Ultra-efficient peroxymonosulfate utilization and trichloroethylene degradation in heterogeneous catalytic system guided by sheet-like Cu2MnO4 nanoparticles: The role of Cu(III)-O species and free radicals.

Synthesizing cubic spinel Cu2MnO4 with nanosheet structure (SCMO) aimed to construct a "non-radical-mediated radical-oxidative reaction", for increasing PMS utilization efficiency, and solving the defects of SO4•- and •OH through indirect PMS activation by electron transfer process. Compared with box-like Cu2MnO4 (11.1%, 0.0035 min-1) and ordinary Cu2MnO4 nanoparticles (21.3%, 0.0070 min-1), SCMO/PMS showed excellent trichloroethylene removal (98.8%, 0.1577 min-1). The pivotal role of Cu(III) was determined based on EPR analysis, quenching experiments, chemical probe experiments, hydrogen temperature-programmed reduction and Raman spectroscopy analysis, in-situ FTIR and Raman analyses. In brief, the interaction between PMS and SCMO could produce surface-bonded reactive complexes and the subsequent breaking of O-O bond in the sub-stable structure allowed the conversion of Cu(II) to Cu(III), which in turn facilitates the generation of •OH and SO4•-. The density functional theory (DFT) calculations provided supporting evidence for the electron donor role of SCMO and the increase of the electron acceptance capacity of PMS. SCMO/PMS system showed good resistance and degradation efficiency to complex composition and combined pollutants in actually contaminated groundwater, respectively. However, the coexistence of high concentrations of arsenic could significantly affect SCMO performance due to their adsorption on -OH groups, which still need in-depth study.

Insight into the role of reactive species on catalyst surface underlying peroxymonosulfate activation by P-Fe2MnO4 loaded on bentonite for trichloroethylene degradation.

In this study, bentonite supporting phosphorus-doped Fe2MnO4 (BPF) was synthesized and applied for PMS activation to degrade TCE. Morphology and structure characterization results indicated the successfully synthesized of BPF, and the BPF/PMS system not only featured high TCE removal (97.4%) but also high reaction rate constant (kobs = 0.0554 min-1) and PMS utilization (70.4%, kobs = 0.0228 min-1). According to the results of various experiments, massive oxygen vacancies on P-Fe2MnO4 alter its charge balance and facilitate the electron transfer process named adjacent transfer (direct electron capture by adsorbed PMS from adjacent TCE). Mn(III) is the main adsorption site for PMS, and the hydroxyl groups on the catalyst (Fe sites of P-Fe2MnO4, Si and Al sites of bentonite) can also offer binding sites for PMS. The hydrogen-bonded PMS on Fe(III) and Mn(III) sites will subsequently accept the discharged electrons to generate free radicals and high-valent metal species. Meanwhile, electron loss of HSO5- that chemically bonded to hydroxyl groups on bentonite will generate SO5•-, which will further produce 1O2 through self-bonding. the active species on the catalyst surface contribute 65% of TCE degradation in the heterogeneous catalytic oxidation system.

Electrokinetically-delivered persulfate coupled with thermal conductive heating for remediation of petroleum hydrocarbons contaminated low permeability soil.

In this study, electrokinetically-delivered persulfate (PS) coupled with thermal conductive heating (TCH) method was proposed for the remediation of petroleum hydrocarbons (PHs) contaminated low-permeability soil, based on the investigation of PS injection and activation by different electric field form, effective heating radius of TCH to activate PS, and their influencing factors. The uniform delivery and effective activation of PS were unrealizable by one-dimensional electric field (1 V/cm) with the operation of cathode injection, anode injection, bipolar injection, polarity-reversal, or bipolar injection coupled polarity-reversal, which would result in large spatial difference of soil pH and PHs residual. Similar results were obtained under the two-dimensional symmetric electric field (TEF) due to the large spatial difference in electric field intensity. Superimposed electric field (SEF, 1 V/cm) that based on the intermittent worked electrode groups coupled with polarity-reversal (every 3 h) and bipolar injection (10% PS solution) operation could achieve homogenized mass transfer of PS (53.8-65.7 g/kg, average 60.0 g/kg) in 15 days, due to the positive correlation between electric field intensity and transport of ionic substance. Meanwhile, the difference in decontamination efficiency caused by difference in PS activation efficiency could be reduced, since the heating rod was placed at the position where the concentrations of PS was the lowest, whereat the removal of PHs could not rely on alkali activated PS (cathode), anodic oxidation (anode), and electrochemical activated PS (cathode and anode). The residual concentration of PHs in soil remediated by SEF/PS-TCH was in the range of 640.7-763.8 mg/kg (average 701.5 mg/kg), and the corresponding removal efficiency was 73.3%-77.6% (average75.4%). The research can provide an in-situ remediation method for organic contaminants in low permeability soil featured with more uniform PS injection and activation, and small spatial differences in remediation efficiency.

