TY - JOUR
T1 - Selective light-driven methane oxidation to ethanol
AU - Xue, Fei
AU - Zhang, Chunyang
AU - Cheng, Cheng
AU - Yan, Xueli
AU - Liu, Feng
AU - Liu, Xiaozhi
AU - Jiang, Biao
AU - Zhang, Qiuyue
AU - Sun, Lin
AU - Peng, Huiping
AU - Huang, Wei Hsiang
AU - Pao, Chih Wen
AU - Hu, Zhiwei
AU - Chen, Mingshu
AU - Su, Dong
AU - Liu, Maochang
AU - Huang, Xiaoqing
AU - Xu, Yong
N1 - Publisher Copyright:
© The Author(s) 2024.
PY - 2024/12
Y1 - 2024/12
N2 - 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.
AB - 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.
UR - https://www.scopus.com/pages/publications/85211157478
U2 - 10.1038/s41467-024-54835-5
DO - 10.1038/s41467-024-54835-5
M3 - 文章
C2 - 39617752
AN - SCOPUS:85211157478
SN - 2041-1723
VL - 15
JO - Nature Communications
JF - Nature Communications
IS - 1
M1 - 10451
ER -