Synthesis of Nitro Compounds from Nitrogen Dioxide Captured in a Metal-Organic Framework

[Image: see text] 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, NO(2), using a robust metal-organic framework (MOF) material, Zr-bptc (H(4)bptc = 3,3′,5,5′-biphenyltetracarboxylic acid), comprising {Zr(6)(μ(3)-O)(4)(μ(3)-OH)(4)(COO)(12)} clusters linked by 4-connected bptc(4–) ligands in an ftw topology. At 298 K, Zr-bptc shows exceptional stability and adsorption of NO(2) at both low (4.9 mmol g(–1) at 10 mbar) and high pressures (13.8 mmol g(–1) at 1.0 bar), as measured by isotherm experiments. Dynamic breakthrough experiments have confirmed the selective retention of NO(2) by Zr-bptc at low concentrations under both dry and wet conditions. The immobilized NO(2) can 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 NO(2) to the {Zr(6)(μ(3)-O)(4)(μ(3)-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.