Cathodized copper porphyrin metal–organic framework nanosheets for selective formate and acetate production from CO2 electroreduction. Issue 7 (2nd January 2019)

• Record Type: Journal Article
• Authors: Wu, Jian-Xiang; Hou, Shu-Zhen; Zhang, Xiang-Da; Xu, Ming; Yang, Hua-Fei; Cao, Pei-Sheng; Gu, Zhi-Yuan
• Is Part Of: Chemical science. Volume 10:Issue 7(2019)
• Page Start: 2199
• Page End: 2205
• Publication Date: 2019-01-02
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/c8sc04344b
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : Highly selective and effective formate and acetate production from CO2 electroreduction on cathodized metal–organic framework nanosheets. Abstract : An efficient and selective Cu catalyst for CO2 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 CO2 reduction and compared them with CuO, Cu2 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, Cu2 O and Cu4 O3, which significantly catalyze CO2 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.