Tailored Metal-Organic Frameworks for Water Purification: Perfluorinated Fe-MOFs for Enhanced Heterogeneous Catalytic Ozonation.

An industrially viable catalyst for heterogeneous catalytic ozonation (HCO) in water purification requires the characteristics of good dispersion of active species on its surface, efficient electron transfer for ozone decay, and maximum active species utilization. While metal-organic frameworks (MOFs) represent an attractive platform for HCO, the metal nodes in the unmodified MOFs exhibit low catalytic activity. Herein, we present a perfluorinated Fe-MOF catalyst by substituting H atoms on the metalated ligands with F atoms (termed 4F-MIL-88B) to induce structure evolution. The Lewis acidity of 4F-MIL-88B was enhanced via the formation of Fe nodes, tailoring the electron distribution on the catalyst surface. As a result of catalyst modification, the rate constant for degradation of the target compounds examined increased by ∼700% compared with that observed for the unmodified catalyst. Experimental evidence and theoretical calculations showed that the modulated polarity and the enhanced electron transfer between the catalyst and ozone molecules contributed to the adsorption and transformation of O3 to •OH on the catalyst surface. Overall, the results of this study highlight the significance of tailoring the metalated ligands to develop highly efficient and stable MOF catalysts for HCO and provide an in-depth mechanistic understanding of their structure-function evolution, which is expected to facilitate the applications of nanomaterial-based processes in water purification.

Ion-Selective Metathesis Design of Flow-Electrode Capacitive Deionization for Energy-Saving and Anti-Scaling Softening of Brackish Water.

While flow-electrode capacitive deionization (FCDI) is recognized as an attractive desalination technology, its practical implementation has been hindered by the ease of scaling and energy-intensive nature of the single-cell FCDI system, particularly when treating brackish water with elevated levels of naturally coexisting SO42- and Ca2+. To overcome these obstacles, we propose and design an innovative ion-selective metathesis FCDI (ISM-FCDI) system, consisting of a two-stage tailored cell design. Results indicate that the specific energy consumption per unit volume of water for the ISM-FCDI is lower (by up to ∼50%) than that of a conventional single-stage FCDI due to the parallel circuit structure of the ISM-FCDI. Additionally, the ISM-FCDI benefits from a conspicuous disparity in the selective removal of ions at each stage. The separate storage of Ca2+ and SO42- by the metathesis process in the ISM-FCDI (46.25% Ca2+, 14.25% SO42- in electrode 1 and 4.75% Ca2+, 35.25% SO42- in electrode 2) can effectively prevent scaling. Furthermore, configuration-performance analysis on the ion-selective migration suggests that the properties of the ion exchange membrane, rather than the carbon species, govern the selectivity of ion removal. This work introduces system-level enhancements aimed at enhancing energy conservation and scaling prevention, providing critical optimization of the FCDI for brackish water softening.

New Insights into the Role of Humic Acid in Permanganate Oxidation of Diclofenac: A Novel Electron Transfer Mechanism.

Humic acid (HA) ubiquitously existing in aquatic environments has been reported to significantly impact permanganate (KMnO4) decontamination processes. However, the underlying mechanism of the KMnO4/HA system remained elusive. In this study, an enhancing effect of HA on the KMnO4 oxidation of diclofenac (DCF) was observed over a wide solution pH range of 5-9. Surprisingly, the mechanism of HA-induced enhancement varied with solution pH. Quenching and chemical probing experiments revealed that manganese intermediates (Mn(III)-HA and MnO2) were responsible for the enhancement under acidic conditions but not under neutral and alkaline conditions. By combining KMnO4 decomposition, galvanic oxidation process experiments, electrochemical tests, and FTIR and XPS analysis, it was interestingly found that HA could effectively mediate the electron transfer from DCF to KMnO4 in neutral and alkaline solutions, which was reported for the first time. The formation of an organic-catalyst complex (i.e., HA-DCF) with lower reduction potential than the parent DCF was proposed to be responsible for the accelerated electron transfer from DCF to KMnO4. This electron transfer likely occurred within the complex molecule formed through the interaction between HA-DCF and KMnO4 (i.e., HA-DCF-KMnO4). These results will help us gain a more comprehensive understanding of the role of HA in the KMnO4 oxidation processes.

