A comprehensive study on the co-removal of Cr (VI) and ciprofloxacin via microbial-photocatalytic coupling: Mechanistic insights and performance evaluation.

The increasing contamination of water systems by antibiotics and heavy metals has become a growing concern. The intimately coupled photocatalysis and biodegradation (ICPB) approach offers a promising strategy for the effective removal of mixed pollutants. Despite some prior research on ICPB applications, the mechanism by which ICPB eliminates mixed pollutants remains unclear. In our current study, the ICPB approach achieved approximately 1.53 times the degradation rate of ciprofloxacin (CIP) and roughly 1.82 times the reduction rate of Cr (VI) compared to photocatalysis. Remarkably, after 30 days, the ICPB achieved a 96.1% CIP removal rate, and a 97.8% reduction in Cr (VI). Our investigation utilized three-dimensional fluorescence analysis and photo-electrochemical characterization to unveil the synergistic effects of photocatalysis and biodegradation in removal of CIP and Cr (VI). Incorporation of B-Bi3O4Cl (B-BOC) photocatalyst facilitated electron-hole separation, leading to production of ·O2-, ·OH, and h+ species which interacted with CIP, while electrons reduced Cr (VI). Subsequently, the photocatalytic products were biodegraded by a protective biofilm. Furthermore, we observed that CIP, acting as an electron donor, promoted the reduction of Cr (VI). The microbial communities revealed that the number of bacteria favoring pollutant removal increased during ICPB operation, leading to a significant enhancement in performance.

Facilitating Redox Cycles of Copper Species by Pollutants in Peroxymonosulfate Activation.

The redox behavior of metal active sites determines the rate of heterogeneous catalysis in peroxymonosulfate activation. Previous reports focused on the construction of catalysts for accelerating interfacial electron transfer. In this work, a new strategy was proposed for facilitating valence cycles of Cu+/Cu2+ by using pollutants. The 2.5Cu/CeO2/PMS system was capable of achieving the efficient removal of pollutants, including tetracycline, oxytetracycline, and rhodamine B, in a wide pH working range. In the presence of tetracycline, a Cu-N bond was formed between the -NH2 group of tetracycline and the Cu site of the catalyst, showing that the coordination of Cu active sites changed to CuO4N1. The charge of CuO4N1 active sites rearranged, making it easier to obtain electrons and promote the PMS oxidation, thereby accelerating the reduction of Cu2+ to Cu+ and PMS activation. The PMS activation system showed excellent sustainability and selectivity for the removal of organic pollutants. This study provides a novel routine to promote peroxymonosulfate activation by utilizing pollutants to accelerate the redox behavior of metal species.

Almost 100 % Peroxymonosulfate Conversion to Singlet Oxygen on Single-Atom CoN2+2 Sites.

Single-atom CoN4 active sites have demonstrated excellent efficiency in peroxymonosulfate activation. However, the identification of CoN4 active sites and the detailed singlet oxygen generation mechanism in peroxymonosulfate activation remains ambiguous. We demonstrate a strategy to regulate the generation of reactive oxygen species by atomically dispersed cobalt anchored on nitrogen-doped carbon. As indicated by experiment and DFT calculations, CoN2+2 was the active site and singlet oxygen was the predominant reactive oxygen species with a proportion of 98.89 %. Spontaneous dissociation of adsorbed peroxymonosulfate on the CoN2+2 active sites was energetically unfavorable because of the weakly positive Co atoms and CoN2+2 coordination, which directed PMS oxidation by a non-radical pathway and with simultaneous singlet oxygen generation. The generated singlet oxygen degraded several organic pollutants with high efficiency across a broad pH range.

Efficient Fenton-like Process for Pollutant Removal in Electron-Rich/Poor Reaction Sites Induced by Surface Oxygen Vacancy over Cobalt-Zinc Oxides.

To achieve high efficiency and low consumption for water treatment in the Fenton reaction, we use the surface oxygen vacancies (OVs) as the electron temporary residences to construct a dual-reaction-center (RDC) Fenton-like catalyst with abundant surface electron-rich/poor areas consisting of OV-rich Co-ZnO microparticles (OV-CoZnO MPs). The lattice-doping of Co into ZnO wurtzite results in the formation of OVs with unpaired electrons (electron-rich OVs) and electron-deficient Co3+ sites according to the structural and electronic characterizations. Both experimental and theoretical calculations prove that the electron-rich OVs are responsible for the capture and reduction of H2O2 to generate hydroxyl radicals, which quickly degrades pollutants, while a large amount of pollutants are adsorbed at the electron-deficient Co3+ sites and act as electron donors for the system, accompanied by their own oxidative degradation. The electrons obtained from the pollutants in the electron-deficient sites are transferred to the OVs through the internal bond bridge to achieve the balance of electron gain/loss. Through this process, pollutants are efficiently converted and degraded by multiple pathways in a wide range of pH (4.5-9.5). The reaction rate of the OV-CoZnO MPs/H2O2 system is increased by ∼17 times compared with the non-DRC system. This discovery provides a sustainable strategy for pollutant utilization, which shows new implications for solving the troublesome issues of the Fenton reaction and for developing novel environmental remediation technologies.

