Enhanced Interfacial Electron Transfer in Photocatalyst-Natural Enzyme Coupled Artificial Photosynthesis System: Tuning Strategies and Molecular Simulations.

Laccase is capable of catalyzing a vast array of reactions, but its low redox potential limits its potential applications. The use of photocatalytic materials offers a solution to this problem by converting absorbed visible light into electrons to facilitate enzyme catalysis. Herein, MIL-53(Fe) and NH2-MIL-53(Fe) serve as both light absorbers and enzyme immobilization carriers, and laccase is employed for solar-driven chemical conversion. Electron spin resonance spectroscopy results confirm that visible light irradiation causes rapid transfer of photogenerated electrons from MOF excitation to T1 Cu(II) of laccase, significantly increasing the degradation rate constant of tetracycline (TC) from 0.0062 to 0.0127 min-1. Conversely, there is only minimal or no electron transfer between MOF and laccase in the physical mixture state. Theoretical calculations demonstrate that the immobilization of laccase's active site and its covalent binding to the metal-organic framework surface augment the coupled system's activity, reducing the active site accessible from 27.8 to 18.1 Å. The constructed photo-enzyme coupled system successfully combines enzyme catalysis' selectivity with photocatalysis's high reactivity, providing a promising solution for solar energy use.

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.

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.

Global evolution of research on green energy and environmental technologies:A bibliometric study.

To better grasp developments and trends in research on green energy and environmental technologies, the published literatures in the Web of Science Core Collection database from 1998 to 2020 were utilized to reveal critical information and guidance on what has been investigated, and what are the changes in research interests using a bibliometric method. Herein, yearly quantitative distribution of literatures, author contribution and collaboration, productive and influential institutions and countries/territories, co-citation analysis, keywords co-occurrence analysis, and research frontier identification are analyzed via information visualization technology. The results show that the publications on green energy and environmental technologies have grown exponentially, that China, the USA, and Italy are the most active countries, but the global cooperation is not close at present. The research frontier identification results reveal that the categories of energy, wastewater, and performance remain stable, while the trending up and emerging categories of catalyst and CO2 emission show clear shift over the last decade, indicating that catalytic production of clean energy and value-added chemicals, strategies to reduce greenhouse gas emissions, and other related studies to solve the global energy crisis and environmental problems are the research frontiers. This bibliometric study provides unique insights and offers research guidance on green energy and environmental technologies.

Unveiling the Effects of Carbon-Based Nanomaterials on Crop Growth: From Benefits to Detriments.

To systematically assess the impact of typical CNMs on the growth effects of cereal crops, we conducted a meta-analysis of 48 independent studies worldwide. The pooled results showed that shoot weight (13.39%) and antioxidant metabolite content (SOD: 106.32%, POD: 32.29%, CAT: 22.63%) of cereal crops exposed to the presence of CNMs were significantly increased, but phytohormones secretion (17.84%) was inhibited. The results of subgroup analysis showed that there were differences in the results of different CNM types with the same exposure concentration on growth effects. Short-term exposure adversely affected the root and photosynthetic capacity of the crop, but prolonged exposure instead showed a promoting effect. Multiple linear regression analysis showed that the concentration of CNMs and cereal variety variables were significantly associated with changes in multiple growth effect values. This work could offer references and fresh perspectives for investigating how nanoparticles and crops interact.

Recent advances in application of heterogeneous electro-Fenton catalysts for degrading organic contaminants in water.

Over the last decades, advanced oxidation processes (AOPs) have been widely used in surface and ground water pollution control. The heterogeneous electro-Fenton (EF) process has gained much attention due to its properties of high catalytic performance, no generation of iron sludge, and good recyclability of catalyst. As of October 2022, the cited papers and publications of EF are around 1.3 × 10-5 and 3.4 × 10-3 in web of science. Among the AOP techniques, the contaminant removal efficiencies by EF process are above 90% in most studies. Current reviews mainly focused on the mechanism of EF and few reviews comprehensively summarized heterogeneous catalysts and their applications in wastewater treatment. Thus, this review focuses on the current studies covering the period 2012-2022, and applications of heterogeneous catalysts in EF process. Two kinds of typical heterogeneous EF systems (the addition of solid catalysts and the functionalized cathode catalysts) and their applications for organic contaminants degradation in water are reviewed. In detail, solid catalysts, including iron minerals, iron oxide-based composites, and iron-free catalysts, are systematically described. Different functionalized cathode materials, containing Fe-based cathodes, carbonaceous-based cathodes, and heteroatom-doped cathodes, are also reviewed. Finally, emphasis and outlook are made on the future prospects and challenges of heterogeneous EF catalyst for wastewater treatments.

Carbonyl and defect of metal-free char trigger electron transfer and O2- in persulfate activation for Aniline aerofloat degradation.

