Tianyao Gong, Guotao Qiu, Mo-Rigen He, Olga V. Safonova, Wei-Chang Yang, David Raciti, Corey Oses, Anthony Shoji Hall
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引用次数: 0
Abstract
The catalytic behavior of a material is influenced by ensembles─the geometric configuration of atoms on the surface. In conventional material systems, ensemble effects and the electronic structure are coupled because these strategies focus on varying the material composition, making it difficult to understand the role of ensembles in isolation. This study introduces a methodology that separates geometric effects from the electronic structure. To tune the Pd ensemble size on the catalyst surface, we compared the reactivity of structurally different but compositionally identical Pd3Bi intermetallic and solid solution alloys. Pd3Bi intermetallics display no reactivity for methanol oxidation (MOR), while their solid solution counterparts show significant reactivity (0.5 mA cmPd–2). Intermetallics form smaller ensembles (1, 3, 4, and 5 atoms across all low-energy facets), whereas solid solution Pd3Bi has several facets that support larger Pd ensembles, with an average size of 5.25 atoms and up to 6 atoms. A partially ordered Pd3Bi (a mixed phase of intermetallic and solid solution) alloy shows intermediate MOR activity (0.1 mA cmPd–2), confirming that methanol oxidation activity tracks with the average ensemble size. All Pd3Bi alloys maintained similar electronic structures, as confirmed by X-ray photoelectron spectroscopy (XPS) valence band spectroscopy and X-ray absorption near edge structure (XANES) measurements, indicating that reactivity differences arise from variations in the ensemble size induced by differences in the atomic ordering. Our findings offer an approach for designing materials with controllable active site configurations while maintaining the catalyst’s electronic structure, thereby enabling more efficient catalyst design.
期刊介绍:
The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.