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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


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
End Date


Principal Investigator

Charles Peden
Pacific Northwest National Laboratory

Team Members

Jose Herrera
Pacific Northwest National Laboratory

Jian-zhi Hu
Pacific Northwest National Laboratory

Yong Wang
Washington State University

Related Publications

Design and operating characteristics of a transient kinetic analysis catalysis reactor system employing in-situ transmission FTIR, Y. Yang, R.S. Disselkamp, J. Szanyi, C.H.F. Peden, C.T. Campbell, J. G. Goodwin, Jr., Review of Scientific Instruments, 77, Art. No. 094104 (2006).
Devaraj A, RJ Colby, WP Hess, DE Perea, and S Thevuthasan. 2013. "The Role of Photoexcitation and Field Ionization in the Measurement of Accurate Oxide Stoichiometry by Laser Assisted Atom Probe Tomography ." The Journal of Physical Chemistry Letters 4(2013):993-998. doi:10.1021/jz400015h
Gu M, I Belharouak, A Genc, Z Wang, D Wang, K Amine, F Gao, G Zhou, S Thevuthasan, DR Baer, J Zhang, ND Browning, J Liu, and CM Wang. 2012. "Conflicting Roles Of Ni In Controlling Cathode Performance In Li-ion Batteries." Nano Letters. doi:10.1021/nl302249v
Gu M, I Belharouak, J Zheng, H Wu, J Xiao, A Genc, K Amine, S Thevuthasan, DR Baer, J Zhang, ND Browning, J Liu, and CM Wang. 2013. "Formation Of The Spinel Phase In The Layered Composite Cathode Used In Li-Ion Batteries." ACS Nano 7(1):760-767. doi:10.1021/nn305065u
Gu M, Y Li, X Li, SY Hu, X Zhang, W Xu, S Thevuthasan, DR Baer, J Zhang, J Liu, and CM Wang. 2012. "In-Situ TEM Study Of Lithiation Behavior Of Silicon Nanoparticles Attached To And Embedded In A Carbon Matrix ." ACS Nano 6(9):8439-8447. doi:10.1021/nn303312m
Kuchibhatla SVNT, V Shutthanandan, TJ Prosa, P Adusumilli, BW Arey, A Buxbaum, YC Wang, T Tessner, RM Ulfig, CM Wang, and S Thevuthasan. 2012. "Three-dimensional Chemical Imaging of Embedded Nanoparticles using Atom Probe Tomography." Nanotechnology 23(21):Article No. 215704. doi:10.1088/0957-4484/23/21/215704
Yang Y, CA Mims, RS Disselkamp, CHF Peden, and CT Campbell. 2009. "Simultaneous MS-IR Studies of Surface Formate Reactivity Under Methanol Synthesis Conditions on Cu/SiO2." Topics in Catalysis 52(10):1440-1447. doi:10.1007/s11244-009-9320-3
Yang Y, C Mims, RS Disselkamp, D Mei, JH Kwak, J Szanyi, CHF Peden, and CT Campbell. 2008. "Isotope effects in methanol synthesis and the reactivity of copper formates on a Cu/SiO2 catalyst." Catalysis Letters 125(3-4):201-208. doi:10.1007/s10562-008-9592-4