PNNL

Abstract

To capture the dominant interactions (surface-mediated and through-space steric) in catalytic hydrodeoxygenation systems, coverage-dependent mean-field models of aromatic adsorption are developed on Pt(111) and Ru(0001). We derive three key insights from this work: (1) we can universally apply mean-field models to capture the coverage-dependent behavior of oxygenated aromatics on transition metal surfaces, (2) we can deconvolute surface-mediated and throughspace steric interactions from the mean-field model, and (3) we can develop relatively accurate models that predict the adsorption energy of aromatics on transition metal surfaces for the full coverage range using the work function at lowest modeled coverage. Our approach enables the rapid prediction of coverage-dependent behavior of oxygenated aromatics on transition metal surfaces, reducing the computational cost associated with these studies by an order of magnitude. N.C., A.J.R.H., and J.S.M. were primarily funded by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Biosciences and Geosciences 13 within the Catalysis Science program, under award number DE-SC0014560. We also thank Greg Collinge for fruitful discussions. Y.W. would like to acknowledge the support from the U.S. Department of Energy (DOE), Office of Science (SC), Basic Energy Sciences (BES), Division of Chemical Sciences, Geosciences, and Biosciences within the Catalysis Science program (DEAC05- RL01830, FWP-47319). This research used resources from the Center for Institutional Research Computing at Washington State University. This work was partially funded by the Joint Center for Deployment and Research in Earth Abundant Materials (JCDREAM) in Washington State. PNNL is a multi-program national laboratory operated for the U.S. DOE by Battelle. N.C., Seattle Chapter ARCS Fellow, gratefully acknowledges financial support from the Achievement Rewards for College Scientists Foundation.