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*RhCl₂)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.

光催化还原反应中电子的产生、转移和利用共同决定了太阳能-化学转化效率。在自然光合作用中，超薄类囊体膜装载大量色素和蛋白质用于光捕获和电子转移，它还整合了铁氧还蛋白-NADP ⁺带有还原酶的分子氢化物，用于 NADPH 再生中的电子利用。受此启发，本文中，共轭聚合物纳米层与 (Cp*RhCl ₂ ) _2配位(CPNL-Rh) 是通过拓扑和化学工程策略开发的，以协同增强电子产生、转移和利用 NADH 再生。具体来说，CPNL-Rh 中分布良好的三嗪部分主要收集可见光以产生电子。电子通过CPNL迅速转移到Rh助催化剂。Rh助催化剂最终在溶液中接受电子和质子形成分子氢化物以实现NADH再生。用于 NADH 再生的 CPNL-Rh 的周转频率达到 44.8 h ^-1，是有史以来报道的最高值，比具有游离 Rh 助催化剂的散装 CP 高约 346%。