Exploiting the NADP+/NADPH-like Hydride-Transfer Redox Cycle with Bis-Imidazolium-Embedded Heterohelicene for Electrocatalytic Hydrogen Evolution Reaction.

Abstract

Generation of clean energy in a viable manner demands efficient and sustainable catalysts. One prospective method of clean energy generation is the electrochemical hydrogen evolution reaction (HER). Over the years, various transition metal-based complexes/polymeric organic materials were utilized in HER. However, the use of a redox-active small organic molecule as a catalyst for HER has not been explored well. The requirements of a strongly acidic solution, very high overpotential, and stability under acidic conditions pose several challenges for applying organic electrocatalysts for HER. Considering these challenges, herein, we demonstrated an NADP+-like organic system (NADP+ = nicotinamide adenine dinucleotide phosphate), a bis-imidazolium-fused heterohelicene, which acts as a catalyst for HER with mild acid (acetic acid) as a proton source at moderate overpotential. The unique structural backbone of this dicationic heterohelicene allowed to exploit the NADP+/NADPH-type (NADPH = reduced nicotinamide adenine dinucleotide phosphate) hydride transfer-based redox cycle efficiently under the applied conditions, where the NADPH-like hydride intermediate transfers the hydride to the proton of the mild acid to generate H2. The Faradaic efficiency and turnover number for the present HER were achieved up to 85 ± 5% and 50 ± 3, respectively. In addition, the maximum turnover frequency, TOFmax, value of 410 s-1 was observed, which is around 400 times that obtained for the existing reported NADP+-like organic compounds used as catalysts for HER. Thorough mechanistic studies were conducted experimentally and computationally to establish a plausible catalytic cycle. This advancement could help in designing efficient organic electrocatalysts for HER from a mild proton source.