Residual flotation reagents in mineral processing wastewater can trigger severe ecological threats to the local groundwater if they are discharged without treatment. Metal-free biochar-induced persulfate-advanced oxidation processes (KCBC/PS) were used in this study to elucidate the degradation of aniline aerofloat (AAF) - a typical flotation reagent. In KCBC/PS system, AAF can be removed at low doses of catalyst (KCBC, 0.05 g/L) and oxidant (PS, 0.3 mM) additions with high efficiency. The analysis revealed the dominance of O2•- among the identified reactive oxygen species (ROS), which achieved deeper mineralization for the AAF degradation in the KCBC/PS system. The role of the electron transfer mechanism was equally important; the importance was corroborated by the chemical quenching experiments, electron spin resonance (ESR) detection, probe experiments, and electrochemical analysis. It benefited from the electron transfer mechanism in the KCBC/PS system and exhibited a wide pH adaptation (3.5-11) and high resistance to inorganic anions for real mining wastewater treatment. Combined with theoretical calculations and other analyses, the carbonyl group was deemed to be the active site of the non-radical pathway of biochar, while the site of the conversion of SO4•- to superoxide radicals by biochar activation represented a defect. These findings revealed a synergistic effect of multiple active sites on PS activation in biochar-based materials. Moreover, the intermediate degradation products of AAF from mass spectrometry indicated a possible pathway through the density functional theory (DFT) method, which was effective in reducing the environmental toxicity of pollutants for the first time according to the T.E.S.T software and seed germination experiments. Overall, our study proposed a novel modification strategy for cost-effective and environmentally friendly biochar-based catalysts, while also deepening our understanding of the mechanism of activation of persulfate by metal-free carbon-based materials.

Biochar in the 21st century: A data-driven visualization of collaboration, frontier identification, and future trend.

The massive amounts of publication data are highly valuable, because in addition to the advancement in science, technology, and policy, such data can provide critical information and guidance on what have been published, what topical changes have evolved, and what are the trending fields deserving more attention. In the 21st century, biochar has played an indispensable role in the long-term global development strategies in response to "Carbon neutralization", "Agricultural management", and "Environmental restoration", and accumulated many high-quality publications. Herein, this study provides a new data-driven bibliometric analysis strategy and framework for mining the core content of massive literature data, and aims at bringing unique insights for the research prospects as well as opportunities of biochar. The results show that biochar researches have made great progress from 1999 to 2020, but cross-disciplinary teamwork should be further emphasized. The research frontier identification reveals that sewage treatment, efficient removal, and functional composite materials will be the issues which must be paid continual attention at present and in the future. Furthermore, studies on global climate impact, biomass resource utilization, carbon sequestration, carbon cycle, and even the negative effects of biochar have gradually begun to be taken seriously.

Tailoring biochar for persulfate-based environmental catalysis: Impact of biomass feedstocks.

Biochar, a carbonaceous material with engineering potential, has gained attention as an efficient catalyst in persulfate-based advanced oxidation processes (PS-AOPs). Although biomass feedstocks are known as a critical factor for the performance of biochar, the relationship between the catalytic efficiency/mechanism and the types of biomass feedstocks is still unclear. Thus, according to recent advances in experimental and theoretical researches, this paper provides a systematic review of the properties of biochar, and the relationship between catalytic performance in PS-AOPs and biomass feedstocks, where the differences in physicochemical properties (surface properties, pore structure, etc.) and activation path of different sourced biochars, are introduced. In addition, how the tailoring of biochar (such as heteroatomic doping and co-pyrolysis of biomass) affects its activation efficiency and mechanism in PS-AOPs is summarized. Finally, the suitable application scenarios or systems of different sourced biochars, appropriate methods to improve the catalytic performance of different types of biochar and the prospects and challenges for the development of biochar in PS-AOPs are proposed.

Periodate activated by manganese oxide/biochar composites for antibiotic degradation in aqueous system: Combined effects of active manganese species and biochar.

Developing efficient catalysts for oxytetracycline (OTC) degradation is an ideal strategy to tackle environmental pollution, and advanced oxidation processes (AOPs) have been widely used for its degradation. However, the studies on the activation of periodate (PI) by biochar and its composites in recent years have been scarcely reported. In this study, we focused on the degradation of OTC by PI activation with manganese oxide/biochar composites (MnxOy@BC). Experimental results showed that the OTC degradation rate of MnxOy@BC/PI system reached almost 98%, and the TOC removal efficiency reached 75%. Various characteristic analysis proved that PI could be activated efficiently by surface functional groups and manganese-active species (Mn(II), Mn(III), and Mn(IV)) on biochar, and various reactive species such as singlet oxygen (1O2), hydroxyl radical (∙OH), and superoxide radical (O2∙-) can be observed via radical quenching experiments. Based on this, three degradation pathways were proposed. Furthermore, MnxOy@BC and PI were combined to degrade environmental pollutants, which achieved excellent practical benefits and had great practical application potential. We hope that it can provide new ideas for advanced oxidation processes (AOPs) applying for wastewater treatment in the future.

