Lead-Free Cs2AgBiBr6/TiO2 S-Scheme Heterojunction for Efficient Photocatalytic Antibiotic Rifampicin Degradation.

Exploring efficient and stable halide perovskite-based photocatalysts is a great challenge due to the balance between the photocatalytic performance, toxicity, and intrinsic chemical instability of the materials. Here, the environmentally friendly lead-free perovskite Cs2AgBiBr6 confined in the mesoporous TiO2 crystal matrix has been designed to enhance the charge carrier extraction and utilization for efficient photocatalytic rifampicin degradation. The as-prepared Cs2AgBiBr6/TiO2 catalyst was stable in air for over 500 days. An S-scheme heterojunction was formed between the (004) plane of Cs2AgBiBr6 and the (101) plane of TiO2 through the Bi-O-Br bonds. The built-in electric field at the interface efficiently promoted the photoinduced charge separation and carrier extraction. The Cs2AgBiBr6/TiO2-200 showed a 92.83% degradation efficiency of rifampicin within 80 min under simulated sunlight illumination (AM 1.5G 100 mW cm-2). This work offers an effective way for the construction of halide perovskite-based photocatalysts with high photocatalytic performance, good stability, and low toxicity simultaneously.

Enhancing Pollutant Mineralization through Organic-Inorganic Defect-Transit Dual S-scheme with a Robust Internal Electric Field.

Achieving superior photomineralization of pollutants relies on a rational design of a dual S-scheme with a robust internal electric field (IEF). In this study, to tackle the low mineralization rate in type-II In2 O3 /In2 S3 (IO/IS) systems, an organic-inorganic dual S-scheme In2 O3 /PDI/In2 S3 (IO/PDI/IS) nanostructured photocatalyst is synthesized via a method combining solvent-induced self-assembly and electrostatic forces. Due to the unique energy band position and strong IEF, the photoinduced defect-transit dual S-scheme IO/PDI/IS facilitates the degradation of lignin and antibiotics. Notably, a promising mineralization rate of 80.9% for sodium lignosulfonate (SL) is achieved. The charge transport pathway of IO/PDI/IS are further validated through the analysis of in situ X-ray photoelectron spectroscopy (in situ XPS), density functional theory calculations, and radical trapping experiments. In-depth, two possible pathways for the photocatalytic degradation of lignin are proposed based on the intermediates monitored by liquid chromatography-mass spectrometry (LC-MS). This study presents a new strategy for the design of organic-inorganic dual S-scheme photocatalysts with a robust IEF for pollutant degradation.

Regulating Oxygen Vacancies and Fermi Level of Mesoporous CeO2-x for Intensified Built-In Electric Field and Boosted Charge Separation of Cs3 Bi2 Br9 /CeO2-x S-Scheme Heterojunction.

Regulating the built-in electric field (BEF) in the heterojunction is is a great challenge in developing high-efficiency photocatalysts. Herein, by tailoring the content of oxygen vacancies in the constituent reduction semiconductor (mesoporous CeO2-x ), a precise Fermi level (EF ) regulation of CeO2-x is realized, yielding an amplified EF gap and intensified BEF in the Cs3 Bi2 Br9 perovskite quantum dots/CeO2-x S-scheme heterojunction. Such an enhanced BEF offers a strong driving force for directional electron transfer, boosting charge separation in the S-scheme heterojunction. As a result, the optimized Cs3 Bi2 Br9 /CeO2-x heterojunction delivers a remarkable CO2 conversion efficiency, with an impressive CO production rate of 80.26 µmol g-1  h-1 and a high selectivity of 97.6%. The S-scheme charge transfer mode is corroborated comprehensively by density functional theory (DFT) calculations, in situ X-ray photoelectron spectroscopy (XPS), and photo-irradiated Kelvin probe force microscopy (KPFM). Moreover, diffuse reflectance infrared Fourier transform spectra (DRIFTS) and theoretical calculations are conducted cooperatively to reveal the CO2 photoreduction pathway.

