Density Functional Theory study of Hydrogen Evolution Reaction Mechanism using D-A Conjugated Polymers
Yves Ira A. Reyes1*, Hsin-Yi Tiffany Chen1, Ho-Hsiu Chou2
1Engineering and Systems Science, National Tsing Hua University, Hsinchu City, Taiwan
2Chemical Engineering, National Tsing Hua University, Hsinchu City, Taiwan
* Presenter:Yves Ira A. Reyes,
Herein, Density Functional Theory (DFT) calculations were applied in to investigate hydrogen evolution reaction (HER) mechanism using conjugated donor-acceptor (D-A) polymer photocatalysts: poly[4,4’-(9-(4-aminophenyl)-9H-carbazole-3,6-diamine-alt-5-oxido-5-phenylbenzo[b]phosphindole-3,7-diyl)dibenzaldehyde] (PCzPO) and poly[N1,N1-bis(4-amino-2-fluorophenyl)-2-fluorobenzene-1,4-diamine-alt-5-oxido-5- phenylbenzo[b]phosphindole-3,7-diyl)dibenzaldehyde] (PNoFPO). Study of the frontier orbitals confirm intramolecular charge transfer during light absorption. Calculation of Gibbs free energy of proton binding (ΔGH) shows that protons bind to acceptor group atoms and form H2 through either intra- or intermolecular mechanisms. This work show the importance of binding sites and H2 formation mechanisms in the future development of D-A polymer catalysts for HER.

Keywords: hydrogen evolution reaction, D-A polymer photocatalysts, density functional theory, optoelectronic properties