Bipolaronic Motifs Induced Spatially Separated Catalytic Sites for Tunable Syngas Photosynthesis From CO2.
Adv Mater
; 36(25): e2401004, 2024 Jun.
Article
em En
| MEDLINE
| ID: mdl-38520181
ABSTRACT
Photocatalytic reduction of CO2 into syngas is a promising way to tackle the energy and environmental challenges; however, it remains a challenge to achieve reaction decoupling of CO2 reduction and water splitting. Therefore, efficient production of syngas with a suitable CO/H2 ratio for Fischer-Tropsch synthesis can hardly be achieved. Herein, bipolaronic motifs including Co(II)-pyridine N motifs and Co(II)-imine N motifs are rationally designed into a crystalline imine-linked 1,10-phenanthroline-5,6-dione-based covalent organic framework (bp-Co-COF) with a triazine core. These featured structures with spatially separated active sites exhibit efficient photocatalytic performance toward CO2-to-syngas conversion with a suitable CO/H2 ratio (11-13). The bipolaronic motifs enable a highly separated electron-hole state, whereby the Co(II)-pyridine N motifs tend to be the active sites for CO2 activation and accelerate the hydrogenation to form *COOH intermediates; whilst, the Co(II)-imine N motifs increase surface hydrophilicity for H2 evolution. The photocatalytic reductions of CO2 and H2O thus decouple and proceed via a concerted way on the bipolaronic motifs of bp-Co-COF. The optimal bp-Co-COF photocatalyst achieves a high syngas evolution rate of 15.8 mmol g-1 h-1 with CO/H2 ratio of 12, outperforming previously reported COF-based photocatalysts.
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Base de dados:
MEDLINE
Idioma:
En
Ano de publicação:
2024
Tipo de documento:
Article
País de afiliação:
China