Kinetics and mechanism analysis of advanced oxidation degradation of PFOA/PFOS by UV/Fe3+ and persulfate: A DFT study.

UV/Fe3+ and persulfate are two promising advanced oxidative degradation systems for in situ remediation of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), yet a lack of comprehensive understanding of the degradation mechanisms. For the first time, we used density functional theory (DFT) to calculate the entire reaction pathways of the degradation of PFOA/PFOS in water by UV/Fe3+ and persulfate. In addition, we have deeply explored the different attack pathways driven by •OH and SO4-•, and found that SO4-• determines PFOA/PFOS to obtain PFOA/PFOS free radicals through single electron transfer to initiate the degradation reaction, while •OH determines the speed of PFOA/PFOS degradation reaction. Both degradation reactions were thermodynamically advantageous and kinetically feasible under calculated conditions. Based on the thermodynamic data, persulfate was found to be more favorable for the advanced oxidative degradation of Perfluorinated compounds (PFCs). Moreover, for SO4-• and •OH co-existing in the persulfate system, pH will affect the presence and concentration of these two types of free radicals, and low pH is not necessary for the degradation of PFOA/PFOS in the persulfate system. These results can considerably advance our understanding of the PFOA/PFOS degradation process in advanced oxidation processes (AOPs), which is driven by •OH and SO4-•. This study provides a DFT calculation process for the mechanism calculation of advanced oxidation degradation of other types of PFCs pollutants, hoping to elucidate the future development of PFCs removal. Further research should focus on determining the advanced oxidation degradation pathways of other types of PFCs, to support the development of computational studies on the advanced oxidation degradation of PFCs.

Enantioselective Synthesis of Axially Chiral Sulfone-Containing Styrenes Based on Ion-Exchange Strategy.

A novel ion exchange strategy has been developed to enable the asymmetric construction of axially chiral sulfone-containing styrenes. This approach provides a practical synthesis pathway for various axially chiral sulfone-containing styrenes with good yields, exceptional enantioselectivities, and nearly complete E/Z selectivities. Additionally, the reaction mechanism is elucidated in detail through density functional theory (DFT) calculations.

Intelligent multifunctional ruthenium monoatomic/ZnAl-LDH photocatalysts for simultaneous detection and rapid degradation of antibiotics.

The construction and precise synthesis of materials based on functional and structural orientations have emerged as a pivotal platform in the field of environmental management. In this paper, an efficient and stable catalyst (RuLDH) was constructed to achieve this goal. RuLDH comprises individual Ru atoms that are uniformly dispersed on ZnAl-LDH, achieved by room temperature stirring. Remarkably, RuLDH exhibits exceptional performance under visible light, effectively triggering the photocatalytic degradation of tetracycline hydrochloride (TC) via peroxymonosulfate (PMS) with a remarkable efficiency of 100%, all while avoiding the generation of highly toxic intermediates. In addition, RuLDH0.2 demonstrated its utility in fluorescence detection of TC, showcasing commendable analytical performance characterized by rapid response, low detection limit, and robust resistance to environmental interferences (with a detection limit of 1.0 mg/L). Notably, the RuLDH0.2/PMS/Vis system exhibited remarkable efficacy in treating actual pesticide wastewater, effectively exerting bactericidal and disinfectant effects. This study serves as a source of inspiration for the design of multifunctional single-atom catalysts, thereby pushing the boundaries of "integration of diagnosis and treatment" in environmental management and control.

Benzethonium chloride affects short chain fatty acids produced from anaerobic fermentation of waste activated sludge: Performance, biodegradation and mechanisms.

