CN115057479B - CoAl (cobalt aluminum alloy) 2 O 4 Preparation method of electrocatalytic material and application of ENRR thereof - Google Patents
CoAl (cobalt aluminum alloy) 2 O 4 Preparation method of electrocatalytic material and application of ENRR thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 43
- 229910002515 CoAl Inorganic materials 0.000 title claims abstract description 33
- 239000003245 coal Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229910000838 Al alloy Inorganic materials 0.000 title claims description 3
- BLJNPOIVYYWHMA-UHFFFAOYSA-N alumane;cobalt Chemical compound [AlH3].[Co] BLJNPOIVYYWHMA-UHFFFAOYSA-N 0.000 title claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000005187 foaming Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 9
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 8
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- CVTZKFWZDBJAHE-UHFFFAOYSA-N [N].N Chemical compound [N].N CVTZKFWZDBJAHE-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910021607 Silver chloride Inorganic materials 0.000 claims 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 10
- 229910052596 spinel Inorganic materials 0.000 abstract description 8
- 239000011029 spinel Substances 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000002341 toxic gas Substances 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 23
- 229910021529 ammonia Inorganic materials 0.000 description 11
- 238000010586 diagram Methods 0.000 description 6
- 241000282414 Homo sapiens Species 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 241000282326 Felis catus Species 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000009620 Haber process Methods 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
-
- 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
- C25B11/073—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
- C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
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Abstract
Spinel CoAl 2 O 4 Preparation method of electrocatalytic material and application of ENRR thereof, belonging to the field of electrocatalytic nitrogen fixation, comprising mechanical mixing of precursors, drying of precursor gel, grinding the obtained foaming precursor, and heating in a muffle furnace at 800 ℃ for 5h to obtain CoAl 2 O 4 And (3) powder. The method is mainly used for preparing the CoAl with better crystallinity and better catalytic effect 2 O 4 Compared with other synthesis methods, the electrocatalytic nitrogen fixation material has the advantages of few used raw materials, simple synthesis process, higher safety, no toxic gas generated in the synthesis process, +2 valence state of Co in the material and excellent catalytic performance for nitrogen reduction.
Description
Technical Field
The invention belongs to the field of preparing ammonia by electrocatalytic reduction of nitrogen, and particularly discloses an electrocatalytic material CoAl for ENRR 2 O 4 Is prepared by the preparation method of (1).
Background
With the continuous development of industry, the excessive use of fossil fuels and non-renewable energy sources greatly pollutes the environment, and thus research on renewable energy sources and clean energy sources is eager. Ammonia gas is an important precursor of industrial products such as agriculture, medicines, explosives and the like, and is used as an important link in nitrogen circulation to promote the exchange of human and natural energy. As a clean renewable energy carrier, the energy density reaches 51kcal g -1 The products of ammonia combustion are mainly nitrogen and water, harmful gases are hardly generated, and the low liquefaction pressure (0.8-1.0 MPa) and the narrower explosion limit not only reduce the cost of the transportation process, but also improve the safety. Therefore, in order to meet the demands of human society development, the development of the Haber-Bosch process has achieved large-scale industrial ammonia production by human beings, but the process needs to be performed at high temperature and high pressure, and a large amount of CO is discharged during the reaction 2 And causes great pollution to the environment. In order to realize the efficient and sustainable development of the human society, a more green and sustainable efficient nitrogen fixation method is to be developed.
Electrocatalytic reduction of nitrogen reactions with N 2 And H 2 Synthesizing NH by taking O as raw material 3 In the process, the raw materials are easy to obtain, the synthesis condition is mild, the equipment is simple, renewable electrons are used as driving force, and the ENRR process does not generate substances harmful to the environment. But N is 2 The molecules have an extremely difficult N.ident.N triple bond to break, with bond energies of up to 941kJ mol -1 And the formation of the key intermediate NNH is limited by the high bond energy of the n≡n triple bond to a limiting step. In addition N 2 The band gap between the highest occupied state and the lowest occupied state of the molecule is wide, so that electrons are difficult to enter pi-reverse bond orbitals to realize activation. Therefore, the design of a novel catalyst to increase NRR is important for electrocatalytic nitrogen reduction. Generally, the catalyst is not only low in synthesis cost but also has good electrical conductivity. The invention synthesizes spinel CoAl by taking cobalt nitrate hexahydrate as a cobalt source and aluminum nitrate nonahydrate as an aluminum source 2 O 4 Nanoparticle and hydrothermal synthesis of CoAl 2 O 4 According to the method, the precursor is synthesized mainly through mechanical stirring, the cost of the used raw materials is low, the experimental process flow is simple, the valence state of Co in the material is +2, and the catalyst has excellent catalytic performance on ENRR and is respectively reflected on excellent ammonia yield and Faraday efficiency.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a method for conveniently and quickly preparing the spinel CoAl for electrocatalytic nitrogen fixation 2 O 4 The method has certain catalytic performance, and the energy consumption for the synthesis of the early-stage material is less, and the process flow is simple.
