CN111847410B - Preparation method of cobalt phosphide hollow microspheres and product and application thereof - Google Patents
Preparation method of cobalt phosphide hollow microspheres and product and application thereof Download PDFInfo
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- CN111847410B CN111847410B CN202010650951.9A CN202010650951A CN111847410B CN 111847410 B CN111847410 B CN 111847410B CN 202010650951 A CN202010650951 A CN 202010650951A CN 111847410 B CN111847410 B CN 111847410B
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- 239000004005 microsphere Substances 0.000 title claims abstract description 90
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 66
- 239000010941 cobalt Substances 0.000 title claims abstract description 66
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 58
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000008367 deionised water Substances 0.000 claims abstract description 35
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 35
- 239000004793 Polystyrene Substances 0.000 claims abstract description 33
- 229920002223 polystyrene Polymers 0.000 claims abstract description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003999 initiator Substances 0.000 claims abstract description 22
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 claims abstract description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 16
- 239000011574 phosphorus Substances 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 14
- 229940011182 cobalt acetate Drugs 0.000 claims abstract description 14
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 14
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052786 argon Inorganic materials 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000000839 emulsion Substances 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 7
- 230000001681 protective effect Effects 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 6
- 230000015556 catabolic process Effects 0.000 claims description 5
- 238000006731 degradation reaction Methods 0.000 claims description 5
- 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 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 3
- 235000011009 potassium phosphates Nutrition 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims 1
- 231100000956 nontoxicity Toxicity 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 12
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 229910000085 borane Inorganic materials 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000000593 degrading effect Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000012448 Lithium borohydride Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001193 catalytic steam reforming Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
-
- 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
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- B01J35/51—
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- 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
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- 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
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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- 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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- 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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Abstract
The invention relates to a preparation method of cobalt phosphide hollow microspheres and a product and application thereof.A method for improving the catalytic performance of the cobalt phosphide hollow microspheres by a template method is characterized in that a styrene monomer and an emulsifier are added into deionized water, and an initiator is added after the mixture is vigorously stirred to form an emulsion and reacts in a water bath kettle to prepare polystyrene microspheres; then adding the cobalt acetate and ammonia water into a mixed solution of deionized water and ethanol, reacting in a water bath, centrifugally washing, drying, and roasting in a tubular furnace under the protection of hydrogen-argon mixed gas; and finally, mixing the powder with a phosphorus source, roasting in a tubular furnace in a protective gas atmosphere, and naturally cooling to room temperature to obtain the cobalt phosphide hollow microspheres. The cobalt phosphide hollow microspheres prepared by the method have the advantages of low price, no toxicity, no harm, large specific surface area, excellent catalytic performance and high hydrogen release rate in catalyzing ammonia borane.
Description
Technical Field
The invention belongs to the field of nano powder preparation, and particularly relates to a preparation method of cobalt phosphide hollow microspheres and a product and application thereof.
Background
In recent years, with rapid development of world economy, demand and consumption of fossil materials have increased greatly. Since fossil raw materials are non-renewable energy sources, the reserves thereof have not been able to meet the needs of people. In addition, the release of carbon dioxide caused by the pollution causes greenhouse effect and also seriously influences the survival of human beings, so that the development of alternative energy sources becomes great trend. Among them, hydrogen has become a hot research point due to its regenerability and non-pollution.
Currently, catalytic steam reforming, coal gasification, petroleum cracking and other methods are mainly used for industrially preparing hydrogen, but these methods generally have some disadvantages, such as high energy consumption, impure prepared hydrogen, large amount of carbon dioxide discharged and the like. The catalytic hydrolysis of borohydride such as sodium borohydride, borane ammonia, lithium borohydride and the like provides an environmentally friendly approach to hydrogen production. Among them, borane ammonia becomes an ideal material for hydrogen production by hydrolysis due to its characteristics of high theoretical hydrogen content, relatively high environmental stability, no toxicity, environmental friendliness, etc. However, large-scale application of borane ammonia also relies on the development of highly efficient, stable and inexpensive catalysts.
