CN111331149B - 一种以球形碳酸钙为模板制备中空Pt纳米球的方法 - Google Patents
一种以球形碳酸钙为模板制备中空Pt纳米球的方法 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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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- 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
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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- C01F11/00—Compounds of calcium, strontium, or barium
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Abstract
本发明公开了一种以球形碳酸钙为模板制备中空Pt纳米球的方法，该方法先采用反相微乳液法制备粒径为0.5～1μm的球形碳酸钙，然后以该球形碳酸钙为模板，氯亚铂酸钾为铂源，抗坏血酸为还原剂，简单高效地制备出形貌规整、尺寸均一，粒径为1～2μm窄分布的中空Pt纳米球。本发明制备方法简单、安全无毒，且成本较低，所得中空Pt纳米球在酸性条件下对甲醇催化氧化反应展现出较高的催化活性和稳定性，在电化学方面具有很好的应用前景。
Description
技术领域
本发明属于催化剂制备技术领域，具体涉及一种以球形碳酸钙为模板制备中空Pt纳米球的方法，该中空Pt纳米球作为催化剂在酸性条件下对甲醇催化氧化反应展现出较高的催化活性和稳定性。
背景技术
贵金属铂、银、铑、钯、钌等，它们具有很多优点，如耐高温、耐腐蚀、抗氧化等，它们的催化活性都较高，是极为重要的催化剂材料。纳米中空贵金属球由于其独特的结构特点，具有低密度、比表面积大、表面活性高、表面渗透性强等特点，因此在化学、生物和材料科学等领域均有重要的应用。
目前，中空球材料的制备方法主要有喷雾干燥法、乳液法和模板合成法，而模板法是应用较广也是较重要的制备中空球的方法。模板法是合成纳米空心材料的一类重要方法，主要分为硬模板法和软模板法，其特点是模板剂几何形态可以间接地影响到纳米空心材料的外观形貌特点，具有有效控制空心结构的壳层厚度、粒径和分散性的显著优点。例如：Hyeon等在2008年报道了以SiO2为模板制备氧化铁纳米胶囊(Piao Y,Kim J,Na H B,etal.Wrap–bake–peel process for nanostructural transformation from β-FeOOHnanorods to biocompatible iron oxide nanocapsules[J].Nature Materials,2008,7(3):242-247.)，Wu等组报道了以聚苯乙烯为模板，通过简单的方法合成中空SiO2球(Deng,Ziwei,Chen,Min,Zhou,Shuxue,等.A Novel Method for the Fabrication ofMonodisperse Hollow Silica Spheres[J].Langmuir the Acs Journal of Surfaces&Colloids,22(14):6403-6407.)，Long等人利用双氧水分解产生的氧气为模板，合成中空TiO2球(Long L,Zhang H,Ye M,et al.Ammonia cation-assisted bubble template forsynthesizing hollow TiO2 nanospheres and their application in lithium ionstorage[J].RSC Advances,2015,5.)