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 (CO2 RR) 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 CO2 RR. Therefore, emphasis will then summarize the strategies for enhancing the photocatalytic and electrocatalytic efficiency of CTFs for CO2 RR 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 CO2 RR. Subsequently, the mechanism of CTF-based materials in photo/electrocatalytic CO2 RR is described. Lastly, the challenges and future prospects of CTFs in photo/electrocatalytic CO2 RR are addressed, which offers a fresh perspective for the future development of CTFs in photo/electrocatalytic CO2 RR.

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.

A review of polybrominated diphenyl ethers and novel brominated flame retardants in Chinese aquatic environment: Source, occurrence, distribution, and ecological risk assessment.

Due to the widespread commercial production and use of brominated flame retardants (BFRs) in China, their potential impact on human health development should not be underestimated. This review searched the literature on Polybrominated diphenyl ethers and Novel brominated flame retardant (PBDEs and NBFRs) (broad BFRs) in the aquatic environment (including surface water and sediment) in China over the last decade. It was found that PBDEs and NBFRs entered the aquatic environment through four main pathways, atmospheric deposition, surface runoff, sewage effluent and microplastic decomposition. The distribution of PBDEs and NBFRs in the aquatic environment was highly correlated with the local economic structure and population density. In addition, a preliminary risk assessment of existing PBDEs and PBDEs in sediments showed that areas with high-risk quotient values were always located in coastal areas with e-waste dismantling sites, which was mainly attributed to the historical legacy of electronic waste. This research provides help for the human health development and regional risk planning management posed by PBDEs and NBFRs.

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.

Metal-carbon hybrid materials induced persulfate activation: Application, mechanism, and tunable reaction pathways.

Proper wastewater treatment has always been the focus of human society, and many researchers have been working to find efficient and stable wastewater treatment technologies. Persulfate-based advanced oxidation processes (PS-AOPs) mainly rely on persulfate activation to form reactive species for pollutants degradation and are considered to be one of the most effective wastewater treatment technologies. Recently, metal-carbon hybrid materials have been diffusely used for PS activation because of their high stability, abundant active sites, and easy applicability. Metal-carbon hybrid materials can successfully overcome the shortcomings of onefold metal catalysts and carbon catalysts by combing the complementary advantages of the two components. This article reviews recent studies about metal-carbon hybrid materials-mediated PS-AOPs for wastewater decontamination. The interactions of metal and carbon materials, as well as the active sites of metal-carbon hybrid materials, are introduced first. Then, the application and mechanism of metal-carbon hybrid materials-mediated PS activation are presented in detail. Lastly, the modulation methods of metal-carbon hybrid materials and their tunable reaction pathways were discussed. The prospect of future development directions and challenges is proposed to facilitate metal-carbon hybrid materials-mediated PS-AOPs to take a step further for practical application.

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.

Unveiling the roles of dissolved organic matters derived from different biochar in biochar/persulfate system: Mechanism and toxicity.

Biochar has been frequently used as a persulfate (PS) activator due to its attractive properties, but dissolved organic matter (DOM) derived from the non­carbonized part of biochar has received less attention, not to mention its specific role and impact in biochar/PS systems. In this study, wheat straw, municipal sludge, and swine bone were selected as the representative feed stocks of biochar. Subsequently, these three types of biochar were adopted to explore the roles of DOM in biochar/PS systems. Although the composition and amount of DOM derived from different biochar were discrepant, they exhibited similar effect in biochar/PS systems. To be specific, the pore-clogging effect of DOM on biochar suppressed the adsorption capacity and catalytic performance of the three biochar. Furthermore, the removal of DOM decreased the environmental risk of these biochar/PS systems and enhanced the stability of the involved biochar. With respect to the variation in degradation mechanism, the removal of DOM increased the proportion of electron transfer pathway in unison, but the diminution in the roles of O2•¯ and 1O2 was more remarkable in bone-derived-biochar/PS systems. Additionally, the toxicity test illustrated that the leakage and accumulation of DOM were toxic to Chlorella sp., and the DOM from sludge-derived-biochar presented the highest toxicity. Overall, this study analyzes the roles of DOM derived from different biochar in biochar/PS systems and evaluates their environmental risk, which contributes to a comprehensive understanding of the fate of DOM derived from biochar.

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.

Enhancing hydrogen peroxide activation of CuCo layered double hydroxide by compositing with biochar: Performance and mechanism.

In this study, CuCo layered double hydroxide/biochar composite (CuCo LDH/BC) was prepared and employed for activating H2O2 to degrade ciprofloxacin (CIP), a common fluroquinolone antibiotic detected in water environment. The as-synthesized catalysts were also comprehensively characterized to study the physiochemical properties. For the catalytic activity, the degradation rate of CuCo LDH/BC to CIP was approximately 1.5 times higher than that of CuCo LDH. The improved catalytic activity can be ascribed to the synergistic effect between CuCo LDH and BC, such as more functional groups, accelerated electron transfer, and varied charge distribution. Meanwhile, CuCo LDH/BC/H2O2 could degrade CIP efficiently in a wider pH range comparing with CuCo LDH/H2O2, and the efficiency was approximately 84.7% at neutral pH within 90 min. The generation of OH, O2- and 1O2 in CuCo LDH/BC/H2O2 system were then verified by electron spin resonance (ESR) technology. The quenching experiments indicated that both non-radical pathway (1O2) and radical pathway (OH, O2-) led to CIP degradation, in which O2- and 1O2 made major contribution. Then, the intermediate products of CIP during catalytic reaction were monitored by high-performance liquid chromatography-mass spectrometry (HPLC-MS), and the environmental risk of these degradation intermediates was tested through seed germination experiments. This study tends to provide valuable information for LDH/BC application in heterogeneous Fenton-like reaction.