Benzethonium chloride (BZC) is viewed as a promising disinfectant and widely applied in daily life. While studies related to its effect on waste activated sludge (WAS) anaerobic fermentation (AF) were seldom mentioned before. To understand how BZC affects AF of WAS, production of short chain fatty acids (SCFAs), characteristics of WAS as well as microbial community were evaluated during AF. Results manifested a dose-specific relationship of dosages between BZC and SCFAs and the optimum yield arrived at 2441.01 mg COD/L with the addition of 0.030 g/g TSS BZC. Spectral results and protein secondary structure variation indicated that BZC denatured proteins in the solid phase into smaller proteins or amino acids with unstable structures. It was also found that BZC could stimulate the extracellular polymeric substances secretion and reduce the surface tension of WAS, leading to the enhancement of solubilization. Beside, BZC promoted the hydrolysis stage (increased by 7.09 % to 0.030 g/g TSS BZC), but inhibited acetogenesis and methanogenesis stages (decreased by 6.85 % and 14.75 % to 0.030 g/g TSS BZC). The microbial community was also regulated by BZC to facilitate the enrichment of hydrolytic and acidizing microorganisms (i.e. Firmicutes). All these variations caused by BZC were conducive to the accumulation of SCFAs. The findings contributed to investigating the effect of BZC on AF of WAS and provided a new idea for the future study of AF mechanism.

Activation Model and Origins of Selectivity for Chiral Phosphoric Acid Catalyzed Diradical Reactions.

To develop new radical synthesis strategies, a profound understanding of the electronic transfer mechanism is critical. An activation model called relayed proton-coupled electron transfer (relayed-PCET) was developed and investigated for chiral phosphoric acid-catalyzed diradical reactions by density functional theory (DFT). The driving force of electron transfer from the nucleophile to the electrophile is the proton transfer that occurs via the chiral phosphoric acid (CPA) catalyst to the electrophile. Moreover, the origins of the selectivity can be explained by distortion of the catalyst, favorable hydrogen bonding, and strong interactions of the substrates with substituents of the CPAs.

Assisted wet deposition targeted synthesis of Co-N coordination single-atom catalysts for efficient Fenton-like catalytic degradation of micropollutants.

Assisted wet deposition methods to localize the active phase metal on the carrier surface and prevent atomic aggregation during conventional heat treatment are strongly preferred. Herein, single-atom cobalt catalysts (SA-Co-PCN) with different metal-central content were target-prepared using a combination of impregnation and secondary annealing on polymerized carbon nitride (PCN) through reticular confinement. Fitting the coordination configuration of the Co-N pathway within the first coordination shell according to quantitative EXAFS indicated that the ligancy of Co-N was 4. The removal efficiency of representative micropollutants in the SA-Co-PCN/PMS system achieved 100% within 15 min. The outstanding degradation properties of micropollutants were ascribed to the SA-Co-PCN boosts PMS to a 1O2-dominated system. Moreover, the effects of substituents on the degradation behavior and ecotoxicology of sulfonamides (SAs) in PMS-activated systems were investigated in depth. The combination of DFT theoretical calculations and LC-MS further confirmed that the similar electron-rich sites on the SAs molecules allowed for commonality in the degradation pathway. Both S-N bond and C-S bond fragments became the initial attack and cleavage sites in the series of SAs. Ecotoxicity predictions indicated that most intermediates of SAs exhibited lower acute and chronic toxicity, especially acute toxicity, than the parent compounds. ENVIRONMENTAL IMPLICATION: Assisted wet deposition to localize the active phase metal on the carrier surface allows easy target formation of single-atom cobalt catalysts (SA-Co-PCN), which could boost PMS to a 1O2-dominated system for efficient oxidation of typical micropollutants. The degradation behavior and ecotoxicology of sulfonamides in the SA-Co-PCN/PMS system were investigated in depth, revealing that most intermediates of sulfonamides exhibited lower acute and chronic toxicity, especially acute toxicity, than the parent compounds. This work provides a strategy for the development of facilely prepared single-atom catalysts and contributes to the development and application potential of PMS advanced oxidation technology for water pollution control.

Pretreatment of free nitrous acid combined with calcium hypochlorite for enhancement of hydrogen production in waste activated sludge.

A variety of variables limit the recovery of resources from anaerobic fermentation of waste activated sludge (WAS), hence pretreatment strategies are necessary to be investigated to increase its efficiency. A combination of free nitrous acid (FNA) and calcium hypochlorite [Ca(ClO)2] was employed in this investigation to significantly improve sludge fermentation performance. The yields of cumulative hydrogen for the blank and FNA treatment group were 1.09 ± 0.16 and 7.36 ± 0.21 mL/g VSS, respectively, and 6.59 ± 0.24 [0.03 g Ca(ClO)2/g TSS], 7.75 ± 0.20 (0.06), and 8.58 ± 0.22 (0.09) mL/g VSS for the Ca(ClO)2 groups. The co-treatment greatly boosted hydrogen generation, ranging from 39.97 ± 2.26 to 76.20 ± 4.78 % as compared to the solo treatment. Mechanism analysis demonstrated that the combined treatment disturbed sludge structure and cell membrane permeability even more, which released more organic substrates and enhanced biodegradability of fermentation broth. This paper describes a unique strategy to sludge pretreatment that expands the use of Ca(ClO)2 and FNA in anaerobic fermentation, with implications for sludge disposal and energy recovery.

