Potential Alignment in Tandem Catalysts Enhances CO2-to-C2H4 Conversion Efficiencies.

The in-tandem catalyst holds great promise for addressing the limitation of low *CO coverage on Cu-based materials for selective C2H4 generation during CO2 electroreduction. However, the potential mismatch between the CO-formation catalyst and the favorable C-C coupling Cu catalyst represents a bottleneck in these types of electrocatalysts, resulting in low tandem efficiencies. In this study, we propose a robust solution to this problem by introducing a wide-CO generation-potential window nickel single atom catalyst (Ni SAC) supported on a Cu catalyst. The selection of Ni SAC was based on theoretical calculations, and its excellent performance was further confirmed by using in situ IR spectroscopy. The facilitated carbon dimerization in our tandem catalyst led to a ∼370 mA/cm2 partial current density of C2H4, corresponding to a faradic efficiency of ∼62%. This performance remained stable and consistent for at least ∼14 h at a high current density of 500 mA/cm2 in a flow-cell reactor, outperforming most tandem catalysts reported so far.

Direct Determination of Absolute Radical Quantum Yields in Hydroxyl and Sulfate Radical-Based Treatment Processes.

The absolute radical quantum yield (Φ) is a critical parameter to evaluate the efficiency of radical-based processes in engineered water treatment. However, measuring Φ is fraught with challenges, as current quantification methods lack selectivity, specificity, and anti-interference capabilities, resulting in significant error propagation. Herein, we report a direct and reliable time-resolved technique to determine Φ at pH 7.0 for commonly used radical precursors in advanced oxidation processes. For H2O2 and peroxydisulfate (PDS), the values of Φ•OH and ΦSO4•- at 266 nm were measured to be 1.10 ± 0.01 and 1.46 ± 0.05, respectively. For peroxymonosulfate (PMS), we developed a new approach to determine Φ•OHPMS with terephthalic acid as a trap-and-trigger probe in the nonsteady state system. For the first time, the Φ•OHPMS value was measured to be 0.56 by the direct method, which is stoichiometrically equal to ΦSO4•-PMS (0.57 ± 0.02). Additionally, radical formation mechanisms were elucidated by density functional theory (DFT) calculations. The theoretical results showed that the highest occupied molecular orbitals of the radical precursors are O-O antibonding orbitals, facilitating the destabilization of the peroxy bond for radical formation. Electronic structures of these precursors were compared, aiming to rationalize the tendency of the Φ values we observed. Overall, this time-resolved technique with specific probes can be used as a reliable tool to determine Φ, serving as a scientific basis for the accurate performance evaluation of diverse radical-based treatment processes.

Bimolecular versus Trimolecular Reaction Pathways for H2O2 with Hypochlorous Species and Implications for Wastewater Reclamation.

The benchmark advanced oxidation technology (AOT) that uses UV/H2O2 integrated with hypochlorous species exhibits great potential in removing micropollutants and enhancing wastewater treatability for reclamation purposes. Although efforts have been made to study the reactions of H2O2 with hypochlorous species, there exist great discrepancies in the order of reaction kinetics, the rate constants, and the molecule-level mechanisms. This results in an excessive use of hypochlorous reagents and system underperformance during treatment processes. Herein, the titled reaction was investigated systematically through complementary experimental and theoretical approaches. Stopped-flow spectroscopic measurements revealed a combination of bi- and trimolecular reaction kinetics. The bimolecular pathway dominates at low H2O2 concentrations, while the trimolecular pathway dominates at high H2O2 concentrations. Both reactions were simulated using direct dynamics trajectories, and the pathways identified in the trajectories were further validated by high-level quantum chemistry calculations. The theoretical results not only supported the spectroscopic data but also elucidated the molecule-level mechanisms and helped to address the origin of the discrepancies. In addition, the impact of the environmental matrix was evaluated by using two waters with discrete characteristics, namely municipal wastewater and ammonium-rich wastewater. Municipal wastewater had a negligible matrix effect on the reaction kinetics of H2O2 and the hypochlorous species, making it a highly suitable candidate for this integration technique. The obtained in-depth reaction mechanistic insights will enable the development of a viable and economical technology for safe water reuse.

