Facile introduction of coordinative Fe into oxygen-enriched graphite carbon nitride for efficient photo-Fenton degradation of tetracycline.

Tetracycline (TC) antibiotics have been widely used over the past decades, and their massive discharge led to serious water pollution. Photo-Fenton process has gained ever-increasing attention for its excellent oxidizing ability and friendly solar energy utilization ability in TC polluted water treatment. This work introduced coordinative Fe into oxygen-enriched graphite carbon nitride (OCN) to form FeOCN composites for efficient photo-Fenton process. Hemin was chosen as the source to provide the source of coordinative Fe-Nx groups. The degradation efficiency of TC reached 82.1 % within 40 min of irradiation, and remained 76.9 % after five runs of reaction. The degradation intermediates of TC were detected and the possible degradation pathways were gained. It was found that h+, OH, and O2- played major roles in TC degradation. Notably, the photo-Fenton performance of FeOCN was stable in highly saline water or strong acid/base environment (pH 3.0-9.0). Besides, H2O2 can be generated in-situ in this photo-Fenton process, which is favorable for practical application. It can be anticipated that the coordinative FeOCN composites will promote the application of photo-Fenton oxidation process in TC polluted water treatment.

Copper Single-Atom Catalysts-A Rising Star for Energy Conversion and Environmental Purification: Synthesis, Modification, and Advanced Applications.

Future renewable energy supply and green, sustainable environmental development rely on various types of catalytic reactions. Copper single-atom catalysts (Cu SACs) are attractive due to their distinctive electronic structure (3d orbitals are not filled with valence electrons), high atomic utilization, and excellent catalytic performance and selectivity. Despite numerous optimization studies are conducted on Cu SACs in terms of energy conversion and environmental purification, the coupling among Cu atoms-support interactions, active sites, and catalytic performance remains unclear, and a systematic review of Cu SACs is lacking. To this end, this work summarizes the recent advances of Cu SACs. The synthesis strategies of Cu SACs, metal-support interactions between Cu single atoms and different supports, modification methods including modification for carriers, coordination environment regulating, site distance effect utilizing, and dual metal active center catalysts constructing, as well as their applications in energy conversion and environmental purification are emphatically introduced. Finally, the opportunities and challenges for the future Cu SACs development are discussed. This review aims to provide insight into Cu SACs and a reference for their optimal design and wide application.

Strategies for Enhancing the Photocatalytic and Electrocatalytic Efficiency of Covalent Triazine Frameworks for CO2 Reduction.

Converting carbon dioxide (CO2) into fuel and high-value-added chemicals is considered a green and effective way to solve global energy and environmental problems. Covalent triazine frameworks (CTFs) are extensively utilized as an emerging catalyst for photo/electrocatalytic CO2 reduction reaction (CO2RR) recently recognized for their distinctive qualities, including excellent thermal and chemical stability, π-conjugated structure, rich nitrogen content, and a strong affinity for CO2, etc. Nevertheless, single-component CTFs have the problems of accelerated recombination of photoexcited electron-hole pairs and restricted conductivity, which limit their application for photo/electrocatalytic CO2RR. Therefore, emphasis will then summarize the strategies for enhancing the photocatalytic and electrocatalytic efficiency of CTFs for CO2RR in this paper, including atom doping, constructing a heterojunction structure, etc. This review first illustrates the synthesis strategies of CTFs and the advantages of CTFs in the field of photo/electrocatalytic CO2RR. Subsequently, the mechanism of CTF-based materials in photo/electrocatalytic CO2RR is described. Lastly, the challenges and future prospects of CTFs in photo/electrocatalytic CO2RR are addressed, which offers a fresh perspective for the future development of CTFs in photo/electrocatalytic CO2RR.

Strategies for improving the stability of perovskite for photocatalysis: A review of recent progress.

Photocatalysis is currently a hot research field, which provides promising processes to produce green energy sources and other useful products, thus eventually benefiting carbon emission reduction and leading to a low-carbon future. The development and application of stable and efficient photocatalytic materials is one of the main technical bottlenecks in the field of photocatalysis. Perovskite has excellent performance in the fields of photocatalytic hydrogen evolution reaction (HER), oxygen evolution reaction (OER), carbon dioxide reduction reaction (CO2RR), organic synthesis and pollutant degradation due to its unique structure, flexibility and resulting excellent photoelectric and catalytic properties. The stability problems caused by perovskite's susceptibility to environmental influences hinder its further application in the field of photocatalysis. Therefore, this paper innovatively summarizes and analyzes the existing methods and strategies to improve the stability of perovskite in the field of photocatalysis. Specifically, (i) component engineering, (ii) morphological control, (iii) hybridization and encapsulation are thought to improve the stability of perovskites while improving photocatalytic efficiency. Finally, the challenges and prospects of perovskite photocatalysts are discussed, which provides constructive thinking for the potential application of perovskite photocatalysts.

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.

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.

Ultrahigh Performance H2 O2 Generation by Single-Atom Fe Catalysts with N/O Bidentate Ligand via Oxalic Acid and Oxygen Molecules Activation.

