In:
Journal of Materials Chemistry A, Royal Society of Chemistry (RSC), Vol. 11, No. 17 ( 2023), p. 9436-9454
Abstract:
Compared with conventional ˙OH, Cl˙ is longer-lived, more selective to destabilizing refractory electron (e − )-donating aqueous aromatics via radicalization, and renewable via e − transfer from aromatics to enable Cl˙ ↔ Cl − inter-conversion. To demonstrate the merits of Cl˙, a Cl pendant (Cl SUP )-functionalized Zr-based metal–organic framework (UiO-66-Cl) was synthesized/modulated to impart mesoporosity for facilitating the diffusion of bulky aromatics into the porous architecture. UiO-66-Cl could site-isolate Cl − anions (Cl − SUP ) near Lewis acidic Zr 4+ cations (LA) and Brønsted acidic –OH (BA), on which ˙OH was produced via homolytic H 2 O 2 dissection, desorbed, and bound to Cl − SUP to yield Cl˙ SUP via exothermic radical inter-conversion of ˙OH → Cl˙ SUP (referred to as the overall ˙OH → Cl˙ SUP route). UiO-66-Cl provided greater LA/BA strengths than UiO-66 un-functionalized with Cl SUP /Cl − SUP , thus requiring a lower energy for ˙OH desorption, which was identified as the rate-determining step of homolytic H 2 O 2 dissection on UiO-66 or the overall ˙OH → Cl˙ SUP route on UiO-66-Cl. Consequently, Cl˙ SUP productivity on UiO-66-Cl was higher than ˙OH productivity on UiO-66 (activity↑). Moreover, UiO-66-Cl exploited Cl˙ SUP as the major decomposer of e − -donating aromatics (selectivity↑) via the e − transfer pathway (recyclability↑), as proved by DFT calculations, EPR spectroscopy, and filtration/scavenging/isotope control runs. Furthermore, UiO-66-Cl was more resistant to structural deformation upon exposure to extreme reaction environments than UiO-66 (stability↑), as verified by DFT calculations/XRD analysis. Hence, UiO-66-Cl (Cl˙ SUP ) outperformed UiO-66 (˙OH), SO 4 2− -functionalized iron oxide (SO 4 ˙ − SUP ), or NO 3 − -modified Mn oxide (NO 3 ˙ SUP ) in degrading e − -donating, ionization-resistant aqueous aromatics (phenol, aniline, acetaminophen, sulfanilamide, and sulfamethoxazole) in terms of activity, selectivity, stability, and/or reusability.
Type of Medium:
Online Resource
ISSN:
2050-7488
,
2050-7496
Language:
English
Publisher:
Royal Society of Chemistry (RSC)
Publication Date:
2023
detail.hit.zdb_id:
2702232-8
Permalink