CN110835103A - Preparation method of cobalt-copper phosphate microspheres and application of cobalt-copper phosphate microspheres in catalyzing ammonia borane hydrolysis to produce hydrogen - Google Patents
Preparation method of cobalt-copper phosphate microspheres and application of cobalt-copper phosphate microspheres in catalyzing ammonia borane hydrolysis to produce hydrogen Download PDFInfo
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- CN110835103A CN110835103A CN201911190956.1A CN201911190956A CN110835103A CN 110835103 A CN110835103 A CN 110835103A CN 201911190956 A CN201911190956 A CN 201911190956A CN 110835103 A CN110835103 A CN 110835103A
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- OFVABKPSLCGISO-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Co+2].[Cu+2] Chemical compound P(=O)([O-])([O-])[O-].[Co+2].[Cu+2] OFVABKPSLCGISO-UHFFFAOYSA-K 0.000 title claims abstract description 17
- 239000004005 microsphere Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 24
- 239000001257 hydrogen Substances 0.000 title claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 22
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 title claims description 11
- 230000007062 hydrolysis Effects 0.000 title claims description 9
- 238000006460 hydrolysis reaction Methods 0.000 title claims description 9
- 239000000243 solution Substances 0.000 claims abstract description 70
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 49
- 238000005406 washing Methods 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 20
- 239000012498 ultrapure water Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 150000001868 cobalt Chemical class 0.000 claims abstract description 6
- 150000001879 copper Chemical class 0.000 claims abstract description 5
- 239000004094 surface-active agent Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000012266 salt solution Substances 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000013877 carbamide Nutrition 0.000 claims description 2
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 claims description 2
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims description 2
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 229960004011 methenamine Drugs 0.000 claims 1
- 239000010949 copper Substances 0.000 abstract description 37
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 8
- 238000009776 industrial production Methods 0.000 abstract description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000003760 magnetic stirring Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 7
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 6
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 6
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 6
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000011232 storage material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 235000005811 Viola adunca Nutrition 0.000 description 2
- 240000009038 Viola odorata Species 0.000 description 2
- 235000013487 Viola odorata Nutrition 0.000 description 2
- 235000002254 Viola papilionacea Nutrition 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910003203 NH3BH3 Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052927 chalcanthite Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000153 copper(II) phosphate Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- 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
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a preparation method of cobalt-copper phosphate microspheres, which comprises the following steps: (1) dissolving a pH regulator, a surfactant and ultrapure water to form solution A; (2) dissolving soluble cobalt salt and copper salt solution in ultrapure water to prepare mixed salt solution B; (3) slowly adding the solution B into the solution A, mixing to form a solution C, and stirring for 0-1 h; (4) slowly dropwise adding 30% of H into the solution C3PO4A solution; (5) transferring the mixture to a reaction kettle, reacting for 2-24 hours at 80-180 ℃, filtering and washing, collecting the product, and drying the product in a vacuum oven at 40-80 DEG C. The invention adopts a hydrothermal synthesis method, and prepares a series of cobalt-copper phosphate microsphere catalysts by selecting, optimizing and controllably synthesizing reaction conditions. The process effectively realizes the setting of the cobalt-copper ratio in the raw materials, the whole preparation process is simple to operate, environment-friendly, very good in experimental reproducibility, low in cost, easy for industrial production and capable of producing Cu in large scale3‑3xCo3x(PO4)2A phosphate salt.
Description
Technical Field
The invention belongs to the field of catalysis and the field of hydrogen storage materials. In particular to a preparation method of cobalt copper phosphate microspheres and application thereof in catalyzing ammonia borane hydrolysis to produce hydrogen.
Background
With the rapid development of world economy, the over consumption of non-renewable energy sources such as coal and oil and the gradual worsening of environmental pollution, the search for a renewable clean energy source has become a hot spot of scientific research. Hydrogen is of great interest because of its high heat value of combustion, no pollution of the product, etc. High-efficiency hydrogen storage and transportation are important factors which restrict the development and utilization of hydrogen energy at present. In order to solve the problems of hydrogen storage and hydrogen transportation, hydrogen production by using hydride becomes a current research hotspot. Among the numerous hydrogen storage materials, ammonia borane (NH)3BH3AB) has high hydrogen content, high hydrogen release rate, good stability and environmental protection, and is considered to be one of the potential hydrogen storage materials. However, the reaction rate is extremely slow under the condition that ammonia borane hydrolysis hydrogen production is not catalyzed by a catalyst at normal temperature, while in the previous research on catalysts, noble metal catalysts show excellent hydrogen production performance, but the noble metals are expensive, so that the industrial application of the noble metals is limited. Therefore, the research focus is to find a non-noble metal catalyst with abundant and low price for rapid hydrogen release in ammonia borane hydrolysis. The introduction of hetero atoms (P, B, N, etc.) is reported to cause the electronic structure of the catalyst to change during the reaction process, thereby reducing the amount of the compound required for B-N bond breaking of the ammonia boraneEnergy, thereby improving catalyst performance.
