Selective light-driven methane oxidation to ethanol.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 39617752.
- Also identified by DOI 10.1038/s41467-024-54835-5 and PMC identifier 11609272.
- Licence recorded as CC BY-NC-ND.
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Abstract
Methane (CH<sub>4</sub>) photocatalytic upgrading to value-added chemicals, especially C<sub>2</sub> 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 CH<sub>4</sub> oxidation to ethanol (C<sub>2</sub>H<sub>5</sub>OH) on crystalline carbon nitride (CCN) modified with Cu<sub>9</sub>S<sub>5</sub> and Cu single atoms (Cu<sub>9</sub>S<sub>5</sub>/Cu-CCN). The integration of photothermal effect and photocatalysis overcomes CH<sub>4</sub>-to-C<sub>2</sub>H<sub>5</sub>OH conversion bottlenecks, with Cu<sub>9</sub>S<sub>5</sub> as a hotspot to convert solar-energy to heat. In-situ characterizations demonstrate that Cu single atoms play as electron acceptor for O<sub>2</sub> reduction to ·OOH/ · OH, while Cu<sub>9</sub>S<sub>5</sub> acts as hole acceptor and site for CH<sub>4</sub> adsorption, C - H activation, and C - C coupling. Theoretical calculations demonstrate that Cu<sub>9</sub>S<sub>5</sub>/Cu-CCN reduces C - C coupling energy barrier by stabilizing ·CH<sub>3</sub> and ·CH<sub>2</sub>O. Impressively, C<sub>2</sub>H<sub>5</sub>OH productivity reaches 549.7 μmol g<sup>-1</sup> h<sup>-1</sup>, with selectivity of 94.8% and apparent quantum efficiency of 0.9% (420 nm). This work provides a sustainable avenue for CH<sub>4</sub> conversion to value-added chemcials.