Construction of Embedded Sulfur-Doped g-C3N4/BiOBr S-Scheme Heterojunction for Highly Efficient Visible Light Photocatalytic Degradation of Organic Compound Rhodamine B.

Constructing S-scheme heterojunction catalysts is a key challenge in visible-light catalysed degradation of organic pollutants. Most heterojunction materials are reported to face significant obstacles in the separation of photogenerated electron-hole pairs owing to differences in the material size and energy barriers. In this study, sulfur-doped g-C3N4 oxidative-type semiconductor materials are synthesized and then coupled with BiOBr reductive-type semiconductor to form S-g-C3N4/BiOBr S-scheme heterojunction. A strong and efficient internal electric field is established between the two materials, facilitating the separation of photogenerated electron-hole pairs. Notably, in situ XPS proved that after visible light irradiation, Bi3+ is converted into Bi(3+ɑ)+, and a large number of photogenerated holes are produced on the surface of BiOBr, which oxidized and activated H2O into •OH.  â€¢OH cooperated with •O2 - and 1O2 to attack Rhodamine B (RhB) molecules to achieve deep oxidation mineralization. The composite material is designed with a LUMO energy level higher than that of RhB, promoting the sensitization of RhB by injecting photogenerated electrons into the heterojunction, thereby enhancing the photocatalytic performance to 22.44 times that of pure g-C3N4. This study provides a new perspective on the efficient degradation of organic molecules using visible light catalysis.

Photoreduction of Aqueous Protons Coupling with Alcohol Oxidation on a S-Scheme Heterojunction Photocatalyst MnO/Carbon Nitride.

Crystalline carbon nitride (CCN), derived from amorphous polymeric CN, is considered as a new generation of metal-free photocatalyst because of its high crystallinity. In order to further promote the photocatalytic performance of CCN, p-type MnO nanoparticles are in situ synthesized and merged with n-type CCN through a one-pot process to form p-n heterojunction. The formed interfacial electric field between the semiconductors with different work functions efficiently breaks the coulomb interaction between MnO and CCN. The prepared catalysts exhibit drastically increased photocatalytic hydrogen evolution (PHE) activity integrated with oxidation of alkyl and aryl alcohols under irradiation of visible light. In the aqueous solution of benzyl alcohol (BzOH), the hydrogen generation rate over MnO/CCN (39.58 µmol h-1) is nearly 7 times and 37 times that of pure CCN (5.76 µmol h-1) and CN (1.06 µmol h-1), respectively, combining with oxidation of BzOH to benzaldehyde. This work proposes an avenue for in situ construction of a novel 2D material-based S-scheme heterojunction and extends its application in solar energy conservation and utilization.

Efficient Exciton Dissociation on Ceria Chelated Cerium-Based MOF Isogenous S-Scheme Photocatalyst for Acetaldehyde Purification.

Long-term exposure to low concentration indoor VOCs of acetaldehyde (CH3CHO) is harmful to human health. Thus, a novel isogenous heterojunction CeO2/Ce-MOF photocatalyst is synthesized via a one-step hydrothermal method for the effective elimination of CH3CHO in this work. This CeO2/Ce-MOF photocatalyst performs well in CH3CHO removal and achieves an apparent quantum efficiency of 7.15% at 420 nm, which presents ≈6.7 and 3.4 times superior to those generated by CeO2 and Ce-MOF, respectively. The enhanced efficiency is due to two main aspects including i) an effective photocarrier separation ability and the prolonged reaction lifetime of excitons play crucial roles and ii) the formation of an internal electric field (IEF) is sufficient to overcome the considerable exciton binding energy, and increases the exciton dissociation efficiency by up to 50.4%. Moreover, the reasonable pathways and mechanisms of CH3CHO degradation are determined by in situ DRIFTS analysis and simulated DFT calculations. Those results demonstrated that S-scheme heterojunction successfully increases the efficiency of harmful volatile organic compounds elimination, and it offers essential guidance for designing rare earth-based MOF photocatalysts.

D-A Conjugated Polymer/CdS S-Scheme Heterojunction with Enhanced Interfacial Charge Transfer for Efficient Photocatalytic Hydrogen Generation.

