CN118173801A - Preparation method of N-NiCu@C electro-hydrogenation catalyst - Google Patents
Preparation method of N-NiCu@C electro-hydrogenation catalyst Download PDFInfo
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- 229910003322 NiCu Inorganic materials 0.000 title claims abstract description 58
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 239000010949 copper Substances 0.000 claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 17
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 15
- 230000003647 oxidation Effects 0.000 claims abstract description 15
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 10
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 10
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 10
- 239000000446 fuel Substances 0.000 claims abstract description 10
- 239000013110 organic ligand Substances 0.000 claims abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 239000010411 electrocatalyst Substances 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 30
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical group O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical group O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 10
- 239000001301 oxygen Substances 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 35
- 239000000463 material Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000012621 metal-organic framework Substances 0.000 description 8
- 229910014291 N—Cu Inorganic materials 0.000 description 6
- 239000003446 ligand Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000010718 Oxidation Activity Effects 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000013148 Cu-BTC MOF Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000005121 nitriding Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- NOSIKKRVQUQXEJ-UHFFFAOYSA-H tricopper;benzene-1,3,5-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1.[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 NOSIKKRVQUQXEJ-UHFFFAOYSA-H 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 101100317222 Borrelia hermsii vsp3 gene Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 240000007789 Pinus pinea Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical class [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention discloses a preparation method of an N-NiCu@C electro-hydrogen oxidation catalyst, which belongs to the field of hydrogen-oxygen fuel cells, wherein a nickel source and a copper source are combined with an organic ligand to obtain a NiCu-BTC precursor, and the NiCu-BTC precursor is calcined with ammonium bicarbonate to obtain the N-NiCu@C electro-hydrogen oxidation catalyst which has excellent electro-catalytic hydrogen oxidation performance under alkaline conditions, is superior to a commercial Pt/C catalyst, has good long-cycle stability, and fully shows great potential of the N-NiCu@C electro-hydrogen oxidation catalyst in the application aspect of hydrogen-oxygen fuel cells.
Description
Technical Field
The invention belongs to the technical field of hydrogen-oxygen fuel cells, and particularly relates to a preparation method of an N-NiCu@C electro-hydrogenation catalyst.
Background
Hydrogen-oxygen fuel cell technology is considered to be a key to the promotion of low hydrocarbon economy due to its excellent hydrogen utilization efficiency and environmental emissions. Among various fuel cells, the Anion Exchange Membrane Fuel Cell (AEMFCs) has attracted attention because of its ability to operate in a less corrosive alkaline environment and its advantage of realizing a high efficiency cathode using an inexpensive non-noble metal catalyst. The anodic oxidation reaction (HOR) as an integral part of AEMFCs affects AEMFCs performance. However, even advanced Pt/C catalysts have unsatisfactory HOR performance in alkaline environments. The kinetics of the anodic oxidation reaction (HOR) in AEMFC is greatly reduced when transitioning from an acidic medium to an alkaline medium. Therefore, the development of efficient and economical environmentally friendly non-noble metal-based HOR electrocatalysts in alkaline media remains a key goal to advance AEMFC.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of an N-NiCu@C electro-hydrogenation catalyst.
In order to achieve the above purpose, the present invention provides the following technical solutions:
one of the technical schemes of the invention is as follows:
The preparation method of the N-NiCu@C electro-hydrogenation catalyst comprises the steps of combining a nickel source and a copper source with an organic ligand to obtain a NiCu-BTC precursor, and calcining the NiCu-BTC precursor and ammonium bicarbonate to obtain the N-NiCu@C electro-hydrogenation catalyst.
Further, the nickel source is nickel chloride hexahydrate, the copper source is copper chloride dihydrate, and the organic ligand is trimesic acid (C 9H6O6).