Transition metal phosphides are a stable and highly efficient class of catalysts. Phosphorus atoms enter transition metal lattices to form interstitial compounds, so that the catalyst has extremely strong conductivity, high thermal stability and chemical stability, and can be used as a catalyst with excellent performance to be applied to the preparation of hydrogen through the catalytic degradation of ammonia borane. Among them, cobalt phosphide attracts researchers' attention due to its excellent properties, but its specific surface area is too low, active sites are too few, and these adverse factors limit the exertion of its catalytic efficiency, so that it still cannot meet the requirement of commercial use.
In order to improve the capability of cobalt phosphide for catalyzing and degrading ammonia borane to prepare hydrogen, the invention improves the surface reaction active site by preparing the cobalt phosphide hollow microsphere, thereby improving the catalytic efficiency. The method comprises the steps of preparing polystyrene spheres, growing and preparing metal cobalt on the surfaces of the polystyrene spheres to prepare cobalt metal hollow microspheres, and preparing the cobalt phosphide hollow microspheres in a phosphating mode. The cobalt phosphide hollow microsphere prepared by the method is low in price, non-toxic, harmless, large in specific surface area, excellent in catalytic performance and high in hydrogen releasing rate when catalyzing ammonia borane.
Disclosure of Invention
Aiming at the defect of low catalytic performance of cobalt phosphide, the invention aims to provide a preparation method of cobalt phosphide hollow microspheres.
Yet another object of the present invention is to: provides a cobalt phosphide hollow microsphere product prepared by the method.
Yet another object of the present invention is to: provides an application of the product.
The purpose of the invention is realized by the following scheme: a preparation method of cobalt phosphide hollow microspheres is characterized in that the method for improving the catalytic performance of the cobalt phosphide hollow microspheres by a template method comprises the following specific steps:
1) Accurately weighing a styrene monomer, an initiator, an emulsifier and deionized water according to a formula, firstly adding the styrene monomer and the emulsifier into the deionized water, violently stirring to form an emulsion, then adding the emulsifier while stirring, reacting in a water bath for a period of time, and filtering and washing to obtain polystyrene microspheres;
2) Adding the prepared polystyrene spheres into a mixed solution of deionized water and ethanol, then adding a certain amount of cobalt acetate, fully stirring, then adding ammonia water, reacting in a water bath kettle for a period of time under the condition of stirring, centrifugally washing, roasting the obtained powder in a tubular furnace at a certain temperature for a period of time under the protection of hydrogen-argon mixed gas, and cooling to obtain the metal cobalt hollow microspheres;
3) Mixing the prepared cobalt hollow microsphere with a phosphorus source, roasting for 0.5-12 h at 200-700 ℃ in a tubular furnace under the protection of protective gas, and naturally cooling to obtain the cobalt phosphide hollow microsphere.
In the step 1), the initiator is one of or a mixture of methyl ethyl ketone peroxide, potassium persulfate, dibenzoyl peroxide or dicumyl peroxide; the emulsifier is one or a mixture of sodium dodecyl benzene sulfonate, hexadecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium chloride, polyvinylpyrrolidone or polyethylene glycol; the mass ratio of the styrene monomer to the initiator is 1.0001-1, and the mass ratio of the styrene monomer to the emulsifier is 1: 0.0001-1; the mass ratio of the styrene to the deionized water is 1: 1-1000; the temperature of the water bath kettle is 30-100 ℃; the water bath reaction time is 1-36 h.
The mass ratio of the deionized water to the ethanol in the step 2) is 1: 0.01-100; the mass ratio of the polystyrene microspheres to the cobalt acetate is 1: 1-500; the mass ratio of the polystyrene microspheres to the ammonia water is 1: 0.001-100; the temperature of the water bath kettle is 30-100 ℃; the water bath reaction time is 1-36 h.
In the step 2), the roasting temperature is 200-700 ℃, and the roasting time is 0.5-12 h.