New insights into atomic layer BiOBr quantum dot/ZnAl-LDH composites in photocatalytic water treatment: Performance and mechanism.

Insufficient absorption sites and low charge separation notably limit the activation of photocatalytic molecular oxygen. In this study, atomic-layer BiOBr (BiOBr-QDs)/ZnAl-LDH composites with a considerable number of edges were developed to address the above-mentioned problems. The result of this study indicated the spatial separation of atomic-layer BiOBr-QDs/ZnAl-LDH's conduction band maximum (CBM) and valence band minimum (VBM). As a result, holes were produced on the substrate surface based on irradiation, and electrons were generated at the sites of the edge, such that ultra-fast charge separation can be carried out. The edges exposed massive adsorption sites in terms of oxygen molecules. Thus, electrons at the sites of the edge led to the reduction of absorbed oxygen molecules, thus exhibiting stronger photocatalytic •O2- production. Furthermore, the result confirmed that the atomic layer BiOBr-QDs/ZnAl-LDH are promising in environmental catalytic degradation for its increased activity of •O2- production. In this study, a novel insight into advanced photocatalyst design based on edge unsaturated ligand engineering at an atomic level is provided.

Tetracycline hydrochloride degradation by activation of peroxymonosulfate with lanthanum copper Ruddlesden-Popper perovskite oxide: Performance and mechanism.

ABO3-type perovskite oxides have been regarded as a kind of potential catalyst for peroxymonosulfate (PMS) activation. But some limitations such as specific pH conditions and coexisting ion interference restrict its practical application. Herein, a lanthanum copper Ruddlesden-Popper perovskite oxide (La2CuO4) was successfully synthesized through the sol-gel process and applied in the activation of PMS. And for the first time the La2CuO4/PMS system was used for tetracycline hydrochloride (TC-HCl) degradation. Results showed that La2CuO4 was a potential PMS activation catalyst in the removal of antibiotics. At optimized condition (0.2 g/L catalysts, 1 mM PMS, pH0 6.9), 96.05% of TC-HCl was removed in 30 min. In experiments of debugging control conditions, over a wide pH range of 3-11, more than 90% of TC-HCl can be removed. In the natural water treatment process, TC-HCl removal rates of about 84.2% and 70.3% were obtained in tap water and River water, respectively. According to the reusability and stability tests and the results of FTIR and XPS analysis, La2CuO4 had high structural and chemical stability. Electron paramagnetic resonance (EPR) suggested that the active species including ·OH, SO4-· and 1O2 were detected in degradation reaction. Finally, reasonable reaction mechanisms and possible degradation pathways of TC-HCl were proposed. These results indicate that La2CuO4 can act as a potential catalyst for PMS activation to degrade TC-HCl in water.

Insights into the Occurrence, Fate, Impacts, and Control of Food Additives in Food Waste Anaerobic Digestion: A Review.

The recovery of biomass energy from food waste through anaerobic digestion as an alternative to fossil energy is of great significance for the development of environmental sustainability and the circular economy. However, a substantial number of food additives (e.g., salt, allicin, capsaicin, allyl isothiocyanate, monosodium glutamate, and nonnutritive sweeteners) are present in food waste, and their interactions with anaerobic digestion might affect energy recovery, which is typically overlooked. This work describes the current understanding of the occurrence and fate of food additives in anaerobic digestion of food waste. The biotransformation pathways of food additives during anaerobic digestion are well discussed. In addition, important discoveries in the effects and underlying mechanisms of food additives on anaerobic digestion are reviewed. The results showed that most of the food additives had negative effects on anaerobic digestion by deactivating functional enzymes, thus inhibiting methane production. By reviewing the response of microbial communities to food additives, we can further improve our understanding of the impact of food additives on anaerobic digestion. Intriguingly, the possibility that food additives may promote the spread of antibiotic resistance genes, and thus threaten ecology and public health, is highlighted. Furthermore, strategies for mitigating the effects of food additives on anaerobic digestion are outlined in terms of optimal operation conditions, effectiveness, and reaction mechanisms, among which chemical methods have been widely used and are effective in promoting the degradation of food additives and increasing methane production. This review aims to advance our understanding of the fate and impact of food additives in anaerobic digestion and to spark novel research ideas for optimizing anaerobic digestion of organic solid waste.

