Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, The Chinese Academy of Sciences, Beijing 100190, P. R. China.
School of Future Technology, University of Chinese Academy of Sciences, Beijing 100049, P. R. China.
J Am Chem Soc. 2022 Sep 14;144(36):16219-16231. doi: 10.1021/jacs.2c02341. Epub 2022 Sep 2.
The odyssey of photochemistry is accompanied by the journey to manipulate "electrons" and "protons" in time, in space, and in energy. Over the past decades, single-electron (1e) photochemical transformations have brought marvelous achievements. However, as each photon absorption typically generates only one exciton pair, it is exponentially challenging to accomplish multielectron and proton photochemical transformations. The multistep differences in thermodynamics and kinetics urgently require us to optimize light harvesting, expedite consecutive electron transfer, manipulate the interaction of catalysts with substrates, and coordinate proton transfer kinetics to furnish selective bond formations. Tandem catalysis enables orchestrating different photochemical events and catalytic transformations from subpicoseconds to seconds, which facilitates multielectron redox chemistries and brings consecutive, value-added reactivities. Joint efforts in molecular and material design, mechanistic understanding, and theoretical modeling will bring multielectron and proton synthetic opportunities for fuels, fertilizers, and chemicals with enhanced versatility, efficiency, selectivity, and scalability, thus taking better advantage of photons (i.e., sunlight) for our sustainable society.
光化学的历程伴随着对“电子”和“质子”在时间、空间和能量上进行操控的探索。在过去的几十年里，单电子（1e）光化学反应已经取得了惊人的成就。然而，由于每次光子吸收通常只能产生一对激子，因此要实现多电子和质子光化学反应极具挑战性。热力学和动力学的多步差异迫切要求我们优化光的捕获，加快连续电子转移，调控催化剂与底物的相互作用，协调质子转移动力学以提供选择性键的形成。串联催化使我们能够在从亚皮秒到秒的时间尺度上协调不同的光化学反应和催化转化，促进多电子氧化还原化学，并带来连续的、增值的反应性。在分子和材料设计、机理理解和理论建模方面的共同努力，将为燃料、肥料和化学品带来多电子和质子合成的机会，提高多功能性、效率、选择性和可扩展性，从而更好地利用光子（即阳光）来构建我们的可持续社会。