The trimesic acid serving as an organic ligand has the main function of constructing a Metal Organic Framework (MOFs) structure in the electrocatalyst, and the influence of the trimesic acid on the performance of the electrocatalyst is mainly reflected in improving the catalytic activity, dynamics and stability. Trimesic acid is a relatively common organic ligand that coordinates to metal ions or metal clusters to form network structured crystals when preparing Metal Organic Frameworks (MOFs). The porous crystalline material exhibits excellent properties in the catalytic field due to its special structural characteristics. For example, by using the trimesic acid anchoring strategy, small-sized nickel iron layered double hydroxides can be prepared, which are superior to commercial catalysts in terms of kinetics, activity and stability. In the selection of other organic ligands, however, it is necessary to consider the structure, functional group, coordination ability with the metal center, and other factors of the ligand. Different organic ligands may cause different metal-organic framework structures to be formed, and further influence the key parameters such as the porosity, the surface property, the catalytic activity and the like of the material. In addition, the molar ratio of Ni to Cu, the introduction of an N source (ammonium bicarbonate) and the calcination temperature are also key technical characteristics affecting the N-NiCu@C electro-hydrogenation catalyst of the invention.
Further, the preparation method of the NiCu-BTC precursor comprises the following steps:
(1) Stirring and dissolving nickel chloride hexahydrate and copper chloride dihydrate in a mixed solution of ethanol and deionized water to form a solution A;
(2) Dissolving trimesic acid in ethanol, and then adding sodium hydroxide aqueous solution to form solution B;
(3) And adding the solution B into the solution A, stirring, standing, and centrifugally drying to obtain the NiCu-BTC precursor.
Further, the aqueous sodium hydroxide solution was an aqueous solution containing 6mmol of sodium hydroxide. This operation is to control the pH of the solution, thereby creating a suitable reaction environment.
Further, the molar ratio of the nickel chloride hexahydrate, the copper chloride dihydrate and the trimesic acid is 3:0.3:2.
Further, the molar ratio of nickel to copper was 10:1.
Further, in the step (1), the volume ratio of the ethanol to the deionized water is 1:1.
Further, the solution B is added into the solution A in a dropwise manner, stirred for 10min, then kept stand for 24h, and centrifugally dried to obtain the NiCu-BTC precursor. Standing provides a stable environment for chemical reactions, facilitating nucleation and growth of precipitated species. The process can make the size and shape of the generated solid particles more uniform, and improve the quality of the product.
Further, the mass ratio of the NiCu-BTC precursor to the ammonium bicarbonate is 100:1. The effect of calcination with ammonium bicarbonate is to incorporate a small amount of N in a variety of ways, such as calcination directly under an ammonia atmosphere, but the process does not allow easy control of the amount of doping. The N-doped mode is novel and the doping amount is easier to control.
Further, the calcination is performed in a mixed atmosphere of hydrogen and argon. The volume ratio of hydrogen to argon is 5:95. The hydrogen has a reducing effect and can reduce the Ni source and the Cu source into simple substance states.
Further, the calcination temperature was 400℃and the time was 2 hours.
The second technical scheme of the invention is as follows:
The invention also provides the N-NiCu@C electro-hydrogenation catalyst prepared by the preparation method.
The third technical scheme of the invention:
The invention also provides an application of the N-NiCu@C electro-catalyst in preparing an oxyhydrogen fuel cell, for example, an alkaline exchange membrane fuel cell can be prepared.
Compared with the prior art, the invention has the following advantages and technical effects:
1. The preparation method is novel and simple, and the prepared N-NiCu@C electro-hydrogen oxidation catalyst has excellent electro-catalytic hydrogen oxidation performance under alkaline conditions, is superior to a commercial Pt/C catalyst, and fully shows great potential in the application of hydrogen-oxygen fuel cells.
2. The N-NiCu@C hydrogen oxidation electrocatalyst is a non-noble metal-based HOR electrocatalyst, has low price and wide raw materials, and is beneficial to large-scale commercialization application. The phase structure after alloying can better regulate and control the electron density of metal, expose more active sites, and further improve the electrocatalytic activity of HOR.
3. The invention explores the performance difference of N-doped and N-undoped electro-hydrogenation catalysts, and the N-doped N-NiCu@C electro-hydrogenation catalyst has the advantages that the N-doped N-NiCu@C electro-hydrogenation catalyst can effectively manipulate the electronic structure of a NiCu metal center, reduce charge transfer resistance and improve conductivity, thereby accelerating HOR reaction kinetics.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:
FIG. 1 is an X-ray powder diffraction pattern of the N-NiCu@C electro-catalyst prepared in example 1 and the N-Ni@C electro-catalyst prepared in comparative example 1 and the N-Cu@C electro-catalyst prepared in comparative example 2.