Catalyst-Free Photochemical Activation of Peroxymonosulfate in Xanthene-Rich Systems for Fenton-Like Synergistic Decontamination: Efficacy of Proton Transfer Process.

Catalyst-free visible light assisted Fenton-like catalysis offers opportunities to achieve the sustainable water decontamination, but the synergistic decontamination mechanisms are still unclear, especially the effect of proton transfer process (PTP). The conversion of peroxymonosulfate (PMS) in photosensitive dye-enriched system was detailed. The photo-electron transfer between excited dye and PMS triggered the efficient activation of PMS and enhanced the production of reactive species. Photochemistry behavior analysis and DFT calculations revealed that PTP was the crucial factor to determine the decontamination performance, leading to the transformation of dye molecules. The excitation process inducing activation of whole system was composed of low energy excitations, and the electrons and holes were almost contributed by LUMO and HOMO. This work provided new ideas for the design of catalyst-free sustainable system for efficient decontamination.

Nitrobenzene reduction promoted by the integration of carbon nanotubes and Geobacter sulfurreducens.

Electron shuttles (ES) can mediate long-distance electron transfer between extracellular respiratory bacteria (ERB) and the surroundings. However, the effects of graphite structure in ES on the extracellular electron transfer (EET) process remain ambiguous. This work investigated the function of graphite structure in the process of nitrobenzene (NB) degradation by Geobacter sulfurreducens PCA, in which highly aromatic carbon nanotubes (CNTs) was studied as a typical ES. The results showed that the addition of 1.5 g L-1 of CNTs improved the NB biodegradation up to 81.2%, plus 18.8% NB loss due to the adsorption property of CNTs, achieving complete removal of 200 µM NB within 9 h. The amendment of CNTs greatly increased the EET rate, indicating that graphite structure exhibited excellent electron shuttle performance. Furthermore, Raman spectrum proved that CNTs obtained better graphite structure after 90 h of cultivation with strain PCA, resulting in higher electrochemical performance. Also, CNTs was perceived as the "Contaminant Reservoir", which alleviated the toxic effect of NB and shortened the distance of EET process. Overall, this work focused on the effects of material graphite structure on the EET process, which enriched the understanding of the interaction between CNTs and ERB, and these results might promote their application in the in-situ bioremediation of nitroaromatic-polluted environment.

Performance and mechanisms of citric acid improving biotransformation of waste activated sludge into short-chain fatty acids.

Numerous effective chemical strategies have been explored for short-chain fatty acids (SCFAs) production from waste activated sludge (WAS), but many technologies have been questioned due to the chemical residues. This study proposed a citric acid (CA) treatment strategy for improving SCFAs production from WAS. The optimum SCFAs yield reached 384.4 mg COD/g VSS with 0.08 g CA/g TSS addition. Meanwhile, CA biodegradation occurred and its contribution to the yield of total SCFAs, especially acetic acid, cannot be ignored. Intensive exploration indicated the sludge decomposition, the biodegradability of fermentation substrates, as well as the abundance of fermenting microorganisms were definitely enhanced in the existence of CA. The optimization of SCFAs production techniques based on this study deserved further study. This study comprehensively revealed the performance and mechanisms of CA enhancing biotransformation of WAS into SCFAs and the findings promotes the research of carbon resource recovery from sludge.

Mechanistic insight into the degradation of ciprofloxacin in water by hydroxyl radicals.

