CN112090436B - Nickel-based catalyst, preparation method and application - Google Patents
Nickel-based catalyst, preparation method and application Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 281
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 142
- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title abstract description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 112
- 239000011787 zinc oxide Substances 0.000 claims abstract description 56
- 239000002071 nanotube Substances 0.000 claims abstract description 27
- 238000004070 electrodeposition Methods 0.000 claims abstract description 25
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004202 carbamide Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 18
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 17
- 239000011733 molybdenum Substances 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011574 phosphorus Substances 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 239000011159 matrix material Substances 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 239000006260 foam Substances 0.000 claims description 50
- 239000007864 aqueous solution Substances 0.000 claims description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 238000000151 deposition Methods 0.000 claims description 25
- 230000008021 deposition Effects 0.000 claims description 20
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 14
- 238000000137 annealing Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000004246 zinc acetate Substances 0.000 claims description 12
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 11
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 8
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 8
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 8
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 claims description 8
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 claims description 8
- 239000001509 sodium citrate Substances 0.000 claims description 8
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 8
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000005530 etching Methods 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 238000011065 in-situ storage Methods 0.000 claims description 6
- 239000011684 sodium molybdate Substances 0.000 claims description 6
- 235000015393 sodium molybdate Nutrition 0.000 claims description 6
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 4
- 239000011807 nanoball Substances 0.000 claims 2
- 239000002073 nanorod Substances 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 239000000758 substrate Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract 2
- 239000000047 product Substances 0.000 description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 229960000314 zinc acetate Drugs 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 229940057499 anhydrous zinc acetate Drugs 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical group [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000002077 nanosphere Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 238000003486 chemical etching Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 3
- 150000002815 nickel Chemical class 0.000 description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 3
- 125000004437 phosphorous atom Chemical group 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 239000002659 electrodeposit Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002052 molecular layer Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- -1 zinc acetate anhydride Chemical class 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- B01J35/33—
-
- B01J35/40—
-
- B01J35/60—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
-
- 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
Abstract
The invention relates to a nickel-based catalyst, a preparation method and application thereof. The catalyst comprises a three-dimensional netlike matrix with conductivity and nickel, molybdenum, phosphorus and oxygen composite porous nanotubes loaded on the surface of the three-dimensional netlike matrix, wherein the porous nanotubes have catalytic activity. The preparation method of the catalyst comprises the following steps: growing zinc oxide nano seed crystal on the substrate, synthesizing a zinc oxide nano rod template, and synthesizing the nickel, molybdenum, phosphorus and oxygen composite porous nano tube electrocatalytic material by an electrodeposition method. The catalyst is excellent in urea oxidation reaction.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly relates to a nickel-based catalyst, a preparation method and application thereof.
Background
The urea oxidation reaction (Urea Oxidation Reaction, UOR for short) is the core half-reaction of new energy technologies such as direct urea fuel cells (Direct Urea Fuel Cell, DUFC for short) and urea-assisted electrolytic hydrogen production. Among them, DUFC is a novel fuel cell device that can generate electricity using urea in industrial wastewater or domestic sewage as fuel. The urea assisted electrolytic hydrogen production is realized by applying voltage to the aqueous solution containing urea, obtaining hydrogen at the cathode of the electrolytic cell and generating UOR at the anode, thereby realizing the dual purposes of clean energy production and urea-rich wastewater purification.
However, the UOR reaction needs to undergo 6e — The transfer process, and thus kinetics are slow; and the reaction initiation oxidation potential is too high, a highly active catalyst is required to promote the reaction rate. The above problems greatly limit the development of new energy technologies in which UOR participates. Although noble metal-based catalysts (e.g. Pt, irO 2 And RuO (Ruo) 2 ) Proved to have high UOR activity but limited their large-scale application due to their high cost and resource scarcity. Therefore, the development of UOR electrocatalysts with low cost, high activity is critical to improving the energy conversion efficiency of DUFCs and urea-assisted electrolytic hydrogen production.
In order to solve the problems of cost and resources, nickel-based UOR electrocatalysts have become a research trend. Including nickel-based alloys, hydroxides, oxides, phosphides, sulfides, composites thereof, and the like. Wherein, the NiMoM (m=p, O, S) composite material doped with transition metal molybdenum and non-metal atoms is excellent in catalytic activity and stability in UOR reaction.