Owing to the improved charge separation and maximized redox capability of the system, Step-scheme (S-scheme) heterojunctions have garnered significant research attention for efficient photocatalysis of H2 evolution. In this work, an innovative linear donor-acceptor (D-A) conjugated polymer fluorene-alt-(benzo-thiophene-dione) (PFBTD) is coupled with the CdS nanosheets, forming the organic-inorganic S-scheme heterojunction. The CdS/PFBTD (CP) composite exhibits an impressed hydrogen production rate of 7.62 mmol g-1 h-1 without any co-catalysts, which is ≈14 times higher than pristine CdS. It is revealed that the outstanding photocatalytic performance is attributed to the formation of rapid electron transfer channels through the interfacial Cd─O bonding as evidenced by the density functional theory (DFT) calculations and in situ X-ray photoelectron spectroscopy (XPS) analysis. The charge transfer mechanism involved in S-scheme heterojunctions is further investigated through the photo-irradiated Kelvin probe force microscopy (KPFM) analysis. This work provides a new point of view on the mechanism of interfacial charge transfer and points out the direction of designing superior organic-inorganic S-scheme heterojunction photocatalysts.

Hollow Cu2-xS@NiFe Layered Double Hydroxide Core-Shell S-Scheme Heterojunctions with Broad-Spectrum Response and Enhanced Photothermal-Photocatalytic Performance.

Designing a reasonable heterojunction is an efficient path to improve the separation of photogenerated charges and enhance photocatalytic activity. In this study, Cu2-xS@NiFe-LDH hollow nanoboxes with core-shell structure are successfully prepared. The results show that Cu2-xS@NiFe-LDH with broad-spectrum response has good photothermal and photocatalytic activity, and the photocatalytic activity and stability of the catalyst are enhanced by the establishment of unique hollow structure and core-shell heterojunction structure. Transient PL spectra (TRPL) indicates that constructing Cu2-xS@NiFe-LDH heterojunction can prolong carrier lifetime obviously. Cu2-xS@NiFe-LDH shows a high photocatalytic hydrogen production efficiency (5176.93 µmol h-1 g-1), and tetracycline degradation efficiency (98.3%), and its hydrogen production rate is ≈10-12 times that of pure Cu2-xS and NiFe-LDH. In situ X-ray photoelectron spectroscopy (XPS) and electron spin resonance (ESR) provide proofs of the S-scheme electron transfer path. The S-scheme heterojunction achieves high spatial charge separation and exhibits strong photoredox ability, thus improving the photocatalytic performance.

Efficient Charge Separation in Ag/PCN/UPDI Ternary Heterojunction for Optimized Photothermal-Photocatalytic Performance via Tandem Electric Fields.

Charge separation driven by the internal electric field is a research hotspot in photocatalysis. However, it remains challenging to accurately control the electric field to continuously accelerate the charge transfer. Herein, a strategy of constructing a tandem electric field to continuously accelerate charge transfer in photocatalysts is proposed. The plasma electric field, interface electric field, and intramolecular electric field are integrated into the Ag/g-C3N4/urea perylene imide (Ag/PCN/UPDI) ternary heterojunction to achieve faster charge separation and longer carrier lifetime. The triple electric fields function as three accelerators on the charge transport path, promoting the separation of electron-hole pairs, accelerating charge transfer, enhancing light absorption, and increasing the concentration of energetic electrons on the catalyst. The H2 evolution rate of Ag/PCN/UPDI is 16.8 times higher than that of pristine PDI, while the degradation rate of oxytetracycline is increased by 4.5 times. This new strategy will provide a groundbreaking idea for the development of high-efficiency photocatalysts.

Hollow g-C3N4@Ag3PO4 Core-Shell Nanoreactor Loaded with Au Nanoparticles: Boosting Photothermal Catalysis in Confined Space.

