Biochar Meets Single-Atom: A Catalyst for Efficient Utilization in Environmental Protection Applications and Energy Conversion.

Single-atom catalysts (SACs), combining the advantages of multiphase and homogeneous catalysis, have been increasingly investigated in various catalytic applications. Carbon-based SACs have attracted much attention due to their large specific surface area, high porosity, particular electronic structure, and excellent stability. As a cheap and readily available carbon material, biochar has begun to be used as an alternative to carbon nanotubes, graphene, and other such expensive carbon matrices to prepare SACs. However, a review of biochar-based SACs for environmental pollutant removal and energy conversion and storage is lacking. This review focuses on strategies for synthesizing biochar-based SACs, such as pre-treatment of organisms with metal salts, insertion of metal elements into biochar, or pyrolysis of metal-rich biomass, which are more simplistic ways of synthesizing SACs. Meanwhile, this paper attempts to 1) demonstrate their applications in environmental remediation based on advanced oxidation technology and energy conversion and storage based on electrocatalysis; 2) reveal the catalytic oxidation mechanism in different catalytic systems; 3) discuss the stability of biochar-based SACs; and 4) present the future developments and challenges regarding biochar-based SACs.

Oxygen Doping Cooperated with Co-N-Fe Dual-Catalytic Sites: Synergistic Mechanism for Catalytic Water Purification within Nanoconfined Membrane.

Atom-site catalysts, especially for graphitic carbon nitride-based catalysts, represents one of the most promising candidates in catalysis membrane for water decontamination. However, unravelling the intricate relationships between synthesis-structure-properties remains a great challenge. This study addresses the impacts of coordination environment and structure units of metal central sites based on Mantel test, correlation analysis, and evolution of metal central sites. An optimized unconventional oxygen doping cooperated with Co-N-Fe dual-sites (OCN Co/Fe) exhibits synergistic mechanism for efficient peroxymonosulfate activation, which benefits from a significant increase in charge density at the active sites and the regulation in the natural population of orbitals, leading to selective generation of SO4 •-. Building upon these findings, the OCN-Co/Fe/PVDF composite membrane demonstrates a 33 min-1 ciprofloxacin (CIP) rejection efficiency and maintains over 96% CIP removal efficiency (over 24 h) with an average permeance of 130.95 L m-2 h-1. This work offers a fundamental guide for elucidating the definitive origin of catalytic performance in advance oxidation process to facilitate the rational design of separation catalysis membrane with improved performance and enhanced stability.

Mediated Peroxymonosulfate Activation at the Single Atom Fe-N3 O1 Sites: Synergistic Degradation of Antibiotics by Two Non-Radical Pathways.

The activation of persulfates to degrade refractory organic pollutants is a hot issue in advanced oxidation right now. Here, it is reported that single-atom Fe-incorporated carbon nitride (Fe-CN-650) can effectively activate peroxymonosulfate (PMS) for sulfamethoxazole (SMX) removal. Through some characterization techniques and DFT calculation, it is proved that Fe single atoms in Fe-CN-650 exist mainly in the form of Fe-N3 O1 coordination, and Fe-N3 O1 exhibited better affinity for PMS than the traditional Fe-N4 structure. The degradation rate constant of SMX in the Fe-CN-650/PMS system reached 0.472 min-1 , and 90.80% of SMX can still be effectively degraded within 10 min after five consecutive recovery cycles. The radical quenching experiment and electrochemical analysis confirm that the pollutants are mainly degraded by two non-radical pathways through 1 O2 and Fe(IV)═O induced at the Fe-N3 O1 sites. In addition, the intermediate products of SMX degradation in the Fe-CN-650/PMS system show toxicity attenuation or non-toxicity. This study offers valuable insights into the design of carbon-based single-atom catalysts and provides a potential remediation technology for the optimum activation of PMS to disintegrate organic pollutants.

Tunable schiff-based networks with different bonding sites for enhanced photocatalytic activity under visible-light irradiation: The effects of steric hindrance.

