Synthetic, spectral, structural and catalytic activities of 3-D metal format/acetate framework materials for CO 2 conversion

• Published in: New journal of chemistry 2023-06, Vol.47 (22), p.10585-10592
• Main Authors: Trivedi, Manoj, Singh, Gurmeet, Sharma, Raj Kishore, Rath, Nigam P., Husain, Ahmad
• Format: Article
• Language: English
• ISSN: 1144-0546; 1369-9261
• DOI: 10.1039/D3NJ01463K

Two new coordination polymers [Cu 2 (HCO 2 ) 2 (H 2 O) 2 ] n (1), and [Na{Ni(CH 3 CO 2 ) 2 (CH 3 CO 2 H)}] n (2) were synthesized using a mild solution chemistry approach and characterized spectroscopically, and the molecular structures of 1, and 2 were determined by the single crystal X-ray diffraction technique. Bridged by CHOO − /CH 3 COO − , M ions form a three-dimensional distorted perovskite-like structure. The solid-state structure revealed that 1 is an infinite three-dimensional (3D) motif in which Cu( ii ) are bridged by formate in a κ 1 manner and four water molecules, while 2 is also an infinite three-dimensional (3D) structure having two nickel coordinated to four acetates in a κ 2 manner and one acetic acid that further interact with sodium ions. 1 has a 6-connected uninodal map topology with the point symbol of {4^4.6^10.8} whereas 2 has a 4-connected uninodaldia net with sqc6 topology and point symbol {6^6}. All the motifs (1–2) could serve as excellent catalysts for CO 2 -based chemical fixation. 2 shows high efficiency for CO 2 cycloaddition with small epoxides but its catalytic activity decreases sharply with the increase in the size of epoxide substrates. The results indicated that the copper( ii ) and nickel( ii )–sodium motifs catalyzed CO 2 cycloaddition of small substrates was carried out within the framework, while large substrates could not enter into the framework for catalytic reactions. The high efficiency and size-dependent selectivity toward small epoxides on catalytic CO 2 cycloaddition make 2, a promising heterogeneous catalyst for carbon fixation.