FIG. 2a is a scanning electron microscope picture of the N-Ni@C electrocatalyst prepared in comparative example 1; b is a scanning electron microscope picture of the N-Cu@C electrocatalyst prepared in comparative example 2; c is a scanning electron microscope picture of the N-NiCu@C electro-hydrogenation catalyst prepared in example 1.
FIG. 3 is a graph showing the comparative electrocatalytic performance of the N-NiCu@C electrocatalyst prepared in example 1 and comparative examples 6-8 at different calcination temperatures, wherein a is a linear scan curve of electrocatalytic hydrogenation under alkaline conditions; b is Tafel image; c is a micropolarized region fitting curve; d is a summary graph of performance parameters of the N-NiCu@C electro-hydrogenation catalyst under alkaline conditions at different calcination temperatures.
FIG. 4 is a graph showing the comparative electrocatalytic performance of N-NiCu@C electrocatalysts prepared in example 1 and comparative examples 9-12 at different NiCu ratios (molar ratios), wherein a is a linear scan curve of electrocatalytic hydrogenation under alkaline conditions; b is Tafel image; c is a micropolarization region fitting curve, and d is a summary graph of performance parameters of the N-NiCu@C electro-hydrogenation catalyst under alkaline conditions at different NiCu ratios (molar ratios).
FIG. 5 is a graph of HOR linear scans for example 1 (N-NiCu@C) and comparative example 4 (N-NiCu@C (no C 9H6O6)).
FIG. 6 shows the electrochemical performance of the materials prepared in example 1, comparative examples 1-3, and commercial Pt/C, where a is the linear scan curve for electrocatalytic hydrogen oxidation under alkaline conditions; b is Tafel image.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The room temperature in the examples of the present invention was calculated as 25.+ -. 2 ℃ unless otherwise specified.
The raw materials used in the examples of the present invention are all commercially available.
The technical scheme of the invention is further described by the following examples.
Example 1
A preparation method of an N-NiCu@C electro-hydrogenation catalyst comprises the following steps:
(1) Preparation of NiCu-BTC precursor using MOF-assisted strategy: 3mmol of nickel chloride hexahydrate and 0.3mmol of copper chloride dihydrate were added to a mixed solution consisting of 25mL of ethanol and 25mL of deionized water to form solution A; 2mmol of trimesic acid is dissolved in 10mL of ethanol solution, then 10mL of aqueous solution containing 6mmol of sodium hydroxide is added, stirring is carried out uniformly to form solution B, solution B is added into solution A in a dropwise manner, stirring is carried out for 10min, then standing is carried out at room temperature for 24h, centrifugation and washing are carried out for three times, and drying is carried out at 60 ℃ for overnight, thus obtaining NiCu-BTC precursor.
(2) Nitriding: 100g of NiCu-BTC precursor and 1g of ammonium bicarbonate are weighed, heated to 400 ℃ in a mixed atmosphere of hydrogen and argon (the volume ratio is 5:95), kept for 2 hours, and naturally cooled to room temperature to obtain the N-NiCu@C electro-hydrogenation catalyst, which is marked as N-Ni 10Cu1 @C.
Comparative example 1 preparation of N-Ni@C electrocatalyst
(1) Preparation of Ni-BTC precursor using MOF-assisted strategy: 3.3mmol of nickel chloride hexahydrate was added to a mixed solution consisting of 25mL of ethanol and 25mL of deionized water to form solution a; 2mmol of trimesic acid is dissolved in 10mL of ethanol solution, then 10mL of aqueous solution containing 6mmol of sodium hydroxide is added, stirring is carried out uniformly to form solution B, solution B is added into solution A in a dropwise manner, stirring is carried out for 10min, then standing is carried out at room temperature for 24 hours, centrifugation and washing are carried out three times, and drying is carried out at 60 ℃ for overnight, thus obtaining the Ni-BTC precursor.