Single-atom catalysts (SACs) for photocatalytic hydrogen peroxide (H2 O2 ) generation are researched but it is still challenging to obtain high H2 O2 yields. Herein, graphite carbon nitride (FeSA /CN) confined single Fe atoms with N/O coordination is prepared, and FeSA /CN shows high H2 O2 production via oxalic acid and O2 activation. Under visible light illumination, the concentration of H2 O2 generated by FeSA /CN can achieve 40.19 mM g-1 h-1 , which is 10.44 times higher than that of g-C3 N4 . The enhanced H2 O2 generation can be attributed to the formation of metal-organic complexes and rapid electron transfer. Moreover, the O2 activation of photocatalysts is revealed by 3,3',5,5'-tetramethylbenzidine oxidation. The results display that the O2 activation capacity of FeSA /CN is higher than that of g-C3 N4 , which facilitates the formation of H2 O2 . Finally, density functional theory calculation demonstrates that O2 is chemically adsorbed on Fe atomic sites. The adsorption energy of O2 is enhanced from -0.555 to -1.497 eV, and the bond length of OO is extended from 1.235 to 1.292 Å. These results exhibit that the confinement of single Fe atoms can promote O2 adsorption and activation. Finally, the photocatalytic mechanism is elaborated, which provides a deep understanding for SACs-catalyzed H2 O2 generation.

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.

Constructing functional metal-organic frameworks by ligand design for environmental applications.

Metal-organic frameworks (MOFs) with unique physical and chemical properties are composed of metal ions/clusters and organic ligands, including high porosity, large specific surface area, tunable structure and functionality, which have been widely used in chemical sensing, environmental remediation, and other fields. Organic ligands have a significant impact on the performance of MOFs. Selecting appropriate types, quantities and properties of ligands can well improve the overall performance of MOFs, which is one of the critical issues in the synthesis of MOFs. This article provides a comprehensive review of ligand design strategies for functional MOFs from the number of different types of organic ligands. Single-, dual- and multi-ligand design strategies are systematically presented. The latest advances of these functional MOFs in environmental applications, including pollutant sensing, pollutant separation, and pollutant degradation are further expounded. Furthermore, an outlook section of providing some insights on the future research problems and prospects of functional MOFs is highlighted with the purpose of conquering current restrictions by exploring more innovative approaches.

Peroxydisulfate activation by sulfur-doped ordered mesoporous carbon: Insight into the intrinsic relationship between defects and 1O2 generation.

The carbon-catalyzed persulfate-based advanced oxidation process (PS-AOP) has recently received much focus owing to the green, economical, and sustainable nature of carbon catalysts. In this study, sulfur-doped ordered mesoporous carbons (S-OMCs) were utilized to activate peroxydisulfate (PDS) for ciprofloxacin (CIP) removal. A synthesis temperature gradient was set to regulate the defect level of S-OMCs, since the thermal decomposition of oxygen- and sulfur-containing groups at different temperatures could release S and O and then create defects. In all S-OMCs/PDS systems, 1O2 dominated CIP degradation. Interestingly, a high linear correlation (R2 = 0.9091) between defect level and 1O2 yield was found, confirming the structure-activity relationship between defects and 1O2 generation. Moreover, the impacts of several important reaction conditions and water matrix on S-OMC-1000/PDS activation system were surveyed. In the S-OMC-1000/PDS activation system, CIP removal could attain 85.84% under the condition of unadjusted pH (pH = 5.3) and small amount of S-OMC-1000 (50 mg/L). The S-OMC-1000/PDS activation system also exhibited relatively stable or even better performance in the presence of common inorganic anions and natural organic matter (NOM), manifesting its good potential for practical applications. In addition, the reusability of S-OMC-1000 was investigated. This study provides a practical and high-efficiency way for decontaminating antibiotic-polluted water, and gives an alternative approach for identifying the active site of catalysts.

Degradation of tetracycline by FeNi-LDH/Ti3C2 photo-Fenton system in water: From performance to mechanism.

Recently, photo-Fenton technology has been widely used to degrade tetracycline (TC) because of its great efficiency and wide application range. Herein, Fe-Ni layered double hydroxides (FeNi-LDH)/Ti3C2 photo-Fenton system was constructed in this study. The results showed the introduction of Ti3C2 solved some problems of FeNi-LDH such as poor conductivity, easy aggregation, and high recombination rate of photoelectron. Benefiting from these advantages, FeNi-LDH/Ti3C2 exhibited excellent TC removal rate of 94.7% while pure FeNi-LDH was only 54%. Besides, FeNi-LDH/Ti3C2 possessed strong pH tolerance (2-11) and the removal efficiency was still up to 82% after the four-cycle experiment. Furthermore, the quenching experiments revealed the reaction mechanism, where ∙OH and ·O2- were the primary active radicals for degrading TC. Last, the results of the simulated wastewater treatment and the inorganic ion interference tests showed that FeNi-LDH/Ti3C2 possessed practical application potential. In brief, this study shows that FeNi-LDH/Ti3C2 can offer a certain theoretical basis for the actual development of hydrotalcite in heterogeneous photo-Fenton systems.

Synergistic effect of flower-like MnFe2O4/MoS2 on photo-Fenton oxidation remediation of tetracycline polluted water.

In this work, a flower-like MnFe2O4-MoS2 (FMW) catalyst was successfully prepared as a catalyst for photo-Fenton oxidation. The flower-like structured FMW possessed large open surface area, which exposed enough active sites and can fully contact with tetracycline (TC). We studied the effect of different FMW composites, H2O2 concentration and light intensity on the photo-Fenton process. 1FMW (MnFe2O4:MoS2 = 1:10 in mol) exhibited the best degradation effect on TC, and 1 mmol/L of H2O2 and 398.73 mW/cm2 of light were the optimum parameters. A p-n heterojunction was formed in 1FMW, ensuring the stability of composite and the fast electron transfer. Holes, •O2- and •OH were generated in photo-Fenton process and participated in TC degradation. Notably, FMW can be recycled quickly under an external magnetic field due to its magnetic properties. Overall, FMW shows good catalytic stability and recoverability in photo-Fenton oxidation process, which has a broad application prospect.

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.