Near-unity CO<sub>2</sub>-to-ethylene photoconversion over low coordination single-atom catalysts.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 41593062.
- Also identified by DOI 10.1038/s41467-026-68830-5 and PMC identifier 12953602.
- 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
Photocatalytic conversion of carbon dioxide to value-added chemicals, particularly multi-carbon products, offers a promising route toward carbon-neutral cycles. However, achieving high activity and selectivity remains extremely challenging due to the instability of key reaction intermediates and limited C-C coupling efficiency. Herein, we report a low-coordination manganese single-atom catalyst embedded in zinc sulfide (Mn<sub>1</sub>-ZnS<sub>v</sub>) that enables efficient and selective CO<sub>2</sub>-to-C<sub>2+</sub> conversion. In-situ spectroscopic analyses and density functional theory calculations reveal that sulfur vacancies are created at the Mn single-atom coordination sites and induce the formation of coordination-unsaturated Mn-S<sub>2</sub> configuration. The asymmetric coordination environment of Mn modulates local charge distribution, strengthens *CO adsorption, and promotes *CO and *CHO coupling to form the *COCHO intermediate for efficient C-C coupling. As a result, the Mn<sub>1</sub>-ZnS<sub>v</sub> catalyst achieved 99.1% selectivity for ethylene with a formation rate of 76.6 μmol g<sup>-1</sup> h<sup>-1</sup>. This study highlights the critical role of atomic-level coordination engineering in advancing photocatalytic CO<sub>2</sub>-to-C<sub>2+</sub> conversion.