(2) Nitriding: 100g of Ni-BTC precursor and 1g of ammonium bicarbonate are weighed, heated to 400 ℃ in a mixed atmosphere of hydrogen and argon (the volume ratio is 5:95), kept for 2 hours, and naturally cooled to room temperature to obtain the N-Ni@C electrocatalyst.
Comparative example 2 preparation of N-Cu@C electrocatalyst
(1) Preparing a Cu-BTC precursor by adopting a MOF-auxiliary strategy: adding 3.3mmol of copper chloride dihydrate to a mixed solution consisting of 25mL of ethanol and 25mL of deionized water to form a solution A; 2mmol of trimesic acid is dissolved in 10mL of ethanol solution, then 10mL of aqueous solution containing 6mmol of sodium hydroxide is added, stirring is carried out uniformly to form solution B, solution B is added into solution A in a dropwise manner, stirring is carried out for 10min, then standing is carried out at room temperature for 24 hours, centrifugation and washing are carried out three times, and drying is carried out at 60 ℃ for overnight, thus obtaining Cu-BTC precursor.
(2) Nitriding: 100g of Cu-BTC precursor and 1g of ammonium bicarbonate are weighed, heated to 400 ℃ in a mixed atmosphere of hydrogen and argon (the volume ratio is 5:95), kept for 2 hours, and naturally cooled to room temperature to obtain the N-Cu@C electrocatalyst.
Comparative example 3 preparation of NiCu@C electrocatalyst
(1) As in example 1.
(2) And (3) pyrolysis treatment: 100g of NiCu-BTC precursor is weighed, heated to 400 ℃ in a mixed atmosphere (volume ratio of hydrogen to argon is 5:95), kept for 2 hours, and naturally cooled to room temperature to obtain the NiCu@C electrocatalyst.
Comparative example 4
The procedure is as in example 1, except that no ligand (trimesic acid) is added during the preparation.
Comparative example 5
The procedure is as in example 1, except that step (2) is calcined in an argon atmosphere.
Comparative example 6
The procedure of example 1 was followed except that the calcination temperature was 350℃and the temperature was increased to 350℃in step (2), to obtain an N-NiCu@C electrocatalyst.
Comparative example 7
The procedure of example 1 was followed except that the calcination temperature was 380℃to obtain an N-NiCu@C electrocatalyst.
Comparative example 8
The procedure of example 1 was followed except that the calcination temperature was 450℃to obtain an N-NiCu@C electrocatalyst.
Comparative example 9
The difference from example 1 was only that the molar ratio of Ni to Cu was 1:1, yielding an N-Ni 1Cu1 @ C electrocatalyst for hydrogen oxidation.
Comparative example 10
The difference from example 1 was only that the molar ratio of Ni to Cu was 5:1, yielding an N-Ni 5Cu1 @ C electrocatalyst for hydrogen oxidation.
Comparative example 11
The difference from example 1 was only that the molar ratio of Ni to Cu was 15:1, yielding an N-Ni 15Cu1 @ C electrocatalyst for hydrogen oxidation.
Comparative example 12
The difference from example 1 is that the molar ratio of Ni to Cu is 20:1, and the N-Ni20Cu1@C electro-catalyst is obtained.
The X-ray powder diffraction patterns of the N-NiCu@C electro-catalyst prepared in example 1 and the N-Ni@C electro-catalyst prepared in comparative example 1 and the N-Cu@C electro-catalyst prepared in comparative example 2 are shown in FIG. 1. As can be seen from FIG. 1, the X-ray diffraction (XRD) pattern of N-NiCu@C detects diffraction peaks of Ni (PDF#87-0712) and Cu (PDF#85-1326) species. Furthermore, the N-nicu@c exhibited a slightly positive shift compared to the single N-ni@c sample, confirming the successful preparation of the nickel-copper alloy structure.
FIG. 2a is a scanning electron microscope picture of the N-Ni@C electrocatalyst prepared in comparative example 1; b is a scanning electron microscope picture of the N-Cu@C electrocatalyst prepared in comparative example 2; c is a scanning electron microscope picture of the N-NiCu@C electro-hydrogenation catalyst prepared in example 1. As can be seen from fig. 2a and b, the morphology of N-ni@c and N-cu@c is a floral rod shape and a cubic shape, respectively; from fig. 2c, it can be seen that N-nicu@c presents a rod-shaped cluster morphology in which clusters are packed together, the surface of which is uniformly attached with polyhedrons, again confirming the successful preparation of NiCu alloy.
