Electrochemical reconstruction of a 1D Cu(PyDC)(HO) MOF into formed Cu-CuO heterostructures on carbon cloth as an efficient electrocatalyst for CO conversion

• Published in: Nanoscale Vol. 16; no. 21; pp. 1458 - 1473
• Main Authors: Kempasiddaiah, Manjunatha, Samanta, Rajib, Panigrahy, Sonali, Trivedi, Ravi Kumar, Chakraborty, Brahmananda, Barman, Sudip
• Format: Journal Article
• Published: 30.05.2024
• ISSN: 2040-3364; 2040-3372
• DOI: 10.1039/d4nr00824c

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. A 1D Cu-MOF was prepared via a hydrothermal method, with the developed Cu-Cu 2 O@CC heterostructures displaying enhanced activity in the electrocatalytic conversion of CO 2 to CH 3 OH and C 2 H 4 with high FE values of 37.4% and 40.53%, respectively.