Transition metal phosphates (Co)3(PO4)2、Cu3(PO4)2Etc.) the nano-material has wide application in the fields of super capacitors, lithium ion batteries, electrocatalysis, photocatalysis, etc. due to the characteristics of special lattice structure, high specific surface area, good conductivity, complex electronic structure, etc.
Chinese patent (CN107096555A) proposes a preparation method of a cobalt carbonate composite cobalt phosphate photocatalyst, which prepares a precursor solution by cobalt nitrate, sodium carbonate and deionized water; stirring and mixing the two solutions to form a colloidal substance, and reacting sodium carbonate with cobalt nitrate in the stirring process to generate cobalt carbonate colloid; placing the cobalt carbonate colloid in a semipermeable membrane bag, washing with distilled water to remove free ions, adding the cobalt carbonate colloid into a sodium phosphate solution with a certain concentration, soaking until cobalt phosphate nano-particles are formed on the surfaces of the cobalt carbonate particles, performing solid-liquid separation, washing the solids with deionized water, and drying to obtain the cobalt carbonate composite cobalt phosphate photocatalyst. But the preparation period is too long and the energy consumption is high, which is not beneficial to industrial application.
Chinese patent (CN104269528A) discloses a preparation method of a cobalt phosphate powder material, wherein the cobalt phosphate powder material can be prepared by simply reacting soluble cobalt salt with soluble phosphate, then adjusting the pH value of a reaction system to be neutral by ammonia water, and further washing, drying, grinding and screening, but the cobalt phosphate powder material prepared by the method has uneven shape distribution.
Therefore, the invention aims to solve the problems of developing a method which has controllable appearance, lower cost and excellent product performance and can be applied to the industrial production of phosphate compounds.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a phosphate catalyst with regular morphology, the synthesis method is simple, the conditions are mild, and the synthesized Cu3-3xCo3x(PO4)2Is spherical and has a diameter ofUniform dispersion, regular appearance and the like.
The invention provides a preparation method of cobalt-copper phosphate microspheres, which comprises the following steps:
(1) dissolving a pH regulator, a surfactant and ultrapure water to form solution A;
(2) dissolving soluble cobalt salt or soluble copper salt or both in ultrapure water to prepare a mixed salt solution B;
(3) slowly adding the solution B into the solution A, mixing to form a solution C, and stirring for 0-1 h;
(4) slowly dropwise adding 30% of H into the solution C3PO4A solution;
(5) and transferring the mixture to a reaction kettle, reacting for 2-24 hours at 80-180 ℃, filtering and washing, collecting the product, and drying at 40-80 ℃ in a vacuum oven.
Preferably, the surfactant in step (1) is one or more selected from sodium dodecyl sulfate, polyvinylpyrrolidone, cetyl trimethyl ammonium bromide and polyethylene glycol.
Preferably, the pH regulator in step (1) is one or more of urea, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ammonia water and hexamethylenetetramine.
Preferably, the soluble cobalt salt in step (2) is selected from one or more of cobalt acetate tetrahydrate, cobalt chloride, cobalt sulfate, cobalt nitrate, cobalt chloride hexahydrate, cobalt sulfate heptahydrate and cobalt nitrate hexahydrate.
Preferably, the soluble copper salt in step (2) is selected from one or more of copper chloride dihydrate, copper sulfate pentahydrate and copper nitrate.
Preferably, the amount of phosphoric acid added in step (4) is in combination with the metal salt Co2+Or Cu2+Or the molar ratio of the two is 2/3-3.
The invention also discloses application of the cobalt-copper phosphate catalyst prepared by the method in catalyzing ammonia borane hydrolysis to produce hydrogen. In conclusion, the preparation method disclosed by the invention has the following beneficial effects:
1. the preparation method is simple, and the synthesized product is microspherical and uniformly dispersed.
2. Can flexibly adjust the proportion of cobalt and copper to synthesize the copper alloy with the chemical general formula of Cu3-3xCo3x(PO4)2Cobalt copper phosphate catalyst.
