Application of high-energy X-rays and Pair-Distribution-Function analysis to nano-scale structural studies in catalysis

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• 作者：Peter J. Chupas ; Karena W. Chapman ; Hailong Chen ; Clare P. Grey
• 关键词：Pair-Distribution-Function ; High-energy X-rays ; Supported catalyst ; In situ studies
• 刊名：Catalysis Today
• 出版年：2009
• 出版时间：30 July 2009
• 年：2009
• 卷：145
• 期：3-4
• 页码：213-219
• 全文大小：645 K

文摘

We investigate the structure of supported Pt catalysts using high-energy X-ray scattering coupled with Pair-Distribution-Function (PDF) analysis. Recently, experimental approaches that enable the collection of PDF data in situ have been developed with time-resolution sufficient to study the structure of Pt nano-particles as they form. The differential PDF approach is utilized which allows the atom–atom correlations involving only Pt to be selectively recovered, enabling structural investigation of the supported particles and the mechanism of their formation. In parallel to the in situ analysis, we have examined samples prepared ex situ. Data collected on the ex situ samples show that the initial deposition of Pt⁴⁺ occurs as the PtCl₆²⁻ species which are retained even when annealed in an oxygen atmosphere. The Pt differential PDFs of the samples reduced in hydrogen at 200 and 500 °C indicated nano-crystalline face-centered-cubic (fcc) metallic Pt particles. The ex situ reduced samples also contain a weak correlations at 2.1 Å, which we assign to Pt–O interactions between the particles and the support surface. The in situ experiments, following the reduction of Pt⁴⁺ from 0 to 227 °C, indicate that the initial Pt nano-particles formed are ca. 1 nm in size, and become larger and more crystalline by 200 °C. The data suggest a particle growth mechanism where the initial particles that form are small (<1 nm), then agglomerate into ensembles of many small particles and lastly anneal to form larger well-ordered particles. Lastly, we discus potential future developments in operando PDF studies, and identify opportunities for synchronous application of complementary methods.