Vajda Stefan, Pellin Michael J, Greeley Jeffrey P, Marshall Christopher L, Curtiss Larry A, Ballentine Gregory A, Elam Jeffrey W, Catillon-Mucherie Stephanie, Redfern Paul C, Mehmood Faisal, Zapol Peter
Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, USA.
Nat Mater. 2009 Mar;8(3):213-6. doi: 10.1038/nmat2384. Epub 2009 Feb 8.
Small clusters are known to possess reactivity not observed in their bulk analogues, which can make them attractive for catalysis. Their distinct catalytic properties are often hypothesized to result from the large fraction of under-coordinated surface atoms. Here, we show that size-preselected Pt(8-10) clusters stabilized on high-surface-area supports are 40-100 times more active for the oxidative dehydrogenation of propane than previously studied platinum and vanadia catalysts, while at the same time maintaining high selectivity towards formation of propylene over by-products. Quantum chemical calculations indicate that under-coordination of the Pt atoms in the clusters is responsible for the surprisingly high reactivity compared with extended surfaces. We anticipate that these results will form the basis for development of a new class of catalysts by providing a route to bond-specific chemistry, ranging from energy-efficient and environmentally friendly synthesis strategies to the replacement of petrochemical feedstocks by abundant small alkanes.
已知小团簇具有其块状类似物中未观察到的反应活性,这使得它们对催化具有吸引力。人们常常推测,它们独特的催化性能源于大量配位不足的表面原子。在这里,我们表明,负载在高比表面积载体上的尺寸预选的Pt(8 - 10)团簇,对于丙烷的氧化脱氢反应,其活性比先前研究的铂和钒催化剂高40 - 100倍,同时对丙烯生成的选择性高于副产物。量子化学计算表明,与延展表面相比,团簇中Pt原子的配位不足是导致其惊人高反应活性的原因。我们预计,这些结果将为开发新型催化剂奠定基础,通过提供一条通向键特异性化学的途径,从节能和环境友好的合成策略到用丰富的小烷烃替代石化原料。