In the step 3), the phosphorus source is one of or a mixture of sodium hypophosphite, potassium phosphate, disodium hydrogen phosphate and sodium dihydrogen phosphate; the protective gas is one of nitrogen and argon or the mixture thereof; the mass ratio of the cobalt hollow microsphere to the phosphorus source is 1.
The invention provides cobalt phosphide hollow microspheres prepared by any one of the methods.
The invention provides an application of cobalt phosphide hollow microspheres as a catalyst in hydrogen production by catalytic degradation of ammonia borane.
The method for preparing the cobalt phosphide hollow microspheres provided by the invention comprises the following steps: weighing a styrene monomer, an initiator, an emulsifier and deionized water, firstly adding the styrene monomer and the emulsifier into the deionized water, violently stirring to form an emulsion, then adding the initiator, and reacting in a water bath to obtain polystyrene microspheres; then adding the cobalt acetate and ammonia water into a mixed solution of deionized water and ethanol, reacting in a water bath, centrifugally washing, drying, and roasting in a tubular furnace under the protection of hydrogen-argon mixed gas; and finally, mixing the powder with a phosphorus source, roasting in a tubular furnace in a protective gas atmosphere, and naturally cooling to room temperature to obtain the cobalt phosphide hollow microspheres.
The cobalt phosphide hollow microspheres prepared by the method have the advantages of low price, no toxicity, no harm, large specific surface area, excellent catalytic performance and high hydrogen release rate in catalyzing ammonia borane.
Drawings
FIG. 1 is a transmission electron micrograph of cobalt phosphide hollow microspheres prepared in example 1 of the present invention.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1
A cobalt phosphide hollow microsphere is prepared by a template method to improve the catalytic performance, and is prepared by the following steps:
1) Preparing polystyrene microspheres: weighing a styrene monomer, an initiator potassium persulfate, an emulsifier sodium dodecyl benzene sulfonate and deionized water, wherein the mass ratio of the styrene monomer to the initiator is 1:0.01, and the mass ratio of the styrene monomer to the emulsifier is 1; the mass ratio of the styrene to the deionized water is 1; firstly, adding a styrene monomer and an emulsifier into deionized water, violently stirring to form an emulsion, then adding an initiator while stirring, reacting for 6 hours in a 70 ℃ water bath kettle, filtering and washing to obtain polystyrene microspheres;
2) Preparing the metal cobalt hollow microspheres: adding the prepared polystyrene microspheres into a mixed solution of deionized water and ethanol, wherein the mass ratio of the deionized water to the ethanol is 1:5; then adding cobalt acetate, wherein the mass ratio of the polystyrene microspheres to the cobalt acetate is 1:10, fully stirring, adding ammonia water, wherein the mass ratio of the polystyrene microspheres to the ammonia water is 1:1, reacting for 10 hours in a water bath kettle at 80 ℃ under the condition of stirring, centrifugally washing, roasting the obtained powder for 5 hours at 300 ℃ in a tubular furnace under the protection of hydrogen-argon mixed gas, and cooling to obtain cobalt hollow microspheres;
3) And (2) mixing the prepared cobalt hollow microspheres with a phosphorus source potassium phosphate, wherein the mass ratio of the cobalt hollow microspheres to the phosphorus source is 1. The transmission electron microscope photo of the prepared cobalt phosphide hollow microsphere is shown in figure 1.
The hydrogen production efficiency of the prepared cobalt phosphide hollow microspheres through catalytic degradation of ammonia borane is as follows: the ammonia borane concentration is 170mmol/L, the molar ratio of the cobalt phosphide to the ammonia borane is 1 2 ) mol/(Cat-M) mol min, see Table 1.
