Dual-Function Precious-Metal-Free Metal-Organic Framework for Photocatalytic Conversion and Chemical Fixation of Carbon Dioxide.

Highly efficient transformation of carbon dioxide (CO) into value-added chemicals is considered a promising route for clean production and future energy sustainability, which is crucial for realizing a carbon-neutral economy. It remains a great challenge to develop highly stable and active catalysts with low-cost, environmentally friendly, and nontoxic materials for catalytic conversion of CO. Herein, a precious-metal-free and heterogeneous MOF (-) catalyst, composed of bis(terpyridine)iron(II) complexes and zirconium(IV) ions, was designed and prepared via a metalloligand approach. -, with a robust framework and regular 1D channels not only can achieve the photocatalytic reduction of CO to HCOOH with a high conversion rate (up to 265 μmol·g·h) under visible-light irradiation but also exhibits exceptional catalytic activities toward the synthesis of cyclic carbonates via cycloaddition reactions of various epoxides and CO in the absence of light. Possible mechanisms for two different conversion processes of CO catalyzed by - have been proposed. represents an ideal dual-function MOF platform for the catalytic conversion and utilization of CO in all weather conditions.