Organic polymers hold great potential in photocatalysis considering their low cost, structural tailorability, and well-controlled degree of conjugation for efficient electron transfer. Among the polymers, Schiff base networks (SNWs) with high nitrogen content have been noticed. Herein, a series of SNWs is synthesized based on the melamine units and dialdehydes with different bonding sites. The chemical and structural variation caused by steric hindrance as well as the related photoelectric properties of the SNW samples are investigated, along with the application exploration on photocatalytic degradation and energy production. The results demonstrate that only SNW-o based on o-phthalaldehyde responds to visible light, which extends to over 550 nm. SNW-o shows the highest tetracycline degradation rate of 0.02516 min-1, under 60-min visible light irradiation. Moreover, the H2O2 production of SNW-o is 2.14 times higher than that of g-C3N4. The enhanced photocatalytic activity could be ascribed to the enlarged visible light adsorption and intramolecular electron transfer. This study indicates the possibility to regulate the optical and electrical properties of organic photocatalysts on a molecular level, providing an effective strategy for rational supramolecular engineering to the applications of organic materials in photocatalysis.

Preparation and Application of Single-Atom Cobalt Catalysts in Organic Synthesis and Environmental Remediation.

The development of high-performance catalysts plays a crucial role in facilitating chemical production and reducing environmental contamination. Single-atom catalysts (SACs), a class of catalysts that bridge the gap between homogeneous and heterogeneous catalysis, have garnered increasing attention because of their unique activity, selectivity, and stability in many pivotal reactions. Meanwhile, the scarcity of precious metal SACs calls for the arrival of cost-effective SACs. Cobalt, as a common non-noble metal, possesses tremendous potential in the field of single-atom catalysis. Despite their potential, reviews about single-atom Co catalysts (Co-SACs) are lacking. Accordingly, this review thoroughly summarized various preparation methodologies of Co-SACs, particularly pyrolysis; its application in the specific domain of organic synthesis and environmental remediation is discussed as well. The structure-activity relationship and potential catalytic mechanism of Co-SACs are elucidated through some representative reactions. The imminent challenges and development prospects of Co-SACs are discussed in detail. The findings and insights provided herein can guide further exploration and development in this charming area of catalyst design, leading to the realization of efficient and sustainable catalytic processes.

Insight into the selection of oxidant in persulfate activation system: The effect of the target pollutant properties.

As a rising branch of advanced oxidation processes, persulfate activation has attracted growing attention. Unlike catalysts that have been widely studied, the selection of persulfate is previously overlooked. In this study, the affecting factors of persulfates were studied. The effect of target pollutant properties on superior persulfate species (the species with a higher degradation efficiency) was investigated by multiwalled carbon nanotube (MWCNT)/persulfate catalytic systems. Innovatively, the EHOMO (or vertical ionization potential (VIP)) value of the target pollutant was proposed to be an index to judge the superior persulfate species, and the threshold is VIP= 6.397-6.674 eV, EHOMO= -8.035∼- 7.810 eV, respectively. To be specific, when the VIP of phenolic compounds is higher (or EHOMO of phenolic compounds is lower) than the threshold, the catalytic performance of peroxymonosulfate would be higher than that of peroxydisulfate. Moreover, the effects of coexisting cations on peroxydisulfate superior species were further investigated. It was illustrated that the hydrated cation radius of coexisting cations would influence the pollutant degradation efficiency under some circumstances. This study provides a new approach to improve the cost of persulfate activation systems and promotes the underlying downstream application of persulfate activation systems.

An overview of recent advances and future prospects of three-dimensional biofilm electrode reactors (3D-BERs).

