Small and narrowly distributed nanoparticles of copper alloyed with gallium supported on silica containing residual GaIII sites can be obtained via surface organometallic chemistry in a two-step process: (i) formation of isolated GaIII surface sites on SiO2 and (ii) subsequent grafting of a CuI precursor, [Cu(OtBu)]4, followed by a treatment under H2 to generate CuGax alloys. This material is highly active and selective for CO2 hydrogenation to CH3OH. In situ X-ray absorption spectroscopy shows that gallium is oxidized under reaction conditions while copper remains as Cu0. This CuGa material only stabilizes methoxy surface species while no formate is detected according to ex situ infrared and solid-state nuclear magnetic resonance spectroscopy.
Contact
Dr Olga Safonova
SuperXAS beamline
Operando spectroscopy group & Laboratory for Synchrotron Radiation and Femtochemistry (LSF)
Swiss Light Source, Paul Scherrer Intitute
5232 Villigen-PSI, Switzerland
Telephone: +41 56 310 58 05
E-mail: olga.safonova@psi.ch
Original Publication
Enhanced CH3OH selectivity in CO2 hydrogenation using Cu-based catalysts generated via SOMC from GaIII single-sites
Erwin Lam, Gina Noh, Ka Wing Chan, Kim Larmier, Dmitry Lebedev, Keith Searles, Patrick Wolf, Olga V. Safonova and Christophe Cop´eret
Chemical Science, 25 February 2020
DOI: 10.1039/d0sc00465k