，Zoldesi等人报道了一种以直接乳液为模板，制备中空SiO2微球和胶囊微球(C.I.Zoldesi,Imhof A.Synthesis of Monodisperse ColloidalSpheres,Capsules,and Microballoons by Emulsion Templating[J].AdvancedMaterials,2005,17(7):924-928.)，Zheng等人以阴离子囊泡为软模板，制备的中空SeCd球(Zheng X,Xie Y,Zhu L,et al.Formation of vesicle-templated CdSe hollow spheresin an ultrasound-induced anionic surfactant solution[J].UltrasonicsSonochemistry,2002,9(6):311-316.)Dong等研发序列模板法制备ZnO多壳结构(Dong Z,Lai X,Halpert J E,et al.Accurate Control of Multishelled ZnO HollowMicrospheres for Dye-Sensitized Solar Cells with High Efficiency[J].AdvancedMaterials,2012,24(8):1046-1049.)康永强等(Kang Yong-Qiang,Xue Qi,Zhao Yue,etal.Selective Etching Induced Synthesis of Hollow Rh NanospheresElectrocatalyst for Alcohol Oxidation Reactions[J].Small:1801239.)以三氯化铑和氯金酸为原料，形成铑-金核壳结构，通过王水去除金核形成空心铑，该方法成本高，且王水毒性大，实验危险系数较高。因此，提供一种简单有效的低成本，无毒性的中空纳米材料的制备方法成为中空材料领域的热点和难点。
发明内容
针对目前硬模板法存在团聚、模板剂尺寸大，去除条件苛刻影响目标产物的问题，本发明基于窄分布、单分散和易去除的球形碳酸钙模板，通过Pt前驱液筛选和实验条件调控，克服了碳酸钙模板溶解和还原产物Pt提前产生，最终提供一种简单有效的以反相微乳液法制备的粒径为0.5～1μm的球形碳酸钙为模板制备中空Pt纳米球的方法。
针对上述目的，本发明所采用的技术方案由下述步骤组成：
1、制备球形碳酸钙模板
将氯化钙固体溶解于去离子水中，并加入聚丙烯酸，搅拌均匀后，再加入十二烷基苯磺酸钠，得到钙离子浓度为0.5～3.5mol/L的钙源溶液；将所得钙源溶液加入到环己烷、复配表面活性剂、助表面活性剂的混合液中，混合均匀，静置，取上清液，得到反相微乳液，以反相微乳液的总体积为100％计，其中钙源溶液占1.0％～7.0％、复配表面活性剂占0.5％～1.5％、助表面活性剂占0.5％～2％，其余为环己烷；向所得反相微乳液中滴加氨水，调节pH值至8～10，然后连续通入CO2气体，在25～28℃下反应0.5～1.5小时，离心、洗涤，得到表面呈多孔状的亚微米级球形碳酸钙。
2、制备空心Pt纳米球
将步骤1制得的球形碳酸钙超声分散于pH为7～10的1.3～1.6mol/L抗坏血酸水溶液中，然后在真空状态下静置2～4小时，迅速倒出上层清夜，并在60～70℃搅拌条件下向下层沉淀中加入pH为8～12的0.01～0.03mol/L氯亚铂酸钾水溶液，搅拌反应1.5～2小时后，离心、洗涤，再加入稀盐酸除碳酸钙，得到中空Pt纳米球。
上述步骤1中，优选所得钙源溶液中钙离子浓度为1.0～3.0mol/L、聚丙烯酸的浓度为0.16～0.24g/L、十二烷基苯磺酸钠的浓度为0.02～0.03mol/L，其中所述聚丙烯酸的数均分子量为5000。
上述步骤1中，以反相微乳液的总体积为100％计，优选其中钙源溶液占2.0％～5.0％、复配表面活性剂占0.7％～1.0％、助表面活性剂占1.5％～2.0％，其余为环己烷。
