Trinuclear Fe Clusters for Highly Efficient CO₂ Photoreduction

Abstract

Photocatalytic reduction of CO2 into valuable chemicals or fuels is considered a promising solution to mitigate the energy crisis. In this work, efficient CO2 to CO conversion was achieved, accompanied by a class of trinuclear Fe clusters as photocatalysts. Under optimal conditions, the highest catalytic rate could be up to 140.9 μmol/h in 6 h with the assistance of photosensitizers (PS). The trinuclear Fe Clusters can be used as secondary building units to construct Fe-based metal–organic frameworks (MOFs). However, the catalytic activity of Fe-based MOFs is weaker than that of clusters in both the cases of extra PS-assisted MOFs and integrated PS into MOFs. The simpler synthesis, lower cost, and higher catalytic activity make the Fe clusters a better catalyst. Additionally, steady-state fluorescence tests confirmed the transfer of photogenerated electrons from PS to the clusters during the photocatalytic reaction.

Vanadium-Doped Bimetallic Nanoporous Metal–Organic Frameworks as Bifunctional Electrocatalysts for Urea-Assisted Hydrogen Production

“…Herein, trinuclear metal clusters (M 3 ) are connected by organic linkers into the target M 3 -MOF structure. In the M 3 cluster, one or more M metal centers of them can be easily replaced by another or more metal centers to form bimetallic, trimetallic, or mixed metal constructed M 1 2 M 2 -MOFs or M 1 M 2 M 3 -MOFs . The introduction of such other second or third metal centers not only can improve the catalyst activity of MOFs based on the synergistic effect of multiple metal centers by adjusting electronic distributions but also can enhance the structural stability of single metal MOF materials by selecting high-valence metal ions to strengthen the electrostatic interaction between the metal center and organic ligands.…”