Density Functional Theory study of Hydrogen Evolution Reaction Mechanism using D-A Conjugated Polymers

Yves Ira A. Reyes^1*, 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, email:yvesirareyes@gmail.com

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 (ΔG_H) 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