In order to make the nickel-based catalytic material with low cost have more accessible catalytic sites and accelerate electron transfer, the catalytic material is often subjected to hydrothermal crystallization, high-temperature calcination, high-temperature phosphating, high-temperature vulcanization, chemical etching template and other processes so as to form microstructures such as nano, porous, hollow and the like. However, these synthetic processes have long routes and complicated steps; the high-temperature treatment and other methods have the problems of high energy consumption and high cost; chemical etching methods often use reagents that are strong acids and bases and produce pH 3 、H 2 S and other toxic gases, causing harm to the environment. In addition, the activity and stability of the synthesized nickel-based catalysts during catalytic applications are not satisfactory.
Disclosure of Invention
The present invention aims to solve at least one of the above technical problems in the prior art.
Therefore, the first aspect of the invention provides a nickel-based catalyst to solve the problems of low catalytic activity and poor stability of the existing nickel-based catalyst.
The second aspect of the invention provides a method for preparing the nickel-based catalyst.
In a third aspect the invention provides the use of the nickel-based catalyst described above for catalysing the oxidation reaction of urea.
In a first aspect the present invention provides a nickel-based catalyst comprising:
a three-dimensional mesh-like substrate having conductivity; and
the porous nano tube is distributed on the surface of the three-dimensional reticular matrix and consists of four elements of nickel, molybdenum, phosphorus and oxygen.
According to one embodiment of the invention, the porous nano tube is formed by stacking mutually connected composite nano spheres, and the composite nano spheres comprise nickel, molybdenum, phosphorus and oxygen.
The composite nanospheres comprise nickel, molybdenum, phosphorus and oxygen, and the single composite nanospheres simultaneously contain the nickel, molybdenum, phosphorus and oxygen.
According to one embodiment of the invention, the three-dimensional mesh substrate may be nickel foam.
According to one embodiment of the present invention, the length of the porous nanotubes is 1 μm to 2 μm.
According to one embodiment of the invention, the diameter of the porous nanotubes is 200nm to 400nm.
According to one embodiment of the invention, the thickness of the tube wall of the porous nano tube is 50 nm-100 nm.
According to one embodiment of the present invention, the porous nanotube has a nickel content of 30wt.% to 70wt.%, a molybdenum content of 1wt.% to 20wt.%, a phosphorus content of 1wt.% to 20wt.%, and an oxygen content of 1wt.% to 30wt.%.
According to a preferred embodiment of the present invention, the porous nanotubes are of amorphous structure.
According to one embodiment of the invention, the tube wall of the porous nanotube is porous structure, and the porous structure and the hollow tube form play a role in increasing the accessible sites of the catalytic reaction in the catalytic reaction.
According to one embodiment of the invention, the porous nanotubes have gaps between them that act to further increase the accessible sites of the catalytic reaction during the catalytic reaction.
According to one embodiment of the invention, the introduction of Mo and P atoms of the nickel-based catalyst adjusts the electronic structure of Ni atoms, nickel and molybdenum atoms are combined with phosphorus atoms through metal bonds, and part of electrons are transferred from micro positive charge centers formed by the nickel and molybdenum atoms to micro negative charge centers of the phosphorus atoms.
According to one embodiment of the invention, the nickel-based catalyst has synergistic effect of nickel, molybdenum, phosphorus and oxygen, so that the catalytic activity can be improved.
The second aspect of the present invention provides a method for preparing a nickel-based catalyst, comprising the steps of:
s1: immersing foam nickel in ethanol solution of zinc acetate;
s2: annealing the foam nickel treated in the step S1;
s3: immersing the foam nickel treated in the step S2 into a mixed aqueous solution of zinc acetate and hexamethylenetetramine for hydrothermal reaction, washing and drying a solid product to obtain the foam nickel loaded with a zinc oxide template;
s4: preparing an electrodeposition aqueous solution, carrying out electrochemical deposition on the foam nickel loaded with the zinc oxide template obtained in the step S3 in the electrodeposition aqueous solution, and carrying out in-situ etching, washing and drying on the zinc oxide template to obtain the nickel-based catalyst.
