title: Catalyst design for enhanced sustainability through fundamental surface chemistry.
abstract: Decreasing energy consumption in the production of platform chemicals is necessary to improve the sustainability of the chemical industry, which is the largest consumer of delivered energy. The majority of industrial chemical transformations rely on catalysts, and therefore designing new materials that catalyse the production of important chemicals via more selective and energy-efficient processes is a promising pathway to reducing energy use by the chemical industry. Efficiently designing new catalysts benefits from an integrated approach involving fundamental experimental studies and theoretical modelling in addition to evaluation of materials under working catalytic conditions. In this review, we outline this approach in the context of a particular catalyst-nanoporous gold (npAu)-which is an unsupported, dilute AgAu alloy catalyst that is highly active for the selective oxidative transformation of alcohols. Fundamental surface science studies on Au single crystals and AgAu thin-film alloys in combination with theoretical modelling were used to identify the principles which define the reactivity of npAu and subsequently enabled prediction of new reactive pathways on this material. Specifically, weak van der Waals interactions are key to the selectivity of Au materials, including npAu. We also briefly describe other systems in which this integrated approach was applied.
authors.affiliation: Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, MA 02138, USA.
authors.forename: Michelle L
authors.initials: ML
authors.lastname: Personick
authors.affiliation: School of Engineering and Applied Sciences, Harvard University, 29 Oxford Street, Cambridge, MA 02138, USA.
authors.forename: Matthew M
authors.initials: MM
authors.lastname: Montemore
authors.affiliation: School of Engineering and Applied Sciences, Harvard University, 29 Oxford Street, Cambridge, MA 02138, USA.
authors.forename: Efthimios
authors.initials: E
authors.lastname: Kaxiras
authors.affiliation: School of Engineering and Applied Sciences, Harvard University, 29 Oxford Street, Cambridge, MA 02138, USA.
authors.forename: Robert J
authors.initials: RJ
authors.lastname: Madix
authors.affiliation: Nanoscale Synthesis and Characterization Laboratory, Lawrence Livermore National Laboratory, Livermore, CA 94550, USA.
authors.forename: Juergen
authors.initials: J
authors.lastname: Biener
authors.affiliation: Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, MA 02138, USA School of Engineering and Applied Sciences, Harvard University, 29 Oxford Street, Cambridge, MA 02138, USA friend@fas.harvard.edu.
authors.forename: Cynthia M
authors.initials: CM
authors.lastname: Friend
keywords: catalysis; nanoporous gold; surface science; sustainability; theoretical modelling