CN111331149B - Method for preparing hollow Pt nanospheres by taking spherical calcium carbonate as template - Google Patents
Method for preparing hollow Pt nanospheres by taking spherical calcium carbonate as template Download PDFInfo
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 90
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 45
- 239000002077 nanosphere Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 18
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 28
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 16
- 239000011591 potassium Substances 0.000 claims abstract description 16
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 7
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 13
- 239000011575 calcium Substances 0.000 claims description 13
- 229910052791 calcium Inorganic materials 0.000 claims description 13
- 239000004530 micro-emulsion Substances 0.000 claims description 11
- 229920002125 Sokalan® Polymers 0.000 claims description 10
- 239000004584 polyacrylic acid Substances 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000004064 cosurfactant Substances 0.000 claims description 8
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000002211 L-ascorbic acid Substances 0.000 claims description 7
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910001424 calcium ion Inorganic materials 0.000 claims description 6
- -1 polyoxyethylene Polymers 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000004359 castor oil Substances 0.000 claims description 3
- 235000019438 castor oil Nutrition 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 33
- 239000002245 particle Substances 0.000 abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 3
- 238000000593 microemulsion method Methods 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 229910052697 platinum Inorganic materials 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
- 239000011805 ball Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000011796 hollow space material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000011807 nanoball Substances 0.000 description 2
- 239000002088 nanocapsule Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- YDZWPBPSQHXITB-UHFFFAOYSA-N [Rh].[Au] Chemical group [Rh].[Au] YDZWPBPSQHXITB-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002072 nanorope Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005287 template synthesis Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B01J35/51—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0549—Hollow particles, including tubes and shells
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
- B22F1/0655—Hollow particles
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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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/181—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/182—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds
- C01F11/183—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds the additive being an organic compound
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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
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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
- C01P2004/50—Agglomerated particles
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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
Abstract
The invention discloses a method for preparing hollow Pt nanospheres by taking spherical calcium carbonate as a template, which comprises the steps of preparing the spherical calcium carbonate with the particle size of 0.5-1 mu m by adopting a reverse microemulsion method, then taking the spherical calcium carbonate as the template, taking potassium platinochloride as a platinum source and taking ascorbic acid as a reducing agent, and simply and efficiently preparing the hollow Pt nanospheres with regular appearance, uniform size and narrow particle size distribution of 1-2 mu m. The preparation method is simple, safe and nontoxic, and low in cost, and the obtained hollow Pt nanospheres have high catalytic activity and stability on the catalytic oxidation reaction of methanol under an acidic condition, and have a good application prospect in the electrochemical aspect.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a method for preparing hollow Pt nanospheres by taking spherical calcium carbonate as a template.
Background
The noble metals such as platinum, silver, rhodium, palladium, ruthenium and the like have many advantages such as high temperature resistance, corrosion resistance, oxidation resistance and the like, and the catalytic activity of the noble metals is high, so that the noble metals are extremely important catalyst materials. The hollow nano noble metal ball has the features of low density, great specific surface area, high surface activity, high surface permeability, etc. and thus has important application in chemical, biological, material science and other fields.