Effect example 1 electrochemical test
Electrochemical hydroxide tests were performed on electrochemical workstations (Shanghai CHI 760E and U.S. PINE) using a three-electrode system. 3mg of the materials prepared in example 1, comparative examples 1 to 3, comparative examples 6 to 8 and comparative examples 9 to 12 and commercial Pt/C (catalyst) were dispersed in a mixed solution of 245. Mu.L of deionized water, 245. Mu.L of isopropyl alcohol and 5. Mu.L of Nafion, and sonicated for 1 hour to obtain uniformly dispersed catalyst ink, which was dropped on a glassy carbon electrode having a diameter of 5mm, and dried at room temperature to obtain different working electrodes. Meanwhile, a carbon rod is used as a counter electrode, a saturated silver-silver chloride electrode is used as a reference electrode, a 0.1mol/L potassium hydroxide solution saturated by H 2 is used as electrolyte, and the test temperature is 25 ℃. Standard hydrogen electrode (RHE) voltage calibration was performed in a standard three electrode system by a Biologic VMP3 multichannel electrochemical workstation.
Reference electrode correction method: two cleaned Pt plates are used as a working electrode and a counter electrode respectively, and Ag/AgCl (saturated KCl solution) is used as a reference electrode for cyclic voltammetry test, and the cyclic voltammetry test is carried out in high-purity H 2 -saturated potassium hydroxide electrolyte with the concentration of 0.1 mol/L. The current-voltage sweep was run at a sweep rate of 5mV/s, taking the average of the two potentials at the zero crossing of the current as the thermodynamic potential of the hydrogen electrode reaction. The pH of the 0.1mol/L potassium hydroxide solution was 12.9, E (RHE) =E (Ag/AgCl) +0.197+0.059pH=E (Ag/AgCl) +0.9581.
The comparative graph of the electrocatalytic performance of the N-NiCu@C electrocatalyst prepared in example 1 and comparative examples 6-8 at different calcination temperatures is shown in FIG. 3. As can be seen from fig. 3a, the N-nicu@c electrocatalyst prepared at 400 ℃ in example 1 has the highest anode current density compared to the other temperature calcined samples, and exhibits excellent hydrogen oxidation activity, confirming that the optimum calcination temperature of the N-nicu@c electrocatalyst prepared according to the invention is 400 ℃. The Tafel image of FIG. 3 b and the micropolarization fitted curve of FIG. 3 c, respectively, intuitively show that the N-NiCu@C electrocatalyst for hydrogen oxidation at a calcination temperature of 400 ℃ has the highest kinetic current density and better intrinsic activity at 50 mV; FIG. 3d summarizes the performance parameters of the N-NiCu@C electrocatalyst under alkaline conditions at different calcination temperatures, further revealing that the N-NiCu@C electrocatalyst prepared in example 1 has excellent activity for hydrogen oxidation at a calcination temperature of 400 ℃.
The comparative graph of the electrocatalytic performance of the N-NiCu@C electrocatalysts prepared in example 1 and comparative examples 9-12 at different NiCu ratios (molar ratios) is shown in FIG. 4. As can be seen from FIG. 4a, the N-Ni 10Cu1 @C prepared at a Ni:Cu molar ratio of 10:1 has the highest anode current density, shows excellent hydrogen oxidation activity, and proves that the optimal NiCu material ratio (molar ratio) of the N-NiCu@C prepared by the method is 10:1; the Tafel image of FIG. 4b and the micropolarization fit curve of FIG. 4C, respectively, intuitively show that the N-Ni 10Cu1 @C prepared by the invention has the highest kinetic current density and optimal intrinsic activity at 50 mV; in FIG. 4 d, the performance parameters of the N-NiCu@C electro-hydrogenation catalyst under alkaline conditions are summarized in different NiCu material ratios (molar ratios), and further, the N-Ni 10Cu1 @C electro-hydrogenation catalyst prepared in example 1 is disclosed to have excellent hydrogen oxidation activity.