3. Cu prepared by the invention3-3xCo3x(PO4)2The microspheres are used for catalyzing ammonia borane hydrolysis to produce hydrogen. Exhibit excellent properties, especially Cu0.6Co2.4(PO4)2Exhibit strong catalytic performance.
Drawings
FIG. 1 shows Cu prepared by the present invention0.6Co2.4(PO4)2SEM picture of (1);
FIG. 2 shows Cu prepared by the present invention0.6Co2.4(PO4)2A TEM image of (B);
FIG. 3 shows Cu prepared by the present invention0.6Co2.4(PO4)2Mapping graph of (1);
FIG. 4 shows Cu prepared by the present invention0.6Co2.4(PO4)2XRD pattern of (a);
FIG. 5 shows Cu prepared by the present invention0.6Co2.4(PO4)2FT-IR diagram of (1);
FIG. 6 shows Cu with different ratios of Co and Cu prepared by the present invention3-3xCo3x(PO4)2The catalyst is used for catalyzing hydrogen production performance.
Detailed Description
The foregoing summary of the invention is described in further detail below with reference to specific embodiments. It should not be understood that the scope of the above-described subject matter of the present invention is limited to the following examples. Various substitutions, alterations, modifications and the like are included in the scope of the present invention according to the common technical knowledge and the conventional means in the field without departing from the technical idea of the present invention.
Example 1
Preparing a precursor: 6.0g of urea and 0.5g of Sodium Dodecyl Sulfate (SDS) were dissolved in 61.3mL of ultrapure water by magnetic stirring to obtain a solution A, and 0.281g of CoS was weighedO4·7H2O was dissolved in 2.7mL of ultrapure water, and dissolved by magnetic stirring to obtain a solution B. Slowly adding the solution B into the solution A dropwise to obtain a solution C, and continuously stirring for 30 min. Slowly dropwise adding 0.326gH into the solution C3PO4(30 wt%), the resulting solution was transferred to a reaction vessel and screwed down for hydrothermal reaction at 90 ℃ for 4 hours. After the reaction is finished, cooling to room temperature, carrying out suction filtration washing, collecting the product, washing for 2-3 times with water and 2-3 times with ethanol, drying at 60 ℃ in a vacuum oven, and taking out the sample to obtain the target product Co after the product is cooled to room temperature3(PO4)2。
Through determination, the Co obtained by the invention3(PO4)2The appearance is spherical, and the color is dark purple.
Example 2
Preparing a precursor: 6.0g of urea and 0.5g of Sodium Dodecyl Sulfate (SDS) were weighed out and dissolved in 61.3mL of ultrapure water, and the solution A was dissolved by magnetic stirring, and 0.225g of CoSO was weighed out4·7H2O and 0.050gCuSO4·5H2O was dissolved in 2.7mL of ultrapure water, and dissolved by magnetic stirring to obtain a solution B. Slowly adding the solution B into the solution A dropwise to obtain a solution C, and continuously stirring for 30 min. Slowly dropwise adding 0.326gH into the solution C3PO4(30 wt%), the resulting solution was transferred to a reaction vessel and screwed down for hydrothermal reaction at 90 ℃ for 4 hours. After the reaction is finished, cooling to room temperature, carrying out suction filtration washing, collecting the product, washing for 2-3 times with water, washing for 2-3 times with ethanol, drying at 60 ℃ in a vacuum oven, and taking out the sample after the product is cooled to room temperature to obtain the target product Cu0.6Co2.4(PO4)2。
Through determination, the Cu obtained by the invention0.6Co2.4(PO4)2The appearance is spherical, and the color is dark purple.
Example 3
Preparing a precursor: 6.0g of urea and 0.5g of Sodium Dodecyl Sulfate (SDS) were weighed out and dissolved in 61.3mL of ultrapure water, and the solution A was dissolved by magnetic stirring, and 0.169g of CoSO was weighed out4·7H2O and 0.100g of CuSO4·5H2O was dissolved in 2.7mL of ultrapure water, and dissolved by magnetic stirring to obtain a solution B. Will be provided withSlowly dripping the solution B into the solution A to obtain a solution C, and continuously stirring for 30 min. Slowly dropwise adding 0.326gH into the solution C3PO4(30 wt%), the resulting solution was transferred to a reaction vessel and screwed down for hydrothermal reaction at 90 ℃ for 4 hours. After the reaction is finished, cooling to room temperature, carrying out suction filtration washing, collecting the product, washing for 2-3 times with water, washing for 2-3 times with ethanol, drying at 60 ℃ in a vacuum oven, and taking out the sample after the product is cooled to room temperature to obtain the target product Cu1.2Co1.8(PO4)2。
Through determination, the Cu obtained by the invention1.2Co1.8(PO4)2The appearance is spherical, and the color is blue-violet.