At present, the preparation methods of the hollow ball material mainly comprise a spray drying method, an emulsion method and a template synthesis method, and the template method is a method which is widely applied and is also more important for preparing the hollow ball. The template method is an important method for synthesizing the nano hollow material, mainly comprises a hard template method and a soft template method, and is characterized in that the geometric form of a template agent can indirectly influence the appearance and appearance characteristics of the nano hollow material, and the template method has the remarkable advantages of effectively controlling the shell thickness, the grain diameter and the dispersity of the hollow structure. For example: hyeon et al, 2008, reported SiO 2 Preparation of iron oxide nanocapsules for template (Piao Y, Kim J, Na H B, et al, wrap-bag-peel process for nanostrucruring from β -FeOOH nanoropes to biocompatible iron oxide nanocapsules [ J]Nature Materials,2008,7(3):242- 2 Balls (Deng, Ziwei, Chen, Min, Zhou, Shuxue, et al. A Novel Method for the simulation of Monodissperse Hollow silicon Spheres [ J].Langmuir the Acs Journal of Surfaces&6403-6407) of Colloids,22(14), Long et al, using oxygen generated by hydrogen peroxide decomposition as a template to synthesize hollow TiO 2 Ball (Long L, Zhang H, Ye M, et al. Ammonia cation-associated ball template for synthesizing hollow TiO) 2 nanospheres and their application in lithium ion storage[J]RSC Advances,2015, 5), Zoldesi et al reported the preparation of hollow SiO using a direct emulsion as template 2 Microspheres and capsule microspheres (C.I. Zoldesi, Imhof A. Synthesis of Monodissperse Colloidal Spheres, Capsules, and Microballoons by Emulsion testing [ J.]Advanced Materials,2005,17(7): 924. sup. 928.), hollow SeCd spheres (Zheng X, Xie Y, Zhu L, et al. Formation of textured CdSe porous spheres in an ultra-induced fibrous surfactant solution [ J., prepared by Zheng et al using anionic vesicles as soft templates]Preparation of ZnO Multi-shell structures (Dong Z, Lai X, Halpert J E, et al. Accurate Control of Multishelled ZnO nanoparticles for Dye-Sensitized Solar Cells with High Efficiency[J]Advanced Materials,2012,24(8):1046-]1801239.) rhodium trichloride and chloroauric acid are used as raw materials to form a rhodium-gold core-shell structure, and gold core is removed by aqua regia to form hollow rhodium. Therefore, providing a simple, effective, low-cost, non-toxic hollow nano material preparation method becomes a hotspot and difficulty in the hollow material field.
Disclosure of Invention
Aiming at the problems of agglomeration, large size of a template agent and harsh removal conditions of the existing hard template method which affect a target product, the invention overcomes the problem that a calcium carbonate template is dissolved and a reduction product Pt is generated in advance by Pt precursor liquid screening and experimental condition regulation and control based on a narrowly distributed, monodisperse and easily removable spherical calcium carbonate template, and finally provides a simple and effective method for preparing hollow Pt nanospheres by using spherical calcium carbonate with the particle size of 0.5-1 mu m prepared by a reverse microemulsion method as the template.
Aiming at the purposes, the technical scheme adopted by the invention comprises the following steps:
1. preparation of spherical calcium carbonate template
Dissolving calcium chloride solid in deionized water, adding polyacrylic acid, stirring uniformly, and then adding sodium dodecyl benzene sulfonate to obtain a calcium source solution with the calcium ion concentration of 0.5-3.5 mol/L; adding the obtained calcium source solution into a mixed solution of cyclohexane, a compound surfactant and a cosurfactant, uniformly mixing, standing, taking supernatant to obtain reverse microemulsion, wherein the total volume of the reverse microemulsion is 100%, the calcium source solution accounts for 1.0-7.0%, the compound surfactant accounts for 0.5-1.5%, the cosurfactant accounts for 0.5-2%, and the balance is cyclohexane; dropwise adding ammonia water into the obtained reverse microemulsion, adjusting the pH value to 8-10, and then continuously introducing CO 2 Reacting the gas at 25-28 ℃ for 0.5-1.5 hours, centrifuging and washing to obtain the porous submicron spheresCalcium carbonate is formed.
2. Preparation of hollow Pt nanospheres
Ultrasonically dispersing the spherical calcium carbonate prepared in the step 1 in 1.3-1.6 mol/L ascorbic acid aqueous solution with the pH value of 7-10, standing for 2-4 hours in a vacuum state, quickly pouring out supernatant, adding 0.01-0.03 mol/L potassium platinochloride aqueous solution with the pH value of 8-12 into lower-layer sediment under the stirring condition of 60-70 ℃, stirring for reacting for 1.5-2 hours, centrifuging, washing, adding dilute hydrochloric acid to remove calcium carbonate, and obtaining the hollow Pt nanosphere.
In the step 1, preferably, the concentration of calcium ions in the obtained calcium source solution is 1.0-3.0 mol/L, the concentration of polyacrylic acid is 0.16-0.24 g/L, and the concentration of sodium dodecyl benzene sulfonate is 0.02-0.03 mol/L, wherein the number average molecular weight of the polyacrylic acid is 5000.