Biogas properties and enzymatic analysis during anaerobic fermentation of Phragmites australis straw and cow dung: influence of nickel chloride supplement.

The importance of nickel (added as NiCl2) on mesophilic anaerobic fermentation of Phragmites australis straw and cow dung was demonstrated by investigating the biogas properties, pH values, organic matter degradation [chemical oxygen demand (COD)] and enzyme activities (cellulase, protease and dehydrogenase) during the fermentation process. The results showed that Ni2+ addition increased the cumulative biogas yields by >18 % by improving the efficiency of first peak stage and bringing forward the second peak stage. The pH values were not significantly influenced by Ni2+ addition (p > 0.05). Biogas yields were associated with variations in COD concentrations rather than momentary concentrations. At the start-up stage of fermentation (4th day), the biogas yields increased gradually together with the increase of dehydrogenase activities at elevated Ni2+ concentrations when cellulase and protease activities were similar in all test groups. It is suggested that Ni2+ addition was mainly dependent on the methanogenic stage. After the start-up stage, the impact of Ni2+ addition on biogas production was mainly dependent on its effect on cellulase activities, rather than protease or dehydrogenase activities.

Effect of ferrous chloride on biogas production and enzymatic activities during anaerobic fermentation of cow dung and Phragmites straw.

The effect of ferrous (added as FeCl2) on the anaerobic co-digestion of Phragmites straw and cow dung was studied by investigating the biogas properties, pH values, organic matter degradation (COD) and enzyme activities (cellulase, protease and dehydrogenase) at different stages of mesophilic fermentation. The results showed that Fe(2+) addition increased the cumulative biogas yields by 18.1 % by extending the peak period with high daily biogas yields. Meanwhile, the methane (CH4) contents in the Fe(2+) added groups were generally higher than the control group before the 15th day. The pH values were not significantly impacted by Fe(2+) concentrations during the fermentation process. The COD concentrations, cellulase, protease and dehydrogenase activities varied with the added Fe(2+) concentrations and the stages of the fermentation process. At the beginning stage of fermentation (4th day), Fe(2+) addition increased the biogas production by improving the cellulase and dehydrogenase activities which caused a decline in COD. At the peak stage of fermentation (8th day), Fe(2+) addition enhanced the cellulase and protease activities, and resulted in lower COD contents than the control group. When the biogas yields decreased again (13th day), the COD contents varied similar with the protease and dehydrogenase activities, whilst cellulase activities were not sensitive to Fe(2+) concentrations. At the end of fermentation (26th day), Fe(2+) addition decreased the cellulase activities, led to lower COD contents and finally resulted the lower biogas yields than the control group. Taking the whole fermentation process into account, the promoting effect of Fe(2+) addition on biogas yields was mainly attributed to the extension of the gas production peak stage and the improvement of cellulase activities.

N, S, and Cl tri-doped carbon boost the switching of radical to non-radical pathway in Fenton-like reactions: Synergism of N species and defects.

Heteroatom doping represents a promising strategy for enhancing the generation of singlet oxygen (1O2) during the activation of peroxymonosulfate (PMS) using carbon-based catalysts; however, it remains a formidable challenge. In this study, we systematically controlled the structure of metal-free carbon-based materials by introducing different heteroatoms to investigate their efficacy in degrading organic pollutants in water via PMS activation. The results of reactive oxygen species detection showed that the dominant free radical in the four samples was different: CN (•SO4- and •OH), CNS (•O2-), CNCl (1O2), and CNClS (1O2). This led to the transformation of active species from free radicals to non-free radicals. The tri-doped carbons with nitrogen, sulfur, and chlorine (CNClS) exhibited exceptional performance in PMS activation and achieved a remarkable degradation efficiency of 95% within just 6 min for tetracycline. Moreover, a strong linear correlation was observed between the ratio of pyridine-N/graphite-N and ID/IG with the yield of 1O2, indicating that N species and defects play a crucial role in CNClS as they facilitate the transition from radical to non-radical pathways during PMS activation. These findings highlight the possibility that adjustable tri-heteroatom doping will expand the Fenton-like reaction for the treatment of actual wastewater.

Enhanced carriers separation in novel in-plane amorphous carbon/g-C3N4 nanosheets for photocatalytic environment remediation.

Although carbon-based materials/g-C3N4 heterostructure with an up-down structure in space can inhibit the recombination of charge carriers, the electron transfer is still suppressed by the interlayer van der Waals force. Herein, amorphous carbon is successfully introduced into the g-C3N4 nanosheet (CNS) by a self-conversion process to form an in-plane heterostructure of amorphous carbon/g-C3N4 (CNSC1). Kelvin probe atomic force microscopy (KPFM) and density functional theory (DFT) confirm that g-C3N4 and amorphous carbon are in the same plane, which can generate the surface electric field of CNSC1, providing a driving force for the transfer of electrons from g-C3N4 to amorphous carbon. Meanwhile, the sp2-hybridized π conjugation bond of amorphous carbon can rapidly capture and store photogenerated electrons, inhibiting charge carrier recombination and thus generating more electrons to facilitate the yield of hydroxyl radicals. The photocatalytic activity of CNSC1 for the degradation of tetracycline and rhodamine B is 2.7 times and 4.8 times higher than that of CNS, respectively, due to the efficient interface charge separation. This work is expected to provide a new idea for the combination of carbon materials and g-C3N4.

