Electrochemical reconstruction of a 1D Cu(PyDC)(H 2 O) MOF into in situ formed Cu-Cu 2 O heterostructures on carbon cloth as an efficient electrocatalyst for CO 2 conversion.

Electrochemical carbon dioxide (CO 2 ) conversion has enormous potential for reducing high atmospheric CO 2 levels and producing valuable products simultaneously; however the development of inexpensive catalysts remains a great challenge. In this work, we successfully synthesised a 1D Cu-based metal-organic framework [Cu(PyDC)(H 2 O)], which crystallizes in an orthorhombic system with the Pccn space group, by the hydrothermal method. Among the different catalysts utilized, the heterostructures of cathodized Cu-Cu 2 O@CC demonstrate increased efficiency in producing CH 3 OH and C 2 H 4 , achieving maximum FE values of 37.4% and 40.53%, respectively. Also, the product formation rates of CH 3 OH and C 2 H 4 reach up to 667 and 1921 μmol h -1 cm -2 . On the other side, Cu-Cu 2 O/NC-700 carbon composites simultaneously produced C1-C3 products with a total FE of 23.27%. Furthermore, a comprehensive study involving detailed DFT simulations is used to calculate the energetic stability and catalytic activity towards the CO 2 reduction of Cu(111), Cu 2 O(111), and Cu@Cu 2 O(111) surfaces. During the early phase of electrochemical treatment, Cu(II) carboxylate nodes (Cu-O) in the Cu(PyDC)(H 2 O) MOF were reduced to Cu and Cu 2 O, with a possible synergistic enhancement from the PyDC ligands. Thus, the improved activity and product enhancement are closely associated with the cathodized reconstruction of Cu-Cu 2 O@CC heterostructures on carbon cloth. Hence, this study provides efficient derivatives of Cu-based MOFs for notable electrocatalytic activity in CO 2 reduction and gives valuable insights towards the advancement of practical CO 2 conversion technology.