In the step 1, the total volume of the reverse microemulsion is 100%, preferably, the calcium source solution accounts for 2.0% -5.0%, the compound surfactant accounts for 0.7% -1.0%, the cosurfactant accounts for 1.5% -2.0%, and the balance is cyclohexane.
The compound surfactant is a mixture of polyoxyethylene castor oil and span-80 in a mass ratio of 55: 45-65: 35, and the cosurfactant is ethanol.
In the step 2, preferably, the spherical calcium carbonate prepared in the step 1 is ultrasonically dispersed in 1.3-1.6 mol/L ascorbic acid aqueous solution with the pH value of 7.5-8.5, then the spherical calcium carbonate is kept stand for 2-4 hours in a vacuum state, the supernatant is quickly poured out, 0.01-0.03 mol/L potassium platinochloride aqueous solution with the pH value of 10-12 is added into the lower-layer precipitate under the stirring condition at the temperature of 60-70 ℃, and the stirring reaction is carried out for 1.5-2 hours.
The pH of the above-mentioned ascorbic acid aqueous solution and potassium chloroplatinite aqueous solution was adjusted by NaOH.
In the step 2, the mass-to-volume ratio of the spherical calcium carbonate to the potassium chloroplatinite aqueous solution is preferably 1g (200-500) mL.
The invention has the following beneficial effects:
the invention firstly adopts a reverse microemulsion method to prepare the porous material with the particle size of 0.5-1 mu m and high specific surface areaSubmicron spherical calcium carbonate, then using the spherical calcium carbonate as a template, potassium chloroplatinite as a platinum source and ascorbic acid as a reducing agent, and utilizing the characteristics of the porous structure of the spherical calcium carbonate to ensure that the ascorbic acid permeates into the spherical calcium carbonate in a vacuum pumping mode, taking out the spherical calcium carbonate when the ascorbic acid is stably stored in the calcium carbonate, and taking out the ascorbic acid molecules to be extracted from CaCO 3 When the inside overflows outwards, the potassium chloroplatinite water solution is quickly added to reduce the potassium chloroplatinite water solution on the surface of the spherical calcium carbonate to form a core-shell structure, and finally, the calcium carbonate is removed through acid dissolution to form the hollow Pt nanospheres.
The preparation method is simple, safe and nontoxic, and low in cost, the prepared hollow Pt nanospheres are regular in shape, uniform in size and narrow in particle size distribution (1-2 microns), and have high catalytic activity and stability for methanol catalytic oxidation reaction under an acidic condition, and the hollow Pt nanospheres have a good application prospect in the aspect of electrochemistry.
Drawings
FIG. 1 is a scanning electron micrograph of submicron spherical calcium carbonate obtained in example 1.
Fig. 2 is an XRD spectrum of the hollow Pt nanoball obtained in example 1.
Fig. 3 is a scanning electron micrograph of the hollow Pt nanospheres obtained in example 1.
Fig. 4 is a partially enlarged view of fig. 3.
Fig. 5 is a transmission electron micrograph of the hollow Pt nanospheres obtained in example 1.
Fig. 6 is a scanning electron micrograph of the hollow Pt nanospheres obtained in example 2.
Fig. 7 is a scanning electron micrograph of the hollow Pt nanospheres obtained in example 3.
Detailed Description
The invention will be further explained in more detail below with reference to the drawings and examples, but the scope of protection of the invention is not limited to these examples.
