Carbon Dots-Decorated Carbon-Based Metal-Free Catalysts for Electrochemical Energy Storage.

In the past ten years, carbon dots-decorated, carbon-based, metal-free catalysts (CDs-C-MFCs) have become the fastest-growing branch in the metal-free materials for energy storage field. However, the further development of CDs-C-MFCs needs to clear up the electronic transmission mechanism rather than primarily relying on trial-and-error approaches. This review presents systematically and comprehensively for the first time the latest advances of CDs-C-MFCs in supercapacitors and metal-air batteries. The structure-performance relationship of these materials is carefully discussed. It is indicated that carbon dots (CDs) can act as the electron-rich regions in CDs-C-MFCs owing to their unique properties, such as quantum confinement effects, abundant defects, countless functional groups, etc. More importantly, specific doping can effectively modify the charge/spin distribution and then facilitate electron transfer. In addition, present challenges and future prospects of the CDs-C-MFCs are also given.

MXenes as Superexcellent Support for Confining Single Atom: Properties, Synthesis, and Electrocatalytic Applications.

Single atom catalysts (SACs) have shown their noticeable potential and gradually become a new favorite in catalytic field due to the particular selectivity, high catalytic performance, and strong durability. The most important factor in the synthesis of SACs is the selection of appropriate support and formation of metal-support interaction. Among a large number of nanomaterials, MXenes can be utilized as benign supports for fixing SACs because of their expansive specific surface area, regulable bandgap, superior electronic conductivity, and strong mechanical stability. The structure and property of MXenes can be manipulated by changing transition metal elements and surface termination. Here, the uniqueness and superiority of MXenes as superexcellent supports for confining SACs are analyzed from structure and property. The synthetic strategy of MXene-supported SACs is also summarized, especially emphasizing the immobilization of isolated atom against aggregation by utilizing the formidable metal-support covalent coordination interaction. In addition, the applications of MXene-supported SACs in electrocatalytic field are highlighted, including hydrogen evolution reaction, oxygen evolution reaction, overall water splitting, oxygen reduction reaction, and nitrogen reduction reaction. Finally, the challenges and prospects are pointed out for the further understanding and practical application of MXene-supported SACs in electrocatalysis.

Boron nitride quantum dots decorated MIL-100(Fe) for boosting the photo-generated charge separation in photocatalytic refractory antibiotics removal.

Metal organic frameworks (MOFs) have great potential for photocatalysis, but only possess moderate activity due to their slow charge transfer and low solar energy conversion. Herein, heterostructures photocatalysts constructed by boron nitride quantum dots (BNQDs) and MIL-100(Fe) (MNB) were successfully fabricated for overcoming these shortcomings. It was indicated that the composites possessed large surface area, mesoporous structure, and enhanced visible light absorption. The MNB photocatalysts exhibited excellent photocatalytic activity for tetracycline hydrochloride (TC-HCl) degradation under visible light irradiation. Compared with MIL-100(Fe), the photodegradation rate of TC-HCl by MNB-1 was 0.02383 min-1, which was 5.3 times higher than that of pure MIL-100(Fe). The close contact of MIL-100(Fe) with BNQDs and the synergistic effect between them were the main reasons for the improved photodegradation performance. This study reveals that a rational combination of MIL-100(Fe) and BNQDs can improve photocatalytic activity to enhance molecular oxygen activation. Therefore, it is reasonable to believe that quantum dots/MOFs photocatalysts have great potential in environmental remediation.

Recent development of advanced biotechnology for wastewater treatment.