According to one embodiment of the present invention, the preparation method further comprises pre-treating the nickel foam prior to step S1.
According to a preferred embodiment of the invention, the pretreatment comprises shearing the nickel foam into nickel foam flakes.
According to one embodiment of the invention, the pretreatment further comprises ultrasonic cleaning and drying of the foam nickel in ethanol, hydrochloric acid and deionized water in sequence.
Among them, the purpose of the washing with ethanol is to remove greasy dirt on the surface of the foam nickel, and the purpose of the washing with hydrochloric acid is to remove oxides possibly present on the surface of the foam nickel.
According to one embodiment of the present invention, the concentration of the ethanol solution of zinc acetate in step S1 is 0.04M to 0.08M.
According to one embodiment of the present invention, the impregnation operation described in step S1 is: soaking the foam nickel in ethanol solution of zinc acetate for 3-5 times for 30s each time.
According to one embodiment of the present invention, in the step S2, the annealing treatment is performed at a temperature of 300 ℃ to 400 ℃ for 20min to 40min.
According to one embodiment of the present invention, in step S2, the annealing treatment is performed at a temperature of 350 ℃ for 30min.
In step S2, the annealing is performed to convert zinc acetate into zinc oxide.
According to one embodiment of the present invention, in the step S3, the hydrothermal reaction is performed at a temperature of 80 to 120 ℃ for a time of 1 to 4 hours.
According to one embodiment of the present invention, in the mixed aqueous solution of step S3, the molar concentration of zinc acetate is 0.01M to 0.06M, and the molar concentration of hexamethylenetetramine is 0.01M to 0.06M.
According to one embodiment of the present invention, in step S3, the zinc acetate may be at least one of zinc acetate dihydrate or zinc acetate anhydride.
According to a preferred embodiment of the present invention, in step S3, the zinc acetate is anhydrous zinc acetate, and the anhydrous zinc acetate is used to synthesize the zinc oxide nanorods with high aspect ratio.
According to one embodiment of the present invention, in step S3, the zinc oxide template is a zinc oxide nanorod.
According to one embodiment of the present invention, in step S3, the zinc oxide template is formed by the following mechanisms (1) - (3):
(CH 2 ) 6 N 4 +10H 2 O→6HCHO+4NH 3 ·H 2 O (1)，
Zn 2+ +2NH 3 ·H 2 O→Zn(OH) 2 +2NH 4 + (2)，
Zn(OH) 2 →ZnO+H 2 O (3)。
according to one embodiment of the present invention, in step S4, the aqueous electrodeposition solution is a mixed solution of nickel salt, molybdate, hypophosphite and complexing agent.
According to one embodiment of the present invention, in the step S4, the electrodeposition aqueous solution contains 0.1M to 0.5M of nickel salt, 0.01M to 0.05M of molybdate, 0.1M to 0.5M of hypophosphite, and 0.1M to 0.5M of complexing agent.
In step S4, the nickel salt serves to provide a nickel source; the role of the molybdate is to provide a molybdenum source; hypophosphite serves to provide a source of phosphorus.
According to a preferred embodiment of the present invention, in step S4, the electrodeposition aqueous solution contains 0.1M to 0.5M of nickel sulfate hexahydrate, 0.01M to 0.05M of sodium molybdate, 0.1M to 0.5M of sodium hypophosphite, and 0.1M to 0.5M of sodium citrate.
According to one embodiment of the present invention, in step S4, the pH of the aqueous electrodeposition solution is 5 to 7, and the agent for adjusting the pH is at least one of a monobasic acid and a dibasic acid aqueous solution.
According to a preferred embodiment of the present invention, in step S4, the agent for adjusting the pH of the electrodeposition aqueous solution is an aqueous solution of sulfuric acid of 1M to 5M.
According to a preferred embodiment of the present invention, in step S4, the constant current deposition is performed by using a three-electrode system, wherein the foamed nickel loaded with the zinc oxide template is used as a working electrode, a Pt foil is used as a counter electrode, and Ag/AgCl is used as a reference electrode.
According to one embodiment of the present invention, in step S4, the electrochemical deposition is a constant current deposition, wherein the current density is 10mA cm -2 ～100mA cm -2 The deposition time is 10 min-60 min.