上述的复配表面活性剂是聚氧乙烯蓖麻油和司班-80质量比为55:45～65:35的混合物，助表面活性剂为乙醇。
上述步骤2中，优选将步骤1制得的球形碳酸钙超声分散于pH为7.5～8.5的1.3～1.6mol/L抗坏血酸水溶液中，然后在真空状态下静置2～4小时，迅速倒出上层清夜，并在60～70℃搅拌条件下向下层沉淀中加入pH为10～12的0.01～0.03mol/L氯亚铂酸钾水溶液，搅拌反应1.5～2小时。
上述抗坏血酸水溶液和氯亚铂酸钾水溶液的pH通过NaOH调节。
上述步骤2中，进一步优选所述球形碳酸钙与氯亚铂酸钾水溶液的质量体积比为1g:(200～500)mL。
本发明的有益效果如下：
本发明先采用反相微乳液法制备粒径为0.5～1μm且具有多孔性和高比表面积的亚微米级球形碳酸钙，然后以该球形碳酸钙为模板，氯亚铂酸钾为铂源，抗坏血酸为还原剂，利用球形碳酸钙多孔结构的特性，通过抽真空的方式使抗坏血酸渗入球形碳酸钙内部，待抗坏血酸稳定存在碳酸钙内部，取出，在抗坏血酸分子即将从CaCO3内部向外溢出时，迅速加入氯亚铂酸钾水溶液，使其在球形碳酸钙表面还原，形成核壳结构，最后再通过酸溶，去除碳酸钙，形成中空Pt纳米球。
本发明制备方法简单、安全无毒，且成本较低，制备的中空Pt纳米球形貌规整、尺寸均一、粒径分布窄(1～2μm)，且在酸性条件下对甲醇催化氧化反应展现出较高的催化活性和稳定性，在电化学方面具有很好的应用前景。
附图说明
图1是实施例1得到的亚微米级球形碳酸钙的扫描电镜照片。
图2是实施例1得到的中空Pt纳米球的XRD谱图。
图3是实施例1得到的中空Pt纳米球的扫描电镜照片。
图4是图3的局部放大图。
图5是实施例1得到的中空Pt纳米球的场发射透射电镜照片。
图6是实施例2得到的中空Pt纳米球的扫描电镜照片。
图7是实施例3得到的中空Pt纳米球的扫描电镜照片。
具体实施方式
下面结合附图和实施例对本发明进一步详细说明，但是本发明的保护范围不仅限于这些实施例。
实施例1
1、制备球形碳酸钙模板
将1.11g纯度为99％以上的氯化钙固体溶解于8mL去离子水中，并向其中加入2mL1.0g/L数均分子量为5000的聚丙烯酸水溶液，搅拌0.5小时后，再向其中加入0.0871g十二烷基苯磺酸钠，搅拌均匀，得到钙源溶液，其中钙离子浓度为1.0mol/L、聚丙烯酸的浓度为0.2g/L、十二烷基苯磺酸钠浓度为0.025mol/L。将0.6g聚氧乙烯蓖麻油和0.4g司班-80混合均匀，向其加入1.0mL乙醇，混合均匀后，在常温搅拌状态下，将所得混合物逐滴加入100mL环己烷中，再向其逐滴加入5mL钙源溶液，搅拌均匀，静置2小时，取上清液，得到反相微乳液。向反相微乳液中滴加氨水，调节pH值至9.4，然后向反相微乳液中连续通入CO2气体，在25℃下静置反应40分钟，离心分离，用乙醇洗涤3次、水洗1次，最后在70℃下真空干燥，得到亚微米级球形碳酸钙。由图1的可见，所得碳酸钙呈球形，形貌规整、尺寸均一、粒径分布较窄，粒径为500nm左右，是由10～20nm的微晶球粒组成，其表面粗糙，呈多孔状。
2、制备中空Pt纳米球
将0.02g步骤1制得的球形碳酸钙超声分散于5mL pH为8.84的1.5mol/L抗坏血酸水溶液(pH用NaOH调节)中，分散均匀后放入真空干燥箱中，抽真空至0.8MPa后放置3小时，迅速取出倒出上层清夜，并放入65℃水浴锅内在搅拌状态下向下层沉淀中加入6mL pH为11的0.025mol/L氯亚铂酸钾水溶液(pH用NaOH调节)，在2～3分钟内氯亚铂酸钾在碳酸钙表面迅速还原成单质Pt，搅拌1.5小时后，离心、洗涤，再加入稀盐酸酸溶2小时除去碳酸钙，最后经过离心、洗涤即得到中空Pt纳米球。由图2可见所得产物确实为单质Pt，由图3～5可以明显看到所得金属Pt呈空心结构，粒径为1μm左右。
实施例2
本实施例中，将0.02g步骤1制得的球形碳酸钙超声分散在5mL pH为7.9的1.5mol/L抗坏血酸水溶液(pH用NaOH调节)中，分散均匀后放入真空干燥箱中，抽真空至0.8MPa后放置2小时。其他步骤与实施例1中相同，得到中空Pt纳米球，其粒径为1μm左右(见图6)。
