Platinum and palladium incorporation into phosphate/viologen-phosphonates of zirconium and hafnium: synthesis and characterization

被引:16
作者
Dokoutchaev, A
Krishnan, VV
Thompson, ME [1 ]
Balasubramanian, M
机构
[1] Univ So Calif, Dept Chem, Los Angeles, CA 90089 USA
[2] Univ Connecticut, Dept Phys, Storrs, CT 06269 USA
关键词
hydrogen peroxide; layered phosphonate; viologen; supported catalyst;
D O I
10.1016/S0022-2860(98)00481-5
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
We have continued previous efforts to synthesize and characterize a microporous metal phosphate/viologen-phosphonate compound, [(ZrF)(2)(PO4)(O3PCH2CH2-4,4'-bipyridinium-CH2CH2PO3)]. F . 2H(2)O, ZrPO<(PV)under bar>. A derivative of this material has been shown to be an efficient catalyst for the production of hydrogen peroxide from hydrogen and oxygen. This paper has two objectives-one is to optimize the synthetic routes leading to the preparation of MPO<(PV)under bar> (M = zirconium or hafnium) and the second is to characterize MPO<(PV)under bar> and the derivatives formed by Pt or Pd incorporation by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray powder diffraction (XRD), inductively coupled plasma-mass spectrometry (ICP-MS) and X-ray absorption fine structure analysis (XAFS). Powder XRD data have shown much higher crystallinity in MPO<(PV)under bar> samples prepared by hydrothermal methods than those prepared by reflux methods. In the hydrothermal synthesis, the amount of mineralizer (HF) present controlled the crystallite size (as determined from TEM micrographs). The larger the quantity of HF in the bomb, the larger the size of the crystals but the lower the yield of the MPO<(PV)under bar> material. Crystal sizes of about 2.5 mu m in length and 0.15 mu m in diameter have been made with very large quantities of HF as mineralizer (10 times the required stoichiometric amount). Ion exchange of the material by PdCl42- has resulted in the incorporation of the PdCl42- ions in place of X- in the material. This has been confirmed by XAFS studies that demonstrate the oxidation state of Pd is 2+ and show four Cl atoms bound to Pd. Upon reduction it has been confirmed (by XAFS) that the palladium exists as metal with oxidation state of zero. Ion exchange by PdCl42- and PtCl42- and subsequent reduction of the material suspension by hydrogen result in the formation of separate Pt and Pd colloids in the close vicinity of the crystallites. TEM micrographs show clearly that the Pt metal obtained after reduction forms much smaller particles in comparison to Pd. These exchanged and reduced materials have also been investigated as catalysts for production of hydrogen peroxide in mixed acetone/water medium. The production of hydrogen peroxide is enhanced by increasing amounts of Pd in the catalyst. Hydrogen peroxide yields are the highest for catalysts containing only Pd as opposed to a mixture of Pt and Pd. (C) 1998 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:191 / 205
页数:15
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