Michael White1 2 Meng Xue2 Kenneth Goodman2 Yilin Ma2 Shizhong Liu2 Ping Liu1

1, Brookhaven National Laboratory, Upton, New York, United States
2, Stony Brook University, Upton, New York, United States

Mass-selected cluster deposition is used to prepare model “inverse” catalysts comprised of small metal oxide (MxOy: M = Ti, Nb, Mo, Ce, W) and sulfide (MxSy: M = Mo, W) clusters deposited on Cu and Au surfaces, respectively, for studies related to the water-gas-shift reaction and CO2 activation. A key advantage of cluster deposition is that it allows control over cluster stoichiometry which provides a means of introducing oxygen/sulfur “vacancies” and varying the average cation oxidation state. Moreover, the use of well-ordered supports and size-selected clusters is ideally suited for computational modeling of structure and reactions using DFT electronic structure theory. Results will be presented for recent studies of water dissociation on oxide clusters deposited on Cu and Cu2O surfaces, including mechanistic studies of reactions at elevated pressures using ambient pressure XPS. Investigations of the binding and reaction of CO2 on alkali-modified surfaces of metal sulfide clusters deposited on Au(111) will also be presented.

This work was carried out at Brookhaven National Laboratory under Contract No. DE-SC0012704 with the U.S Department of Energy, Office of Science, and supported by its Division of Chemical Sciences, Geosciences, and Biosciences within the Office of Basic Energy Sciences.