The importance of highly efficient wastewater treatment is evident from aggravated water crises. With the development of green technology, wastewater treatment is required in an eco-friendly manner. Biotechnology is a promising solution to address this problem, including treatment and monitoring processes. The main directions and differences in biotreatment process are related to the surrounding environmental conditions, biological processes, and the type of microorganisms. It is significant to find suitable biotreatment methods to meet the specific requirements for practical situations. In this review, we first provide a comprehensive overview of optimized biotreatment processes for treating wastewater during different conditions. Both the advantages and disadvantages of these biotechnologies are discussed at length, along with their application scope. Then, we elaborated on recent developments of advanced biosensors (i.e. optical, electrochemical, and other biosensors) for monitoring processes. Finally, we discuss the limitations and perspectives of biological methods and biosensors applied in wastewater treatment. Overall, this review aims to project a rapid developmental path showing a broad vision of recent biotechnologies, applications, challenges, and opportunities for scholars in biotechnological fields for "green" wastewater treatment.

Recent advances in covalent organic frameworks (COFs) as a smart sensing material.

As a newly emerging kind of porous material, covalent organic frameworks (COFs) have drawn much attention because of their fascinating structural features (e.g., divinable structure, adjustable porosity and total organic backbone). Since the seminal work of Yaghi and co-workers reported in 2005, the COF materials have shown superior potential in diverse applications, such as gas storage, adsorption, optoelectronics, catalysis, etc. Recently, COF materials have shown a new trend in sensing fields. This critical review briefly describes the synthesis routes for COF powders and thin films. What's more, the most fascinating and significant applications of COFs in sensing fields including explosive sensing, humidity sensing, pH detection, biosensing, gas sensing, metal ion sensing, and other substance sensing are summarized and highlighted. Finally, the major challenges and future trends of COFs with respect to their preparation and sensing applications are discussed.

Peroxidase-Like Activity of Smart Nanomaterials and Their Advanced Application in Colorimetric Glucose Biosensors.

Diabetes is a dominating health issue with 425 million people suffering from the disease worldwide and 4 million deaths each year. To avoid further complications, the diabetic patient blood glucose level should be strictly monitored despite there being no cure for diabetes. Colorimetric biosensing has attracted significant attention because of its low cost, simplicity, and practicality. Recently, some nanomaterials have been found that possess unexpected peroxidase-like activity, and great advances have been made in fabricating colorimetric glucose biosensors based on the peroxidase-like activity of these nanomaterials using glucose oxidase. Compared with natural horseradish peroxidase, the nanomaterials exhibit flexibility in structure design and composition, and have easy separation and storage, high stability, simple preparation, and tunable catalytic activity. To highlight the significant progress in the field of nanomaterial-based peroxidase-like activity, this work discusses the various smart nanomaterials that mimic horseradish peroxidase and its mechanism and development history, and the applications in colorimetric glucose biosensors. Different approaches for tunable peroxidase-like activity of nanomaterials are summarized, such as size, morphology, and shape; surface modification and coating; and metal doping and alloy. Finally, the conclusion and challenges facing peroxidase-like activity of nanomaterials and future directions are discussed.

Black Phosphorus, a Rising Star 2D Nanomaterial in the Post-Graphene Era: Synthesis, Properties, Modifications, and Photocatalysis Applications.

Semiconductor photocatalysis, a sustainable and renewable technology, is deemed to be a new path to resolve environmental pollution and energy shortage. The development of effective photocatalysts, especially the metal-free photocatalysts, is a critical determinant of this technique. The recently emerged 2D material of black phosphorus with distinctive properties of tunable direct bandgap, ultrahigh charge mobility, fortified optical absorption, large specific surface area, and anisotropic structure has captured enormous attention since the first exfoliation of bulk black phosphorus into mono- or few layered phosphorene in 2014. In this article, the state-of-the-art preparation methods are first summarized for bulk black phosphorus, phosphorene, and black phosphorus quantum dot and then the fundamental structure and electronic and optical properties are analyzed to evaluate its feasibility as a metal-free photocatalyst. Various modifications on black phosphorus are also summarized to enhance its photocatalytic performance. Furthermore, the multifarious applications such as solar to energy conversion, organic removal, disinfection, nitrogen fixation, and photodynamic therapy are discussed and some of the future challenges and opportunities for black phosphorus research are proposed. This review reveals that the rising star of black phosphorus will be a multifunctional material in the postgraphene era.

