An Uncommon Carboxyl‐Decorated Metal–Organic Framework with Selective Gas Adsorption and Catalytic Conversion of CO 2

A new three‐dimensional (3D) framework, [Ni(btzip)(H 2 btzip)] ⋅ 2 DMF ⋅ 2 H 2 O ( 1 ) (H 2 btzip=4,6‐bis(triazol‐1‐yl)isophthalic acid) as an acidic heterogeneous catalyst was constructed by the reaction of nickel wire and a triazolyl‐carboxyl linker. Framework 1 possesses intersected 2D channels decorated by free COOH groups and uncoordinated triazolyl N atoms, leading to not only high CO 2 and C 2 H 6 adsorption capacity but also significant selective capture for CO 2 and C 2 H 6 over CH 4 and CO in 273–333 K. Moreover, 1 reveals chemical stability toward water. Grand Canonical Monte Carlo simulations confirmed the multiple CO 2 ‐ and C 2 H 6 ‐philic sites. As a result of the presence of accessible Brønsted acidic COOH groups in the channels, the activated framework demonstrates highly efficient catalytic activity in the cycloaddition reaction of CO 2 with propylene oxide/4‐chloromethyl‐1,3‐dioxolan‐2‐one/3‐butoxy‐1,2‐epoxypropane into cyclic carbonates.