Topologically and chemically engineered conjugated polymer with synergistically intensified electron generation, transfer and utilization for photocatalytic nicotinamide cofactor regeneration

Electron generation, transfer and utilization in photocatalytic reduction reactions jointly govern the solar-to-chemical conversion efficiency. In natural photosynthesis, the ultrathin thylakoid membrane loads numerous pigments and proteins for light harvesting and electron transfer, which also integrates ferredoxin-NADP + reductase bearing molecule hydrides for electron utilization in NADPH regeneration. Inspired by this, herein, conjugated polymer nanolayer coordinated with (Cp*RhCl 2 ) 2 (CPNL-Rh) is developed through a topological and chemical engineering strategy to synergistically intensify electron generation, transfer and utilization for NADH regeneration. Specifically, the triazine moieties well distributed in CPNL-Rh largely harvest visible light to generate electrons. The electrons are rapidly transferred to Rh cocatalyst through CPNL. Rh cocatalyst finally accepts electrons and protons in solution to form molecule hydrides for implementing NADH regeneration. The turnover frequency of CPNL-Rh for NADH regeneration reaches 44.8 h −1 , among the highest value ever reported and ~346% higher than that of bulk CP with free Rh cocatalyst. Inspired by the structure and function of thylakoid, in this study, conjugated polymer nanolayer coordinated with (Cp*RhCl 2 ) 2 (CPNL-Rh) is developed through a topological and chemical engineering strategy to synergistically intensify electron generation, transfer and utilization for photocatalytic NADH regeneration. The CPNL-Rh photocatalyst provides large surface to incorporate numerous triazine groups for light harvestng, afforded ultrathin membrane structure to confine the electron transfer pathway, and finally anchored Rh catalytic centre to accept and strore electrons to trigger NADH regeneration, thus achieving the synergistic intensificaiton of electron generation, transfer and utilization. Overall, the turnover frequency of CPNL-Rh for NADH regeneration reaches 44.8 h −1 , among the highest value ever reported and ~346% higher than that of bulk CP with free Rh cocatalyst. • Conjugated polymer nanolayer coordinated with (Cp*RhCl 2 ) 2 (CPNL-Rh) is prepared. • A topological and chemical engineering strategy is proposed to prepare CPNL-Rh. • Electron generation, transfer and utilization are intensified through CPNL-Rh. • CPNL-Rh exhibited high turnover frequency for photocatalytic NADH regeneration. • An enzyme-photo-coupled catalytic system is constructed based on CPNL-Rh.