Electrochemical biosensor for amplified detection of Pb2+ based on perfect match of reduced graphene oxide-gold nanoparticles and single-stranded DNAzyme.

In this study, a sensitive amplification strategy for Pb2+ detection using reduced graphene oxide (RGO) and gold nanoparticles (AuNPs) was proposed. Thiol-modified DNAzyme is specific for Pb2+ self-assembly on RGO-AuNPs-modified electrode surface. Ferrocene labeled single-stranded DNAzyme (Fc-ssDNAzyme) self-hybridizes to form a DNA hairpin structure. The amount of Fc adsorbed on the electrode surface changes after the appearance of Pb2+, leading to a change of electrical signal. This change can be sensitively identified by differential pulse voltammetry (DPV) assisted by ferricyanide ([Fe(CN)6]3-/4-) in the electrolyte. The high conductivity and specific surface area of RGO and the strong chemical bond adsorption effect between DNAzyme and AuNPs are responsible for the amplified detection of Pb2+, which realize a detection range of 0.05-400,000.0 nM and a minimum detection limit of 0.015 nM. Moreover, the selectivity test results indicated that the biosensor had specificity for Pb2+, even if there was interference from other high-concentration metal ions. This simple biosensor also exhibited good responsiveness in actual sample detection, which provides a good application prospect for field detection of Pb2+ in water. Graphical abstract.

Colorimetric determination of mercury(II) using gold nanoparticles and double ligand exchange.

A colorimetric assay is described for highly selective and sensitive determination of Hg(II) ions by using gold nanoparticles (AuNPs) functionalized with dithioerythritol (DETL). This method relies on the unique optical properties of DETL-functionalized AuNPs as well as the thiophilicity of both AuNPs and Hg(II). In the presence of DETL, the AuNPs aggregate due to ligand exchange between thiol groups of DETL and the citrate ions on the surface of AuNPs. This induces a color change from red to blue. On addition of Hg(II), the thiol groups preferably interact with Hg(II) rather than with AuNPs. Thus, the DETL is released from the surface of the AuNPs and binds to Hg(II). This triggers the redispersion of the AuNPs. The ratio of absorbances at 650 and 525 nm drops linearly in two Hg(II) concentration ranges (viz. from 0.1 to 0.5 µM, and from 0.5 to 5 µM). The ions Cu(II), Pb(II), and Cd(II) do not interfere even in the absence of masking agents. The detection limit is as low as 24 nM. Graphical abstract A highly selective colorimetric method based on gold nanoparticles via double ligand exchange reaction is described for determination of Hg2+. This assay can selective detect Hg2+ with no response to major interfering metal ions such as Cu2+, Pb2+, and Cd2+ in the absence of masking agents compared with previous works.

Microplastic-derived dissolved organic matter: Generation, characterization, and environmental behaviors.

Microplastics (MPs) represent a substantial and emerging class of pollutants distributed widely in various environments, sparking growing concerns about their environmental impact. In environmental systems, dissolved organic matter (DOM) is crucial in shaping the physical, chemical, and biological processes of pollutants while significantly contributing to the global carbon budget. Recent findings have revealed that microplastic-derived dissolved organic matter (MP-DOM) constitutes approximately 10 % of the DOM present on the ocean surface, drawing considerable attention. Hence, this study's primary objective is to explore, the generation, characterization, and environmental behaviors of MP-DOM. The formation and characteristics of MP-DOM are profoundly influenced by leaching conditions and types of MPs. This review delves into the mechanisms of the generation of MP-DOM and provides an overview of a wide array of analytical techniques, including ultraviolet-visible (UV-Vis) spectroscopy, fluorescence spectroscopy, Fourier transform infrared spectroscopy (FTIR), and mass spectroscopy, used to assess the MP-DOM characteristics. Furthermore, this review investigates the environmental behaviors of MP-DOM, including its impacts on organisms, photochemical processes, the formation of disinfection by-products (DBPs), adsorption behavior, and its interaction with natural DOM. Finally, the review outlines research challenges, perspectives for future MP-DOM research, and the associated environmental implications.

