Cathodized copper porphyrin metal–organic framework nanosheets for selective formate and acetate production from CO(2) electroreduction

An efficient and selective Cu catalyst for CO(2) electroreduction is highly desirable since current catalysts suffer from poor selectivity towards a series of products, such as alkenes, alcohols, and carboxylic acids. Here, we used copper(ii) paddle wheel cluster-based porphyrinic metal–organic framework (MOF) nanosheets for electrocatalytic CO(2) reduction and compared them with CuO, Cu(2)O, Cu, a porphyrin–Cu(ii) complex and a CuO/complex composite. Among them, the cathodized Cu-MOF nanosheets exhibit significant activity for formate production with a faradaic efficiency (FE) of 68.4% at a potential of –1.55 V versus Ag/Ag(+). Moreover, the C–C coupling product acetate is generated from the same catalyst together with formate at a wide voltage range of –1.40 V to –1.65 V with the total liquid product FE from 38.8% to 85.2%. High selectivity and activity are closely related to the cathodized restructuring of Cu-MOF nanosheets. With the combination of X-ray diffraction, X-ray photoelectron spectroscopy, high resolution transmission electron microscopy and Fourier transform infrared spectroscopy, we find that Cu(ii) carboxylate nodes possibly change to CuO, Cu(2)O and Cu(4)O(3), which significantly catalyze CO(2) to formate and acetate with synergistic enhancement from the porphyrin–Cu(ii) complex. This intriguing phenomenon provides a new opportunity for the rational design of high-performance Cu catalysts from pre-designed MOFs.