Effects of biochar-based materials on the bioavailability of soil organic pollutants and their biological impacts.

Motivated by the unique structure and superior properties, biochar-based materials, including pristine biochar and composites of biochar with other functional materials, are considered as new generation materials for diverse multi-functional applications, which may be intentionally or unintentionally released to soil. The influencing mechanism of biochar-based material on soil organisms is a key aspect for quantifying and predicting its benefits and trade-offs. This work focuses on the effects of biochar-based materials on soil organisms within the past ten years. 206 sources are reviewed and available knowledge on biochar-based materials' impacts on soil organisms is summarized from a diverse perspective, including the pollutant bioavailability changes in soil, and potential effects of biochar-based materials on soil organisms. Herein, effects of biochar-based materials on the bioavailability of soil organic pollutants are detailed, from the perspective of plant, microorganism, and soil fauna. Potential biological effects of pristine biochar (PBC), metal/metal compounds-biochar composites (MBC), clay minerals-biochar composites (CMBC), and carbonaceous materials-biochar composites (CBC) on soil organisms are highlighted for the first time. And possible mechanisms are presented based on the different characters of biochar-based materials as well as various environmental interactions. Finally, the bottleneck and challenges of risk assessment of biochar-based materials as well as future prospects are proposed. This work not only promotes the development of risk assessment system of biochar-based materials, but broadens the strategy for the design and optimization of environmental-friendly biochar materials.

Potential hazards of biochar: The negative environmental impacts of biochar applications.

Biochar has been widely used as an environmentally friendly material for soil improvement and remediation, water pollution control, greenhouse gas emission reduction, and other purposes because of its characteristics such as a large surface area, porous structure, and abundant surface O-containing functional groups. However, some surface properties (i.e., (i) some surface properties (i.e., organic functional groups and inorganic components), (ii) changes in pH), and (iii) chemical reactions (e.g., aromatic C ring oxidation) that occur between biochar and the application environment may result in the release of harmful components. In this study, biochars with a potential risk to the environment were classified according to their harmful components, surface properties, structure, and particle size, and the potential negative environmental effects of these biochars and the mechanisms inducing these negative effects were reviewed. This article presents a comprehensive overview of the negative environmental impacts of biochar on soil, water, and atmospheric environments. It also summarizes various technical methods of environment-related risk detection and evaluation of biochar application, thereby providing a baseline reference and guiding significance for future biochar selection and toxicity detection, evaluation, and avoidance.

Catalyst-free activation of permanganate under visible light irradiation for sulfamethazine degradation: Experiments and theoretical calculation.

In this study, visible light (VL) was adopted for permanganate (PM) activation without additional catalyst, where sulfamethazine (SMT) was selected as the probe compound. Experiment results showed that the VL/PM system can effectively degrade SMT through pseudo-first-order reaction kinetics. Influencing factors including PM dosage, solution pH, humid acid (HA) and coexisting anions (CO32-, SO42-, Cl- and NO3-) which affect SMT photo-degradation were also examined. Pyrophosphate (PP) had an inhibitory effect on SMT degradation due to the complexation of PP with Mn (III). Electron spin resonance (ESR) spectrometry and UV-Vis spectrophotometer proved that VL can activate PM to generate ·O2- and Mn (III) reactive species. Furthermore, based on the active site prediction, intermediates identification and Density Functional Theory (DFT) calculation, two main degradation pathways involving SMT molecular rearrangement and cleavage of S-N bond were proposed. Moreover, the energy barriers of the two degradation pathways were also calculated. This study offers a novel approach for aqueous SMT removal and deepens our understanding of the degradation mechanism of SMT through DFT calculation, which hopes to shed light on the future development of VL/PM treatment.

Degradation of sulfamethazine by biochar-supported bimetallic oxide/persulfate system in natural water: Performance and reaction mechanism.

The rapid development of aquaculture results in the increased concentrations and kinds of antibiotics in water environment, and the sharply growing antibiotic contamination has caused increasing concerns. Herein, an innovative sulfamethazine (SMT) removal approach was developed by activation of persulfate (PS) using biochar-based materials prepared by co-precipitation and pyrolysis: Fe-Mg oxide/biochar (FeMgO/BC). Experiments on the activation of PS by FeMgO/BC under different factors were carried out. The involved mechanism and degradation pathway were also studied. Notably, the SMT removal rate reached 99 % under the optimum reaction condition, while the TOC removal efficiency reached 77.9 %. PS was activated by FeMgO/BC and the dominated active radical was SO4•-. Fe2+ from FeMgO and the hydroxyl and carboxyl groups on the surface of biochar contributed to the production of SO4•-. The dehydrogenation, bond cracking and unsaturated bond addition process occurred in the degradation of SMT. Furthermore, FeMgO/BC exhibits excellent reusability and stability. Considering the outstanding actual water application performances and the weak biotoxicity, FeMgO/BC shows a promising potential in the removal of antibiotics under actual water conditions.