The HOR linear scan graphs of example 1 and comparative example 4 are shown in fig. 5. It can be seen that the samples with added ligand showed superior electrocatalytic properties than the samples without ligand. This is because the presence of the ligand can form a MOF structure, forming a carbon skeleton after calcination, can enhance the stability of the sample, and also change the activity of the catalyst.
The electrochemical performance of the materials prepared in inventive example 1, comparative examples 1-3 and commercial Pt/C is shown in FIG. 6, where a is the electrocatalytic linear scan curve of different materials in 0.1mol/L KOH solution saturated with H 2 and b is the HOR polarization curve of the materials prepared in example 1 and commercial Pt/C before and after 1000 cycles in 0.1mol/L KOH saturated with H 2. As can be seen from fig. 6a, the N-nicu@c electro-hydrogenation catalyst prepared in example 1 had the highest anode current density, confirming that the N-nicu@c electro-hydrogenation catalyst prepared in example 1 had excellent hydrogen oxidation activity. As can be seen from FIG. 6 b, the N-NiCu@C electro-catalyst prepared in example 1 has no obvious degradation after 1000 cycles, and the degradation of the commercial Pt/C catalyst is obvious in the contrary, so that the N-NiCu@C electro-catalyst prepared in the invention has excellent long-term stability.
In conclusion, the N-NiCu@C electro-oxidation catalyst prepared by the method disclosed by the invention has the electro-catalytic hydrogen oxidation performance which is comparable with or even surpassed that of commercial Pt/C under alkaline conditions; meanwhile, as a non-noble metal-based HOR electrocatalyst, the catalyst has low price and wide raw materials, and is favorable for large-scale commercialization; the phase structure after alloying can better regulate and control the electron density of metal, expose more active sites, and further improve the electrocatalytic activity of HOR.
The present application is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present application are intended to be included in the scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.
Claims (10)
1. A preparation method of an N-NiCu@C electro-hydrogenation catalyst is characterized in that a NiCu-BTC precursor is obtained after a nickel source and a copper source are combined with an organic ligand, and the NiCu-BTC precursor and ammonium bicarbonate are calcined to obtain the N-NiCu@C electro-hydrogenation catalyst.
2. The method for preparing an N-nicu@c electrocatalyst according to claim 1, wherein the nickel source is nickel chloride hexahydrate, the copper source is copper chloride dihydrate, and the organic ligand is trimesic acid.
3. The method for preparing the N-NiCu@C electro-hydrogenation catalyst according to claim 2, wherein the method for preparing the NiCu-BTC precursor is as follows:
(1) Stirring and dissolving nickel chloride hexahydrate and copper chloride dihydrate in a mixed solution of ethanol and deionized water to form a solution A;
(2) Dissolving trimesic acid in ethanol, and then adding sodium hydroxide aqueous solution to form solution B;
(3) And adding the solution B into the solution A, stirring, standing, and centrifugally drying to obtain the NiCu-BTC precursor.
4. The method for preparing the N-NiCu@C electro-hydrogenation catalyst according to claim 3, wherein the molar ratio of the nickel chloride hexahydrate to the copper chloride dihydrate to the trimesic acid is 3:0.3:2.
5. The method for preparing an N-NiCu@C electrocatalyst according to claim 3, wherein in step (1), the volume ratio of ethanol to deionized water is 1:1.
6. The method for preparing the N-NiCu@C electro-hydrogenation catalyst according to claim 1, wherein the mass ratio of the NiCu-BTC precursor to the ammonium bicarbonate is 100:1.
7. The method for preparing an N-nicu@c electrocatalyst according to claim 1, wherein the calcination is performed in a mixed atmosphere of hydrogen and argon.
8. The method for preparing the N-NiCu@C electro-hydrogenation catalyst according to claim 1, wherein the calcining temperature is 400 ℃ and the time is 2 hours.
9. An N-nicu@c electrocatalyst for hydrogen oxidation, characterized by being prepared according to the preparation method of any one of claims 1 to 8.
10. Use of the N-nicu@c electrocatalyst according to claim 9 for the preparation of an oxyhydrogen fuel cell.
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