Ciprofloxacin (CIP), an effective antibacterial drug, is widely used to treat bacterial infections in humans and animals. However, drug pollution from residues and the development of resistant genes may pose serious ecological risks. Among the known methods of CIP degradation, advanced oxidation technology initiated by hydroxyl radicals exhibits great potential. However, an in-depth study of the degradation mechanism is difficult because of the limitations of the testing methods. In this study, CIP oxidation by hydroxyl radicals was evaluated using density functional theory (DFT), and the thermodynamics, kinetics, and toxicity were investigated. The results show that CIP oxidation occurs mainly through the piperazine ring, benzene ring, and CC. High reactivity is achieved in the initial reactions, where only five reactions are not thermodynamically spontaneous. Reactions involving direct hydrogen abstraction by oxygen in this system are superior to the indirect reactions. Some theoretically predicted products, such as P6 and P11, are consistent with those reported in previous experiments, indicating that the theoretical study can provide supplementary information about the oxidation paths. The branching ratios for the hydrogen atom abstraction and addition reactions were 37. 45% and 62.55%, respectively. Finally, this reaction system is completely nontoxic based on toxicity assessment.

Mechanistic views and computational studies on transition-metal-catalyzed reductive coupling reactions.

Transition-metal-catalyzed reductive coupling reactions have been considered as a powerful tool to convert two electrophiles into value-added products. Numerous related reports have shown the fascinating potential. Mechanistic studies, especially theoretical studies, can provide important implications for the design of novel reductive coupling reactions. In this review, we summarize the representative advancements in theoretical studies on transition-metal-catalyzed reductive coupling reactions and systematically elaborate the mechanisms for the key steps of reductive coupling reactions. The activation modes of electrophiles and the deep insights of selectivity generation are mechanistically discussed. In addition, the mechanism of the reduction of high-oxidation-state catalysts and further construction of new chemical bonds are also described in detail.

The fate of diclofenac in anaerobic fermentation of waste activated sludge.

Diclofenac (DCF), a nonsteroidal anti-inflammatory drug, is one of the most commonly detected pharmaceuticals in wastewater treatment plants. However, the fate of DCF in waste activated sludge (WAS) anaerobic fermentation has not been well-understood so far. This work therefore aims to comprehensively reveal whether and how DCF is transformed in WAS mesophilic anaerobic fermentation through both experimental investigation and density functional theory (DFT) calculation. Experimental results showed that ∼28.8% and 45.8% of DCF were respectively degraded during the batch and long-term fermentation processes. Based on the detected intermediates and DFT-predicted active sites, three metabolic pathways, i.e., chlorination, hydroxylation, and dichlorination, responsible for DCF transformation were proposed. DFT calculation also showed that the Gibbs free energy (ΔG) of the three transformation pathways was respectively 19.0, -4.3, and -19.3 kcal/mol, suggesting that the latter two reactions (i.e., hydroxylation and dichlorination) were thermodynamically favorable. Illumina MiSeq sequencing analyses revealed that DCF improved the populations of complex organic degradation microbes such as Proteiniclasticum and Tissierellales, which was in accord with the chemical analyses above. This work updates the fundamental understanding of the degradation of DCF in WAS anaerobic fermentation process and enlightens engineers to apply theoretical calculation to the field of sludge treatment or other complex microbial ecosystems.

Recycling of waste power lithium-ion batteries to prepare nickel/cobalt/manganese-containing catalysts with inter-valence cobalt/manganese synergistic effect for peroxymonosulfate activation.

Developing a high-efficiency peroxymonosulfate (PMS) activator is of great significance for the elimination and mineralization of organic contaminants. Herein, a catalyst (LiNi0.5Co0.2Mn0.3O2, NCM) was constructed using the cathode scrap of spent lithium-ion battery (LIB) for activation of PMS to remove Rhodamine B (RhB). The excellent catalytic capacity of NCM-650 was observed, as RhB was completely removed after 25 min. The NCM-650/PMS process could function effectively over a broad pH scope with favorable reusability and adaptability. The non-radical channels (singlet oxygen and mediated charge transfer) played a dominant role in the removal of RhB. Several reactive radical species (sulfate radicals, hydroxyl radicals and superoxide radicals) also facilitated the degradation of RhB, where the Co2+ and Mn4+ on the surface served as active sites to activate PMS. The synergistic effect of inter-valence cobalt and manganese in the catalyst was the predominant medium during the whole reaction process. According to the intermediates identified by High performance liquid chromatograph-mass spectrometry (HPLC-MS) and the analysis of density function theory (DFT) calculations, N-de-ethylation, chromophore cleavage, ring opening, and mineralization were regarded as the primary decomposition pathways. This research provided a novel perspective on the potential application of waste LIBs for the effective activation of PMS.