In order to solve the technical problems, the invention provides a spinel CoAl 2 O 4 The preparation method of the electrocatalytic material comprises the following steps:
(1) Mechanical mixing of the precursor solution: mechanically mixing cobalt nitrate hexahydrate, aluminum nitrate nonahydrate, citric acid and deionized water;
(2) Drying the obtained gel in a baking oven at 120 ℃ for 6 hours to obtain a foaming precursor;
(3) Grinding the foaming precursor into powder, and calcining in a muffle furnace at 800 ℃ for 5 hours to obtain CoAl 2 O 4 A powder;
further, the cobalt nitrate hexahydrate, aluminum nitrate nonahydrate, citric acid and deionized water in the step (1) were used in an amount of 0.9g of aluminum nitrate nonahydrate per 1.75g of cobalt nitrate hexahydrate, respectively, and were mixed in 9ml of 1.5m citric acid solution. The mechanical mixing is to place the mixed solution in a round bottom flask and heat the mixed solution for 5 hours at a constant temperature of 80 ℃ to obtain gel.
Further, the specific drying process in the step (2) is as follows: the gel obtained was placed in an oven and dried at 120 ℃ for 6 hours to obtain a foamed precursor.
The specific conditions of the calcination in the step (3) are as follows: calcining for 5h at 800 ℃ under the air atmosphere.
Spinel CoAl of the invention 2 O 4 Electrocatalytic material for ENRR reactions, i.e. ammonia production with nitrogen, for coating with CoAl 2 O 4 Carbon paper of (2) is a working electrode; ag/Agcl is used as a reference electrode; a platinum mesh electrode is used as a counter electrode; and (3) taking HCl solution (such as 0.1M concentration) as electrolyte, and taking HCl as hydrogen source under the condition of introducing nitrogen, and carrying out nitrogen ammonia production, wherein the potential is set to be-0.1-0.5V vs.
The invention shortens the time required by material synthesis, reduces the energy consumption in the preparation process while ensuring certain catalytic activity of the prepared material, and the obtained material has uniform microstructure and concentrated size distribution (CoAl 2 O 4 The electrocatalytic material spinel structure) can exist stably in the air, and the characteristics help the deep research of the ENRR process.
Drawings
FIG. 1 shows the electrocatalytic material CoAl for ENRR of the present invention 2 O 4 Is a microscopic morphology diagram;
FIG. 2 shows the electrocatalytic material CoAl for ENRR of the present invention 2 O 4 An X-ray diffraction spectrum diagram of (2);
FIG. 3 shows the electrocatalytic material CoAl for ENRR of the present invention 2 O 4 X-ray photoelectron spectroscopy of (2)Intent;
FIG. 4 shows the electrocatalytic material CoAl for ENRR of the present invention 2 O 4 Raman spectrum of (a);
FIG. 5 shows the electrocatalytic material CoAl for ENRR of the present invention 2 O 4 A linear sweep voltammetric schematic of (2);
FIG. 6 shows the electrocatalytic material CoAl for ENRR of the present invention 2 O 4 Is a timing ampere diagram of (a);
FIG. 7 shows the electrocatalytic material CoAl for ENRR of the present invention 2 O 4 Is a schematic of ammonia yield;
FIG. 8 shows the electrocatalytic material CoAl for ENRR of the present invention 2 O 4 Is a schematic diagram of Faraday efficiency;
FIG. 9 is a schematic view showing the structure of an electrolytic cell for ENRR according to the present invention.
Detailed Description
The present invention will be described in further detail by way of the following specific embodiments, but the present invention is not limited to the following examples.
Referring to FIG. 1, an electrocatalytic material CoAl for ENRR is shown 2 O 4 The material consists essentially of spinel nanoparticles.
The preparation method comprises the following steps: 1.75g of cobalt nitrate hexahydrate and 0.9g of aluminum nitrate nonahydrate were mixed in 9ml of a 1.5M citric acid solution, placed in a round bottom flask, magnetically stirred for 5 hours under heating at 80℃and the mixed solution gradually thickened and became gel. The gel was transferred to a reaction vessel and dried in an oven at 120℃for 6 hours to obtain a foaming precursor. Grinding the precursor into powder, placing the powder into a magnetic boat, and placing the magnetic boat into a muffle furnace for calcination, wherein the specific conditions of calcination are as follows: at 800 ℃ for 5 hours, finally obtaining blue CoAl 2 O 4 And (3) powder.
Electrode preparation: weigh 5mg CoAl 2 O 4 Dispersing the powder in a liquid mixed with 20 μl of membrane solution (Nafion), 326 μl of ultrapure water and 654 μl of absolute ethanol, and performing ultrasonic treatment for 1 hr to obtain an ink-like liquid, uniformly coating 20 μl of the ink-like liquid on 1 x 2cm carbon paper, with a coating area of 1cm 2 。
Electrochemical system: to be coated with CoAl 2 O 4 Carbon of (2)Paper is a working electrode; ag/Agcl is used as a reference electrode; a platinum mesh electrode is used as a counter electrode; HCl solution (0.1M concentration) was used as electrolyte.
