Li Weiyao, Li Jiangnan, Duong Thien D, Sapchenko Sergei A, Han Xue, Humby Jack D, Whitehead George F S, Victórica-Yrezábal Iñigo J, da Silva Ivan, Manuel Pascal, Frogley Mark D, Cinque Gianfelice, Schröder Martin, Yang Sihai
Department of Chemistry, University of Manchester, Manchester M13 9PL, U.K.
ISIS Facility, STFC Rutherford Appleton Laboratory, Chilton, Oxfordshire OX11 0QX, U.K.
J Am Chem Soc. 2022 Jul 27;144(29):13196-13204. doi: 10.1021/jacs.2c03280. Epub 2022 Jul 18.
The development of efficient sorbent materials for sulfur dioxide (SO) is of key industrial interest. However, due to the corrosive nature of SO, conventional porous materials often exhibit poor reversibility and limited uptake toward SO sorption. Here, we report high adsorption of SO in a series of Cu(II)-carboxylate-based metal-organic framework materials. We describe the impact of ligand functionalization and open metal sites on the uptake and reversibility of SO adsorption. Specifically, MFM-101 and MFM-190(F) show fully reversible SO adsorption with remarkable capacities of 18.7 and 18.3 mmol g, respectively, at 298 K and 1 bar; the former represents the highest reversible uptake of SO under ambient conditions among all porous solids reported to date. neutron powder diffraction and synchrotron infrared microspectroscopy enable the direct visualization of binding domains of adsorbed SO molecules as well as host-guest binding dynamics. We have found that the combination of open Cu(II) sites and ligand functionalization, together with the size and geometry of metal-ligand cages, plays an integral role in the enhancement of SO binding.
开发高效的二氧化硫（SO₂）吸附剂材料具有关键的工业意义。然而，由于SO₂的腐蚀性，传统多孔材料在SO₂吸附方面往往表现出较差的可逆性和有限的吸附量。在此，我们报道了一系列基于羧酸铜（II）的金属有机骨架材料对SO₂具有高吸附性能。我们描述了配体功能化和开放金属位点对SO₂吸附的吸附量和可逆性的影响。具体而言，MFM-101和MFM-190（F）在298K和1巴下表现出完全可逆的SO₂吸附，吸附量分别高达18.7和18.3 mmol/g；前者是迄今为止报道的所有多孔固体在环境条件下对SO₂的最高可逆吸附量。中子粉末衍射和同步辐射红外显微光谱能够直接观察吸附的SO₂分子的结合域以及主客体结合动力学。我们发现，开放的Cu（II）位点和配体功能化的结合，以及金属-配体笼的尺寸和几何形状，在增强SO₂结合方面起着不可或缺的作用。
