化学学报 ›› 2003, Vol. 61 ›› Issue (11): 1758-1764. 上一篇    下一篇

研究论文

前驱体水解对纳米铂形状控制合成的影响

于迎涛;徐柏庆   

  1. 清华大学化学系
  • 发布日期:2003-11-15

Effect of Precursor Hydrolysis on Shape-controlled Synthesis of Pt Nanocrystals

Yu Yingtao;Xu Boqing   

  1. State Key Lab of C Chemistry & Technology, Department of Chemistry, Tsinghua University
  • Published:2003-11-15

以聚丙烯酸钠(NaPA: M_w ≈ 2100)为保护剂,对比研究了H_2还原K_2PtCl_4 和K_2PtCl_6水溶液制备纳米铂晶粒的形状选择性,揭示了前驱体的水解对纳米铂 晶粒的形状控制合成具有显著影响。文献中通常采用的合成立方形状纳米铂的 K_2PtCl_4前驱体在水溶液中不稳定,避光静置一周会析出黑色沉淀。这种不稳定 性导致了以K_2PtCl_4为Pt前驱体的合成结果难以重复。相比而言,避光静墨的 K_2PtCl_6水溶液很稳定,以它为前驱体合成的纳米铂通常为削角八面体。 K_2PtCl_6水溶液暴露于室内光线中会出现[PtCl_6]~(-2)的光致水解。当[PtCl_6] ~(2-)的紫外特征吸收峰(260nm)由于光致水解完全消失后,以聚丙烯酸钠为保护剂 ,通过H_2还原可以有选择性地(约80%)合成由{100}晶面包裹的立方体形状的纳米 铂。

关键词: 铂, 氢, 氯化铂钾, 水解, 晶粒, 纳米相材料, 还原

With sodium polyacrylate (NaPA: M_w≈2100) as a protector, H_2 reduction of aqueous K_2PtCl_4 and K_2PtCl_6 were performed for shape- controlled synthesis of platinum (Pt) nanocrystals. It was found that the hydrolysis of the Pt precursors affected significantly the shape of Pt nanocrystals synthesized. Aqueous K_2PtCl_4, which was frequently used in earlier literature works for producing cubic Pt nanocrystals, proved not stable in the present work, it was hydrolyzed to fonn a black deposit when the solution was aged in dark for a week. While the aqueous K_2PtCl_6 was fairly stable in the dark aging, synthesis with fresh K_2PtCl_6 solution produced mainly truncated- octahedral Pt nanocrystals by H_2 reduction with NaPA as the protector. An exposure to ambient light was shown to induce a hydrolysis of [PtCl_6]~(2-) in the K_2PtCl_6 solution. When the characteristic absorption of [PtCl_6]~(2-) ions (260 ran) disappeared entirely by exposing the K_2PtCl_6 solution to the ambient light, cubic Pt nanocrystals enclosed with {100} facets were produced selectively (ca. 80%) from thereafter H2 reduction under NaPA protection. It is emphasized that a proper control of the hydrolysis or light-induced hydrolysis of the Pt precursora is crucial for the synthesis of cubic Pt nanocrystals.

Key words: PLATINUM, HYDROGEN, POTASSIUM PLATINUM CHLORIDE, HYDROLYSIS, GRAIN, NANOPHASE MATERIALS, REDUCTION

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