CN114807973A - Cerium-modified nickel-based catalyst and preparation method and application thereof - Google Patents
Cerium-modified nickel-based catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN114807973A CN114807973A CN202210608291.7A CN202210608291A CN114807973A CN 114807973 A CN114807973 A CN 114807973A CN 202210608291 A CN202210608291 A CN 202210608291A CN 114807973 A CN114807973 A CN 114807973A
- Authority
- CN
- China
- Prior art keywords
- nickel
- cerium
- based catalyst
- catalyst material
- reaction
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 150000002815 nickel Chemical class 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 69
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 69
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 34
- 239000002243 precursor Substances 0.000 claims abstract description 24
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims abstract description 22
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 13
- 239000003792 electrolyte Substances 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004070 electrodeposition Methods 0.000 claims abstract description 9
- 230000009471 action Effects 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 22
- 239000002135 nanosheet Substances 0.000 claims description 15
- 230000035484 reaction time Effects 0.000 claims description 14
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 8
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 4
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- -1 cerium modified nickel Chemical class 0.000 abstract description 17
- 230000004888 barrier function Effects 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000001257 hydrogen Substances 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229910052573 porcelain Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 238000011534 incubation Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 2
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 150000004771 selenides Chemical class 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper 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
- 230000032798 delamination Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003624 transition metals Chemical class 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
-
- 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
- C25B11/067—Inorganic compound e.g. ITO, silica or titania
-
- 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
Abstract
The invention discloses a cerium modified nickel-based catalyst, a preparation method and application thereof, wherein the catalyst is loaded with CeO 2 Ni of (2) 3 S1, carrying out hydrothermal reaction on a nickel salt serving as a raw material and a conductive substrate serving as a carrier under the action of a structure directing agent to obtain a nickel hydroxide precursor; s2, calcining the nickel hydroxide precursor in a nitrogen-containing atmosphere to form a nickel-based catalyst material; s3, placing the nickel-based catalyst material in cerium-containing electrolyte for electrodeposition reaction to obtain the cerium-modified nickel-based catalyst material, wherein the number of active sites and the electronic structure on the surface of the material can be adjusted, and the cerium-modified nickel-based catalyst material has low resistance, low energy barrier, high anode catalytic performance and high stabilityQualitative characteristics.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a cerium-modified nickel-based catalyst and a preparation method and application thereof.
Background
Traditional fossil fuels are still the main energy supply objects, but the environmental problems caused by the combustion of the fossil fuels seriously affect the global environment, so scientists are dedicated to searching renewable clean fuels to replace the fossil fuels, and the hydrogen is taken as the energy source of automobiles to prevent the emission of carbon dioxide in tail gas because the product after the combustion of the hydrogen is only water. The production and conversion of hydrogen energy into a hot problem for the research of scientists in recent years in order to develop and utilize hydrogen energy reasonably and efficiently. Electrocatalytic decomposition of water is considered to be the fastest, safest, greenest sustainable method to produce high purity hydrogen, and also an indirect way of storing energy on a large scale.
The preparation of hydrogen energy as secondary energy not only needs to consume a large amount of energy, but also has low efficiency, and the hydrogen production by electrolyzing water is considered as a practical pollution-free hydrogen production method due to the characteristics of sustainability and simple operation, and is widely concerned. The electrolysis of water with Hydrogen Evolution Reaction (HER) at the cathode and Oxygen Evolution Reaction (OER) at the anode plays an important role in the conversion of water to hydrogen. The overpotential required by the reaction can be effectively reduced under the action of the catalyst, so that the hydrogen production efficiency is improved.
In the electrocatalytic water decomposition reaction, a common catalyst consists of precious metals such as Pt, Ru and Ir, and alloys and compounds thereof, but the high cost and natural scarcity hinder the wider application, so that the development of an economical, stable and efficient novel catalyst is urgently needed. In recent years, with the rapid emergence of the field of electrocatalysis, non-noble metal catalysts such as transition metal chalcogenides, nitrides, carbides, selenides and phosphides have brought new opportunities to this field.
