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Micelle-templated synthesis of Pt hollow nanospheres for catalytic hydrogen evolution

机译：胶束模特合成Pt中空纳米球催化氢气进化

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As an alternative to galvanic replacement reactions and hard-template strategies, we report an efficient, mild and simple synthesis strategy for fabrication of colloidal platinum (Pt) hollow nanospheres. An aqueous asymmetric triblock copolymer poly(styrene- b -vinyl-2-pyridine- b -ethylene oxide) [PS(20.1k)–PVP(14.2k)–PEO(26.0)] micelle with core–shell–corona architecture has been found to be an efficient soft scaffold for the synthesis of Pt hollow nanospheres using K _(2) PtCl _(6) as a metal precursor and NaBH _(4) as a reducing agent. In the core–shell–corona type micelles, the core serves as a template for void volume creation, the shell domain acts reaction site for inorganic precursors, and the corona stabilizes the composite particles. The polymer/Pt composite particles were solvent-extracted by refluxing with dimethyl formamide (DMF) at 160 °C to remove polymeric materials and obtain hollow particles. Investigation of precursor concentrations suggested that the wall-structures become irregular and uneven as the molar ratio of PVP/Pt( IV ) increases from 1?:?12 to 1?:?25, whereas the use of polymers with large PS block length [PS(45k)–PVP(16k)–PEO(8.5)] results in the formation of spherical particles with slightly increased hollow void-space diameters. The polymeric micelles and Pt hollow nanospheres were thoroughly characterized by transmission electron microscope (TEM), X-ray diffraction (XRD), infra-red (FT IR), thermal (TG/DTA) and nitrogen sorption analyses. The catalytic activity of the Pt hollow nanospheres was investigated for hydrogen liberation from ammonia–borane (AB) by hydrolysis reaction at room temperature. The catalytic activity of the Pt hollow nanospheres reveals that they can serve as a promising heterogeneous catalyst towards hydrogen generation system using AB as solid hydrogen storage materials.
机译：作为电常用替代反应和硬模板策略的替代方案，我们报告了一种有效，轻度和简单的合成策略，用于制备胶体铂（Pt）中空纳米球。一般不对称三嵌段共聚物聚（苯乙烯-B-乙烯基-2-吡啶 - B-内容甲）[PS（20.1K）-PVP（14.2K）-PEO（26.0）]胶束，具有核心 - 壳 - 电晕架构发现是使用K _（2）PtCl _（6）作为金属前体和NaBH _（4）作为还原剂的合成Pt中空纳米球的有效软支架。在核心壳 - 电晕型胶束中，核心用作空隙体积产生的模板，壳结构域作用于无机前体的反应位点，并且电晕稳定复合颗粒。通过在160℃下用二甲基甲酰胺（DMF）回流溶剂萃取聚合物/ Pt复合颗粒以除去聚合物材料并获得中空颗粒。前体浓度的研究表明，随着PVP / Pt（IV）的摩尔比从1的摩尔比增加，壁结构变得不正常，并且从1？：12至1增加？：25，而使用大的PS块长度的聚合物[ PS（45K）-PVP（16K）-PEO（8.5）]导致球形颗粒的形成，空隙空隙空隙直径略微增加。通过透射电子显微镜（TEM），X射线衍射（XRD），红外（FT IR），热（TG / DTA）和氮吸附分析，彻底地表征了聚合物胶束和PT中空纳米球。研究了PT中空纳米球的催化活性，通过在室温下通过水解反应从氨基硼烷（AB）中释放氢气。 PT中空纳米球的催化活性显示，它们可以用作使用AB作为固体储氢材料的氢发电系统的有前途的非均相催化剂。

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