Modulating the MOF\nCoordination Environment to Derive\nNanoparticles for CO<sub>2</sub> Electroreduction to Formate

Metal–organic framework (MOF)-derived catalysts\nare widely\nused for CO<sub>2</sub> electroreduction to formate. However, the\neffect of the local coordination environment of MOF precursors on\nCO<sub>2</sub> electroreduction activity is still unclear. Herein,\nPb-MOF precursors with different coordination environments were synthesized\nby electrodeposition (Pb-MOF-e) and hydrothermal (Pb-MOF-t) methods,\nrespectively. The coordination environment in Pb-MOF-t has eight O\nsites of benzene-1,3,5-tricarboxylate (BTC) ligands and one O site\nfrom H<sub>2</sub>O, while Pb-MOF-e has seven O sites of BTC ligands\nand two O sites from H<sub>2</sub>O. Pb-MOF-e and Pb-MOF-t could be\nderived into 4 and 70 nm particles on Pb and carbon paper (CP), and\nthe catalysts are named Pb NP-e/Pb, Pb NP-e/CP, and Pb NP-t/CP. In\nparticular, Pb NP-e/Pb exhibited higher formate selectivity (92.0%),\nwith a maximum formate formation rate of 2734.5 μmol cm<sup>–1</sup> h<sup>–1</sup> at −2.4 V (vs Ag/Ag<sup>+</sup>), which is 4.7 and 5.8 times higher than that Pb NP-e/CP\nand Pb NP-t/CP. The experimental results showed that Pb-MOF-e has\nevolved structurally to form Pb nanoparticles with large an electrochemically\nactive surface area, low interfacial transport resistance, and low\nadsorption potential of CO<sub>2</sub><sup>·–</sup> intermediates.\nIn addition, the edge of Pb nanoparticles as the active site could\nefficiently stabilize the *OCHO intermediate and enhance the activity.\nThe obtained Pb NP-e/Pb catalyst shows promising prospects in CO<sub>2</sub> electroreduction applications.