Porphyrin‐based Bi‐MOFs with Enriched Surface Bi Active Sites for Boosting Photocatalytic CO₂ Reduction

Abstract

The inherent challenges in using metal‐organic frameworks (MOFs) for photocatalytic CO2 reduction are the combination of wide‐range light harvesting, efficient charge separation and transfer as well as highly exposed catalytic active sites for CO2 activation and reduction. We present here a promising solution to satisfy these requirements together by modulating the crystal facet and surface atomic structure of a porphyrin‐based bismuth‐MOF (Bi‐PMOF). The series of structural and photo‐electronic characterizations together with photocatalytic CO2 reduction experiment collectively establish that the enriched Bi active sites on the (010) surface prefer to promote efficient charge separation and transfer as well as the activation and reduction of CO2. Specifically, the Bi‐PMOFs‐120‐F with enriched surface Bi active sites exhibits optimum photocatalytic CO2 reduction performance to CO (28.61 umol·h‐1g‐1) and CH4 (8.81 umol·h‐1g‐1). This work provides new insights to synthesize highly efficient main group p‐block metal Bi‐MOF photocatalysts for CO2 reduction through a facet‐regulation strategy and sheds light on the surface structure‐activity relationships of the MOFs.

Porphyrin-based MOFs for photocatalysis in water: advancements in solar fuels generation and pollutants degradation

“…Solar fuels refer to small molecules obtained through the redox reactions of H 2 O, CO 2 or N 2 such as H 2 , C 1 or C 2+ products and NH 3 , respectively. 38,39 This review is limited to solar fuel generation through photocatalytic water splitting using PMOFs; however, it is important to highlight that PMOFs have also been used as photocatalysts for CO 2 reduction in the presence of water, as recently reported in numerous studies and reviews, 40–46 and activity for N 2 reduction was also reported. 47…”

Porphyrin-based metal–organic frameworks for photo(electro)catalytic CO2 reduction

“…The adsorption and activation of CO 2 on porphyrin-based MOFs are intricate processes that rely on the strategic design of the structure of porphyrin-based MOFs, composition, and functionality. 108 By optimizing these factors, researchers can enhance the interaction between CO 2 and the catalytic sites, thereby improving the efficiency and selectivity of CO 2 reduction reactions. Understanding and manipulating these mechanisms are critical steps towards developing advanced materials for sustainable energy conversion and carbon utilization technologies.…”