Three-dimensional biofilm electrode reactors (3D-BERs) have attracted extensive attention in recent years due to their wide application range, high efficiency and energy saving. On the basis of traditional bio-electrochemical reactor, 3D-BERs are filled with particle electrodes, also known as the third electrodes, which can not only be used as a carrier for microbial growth, but also improve the electron transfer rate of the whole system. This paper reviews the constitution, advantages and basic principles of 3D-BERs as well as current research status and progress of 3D-BERs in recent years. The selection of electrode materials, including cathode, anode and particle electrode are listed and analyzed. Different constructions of reactors, like 3D-unipolar extended reactor and coupled 3D-BERs are introduced and discussed. Various contaminants degraded by 3D-BERs including nitrogen, azo dyes, antibiotics and the others are calculated and the corresponding degradation effects are described. The influencing factors and mechanisms are also introduced. At the same time, according to the research advances of 3D-BERs, the shortcomings and weakness of this technology in the current research process are analyzed, and the future research direction of this technology is prospected. This review aims to summarize recent studies of 3D-BERs in bio-electrochemical reaction and open a bright window to this booming research theme.

Tuning the intrinsic catalytic sites of magnetite to concurrently enhance the reduction of H2O2 and O2: Mechanism analysis and application potential evaluation.

Heterogeneous Fenton-like process based on H2O2 activation has been widely tested for water purification, but its application still faces some challenges such as the use of high doses of chemicals (including catalysts and H2O2). Herein, a facile co-precipitation method was utilized for small-scale production (∼50 g) of oxygen vacancies (OVs)-containing Fe3O4 (Vo-Fe3O4) for H2O2 activation. Experimental and theoretical results collaboratively verified that H2O2 adsorbed on the Fe site of Fe3O4 tended to lose electrons and generate O2•-. While the localized electron from OVs of Vo-Fe3O4 could assist in donating electrons to H2O2 adsorbed on OVs sites, this allowed more H2O2 to be activated to •OH, which was 3.5 folds higher than Fe3O4/H2O2 system. Moreover, the OVs sites promoted dissolved oxygen activation and decreased the quenching of O2•- by Fe(III), thus promoting the generation of 1O2. Consequently, the fabricated Vo-Fe3O4 achieved much higher oxytetracycline (OTC) degradation rate (91.6%) than Fe3O4 (35.4%) at a low catalyst (50 mg/L) and H2O2 dosage (2 mmol/L). Importantly, further integration of Vo-Fe3O4 into fixed-bed Fenton-like reactor could effectively eliminate OTC (>80%) and chemical oxygen demand (COD) (21.3%∼50%) within the running period. This study provides promising strategies for enhancing the H2O2 utilization of Fe mineral.

Transition Metal Single-Atom Catalysts for the Electrocatalytic Nitrate Reduction: Mechanism, Synthesis, Characterization, Application, and Prospects.

Excessive accumulation of nitrate in the environment will affect human health. To combat nitrate pollution, chemical, biological, and physical technologies have been developed recently. The researcher favors electrocatalytic reduction nitrate reaction (NO3 RR) because of the low post-treatment cost and simple treatment conditions. Single-atom catalysts (SACs) offer great activity, exceptional selectivity, and enhanced stability in the field of NO3 RR because of their high atomic usage and distinctive structural characteristics. Recently, efficient transition metal-based SACs (TM-SACs) have emerged as promising candidates for NO3 RR. However, the real active sites of TM-SACs applied to NO3 RR and the key factors controlling catalytic performance in the reaction process remain ambiguous. Further understanding of the catalytic mechanism of TM-SACs applied to NO3 RR is of practical significance for exploring the design of stable and efficient SACs. In this review, from experimental and theoretical studies, the reaction mechanism, rate-determining steps, and essential variables affecting activity and selectivity are examined. The performance of SACs in terms of NO3 RR, characterization, and synthesis is then discussed. In order to promote and comprehend NO3 RR on TM-SACs, the design of TM-SACs is finally highlighted, together with the current problems, their remedies, and the way forward.

When biochar is involved in rhizosphere dissipation and plant absorption of pesticides: A meta-analysis.

