Oxygen Vacancy-Mediated CuCoFe/Tartrate-LDH Catalyst Directly Activates Oxygen to Produce Superoxide Radicals: Transformation of Active Species and Implication for Nitrobenzene Degradation.

Oxygen vacancies play a vital role in the catalytic activity of layered double hydroxide (LDH) catalysts in wastewater treatment. However, the mechanism of oxygen vacancy-mediated LDH-activated oxygen to produce reactive oxygen species (ROS) still lacks a reasonable explanation. In this work, a tartrate-modified CuCoFe-LDH (CuCoFe/Tar-LDH) with abundant oxygen vacancies was designed, which can efficiently degrade nitrobenzene (NB) under room conditions. The technical energy consumption is 0.011 kW h L-1. According to the characterization and calculation results, it is proposed that oxygen vacancies are formed because of the oxygen deficiency which is caused by the reduction of the energy between the metal ion and oxygen, and the metal ion transitions to a lower state. Compared with CuCoFe-LDH, the oxygen vacancy formation energy of CuCoFe/Tar-LDH decreased from 1.98 to 1.13 eV. The O2 bond length adsorbed on the oxygen vacancy is 1.27 Å, close to the theoretical length of superoxide radicals (•O2-) (1.26 Å). Radical trapping experiments and electron spin-resonance spectroscopy spectrum prove that •O2- is an important precursor of •OH. This work is dedicated to the in-depth exploration of the oxygen vacancy-mediated CuCoFe/Tar-LDH catalyst activation mechanism for molecular oxygen and the conversion relationship between ROS.

Bifunctional Ni@NiO catalyst supported on loofah sponge-derived carbon for electrocatalytic air oxidation of biorefractory pollutant in a coupling system.

Oxygen (O2) in the air is a green oxidant, and utilization of air for pollutant removal is highly desired. Herein, we report the preparation and utilization of a novel biomass-based three-dimensional (3D) Ni@NiO/carbon composite for the electro-activation of O2 under room condition. The carbon-coated Ni@NiO nanoparticles are fabricated on a hierarchical 3D porous loofah sponge-derived carbon (LSC) support as the bifunctional catalyst for the activation of O2 via both the electro-oxidation and electro-reduction reactions. An electrocatalytic air oxidation coupling system is constructed with the Ni@NiO/LSC shell-core electrodes for pollutant degradation. A variety of organic pollutants, including pharmaceutics and personal care products (PPCPs), dyes, phenolic compounds, and real waters are mineralized by more than 60% with significantly enhanced biodegradability. Notably, the coupling system obtains high mineralization efficiency of 70.2 ± 1.9% on landfill leachate with significant biodegradability enhancement. The specific energy consumptions of the coupling system are only 6.8 ± 0.7 to 60.2 ± 3.6 kWh kg-TOC-1 in mineralizing different pollutants. The hollow structure of the LSC fibers endows the loaded Ni@NiO with superior intrinsic catalytic activity, which is associated with low reaction resistance and facile electron transfer. The Ni@NiO on LSC presents an electrocatalytic wet air oxidation (ECWAO) catalytic activity higher by 35.8% and cathodic air oxidation (CAO) catalytic activity higher by 22.7% as compared to that loaded on commercial graphite felt.

Electro-activation of O2 on MnO2/graphite felt for efficient oxidation of water contaminants under room condition.

The activation of oxygen (O2) under room condition is highly desirable for oxidative removal of organic pollutants in water. Herein, we report a graphite felt (GF)-supported α-MnO2 catalyst which is active for activating O2 with assistance of an anodic electric field. The electro-assisted catalytic wet air oxidation (ECWAO) process on MnO2/GF is able to rapidly degrade a variety of dyes, pharmaceutics and personal care products (PPCPs) under room condition. The congo red, basic fuchsin, neutral red and methylene blue are completely mineralized in 160 min, and the bisphenol A, triclosan and ciprofloxacin are mineralized by 89.9%, 81.5% and 65.4%, respectively, in 300 min. Mechanistic study indicates a surface-catalyzed non-free radical pathway for the oxidation of organic pollutants by O2 in the ECWAO process. The oxygen vacancies on MnO2 are identified as the catalytically active sites, at which oxygen atom is transferred from O2 to organic molecule through chemisorbed oxygen species. The anodic electric field assists such an oxygen transfer pathway by activating the complex of chemisorbed oxygen species and organic molecule through electro-oxidation reaction. The ECWAO process on MnO2/GF electrode exhibits a great potential for practical wastewater treatment under room condition.