Robust {Pb10}-Cluster-Based Metal-Organic Framework for Capturing and Converting CO2 into Cyclic Carbonates under Mild Conditions.

Abstract

Developing a highly active catalyst that can efficiently capture and convert carbon dioxide (CO2) into high-value-added energy materials remains a severe challenge, which inspires us to explore effective metal-organic frameworks (MOFs) with high chemical stability and high-density active sites. Herein, we report a robust 3D lead(II)-organic framework of {(Me2NH2)2[Pb5(PTTPA)2(H2O)3]·2DMF·3H2O}n (NUC-111) with unreported [Pb10(COO)22(H2O)6] clusters (abbreviated as {Pb10}) as nodes (H6PTTPA = 4,4',4″-(pyridine-2,4,6-triyl)triisophthalic acid). After thermal activation, NUC-111a is functionalized by the multifarious symbiotic acid-base active sites of open Pb2+ sites and uncoordinated pyridine groups on the inner surface of the void volume. Gas adsorption tests confirm that NUC-111a displays a higher separation performance for mixed gases of f CO2 and CH4 with the selectivity of CO2/CH4 at 273 K and 101 kPa being 31 (1:99, v/v), 23 (15:85, v/v), and 8 (50:50, v/v), respectively. When the temperature rises to 298 K, the selectivity of CO2/CH4 at 101 kPa is 26 (1:99, v/v), 22 (15:85, v/v), and 11 (50:50, v/v). Moreover, activated NUC-111a exhibited excellent catalytic performance, stability, and recyclability for the cycloaddition of CO2 with epoxides under mild conditions. Hence, this work provides valuable insight into designing MOFs with multifunctionality for CO2 capture, separation, and conversion.