Example 1
1. Preparation of spherical calcium carbonate template
1.11g of calcium chloride solid having a purity of 99% or more was dissolved in 8mL of deionized water, and 2 was added theretoAnd (3) stirring 1.0g/L of polyacrylic acid aqueous solution with the number average molecular weight of 5000 for 0.5 hour, then adding 0.0871g of sodium dodecyl benzene sulfonate into the aqueous solution, and uniformly stirring the mixture to obtain a calcium source solution, wherein the concentration of calcium ions is 1.0mol/L, the concentration of polyacrylic acid is 0.2g/L, and the concentration of sodium dodecyl benzene sulfonate is 0.025 mol/L. 0.6g of polyoxyethylene castor oil and 0.4g of span-80 are uniformly mixed, 1.0mL of ethanol is added into the mixture, after uniform mixing, the obtained mixture is dropwise added into 100mL of cyclohexane under the state of stirring at normal temperature, 5mL of calcium source solution is dropwise added into the mixture, the mixture is uniformly stirred and stands for 2 hours, and supernatant is taken to obtain the reverse microemulsion. Dropwise adding ammonia water into the reverse microemulsion, adjusting the pH value to 9.4, and then continuously introducing CO into the reverse microemulsion 2 Standing the gas at 25 ℃ for 40 minutes for reaction, centrifugally separating, washing with ethanol for 3 times, washing with water for 1 time, and finally drying in vacuum at 70 ℃ to obtain the submicron spherical calcium carbonate. As shown in figure 1, the obtained calcium carbonate is spherical, has regular appearance, uniform size and narrow particle size distribution, has the particle size of about 500nm, is composed of 10-20 nm microcrystalline spherical particles, and has a rough surface and a porous shape.
2. Preparation of hollow Pt nanospheres
Ultrasonically dispersing 0.02g of the spherical calcium carbonate prepared in the step 1 in 5mL of 1.5mol/L ascorbic acid aqueous solution (the pH is adjusted by NaOH) with the pH of 8.84, uniformly dispersing, then placing in a vacuum drying box, vacuumizing to 0.8MPa, standing for 3 hours, quickly taking out and pouring out the supernatant, placing in a 65 ℃ water bath kettle, adding 6mL of 0.025mol/L potassium chloroplatinite aqueous solution (the pH is adjusted by NaOH) with the pH of 11 into the lower-layer precipitate in a stirring state, quickly reducing the potassium chloroplatinite on the surface of the calcium carbonate into simple substance Pt within 2-3 minutes, stirring for 1.5 hours, centrifuging, washing, adding dilute hydrochloric acid for 2 hours to remove the calcium carbonate, and finally centrifuging and washing to obtain the hollow Pt nanospheres. The product obtained is really simple substance Pt as can be seen from figure 2, and the obtained metal Pt is obviously seen from figures 3-5 to be in a hollow structure with the grain size of about 1 μm.
Example 2
In this example, 0.02g of the spherical calcium carbonate prepared in step 1 was ultrasonically dispersed in 5mL of a 1.5mol/L ascorbic acid aqueous solution (pH adjusted with NaOH) having a pH of 7.9, and after uniform dispersion, the spherical calcium carbonate was placed in a vacuum drying oven, and after evacuation to 0.8MPa, the spherical calcium carbonate was left to stand for 2 hours. The other steps were the same as in example 1 to obtain hollow Pt nanoballs having a particle size of about 1 μm (see fig. 6).
Example 3
In this example, 0.02g of the spherical calcium carbonate prepared in step 1 was ultrasonically dispersed in 5mL of 1.5mol/L ascorbic acid aqueous solution (pH adjusted with NaOH) having a pH of 8.84, after uniform dispersion, the spherical calcium carbonate was placed in a vacuum drying oven, after evacuation to 0.8MPa, the spherical calcium carbonate was left for 3 hours, the upper clear solution was quickly taken out and poured out, and the spherical calcium carbonate was placed in a 70 ℃ water bath, and 6mL of 0.025mol/L potassium platinate aqueous solution (pH adjusted with NaOH) having a pH of 11.5 was added to the lower precipitate under stirring, and the potassium platinate was quickly reduced to elemental Pt on the surface of calcium carbonate within 2 to 3 minutes, and stirred for 1.5 hours. The other steps were the same as in example 1 to obtain hollow Pt spheres having a particle size of about 1 μm (see fig. 7).
Example 4
In this example, 3.33g of calcium chloride solid with a purity of 99% or more was dissolved in 8mL of deionized water, 2mL of a 1.0g/L polyacrylic acid aqueous solution with a number average molecular weight of 5000 was added thereto, and after stirring uniformly, 0.0871g of sodium dodecylbenzenesulfonate was added thereto, and stirring uniformly was carried out to obtain a calcium source solution with a calcium ion concentration of 3.0mol/L, a polyacrylic acid concentration of 0.2g/L, and a sodium dodecylbenzenesulfonate concentration of 0.025 mol/L. The other steps were the same as in example 1 to obtain hollow Pt nanospheres.
