Photocatalytic CO<sub>2</sub>-to-ethanol conversion via multiple enrichment effects in porous liquids.
basic_science · Level V
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- Record sourced from PubMed, PMID 42616882.
- Also identified by DOI 10.1126/sciadv.aeg8278.
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Abstract
Photocatalytic CO<sub>2</sub> reduction to multi-carbon products like ethanol remains challenging. We report a porous liquid (PL) system, PL(Cu-Cu<sub>2</sub>O@NU), driving selective CO<sub>2</sub>-to-ethanol conversion. It features Cu<sup>0</sup>/Cu<sup>+</sup> dual sites in NH<sub>2</sub>-UiO-66 (NU) hybridized with a methoxypolyethylene glycol-functionalized imidazolium ionic liquid (IL). This system facilitates C-C coupling via a triple enrichment mechanism: IL and NU synergistically enrich CO<sub>2</sub>, IL enriches electrons at Cu sites, and confined pores enrich intermediates. Consequently, PL(Cu-Cu<sub>2</sub>O@NU) achieves an 83.3 μmol·g<sup>-1</sup>·h<sup>-1</sup> ethanol yield with 95.2% selectivity, outperforming Cu-Cu<sub>2</sub>O@NU by 4.7-fold. Control experiments (showing no ethanol over isolated NU, IL, or Cu-Cu<sub>2</sub>O) directly validate this mechanism. Supplemental computations substantiate these findings: molecular dynamics confirm confined pores reduce *CO diffusion for enrichment, while density functional theory reveals lowered C-C coupling barriers. Furthermore, d-band upshifts enhance CO<sub>2</sub>-Cu overlap, and Cu<sup>0</sup>/Cu<sup>+</sup> sites mediate the critical *CO → *COCO transition. These integrated observations firmly establish PLs as robust confinement-driven platforms for selective CO<sub>2</sub>-to-C<sub>2</sub><sup>+</sup> conversion.