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利用X射线吸收对Pt-LiCoO₂催化硼氢化钠水解的机理进行研究。

Investigation on mechanism of catalysis by Pt-LiCoO2 for hydrolysis of sodium borohydride using X-ray absorption.

作者信息

Liu R S, Lai H C, Bagkar N C, Kuo H T, Chen H M, Lee J-F, Chung H J, Chang S M, Weng B J

机构信息

Department of Chemistry, National Taiwan University, Taipei, Taiwan 106.

出版信息

J Phys Chem B. 2008 Apr 24;112(16):4870-5. doi: 10.1021/jp075592n. Epub 2008 Apr 3.

Abstract

The synthesis of platinum nanoparticle loaded LiCoO2 (Pt-LiCoO2) was carried out successfully by an impregnation method followed by sintering at different temperatures. The catalytic role of Pt-LiCoO2 composite in hydrogen generation during hydrolysis of sodium borohydride (NaBH4) was studied for fuel cell applications. X-ray diffraction (XRD), transmission electron microscopy (TEM), and inductively coupled plasma-atomic emission spectroscopy (ICP-AES) have been used to elucidate the structural and catalytic properties of Pt-LiCoO2. It was found that the 15 wt % of Pt nanoparticles on LiCoO2 sintered at 450 degrees C support showed the maximum efficiency for the catalysis reaction of hydrogen production. X-ray absorption near edge structure (XANES) analysis and extended X-ray absorption fine structure (EXAFS) analysis using a synchrotron radiation source were performed to carry out ex situ measurements in order to understand the mechanism of the catalytic process for the production of hydrogen during the hydrolysis of NaBH4. Co K-edge XANES showed a small percentage of cobalt in the metallic form after hydrogen generation which suggests the reduction of the cobalt during the hydrolysis of NaBH4.

摘要

通过浸渍法并在不同温度下烧结成功合成了负载铂纳米颗粒的LiCoO₂(Pt-LiCoO₂)。研究了Pt-LiCoO₂复合材料在硼氢化钠(NaBH₄)水解制氢过程中的催化作用,用于燃料电池应用。采用X射线衍射(XRD)、透射电子显微镜(TEM)和电感耦合等离子体原子发射光谱(ICP-AES)来阐明Pt-LiCoO₂的结构和催化性能。结果发现,在450℃烧结的LiCoO₂载体上负载15 wt%的铂纳米颗粒对制氢催化反应显示出最高效率。利用同步辐射源进行了X射线吸收近边结构(XANES)分析和扩展X射线吸收精细结构(EXAFS)分析,以进行非原位测量,从而了解NaBH₄水解制氢催化过程的机理。Co K边XANES显示,产氢后金属形式的钴占比很小,这表明在NaBH₄水解过程中钴发生了还原。

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