Clarifying the influences of biochar input on the rhizosphere dissipation and plant absorption of pesticides is a crucial prerequisite for utilizing biochar in the restoration of pesticide-contaminated soils. Nevertheless, the application of biochar to pesticide-contaminated soils does not always achieve consistent results on the rhizosphere dissipation and plant absorption of pesticides. Under the new situation of vigorously promoting the application of biochar in soil management and carbon sequestration, a timely review is needed to further understand the key factors affecting biochar remediation of pesticide-contaminated soil. In this study, a meta-analysis was conducted utilizing variables from three dimensions of biochar, remediation treatment, and pesticide/plant type. The pesticide residues in soil and the pesticide uptake by plant were used as response variables. Biochar with high adsorption capacity can impede the dissipation of pesticides in soil and mitigate their absorption by plants. The specific surface area of biochar and the type of pesticide are critical factors that affect pesticide residues in soil and plant uptake, respectively. Applying biochar with high adsorption capacity, based on specific dosages and soil characteristics, is recommended for the remediation of continuously cultivated soil contaminated with pesticides. This article aims to provide a valuable reference and understanding for the application of biochar-based soil remediation technology and the treatment of pesticide pollution in soil.

Lysogenic bacteriophages encoding arsenic resistance determinants promote bacterial community adaptation to arsenic toxicity.

Emerging evidence from genomics gives us a glimpse into the potential contribution of lysogenic bacteriophages (phages) to the environmental adaptability of their hosts. However, it is challenging to quantify this kind of contribution due to the lack of appropriate genetic markers and the associated controllable environmental factors. Here, based on the unique transformable nature of arsenic (the controllable environmental factor), a series of flooding microcosms was established to investigate the contribution of arsM-bearing lysogenic phages to their hosts' adaptation to trivalent arsenic [As(III)] toxicity, where arsM is the marker gene associated with microbial As(III) detoxification. In the 15-day flooding period, the concentration of As(III) was significantly increased, and this elevated As(III) toxicity visibly inhibited the bacterial population, but the latter quickly adapted to As(III) toxicity. During the flooding period, some lysogenic phages re-infected new hosts after an early burst, while others persistently followed the productive cycle (i.e., lytic cycle). The unique phage-host interplay contributed to the rapid spread of arsM among soil microbiota, enabling the quick recovery of the bacterial community. Moreover, the higher abundance of arsM imparted a greater arsenic methylation capability to soil microbiota. Collectively, this study provides experimental evidence for lysogenic phages assisting their hosts in adapting to an extreme environment, which highlights the ecological perspectives on lysogenic phage-host mutualism.

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.

Spatial confinement: A green pathway to promote the oxidation processes for organic pollutants removal from water.

Organic pollutants removal from water is pressing owing to the great demand for clean water. Oxidation processes (OPs) are the commonly used method. However, the efficiency of most OPs is limited owing to the poor mass transfer process. Spatial confinement is a burgeoning way to solve this limitation by use of nanoreactor. Spatial confinement in OPs would (i) alter the transport characteristics of protons and charges; (ii) bring about molecular orientation and rearrangement; (iii) cause the dynamic redistribution of active sites in catalyst and reduce the entropic barrier that is high in unconfined space. So far, spatial confinement has been utilized for various OPs, such as Fenton, persulfate, and photocatalytic oxidation. A comprehensive summary and discussion on the fundamental mechanisms of spatial confinement mediated OPs is needed. Herein, the application, performance and mechanisms of spatial confinement mediated OPs are overviewed firstly. Subsequently, the features of spatial confinement and their effects on OPs are discussed in detail. Furthermore, environmental influences (including environmental pH, organic matter and inorganic ions) are studied with analyzing their intrinsic connection with the features of spatial confinement in OPs. Lastly, challenges and future development direction of spatial confinement mediated OPs are proposed.

Insight into the effect of pyrolysis temperature on photoreactivity of biochar-derived dissolved organic matter: Impacts of aromaticity and carbonyl groups.