However, in the electrocatalytic water decomposition reaction of the above non-metal catalyst, the hydrogen production efficiency is often limited by the slower dynamic process of the anode reaction, thereby affecting the overall hydrogen production efficiency.
Disclosure of Invention
The invention aims to provide a cerium-modified nickel-based catalyst and a preparation method and application thereof, and the efficiency of water electrolysis is improved.
In order to achieve the technical purpose, the following technical scheme is adopted in the application:
in a first aspect,the application provides a cerium-modified nickel-based catalyst material which is loaded with CeO 2 Ni of (2) 3 N nano-sheet.
In a second aspect, the present application provides a method for preparing a cerium-modified nickel-based catalyst material, comprising the steps of:
s1, taking nickel salt as a raw material, taking a conductive substrate as a carrier, and carrying out hydrothermal reaction under the action of a structure directing agent to obtain a nickel hydroxide precursor;
s2, calcining the nickel hydroxide precursor in a nitrogen-containing atmosphere to form a nickel-based catalyst material;
and S3, placing the nickel-based catalyst material in cerium-containing electrolyte, and performing electrodeposition reaction to obtain the cerium-modified nickel-based catalyst material.
Preferably, the structure directing agent is a mixture of urea and ammonium fluoride.
Preferably, the molar ratio of the nickel salt, the urea and the ammonium fluoride is 1-4:5-10: 2-5.
Preferably, the nickel salt comprises one or more of nickel nitrate, nickel chloride, nickel phosphide, nickel bromide and nickel sulfate.
Preferably, the cerium-containing electrolyte comprises one or more of a cerium nitrate solution, a cerium chloride solution and a cerium sulfate solution.
Preferably, in step S1, the hydrothermal reaction is carried out at a temperature of 90-200 ℃ for a time of 4-24 hours.
Preferably, in step S2, the temperature rise rate of the calcination is 1-25 deg.C/min, the final temperature is 150 deg.C-700 deg.C, and the heat preservation time is 20-360 min.
Preferably, in step S3, the voltage of the electrodeposition reaction is 0.05-10V, and the reaction time is 1-30 h.
In a third aspect, the present application provides a use of a cerium-modified nickel-based catalyst material as an anode electrode in electrocatalytic oxygen evolution.
The invention has the beneficial effects that:
1. the cerium-modified nickel-based catalyst material is obtained by depositing cerium on a nickel nitride nano-sheet by combining a hydrothermal method, chemical vapor deposition and an electrodeposition technology, the number of active sites and the electronic structure on the surface of the material can be adjusted, and the material has the characteristics of low resistance, low energy barrier, high anode catalytic performance and high stability;
2. the cerium-modified nickel-based catalyst material obtained by the application increases the activity of the catalyst and the electron transmission performance of the material in the oxygen evolution reaction, promotes the generation of a dynamic process, and improves the water electrolysis efficiency;
3. the preparation method is simple in preparation process, low in cost and suitable for large-scale production.
Drawings
FIG. 1 is a graph of oxygen evolution polarization for different electrocatalytic materials.
Fig. 2 is a graph of impedance curves for different electrocatalytic materials.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
It has been generally recognized that non-noble metal catalysts such as transition metal chalcogenide, nitride, carbide, selenide and phosphide can be used as catalysts for electrocatalytic water decomposition oxygen evolution reaction, but because such catalyst materials have a high class barrier and a slow dynamic reaction process, the efficiency of water electrolysis is reduced, and through the doping coordination of non-metals, the internal resistance of the materials can be improved, the energy barrier required by the anode reaction can be reduced, so as to promote the whole dynamic process and the hydrogen production process, particularly the existence of nitrogen element can play a role in adjusting the crystal lattice of the materials, the distortion degree of the crystal lattice can be increased, the adsorption and stripping of hydrogen ions can be promoted, the reaction energy barrier is reduced, the catalytic activity is enhanced, and the efficiency of water electrolysis is increased, thereby the application is created.
Embodiments of the present application provide a cerium-modified nickel-based catalyst material that is loaded with CeO 2 Ni of (2) 3 N nanosheets, by ceriumThe modification reduces the internal resistance of the material and reduces the energy barrier required by the anode reaction, thereby promoting the whole dynamic process and improving the catalytic performance of the electrolyzed water.