Example 2
The cobalt phosphide hollow microsphere is similar to that in example 1 and prepared by the following steps:
1) Preparing polystyrene microspheres: weighing a styrene monomer, an initiator methyl ethyl ketone peroxide, an emulsifier cetyl trimethyl ammonium bromide and deionized water, wherein the mass ratio of the styrene monomer to the initiator is 1; the mass ratio of the styrene to the deionized water is 1; firstly, adding a styrene monomer and an emulsifier into deionized water, violently stirring to form an emulsion, then adding an initiator while stirring, reacting for 12 hours in a water bath kettle at 80 ℃, filtering and washing to obtain polystyrene microspheres;
2) Preparing the metal cobalt hollow microspheres: adding the prepared polystyrene microspheres into a mixed solution of deionized water and ethanol, wherein the mass ratio of the deionized water to the ethanol is 1: 1; then adding cobalt acetate, wherein the mass ratio of the polystyrene microspheres to the cobalt acetate is 1:100, fully stirring, adding ammonia water, wherein the mass ratio of the polystyrene microspheres to the ammonia water is 1:5, reacting for 10 hours in a 65 ℃ water bath kettle under the condition of stirring, centrifugally washing, roasting the obtained powder for 2 hours at the temperature of 400 ℃ in a tubular furnace under the protection of hydrogen-argon mixed gas, and cooling to obtain cobalt hollow microspheres;
3) And mixing the prepared cobalt hollow microspheres with phosphorus source sodium hypophosphite, wherein the mass ratio of the cobalt hollow microspheres to the phosphorus source is 1.
The detection method of the hydrogen production efficiency of the prepared cobalt phosphide hollow microspheres for catalyzing and degrading ammonia borane is the same as the embodiment mode, and the TOF value is 42.3 (H) 2 ) mol/(Cat-M) mol min, see Table 1.
Example 3
A cobalt phosphide hollow microsphere, similar to the preparation method of the example 1, which comprises the following steps:
1) Preparing polystyrene microspheres: weighing a styrene monomer, an initiator dibenzoyl peroxide, an emulsifier polyvinylpyrrolidone and deionized water, wherein the mass ratio of the styrene monomer to the initiator is 1; the mass ratio of the styrene to the deionized water is 1; firstly, adding a styrene monomer and an emulsifier into deionized water, violently stirring to form an emulsion, then adding an initiator while stirring, reacting for 6 hours in a 65 ℃ water bath kettle, and filtering and washing to obtain polystyrene microspheres;
2) Preparing the metal cobalt hollow microspheres: adding the prepared polystyrene microspheres into a mixed solution of deionized water and ethanol, wherein the mass ratio of the deionized water to the ethanol is 1; then adding cobalt acetate, wherein the mass ratio of the polystyrene microspheres to the cobalt acetate is 1:100, fully stirring, adding ammonia water, wherein the mass ratio of the polystyrene microspheres to the ammonia water is 1:1, reacting for 12 hours in a water bath kettle at 80 ℃ under the condition of stirring, centrifugally washing, roasting the obtained powder for 6 hours at 350 ℃ in a tubular furnace under the protection of hydrogen-argon mixed gas, and cooling to obtain cobalt hollow microspheres;
3) And (2) mixing the prepared cobalt hollow microspheres with a phosphorus source disodium hydrogen phosphate, wherein the mass ratio of the cobalt hollow microspheres to the phosphorus source is 1.
The detection of the hydrogen production efficiency of the prepared cobalt phosphide hollow microsphere for catalyzing and degrading ammonia borane is the same as the embodiment mode, and the TOF value is 45.7 (H) 2 ) mol/(Cat-M) mol min, see Table 1.
Example 4
The cobalt phosphide hollow microsphere is similar to that in example 1 and prepared by the following steps:
1) Preparing polystyrene microspheres: weighing a styrene monomer, an initiator dicumyl peroxide, an emulsifier polyethylene glycol and deionized water, wherein the mass ratio of the styrene monomer to the initiator is 1; the mass ratio of the styrene to the deionized water is 1; firstly, adding a styrene monomer and an emulsifier into deionized water, violently stirring to form an emulsion, then adding an initiator while stirring, reacting for 3 hours in a water bath kettle at 90 ℃, filtering and washing to obtain polystyrene microspheres;
2) Preparing the metal cobalt hollow microspheres: adding the prepared polystyrene microspheres into a mixed solution of deionized water and ethanol, wherein the mass ratio of the deionized water to the ethanol is 1: 0.2; then adding cobalt acetate, wherein the mass ratio of the polystyrene microspheres to the cobalt acetate is 1:100, fully stirring, then adding ammonia water, wherein the mass ratio of the polystyrene microspheres to the ammonia water is 1;
3) And (2) mixing the prepared cobalt hollow microspheres with phosphorus source sodium hypophosphite, wherein the mass ratio of the cobalt hollow microspheres to the phosphorus source is 1.