Practical application of biochar may result in more biochar-derived dissolved organic matter (denoted as BDOM) inevitably release into surface waters by infiltration and surface runoff. The photochemical reaction of BDOM has gained intense attention, which played a key role in the fate of organic contaminants. However, the relationships between specific characteristics of BDOM and its photoreactivity are still uncertain. In this study, the characteristics of BDOM pyrolyzed from rice husk derived biochar at different temperature (from 400 °C to 700 °C) and their effect on the photodegradation of oxytetracycline (OTC) were carefully investigated. The 13C NMR and EEM results indicated the dominated component of BDOM was gradually turned from humic acid like substances with low aromaticity to high aromaticity with abundant oxygen-containing functional groups as pyrolytic temperature increases. Experimental results showed that the apparent rate constants (kobs) of BDOM700 (4.53 × 10-2 min-1) for OTC photodegradation was approximately one order of magnitude higher than BDOM400 (4.52 × 10-3 min-1), which was closely correlated with their aromaticity (R2 = 0.944). It was found that 3BDOM* rather than 1O2 played the major role in BDOM mediated photodegradation of OTC (80.13 % vs 14.34 %), and the carbonyl-containing group was identified as the main 3BDOM* precursor by NaBH4 reduction experiment. This work highlighted both aromaticity and carbonyl group contents were critical indicators for assessing the potential to generate 3BDOM* and corresponding photoreactivity.

Rational design of cobalt sulfide anchored on nitrogen-doped carbon derived from cyanobacteria waste enables efficient activation of peroxymonosulfate for organic pollutants oxidation.

With the increasing of eutrophication in water body, algae blooms have become one of the global environmental problems. The cyanobacteria waste has placed a severe burden on the environment and transforming cyanobacteria into functional materials may be a wise approach. Herein, cobaltous sulfide/nitrogen-doped biochar (N-BC/CoSx) composite was synthesized by pyrolysis of cyanobacteria waste. The N-BC/CoSx showed excellent performance in peroxymonosulfate (PMS) activation for enrofloxacin (ENR) degradation, which could remove more than 90% ENR within 60 min. The influencing factors of pH and catalyst dosage on ENR removal efficiency were studied. The N-BC/CoSx showed good recyclability in the cycle runs. The radicals (O2•-, OH andSO4•-) and the non-radical species (charge transfer and 1O2) were generated in the ENR degradation. The cycle of Co(II)/Co(III) m ay contribute to the radical generation process. This work proved that metal sulfide modified cyanobacteria biochar has a specific application value in water pollution control and provides a new method for resource utilization of cyanobacteria.

Structure-performance correlation guided cerium-based metal-organic frameworks: Superior adsorbents for fluoride removal in water.

Fluoride in the hydrosphere exceeds the standard, which could be critically hazardous to human health and the natural environment. The adsorption method is a mature and effective way to remove pollutants in water, including fluoride. In this study, we synthesized three kinds of cerium-based metal-organic frameworks (Ce-MOFs) with different structures and properties by modulating the organic ligands (i.e., trimesic acid (BTC), 1,2,4,5-benzenetetracarboxylic acid (PMA), and terephthalic acid (BDC)) via the solvothermal method. The adsorption kinetics of Ce-MOFs on fluoride well fit the pseudo second order model, and their adsorption isotherms also conform to Langmuir isothermal model. The thermodynamic study reveals that the adsorption process is a spontaneous endothermic reaction. The maximum saturated adsorption capacities of Ce-BTC, Ce-PMA, and Ce-BDC are 70.7, 159.6, and 139.5 mg g-1, respectively. Ce-MOFs have stable and excellent adsorption capacity at pH = 3-9. Coexisting anions (Cl-, SO42-, and NO3-) do not affect the performance of Ce-MOFs for fluoride removal. Moreover, Ce-MOFs also show their broad prospect as superior fluoride adsorbents because of their excellent performance and reusability in real water samples. Organic ligands have a remarkable influence on the defluoridation performance of Ce-MOFs. This work will provide a feasible idea for designing MOFs as superiors adsorbents for defluoridation.

Single atom Mn anchored on N-doped porous carbon derived from spirulina for catalyzed peroxymonosulfate to degradation of emerging organic pollutants.

