Chakraborty Gouri, Das Prasenjit, Mandal Sanjay K
Department of Chemical Sciences, Indian Institute of Science Education and Research (IISER) Mohali, Sector 81, Manauli PO, S.A.S. Nagar, Mohali, Punjab 140306, India.
Inorg Chem. 2021 Apr 5;60(7):5071-5080. doi: 10.1021/acs.inorgchem.1c00101. Epub 2021 Mar 11.
A polar sulfone-appended copper(II) metal-organic framework (MOF; ) has been synthesized from the dual-ligand approach comprised of tetrakis(4-pyridyloxymethylene)methane and dibenzothiophene-5,5'-dioxide-3,7-dicarboxylic acid under solvothermal conditions. This has been studied by different techniques that included single-crystal X-ray diffractometry, based on which the presence of Lewis acidic open-metal sites as well as polar sulfone groups aligned on the pore walls is identified. MOF displays a high uptake of CO over N and CH with an excellent selectivity ( = 883) for CO/N (15:85) at 298 K under flue gas combustion conditions. Additionally, the presence of Lewis acidic metal centers facilitates an efficient size-selective catalytic performance at ambient conditions for the conversion of CO into industrially valuable cyclic carbonates. The experimental investigations for this functional solvent-free heterogeneous catalyst are also found to be in good correlation with the computational studies provided by configurational bias Monte Carlo simulation for both CO capture and its conversion.
通过溶剂热条件下由四（4-吡啶氧基甲基）甲烷和二苯并噻吩-5,5'-二氧化物-3,7-二羧酸组成的双配体方法合成了一种附着有极性砜的铜（II）金属有机框架（MOF）。已通过包括单晶X射线衍射法在内的不同技术对其进行了研究，在此基础上确定了路易斯酸性开放金属位点以及排列在孔壁上的极性砜基团的存在。MOF在298K的烟气燃烧条件下对CO的吸收高于N和CH，对CO/N（15:85）具有出色的选择性（α = 883）。此外，路易斯酸性金属中心的存在有助于在环境条件下实现高效的尺寸选择性催化性能，将CO转化为具有工业价值的环状碳酸酯。还发现这种无溶剂非均相功能催化剂的实验研究与构型偏差蒙特卡罗模拟提供的关于CO捕获及其转化的计算研究具有良好的相关性。
