Oxide Clusters - Electronic Structure and Chemical Bonding Using Photoelectron Spectroscopy
EMSL Project ID
25396
Abstract
The proposed work is associated with a DOE BES project (catalysis center program), under EMSL User Proposal #17812. The oxide clusters studies are aimed at obtaining a microscopic understanding of defect structures on oxide surfaces and catalytic reaction mechanisms using cluster models. Gas phase clusters provide molecular systems with controlled and well-defined structures and atomic connectivity. As a result, their spectroscopic features provide a mechanism for validating and improving the atomic and electronic structure calculations that form a central part of the program. In the same manner as organometallic molecules have provided useful models for surface chemistry concepts, the chemical properties of gas phase transition metal oxide clusters will be useful in addressing issues related to the nature of the reactive sites of supported clusters. The dependence of chemical reactivity on cluster size and composition is well established. However, there have been very few, if any, spectroscopic studies on early transition metal oxide clusters and very little is known about their electronic and structural properties. In previous studies, we have used photoelectron spectroscopy to provide both electronic and spectroscopic information on small tungsten oxide clusters and other model systems. Combined with ab initio calculations, information about the cluster structure and chemical bonding has also been obtained. We propose to work on a number of oxide cluster systems of current interest in oxide catalysis. We also plan to explore novel chemical bonding in oxide clusters. The proposed tasks include: (1) WmOn- clusters (m = 4-6) and comparative studies of Cr, Mo, and W oxide clusters; (2) Stoichiometric titanium oxide clusters and molecular-to-bulk energy gap evolution; (3) Polyhedral vanadium oxide cage clusters; (4) Exploration of novel chemical bonding in metal oxide clusters; (5) Polyoxoanions and stable oxide clusters from solution.
Project Details
Project type
Large-Scale EMSL Research
Start Date
2007-06-01
End Date
2010-09-30
Status
Closed
Released Data Link
Team
Principal Investigator
Team Members
Related Publications
Hua-Jin Zhai, Bin Wang, Xin Huang, and Lai-Sheng Wang. 2009. "Probing the Electronic and Structural Properties of the Niobium Trimer Cluster and Its Mono- and Dioxides: Nb3On
- and Nb3On (n ) 0-2)." J. Phys. Chem. A 2009, 113, 3866–3875. doi: 10.1021/jp809945n
J. Su, P. D. Dau, Y.-H. Qiu, H.-T. Liu, C.-F. Xu, D.-L. Huang, L.-S. Wang, J. Li, "Probing the Electronic Structure and Chemical Bonding in Tricoordinate Uranyl Complexes UO2X3?(X = F, Cl, Br, I): Competition between Coulomb Repulsion and U?X Bonding", Inorg. Chem., 2013, 52(11), 6617-6626, DOI:10.1021/ic4006482
J. Su, W.-L. Li, G. V. Lopez, T. Jian, G.-J. Cao, W.-L. Li, W.H.E. Schwarz, L.-S. Wang, J. Li, "Probing the Electronic Structure and Chemical Bonding of Mono-Uranium Oxides with Different Oxidation States: UOx- and UOx (x = 3-5) ", J. Phys. Chem. A, 2016, 120(7), 1084-1096, DOI: 10.1021/acs.jpca.5b11354
Sierka M, J Dobler, J Sauer, HJ Zhai, and LS Wang. 2009. "The [(AI2O3)2]- Anion Cluster: Electron Localization-Delocalization Isomerism." Chemphyschem 10(14):2410-2413.
Zhai HJ, C Burgel, V Bonacic-Koutecky, and LS Wang. 2008. "Probing the Electronic Structure and Chemical Bonding of Gold Oxides and Sulfides in AuOn- and AuSn- (n=1, 2)." Journal of the American Chemical Society 130(28):9156-9167. doi:10.1021/ja802408b