Nitrogen-doping coupled with cerium oxide loading co-modified graphitic carbon nitride for highly enhanced photocatalytic degradation of tetracycline under visible light.

The increasingly serious pollution of antibiotics brings an enormous threat to the ecological environment and human health. Graphite phase carbon nitride (g-C3N4), as a popular photocatalytic material, is widely used in photocatalytic degradation of antibiotics in water. In order to make up for the shortage of g-C3N4 monomer, CeO2/N-doped g-C3N4 (CeNCN) composite photocatalysts co-modified with nitrogen doping and CeO2 loading were designed and synthesized with the idea of expanding visible light absorption and promoting photogenerated carrier separation. CeNCN exhibits excellent photodegradation performance, the removal rate of tetracycline reached 80.09% within 60 min, which is much higher than that of g-C3N4 (CN) and N-doped g-C3N4 (NCN); and the quasi-first-order degradation rate constant is 0.0291, which is 7.86 and 2.29 times higher than CN and NCN. Electron spin resonance and free radical trapping experiments confirmed that h+, O2- and OH are the active substances in the photocatalytic system. After 5 cycles, the degradation efficiency of tetracycline still exceeds 75%, which indicates that CeNCN has good stability. This work proves that N-doping and CeO2 loading can effectively broaden the photoresponse range of g-C3N4, facilitate the separation of photogenerated electron-hole pairs, and provide a reference for the construction of g-C3N4-based photocatalyst with high-efficiency photodegradation activity.

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.

Facile synthesis of Mn, Ce co-doped g-C3N4 composite for peroxymonosulfate activation towards organic contaminant degradation.

Peroxymonosulfate (PMS)-based advanced oxidation processes for wastewater treatment have received extensive attention in the past years. Here, a novel Mn, Ce co-modified g-C3N4 (MnCe-CN) composite was successfully synthesized by one-step pyrolysis for activating PMS. The physical and chemical characterization of MnCe-CN/PMS was conducted, indicating that Mn and Ce were evenly distributed on g-C3N4 and existed in the form of Mn-N structure and CeO2, respectively. The MnCe-CN/PMS system could effectively degrade pollutants such as acetaminophen (ACT), methylparaben (MeP), p-nitrophenol (PNP), and 2,4-dichlorophenol (2,4-DCP). Among them, 2,4-DCP could be rapidly degraded, reaching 100% within 30 min. The masking experiments and electrochemical testing results revealed that 2,4-DCP was degraded via superoxide radicals (O2˙-), singlet oxygen (1O2), and electron transfer path. The cyclic experiments and real water treatment experiments testified that the oxidative system had excellent stability and applicability. This study provides a facile synthetic method to fabricate bimetallic co-modified g-C3N4 for the enhancement of PMS activation.

Facile one-pot synthesis of carbon self-doped graphitic carbon nitride loaded with ultra-low ceric dioxide for high-efficiency environmental photocatalysis: Organic pollutants degradation and hexavalent chromium reduction.

In the present study, an innovative carbon self-doped g-C3N4 (CCN) loaded with ultra-low CeO2 (0.067-0.74 wt%) composite photocatalyst is successfully synthesized via a facile one-pot hydrothermal and calcination method. The CeO2/CCN exhibits superior photocatalytic performance for tetracycline degradation (78.9% within 60 min), H2O2 production (151.92 µmol L-1 within 60 min), and Cr(VI) reduction (99.5% within 40 min), which much higher than that of g-C3N4, CCN, CeO2, and CeO2/g-C3N4. The enhanced photocatalytic performance is originated from the fact that the doping of C can efficaciously broaden the utilization range of solar light and improve the reduction ability of photogenerated electrons. Meanwhile, the ultra-low loading of CeO2 can effectually promote the migration of photogenerated electrons and enhance the specific surface area. Besides, the experiments of pH effect and cycle ability indicate that CeO2/CCN has excellent durability and stability. Finally, the photocatalytic mechanism of CeO2/CCN is systematically discussed. This work proves that combining element doping and semiconductor coupling is a promising strategy to design high-efficiency g-C3N4-based photocatalysts.

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.

Facile synthesis of CeO2/carbonate doped Bi2O2CO3 Z-scheme heterojunction for improved visible-light photocatalytic performance: Photodegradation of tetracycline and photocatalytic mechanism.

CeO2 nanoparticles are successfully loaded on carbonate doped Bi2O2CO3 (CBOC) nanosheets by a facile hydrothermal and low-temperature calcination method. CeO2/CBOC heterojunction shows significantly enhanced photocatalytic activity, when 35 mg of CeO2/CBOC photocatalyst is added to tetracycline (TC) solution (20 mg/L, 100 mL), about 79.5% TC is degraded within 90 min under visible light irradiation, which is much higher than that of original CeO2 and CBOC. According to photoelectrochemical characterization and active radical capture experiments, the Z-scheme electron transfer mechanism is the reason for the significant enhancement of photocatalytic activity. Besides, the XPS results indicate that Ce4+/Ce3+ redox pairs are formed at the contact interface between CeO2 and CBOC, which is conducive to the transfer of photoexcited electrons and production of superoxide radicals. Additionally, the photocatalytic mechanism and possible degradation pathway of TC is proposed through free radical trapping experiments and liquid chromatography-mass (LC-MS) analysis. This study will accumulate experience for the combination of CeO2 and bismuth-based nanomaterials, and provide a feasible way to design wide band-gap bismuth-based photocatalysts, thereby achieving efficient visible light degradation of environmental pollutants.