Department of Chemistry, University of Manchester, Manchester, M13 9PL, UK.
Photon Science Institute, University of Manchester, Manchester, M13 9PL, UK.
Angew Chem Int Ed Engl. 2023 Jul 10;62(28):e202302602. doi: 10.1002/anie.202302602. Epub 2023 Jun 2.
We report the modulation of reactivity of nitrogen dioxide (NO ) in a charged metal-organic framework (MOF) material, MFM-305-CH in which unbound N-centres are methylated and the cationic charge counter-balanced by Cl ions in the pores. Uptake of NO into MFM-305-CH leads to reaction between NO and Cl to give nitrosyl chloride (NOCl) and NO anions. A high dynamic uptake of 6.58 mmol g at 298 K is observed for MFM-305-CH as measured using a flow of 500 ppm NO in He. In contrast, the analogous neutral material, MFM-305, shows a much lower uptake of 2.38 mmol g . The binding domains and reactivity of adsorbed NO molecules within MFM-305-CH and MFM-305 have been probed using in situ synchrotron X-ray diffraction, inelastic neutron scattering and by electron paramagnetic resonance, high-field solid-state nuclear magnetic resonance and UV/Vis spectroscopies. The design of charged porous sorbents provides a new platform to control the reactivity of corrosive air pollutants.
我们报告了在带电金属有机骨架（MOF）材料 MFM-305-CH 中调节二氧化氮（NO ）反应性的情况，其中未结合的 N 中心被甲基化，而阳离子电荷由孔中的 Cl 离子平衡。NO 进入 MFM-305-CH 会导致 NO 和 Cl 之间的反应，生成亚硝酰氯（NOCl）和 NO 阴离子。使用 500 ppm 的 He 中 NO 的流量测量时，在 298 K 下，MFM-305-CH 的动态吸收量高达 6.58 mmol·g 。相比之下，类似的中性材料 MFM-305 的吸收量要低得多，为 2.38 mmol·g 。使用原位同步加速器 X 射线衍射、非弹性中子散射以及电子顺磁共振、高磁场固态核磁共振和紫外/可见光谱研究了 MFM-305-CH 和 MFM-305 中吸附的 NO 分子的结合域和反应性。带电荷的多孔吸附剂的设计提供了控制腐蚀性空气污染物反应性的新平台。