Low solar energy utilization efficiency and serious charge recombination remain major challenges for photocatalytic systems. Herein, a hollow core-shell Au/g-C3N4@Ag3PO4 photothermal nanoreactor is successfully prepared by a two-step deposition method. Benefit from efficient spectral utilization and fast charge separation induced by the unique hollow core-shell heterostructure, the H2 evolution rate of Au/g-C3N4@Ag3PO4 is 16.9 times that of the pristine g-C3N4, and the degradation efficiency of tetracycline is increased by 88.1%. The enhanced catalytic performance can be attributed to the ordered charge movement on the hollow core-shell structure and a local high-temperature environment, which effectively accelerates the carrier separation and chemical reaction kinetics. This work highlights the important role of the space confinement effect in photothermal catalysis and provides a promising strategy for the development of the next generation of highly efficient photothermal catalysts.

Cocatalyst Embedded Ce-BDC-CeO2 S-Scheme Heterojunction Hollowed-Out Octahedrons With Rich Defects for Efficient CO2 Photoreduction.

Constructing heterojunction photocatalysts with optimized architecture and components is an effective strategy for enhancing CO2 photoreduction by promoting photogenerated carrier separation, visible light absorption, and CO2 adsorption. Herein, defect-rich photocatalysts (Ni2P@Ce-BDC-CeO2 HOOs) with S-scheme heterojunction and hollowed-out octahedral architecture are prepared by decomposing Ce-BDC octahedrons embedded with Ni2P nanoparticles and subsequent lactic acid etching for CO2 photoreduction. The hollowed-out octahedral architecture with multistage pores (micropores, mesopores, and macropores) and oxygen vacancy defects are simultaneously produced during the preparation process. The S-scheme heterojunction boosts the quick transfer and separation of photoinduced charges. The formed hollowed-out multi-stage pore structure is favorable for the adsorption and diffusion of CO2 molecules and gaseous products. As expected, the optimized photocatalyst exhibits excellent performance, producing CO with a yield of 61.6 µmol h-1 g-1, which is four times higher than that of the original Ce-BDC octahedrons. The X-ray photoelectron spectroscopy, scanning Kelvin probe, and electron spin resonance spectroscopy characterizations confirm the S-schematic charge-transfer route. The key intermediate species during the CO2 photoreduction process are detected by in situ Fourier transform infrared spectroscopy to support the proposed mechanism for CO2 photoreduction. This work presents a synthetic strategy for excellent catalysts with potential prospects in photocatalytic applications.

Photothermal-Enhanced S-Scheme Heterojunction of Hollow Core-Shell FeNi2S4@ZnIn2S4 toward Photocatalytic Hydrogen Evolution.

Herein, guided by the results of density functional theory prediction, the study rationally designs a hollow core-shell FeNi2S4@ZnIn2S4 (FNS@ZIS) Step-scheme (S-scheme) heterojunction for photocatalytic H2 evolution with photothermal-assisted. The hollow FNS spheres offered substrate for coating the ZIS nanosheets, which can inhibit ZIS nanosheets from agglomerating into pellet, enrich the active site, increase specific surfaces, and raise the light absorption. Notably, due to its excellent photothermal properties, FNS core generated heat unceasingly inside under visible-light irradiation and effectively prevent the heat loss of the reaction system, which increased the local temperature of photocatalysts and thus accelerated the charge migration. In addition, the S-scheme heterojunction construction via in situ growth has a tight interface, which can facilitate the separation and transfer of carriers and achieve high redox potential. Owning to the distinctive construction, the hollow core-shell FNS@ZIS S-scheme heterojunction show extraordinary stability and photocatalytic H2 evolution rate with 7.7 mmol h-1 g-1, which is ≈15.2-fold than pristine ZIS. Based on the double evidence of theoretical predictions and experimental confirmations, the photothermal effect and electron transfer mechanism of this innovative material are investigated in depth by the following infrared thermography technology and deep DFT calculations.

Dual Channel H2O2 Photosynthesis in Pure Water over S-Scheme Heterojunction Cs3PMo12/CC Boosted by Proton and Electron Reservoirs.

