Engineering d-orbital of copper single-atom sites toward industrial-level electrocatalytic methanation.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 41688435.
- Also identified by DOI 10.1038/s41467-026-69260-z and PMC identifier 13013686.
- Licence recorded as CC BY-NC-ND.
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Abstract
Copper (Cu)-based single-atom catalysts (SACs) enable electrocatalytic CO<sub>2</sub> reduction into methane (CH<sub>4</sub>) fuel for thermal power plant decarbonization, yet conventional Cu SACs face industrial deployment barriers like instability and sluggish kinetics caused by d - p orbital coupling. Herein, we develop a Cu-Ti<sub>1</sub>O<sub>3</sub> catalyst with localized Cu single-atom sites by oxygen vacancy (O<sub>v</sub>)-involved orbital engineering, achieving industrial-level CH<sub>4</sub> production. Theoretical and in-situ studies reveal the intensification of the d - d coupling at Cu sites triggered by [Cu-O<sub>v</sub> - Ti] motifs, which enhances d-π* polar interactions upon *CO<sub>2</sub> and accelerates C - O bond cleavage in *OCH<sub>3</sub> intermediate. As a result, Cu-Ti<sub>1</sub>O<sub>3</sub> achieves a competitive performance, i.e., the highest Faradaic efficiency of 76% and a peak partial current density of 670 mA cm<sup>-2</sup> toward CH<sub>4</sub> (corresponding turnover frequency = 24,930 h<sup>-1</sup>), ~3.5-fold promotion over conventional Cu SACs. Furthermore, it demonstrates high durability (>1,230 hours) at an industrial-level current density, exceeding the longevity of conventional Cu SACs by over 20 times. Our findings highlight the prospect of d-orbital engineering in enabling industrial-level electrocatalytic methanation, offering promising implications for decarbonizing traditional power plants.