Highly efficient single atom catalysts are critical to substantially promote for peroxymonosulfate (PMS) activation to organic pollutant degradation, but it remains a challenge at present. Herein, single atom Mn anchored on N-doped porous carbon (SA-Mn-NSC) was synthesized by ball milling of Mn-doped carbon nitride and spirulina biochar to dominantly activate PMS. The precursor of carbon nitride and spirulina possessed a strong coordinating capability for Mn(II), facilitating the formation of highly dispersed nitrogen-coordinated Mn sites (Mn-N4). The SA-Mn-NSC catalyst exhibited high activity and stability in the heterogeneous activation of PMS to degrade a wide range of pollutants within 10 min, showing an outstanding degradation rate constant of 0.31 min-1 in enrofloxacin (ENR) degradation. The high surface density of Mn-N4 sites and abundant interconnected meso-macro pores were highly favorable for activating PMS to produce 1O2 and high-valent manganese (Mn(IV)) for pollutant degradation. This work offers a new pathway of using a low-cost and easily accessible single-atom catalysts (SACs) and could inspire more catalytic oxidation strategies.

Effects of activated carbon, biochar, and carbon nanotubes on the heterogeneous Fenton oxidation catalyzed by pyrite for ciprofloxacin degradation.

Pyrite and engineering carbon materials have received increasing attention for their catalytic potential in Fenton reactions due to their extensive sources and low cost. However, effects of carbon materials on the degradation of pollutants by pyrite-catalyzed heterogeneous Fenton oxidation have not been fully understood. In this study, the performance of pyrite-catalyzed heterogeneous Fenton system on the degradation of ciprofloxacin (CIP) was investigated in the presence of activated carbon (AC), biochar (BC), and carbon nanotubes (CNTs). Synchronous and asynchronous experiments (adsorption and catalysis) were conducted to elucidate the roles of the carbon materials in pyrite-catalyzed Fenton reactions. The results demonstrated that all the three carbon materials accelerated the pyrite-catalyzed Fenton oxidation of CIP. Under the experimental conditions, the reaction rates, which were obtained by fitting the synchronous experimental results with the pseudo-first-order kinetic model, of pyrite/AC, pyrite/BC and pyrite/CNTs with H2O2 for the removal of CIP were 8.28, 3.40 and 3.37 times faster than that of pyrite alone. Adsorption experiments and characterization analysis showed that AC had a higher adsorption capacity than BC and CNTs for CIP, which enabled it to distinguish itself in assisting the pyrite-catalyzed Fenton oxidation. In the presence of the carbon materials, the adsorption effect should not be neglected when studying the catalytic performance of pyrite. Free radical quenching experiments and electron spin-resonance spectroscopy (ESR) were used to detect and identify free radical species in the reactions. The results showed that hydroxyl radicals (•OH) contributed significantly to the degradation of CIP. The addition of carbon materials promoted the production of •OH, which favored the degradation of CIP. The results of this study suggested that the synergistic effect of oxidation and adsorption promoted the removal of CIP in pyrite/carbon materials/H2O2 systems, and coupling pyrite and carbon materials shows great potential in treating antibiotic wastewater.

Processable Conjugated Microporous Polymer Gels and Monoliths: Fundamentals and Versatile Applications.

Conjugated microporous polymers (CMPs) as a new type of conjugated polymers have attracted extensive attention in academia and industry because of the combination of microporous structure and π-electron conjugated structure. The construction and application of gels and monoliths based on CMPs constitute a fertile area of research, promising to provide solutions to complex environmental and energy issues. This review summarizes and objectively analyzes the latest advances in the construction and application of processable CMP gels and monoliths, linking the basic and enhanced properties to widespread applications. In this review, we open with a summary of the construction methods used to build CMP gels and monoliths and assess the feasibility of different preparation techniques and the advantages of the products. The CMP gels and monoliths with enhanced properties involving various special applications are then deliberated by highlighting relevant scientific literature and discussions. Finally, we present the issues and future of openness in the field, as well as come up with the major challenges hindering further development, to guide researchers in this field.