According to a preferred embodiment of the present invention, in step S4, the constant current deposition has a current density of 80mA cm -2 ～100mA cm -2 The deposition time was 30min.
According to one embodiment of the present invention, in step S4, the reaction of the constant current deposition occurs as shown in formulas (4) - (10):
H 2 PO 2 - →(HPO 2 - ) ads +(H) ads (4)，
(HPO 2 - ) ads +OH - →H 2 PO 3 +2e - (5)，
Ni 2+ +2e - →Ni (6)，
H 2 PO 2 - +2H + +e - →P+2H 2 O (7)，
(H) ads +H + +e - →H 2 (8)，
MoO 4 2- +[NiCit] 2+ +2H 2 O+2e - →[NiCitMoO 2 ] 2+ +4OH - (9)，
[NiCitMoO 2 ] 2+ +2H 2 O+4e - →Mo+[NiCit] 2+ +4OH - (10)。
according to one embodiment of the present invention, in step S4, the zinc oxide template is etched in situ, and the mechanism is chemical etching, as shown in formula (11):
ZnO+2H + →Zn 2+ +H 2 O (11)。
in a third aspect the invention provides the use of a nickel-based catalyst for catalysing the oxidation of urea.
According to one embodiment of the invention, the nickel-based catalyst may be applied to a direct urea fuel cell.
According to one embodiment of the invention, the nickel-based catalyst can be applied to the technical field of new energy sources such as urea-assisted hydrogen production.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The nickel-based catalyst provided by the invention has a porous nano tube structure, gaps exist among the nano tubes, and the number of catalytic sites which can be contacted in the catalytic reaction of the catalyst with unit mass is increased;
(2) The nickel-based catalyst provided by the invention has the advantages that metal atoms of nickel and molybdenum and non-metal atoms of phosphorus and oxygen have synergistic effect, so that the catalytic activity is improved;
(3) According to the preparation method of the nickel-based catalyst, in the process of forming the porous nanotube catalyst by an electrochemical deposition method, the nano rod-shaped zinc oxide template is etched until disappearing, so that the process flow is short and the process is simple;
(4) The preparation method of the nickel-based catalyst provided by the invention does not need to use strong acid and strong alkali to etch the template; nor generate pH 3 Harmful gases such as the like, and is environment-friendly;
(5) The preparation method of the nickel-based catalyst provided by the invention adopts the raw materials of nickel, molybdenum and phosphorus salt, and has low cost compared with the noble metal-based catalyst applied industrially;
(6) The nickel-based catalyst provided by the invention is applied to catalyzing urea oxidation reaction, and in a KOH (1.0M) solution containing 0.5M urea, the initial potential is only 1.30V (vs. RHE) to reach 100mA cm -2 Only 1.41V (vs. rhe) is required, exhibiting excellent UOR activity;
(7) The invention provides the application of the nickel-based catalyst in catalyzing urea oxidation reaction, and the current density of the nickel-based catalyst is 20mA cm in KOH (1.0M) aqueous solution containing 0.5M urea -2 After continuous catalysis for 20 hours, the UOR current density retention rate reaches 88.6%; shows better stability.
Drawings
FIG. 1 is a scanning electron microscope image of the product obtained in example 1.
FIG. 2 is an X-ray diffraction pattern of the product obtained in examples 1-3 and a standard pattern of crystalline zinc oxide.
FIG. 3 is a scanning electron microscope image of the product obtained in example 2.
FIG. 4 is a scanning electron microscope image of the product obtained in example 3.
FIG. 5 is a scanning electron microscope image of the product obtained in example 4.
FIG. 6 is a transmission electron micrograph of the product obtained in example 4.
FIG. 7 is an X-ray diffraction pattern of the product obtained in example 4.
FIG. 8 is an X-ray photoelectron spectrum of the product obtained in example 4.
FIG. 9 is a scanning electron microscope image of the product obtained in comparative example 1.
FIG. 10 is a transmission electron microscopic image of the product obtained in comparative example 2.
FIG. 11 is a graph of the UOR polarization of the products obtained in example 4 and comparative examples 1-2.
FIG. 12 is a graph showing the results of UOR stability testing of the product obtained in example 4.
