Modulation\nof <i>p</i>‑Block Electron\nOrbits in Metal–Organic Frameworks for CO<sub>2</sub> Capture\nand Electrochemical Reduction

Developing catalysts with excellent CO<sub>2</sub> capture\ncapability\nand electrochemical CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) at a wide potential range simultaneously is significant but remains\na formidable challenge. Here, two novel InMg defective trinuclear\ncluster-based MOFs (SNNU-41 and SNNU-42) with abundant <i>p</i>-block unsaturated coordinated sites were reported and exhibited\ngood CO<sub>2</sub> capture and CO<sub>2</sub>RR performance simultaneously.\nDue to the suitable micropores, SNNU-41 showed higher CO<sub>2</sub> capture ability at different adsorption pressure conditions. On\naccount of the rigid framework and the closer <i>p</i> band\ncenter to Fermi level, SNNU-42 accelerated the conversion of CO<sub>2</sub> molecule to C1 efficiency. Notably, via adjusting the ratio\nof <i>p</i>-block metal (In) in the SNNU-42 framework, the\nperformance of the CO<sub>2</sub>RR was promoted drastically. SNNU-42\nwith the InMg (1:1.8) mixed cluster delivered an excellent Faradaic\nefficiency of 91.3% for C1 products and high selectivity of 72.0%\nfor HCOOH at −2.5 V (vs Ag/Ag<sup>+</sup>) with a total current\ndensity of 77.2 mA cm<sup>–2</sup>. This work provides a possibility\nfor efficient CO<sub>2</sub> capture and CO<sub>2</sub>RR electrocatalysts\nthrough the modulation of electronic structures and composition in\nMOFs.