Single cobalt atom anchored on carbon nitride with cobalt nitrogen/oxygen active sites for efficient Fenton-like catalysis.

As one of the tactics to produce reactive oxygen radicals, the Fenton-like process has been widely developed to solve the increasingly severe problem of environmental pollution. However, establishing advanced mediators with sufficient stability and activity for practical application is still a long-term objective. Herein, we proposed a facile strategy through polymeric carbon nitride (pCN) in-situ growth single cobalt atom for efficient degradation of antibiotics by peroxymonosulfate (PMS) activation. X-ray absorption spectroscopy and high-angle annular dark field-scanning transmission electron microscopy prove the single cobalt atoms are successfully anchored on pCN. Moreover, extended X-ray absorption fine structure analysis shows that the embedded cobalt atoms are constructed by covalently forming the Co-N bond and Co-O bond, which endow the single-atom cobalt catalyst with high stability. Experiment results indicate that the prepared single-atom cobalt catalyst can be used for efficient PMS activation catalytic degradation of tetracycline with a high degradation rate of 98.7 % in 60 min. And the CoN/O sites with single cobalt atoms serve as the active site for generating active radical species (singlet oxygen) from PMS activation. This work may expand the strategy for constructing single-atom catalysts and extend its application for the advanced oxidation process.

Surface functional groups and biofilm formation on microplastics: Environmental implications.

Microplastics (MPs) contamination is becoming a significant environmental issue, as the widespread omnipresence of MPs can cause many adverse consequences for both ecological systems and humans. Contrary to what is commonly thought, the toxicity-inducing MPs are not the original pristine plastics; rather, they are completely transformed through various surface functional groups and aggressive biofilm formation on MPs via aging or weathering processes. Therefore, understanding the impacts of MPs' surface functional groups and biofilm formation on biogeochemical processes, such as environmental fate, transport, and toxicity, is crucial. In this review, we present a comprehensive summary of the distinctive impact that surface functional groups and biofilm formation of MPs have on their significant biogeochemical behavior in various environmental media, as well as their toxicity and biological effects. We place emphasis on the role of surface functional groups and biofilm formation as a means of influencing the biogeochemical processes of MPs. This includes their effects on pollutant fate and element cycling, which in turn impacts the aggregation, transport, and toxicity of MPs. Ultimately, future research studies and tactics are needed to improve our understanding of the biogeochemical processes that are influenced by the surface functional groups and biofilm formation of MPs.

Phage-host interactions: The neglected part of biological wastewater treatment.

In wastewater treatment plants (WWTPs), the stable operation of biological wastewater treatment is strongly dependent on the stability of associated microbiota. Bacteriophages (phages), viruses that specifically infect bacteria and archaea, are highly abundant and diverse in WWTPs. Although phages do not have known metabolic functions for themselves, they can shape functional microbiota via various phage-host interactions to impact biological wastewater treatment. However, the developments of phage-host interaction in WWTPs and their impact on biological wastewater treatment are overlooked. Here, we review the current knowledge regarding the phage-host interactions in biological wastewater treatment, mainly focusing on the characteristics of different phage populations, the phage-driven changes in functional microbiota, and the potential driving factors of phage-host interactions. We also discuss the efforts required further to understand and manipulate the phage-host interactions in biological wastewater treatment. Overall, this review advocates more attention to the phage dynamics in WWTPs.

Swift reduction of nitroaromatics by gold nanoparticles anchored on steam-activated carbon black via simple preparation.

