(81d) Formic Acid Decomposition On Transition Metals: Trends Through Density Functional Theory Studies

Tonelli, S. D. - Presenter, University of Wisconsin-Madison
Singh, S. - Presenter, University of Wisconsin-Madison
Dumesic, J. A. - Presenter, University of Wisconsin-Madison
Mavrikakis, M. - Presenter, University of Wisconsin - Madison


The investigation of formic acid (HCOOH) decomposition on transition metals is important in order to derive useful insights for vapor phase catalysis involving HCOOH and for direct HCOOH fuel cells. Here we present the main results obtained from periodic, self-consistent Density Functional Theory (DFT-GGA) calculations concerning the gas-phase decomposition of HCOOH on Pt(111), Pd(111) and Cu(111) surfaces. Accordingly, we analyzed the minimum energy paths for HCOOH decomposition into CO2 and H­2 through the carboxyl (COOH) and formate (HCOO) intermediates, along with alternative bond-breaking possible steps in those intermediates. The DFT-derived parameters have been employed in a microkinetic model and then used to compare modeling results with experimental reaction kinetics data. This work will be discussed in the context of thermochemistry trends for the same reaction on a number of other late transition metal closed-packed surfaces.


This material is based upon work supported as part of the Institute for Atom-efficient Chemical Transformations (IACT), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.