Degradation behaviors of Nabumetone and its metabolite during UV/monochloramine process: Experimental and theoretical study.

This study investigated degradation behaviors of a nonsteroidal anti-inflammatory drug Nabumetone (NMT) and its major metabolite 6-methoxy-2-naphthylacetic acid (MNA) in the coupling process of ultraviolet and monochloramine (UV/NH2Cl). The second-order rate constants of the contaminants reacting with reactive radicals (HO•, Cl•, Cl2•⁻, and CO3•⁻) were determined by laser flash photolysis experiments. HO• and Cl• contributed predominantly with 52.3% and 21.7% for NMT degradation and 60.8% and 22.3% for MNA degradation. The presence of chlorides retarded the degradation of NMT, while promoted the destruction of MNA, which was ascribed to the photosensitization effects of MNA under UV irradiation. Density functional theory (DFT) calculations revealed that radical adduct formation (RAF) was dominant pathway for both HO• and Cl• reacting with the contaminants, and hydrogen atom transfer (HAT) preferred to occur on side chains of NMT and MNA. NMT reacted with NO2• through single electron transfer (SET) with the second-order rate constant calculated to be 5.35 × 107 (mol/L)-1 sec-1, and the contribution of NO2• was predicted to be 13.0% of the total rate constant of NMT in pure water, which indicated that NO2• played a non-negligible role in the degradation of NMT. The acute toxicity and developmental toxicity of NMT were enhanced after UV/NH2Cl treatment, while those of MNA were alleviated. The transformation products of both NMT and MNA exhibited higher mutagenicity than their parent compounds. This study provides a deep understanding of the mechanism of radical degradation of NMT and MNA in the treatment of UV/NH2Cl.

Kinetic and Mechanistic Considerations of the Photosensitized Transformation of Chlorine in Chromophoric Dissolved Organic Matter Solutions under Simulated Solar Irradiation.

Chlorination is one of the most common disinfection methods for water treatments. Although the direct photolysis of free available chlorine (FAC) induced by solar irradiation has been extensively investigated, the photosensitized transformation of FAC caused by chromophoric dissolved organic matter (CDOM) has not previously been examined. Our results suggest that the photosensitized transformation of FAC can occur in sunlit CDOM-enriched solutions. Interestingly, the photosensitized decay of FAC can be fitted using a combined zero- and first-order kinetic model. The photogenerated O2•- from CDOM contributes to the zero-order kinetic component. The reductive triplet CDOM (3CDOM*) contributes to the pseudo-first-order decay kinetic component. The bimolecular reaction rate constants of the model triplet (3-methoxyacetophenone) with HOCl and OCl- were (3.6 ± 0.2) × 109 and (2.7 ± 0.3) × 109 M-1 s-1, respectively. Under simulated solar irradiation, the quantum yield coefficient of the reductive 3CDOM* toward FAC attenuation (fFAC = 840 ± 40 M-1) was 13 times greater than that of the oxidative 3CDOM* toward trimethylphenol (TMP) attenuation (fTMP = 64 ± 4 M-1). This study provides new insights into the photochemical transformation of FAC in sunlit surface waters, and the results are applicable when sunlight/FAC system is employed as an advanced oxidation process.

Overlooked Transformation of Nitrated Polycyclic Aromatic Hydrocarbons in Natural Waters: Role of Self-Photosensitization.

Photochemical transformation is an important process that involves trace organic contaminants (TrOCs) in sunlit surface waters. However, the environmental implications of their self-photosensitization pathway have been largely overlooked. Here, we selected 1-nitronaphthalene (1NN), a representative nitrated polycyclic aromatic hydrocarbon, to study the self-photosensitization process. We investigated the excited-state properties and relaxation kinetics of 1NN after sunlight absorption. The intrinsic decay rate constants of triplet (31NN*) and singlet (11NN*) excited states were estimated to be 1.5 × 106 and 2.5 × 108 s-1, respectively. Our results provided quantitative evidence for the environmental relevance of 31NN* in waters. Possible reactions of 31NN* with various water components were evaluated. With the reduction and oxidation potentials of -0.37 and 1.95 V, 31NN* can be either oxidized or reduced by dissolved organic matter isolates and surrogates. We also showed that hydroxyl (•OH) and sulfate (SO4•-) radicals can be generated via the 31NN*-induced oxidation of inorganic ions (OH- and SO42-, respectively). We further investigated the reaction kinetics of 31NN* and OH- forming •OH, an important photoinduced reactive intermediate, through complementary experimental and theoretical approaches. The rate constants for the reactions of 31NN* with OH- and 1NN with •OH were determined to be 4.22 × 107 and 3.95 ± 0.01 × 109 M-1 s-1, respectively. These findings yield new insights into self-photosensitization as a pathway for TrOC attenuation and provide more mechanistic details into their environmental fate.