Gold (Au) nanoparticles supported on certain platforms display highly efficient activity on nitroaromatics reduction. In this study, steam-activated carbon black (SCB) was used as a platform to fabricate Au/SCB composites via a green and simple method for 4-nitrophenol (4-NP) reduction. The obtained Au/SCB composites exhibit efficient catalytic performance in reduction of 4-NP (rate constant kapp = 2.1925 min-1). The effects of SCB activated under different steam temperature, Au loading amount, pH, and reaction temperature and NaBH4 concentration were studied. The structural advantages of SCB as a platform were analyzed by various characterizations. Especially, the result of N2 adsorption-desorption method showed that steam activating process could bring higher surface area (from 185.9689 to 249.0053 m2/g), larger pore volume (from 0.073268 to 0.165246 cm3/g), and more micropore for SCB when compared with initial CB, demonstrating the suitable of SCB for Au NP anchoring, thus promoting the catalytic activity. This work contributes to the fabrication of other supported metal nanoparticle catalysts for preparing different functional nanocomposites for different applications.

Recent progress of noble metals with tailored features in catalytic oxidation for organic pollutants degradation.

With the increasing serious water pollutions, an increasing interest has given for the nanocomposites as environmental catalysts. To date, noble metals-based nanocomposites have been extensively studied by researchers in environmental catalysis. In detail, serving as key functional parts, noble metals are usually combined with other nanomaterials for rationally designing nanocomposites, which exhibit enhanced catalytic properties in pollutants removal. Noble metals in the nanocomposites possess tailored properties, thus playing different important roles in catalytic oxidation reactions for pollutants removal. To motivate the research and elaborate the progress of noble metals, this review (i) summarizes advanced characterization techniques and rising technology of theoretical calculation for evaluating noble metal, and (ii) classifies the roles according to their disparate mechanism in different catalytic oxidation reactions. Meanwhile, the enhanced mechanism and influence factors are discussed. (iii) The conclusions, facing challenges and perspectives are proposed for further development of noble metals-based nanocomposites as environmental catalysts.

Activation of persulfate by swine bone derived biochar: Insight into the specific role of different active sites and the toxicity of acetaminophen degradation pathways.

Recently, persulfate (PS) activation system has grown up as a primary branch of advanced oxidation processes, and biochar has been recognized as a potential nonmetal material in this field. However, few studies have focused on the corresponding relationship between actives sites on biochar and active species in AOPs. To pave this way, similar biochar (obtained from different pyrolysis temperature) with different functional structures were involved. In this study, biochar derived from swine bone (BBC) was applied in PS activation system to degrade acetaminophen (ACT). The results showed that both radical and non-radical pathway worked in the PS/BBCs systems, and the degradation rate (from 0.1042 to 0.4364 min-1) climbed with the increase of pyrolysis temperature (from 700 to 900 °C). To probe into the corresponding relationship between functional structure and active species, the effect of pyrolysis temperature on functional structure was analyzed. It came out that 1) defects could act as active sites for various active species; 2) persistent free radicals could do favor to the generation of 1O2 and O2-; 3) hydroxyapatite in swine bone only served as hard templet for the porous structure. ACT degradation process was measured by Liquid chromatograph-mass spectrometer, and Scendesmus obliquus was applied to investigate the toxicity of PS/BBCs system. It illustrated that the existence of SO4- mainly contributed to the generation of high toxic intermediates (such as biphenyl and diphenyl ether) in the PS/BBCs system. Furthermore, the enhancement of adsorption capacity would mitigate the toxicity of PS/BBCs systems to some extent.

Oxygen vacancy-rich doped CDs@graphite felt-600 heterostructures for high-performance supercapacitor electrodes.

Carbon dots (CDs) have attracted much attention owing to their distinctive 0D chemical structure, ultra-small size, and intrinsic surface/edge defects, and have been widely used in many kinds of research fields. In this work, a facile method to synthesize an oxygen vacancy-rich doped CDs@graphite felt-600 heterostructure with outstanding electrochemical properties is presented. The electron spin resonance (ESR) provides clear evidence for the existence of abundant oxygen vacancies in the CDs@graphite felt-600 heterostructure. The as-synthesized CDs@graphite felt-600 shows superior areal specific capacitance (5.99 F cm-2), due to abundant oxygen vacancies and extensive surface/edge defects in the heterostructure. In addition, a home-made coin cell supercapacitor (SC) with CDs@graphite felt-600 as the electrode delivers a large areal energy density of 20.7 µW h cm-2 at a power density of 150.0 µW cm-2. To determine the charge storage mechanism at the interface of CDs@graphite felt-600, the binding energies between the CDs and graphite felt are calculated by density functional theory (DFT).

