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Early Transition Metal Oxides as Catalysts: Crossing Scales from Clusters to Single Crystals to Functioning Materials


EMSL Project ID
19799

Abstract

Current commercial heterogeneous catalysts are structurally and chemically complex and their experimental assessment can seldom be interpreted with atomic-level precision. We seek to reduce the complexity of TMO catalysts to levels addressable and controllable at the atomic level, while maintaining rigorous connections with practical catalysis and catalytic materials. We employ an integrated experimental/theoretical approach with an overall objective to advance significantly our ability to understand, design, and control chemical transformations on transition metal oxide catalysts, specifically for redox and acid-base chemistries. The approach combines novel synthesis methods for preparing supported metal oxides with controlled structures and atomic connectivity on a wide range of well-defined "scaffolds", structural and functional characterization of these realistic and model catalysts, mechanistic organic chemistry, as well as a strong coupling of calculations of electronic structure and of chemical dynamics with experiments. Our early work has focused on single-site catalyst synthesis and aimed at realizing nanometer-scale spatial resolution of the structure and distribution of active sites in the materials. These synthetic strategies are combined with in-situ methods for the elucidation of inorganic structures and with detailed characterization of their function. Probes of the catalytic chemistry of these model catalysts are being utilized along with electronic structure and kinetics computations to define the mechanisms of these processes and the nature of the catalytically active sites. For the latter, we have used the acid-catalyzed dehydration of butanol and the oxidation of methanol to formaldehyde, methylformate, and dimethoxymethane. This program involves integrated collaborative efforts at Pacific Northwest National Laboratory, The University of Alabama, and the University of California, Berkeley.

Project Details

Project type
Large-Scale EMSL Research
Start Date
2006-07-21
End Date
2009-09-30
Status
Closed

Team

Principal Investigator

Charles Peden
Institution
Pacific Northwest National Laboratory

Team Members

Jong Ki Jeon
Institution
Kongju National University

Liang Zhang
Institution
Pacific Northwest National Laboratory

Sung June Cho
Institution
Chonnam National University

Kwan Young Lee
Institution
Korea University

Boqing Xu
Institution
Tsinghua University

Yu Wu
Institution
Tsinghua University

Vanessa Dagle
Institution
Pacific Northwest National Laboratory

Xiaoyan She
Institution
Pacific Northwest National Laboratory

Guanguang (Gordon) Xia
Institution
Pacific Northwest National Laboratory

Jun Liu
Institution
Yale University

Ja Hun Kwak
Institution
Ulsan National Institute of Science and Technology

Jian-zhi Hu
Institution
Pacific Northwest National Laboratory

Mark Engelhard
Institution
Environmental Molecular Sciences Laboratory

Enrique Iglesia
Institution
University of California, Berkeley

Do Heui Kim
Institution
Seoul National University

James White
Institution
Pacific Northwest National Laboratory

David Dixon
Institution
University of Alabama

Yong Wang
Institution
Washington State University

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