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Transition‐Metal‐Containing Porphyrin Metal–Organic Frameworks as π‐Backbonding Adsorbents for NO 2 Removal
Author(s) -
Shang Shanshan,
Yang Chao,
Wang Chenguang,
Qin Junsheng,
Li Yi,
Gu Qinfen,
Shang Jin
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202007054
Subject(s) - adsorption , metal organic framework , transition metal , porphyrin , hydrogen bond , materials science , chemical engineering , porosity , inorganic chemistry , metal , chemistry , photochemistry , molecule , organic chemistry , catalysis , engineering
Mitigating ambient nitrogen dioxide (NO 2 ) pollution via selective adsorption on porous materials is a promising approach to tackle such an increasingly pressing environmental health issue. However, very few porous adsorbents have sufficiently high NO 2 adsorption capacity and good regenerability simultaneously. Here we attempt to address this challenge by developing π‐backbonding adsorbents in the transition metal (TM) incorporated porphyrin metal–organic frameworks (PMOFs). Breakthrough experiments show that PMOFs with inserted TMs achieve appreciable NO 2 capacity and good regenerability. Combined in situ DRIFTS, synchrotron powder XRD, and DFT calculations reveal the adsorption mechanism: NO 2 partially transforms to N 2 O 4 and interacts with transition metal via π‐backbonding and Al‐node via hydrogen bonding. This work affords new insights for designing next‐generation adsorbents for ambient NO 2 removal and presents PMOFs as a platform to tailor π‐backbonding adsorbents.