Example 4
Preparing a precursor: 6.0g of urea and 0.5g of Sodium Dodecyl Sulfate (SDS) were weighed out and dissolved in 61.3mL of ultrapure water, and the solution A was dissolved by magnetic stirring, and 0.141g of CoSO was weighed out4·7H2O and 0.125gCuSO4·5H2O was dissolved in 2.7mL of ultrapure water, and dissolved by magnetic stirring to obtain a solution B. Slowly adding the solution B into the solution A dropwise to obtain a solution C, and continuously stirring for 30 min. Slowly dropwise adding 0.326gH into the solution C3PO4(30 wt%), the resulting solution was transferred to a reaction vessel and screwed down for hydrothermal reaction at 90 ℃ for 4 hours. After the reaction is finished, cooling to room temperature, carrying out suction filtration washing, collecting the product, washing for 2-3 times with water, washing for 2-3 times with ethanol, drying at 60 ℃ in a vacuum oven, and taking out the sample after the product is cooled to room temperature to obtain the target product Cu1.5Co1.5(PO4)2。
Through determination, the Cu obtained by the invention1.5Co1.5(PO4)2The appearance is spherical, and the color is blue-violet.
Example 5
Preparing a precursor: 6.0g of urea and 0.5g of Sodium Dodecyl Sulfate (SDS) were weighed out and dissolved in 61.3mL of ultrapure water, and the solution A was dissolved by magnetic stirring, and 0.225g of CoSO was weighed out4·7H2O and 0.050gCuSO4·5H2O was dissolved in 2.7mL of ultrapure water, and dissolved by magnetic stirring to obtain a solution B. Slowly dripping the solution B into the solution A to obtain a solution C, and continuously stirringAnd (3) 30 min. Slowly dropwise adding 0.625gH into the solution C3PO4(30 wt%), the resulting solution was transferred to a reaction vessel and screwed down for hydrothermal reaction at 90 ℃ for 4 hours. After the reaction is finished, cooling to room temperature, carrying out suction filtration washing, collecting the product, washing for 2-3 times with water, washing for 2-3 times with ethanol, drying at 60 ℃ in a vacuum oven, and taking out the sample after the product is cooled to room temperature to obtain the target product Cu0.6Co2.4(PO4)2。
Through determination, the Cu obtained by the invention0.6Co2.4(PO4)2The appearance is spherical, and the color is dark purple.
Example 6
Preparing a precursor: 6.0g of urea and 0.5g of cetyltrimethylammonium bromide (CTAB) were weighed out and dissolved in 61.3mL of ultrapure water, and dissolved by magnetic stirring to obtain a solution A, and 0.225g of CoSO was weighed out4·7H2O and 0.050gCuSO4·5H2O was dissolved in 2.7mL of ultrapure water, and dissolved by magnetic stirring to obtain a solution B. Slowly adding the solution B into the solution A dropwise to obtain a solution C, and continuously stirring for 30 min. Slowly dropwise adding 0.326gH into the solution C3PO4(30 wt%), the resulting solution was transferred to a reaction vessel and screwed down for hydrothermal reaction at 90 ℃ for 4 hours. After the reaction is finished, cooling to room temperature, performing suction filtration washing to collect a product, washing for 2-3 times with water, washing for 2-3 times with ethanol, drying at 60 ℃ in a vacuum oven, cooling to room temperature, taking out a sample to obtain a target product Cu0.6Co2.4(PO4)2。
Through determination, the Cu obtained by the invention0.6Co2.4(PO4)2The appearance is spherical, and the color is dark purple.
