Optimal functionalization of a molecular electrocatalyst for hydride transfer
Abstract
Catalytic reduction reactions via hydride transfer (HT) are ubiquitous in (photo)electrochemical systems being explored for sustainable production of fuels and chemicals. Optimizing the hydride donor—the key catalytic intermediate—is essential to improving performance. Using a well-vetted density functional theory (DFT)-based solvated embedded cluster model, we find that molecular functionalization could significantly enhance the stability (against protonation) of adsorbed 2-pyridinide, which is the probable hydride donor in heterogeneous CO 2 reduction to methanol on GaP photoelectrodes. Specifically, the hydride donor’s performance correlates strongly with the electron-withdrawing capability of substituents. Among all those considered, the –CH 2 –CH 2 F functional group appears to be the optimal substituent, which is determined by balancing the trade-off between stability enhancement and HT-barrier increase of functionalized hydride donors.
Document Details
- Document Type
- Pub Defense Publication
- Publication Date
- Oct 28, 2019
- Source ID
- 10.1073/pnas.1911948116
Entities
People
- Emily A. Carter
- Shenzhen Xu
Organizations
- Air Force Office of Scientific Research
- Princeton University
- University of California