Photoelectrochemical Water Oxidation over Novel Semiconducting Zinc-Based Metal-Thiolate Framework

Designing an efficient catalyst for a sustainable photoelectrochemical water oxidation reaction is very challenging in the context of renewable energy research. Here, we have introduced a new semiconducting porous zinc-thiolate framework via successful stitching of an "N" donor linker with a triazine-based tristhiolate secondary building unit in the overall architecture. The introduction of both linker and tristhiolate ligand synergistically modifies the architecture by making it a rigid, crystalline, three-dimensional, thermally stable, and porous framework. Our novel zinc-thiolate framework is used as an n-type semiconductor as revealed from the solid-state UV-vis DRS spectroscopic analysis, ac and dc conductivity analysis, and Mott-Schottky plot. This n-type semiconductor-based zinc-thiolate framework is utilized in the photoelectrochemical water oxidation reaction. It displayed a very high efficiency for a visible-light-driven oxygen evolution reaction (OER) in a KOH medium using standard Ag/AgCl as the reference electrode. The superiority of this material was further revealed from the low onset potential (0.822 mV vs RHE), high photocurrent density (0.204 mA cm^-2), good stability, and high O₂ evolution rate (77 μmol g^-1 of oxygen evolution within 2 h), and a good efficiency (ABPE 0.42%, IPCE 29.6% and APCE 34.5%). Furthermore, the porosity in the overall framework seems to be a blessing to the photoelectrochemical performance due to better mass diffusion of the electrolyte. A detailed mechanism for the OER reaction was analyzed through density functional theory analysis suggesting the potential future of this Zn-thiolate framework for achieving a high efficiency in the sustainable water oxidation reaction.