Merits and Limitations of Radical vs. Nonradical Pathways in Persulfate-Based Advanced Oxidation Processes.

Urbanization and industrialization have exerted significant adverse effects on water quality, resulting in a growing need for reliable and eco-friendly treatment technologies. Persulfate (PS)-based advanced oxidation processes (AOPs) are emerging as viable technologies to treat challenging industrial wastewaters or remediate groundwater impacted by hazardous wastes. While the generated reactive species can degrade a variety of priority organic contaminants through radical and nonradical pathways, there is a lack of systematic and in-depth comparison of these pathways for practical implementation in different treatment scenarios. Our comparative analysis of reaction rate constants for radical vs. nonradical species indicates that radical-based AOPs may achieve high removal efficiency of organic contaminants with relatively short contact time. Nonradical AOPs feature advantages with minimal water matrix interference for complex wastewater treatments. Nonradical species (e.g., singlet oxygen, high-valent metals, and surface activated PS) preferentially react with contaminants bearing electron-donating groups, allowing enhancement of degradation efficiency of known target contaminants. For byproduct formation, analytical limitations and computational chemistry applications are also considered. Finally, we propose a holistically estimated electrical energy per order of reaction (EE/O) parameter and show significantly higher energy requirements for the nonradical pathways. Overall, these critical comparisons help prioritize basic research on PS-based AOPs and inform the merits and limitations of system-specific applications.

Mechanistic Understanding of Superoxide Radical-Mediated Degradation of Perfluorocarboxylic Acids.

Perfluorocarboxylic acids (PFCAs) exhibit strong persistence in sunlit surface waters and in radical-based treatment processes, where superoxide radical (O2•-) is an important and abundant reactive oxygen species. Given that the role of O2•- during the transformation of PFCAs remains largely unknown, we investigated the kinetics and mechanisms of O2•--mediated PFCAs attenuation through complementary experimental and theoretical approaches. The aqueous-phase rate constants between O2•- and C3-C8 PFCAs were measured using a newly designed in situ spectroscopic system. Mechanistically, bimolecular nucleophilic substitution (SN2) is most likely to be thermodynamically feasible, as indicated by density functional theory calculations at the CBS-QB3 level of theory. This pathway was then investigated by ab initio molecular dynamics simulation with free-energy samplings. As O2•- approaches PFCA, the C-F bond at the alpha carbon is spontaneously stretched, leading to the bond cleavage. The solvation mechanism for O2•--mediated PFCA degradation was also elucidated. Our results indicated that although the less polar solvent enhanced the nucleophilicity of O2•-, it also decreased the desolvation process of PFCAs, resulting in reduced kinetics. With these quantitative and mechanistic results, we achieved a defined picture of the O2•--initiated abatement of PFCAs in natural and engineered waters.

Reactivity and reaction mechanisms of sulfate radicals with lindane: An experimental and theoretical study.

Advanced oxidation technologies (AOTs) have been intensely used to eliminate various organic pollutants in engineering waters. In this context, we investigated the kinetics and mechanisms of the sulfate radical (SO4-)-mediated degradation of lindane in UV/peroxydisulfate system, and compared results with previous studies on SO4--based AOTs for destruction of lindane. The second order rate constant (k) value between SO4- and lindane was determined to be (8.95 ± 0.29) × 106 M-1 s-1via competition kinetics using p-cyanobenzoic acid as reference compound, which is close to the theoretically calculated value of 4.41 × 107 M-1 s-1, that was performed at SMD/M05-2X/6-311++G**//M05-2X/6-31+G** level of theory using density functional theory (DFT) approach. H-atom abstraction pathway was calculated to be thermodynamically favorable and kinetically dominant. In the combined experimental and theoretical study, we aim for a better understanding on the degradation kinetics and mechanisms of lindane, serving as a starting point for more attention to SO4--mediated degradation kinetics of cycloaliphatic compounds in future.

