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

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 bptc^4- ligands in an ftw topology. At 298 K, Zr-bptc shows exceptional stability and adsorption of NO₂ 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 NO₂ by Zr-bptc at low concentrations under both dry and wet conditions. The immobilized NO₂ 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 NO₂ to 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.