The technical difficulty that the modification of the nickel-based catalyst material is poor in stability exists in the prior art, so that the loaded modification material is few and is easy to fall off, and the efficiency of the modified nickel-based catalyst material in the water electrolysis process needs to be improved, and the application provides a preparation method of the cerium-modified nickel-based catalyst material, which comprises the following steps:
s1, carrying out hydrothermal reaction by taking nickel salt as a raw material, taking a conductive substrate as a carrier and taking urea and ammonium fluoride as structure directing agents to obtain a nickel hydroxide precursor;
s2, calcining the nickel hydroxide precursor in a nitrogen-containing atmosphere to form a nickel-based catalyst material, namely a conductive substrate loaded with nickel nitride;
and S3, placing the nickel-based catalyst material in a cerium-containing electrolyte, and carrying out an electrodeposition reaction to obtain the cerium-modified nickel-based catalyst material.
According to the method, nickel salt is dissolved and recrystallized on a conductive substrate under the conditions of high temperature and high pressure through a hydrothermal method to prepare a nickel hydroxide-containing precursor, the precursor is reacted in a nitrogen atmosphere through a chemical vapor deposition method to obtain a nickel nitride nanosheet, and cerium is diffused to the surface of the nanosheet under the action of current through an electrodeposition technology to form the cerium-modified nickel-based catalyst material by combining with nickel nitride.
According to the method, urea and ammonium fluoride are used as structure directing agents and used for controlling the morphology of a precursor to form an irregular nanosheet structure, the nanosheet structure is descended under the action of high temperature and high pressure and attached to a conductive substrate, the nanosheet morphology is maintained under the action of urea and ammonium fluoride to form a nickel hydroxide precursor, the nickel hydroxide precursor enables the nanosheet structure to be more stable, the method is more suitable for the growth and compounding of cerium oxide, the stability of a catalytic material is improved, the number of active sites and the electronic structure on the surface of the material are adjusted, the activity of a catalyst in oxygen evolution reaction is increased, the electronic transmission performance of the material is enhanced, and therefore the efficiency of water electrolysis is improved.
In the application, the nickel salt is a cationic solution containing transition metal nickel, and includes one or more of nickel nitrate, nickel chloride, nickel phosphide, nickel bromide or nickel sulfate, and further, the nickel salt is nickel chloride.
In the present application, the cerium-containing electrolyte includes one or more of a cerium nitrate solution, a cerium chloride solution, and a cerium sulfate solution.
In some embodiments, the molar ratio of nickel salt, urea, and ammonium fluoride is from 1-4:5 to 10:2-5, such as 1:5:2, 1:7:3, and 4:10:5, but is not limited to the recited values, and values not recited in this range are equally applicable.
Integrating the electrocatalytic material with the conductive substrate generally improves its performance and stability, since compounding the electrocatalyst directly with the conductive substrate ensures lower electron transmission path impedance and reduces the possibility of physical delamination of the electrocatalyst, and the electronic coupling between the conductive substrate and the electrocatalyst can synergistically increase intrinsic activity, in this application, the conductive substrate comprises one of carbon cloth, fiber paper, nickel foam, copper foam, and the like, and further, the conductive substrate is carbon cloth.
In the application, the nitrogen-containing atmosphere refers to an atmosphere containing nitrogen elements, and includes one of ammonia gas, nitrogen gas and argon gas mixture, and further, the nitrogen atmosphere is nitrogen gas, and the nitrogen-containing atmosphere provides a nitrogen source for the reaction, so that the nickel element in the precursor nickel hydroxide and the nitrogen element are subjected to a chemical reaction to obtain the nickel nitride.
In some embodiments, in step S1, the hydrothermal reaction is performed at a reaction temperature of 90 to 200 ℃, such as 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, but not limited to the recited values, and the hydrothermal reaction time is 4 to 24 hours, such as 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, and 20 hours, but not limited to the recited values, and the non-recited values are also applicable.
