Tuning the photocatalytic properties of porphyrins for hydrogen evolution reaction: An in-silico design strategy

Abstract

Porphyrins constitute a class of attractive materials for harvesting sunlight and promote chemical reactions following their natural activity for the photosynthetic process in plants. In this work, we employ an in-silico design strategy to propose novel porphyrin-based materials as photocatalysts for hydrogen evolution reaction (HER). More specifically, a set of meso-substituted porphyrins with donor-acceptor architecture are evaluated within the density functional theory (DFT) framework, according to these screening criteria: i) broad absorption spectrum in the ultraviolet–visible (UV–Vis) and near infrared (NIR) range, ii) suitable redox potentials to drive the uphill reaction that lead to molecular hydrogen formation, iii) low exciton binding free energy ( E b ), and iv) low hydrogen binding free energy (ΔG H ), a quantity that should present low HER overpotentials, ideally ΔG H = 0. The outcomes indicate that the Se-containing compound, where the donor ligands are attached to the porphyrin core by the spacer, outstands as the most promising candidate that is presented in this work. It displays a broad absorption in the visible and NIR regions to up to 1000 nm, suitable catalytic power, low E b (in special in high dielectric constant environment, such as water) and the lowest ΔG H = +0.082 eV. This is comparable, in absolute values, to the value exhibited by platinum (ΔG H = −0.10 eV), one of the most efficient catalysts for HER. • Novel porphyrin-based materials are proposed as photocatalysts for HER. • The screening strategy includes the UV–Vis absorption profile, catalytic power and ΔG H . • All candidates have catalytic power for electron transfer. • The Se-based compound is the most promising candidate in the series. • Nitrogen is the most relevant catalytic site for hydrogen production in these materials.