A {Ni12 }-Wheel-Based Metal-Organic Framework for Coordinative Binding of Sulphur Dioxide and Nitrogen Dioxide

Zongsu Han; Jiangnan Li; Wanpeng Lu; Kunyu Wang; Yinlin Chen; Xiaoping Zhang; Longfei Lin; Xue Han; Simon J Teat; Mark D Frogley; Sihai Yang; Wei Shi; Peng Cheng

doi:10.1002/anie.202115585

A {Ni₁₂ }-Wheel-Based Metal-Organic Framework for Coordinative Binding of Sulphur Dioxide and Nitrogen Dioxide

Angew Chem Int Ed Engl. 2022 Feb 1;61(6):e202115585. doi: 10.1002/anie.202115585. Epub 2022 Jan 10.

Authors

Zongsu Han¹, Jiangnan Li², Wanpeng Lu², Kunyu Wang¹, Yinlin Chen², Xiaoping Zhang¹, Longfei Lin³, Xue Han², Simon J Teat⁴, Mark D Frogley⁵, Sihai Yang², Wei Shi¹, Peng Cheng¹

Affiliations

¹ Department of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (MOE) and Renewable Energy Conversion and Storage Center (RECAST), College of Chemistry, Nankai University, Tianjin, 300071, China.
² Department of Chemistry, University of Manchester, Manchester, M13 9PL, UK.
³ Beijing National Laboratory for Molecular Science, Key Laboratory of Colloid and Interface and Thermodynamics Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China.
⁴ Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA.
⁵ Diamond Light Source, Harwell Science Campus, Oxfordshire, OX11 0DE, UK.

PMID: 34843165
DOI: 10.1002/anie.202115585

Abstract

Air pollution by SO₂ and NO₂ has caused significant risks on the environment and human health. Understanding the mechanism of active sites within capture materials is of fundamental importance to the development of new clean-up technologies. Here we report the crystallographic observation of reversible coordinative binding of SO₂ and NO₂ on open Ni^II sites in a metal-organic framework (NKU-100) incorporating unprecedented {Ni₁₂ }-wheels; each wheel exhibits six open Ni^II sites on desolvation. Immobilised gas molecules are further stabilised by cooperative host-guest interactions comprised of hydrogen bonds, π⋅⋅⋅π interactions and dipole interactions. At 298 K and 1.0 bar, NKU-100 shows adsorption uptakes of 6.21 and 5.80 mmol g^-1 for SO₂ and NO₂ , respectively. Dynamic breakthrough experiments have confirmed the selective retention of SO₂ and NO₂ at low concentrations under dry conditions. This work will inspire the future design of efficient sorbents for the capture of SO₂ and NO₂ .

Keywords: SO2 and NO2 adsorption; binding sites; in situ synchrotron single-crystal X-ray diffraction; metal-organic frameworks.

Publication types

Research Support, Non-U.S. Gov't