In this application, the calcination process is a process of vapor deposition of the nickel hydroxide precursor, and the specific means is to heat up the nickel hydroxide precursor to a final temperature at a certain rate, and then keep the temperature for a period of time, in some specific embodiments, in step S2, the calcination temperature is raised at a rate of 1-25 ℃/min, such as 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, 10 ℃/min, 11 ℃/min, 12 ℃/min, 13 ℃/min, 14 ℃/min, 15 ℃/min, 16 ℃/min, 17 ℃/min, 18 ℃/min, 19 ℃/min, 20 ℃/min, 21 ℃/min, 22 ℃/min, 23 ℃/min, 24 ℃/min, 25 ℃/min, but not limited to the recited values, the same applies to the values not recited in the numerical range, the same applies to the final temperature of 150 ℃ 700 ℃, such as 150 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, but not limited to the recited values, the same applies to the values not recited in the numerical range, the same applies to the incubation time of 20-360min, such as 20min, 40min, 60min, 100min, 150min, 200min, 250min, 360min, but not limited to the recited values, the same applies to the values not recited in the numerical range, as used herein, the "final temperature" refers to the final reaction temperature at which the nickel hydroxide precursor is subjected to vapor deposition, and the "incubation time" refers to the reaction time at which the nickel hydroxide precursor is subjected to vapor deposition.
In some embodiments, in step S3, the voltage of the electrodeposition reaction is 0.05V to 10V, such as 0.05V, 0.1V, 0.5V, 1V, 2V, 4V, 6V, 8V, 10V, but not limited to the recited values, and the reaction time is 1h to 30h, such as 1h, 5h, 10h, 20h, 25h, 30h, but not limited to the recited values, and the reaction time is 1h to 30h, such as 0.05V, 0.1V, 0.5V, 1V, 2V, 4V, 6V, 8V, 10V, but not limited to the recited values, and the reaction time is also within the recited values.
In a third aspect, the present application provides a use of a cerium-modified nickel-based catalyst material as an anode electrode in electrocatalytic oxygen evolution.
The present invention is illustrated in more detail with reference to the following examples.
Example 1
A cerium-modified nickel-based catalyst material which is loaded with CeO 2 Ni of (2) 3 The preparation method of the N nanosheet comprises the following steps:
s1, dissolving 1mmol/L nickel nitrate, 5mmol/L urea and 2mmol ammonium fluoride in 35ml deionized water, stirring for 30min, immersing the foamed nickel in the mixed solution, heating to 120 ℃ for reaction for 6h, taking out the foamed nickel after reaction, washing with deionized water for 3 times, and drying to obtain a nickel hydroxide precursor.
S2, placing the obtained nickel hydroxide precursor on a porcelain boat, placing the porcelain boat in a tubular furnace, introducing ammonia gas, and calcining to obtain the nickel-based catalyst material, wherein the heating rate is 5 ℃/min, the reaction temperature is 300 ℃, and the heat preservation time is 30 min.
And S3, placing the obtained nickel-based catalyst material in cerium sulfate electrolyte, and reacting in a three-electrode system to obtain the cerium-modified nickel-based catalyst material, wherein the reaction voltage is 0.5V, and the reaction time is 5 h.
Example 2
A cerium-modified nickel-based catalyst material which is loaded with CeO 2 Ni of (2) 3 The preparation method of the N nanosheet comprises the following steps:
s1, dissolving 2mmol/L nickel sulfate, 7mmol/L urea and 3mmol ammonium fluoride in 28ml deionized water, stirring for 60min, immersing carbon cloth in the solution, heating to 100 ℃ for reaction for 8h, taking out the carbon cloth after the reaction, washing with the deionized water for 3 times, and drying to obtain a nickel hydroxide precursor;
s2, placing the obtained nickel hydroxide precursor on a porcelain boat, placing the porcelain boat in a tubular furnace, introducing nitrogen, and calcining to obtain a nickel-based catalyst material, wherein the heating rate is 10 ℃/min, the reaction temperature is 400 ℃, and the heat preservation time is 60 min;
and S3, placing the obtained nickel-based catalyst material in a cerium nitrate electrolyte, and reacting in a three-electrode system to obtain the cerium-modified nickel-based catalyst material, wherein the reaction voltage is 0.7V, and the reaction time is 9 h.
