Early transition metal oxides as catalysts: Crossing scales from clusters to single crystals to functioning materials - Catalysis Science (Chuck Peden's BES Project - 45385)
EMSL Project ID
6696
Abstract
We propose a multidisciplinary, multi-institution program to develop and demonstrate a new approach to the grand challenge of controlling chemical transformations using catalysis. We propose an integrated experimental/theoretical approach to advance our current ability to understand, design, and control the catalytic and surface chemistry of transition metal oxides, specifically for redox and acid-base chemistries. The approach combines novel solid-state inorganic synthesis, surface science, experimental and theoretical/computational chemical physics, and mechanistic organic chemistry to address this complex and important challenge. We will first focus on two representative reactions: (1) oxidation reactions of CH3OH and (2) acid catalyzed dehydration of butanol to benchmark and then demonstrate our new approach. We will then apply this approach to more complex and useful reactions: oxidation and and isomerization/alkylation of alkanes. Two core tenets of our approach are the importance of (1) nano-scaled synthesis of active metal oxides with controlled structures and atomic connectivity on “scaffolds” crossing scales from planar to uniform porous substrates, which are essential to establish accurate and robust structural and functional relationship and (2) coupling between accurate electronic structure and kinetic calculations and the experiments in which the results of the calculations are used to interpret data and to guide the design of new structures with specific function. We will develop and implement novel methods for depositing active metal oxides onto thin oxide films on metals or semiconductors in order to apply electron-based atomic level probes and site-specific laser techniques, including a variety of microscopies, and for anchoring aquo-oxo complexes or molecular oxide clusters to uniform porous scaffolds in order to apply in-situ spectroscopy techniques and detailed kinetic and mechanistic analyses on single-site structures. These complementary techniques on well-defined materials will enable structural characterization with atomic-level precision, the measurement of electronic properties, and studies of site-specific reaction pathways, all of which must come together in order to understand catalytic transformations. Linking these experiments are high-level density functional and molecular orbital theory calculations using modern massively parallel computers, which provide detailed thermodynamic, spectroscopic, electronic structure, and kinetic information at the molecular level.
Project Details
Project type
Exploratory Research
Start Date
2004-01-05
End Date
2006-11-13
Status
Closed
Released Data Link
Team
Principal Investigator
Team Members