The detection of the hydrogen production efficiency of the prepared cobalt phosphide hollow microsphere for catalyzing and degrading ammonia borane is the same as the embodiment mode, and the TOF value is 51.5 (H) 2 ) mol/(Cat-M) mol min, see Table 1.
Table 1 shows TOF values of hydrogen production efficiency by catalytic degradation of borane ammonia by using the catalyst prepared in each example (borane ammonia concentration is 170mmol/L, and the molar ratio of cobalt phosphide to borane ammonia is 1:
Claims (5)
1. a preparation method of cobalt phosphide hollow microspheres is characterized in that the method for improving the catalytic performance of the cobalt phosphide hollow microspheres by a template method comprises the following steps:
1) Preparing polystyrene microspheres: weighing styrene monomer, initiator, emulsifier and deionized water, wherein the mass ratio of the styrene monomer to the initiator is 1 (0.0001-1), and the mass ratio of the styrene monomer to the emulsifier is 1 (0.0001-1); the mass ratio of the styrene to the deionized water is 1 (1-1000); firstly, adding a styrene monomer and an emulsifier into deionized water, violently stirring to form an emulsion, then adding an initiator while stirring, reacting in a water bath, filtering and washing to obtain polystyrene microspheres;
2) Preparing the metal cobalt hollow microspheres: adding the prepared polystyrene microspheres into a mixed solution of deionized water and ethanol, and then adding cobalt acetate, wherein the mass ratio of the polystyrene microspheres to the cobalt acetate is 1: 1-500; adding ammonia water after fully stirring, wherein the mass ratio of the polystyrene microspheres to the ammonia water is 1: 0.001-100; reacting in a water bath kettle under the condition of stirring, roasting the obtained powder in a tubular furnace under the protection of hydrogen-argon mixed gas after centrifugal washing, and cooling to obtain the cobalt hollow microspheres;
3) Mixing the prepared cobalt hollow microspheres with a phosphorus source, roasting in a tubular furnace at 200-700 ℃ for 0.5-12 h under the protection of protective gas, and naturally cooling to obtain cobalt phosphide hollow microspheres; wherein the content of the first and second substances,
in the step 1), the initiator is one of or a mixture of methyl ethyl ketone peroxide, potassium persulfate, dibenzoyl peroxide or dicumyl peroxide; the emulsifier is one or a mixture of sodium dodecyl benzene sulfonate, hexadecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium chloride, polyvinylpyrrolidone or polyethylene glycol; the water bath kettle is used for carrying out water bath reaction for 1 to 36 hours at the temperature of between 30 and 100 ℃;
the mass ratio of the deionized water to the ethanol in the step 2) is 1: 0.01-100; the temperature of the water bath kettle is 30-100 ℃; the water bath reaction time is 1-36 h.
2. The preparation method of the cobalt phosphide hollow microspheres according to claim 1, wherein the roasting temperature in the step 2) is 200-700 ℃ and the roasting time is 0.5-12 h.
3. The method for preparing the cobalt phosphide hollow microspheres according to claim 1, wherein the phosphorus source in the step 3) is one of or a mixture of sodium hypophosphite, potassium phosphate, disodium hydrogen phosphate and sodium dihydrogen phosphate; the protective gas is one of nitrogen and argon or the mixture thereof; the mass ratio of the cobalt hollow microsphere to the phosphorus source is 1.
4. Hollow cobalt phosphide microspheres prepared according to the process of any one of claims 1 to 3.
5. The application of the cobalt phosphide hollow microspheres as claimed in claim 4 as a catalyst in hydrogen production by catalytic degradation of ammonia borane.
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