Mechanistic Study on the Role of Soluble Microbial Products in Sulfate Radical-Mediated Degradation of Pharmaceuticals.

The role of soluble microbial products (SMP), the most important component of effluent organic matter from municipal wastewater treatment plants, in sulfate radical (SO4•-)-based advanced oxidation technologies (AOTs) remains substantially unclear. In this study, we first utilized a suite of macro- and microanalytical techniques to characterize the SMP from a membrane bioreactor for its fundamental molecular, spectroscopic, and reactivity properties. The degradation kinetics of three representative pharmaceuticals (i.e., naproxen, gemfibrozil, and sulfadiazine) in the presence of SMP was significantly reduced as compared to in its absence. Possible mechanisms for the interference by SMP in degrading these target compounds (TCs) were investigated. The low percentage of bound TCs to SMP ruled out the cage effect. The measurement of steady-state 1O2 concentration indicated that formation of 1O2 upon UV irradiation on SMP was not primarily responsible for the degradation of TCs. However, the comparative and quenching results reveal that SMP absorbs UV light acting as an inner filter toward the TCs, and meanwhile scavenges SO4•- with a high second-order rate constant of 2.48 × 108 MC-1 s-1.

Hydroxyl Radical Based Photocatalytic Degradation of Halogenated Organic Contaminants and Paraffin on Silica Gel.

Photochemical materials are of scientific and practical importance in the field of photocatalysis. In this study, the photochemistry of several organic contaminants, including decabromodiphenyl ether (BDE-209), halogenated phenols (C6 X5OH, X = F, Cl, Br) and paraffin, on silica gel (SG) surface was investigated under simulated solar irradiation conditions. Photolysis of these compounds at the solid/air interface proceeds with different rates yielding various hydroxylation products, and hydroxyl radical was determined as the major reactive species. According to density functional theory (DFT) calculations, the reaction of physically adsorbed water with reactive silanone sites (>Si═O) on silica was indispensable for the generation of •OH radical, where the required energy matches well with the irradiation energy of visible light. Then, the BDE-209 was selected as a representative compound to evaluate the photocatalytic performance of SG under different conditions. The SG material showed good stability in the photodegradation process, and was able to effectively eliminate BDE-209 under natural sunlight. These findings provide new insights into the potential application of SG as a solid surface photocatalyst for contaminants removal.

Understanding Mechanisms of Synergy between Acidification and Ultrasound Treatments for Activated Sludge Dewatering: From Bench to Pilot-Scale Investigation.

Enhancing activated sludge dewaterability is of scientific and engineering importance in the face of accelerated urbanization and stringent environmental regulations. In this study, we investigated the integration of acidification and ultrasound (A/US) treatment for improving sludge dewaterability at both bench- and pilot-scales. Our results showed that the A/US process exhibited significantly improved sludge dewatering performance, characterized by capillary suction time, cake moisture, and water/solid content of sludge cake. Synergistic dewatering mechanisms were elucidated with a suite of macro and spectroscopic evidence. Characterization of treated sludge revealed that US-induced thermal, mechanical shearing force, and radical oxidation effects disrupts floc cells and accelerates the decomposition of extracellular polymeric substances (EPS), releasing bound water into the bulk phase. In addition to enhancing hydrolysis of EPS, the acidic pH environment caused the protonation of functional groups on EPS, facilitating the reflocculation of US decomposed sludge for improved filterability. Our bench-scale and pilot-scale investigations provide a mechanistic basis for better understanding of the A/US process, and enable development of a viable and economical dewatering technology.

Stabilization of Cd-, Pb-, Cu- and Zn-contaminated calcareous agricultural soil using red mud: a field experiment.