Enhancing iron redox cycling for promoting heterogeneous Fenton performance: A review.

Conventional water treatment methods are difficult to remove stubborn pollutants emerging from surface water. Advanced oxidation processes (AOPs) can achieve a higher level of mineralization of stubborn pollutants. In recent years, the Fenton process for the degradation of pollutants as one of the most efficient ways has received more and more attention. While homogeneous catalysis is easy to produce sludge and the catalyst cannot be cycled. In contrast, heterogeneous Fenton-like reaction can get over these drawbacks and be used in a wider range. However, the reduction of Fe (III) to Fe(II) by hydrogen peroxide (H2O2) is still the speed limit step when generating reactive oxygen species (ROS) in heterogeneous Fenton system, which restricts the efficiency of the catalyst to degrade pollutants. Based on previous research, this article reviews the strategies to improve the iron redox cycle in heterogeneous Fenton system catalyzed by iron materials. Including introducing semiconductor, the modification with other elements, the application of carbon materials as carriers, the introduction of metal sulfides as co-catalysts, and the direct reduction with reducing substances. In addition, we also pay special attention to the influence of the inherent properties of iron materials on accelerating the iron redox cycle. We look forward that the strategy outlined in this article can provide readers with inspiration for constructing an efficient heterogeneous Fenton system.

Stabilization of lead in polluted sediment based on an eco-friendly amendment strategy: Microenvironment response mechanism.

Stabilization is the most important remediation mechanisms for sediment polluted heavy metals. However, little research has been done on the identification of microenvironmental response and internal correlation, as well as synergistic mechanisms during heavy metal remediation. This study aims to investigate the inner response mechanisms of microenvironment after the lead (Pb) are gradually stabilized in sediment. An eco-friendly amendment strategy which firstly used 100% biodegradable sophorolipids (SOP) to modify chlorapatite (ClAP) for the fabrication of SOP@nClAP was applied in this study. The stabilization efficiency of Pb was significantly improved by SOP@nClAP compared with ClAP. Most importantly, the high-throughput sequencing showed that the dominant species in the sediment changed with the stabilization of Pb. The decrease of Proteobacteria and increase of Firmicutes, especially the Sedimentibacter within the phylum Firmicute directly suggested that large amounts of Pb were stabilized. This research is not only devoted to stabilize Pb in sediment by eco-friendly amendment strategy, but also keep a watchful eye on microenvironment response mechanisms during the Pb stabilization in sediment. Therefore, this study lays a foundation for the future application of more heavy metal amendment strategies in the sediment environment and improves the possibility of large-scale site amendment.

Critical review of advanced oxidation processes in organic wastewater treatment.

With the development of industrial society, organic wastewater produced by industrial manufacturing has caused many environmental problems. The vast majority of organic pollutants in water bodies are persistent in the environment, posing a threat to human and animal health. Therefore, efficient treatment methods for highly concentrated organic wastewater are urgently needed. Advanced oxidation processes (AOPs) are widely noticed in the area of treating organic wastewater. Compared with other chemical methods, AOPs have the characteristics of high oxidation efficiency and no secondary pollution. In this paper, the mechanisms, advantages, and limitations of AOPs are comprehensively reviewed. Besides, the basic principles of combining different AOPs to enhance the treatment efficiency are described. Furthermore, the applications of AOPs in various wastewater treatments, such as oily wastewater, dyeing wastewater, pharmaceutical wastewater, and landfill leachate, are also presented. Finally, we conclude that the main direction in the future of AOPs are the modification of catalysts and the optimization of operating parameters, with the challenges focusing on industrial applications.