Mechanism and Origin of Stereoselectivity of Ni-Catalyzed Cyclization/Carboxylation of Bromoalkynes with CO2.

Bromoalkynes play important roles in coupling reactions because they can show obvious stereoselectivity to form E- and Z-isomers when substituents are different. However, the origin of the stereoselectivity in the bromoalkynes reaction is still unclear. Density functional theory (DFT) calculations were performed to provide an in-depth study of the reaction mechanism, clarifying the mechanistic details of the main reaction and the origin of the stereoselectivity. By comparing the syn-insertion mechanism of alkynes and the radical pathway, it is indicated that the electrostatic effect caused by the different charge distributions of the reactants is the main reason that Ni(I) species are more prone to syn-insertion of alkynes than Ni(II) species. In addition, the lower reaction energy barrier in the radical pathway suggests that it is more advantageous in terms of kinetics. The bond between Ni(I) species and alkenylation products has two directions to generate products of different configurations, which are the direct stereoselectivity-determining stages. The distortion/interaction analysis shows that the distortion energy mainly affects the product configuration, and the steric hindrance is the main factor controlling the stereoselectivity.

Evaluating the effect of diclofenac on hydrogen production by anaerobic fermentation of waste activated sludge.

Hydrogen production from waste-activated sludge (WAS) anaerobic fermentation is considered to be an effective method of resource recovery. However, the presence of a large number of complex organic compounds in sludge will affect the biological hydrogen production process. As an extensively applied prevalent anti-inflammatory drug, diclofenac (DCF) is inevitably released into the environment. However, the effect of diclofenac on hydrogen production from WAS anaerobic fermentation has not been fully investigated. This work therefore aims to comprehensively investigate the removal efficiency of DCF in mesophilic anaerobic fermentation of WAS and its effect on hydrogen yield. Experiment results showed that 32.5%-38.3% of DCF was degraded in the fermentation process when DCF concentration was ranged from 6 to 100 mg/kg TSS (total suspended solids). DCF at environmental level inhibited hydrogen production, the maximal hydrogen yield decreased from 24.2 to 15.3 mL/g VSS (volatile suspended solids) with an increase of DCF addition from 6 to 100 mg/kg TSS. This is because the presence of DCF caused inhibitions to acetogenesis and acidogenesis, the processes responsible for hydrogen production, probably due to that the polar groups of DCF (i.e., carboxyl group) could readily bind to active sites of [FeFe]- Hydrogenase. Besides, the microbial analysis revealed that DCF increased the microbial diversity but had few influences on the microbial structure.

How Does Chitosan Affect Methane Production in Anaerobic Digestion?

The expanding use of chitosan in sewage and sludge treatment processes raises concerns about its potential environmental impacts. However, investigations of the impacts of chitosan on sewage sludge anaerobic digestion where chitosan is present at substantial levels are sparse. This study therefore aims to fill this knowledge gap through both long-term and batch tests. The results showed that 4 g/kg total suspended solid (TSS) chitosan had no acute effects on methane production, but chitosan at 8-32 g/kg TSS inhibited methane production by 7.2-30.3%. Mass balance and metabolism of organic analyses indicated that chitosan restrained the transfer of organic substrates from solid phase to liquid phase, macromolecules to micromolecules, and finally to methane. Further exploration revealed that chitosan suppressed the secretion of extracellular polymeric substances of anaerobes by occupying the connection sites of indigenous carbohydrates and increased the mass transfer resistance between anaerobes and substrates, which thereby lowered the metabolic activities of anaerobes. Although chitosan could be partly degraded by anaerobes, it is much more persistent to be degraded compared with indigenous organics in sludge. Microbial community and key enzyme encoding gene analyses further revealed that the inhibition of chitosan to CO2-dependent methanogenesis was much severer than that to acetate-dependent methanogenesis.