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Title: Catalysis applications of size-selected cluster deposition

In this Perspective, we review recent studies of size-selected cluster deposition for catalysis applications performed at the U.S. DOE National Laboratories, with emphasis on work at Argonne National Laboratory (ANL) and Brookhaven National Laboratory (BNL). The focus is on the preparation of model supported catalysts in which the number of atoms in the deposited clusters is precisely controlled using a combination of gas-phase cluster ion sources, mass spectrometry, and soft-landing techniques. This approach is particularly effective for investigations of small nanoclusters, 0.5-2 nm (<200 atoms), where the rapid evolution of the atomic and electronic structure makes it essential to have precise control over cluster size. Cluster deposition allows for independent control of cluster size, coverage, and stoichiometry (e.g., the metal-to-oxygen ratio in an oxide cluster) and can be used to deposit on any substrate without constraints of nucleation and growth. Examples are presented for metal, metal oxide, and metal sulfide cluster deposition on a variety of supports (metals, oxides, carbon/diamond) where the reactivity, cluster-support electronic interactions, and cluster stability and morphology are investigated. Both UHV and in situ/operando studies are presented that also make use of surface-sensitive X-ray characterization tools from synchrotron radiation facilities. Novel applications of cluster deposition tomore » electrochemistry and batteries are also presented. This review also highlights the application of modern ab initio electronic structure calculations (density functional theory), which can essentially model the exact experimental system used in the laboratory (i.e., cluster and support) to provide insight on atomic and electronic structure, reaction energetics, and mechanisms. As amply demonstrated in this review, the powerful combination of atomically precise cluster deposition and theory is able to address fundamental aspects of size-effects, cluster-support interactions, and reaction mechanisms of cluster materials that are central to how catalysts function. Lastly, the insight gained from such studies can be used to further the development of novel nanostructured catalysts with high activity and selectivity.« less
Authors:
 [1] ;  [2]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division; Argonne National Lab. (ANL), Argonne, IL (United States). Nanoscience and Technology Division; Univ. of Chicago, IL (United States). Inst. for Molecular Engineering; Yale Univ., New Haven, CT (United States). Dept. of Chemical and Environmental Engineering
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Dept. of Chemistry; Stony Brook Univ., NY (United States). Dept. of Chemistry
Publication Date:
OSTI Identifier:
1236817
Grant/Contract Number:
AC02-06CH11357; SC0012704
Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 5; Journal Issue: 12; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; cluster deposition; heterogeneous catalysis; metal oxide; molybdenum sulfide; size-selected; transition metal; work function