Abstract
Increasing levels of air pollution are driving the need for the development of new processes that take "waste-to-chemicals". Herein, we report the capture and conversion under ambient conditions of a major air pollutant, NO2, using a robust metal-organic framework (MOF) material, Zr-bptc (H4bptc = 3,3′,5,5′-biphenyltetracarboxylic acid), comprising {Zr6(μ3-O)4(μ3-OH)4(COO)12} clusters linked by 4-connected bptc4-ligands in an ftw topology. At 298 K, Zr-bptc shows exceptional stability and adsorption of NO2at both low (4.9 mmol g-1at 10 mbar) and high pressures (13.8 mmol g-1at 1.0 bar), as measured by isotherm experiments. Dynamic breakthrough experiments have confirmed the selective retention of NO2by Zr-bptc at low concentrations under both dry and wet conditions. The immobilized NO2can be readily transformed into valuable nitro compounds relevant to construction, agrochemical, and pharmaceutical industries. In situ crystallographic and spectroscopic studies reveal strong binding interactions of NO2to the {Zr6(μ3-O)4(μ3-OH)4(COO)12} cluster node. This study paves a circular pathway to enable the integration of nitrogen-based air pollutants into the production of fine chemicals.
Original language | English |
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Pages (from-to) | 18967-18975 |
Number of pages | 9 |
Journal | Journal of the American Chemical Society |
Volume | 144 |
Issue number | 41 |
DOIs | |
State | Published - Oct 19 2022 |
Funding
The authors thank EPSRC (EP/I011870), the Royal Society, and the University of Manchester for funding. This project has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation program (grant agreement No. 742401, NANOCHEM). The authors are grateful to Diamond Light Source and Oak Ridge National Laboratory (ORNL) for access to Beamlines I11 and VISION (a DOE Office of Science User Facility), respectively. The computing resources were made available through the VirtuES and the ICE-MAN projects, funded by Laboratory Directed Research and Development program and Compute and Data Environment for Science (CADES) at ORNL. We acknowledge EPSRC for funding the UK National EPR Facility.