Example 3
A cerium-modified nickel-based catalyst material which is loaded with CeO 2 Ni of (2) 3 The preparation method of the N nanosheet comprises the following steps:
s1, dissolving 4mmol/L nickel bromide, 10mmol/L urea and 5mmol ammonium fluoride in 40ml deionized water, stirring for 30min, soaking foamed nickel in the solution, and heating to 150 ℃ for reaction for 12 h. Taking out the foamed nickel after reaction, washing the foamed nickel for 3 times by using deionized water, and drying to obtain a nickel hydroxide precursor;
s2, placing the obtained nickel hydroxide precursor on a porcelain boat, placing the porcelain boat in a tubular furnace, introducing ammonia gas, and calcining to obtain the nickel-based catalyst material, wherein the heating rate is 15 ℃/min, the reaction temperature is 450 ℃, and the heat preservation time is 120 min.
And S3, placing the obtained nickel-based catalyst material in a cerium chloride electrolyte, and reacting in a three-electrode system to obtain the cerium-modified nickel-based catalyst material, wherein the reaction voltage is 0.9V, and the reaction time is 12 h.
Example 4
A cerium-modified nickel-based catalyst material which is loaded with CeO 2 Ni of (2) 3 The preparation process of the N nanosheet was substantially the same as in example 1, except that the heating temperature was 90 ℃ and the reaction time was 24 hours in step S1, the temperature increase rate was 1 ℃/min and the reaction temperature was 150 ℃ and the incubation time was 360 minutes in step S2, and the reaction voltage was 0.05V and the reaction time was 30 hours in step S3.
Example 5
A cerium-modified nickel-based catalyst material which is loaded with CeO 2 Ni of (2) 3 The preparation process of the N nanosheet was substantially the same as in example 1, except that the heating temperature was 200 ℃ and the reaction time was 4 hours in step S1, the temperature rise rate was 25 ℃/min in step S2, the reaction temperature was 700 ℃, the incubation time was 20 minutes, the reaction voltage was 10V in step S3, and the reaction time was 1 hour.
Comparative example 1
A nickel-based catalyst material was prepared in substantially the same manner as in example 1, except that step S3 was not included.
Test example
The cerium-modified nickel-based catalyst material prepared in example 1 and the nickel-based catalyst material of comparative example 1 were subjected to a Linear Sweep Voltammetry (LSV) test, which was performed on an electrochemical workstation of CHI660e, using a three-electrode system,the electrode of the cerium-modified nickel-based catalyst material prepared in the example is a working electrode, Hg/HgCl 2 The reference electrode, the graphite rod and the electrolyte are used as reference electrodes, the electrolyte is 1MKOH, and the test sweep rate of the polarization curves of HER and OER is 5mV s -1 . The conversion formula between the applied voltage and the reversible hydrogen electrode is ERHE EHg/HgCl 2 +0.0591pH + 0.242; FIG. 1 is a graph showing the oxygen evolution polarization curves of a cerium-modified nickel-based catalyst material and a pure nickel nitride electrocatalytic material according to an embodiment of the present invention, from which a pure nickel nitride catalyst requires a voltage of 1.86V to drive a reaction to reach 100mA cm -2 The current density of the cerium modified nickel-based catalyst is only 1.67V, the required energy is less, the integral reaction can better achieve the ideal effect, and the cerium modified nickel-based catalyst material prepared by the scheme has better oxygen evolution performance.
The cerium-modified nickel-based catalyst material prepared in example 1 and the nickel-based catalyst material in comparative example 1 were subjected to an electrochemical impedance test, and a three-electrode system was still used for the test, and the electrochemical impedance test (EIS) was mainly used to explore the electrode reaction kinetics and the interface effect between the electrode and the electrolyte. In the test process, the constant voltage applied to the electrode system is 1.6V, the frequency range is 0.1-100000 Hz, and small sine wave disturbance signals with different frequencies are converted into corresponding electrochemical signals. By analyzing the impedance diagram, the reaction kinetics speed of different catalysts can be compared. The result is shown in fig. 2, wherein the radius size represents the internal resistance of the catalyst, and the smaller the radius, the smaller the internal resistance, which indicates that the cerium modified nickel-based catalyst material prepared by the scheme has smaller charge transport resistance than pure nickel nitride, can enable the reaction to occur faster, and is more favorable for promoting the reaction kinetics.