实施例3
本实施例中，将0.02g步骤1制得的球形碳酸钙超声分散在5mL pH为8.84的1.5mol/L抗坏血酸水溶液(pH用NaOH调节)中，分散均匀后放入真空干燥箱中，抽真空至0.8MPa后放置3小时，迅速取出倒出上层清夜，并放入70℃水浴锅内在搅拌状态下向下层沉淀中加入6mL pH为11.5的0.025mol/L氯亚铂酸钾水溶液(pH用NaOH调节)，在2～3分钟内氯亚铂酸钾在碳酸钙表面迅速还原成单质Pt，搅拌1.5小时。其他步骤与实施例1相同，得到空心Pt球，其粒径为1μm左右(见图7)。
实施例4
本实施例中，将3.33g纯度为99％以上的氯化钙固体溶解于8mL去离子水中，并向其中加入2mL 1.0g/L数均分子量为5000的聚丙烯酸水溶液，搅拌均匀后，再向其中加入0.0871g十二烷基苯磺酸钠，搅拌均匀，得到钙源溶液，其中钙离子浓度为3.0mol/L、聚丙烯酸的浓度为0.2g/L、十二烷基苯磺酸钠浓度为0.025mol/L。其他步骤与实施例1中相同，得到中空Pt纳米球。
Claims (6)
1.一种以球形碳酸钙为模板制备中空Pt纳米球的方法，其特征在于它由下述步骤组成：
（1）制备球形碳酸钙模板
将氯化钙固体溶解于去离子水中，并加入聚丙烯酸，搅拌均匀后，再加入十二烷基苯磺酸钠，得到钙离子浓度为0.5～3.5 mol/L的钙源溶液；将所得钙源溶液加入到环己烷、复配表面活性剂、助表面活性剂的混合液中，混合均匀，静置，取上清液，得到反相微乳液，以反相微乳液的总体积为100 %计，其中钙源溶液占1.0%～ 7.0%、复配表面活性剂占0.5%～1.5%、助表面活性剂占0.5%～2.0%，其余为环己烷，所述的复配表面活性剂是聚氧乙烯蓖麻油和司班-80质量比为55:45～65:35的混合物，所述的助表面活性剂为乙醇；向所得反相微乳液中滴加氨水，调节pH值至8～10，然后连续通入CO2气体，在25～28 ℃下反应0.5～1.5小时，离心、洗涤，得到表面呈多孔状的亚微米级球形碳酸钙；
（2）制备空心Pt纳米球
将步骤（1）制得的球形碳酸钙超声分散于pH为7～10的1.3～1.6 mol/L抗坏血酸水溶液中，然后在真空状态下静置2～4小时，迅速倒出上层清液，并在60～ 70 ℃搅拌条件下向下层沉淀中加入pH为8～12的0.01～0.03 mol/L氯亚铂酸钾水溶液，搅拌反应1.5～2小时后，离心、洗涤，再加入稀盐酸除碳酸钙，得到中空Pt纳米球。
2.根据权利要求1所述的制备中空Pt纳米球的方法，其特征在于：步骤（1）中，所得钙源溶液中钙离子浓度为1.0～3.0 mol/L、聚丙烯酸的浓度为0.16～0.24 g/L、十二烷基苯磺酸钠的浓度为0.02～0.03 mol/L，其中所述聚丙烯酸的数均分子量为5000。
3.根据权利要求1所述的制备中空Pt 纳米球的方法，其特征在于：步骤（1）中，以反相微乳液的总体积为100%计，其中钙源溶液占2.0%～5.0%、复配表面活性剂占0.7%～1.0%、助表面活性剂占1.5%～2.0%，其余为环己烷。
4.根据权利要求1所述的制备中空Pt纳米球的方法，其特征在于：步骤（2）中，将步骤（1）制得的球形碳酸钙超声分散于pH为7.5～8.5的1.3～1.6 mol/L抗坏血酸水溶液中，然后在真空状态下静置2～4小时，迅速倒出上层清夜，并在60～ 70 ℃搅拌条件下向下层沉淀中加入pH为10～12的0.01～0.03 mol/L氯亚铂酸钾水溶液，搅拌反应1.5～2小时。
5.根据权利要求1或4所述的制备中空Pt纳米球的方法，其特征在于：步骤（2）中，所述抗坏血酸水溶液和氯亚铂酸钾水溶液的pH通过NaOH调节。
6.根据权利要求1或4所述的制备中空Pt纳米球的方法，其特征在于：步骤（2）中，所述球形碳酸钙与氯亚铂酸钾水溶液的质量体积比为1g:（200～500）mL。
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