Oxidation of amine-based pharmaceuticals with unactivated peroxymonosulfate: Kinetics, mechanisms, and elimination efficiency of NDMA formation.

Amine-based pharmaceuticals are a significant class of N-nitrosodimethylamine (NDMA) precursors. This study investigated the use of unactivated peroxymonosulfate (PMS) to control amine-based pharmaceuticals and their NDMA formation potential. Kinetic analysis and product identification revealed that sumatriptan and doxylamine primarily underwent reactions at their tertiary amine group, while ranitidine and nizatidine had both tertiary amine and thioether group as reaction sites. The NDMA formation from sumatriptan and doxylamine during post-chloramination was significantly reduced with the abatement of the parent contaminants, while the formation of NDMA remained high even if full abatement of ranitidine and nizatidine was achieved. Product formation kinetics and reference standard tests revealed the great contribution of transformation products to NDMA formation. Ranitidine could be oxidized to sulfoxide-type product ranitidine-SO and N-oxide type product ranitidine-NO. Ranitidine-SO exhibited a high NDMA yield comparable to that of ranitidine (>90%), while ranitidine-NO showed a low NDMA yield (2%). With further oxidation of ranitidine-SO at the tertiary amine group, NDMA formation was reduced by more than 90%. The underlying mechanism for the importance of the tertiary amine group in NDMA formation was demonstrated by quantum chemical calculation. These findings underscore the potential of PMS pre-oxidation on NDMA control.

Energy-efficient treatment of refractory industrial effluent using flow-through electrochemical processes: Oxidation mechanisms and reduction of chlorinated byproducts.

While flow-through anodic oxidation (FTAO) technique has demonstrated high efficiency to treat various refractory waste streams, there is an increasing concern on the secondary hazard generation thereby. In this study, we developed an integrated system that couples FTAO and cathodic reduction processes (termed FTAO-CR) for sustainable treatment of chlorine-laden industrial wastewater. Among four common electrode materials (i.e., Ti4O7, ß-PbO2, RuO2, and SnO2-Sb), RuO2 flow-through anode exhibited the best pollutant removal performance and relatively low ClO3 and ClO4 yields. Because of the significant scavenging effect of Cl- in real wastewater treatment, the direct electron transfer process played a dominant role in contaminant degradation for both active and nonactive anodes though active species (i.e., active chlorine) were involved in the subsequent transformation of the organic matter. A continuous FTAO-CR system was then constructed for simultaneous COD removal and organic and inorganic chlorinated byproduct control. The quality of the treated effluent could meet the national discharge permit limit at low energy cost (∼4.52 kWh m3 or ∼0.035 kWh g1-COD). Results from our study pave the way for developing novel electrochemical platforms for the purification of refractory waste streams whilst minimizing the secondary pollution.

Pulsed electric field drives chemical-free membrane stripping for high ammonia recovery from urine.

Recovering ammonia from waste streams (e.g., urine) is highly desirable to reduce natural gas-based NH3 production and nitrogen discharge into the water environment. Electrochemical membrane stripping is an attractive alternative because it can drive NH4+ transformation to NH3 via cathodic OH- production; however, the conventional configurations suffer from relatively low ammonia recovery (<80 %) and significant acid/material usage for ammonia adsorption. To this end, we develop a novel stack system that simply uses an oxygen evolution reaction to in-situ produce acid from water, enabling chemical-free ammonia recovery from synthetic urine. In batch mode, the percentage removal and recovery increased respectively from 74.5 % to 97.9 % and 81.8 % to 92.7 % when the electrode pairs increased from 2 to 4 in the stack system. To address the gas-sparging issue that deteriorated ammonia recovery in continuous operation, pulsed electric field (PEF) mode was applied, resulting in ∼100 % recovery under optimized conditions. At an ammonia removal rate of 35.1 g-N m-2 h-1 and electrical energy consumption of 28.9 kWh kg-N-1, our chemical-free system in PEF mode has achieved significantly higher ammonia recovery (>90 %) from synthetic urine. The total cost to recover 1 kg of NH3-N from real human urine was $15.9 in the proposed system. Results of this study demonstrate that this novel approach holds great promise for high ammonia recovery from waste streams, opening a new pathway toward sustainable nitrogen management.