It should be noted that the above embodiments belong to the same inventive concept, and the description of each embodiment has a different emphasis, and reference may be made to the description in other embodiments where the description in individual embodiments is not detailed.
The above examples only express embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (10)
1. A cerium-modified nickel-based catalyst material is characterized by being loaded with CeO 2 Ni of (2) 3 N nano-sheet.
2. A method of preparing the cerium-modified nickel-based catalyst material of claim 1, comprising the steps of:
s1, taking nickel salt as a raw material, taking a conductive substrate as a carrier, and carrying out hydrothermal reaction under the action of a structure directing agent to obtain a nickel hydroxide precursor;
s2, calcining the nickel hydroxide precursor in a nitrogen-containing atmosphere to form a nickel-based catalyst material;
and S3, placing the nickel-based catalyst material in a cerium-containing electrolyte, and carrying out an electrodeposition reaction to obtain the cerium-modified nickel-based catalyst material.
3. The method of preparing a cerium-modified nickel-based catalyst material as claimed in claim 2, wherein the structure directing agent is a mixture of urea and ammonium fluoride.
4. The method of preparing a cerium-modified nickel-based catalyst material as claimed in claim 3, wherein the molar ratio of the nickel salt, urea, ammonium fluoride is 1-4:5-10: 2-5.
5. The method of claim 2, wherein the nickel salt comprises one or more of nickel chloride, nickel sulfate, and nickel nitrate.
6. The method of claim 2, wherein the cerium-containing electrolyte comprises one or more of a cerium nitrate solution, a cerium chloride solution, and a cerium sulfate solution.
7. The method of claim 2, wherein the hydrothermal reaction is performed at 90-200 ℃ for 4-24h in step S1.
8. The method as claimed in claim 2, wherein the temperature increase rate of the calcination in step S2 is 1-25 ℃/min, the final temperature is 150-.
9. The method of preparing a cerium-modified nickel-based catalyst material as claimed in claim 2, wherein the voltage of the electrodeposition reaction is 0.05 to 10V and the reaction time is 1 to 30 hours in step S3.
10. Use of a cerium-modified nickel-based catalyst material obtained by the preparation method according to any one of claims 2 to 9 as an anode electrode in electrocatalytic oxygen evolution.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210608291.7A CN114807973A (en) | 2022-05-31 | 2022-05-31 | Cerium-modified nickel-based catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210608291.7A CN114807973A (en) | 2022-05-31 | 2022-05-31 | Cerium-modified nickel-based catalyst and preparation method and application thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN114807973A true CN114807973A (en) | 2022-07-29 |
Family
ID=82519270
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210608291.7A Pending CN114807973A (en) | 2022-05-31 | 2022-05-31 | Cerium-modified nickel-based catalyst and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114807973A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115490217A (en) * | 2022-09-28 | 2022-12-20 | 中山大学 | Nickel phosphide nano material, fuel cell, preparation method and application thereof |
CN115739148A (en) * | 2022-10-21 | 2023-03-07 | 无锡隆基氢能科技有限公司 | Composite material, preparation method thereof, electrode containing composite material and application |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109806879A (en) * | 2019-02-28 | 2019-05-28 | 北京化工大学 | A kind of CeO2-NiCo2O4/ NF composite electro catalytic material and its preparation method and application |
CN110721720A (en) * | 2019-10-25 | 2020-01-24 | 山东大学 | Molybdenum nitride/cerium oxide composite material and preparation method and application thereof |
CN110965076A (en) * | 2019-12-06 | 2020-04-07 | 吉林大学 | Preparation method of electrolytic water electrode with double-function three-dimensional layered core-shell structure |
CN114045525A (en) * | 2021-12-03 | 2022-02-15 | 张黎丽 | Nickel-based self-supporting water electrolysis catalyst and preparation method thereof |
-
2022