Chelating surfactant N-lauroyl ethylenediamine triacetate enhanced electrokinetic remediation of copper and decabromodiphenyl ether co-contaminated low permeability soil: Applicability analysis.

In this study, chelating surfactant N-lauroyl ethylenediamine triacetate (N-LED3A) was used as strengthening agent for electrokinetic (EK) remediation of copper (Cu) and decabromodiphenyl ether (BDE209) co-contaminated low permeability soil. The results indicated that negligible amount of N-LED3A would be adsorbed on the experimental soil. The synchronous elution efficiencies (SEEs) of Cu and BDE209 had reached 65.4% and 49.9%, respectively, when the concentration of N-LED3A was 4000 mg/L, and they kept almost unchanged as the concentration of N-LED3A further increased. Meanwhile, the optimal SEEs were obtained at the pH condition within 6-8. The removal efficiencies of Cu (55.3%-65.8%) and BDE209 (31.4%-46.4%) would be increased with the applied voltage gradient and concentration of N-LED3A. In addition, BDE209 and Cu contaminants were also detected in the catholyte and anolyte, respectively, and their concentrations still showed an uptrend by the end of the experiments. While in the control experiments, the removal efficiency of Cu was in the range of 18.2%-23.6%, and almost no BDE209 was migrated out. The electric current would be increased with N-LED3A concentration increased, further resulting in the enhancement of cumulative electro-osmotic flow (EOF). However, the increment of EOF was limited after an 8-day treatment due to the declined capacity of the soil water supply, and the removal efficiency of BDE209 did not change proportionally to the cumulative EOF as a consequence. The accumulated (21 days) energy consumption under the optimal operation conditions (voltage gradient 1 V/cm, N-LED3A 1 g/L) was 377.28 KWh/m3. Efficiently synchronous removal of BDE209 and Cu could be achieved by the N-LED3A enhanced EK technique, exhibiting a promising application potential in the organic pollutant and heavy metal co-contaminated soil remediation.

Direct and efficient reduction of perfluorooctanoic acid using bimetallic catalyst supported on carbon.

A variety of metal elements have exhibited strong reductive and dehalogenative capabilities for the removal of persistent organic pollutants, owing to electron transfer or electron-hole activation through various methods. Herein, a bimetallic CNi-Al2O3 structure (AlCNi) was successfully synthesized to simultaneously function as sorbent and catalyst in the reduction of perfluoroalkyl carboxylic acids (PFOA) polluted wastewater. Using a reaction period of 3 h, 98% of PFOA was removed by AlCNi through a mechanochemical stirring method and 70.43% of fluorine ions was released from PFOA anchored onto the surface of AlCNi. Both thermocatalysis and photocatalysis technologies were incorporated and compared when utilized in tandem with AlCNi to mitigate the PFOA. In addition, peroxymonosulfate (PMS) and sodium sulfite (Na2SO3) were also integrated into experiments, separately, as a strong oxidant and reductant to improve the degradation effect of PFOA. However, the degradation efficiency of both were lower than that of AlCNi, even when assisted by elevated temperatures and ultraviolet irradiation. The feasibility of employing AlCNi for PFOA degradation was further investigated at various temperature and pH conditions. The data obtained from HPLC-MS/MS, TOC, and IC with multiple characterizations of AlCNi/PFOA, proposed the predominant degradation pathways comprising adsorption, defluorination-hydroxylation, and decarboxylation. This study provides a valuable remediation method without utilizing chemical agents and special activation for PFOA by AlCNi, which can be suitable for large-scale sewage treatment applications.