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REDUCTION BEHAVIOR OF METALS SUPPORTED ON HYDROUS TITANIUM OXIDE ION-EXCHANGE MATERIALS

机译:水合二氧化钛离子交换材料上金属的还原行为

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Hydrous titanium oxide (HTO) ion-exchange materials provide a unique and versatile platform for obtaining high loadings of supported transition metal cations with essentially atomic dispersion. Strong interactions between the atomically dispersed metal cations and the support alter the reduction behavior of metal cations as compared to other support materials and preparation methods. X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), and secondary ion mass spectrometry (SIMS) measurements of the reduction of Ph, Ni, and Fe supported on HTO materials provide a representative cross section of possible behaviors. The results suggest that metals with high melting points and low surface mobility, such as Ph, Pt, and Pd, should retain high dispersions even after reduction at temperatures up to 300 degrees C. Lower melting point metals such as Ni, Co, and Cu, that exhibit moderate heats of oxide formation, will likely undergo extensive sintering at temperatures above 250 degrees C, largely negating the high dispersions characteristic of the freshly ion-exchanged state. Finally, lower melting point metals with very high heats of oxide formation, such as Fe and Cr, will be difficult to reduce due to unfavorable thermodynamics in the presence of the support. The results indicate that for certain types of metals, HTO support materials allow the preparation of catalysts with both high loadings and high metal dispersions. This capability provides a new pathway toward more efficient usage of expensive noble metals that is unavailable using conventional catalyst supports and preparation methods. (C) 1995 Academic Press, Inc. [References: 35]
机译:含水二氧化钛(HTO)离子交换材料提供了独特而通用的平台,可在基本原子分散的情况下获得高负载的负载过渡金属阳离子。与其他载体材料和制备方法相比,原子分散的金属阳离子与载体之间的强相互作用改变了金属阳离子的还原行为。 X射线光电子能谱(XPS),俄歇电子能谱(AES)和二次离子质谱(SIMS)测量了HTO材料上负载的Ph,Ni和Fe的还原,提供了可能的行为的代表性截面。结果表明,即使在最高300摄氏度的温度下还原后,具有高熔点和低表面迁移率的金属(如Ph,Pt和Pd)也应保持较高的分散性。较低熔点的金属(如Ni,Co和Cu)表现出适度的氧化物形成热的Fe 2 O 3,可能会在高于250摄氏度的温度下进行广泛的烧结,从而大大削弱了新的离子交换态的高分散性。最后,由于在载体存在下不利的热力学,具有非常高的氧化物形成热的较低熔点金属,例如Fe和Cr,将难以还原。结果表明,对于某些类型的金属,HTO载体材料可以制备高载量和高金属分散度的催化剂。此功能提供了一条更有效地使用昂贵的贵金属的新途径,而这是使用常规催化剂载体和制备方法无法获得的。 (C)1995 Academic Press,Inc. [参考:35]

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