Earth Abundant Oxidation Catalysts for Removal of Contaminants of Emerging Concern from Wastewater: Homogeneous Catalytic Screening of Monomeric Complexes

Overview

Journal Molecules

Publisher MDPI

Specialty Biology

Date 2023 Sep 28

PMID 37764242

Authors

Leslie Garcia

Makynna R Koper

Somrita Mondal

Joshua T Priddle

William A Truong

Elisabeth M A Allbritton

Ashtyn G McAdoo

Desiray J Cannon-Smith

Neil L Funwie

Tuyet Hoang

Inseo Kim

David J Hubin

Jeanette A Krause

Allen G Oliver

Timothy J Prior

Timothy J Hubin

Affiliations

Soon will be listed here.

Abstract

Twenty novel Mn, Fe, and Cu complexes of ethylene cross-bridged tetraazamacrocycles with potentially copolymerizable allyl and benzyl pendant arms were synthesized and characterized. Multiple X-ray crystal structures demonstrate the cis-folded pseudo-octahedral geometry forced by the rigidifying ethylene cross-bridge and show that two cis coordination cites are available for interaction with substrate and oxidant. The Cu complexes were used to determine kinetic stability under harsh acidic and high-temperature conditions, which revealed that the cyclam-based ligands provide superior stabilization with half-lives of many minutes or even hours in 5 M HCl at 50-90 °C. Cyclic voltammetry studies of the Fe and Mn complexes reveal reversible redox processes indicating stabilization of Fe/Fe and Mn/Mn/Mn oxidation states, indicating the likelihood of catalytic oxidation for these complexes. Finally, dye-bleaching experiments with methylene blue, methyl orange, and rhodamine B demonstrate efficient catalytic decolorization and allow selection of the most successful monomeric catalysts for copolymerization to produce future heterogeneous water purification materials.

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