In the embodiment, the microscopic morphology of the electrode is represented and analyzed by using a scanning electron microscope and a transmission electron microscope
It can be seen in fig. 1 that the material is composed mainly of spinel nanoparticles.
FIG. 2 shows the electrocatalytic material CoAl for ENRR of the present invention 2 O 4 An X-ray diffraction spectrum diagram of (2);
FIG. 3 is a material of the invention CoAl 2 O 4 An X-ray photoelectron spectroscopy schematic of (c);
FIG. 4 is a material of the invention CoAl 2 O 4 Raman spectrum of (a);
FIG. 5 is a schematic view of linear sweep voltammetry of a material of the present invention; the specific experimental parameters are as follows: the initial potential is 0V; the termination potential is-1.8V; the scanning rate is 0.05V/s; the interval between the sampling points is 0.001V; sensitivity is 0.1A/V; the different atmospheres were continuously vented to the cell as shown in FIG. 8 for 30min at a gas flow rate of 30 mL/min. From fig. 5, it can be seen that the current of the material is obviously greater than that of the material in the argon atmosphere in the nitrogen atmosphere, and the material has certain electrocatalytic nitrogen fixation performance.
FIG. 6 is a timing amperometric schematic of the material of the invention; the specific parameters are as follows: the potential settings are-0.1, -0.2, -0.3, -0.4, -0.5V vs. RHE, respectively; the interval between the sampling points is 0.05s; the running time is 7200s; the sensitivity was 0.1A/V. As can be seen from fig. 6, at different potentials, the corresponding currents fluctuate within a small range, which proves that the material has certain catalytic stability.
FIG. 7 is a schematic diagram of ammonia production from the material of the present invention; as can be seen from FIG. 7, the material of the present invention produced up to 23.84 mu g h ammonia at a potential of-0.2V vs. RHE -1 mg cat -1 The material has relatively excellent electrocatalytic ammonia production performance. The calculation formula of the ammonia production amount is as follows:
for ammonia production, the unit is-> Is NH in electrolyte 4 Cl concentration in μg mL -1 The method comprises the steps of carrying out a first treatment on the surface of the V is the volume of the electrolyte, and the unit is mL; t is electrolysis time, and the unit is h; m is m cat The unit is mg, which is the mass of the electrode material.
Figure 8 is a schematic representation of the faraday efficiency of the material of the present invention; as can be seen from FIG. 8, the FE value of the material of the present invention reaches 12.79% at a potential of-0.2V vs. RHE, which proves that the material of the present invention has higher selectivity. The FE calculation formula is as follows:
FE is Faraday efficiency in units of; f is Faraday constant, and its value is 96500C mol -1 The method comprises the steps of carrying out a first treatment on the surface of the Q is the total charge consumption of the electrolysis process, in C.
FIG. 9 is a schematic view of the structure of an electrolytic cell of the material of the present invention.
The foregoing is merely exemplary embodiments of the present invention, and specific structures and features that are well known in the art are not described in detail herein. It should be noted that modifications and improvements can be made by those skilled in the art without departing from the structure of the present invention, and these should also be considered as the scope of the present invention, which does not affect the effect of the implementation of the present invention and the utility of the patent.
Claims (2)
1. CoAl (cobalt aluminum alloy) 2 O 4 Use of electrocatalytic material for ENRR reactions to coat with CoAl 2 O 4 Carbon paper of (2) is a working electrode; ag/AgCl is used as a reference electrode; a platinum mesh electrode is used as a counter electrode; taking HCl solution as electrolyte, taking HCl as hydrogen source under the condition of introducing nitrogen, and carrying out nitrogen ammonia production, wherein the potential is set to be-0.1-0.5V vs. RHE;
wherein CoAl 2 O 4 The preparation method of the electrocatalytic material comprises the following steps:
mechanical mixing of the precursor solution: mechanically mixing cobalt nitrate hexahydrate, aluminum nitrate nonahydrate, citric acid and deionized water;
drying the obtained gel in a baking oven at 120 ℃ for 6 hours to obtain a foaming precursor;
grinding the foaming precursor into powder, and calcining in a muffle furnace at 800 ℃ for 5 hours to obtain CoAl 2 O 4 And (3) powder.
2. The use according to claim 1, wherein the cobalt nitrate hexahydrate, aluminum nitrate nonahydrate, citric acid and deionized water of step (1) are used in an amount of 0.9g of aluminum nitrate nonahydrate per 1.75g of cobalt nitrate hexahydrate, respectively, mixed in 9ml of 1.5m citric acid solution; the mechanical mixing is to place the mixed solution in a round bottom flask and heat the mixed solution for 5 hours at a constant temperature of 80 ℃ to obtain gel.
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| Title |
|---|
| electrochemical synthesis of ammonia from nitrogen catalyzed by CoMoO4 nanorods under ambient conditions;Yizhen Zhang;Journal of Materials Chemistry A;第5060-5066页 * |
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