Claims (6)
1. A method for preparing hollow Pt nanospheres by taking spherical calcium carbonate as a template is characterized by comprising the following steps:
(1) preparation of spherical calcium carbonate template
Dissolving calcium chloride solid in deionized water, adding polyacrylic acid, stirring uniformly, and then adding sodium dodecyl benzene sulfonate to obtain a calcium source solution with the calcium ion concentration of 0.5-3.5 mol/L; adding the obtained calcium source solution into mixed solution of cyclohexane, compound surfactant and cosurfactant, mixing uniformly, standing, taking supernatant to obtain reversed-phase microemulsion, and reversing the phaseThe total volume of the microemulsion is 100%, wherein the calcium source solution accounts for 1.0-7.0%, the compound surfactant accounts for 0.5-1.5%, the cosurfactant accounts for 0.5-2.0%, and the balance is cyclohexane, the compound surfactant is a mixture of polyoxyethylene castor oil and span-80 in a mass ratio of 55: 45-65: 35, and the cosurfactant is ethanol; dropwise adding ammonia water into the obtained reverse microemulsion, adjusting the pH value to 8-10, and then continuously introducing CO 2 Reacting the gas at 25-28 ℃ for 0.5-1.5 hours, centrifuging and washing to obtain submicron spherical calcium carbonate with a porous surface;
(2) preparation of hollow Pt nanospheres
Ultrasonically dispersing the spherical calcium carbonate prepared in the step (1) in 1.3-1.6 mol/L ascorbic acid aqueous solution with the pH value of 7-10, standing for 2-4 hours in a vacuum state, quickly pouring out supernatant, adding 0.01-0.03 mol/L potassium chloroplatinite aqueous solution with the pH value of 8-12 into the lower-layer precipitate under the stirring condition of 60-70 ℃, stirring for reacting for 1.5-2 hours, centrifuging, washing, adding dilute hydrochloric acid to remove calcium carbonate, and obtaining the hollow Pt nanosphere.
2. A method of making hollow Pt nanospheres according to claim 1 characterized in that: in the step (1), the concentration of calcium ions in the obtained calcium source solution is 1.0-3.0 mol/L, the concentration of polyacrylic acid is 0.16-0.24 g/L, the concentration of sodium dodecyl benzene sulfonate is 0.02-0.03 mol/L, and the number average molecular weight of the polyacrylic acid is 5000.
3. A method of making hollow Pt nanospheres according to claim 1 characterized in that: in the step (1), the total volume of the reverse microemulsion is 100%, wherein the calcium source solution accounts for 2.0-5.0%, the compound surfactant accounts for 0.7-1.0%, the cosurfactant accounts for 1.5-2.0%, and the balance is cyclohexane.
4. A method of making hollow Pt nanospheres according to claim 1 characterized in that: in the step (2), the spherical calcium carbonate prepared in the step (1) is dispersed in 1.3-1.6 mol/L ascorbic acid aqueous solution with the pH value of 7.5-8.5 in an ultrasonic mode, then the mixture is kept stand for 2-4 hours in a vacuum state, the supernatant is poured out quickly, 0.01-0.03 mol/L potassium platinochloride aqueous solution with the pH value of 10-12 is added into the lower-layer sediment under the stirring condition of 60-70 ℃, and the stirring reaction is carried out for 1.5-2 hours.
5. A method of making hollow Pt nanospheres according to claim 1 or 4 characterized in that: in the step (2), the pH values of the ascorbic acid aqueous solution and the potassium chloroplatinite aqueous solution are adjusted by NaOH.
6. A method of making hollow Pt nanospheres according to claim 1 or 4 characterized in that: in the step (2), the mass-to-volume ratio of the spherical calcium carbonate to the potassium chloroplatinite aqueous solution is 1g (200-500 mL).
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| CN101923907A (en) * | 2010-08-11 | 2010-12-22 | 池州学院 | Calcium carbonate/nickel composite conductive powder and preparation method thereof |
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