Minerals and transitional metal oxides of earth-abundant elements are desirable catalysts for in situ chemical oxidation in environmental remediation. However, catalytic activation of peroxydisulfate (PDS) by manganese oxides was barely investigated. In this study, one-dimension manganese dioxides (α-and β-MnO2) were discovered as effective PDS activators among the diverse manganese oxides for selective degradation of organic contaminants. Compared with other chemical states and crystallographic structures of manganese oxide, β-MnO2 nanorods exhibited the highest phenol degradation rate (0.044 min-1 , 180 min) by activating PDS. A comprehensive study was conducted utilizing electron paramagnetic resonance, chemical probes, radical scavengers, and different solvents to identity the reactive oxygen species (ROS). Singlet oxygen (1 O2) was unveiled to be the primary ROS, which was generated by direct oxidation or recombination of superoxide ions and radicals from a metastable manganese intermediate at neutral pH. The study dedicates to the first mechanistic study into PDS activation over manganese oxides and provides a novel catalytic system for selective removal of organic contaminants in wastewater.

Environmentally friendly and low-cost catalysts are important for the rapid mineralization of organic contaminants in powerful advanced oxidation processes (AOPs). In this study, we reported N-doped graphitic biochars (N-BCs) as low-cost and efficient catalysts for peroxydisulfate (PDS) activation and the degradation of diverse organic pollutants in water treatment, including Orange G, phenol, sulfamethoxazole, and bisphenol A. The biochars at high annealing temperatures (>700 °C) presented highly graphitic nanosheets, large specific surface areas (SSAs), and rich doped nitrogen. In particular, N-BC derived at 900 °C (N-BC900) exhibited the highest degradation rate, which was 39-fold and 6.5-fold of that on N-BC400 and pristine biochar, respectively, and the N-BC900 surpassed most popular metal or nanocarbon catalysts. Different from the radical-based oxidation in N-BC400/PDS via the persistent free radicals (PFRs), singlet oxygen and nonradical pathways (surface-confined activated persulfate-carbon complexes) were discovered to dominate the oxidation processes in N-BC900/PDS. Moreover, the adsorption of organics was determined to be the key step determining reaction rate, revealing that the pre-adsorption of reactants significantly accelerated the nonradical oxidation pathway. This study not only provides robust and cheap carbonaceous materials for environmental remediation but also enables the first insight into the graphitic biochar-based nonradical catalysis.

Ubiquitous oxygen vacancies (Vo) existing in metallic compounds can activate peroxymonosulfate (PMS) for water treatment. However, under environmental conditions, especially oxygenated surroundings, the interactions between Vo and PMS as well as the organics degradation mechanism are still ambiguous. In this study, we provide a novel insight into the PMS activation mechanism over Vo-containing Fe−Co layered double hydroxide (LDH). Experimental results show that Vo/PMS is capable of selective degradation of organics via a single-electron-transfer nonradical pathway. Moreover, O 2 is firstly demonstrated as the most critical trigger in this system. Mechanistic studies reveal that, with abundant electrons confined in the vacant electron orbitals of Vo, O 2 is thermodynamically enabled to capture electrons from Vo to form O 2•− under the imprinting effect and start the activation process. Simultaneously, Vo becomes electron-deficient and withdraws the electrons from organics to sustain the electrostatic balance and achieve organics degradation (32% for Bisphenol A without PMS). Different from conventional PMS activation, under the collaboration of kinetics and thermodynamics, PMS is endowed with the ability to donate electrons to Vo as a reductant other than an oxidant to form 1 O 2 . In this case, 1 O 2 and O 2•− act as the indispensable intermediate species to accelerate the circulation of O 2 (as high as 14.3 mg/L) in the micro area around Vo, and promote this nanoconfinement electron-recycling process with 67% improvement of Bisphenol A degradation. This study provides a brand-new perspective for the nonradical mechanism of PMS activation over Vo-containing metallic compounds in natural environments.

It has been reported that zerovalent iron can help biochar improve efficiency in heavy metal (HM) absorption, but the surface chemical behaviors and HM removal mechanisms remain unclear. We successfully synthesized the magnetic nanoscale zerovalent iron assisted biochar (nZVI-BC). The porosity, crystal structure, surface carbon/iron atom state, and element distribution were comprehensively investigated to understand nZVI-BC’s interfacial chemical behaviors and HM removal mechanisms. We clearly revealed the formation of a nanoscale Fe0 core–Fe3O4 shell on the surface/pores/channels of biochar. With the combination of iron nanoparticles and biochar, C–O/COOH groups were cracked with the formation of CO/CC, indicating the C–O–Fe acted as an electron acceptor during the reduction reaction. We also demonstrated that the stabilization was dramatically improved in the nZVI-BC, while more reduced iron and better homogeneity were observed. These results, showing the surface chemical behaviors of nZVI-BC, would help increase our understanding of the HM removal mechanisms. Moreover, our demonstration of the superior removal ability of multiple HM (Pb2+, Cd2+, Cr6+, Cu2+, Ni2+, Zn2+) from a solution can provide a breakthrough in making a feasible material for removing HM from polluted water resources.

Redox processes mediated by biochar(BC) enhanced the transformation of Cr(VI), which is largely dependent on the presence of PFRs as electron donors. Natural or artificial dopants in BC's could regulate inherent carbon configuration and PFRs. Until recently, the modulation of PFRs and transformation of Cr(VI) in BC by nonmetalheterocyclic dopants was barely studied. In this study, changes in PFRs introduced by various nitrogen-dopants within BC are presented and the capacity for Cr(VI) transformation without light was investigated. It was found N-dopants were effectively embedded in carbon lattices through activated-Maillard reaction thus altering their charge and PFRs. Transformation of Cr(VI) in N doped biochar relied on mediated direct reduction by surface modulatory PFRs. The kinetic rate of transformation of Cr(VI) was increased 1.4−5 fold in N-BCs compared to nondoped BCs. Theortical calculation suggested a deficiency in surface electrons induced Lewis acid−base bonding which could acted as a bridge for electron transfer. Results of PCA and orbital energy indicated a colinear relationship between PFRs and pyrrolic N, as well as its dual-mode transformation of Cr(VI). This study provides an improved understanding of how N-doped BC contributes to the evolution of PFRs and their corresponding impacts on the transformation of Cr(VI) in environments.

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Manganese oxides, with low toxicity and wide adaptability, have been demonstrated as promising catalysts for substituting noble metals/oxides in a diversity of chemical reactions.