Search

Nonradical oxidation has been determined to be a promising pathway for the degradation of organic pollutants in heterogeneous catalytic ozonation (HCO). However, the bottlenecks are the rational design of catalysts to selectively induce nonradicals and the interpretation of detailed nonradical generation mechanisms. Herein, we propose a new HCO process based on single-atom iron catalysts, in which Fe-N4sites anchored on the carbon skeleton exhibited outstanding catalytic ozonation activity and stability for the degradation of oxalic acid (OA) and p-hydroxybenzoic acid (pHBA) as well as the advanced treatment of a landfill leachate secondary effluent. Unlike traditional radical oxidation, nonradical pathways based on surface-adsorbed atomic oxygen (*Oad) and singlet oxygen (1O2) were identified. A substrate-dependent behavior was also observed. OA was adsorbed on the catalyst surface and mainly degraded by *Oad, while pHBA was mostly removed by O3and 1O2in the bulk solution. Density functional theory calculations and molecular dynamics simulations revealed that one terminal oxygen atom of ozone preferred bonding with the central iron atom of Fe-N4, subsequently inducing the cleavage of the O–O bond near the catalyst surface to produce *Oadand 1O2. These findings highlight the structural design of an ozone catalyst and an atomic-level understanding of the nonradical HCO process.

Nitrite oxidation is the primary pathway that generates nitrate in engineered systems. However, little is known about the role of a novel nitrite-oxidizing bacteria (NOB) genus CandidatusNitrotoga in activated sludge systems. To elucidate key factors that impact NOB community composition, laboratory-scale sequencing batch reactors (SBRs) were designed and operated under the same conditions as real wastewater treatment plants to achieve considerable nitrogen removal and similar community; then, different conditions including temperature (T), dissolved oxygen (DO), free nitrous acid (FNA), and free ammonia (FA) were applied. The 16S rRNA gene-based PCR and sequence analysis illustrated that Ca. Nitrotoga were abundant even at ambient temperature, thus further challenging the previous conception of them being solely cold-adapted. Ca. Nitrotoga are less competitive than Nitrospiraduring oxygen deficiency, indicating its lower affinity to dissolved oxygen. Ca. Nitrotoga are the dominant nitrite oxidizers under regular exposure to FNA and FA due to their relatively higher resistance than other NOB toward these two effective biocides. Therefore, this study demonstrates that Ca. Nitrotoga can play an important role in biological nitrogen removal and also highlights the need for multiple strategies for NOB suppression for the next-generation, shortcut nitrogen removal.

Flow-electrode electrochemical desalination (FEED) processes (e.g., flow-electrode capacitive deionization), which use flowable carbon particles as the electrodes, have attracted increasing attention, holding the promise for continuous desalination and high desalting efficiency. While it is generally believed that carbon particles with abundant microporous and large specific capacitances (e.g., activated carbon, AC) should be ideal candidates for FEED electrodes, we provide evidence to the contrary, showing that highly conductive electrodes with low specific surface area can outperform microporous AC-based electrodes. This study revealed that FEED using solely high surface area AC particles (∼2000 m2g–1, specific capacitance of ∼44 F g–1, average salt adsorption rate of ∼0.15 μmol cm–2min–1) was vastly outperformed by electrodes based solely on low-surface area carbon black (CB, ∼70 m2g–1, ∼0.5 F g–1, ∼0.75 μmol cm–2min–1). Electrochemical impedance spectroscopy results suggest that the electrode formed by CB particles led to more effective electronic charge percolation, likely contributing to the improved desalination performance. In addition, we propose and demonstrate a novel operation mode, termed single cycle (SC), which greatly simplified the FEED cell configuration and enabled simultaneous charging and discharging. Using SC mode with CB flow electrodes delivered an increased average salt removal rate relative to the more traditional short-circuited closed cycle (SCC) mode, achieving up to 1.13 μmol cm–2min–1. Further investigations demonstrate that up to 50% of energy input would be avoided when using CB flow electrodes operated under SC mode as compared to that of AC flow electrodes operated under SCC mode. In summary, the FEED process presented in this study provided an innovative and promising approach toward high-efficient and low-cost brackish water desalination.

Heterogeneous catalytic ozonation is regarded as a feasible technology in advanced wastewater treatment. Catalytic performance, mass transfer, and mechanical strength are the key elements for large-scale applications of catalysts. To optimize those elements, Fe was selected for its dual role in graphitization and catalytic ozonation. A Fe/N-doped micron-scale carbon–Al2O3framework (CAF) was designed and applied to a fluidized catalytic process for the treatment of secondary effluent from coal gasification. The chemical oxygen demand removal rate constant and the hydroxyl radical generation efficiency (Rct) of the Fe/N-doped CAF were 190% and 429% higher than those of pure ozone, respectively. Theoretical calculations revealed that higher Fe valence promoted ozone decomposition, which implied increasing FeIIIcontent for further catalyst optimization. The rate constant and Rctwith a higher FeIII-proportion catalyst were increased by 13% and 16%, respectively, compared to those with the lower one. Molecular dynamics and density functional theory calculations were performed to analyze the reaction kinetics qualitatively and quantitatively. The energy barrier corresponding to FeIIIconfiguration was 1.32 kcal mol–1, 27% lower than that for FeIIconfiguration. These theoretical calculations guided the catalyst optimization and provided a novel solution for designing ozonation catalysts. The Fe/N-doped CAF demonstrated a great potential for practical applications.