Shifting from one- to two-electron transfer towards water-donating photocatalytic hydrogenation

Open AccessCCS ChemistryRESEARCH ARTICLES22 Sep 2025Shifting from one- to two-electron transfer towards water-donating photocatalytic hydrogenation Tongtong Jia, Yufan Zhang, Yu Lei, Bangrong Ming, Ran Duan, Hongwei Ji, Jikun Li, Hua Sheng, Chuncheng Chen, Wenjing Song and Jincai Zhao Tongtong Jia , Yufan Zhang , Yu Lei , Bangrong Ming , Ran Duan , Hongwei Ji , Jikun Li , Hua Sheng , Chuncheng Chen , Wenjing Song and Jincai Zhao https://doi.org/10.31635/ccschem.025.202506308 SectionsSupplemental MaterialAboutPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Photocatalysis opens unique pathways for reductive hydrogenation under mild conditions. Typically, photocatalytic hydrogenation proceeds via single electron transfer (SET), followed by hydrogen atom transfer (HAT). Herein, we elucidate that the deliberate arrangement of an electron reservoir with Ni catalysts enables a transition from photoinduced one- to two-electron transfer, yielding desired products via proton acquisition. Specifically, arranging carbon nitride (CN) that stores multiple photogenerated electrons in proximity to a chemically bonded Ni site accomplishes competitive two-electron/proton hydrogenation of halogenated substrates using water as the hydrogen source, outperforming the SET-mediated process. In contrast, non-chemically bonded Ni and CN system exhibits poor activity for 2e−/H+ hydrogenation. Mechanistic studies further reveal the low-valent Ni+ and CN(e−) cooperate to transfer two electrons to the substrate. The catalytic utility of this two-electron mechanism is further underscored by the deuterium labeling of diverse (hetero)arenes and bioactive molecules in D2O, achieving deuterium incorporation of up to 99%. Our work highlights the value of light-driven multiple-electron catalysis that reaches otherwise challenging transformations. Download figure Download PowerPoint Previous articleNext article FiguresReferencesRelatedDetails Issue AssignmentNot Yet AssignedSupporting Information Copyright & Permissions© 2025 Chinese Chemical Society Downloaded 0 times PDF downloadLoading ...