Selectively Regulating Lewis Acid–Base Sites in Metal–Organic Frameworks for Achieving Turn‐On/Off of the Catalytic Activity in Different CO₂Reactions

Regulating Lewis acid-base sites in catalysts to investigate their influence in the chemical fixation of CO₂ is significant but challenging. A metal-organic framework (MOF) with open metal Co sites, {(NH₂ Me₂ )[Co₃ (μ₃ -OH)(BTB)₂ (H₂ O)]⋅9 H₂ O⋅5 DMF}n (1), was obtained and the results of the catalytic investigation show that 1 can catalyze cycloaddition of CO₂ and aziridines to give 99 % yield. The efficiency of the cyclization of CO₂ with propargyl amines is only 32 %. To improve the catalytic ability of 1, ligand XN with Lewis base sites was introduced into 1 and coordinated with the open Co sites, resulting in a decrease of the Lewis acid sites and an increase in the Lewis base sites in a related MOF 2 ({(NH₂ Me₂ )[Co₃ (μ₃ -OH)(NHMe₂ )(BTB)₂ (XN)]⋅8 H₂ O⋅4 DMF}n ). Selective regulation of the type of active centers causes the yield of oxazolidinones to be enhanced by about 2.4 times, suggesting that this strategy can turn on/off the catalytic activity for different reactions. The catalytic results from 2 treated with acid solution support this conclusion. This work illuminates a MOF-construction strategy that produces efficient catalysts for CO₂ conversion.