Cu-Fe bimetallic MOFs with long lifetime separated-state charge for enhancing selectivity for CO2 photoreduction to CH4

Abstract

Improving the CO to CH conversion efficiency of Cu metal-organic frameworks (Cu-MOFs) catalysts is important for promoting carbon capture and utilization. In this work, a series of novel Cu-Fe bimetallic MOFs photocatalysts (Cu-BTB-Fe with 0.5 wt%, 1.0 wt%, 2.0 wt%, and 4.0 wt% of Fe; HBTB = 1,3,5-tris(4-carboxyphenyl) benzene) were synthesized by a bimetallic site (Cu and Fe) design strategy in order to improve the electron-hole separation efficiency and CO adsorption activation. Findings indicated that the as-synthesized Cu-BTB-2 wt% Fe catalyst exhibited excellent catalytic performance for the conversion of CO to CH and CO under simulated sunlight irradiation, providing a yield of 32.20 mol∙g∙h and a selectivity of 69.24 % for CO to CH conversion as well as a yield of 14.29 mol∙g∙h for CO to CO conversion without liquid phase products. This is because the Cu-Fe bimetallic sites can continuously supply photoinduced electrons with long separated-state decay lifetime to efficiently activate CO. Specifically, the Cu-BTB-Fe catalysts provided a high proportion of effective photoinduced electrons with long decay lifetime for the CO* hydrogenation process through a unique electron transfer mechanism, while the strong affinity between CO and [Cu(COO)]-Fe active units enabled high CO adsorption activation and rapid CO reduction. The present approach, hopefully, would help to establish feasible pathway for the development of novel highly selective Cu-based MOFs photocatalysts for CO photocatalytic reduction yielding CH.