Detailed Description
The present invention will be described in further detail with reference to examples, comparative examples, application examples and drawings. The embodiments described below by referring to the drawings are illustrative only and are not to be construed as limiting the invention.
In the present invention, all raw materials used are commercially available unless otherwise specifically defined.
Example 1
The foam nickel loaded with the zinc oxide template is prepared in the embodiment, and the specific preparation method comprises the following steps:
(1) Foam nickel pretreatment: cutting foam nickel into pieces with the maximum surface area of 1cm or 2cm, sequentially placing the pieces in ethanol, hydrochloric acid and deionized water, respectively carrying out ultrasonic treatment for 10min, and drying for later use;
(2) Growing zinc oxide seed crystal: immersing the foam nickel obtained in the step (1) in an absolute ethanol solution containing 0.06M zinc acetate dihydrate for 3 times and 30s each time, and then placing the immersed foam nickel in a tube furnace for annealing treatment under the air atmosphere, wherein the annealing temperature is 350 ℃ and the annealing time is 30min;
(3) Preparing foam nickel loaded with a zinc oxide template: preparing a mixed aqueous solution of anhydrous zinc acetate and hexamethylenetetramine, wherein the concentration of the anhydrous zinc acetate is 0.03M, and the concentration of the hexamethylenetetramine is 0.03M; and (3) placing the foam nickel obtained in the step (2) into the mixed aqueous solution, then transferring the mixed aqueous solution into a reaction kettle, carrying out hydrothermal reaction for 4 hours in a 95 ℃ oven, and washing and drying a solid product after the reaction is finished to obtain the foam nickel loaded with the zinc oxide template.
The scanning electron microscope diagram of the prepared product is shown in figure 1. The zinc oxide template can be seen to exist in the form of nano rods, gaps exist among the nano rods, and the zinc oxide template is uniformly attached to the surface of the three-dimensional foam nickel substrate; the length of the zinc oxide nano rod is 1-2 mu m, and the diameter of the rod is 100-200 nm.
The X-ray diffraction pattern of the prepared zinc oxide nano rod array is shown in figure 2. The pattern showed that the product showed only peaks of crystalline nickel and crystalline zinc oxide, consistent with the design product of this example, i.e., nickel foam loaded with zinc oxide templates.
Example 2
The nickel-based catalyst is prepared by the method specifically comprising the following steps:
(1) The method of example 1 was used to prepare nickel foam loaded with zinc oxide templates;
(2) Preparing an electrodeposition aqueous solution: the electrodeposited aqueous solution is a mixed aqueous solution, and the solute is composed of nickel sulfate hexahydrate, sodium molybdate, sodium hypophosphite and sodium citrate, wherein the concentration of the nickel sulfate hexahydrate is 0.2M, the concentration of the sodium molybdate is 0.04M, the concentration of the sodium hypophosphite is 0.15M, the concentration of the sodium citrate is 0.3M, and then the mixed aqueous solution is regulated to pH approximately 6 by using a 3M sulfuric acid aqueous solution;
(3) Preparation of a nickel-based catalyst: using foam nickel loaded with zinc oxide template as working electrode, and using constant current deposition method to deposit the compound containing Ni, mo, P, O four elements on the surface of zinc oxide template in the electrodeposited water solution obtained in step (2), wherein the deposition current density is 100mA cm -2 The deposition time is 10min, and during the deposition process, part of the zinc oxide template is etched in situ, cleaned and dried to obtain the nickel-based catalyst.
The scanning electron microscope image of the prepared nickel-based catalyst is shown in fig. 3, and compared with fig. 1, fig. 3 shows that the surface of the nanorod is roughened, but no nanotube appears, which indicates that: (1) The elements in the electrodeposited aqueous solution are deposited on the surface of the zinc oxide nanorods to form a nano layer, (2) the zinc oxide template is not completely etched.
The X-ray diffraction diagram of the nickel-based catalyst prepared in this example is shown in fig. 2, and fig. 2 shows that the product obtained in this example only shows characteristic peaks of crystalline nickel and crystalline zinc oxide, which illustrates: (1) Deposition time of 10min, zinc oxide template is not completely etched, (2): the nano-deposited layer formed on the surface has no characteristic peak and is amorphous.
