Oxo dicopper anchored on carbon nitride for selective oxidation of methane.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 35296655.
- Also identified by DOI 10.1038/s41467-022-28987-1 and PMC identifier 8927601.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
Selective conversion of methane (CH<sub>4</sub>) into value-added chemicals represents a grand challenge for the efficient utilization of rising hydrocarbon sources. We report here dimeric copper centers supported on graphitic carbon nitride (denoted as Cu<sub>2</sub>@C<sub>3</sub>N<sub>4</sub>) as advanced catalysts for CH<sub>4</sub> partial oxidation. The copper-dimer catalysts demonstrate high selectivity for partial oxidation of methane under both thermo- and photocatalytic reaction conditions, with hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) and oxygen (O<sub>2</sub>) being used as the oxidizer, respectively. In particular, the photocatalytic oxidation of CH<sub>4</sub> with O<sub>2</sub> achieves >10% conversion, and >98% selectivity toward methyl oxygenates and a mass-specific activity of 1399.3 mmol g Cu<sup>-1</sup>h<sup>-1</sup>. Mechanistic studies reveal that the high reactivity of Cu<sub>2</sub>@C<sub>3</sub>N<sub>4</sub> can be ascribed to symphonic mechanisms among the bridging oxygen, the two copper sites and the semiconducting C<sub>3</sub>N<sub>4</sub> substrate, which do not only facilitate the heterolytic scission of C-H bond, but also promotes H<sub>2</sub>O<sub>2</sub> and O<sub>2</sub> activation in thermo- and photocatalysis, respectively.