- 2022-05-31 CN CN202210608291.7A patent/CN114807973A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109806879A (en) * | 2019-02-28 | 2019-05-28 | 北京化工大学 | A kind of CeO2-NiCo2O4/ NF composite electro catalytic material and its preparation method and application |
CN110721720A (en) * | 2019-10-25 | 2020-01-24 | 山东大学 | Molybdenum nitride/cerium oxide composite material and preparation method and application thereof |
CN110965076A (en) * | 2019-12-06 | 2020-04-07 | 吉林大学 | Preparation method of electrolytic water electrode with double-function three-dimensional layered core-shell structure |
CN114045525A (en) * | 2021-12-03 | 2022-02-15 | 张黎丽 | Nickel-based self-supporting water electrolysis catalyst and preparation method thereof |
Non-Patent Citations (6)
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115490217A (en) * | 2022-09-28 | 2022-12-20 | 中山大学 | Nickel phosphide nano material, fuel cell, preparation method and application thereof |
CN115739148A (en) * | 2022-10-21 | 2023-03-07 | 无锡隆基氢能科技有限公司 | Composite material, preparation method thereof, electrode containing composite material and application |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109019602B (en) | Molybdenum carbide material, molybdenum carbide @ molybdenum sulfide composite material, and preparation method and application thereof | |
CN110052277B (en) | Preparation method of transition metal group metal sulfide oxygen evolution catalyst | |
CN109267092B (en) | Molybdenum disulfide composite material and preparation method and application thereof | |
CN114807973A (en) | Cerium-modified nickel-based catalyst and preparation method and application thereof | |
CN111501060B (en) | Copper-doped bismuth bimetallic material and preparation and application thereof | |
CN111636074B (en) | Preparation and application of copper electrode for electrochemical reduction of carbon dioxide | |
CN110846678A (en) | Dual-function catalyst electrode for urea electrolysis-assisted hydrogen production by foam nickel load | |
CN110257856B (en) | Composite electrode, preparation method and application thereof, and electrocatalytic full-hydrolysis device | |
CN109621969B (en) | Self-supporting bimetal nickel-tungsten carbide fully-hydrolyzed material and preparation method thereof | |
CN113463128B (en) | Water splitting catalyst and its prepn and application | |
CN113279005A (en) | Cobalt doped MoS2/NiS2Preparation method of porous heterostructure material and application of material in electrocatalytic hydrogen evolution | |
CN111229267B (en) | Supported phosphorus-doped metal oxyhydroxide nanosheet material and preparation method and application thereof | |
CN113832478A (en) | Preparation method of high-current oxygen evolution reaction electrocatalyst with three-dimensional heterostructure | |
CN110180574B (en) | Preparation and application of nitrogen-doped ternary sulfide electrocatalyst material | |
CN110841658A (en) | Preparation method of cobalt-based sulfide nanorod array | |
CN111778517A (en) | Electrode material and preparation method and application thereof | |
CN110629248A (en) | Fe-doped Ni (OH)2Preparation method of/Ni-BDC electrocatalyst | |
CN111036307A (en) | Preparation method of composite efficient oxygen evolution catalyst | |
CN114182287A (en) | Nickel-molybdenum nickel nitride composite catalyst and preparation method and application thereof | |
CN112058282A (en) | Preparation method of pH-wide-range catalyst based on molybdenum-tungsten-based layered material and application of pH-wide-range catalyst to electrolytic water-evolution hydrogen reaction | |
CN114405521A (en) | Preparation method of zinc-doped molybdenum disulfide nanosheet hydrogen evolution electrocatalyst with rich defects | |
CN113846346A (en) | Composite material, preparation method thereof and method for preparing hydrogen by electrocatalytic hydrolysis | |
CN111804317A (en) | Method for directly growing high-density cobalt phosphide nano-wire electrocatalyst on conductive substrate and application thereof | |
CN111589459A (en) | Bifunctional catalyst for efficiently electrolyzing water, and preparation method and application thereof | |
CN113789545B (en) | Electrolytic water 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 |