Example 3
This example produced a nickel-based catalyst, differing from example 2 in that in step (3), the deposition time was 20min.
The scanning electron microscope of the nickel-based catalyst is shown in figure 4, and compared with figures 1 and 3, figure 4 shows that the surface roughness of the zinc oxide template is improved, and meanwhile, a small amount of nanotubes exist, which shows that: (1) The elements in the electrodeposited aqueous solution deposited on the surface of the zinc oxide nanorods formed a nanolayer, (2) the zinc oxide template was not completely etched, but the degree of etching was increased compared to example 1, the degree of immediate etching being positively correlated to the time of electrochemical deposition.
The X-ray diffraction pattern of the nickel-based catalyst obtained in this example is shown in fig. 2, and fig. 2 shows that, compared with the products obtained in examples 1 and 2, the characteristic peaks of crystalline zinc oxide are significantly reduced, and no characteristic peaks of the deposited layer appear. The results illustrate: (1) The electrochemical deposition time is positively correlated with the etching degree of the zinc oxide template, and compared with the deposition time of 10min in the embodiment 2, the deposition time of 20min in the embodiment can not completely etch the template, but the etching degree is improved; (2) The deposited layer deposited from the aqueous electrodeposition solution onto the surface of the zinc oxide template is amorphous.
Example 4
This example produced a nickel-based catalyst, differing from example 2 in that in step (3), the deposition time was 30min.
The scanning electron microscope of the prepared nickel-based catalyst is shown in fig. 5, and fig. 5 shows: the method comprises the steps of (1) etching all zinc oxide nano rod templates completely, namely that the zinc oxide templates can be etched completely in the electrodeposition time of 30min, (2) forming the three-dimensional foam nickel substrate surface, wherein the three-dimensional foam nickel substrate surface is composed of hollow nano tubes, the length of each nano tube is 1-2 mu m, the outer diameter of each nano tube is 200-400 nm, and (3) the tube walls of the nano tubes are formed by stacking connected pellets.
The transmission electron microscope of the nickel-based catalyst prepared is shown in fig. 6, and it can be seen that the thickness of the nanotube wall of the nickel-based catalyst prepared in this example is about 50 nm-100 nm, and the nanotube wall presents a porous structure.
The X-ray diffraction pattern of the nickel-based catalyst prepared is shown in fig. 7, and compared with the X-ray diffraction patterns of examples 1-3 shown in fig. 2, the patterns of the product obtained in the example shown in fig. 7 do not show obvious characteristic peaks. The above results indicate that: (1) The nickel-based catalyst obtained in this example was amorphous, (2) the zinc oxide template had been etched completely in situ during the 30min electrodeposition process.
The X-ray photoelectron spectrum of the prepared nickel-based catalyst is shown in figure 8, and the material is composed of Ni, mo, P and O elements, and the mass percentages of the Ni, mo, P and O elements are respectively as follows: 49.32wt.%, 11.99wt.%, 12.60wt.% and 26.09wt.%. The results demonstrate that (1) the composition of the porous nanotubes consisted of a composite of Ni, mo, P and O elements, (2) the composition of the product obtained in this example was 49.32wt.% nickel, 11.99wt.% molybdenum, 12.60wt.% phosphorus and 26.09wt.% oxygen.
The catalyst loading on the substrate in this example was calculated by the differential method according to formula (12):
load = (nickel-based catalyst mass-foam nickel matrix mass)/foam nickel maximum area (12).
Through calculation, in the material, the loading of the porous nano tubular catalyst on the foam nickel matrix is 5mg cm -2 。
Comparative example 1
The nickel-based catalyst without the zinc oxide template is prepared by the method specifically comprising the following steps:
(1) Foam nickel pretreatment: cutting foam nickel into pieces with the maximum surface area of 1cm x 2cm, sequentially placing the pieces in ethanol, hydrochloric acid and deionized water, respectively carrying out ultrasonic treatment for 10min, and drying for later use;
(2) Preparing an electrodeposition aqueous solution: the electrodeposit aqueous solution is a mixed aqueous solution, and the solute consists of nickel sulfate hexahydrate, sodium molybdate, sodium hypophosphite and sodium citrate, wherein the concentration of the nickel sulfate hexahydrate is 0.2M, the concentration of the sodium molybdate is 0.04M, the concentration of the sodium hypophosphite is 0.15M, and the concentration of the sodium citrate is 0.3M; adjusting the precursor solution to pH approximately 6 with 3M sulfuric acid aqueous solution;
(3) Preparing a nickel-based catalyst without a zinc oxide template: using the foam nickel obtained in the step (1) as a working electrode, directly depositing a composite containing Ni, mo, P, O four elements on the surface of a foam nickel substrate in the electrodeposited aqueous solution obtained in the step (2) by using a constant current deposition method, wherein the deposition current density is 100mA cm -2 The deposition time is 30min, and the Ni-Mo-P-O composite nano particle film material is obtained after cleaning and drying.
