Selective light-driven methane oxidation to ethanol

作者：Fei Xue, Chun‐yang Zhang, Cheng Cheng, Xueli Yan, Feng Liu, Xiaozhi Liu, Biao Jiang, Qiuyue Zhang, Lin Sun, Huiping Peng, Wei‐Hsiang Huang, Chih‐Wen Pao, Zhiwei Hu, Mingshu Chen, Dong Su, Maochang Liu, Xiaoqing Huang, Yong Xu · 发表于：Nature Communications · 年份：2024 · DOI：10.1038/s41467-024-54835-5 · 被引用次数：37 · 研究领域：Advanced Photocatalysis Techniques、Catalytic Processes in Materials Science、Perovskite Materials and Applications

Methane (CH4) photocatalytic upgrading to value-added chemicals, especially C2 products, is significant yet challenging due to sluggish energy/mass transfer and insufficient chemical driven-force in single photochemical process. Herein, we realize solar-driven CH4 oxidation to ethanol (C2H5OH) on crystalline carbon nitride (CCN) modified with Cu9S5 and Cu single atoms (Cu9S5/Cu-CCN). The integration of photothermal effect and photocatalysis overcomes CH4-to-C2H5OH conversion bottlenecks, with Cu9S5 as a hotspot to convert solar-energy to heat. In-situ characterizations demonstrate that Cu single atoms play as electron acceptor for O2 reduction to ·OOH/ · OH, while Cu9S5 acts as hole acceptor and site for CH4 adsorption, C − H activation, and C − C coupling. Theoretical calculations demonstrate that Cu9S5/Cu-CCN reduces C − C coupling energy barrier by stabilizing ·CH3 and ·CH2O. Impressively, C2H5OH productivity reaches 549.7 μmol g–1 h–1, with selectivity of 94.8% and apparent quantum efficiency of 0.9% (420 nm). This work provides a sustainable avenue for CH4 conversion to value-added chemcials. Methane (CH4) photocatalytic upgrading to value-added chemicals, especially C2 products, is significant yet challenging. Here the authors realize solar-driven CH4 oxidation to ethanol on carbon nitride modified with Cu9S5 and Cu single atoms with a record-high selectivity of ~95%.