Example 7
Preparing a precursor: 6.0g of hexamethylenetetramine and 0.5g of Sodium Dodecyl Sulfate (SDS) were weighed out and dissolved in 61.3mL of ultrapure water by magnetic stirring to obtain a solution A, and 0.225g of CoSO was weighed out4·7H2O and 0.050gCuSO4·5H2O was dissolved in 2.7mL of ultrapure water, and dissolved by magnetic stirring to obtain a solution B. Slowly adding the solution B into the solution A dropwise to obtain a solution C, and continuously stirring for 30 min. Slowly dropwise adding 0.32 into the solution C6gH3PO4(30 wt%), the resulting solution was transferred to a reaction vessel and screwed down for hydrothermal reaction at 90 ℃ for 4 hours. After the reaction is finished, cooling to room temperature, carrying out suction filtration washing, collecting the product, washing for 2-3 times with water, washing for 2-3 times with ethanol, drying at 60 ℃ in a vacuum oven, and taking out the sample after the product is cooled to room temperature to obtain the target product Cu0.6Co2.4(PO4)2。
Through determination, the Cu obtained by the invention0.6Co2.4(PO4)2The appearance is spherical, and the color is dark purple.
Below with Cu0.6Co2.4(PO4)2For example, the structure and properties of the composite phosphate prepared according to the present invention were analyzed and tested.
1. SEM analysis
FIG. 1 shows Cu prepared by the present invention0.6Co2.4(PO4)2SEM image of (d). As can be seen from the scanning electron micrograph, the synthesized Cu0.6Co2.4(PO4)2The morphology is spherical, and the particle size is about 500 nm.
2. TEM analysis
FIG. 2 shows Cu prepared by the present invention0.6Co2.4(PO4)2A TEM image of (a). As can be seen from the scanning image of the transmission electron microscope, the synthesized Cu0.6Co2.4(PO4)2The appearance is spherical, the grain diameter is about 500nm, and the inside is a solid structure.
3. Elemental distribution test
FIG. 2 shows Cu prepared by the present invention0.6Co2.4(PO4)2The Mapping graph shows that Cu, Co, P and O elements are uniformly distributed.
4. XRD analysis
FIG. 4 shows Cu prepared by the present invention0.6Co2.4(PO4)2XRD test of (1).
5. Infrared analysis
FIG. 5 shows Cu prepared by the present invention0.6Co2.4(PO4)2FT-IR test of (1).
6. Testing of catalytic Hydrogen production Performance
FIG. 6 shows the preparation of Cu with different ratios of Co and Cu according to the present invention3-3xCo3x(PO4)2Performance test of ammonia borane hydrolysis to hydrogen as catalyst, NH3BH3The dosage is 3mmol, the dosage is 20mmol and the catalyst is 5 mg. Measuring Cu at 25 ℃3-3xCo3x(PO4)2Hydrogen production rate curve.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (7)
1. The preparation method of the cobalt-copper phosphate microspheres is characterized by comprising the following steps of:
(1) dissolving a pH regulator, a surfactant and ultrapure water to form solution A;
(2) dissolving soluble cobalt salt or soluble copper salt or both in ultrapure water to prepare a mixed salt solution B;
(3) slowly adding the solution B into the solution A, mixing to form a solution C, and stirring for 0-1 h;
(4) slowly dropwise adding 30% of H into the solution C3PO4A solution;
(5) and transferring the mixture to a reaction kettle, reacting for 2-24 hours at 80-180 ℃, filtering and washing, collecting the product, and drying at 40-80 ℃ in a vacuum oven.
2. The method for preparing cobalt copper phosphate microspheres according to claim 1, wherein the method comprises the following steps: in the step (1), the pH regulator is one or more of urea, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ammonia water and hexamethylene tetramine.
3. The method for preparing cobalt copper phosphate microspheres according to claim 1, wherein the method comprises the following steps: in the step (1), the surfactant is one or more of cetyl trimethyl ammonium bromide, sodium dodecyl sulfate and polyethylene glycol.
4. The method for preparing cobalt copper phosphate microspheres according to claim 1, wherein the method comprises the following steps: in the step (2), the soluble cobalt salt is selected from one or more of cobalt acetate tetrahydrate, cobalt sulfate, cobalt nitrate, cobalt chloride hexahydrate, cobalt sulfate heptahydrate and cobalt nitrate hexahydrate.
5. The method for preparing cobalt copper phosphate microspheres according to claim 1, wherein the method comprises the following steps: in the step (2), the soluble copper salt is selected from one or more of copper chloride dihydrate, copper sulfate pentahydrate and copper nitrate.
6. The method for preparing cobalt copper phosphate microspheres according to claim 1, wherein the method comprises the following steps: the amount of phosphoric acid added in the step (4) and the metal salt Co2+Or Cu2+Or the molar ratio of the two is 2/3-3.
7. Use of the cobalt copper phosphate prepared by the preparation method according to any one of claims 1 to 6 as a catalyst for catalyzing ammonia borane hydrolysis to produce hydrogen.
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