Dynamic Responsive Cd-MOF upon the Stimulation of Temperature and Solvent for Photocatalytic CO2RR

Precise construction of stimuli-responsive MOF (SRMOF)materialswith excellent catalytic properties is a daunting challenge. Herein,two flexible ligands 4,4 & PRIME;,4 & DPRIME;-(nitrilotris(methylene))tribenzoicacid (H3L) and 1,4-bis((1H-imidazol-1-yl)methyl)benzene(BMB) have been used to construct a Cd-MOF (AQNU-5, AQNUnamed Anqing Normal University) containing three-dimensional poresand rod SBUs. Due to the flexible ligand-induced dynamicframework, AQNU-5 exhibits structural flexibility withstimuli-responsive properties in photocatalytic CO2 reduction,which depends on both temperature and solvent. The results showedthat the CO2-to-CO reduction rate reached an optimum of56.2 & mu;mol g(-1) h(-1) at 150 & DEG;C without the addition of any photosensitizer. Interestingly,this dynamic response is reversible, with the skeleton remaining unchangedfrom the parent structure before and after the catalytic reaction.The strategy of using flexible ligands in this work may provide aunique opportunity to obtain novel crystal framework materials withdesirable properties. Astimuli-responsive MOF with rod SBUs (AQNU-5) was designedand synthesized. As a photocatalyst, AQNU-5 shows thehighest CO2-to-CO catalytic activity (56.2 & mu;mol & BULL;g(-1)& BULL;h(-1))in cyclohexanosne at 150 & DEG;C.