydrogen evolution | |
CN114232020B (en) | Water splitting catalyst and its prepn and application | |
CN113026049B (en) | Two-step solvothermal method for preparing NiFe (CN)5NO-Ni3S2-NF composite catalyst and application thereof | |
CN114959783B (en) | Co grown in situ in N-C framework 4 Preparation method of N quantum dot electrode material | |
CN115747875B (en) | Citric acid doped ferronickel catalyst, preparation method thereof and application thereof in hydrogen production by water electrolysis | |
CN113769769B (en) | Nickel-iron phosphide/graphene/nickel composite material, and preparation method and application thereof | |
CN115491690A (en) | Hydrogen evolution reaction catalyst and preparation method and application thereof | |
CN117512683A (en) | Copper-based nano catalyst with two phases, preparation method thereof and application thereof in electrocatalytic carbon dioxide reduction | |
CN118007170A (en) | Ruthenium-loaded molybdenum carbide catalyst, membrane electrode, and preparation methods and applications thereof | |
CN111939941A (en) | Ruthenium-based catalyst and preparation method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WW01 | Invention patent application withdrawn after publication |
Application publication date: 20220812 |
|
WW01 | Invention patent application withdrawn after publication |