Red mud (RM) was used to remediate heavy metal-contaminated soils. Experiments with two different dosages of RM added to soils were carried out in this study. It was found that soil pH increased 0.3 and 0.5 unit with the dosage of 3 and 5% (wt%), respectively. At the dosage of 5%, the highest stabilization efficiencies for Cd, Pb, Cu and Zn reached 67.95, 64.21, 43.73 and 63.73%, respectively. The addition of RM obviously transferred Cd from the exchangeable fraction to the residual fraction. Meanwhile, in comparison with the control (no RM added), it reduced 24.38, 49.20, 19.42 and 8.89% of Cd, Pb, Cu and Zn in wheat grains at the RM addition dosage of 5%, respectively. At the same time, the yield of wheat grains increased 17.81 and 24.66% at the RM addition dosage of 3 and 5%, respectively. Finally, the addition of RM did not change the soil bacterial community. These results indicate that RM has a great potential in stabilizing heavy metals in calcareous agricultural soils.

Subcellular distribution and chemical forms of antimony in Ficus tikoua.

Ficus tikoua (F. tikoua) was a potential species for antimony (Sb) phytoremediation due to its wide growth in the mining area. However, little was known about its tolerance mechanisms toward Sb. The determination of the distribution and chemical speciation of Sb in F. tikoua is essential for understanding the mechanisms involved in Sb accumulation, transportation, and detoxification. The present study investigated the subcellular distribution and chemical forms of Sb in F. tikoua. The plant was exposed to different Sb concentrations (0, 30, 90, and 180 µmol/L) for 30 days. The results showed that F. tikoua possessed a marked ability to tolerate and accumulate Sb. The proportional Sb increased with increasing Sb concentration in the solution, and the highest Sb concentration occurred in roots (1274.5-1580.9 mg/kg), followed by stems (133.5-498.9 mg/kg) and leaves (4.1-15.7 mg/kg). In the subcellular sequestration of Sb in F. tikoua, the largest accumulation of Sb occurred in cell walls (72.4-87.5%) followed by cytoplasmic organelles (8.2-18.6%) and cytoplasmic supernatant. The results suggested that cell walls act as important protective barriers against Sb toxicity in F. tikoua. Although Sb in all plant tissues found primarily in the fractions extracted by ethanol and distilled water, the current study found that the Sb amounts in the HAc-extractable fraction, HCl-extractable fraction, and residue fraction increased at the highest Sb level (180 µmol/L) compared to that under lower Sb levels. These results indicate that excessive Sb accumulated in F. tikoua under Sb stress is bound to non-dissolved or low-bioavailable compounds, a biochemical mechanism that benefits F. tikoua because it helps alleviate Sb toxicity.

Kinetics and Mechanism of the Oxidation of Cyclic Methylsiloxanes by Hydroxyl Radical in the Gas Phase: An Experimental and Theoretical Study.

The ubiquitous presence of cyclic volatile methylsiloxanes (cVMS) in the global atmosphere has recently raised environmental concern. In order to assess the persistence and long-range transport potential of cVMS, their second-order rate constants (k) for reactions with hydroxyl radical ((•)OH) in the gas phase are needed. We experimentally and theoretically investigated the kinetics and mechanism of (•)OH oxidation of a series of cVMS, hexamethylcyclotrisiloxane (D3), octamethycyclotetrasiloxane (D4), and decamethycyclopentasiloxane (D5). Experimentally, we measured k values for D3, D4, and D5 with (•)OH in a gas-phase reaction chamber. The Arrhenius activation energies for these reactions in the temperature range from 313 to 353 K were small (-2.92 to 0.79 kcal·mol(-1)), indicating a weak temperature dependence. We also calculated the thermodynamic and kinetic behaviors for reactions at the M06-2X/6-311++G**//M06-2X/6-31+G** level of theory over a wider temperature range of 238-358 K that encompasses temperatures in the troposphere. The calculated Arrhenius activation energies range from -2.71 to -1.64 kcal·mol(-1), also exhibiting weak temperature dependence. The measured k values were approximately an order of magnitude higher than the theoretical values but have the same trend with increasing size of the siloxane ring. The calculated energy barriers for H-atom abstraction at different positions were similar, which provides theoretical support for extrapolating k for other cyclic siloxanes from the number of abstractable hydrogens.

