Mechanisms of nanoscale zero-valent iron mediating aerobic denitrification in Pseudomonas stutzeri by promoting electron transfer and gene expression.

Aerobic denitrification and its mechanism by P. stutzeri was investigated in the presence of nanoscale zero-valent iron (nZVI). The removal of nitrate and ammonia was accelerated and the nitrite nitrogen accumulation was reduced by nZVI. The particle size and dosage of nZVI were key factors for enhancing aerobic denitrification. nZVI reduced the negative effects of low carbon/nitrogen, heavy metals, surfactants and salts to aerobic denitrification. nZVI and its dissolved irons were adsorbed into the bacteria cells, enhancing the transfer of electrons from nicotinamide adenine dinucleotide (NADH) to nitrate reductase. Moreover, the activities of NADH-ubiquinone reductase involved in the respiratory system, and the denitrifying enzymes were increased. The expression of denitrifying enzyme genes napA and nirS, as well as the iron metabolism gene fur, were promoted in the presence of nZVI. This work provides a strategy for enhancing the biological denitrification of wastewater using the bio-stimulation of nanomaterials.

Activation of peroxymonosulfate by biochar-supported Fe3O4 derived from oily sludge to enhance the oxidative degradation of tetracycline hydrochloride.

Carbon materials used for catalysis in advanced oxidation processes tend to be obtained from cheap and readily available raw materials. We constructed a carbon material, OSC@Fe3O4, by loading Fe3O4 onto the pyrolyzed hazardous waste oily sludge. OSC@Fe3O4 was then used to activate peroxymonosulfate (PMS) for the removal of tetracycline hydrochloride (TTCH) from water. At 298 K, 0.2 g⋅L-1 of catalyst and 0.3 g⋅L-1 of PMS, the reaction rate constant of the OSC@I-2/PMS system reached 0.079 min-1, with a TTCH removal efficiency of 92.6%. The degradation efficiency of TTCH remained at 81% after five cycles. The specific surface area and pore volume of OSC@I-2 were 263.9 m2⋅g-1 and 0.42 cm3⋅g-1, respectively, which improved the porous structure of the carbon material and provided more active points, thus improving the catalytic performance. N and S were doped into the oily sludge carbon due to the presence of N- and S-containing compounds in the raw oily sludge. N and S doping led to more electron-rich sites with higher negative charges in OSC@I-2 and gave the oily sludge carbon a higher affinity to PMS, thereby promoting its ability to activate PMS. Sulfate radicals (SO4•‾) played a dominant role in the degradation of TTCH, with demethylation and the breaking of double bonds being a possible degradation pathway. A biotoxicity test showed that the microbial toxicity of the degradation intermediates was significantly reduced. This work provides a strategy for the application of PMS-based catalysts derived from waste carbon resources.

Selective oxidation of organic pollutants based on reactive oxygen species and the molecular structure: Degradation behavior and mechanism analysis.

The selective and rapid elimination of refractory organic pollutants from surface water is significant. However, the relationship of between reactive oxygen species (ROSs) and diversified pollutants molecular structures still needs to be further clarified. Here, we utilize polydopamine (PDA)-assisted coating strategy to prepare hollow 2D carbon nanosheet (ZPL-HCNS) and 2D Co3O4 nanosheet (ZPL-Co3O4) by thermolysis of PDA coated ZIF-L (ZIF-L@PDA) precursor under different gas atmosphere, which realizes the controlled generation of radicals and non-radicals. Organic pollutants including bisphenols, sulfonamides, quinolones, tetracyclines, and azo dyes are applied to assess the catalytic performance. Results show that dyes containing azo structure are more likely to be degraded by radical process, which is due to that the energy (ΔE) requirements to break the azo bond is higher than energy released from singlet oxygen to oxygen molecule and lower than that of sulfate radical to sulfate. Frontier molecular orbital theory HOMO-LUMO and Fukui function expounded the possible selectivity mechanism. In addition, the degradation pathway and biotoxicity test are carried out. This work provides a reference to illustrate the selective degradation for ROSs and molecular structure of pollutants.

A confined expansion pore-making strategy to transform Zn-MOF to porous carbon nanofiber for water treatment: Insight into formation and degradation mechanism.

Electrospinning MOFs nanoparticles derived porous carbon nanofibers with rational structure and design are recently as environmentally friendly and highly efficient catalytic materials for wastewater treatment. However, most of the pore-making strategies are based on precursors structural shrinkage during pyrolysis, which is a challenge to create abundant large pores and open channels. Here, a confined expansion pore-making strategy with active MOF is introduced, where energetic Zn-MOF (Zn2+/triazole) and ZIF-67 (Co2+/dimethylimidazole) are utilized as pore forming additive and precursor of active sites, respectively. The high nitrogen content gives triazole the ability to puff up and realizes N-doped during pyrolysis. Moreover, degradation mechanisms and pathways of pollutants were measured by 3D EEM, LC-MS, quenching experiments, and Fukui function. This pore-making strategy via energetic MOF local contraction and expansion provides a novel method to prepare diversiform function porous carbon materials for environmental remediation.