The schematic diagram of the scanning electron microscope of the prepared nickel-based catalyst without the zinc oxide template is shown in the attached figure 9; the nickel-based catalyst of this example can be seen to be a compact, large-sized nanoparticle close-packed, illustrating that: the introduction of zinc oxide templates is a necessary condition for the formation of porous nano-tubular nickel-based catalysts.
Comparative example 2
The nickel-based catalyst without molybdenum is prepared by the specific preparation method, which comprises the following steps:
(1) Foam nickel pretreatment: cutting foam nickel into pieces with the maximum surface area of 1cm x 2cm, sequentially placing the pieces in ethanol, hydrochloric acid and deionized water, respectively carrying out ultrasonic treatment for 10min, and drying for later use.
(2) Growing zinc oxide seed crystal: immersing the foam nickel obtained in the step (1) in 100mL of absolute ethyl alcohol solution containing 0.06M zinc acetate dihydrate for 3 times and 30s each time, and then placing the immersed foam nickel in a tube furnace for annealing treatment under the air atmosphere, wherein the annealing temperature is 350 ℃ and the annealing time is 30min;
(3) Preparing foam nickel loaded with a zinc oxide template: preparing a mixed aqueous solution of anhydrous zinc acetate and hexamethylenetetramine, wherein the concentration of the anhydrous zinc acetate is 0.03M and the concentration of the hexamethylenetetramine is 0.03M; putting the foam nickel obtained in the step (2) into the mixed aqueous solution, then transferring the mixed aqueous solution into a reaction kettle, carrying out hydrothermal reaction in a baking oven at 95 ℃ for 4 hours, and washing and drying a solid product after the reaction is finished to obtain the foam nickel loaded with the zinc oxide template;
(4) Preparing an electrodeposition aqueous solution: the electrodeposit aqueous solution is a mixed aqueous solution, and the solute consists of nickel sulfate hexahydrate, sodium hypophosphite and sodium citrate, wherein the concentration of the nickel sulfate hexahydrate is 0.2M, the concentration of the sodium hypophosphite is 0.15M, and the concentration of the sodium citrate is 0.3M; adjusting the precursor solution to pH approximately 6 with 3M sulfuric acid aqueous solution;
(5) Preparing a nickel-based catalyst without molybdenum: using the foam nickel loaded with the zinc oxide template obtained in the step (3) as a working electrode, and depositing a compound containing three elements of Ni, P and O on the surface of the zinc oxide template in the electrodeposited aqueous solution obtained in the step (4) by using a constant current deposition method, wherein the deposition current density is 100mA cm -2 The deposition time is 30min, and the zinc oxide template is etched in situ in the deposition process, and the nickel-based catalyst without introducing molybdenum element is obtained after cleaning and drying.
The scanning electron microscope of the prepared nickel-based catalyst without introducing molybdenum element is shown in figure 10, and the morphology of the prepared nickel-based catalyst is similar to that of the nickel-based catalyst obtained in example 4.
Application example
The products prepared in example 4 and comparative examples 1-2 above were used as working electrodes, carbon rods as counter electrodes, ag/AgCl electrodes as reference electrodes, and their UOR electrocatalytic activity and stability were evaluated by linear cyclic voltammetry and current-time response tests under a three electrode system with 0.5M urea+1.0M potassium hydroxide mixed solution as the electrolyte.