Quantitative Structure--Activity Relationship (QSAR) for the Oxidation of Trace Organic Contaminants by Sulfate Radical.

The sulfate radical anion (SO4•­) based oxidation of trace organic contaminants (TrOCs) has recently received great attention due to its high reactivity and low selectivity. In this study, a meta-analysis was conducted to better understand the role of functional groups on the reactivity between SO4•­ and TrOCs. The results indicate that compounds in which electron transfer and addition channels dominate tend to exhibit a faster second-order rate constants (kSO4•­) than that of H­atom abstraction, corroborating the SO4•­ reactivity and mechanisms observed in the individual studies. Then, a quantitative structure activity relationship (QSAR) model was developed using a sequential approach with constitutional, geometrical, electrostatic, and quantum chemical descriptors. Two descriptors, ELUMO and EHOMO energy gap (ELUMO­EHOMO) and the ratio of oxygen atoms to carbon atoms (#O:C), were found to mechanistically and statistically affect kSO4•­ to a great extent with the standardized QSAR model: ln kSO4•­ = 26.8­3.97 × #O:C ­ 0.746 × (ELUMO­EHOMO). In addition, the correlation analysis indicates that there is no dominant reaction channel for SO4•­ reactions with various structurally diverse compounds. Our QSAR model provides a robust predictive tool for estimating emerging micropollutants removal using SO4•­ during wastewater treatment processes.

Kinetics and mechanism of sonochemical degradation of pharmaceuticals in municipal wastewater.

A series of six pharmaceuticals were degraded by continuous wave (CW) and pulsed wave (PW) ultrasound at 205 kHz using deionized water, wastewater effluent, and its isolated organic matter matrices. In deionized water, we observed that hydrophobicity is superior to diffusivity (D(W)) for predicting degradation kinetics. Enhancements in degradation kinetics by the PW mode were greatest for the highest DW (i.e., fluorouracil (5-FU)) and K(OW) (i.e., lovastatin (LOVS)) compounds, indicating that a pharmaceutical with either high diffusivity and low hydrophobicity or low diffusivity and high hydrophobicity benefits from additional time to populate the bubble-water interface during the silent cycle of PW ultrasound. Degradation of 5-FU and LOVS were inhibited by wastewater effluent to a greater extent than the other pharmaceuticals. In addition, a pulse enhancement (PE) for 5-FU and LOVS was not present in wastewater effluent. Irradiating 5-FU and LOVS in hydrophobic (HPO), transphilic (TPI), and hydrophilic (HPI) fractions of effluent organic matter (EfOM) showed that the TPI fraction reduced the PE the most, followed by the HPI and HPO fractions. The smaller size of the TPI over the HPO fraction and higher hydrophobicity of TPI over HPI implicate both size and hydrophobicity of EfOM in hindering degradation of pharmaceuticals.

Environmental implications of superoxide radicals: From natural processes to engineering applications.

The roles of superoxide radical (O2•-) in the domains of physiological, physical, and material chemistry are becoming increasingly recognized. Although extensive efforts have been directed to understand O2•- functions in diverse aquatic systems, there is a lack of systematic and in-depth review for its kinetics and mechanisms in various environmental scenarios. This review aims to bridge this gap through discussion of O2•- generation pathways under both natural and controlled conditions. The merits and limitations of the generation and detection methods under various conditions are compared, with emphasis on different approaches for the determination of O2•--triggered reaction kinetics. We summarize the reaction rate constants of O2•- with organic contaminants covering a wide diversity of structures and reactivity. The comparison indicates that O2•- exhibits weak reactivity with most contaminants and lacks selectivity towards compounds with different functional groups, except with quinones which exhibit higher reactivity compared to non-quinones. Further, the reaction mechanisms, namely single electron transfer, nucleophilic substitution, hydrogen atom abstraction, and radical-adduct formation, are critically evaluated. Various environmental implications of O2•- are highlighted including maintenance of biogeochemical iron cycle, synthesis of nanoparticles for antibacterial purposes, desorption of contaminants from heterogeneous interfaces, and synergetic degradation of contaminants.