Photo-electro-Fenton-like process for rapid ciprofloxacin removal: The indispensable role of polyvalent manganese in Fe-free system.

The residual ciprofloxacin (CIP) in water seriously menaces the ecological safety and public health. Here, a Fe-free photo-electro-Fenton-like (PEF) system was designed for efficient degradation of CIP in water. A Z-scheme MnOx/g-C3N4 (MCN) nanocomposite with low-cost, large specific surface area and abundant active sites was successfully synthesized as a photoelectric catalyst. The XPS analysis indicated the presence of Mn2+, Mn3+ and Mn4+ in the MCN (1:6) composite, and the conversion among polyvalent manganese made the decomposition of H2O2 more efficient. Therefore, the manganese ions replaced the Fe element in traditional Fenton system. With the MCN (1:6), the PEF system could also produce O2-, OH and h+ under the visible light irradiation. The synergetic excitation of multiple active species promoted the rapid decomposition of CIP. Besides, the polyvalent property of manganese oxide resulted in the presence of oxygen vacancies which could improve the electrocatalytic reactivity of the catalyst. Finally, the degradation efficiency of CIP was 96.23% in 120 min and the mineralization efficiency was 80.02% in 240 min.

3D Graphene-Based Macrostructures for Water Treatment.

Recently, 3D graphene-based macrostructures (3D GBMs) have gained increased attention due to their immense application potential in water treatment. The unique structural features (e.g., large surface area and physically interconnected porous network) as well as fascinating properties (e.g., high electrical conductivity, excellent chemical/thermal stability, ultralightness, and high solar-to-thermal conversion efficiency) render 3D GBMs as promising materials for water purification through adsorption, capacitive deionization, and solar distillation. Moreover, 3D GBMs can serve as scaffolds to immobilize powder nanomaterials to build monolithic adsorbents and photo-/electrocatalysts, which significantly broadens their potential applications in water treatment. Here, recent advances in their synthesis and application toward water purification are highlighted. Remaining challenges and future perspectives are elaborated to highlight future research directions.

Highly Efficient Degradation of Polyacrylamide by an Fe-Doped Ce0.75Zr0.25O2 Solid Solution/CF Composite Cathode in a Heterogeneous Electro-Fenton Process.

Polyacrylamide (PAM) in environmental water has become a major problem in water pollution management due to its high molecular mass, corrosion resistance, high viscosity, and nonabsorption by soil. The composite of Fe-doped Ce0.75Zr0.25O2 solid solution (Fe-Ce0.75Zr0.25O2) loaded on carbon felt (CF) was fabricated by a hydrothermal synthesis method, which was used as the cathode in a heterogeneous electro-Fenton system for the degradation of PAM. It showed that the degradation efficiency of PAM by the Fe-Ce0.75Zr0.25O2/CF cathode was 86% after 120 min and the molecular mass of PAM decreased by more than 90% after 300 min. Total organic carbon removal reached 78.86% in the presence of Fe-Ce0.75Zr0.25O2/CF, while the value was only 38.01% in the absence of Fe-Ce0.75Zr0.25O2. Further studies showed that the breaking of the chain begins with the amide bond, and then, the carbon chain was cracked into a short alkyl chain. As degradation progressed, both the complex viscosity and elasticity modulus of PAM solutions decreased nearly 50% at 300 min. It indicated that •OH were the most significant active species for the degradation of PAM. This novel Fe-Ce0.75Zr0.25O2/CF composite is an efficient and promising electrode for the removal of PAM in wastewater.

Enhanced catalytic degradation by using RGO-Ce/WO3 nanosheets modified CF as electro-Fenton cathode: Influence factors, reaction mechanism and pathways.

Development of an efficient cathode in advanced oxidation process is an important challenge. In this work, we synthesized a low-cost, high-catalytic-active and stable reduced graphene oxide (RGO)-Ce/WO3 nanosheets (RCW) to modify carbon felt (CF) as cathode to degrade ciprofloxacin (CIP) in electro-Fenton process. Compared to traditional heterogeneous electro-Fenton process, carbon black was substituted by RGO and poly tetra fluoroethylene was avoided to be used as binder. We found that RCW/CF cathode reached about 100% degradation efficiency of CIP after 1 h and 98.55% mineralization degree after 8 h. Meanwhile, it had a very high current density, about 2.5 times that of CF. RCW/CF cathode produced more O2-, H2O2 and OH via one-electron reduction process (O2→O2- →H2O2). The modified cathode kept a stable performance for high CIP degradation efficiency during 5 cycles. The introduction of RGO could promote electron transfer, and the adding of Ce into the WO3 lattice provided superior conditions for the adsorption and activation of oxygen molecules, thus promoting the formation of active oxygen species on the surface of RCW. This novel RCW/CF composite is an efficient and promising electrode for removal of CIP in the wastewater.