Will commercial RuO 2 (99.95 wt.%) the catalyst was supported on the foam nickel surface at the same loading as a comparison, and the preparation method was: will calculate commercial RuO 2 (99.95 wt.%) dispersing the catalyst in absolute ethyl alcohol solution, then dripping it on clean foam nickel to obtain RuO 2 Nickel foam (RuO) 2 /NF) electrodes, UOR activity was tested in the same manner as described above.
FIG. 11 shows the samples obtained in example 4, comparative examples 1-2 and RuO 2 UOR polarization curve of/NF in 0.5M urea+1.0M potassium hydroxide mixed solution. As can be seen from the figure, the catalyst UOR prepared in example 4 of the present invention has an initial potential of only1.30V (vs. RHE) to 100mA cm -2 Only 1.41V (vs. RHE) was required for the high current density of (C), which is significantly superior to the catalysts prepared in comparative examples 1 and 2 and the commercial noble metal-based catalyst (RuO) 2 /NF)。
Table 1 lists UOR current densities for each catalyst sample at different electrode potentials.
Table 1 comparison of UOR current density for each catalyst sample
It can be seen that (1) the nickel-based catalyst obtained in example 4 of the present invention has a higher activity than the catalysts prepared in comparative examples 1 and 2 and the commercial noble metal-based catalyst (RuO 2 /NF) higher UOR current density; (2) Under the same test conditions, as compared to comparative examples 1-2 and commercial RuO 2 NF catalyst, the nickel-based catalyst obtained in example 4 had the lowest UOR initiation potential.
FIG. 12 is a graph of the UOR current-time response of the nickel-based catalyst prepared in example 4. As shown in FIG. 12, the catalyst was used at 20mA cm -2 After continuous catalysis for 20 hours under the high current density of (2), the UOR current density retention rate reaches 88.6%, and the stability is better.
The present invention has been described in detail with reference to the embodiments, but the present invention is not limited to the embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (7)
1. A nickel-based catalyst, characterized in that the nickel-based catalyst consists of a three-dimensional network matrix and porous nanotubes;
the three-dimensional net-shaped matrix has conductivity; the porous nano tubes are distributed on the surface of the three-dimensional reticular matrix, the porous nano tubes are formed by stacking mutually connected composite nano balls, and the composite nano balls are composed of nickel, molybdenum, phosphorus and oxygen.
2. The nickel-based catalyst according to claim 1, wherein the three-dimensional mesh-like matrix is foamed nickel.
3. A method for preparing the nickel-based catalyst according to claim 1 or 2, comprising the steps of:
s1: immersing foam nickel in ethanol solution of zinc acetate;
s2: annealing the foam nickel treated in the step S1;
s3: immersing the foam nickel treated in the step S2 into a mixed aqueous solution of zinc acetate and hexamethylenetetramine for hydrothermal reaction, washing and drying a solid product to obtain the foam nickel loaded with a zinc oxide template;
s4: preparing an electrodeposition aqueous solution, performing electrochemical deposition on the foam nickel loaded with the zinc oxide template obtained in the step S3 in the electrodeposition aqueous solution, and performing in-situ etching, washing and drying on the zinc oxide template to obtain the nickel-based catalyst
The electrodeposition aqueous solution contains 0.1-0.5M nickel sulfate hexahydrate, 0.01-0.05M sodium molybdate, 0.1-0.5M sodium hypophosphite and 0.1-0.5M sodium citrate; the pH of the electrodeposition aqueous solution is 5-7;
the electrochemical deposition is constant current deposition, and the current density of the constant current deposition is 80mA cm -2 ～100mA cm -2 The deposition time was 30min.
4. The method for preparing a nickel-based catalyst according to claim 3, wherein in the step S2, the annealing treatment is performed at 300 ℃ to 400 ℃ for 20min to 40min.
5. The method for preparing a nickel-based catalyst according to claim 3, wherein in the step S3, the hydrothermal reaction is performed at a temperature of 80-120 ℃ for a time of 1 h-4 h.
6. The method of preparing a nickel-based catalyst according to claim 3, wherein in the step S3, the molar concentration of zinc acetate in the mixed aqueous solution is 0.01-M-0.06M and the molar concentration of hexamethylenetetramine is 0.01-M-0.06M.
7. Use of a nickel-based catalyst according to claim 1 or 2 for catalyzing urea oxidation reactions.
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