Synthesis of nitro compounds from nitrogen dioxide captured in a metal-organic framework

DOI: 10.1021/jacs.2c07283

Authors: Jiangnan Li (University of Manchester) , Zi Wang (University of Manchester) , Yinlin Chen (University of Manchester) , Yongqiang Cheng (Oak Ridge National Laboratory) , Luke L. Daemen (Oak Ridge National Laboratory) , Floriana Tuna (University of Manchester) , Eric J. L. Mcinnes (The University of Manchester) , Sarah J. Day (Diamond Light Source) , Anibal J. Ramirez-Cuesta (Oak Ridge National Laboratory) , Martin Schroeder (University of Manchester) , Sihai Yang (University of Manchester)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Journal Of The American Chemical Society , VOL 24

State: Published (Approved)
Published: October 2022
Diamond Proposal Number(s): 31365

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 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.

Diamond Keywords: Gas Separation

Subject Areas: Materials, Chemistry, Environment


Instruments: I11-High Resolution Powder Diffraction

Added On: 07/10/2022 08:41

Documents:
jacs.2c07283.pdf

Discipline Tags:

Desertification & Pollution Earth Sciences & Environment Chemistry Materials Science Metal-Organic Frameworks Metallurgy Organometallic Chemistry

Technical Tags:

Diffraction X-ray Powder Diffraction