caa a22 4500 606173226 CHVBK 20210128100732.0 cr unu---uuuuu 210128e20150201xx s 000 0 eng 10.1007/s11244-014-0341-1 doi (NATIONALLICENCE)springer-10.1007/s11244-014-0341-1 Cluster Models for Studying CO2 Reduction on Semiconductor Photoelectrodes [Elektronische Daten] [John Keith, Ana Muñoz-García, Martina Lessio, Emily Carter] Sunlight-powered CO2-photoelectroreduction is a promising and potentially sustainable route to recycle CO2 byproducts back into energy-dense liquid fuels. One of the most intriguing processes known to date is the pyridinium-catalyzed CO2 reduction on p-type GaP photoelectrodes, where conversion to methanol has reported faradaic efficiencies nearing 100%. Modeling this reactive environment requires understanding energetics of differently charged species at semiconductor electrodes, so we develop a cluster model and benchmark binding energies from it to those from Kohn-Sham density functional theory calculations that employ periodic boundary conditions. We then use this cluster model to theoretically predict structures and binding energies for charged and neutral adsorbates on the GaP(110) surface with and without the presence of van der Waals interactions and implicit solvation. We discuss the relative magnitudes of binding energy contributions for different adsorbates considered relevant in this CO2 reduction process and provide details showing pitfalls when using cluster models. Springer Science+Business Media New York, 2014 Carbon dioxide reduction nationallicence Gallium phosphide photoelectrodes nationallicence Density functional theory calculations nationallicence Keith John Department of Mechanical and Aerospace Engineering, Princeton University, 08544-5263, Princeton, NJ, USA aut Muñoz-García Ana Department of Chemical Sciences, University of Naples Federico II, 80126, Naples, Italy aut Lessio Martina Department of Chemistry, Princeton University, 08544, Princeton, NJ, USA aut Carter Emily Department of Mechanical and Aerospace Engineering, Princeton University, 08544-5263, Princeton, NJ, USA aut Topics in Catalysis Springer US; http://www.springer-ny.com 58/1(2015-02-01), 46-56 1022-5528 58:1<46 2015 58 11244 https://doi.org/10.1007/s11244-014-0341-1 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s11244-014-0341-1 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Keith John Department of Mechanical and Aerospace Engineering, Princeton University, 08544-5263, Princeton, NJ, USA aut NATIONALLICENCE 700 1- Muñoz-García Ana Department of Chemical Sciences, University of Naples Federico II, 80126, Naples, Italy aut NATIONALLICENCE 700 1- Lessio Martina Department of Chemistry, Princeton University, 08544, Princeton, NJ, USA aut NATIONALLICENCE 700 1- Carter Emily Department of Mechanical and Aerospace Engineering, Princeton University, 08544-5263, Princeton, NJ, USA aut NATIONALLICENCE 773 0- Topics in Catalysis Springer US; http://www.springer-ny.com 58/1(2015-02-01), 46-56 1022-5528 58:1<46 2015 58 11244