Dual channel photo-driven H2O2 production in pure water on small-scale on-site setups is a promising strategy to provide low-concentrated H2O2 whenever needed. This process suffers, however, strongly from the fast recombination of photo-generated charge carriers and the sluggish oxidation process. Here, insoluble Keggin-type cesium phosphomolybdate Cs3PMo12O40 (abbreviated to Cs3PMo12) is introduced to carbonized cellulose (CC) to construct S-scheme heterojunction Cs3PMo12/CC. Dual channel H2O2 photosynthesis from both H2O oxidation and O2 reduction in pure water has been thus achieved with the production rate of 20.1 mmol L-1 gcat. -1 h-1, apparent quantum yield (AQY) of 2.1% and solar-to-chemical conversion (SCC) efficiency of 0.050%. H2O2 accumulative concentration reaches 4.9 mmol L-1. This high photocatalytic activity is guaranteed by unique features of Cs3PMo12/CC, namely, S-scheme heterojunction, electron reservoir, and proton reservoir. The former two enhance the separation of photo-generated charge carriers, while the latter speeds up the torpid oxidation process. In situ experiments reveal that H2O2 is formed via successive single-electron transfer in both channels. In real practice, exposing the reaction system under natural sunlight outdoors successfully results in 0.24 mmol L-1 H2O2. This work provides a key practical strategy for designing photocatalysts in modulating redox half-reactions in photosynthesis.

Efficient ofloxacin degradation via peroxymonosulfate activation using an S-scheme MoS2/Co3O4 heterojunction composite under visible light: Performance and mechanistic insights.

Sulfate-radical-mediated photocatalysis technology peroxymonosulfate (PMS) activation via visible light irradiation shows great promise for water treatment applications. However, its effectiveness largely depends on the bifunctional performance of photocatalysis and PMS activation provided by the catalysts. In this study, we successfully synthesized a novel S-scheme MoS2/Co3O4 (MC) heterojunction composite by a hydrothermal method and employed it for the first time to activate PMS for ofloxacin (OFX) degradation under visible light irradiation. The MC-5/PMS/Vis system achieved an impressive 85.11% OFX degradation efficiency within 1 min and complete OFX removal within 15 min under optimal conditions, with an apparent first-order kinetics rate constant of 0.429 min-1. Reactive species trapping experiments and electron spin resonance analysis identified 1O2, h+, and •O2- as the primary active species responsible for OFX degradation. Photoelectrochemical analyses and density functional theory calculations indicated the formation of a built-in electric field between MoS2 and Co3O4, which enhanced the separation and migration of photoinduced carriers. Additionally, the Co-Mo interaction further increased the yield of dominant reactive species, thereby boosting photocatalytic activity. This work underscores the potential of visible-light-assisted PMS-mediated photocatalysis using Co3O4-based catalysts for effective pollutant control.

Constructing 3D flower-like S-scheme N-Bi2O2CO3/g-C3N4 heterojunction with enhanced photocatalytic performance.

Mineral processing wastewater contains a lot of organic matter and heavy metal ions, and poor self-degradation ability makes it a key treatment object in environmental treatment. Photocatalysis is a promising technology to efficiently mineralize refractory contaminants from wastewater. In this work, 3D flower-like S-scheme N-Bi2O2CO3/g-C3N4 heterostructures were successfully constructed by hydrothermal method with the auxiliary of ionic liquids. The photocatalytic experiments show that the catalytic activity of heterojunction photocatalysts was significantly higher than that of bare g-C3N4 and N-Bi2O2CO3 for the degradation of two pollutants. NBOC/CN-2 shows the highest photocatalytic performance, and the degradation efficiency of sodium isobutyl xanthate (SIBX) on NBOC/CN-2 is 1.85 and 3 times that of bare g-C3N4 and Bi2O2CO3, respectively. The degradation efficiency of m-Cresol on NBOC/CN-2 is 8.34 and 6.93 times that of bare g-C3N4 and N-Bi2O2CO3, respectively. This significantly enhanced photocatalytic activity is attributed to the formation of flower-like heterojunctions, which can greatly increase the specific surface area and facilitate the separation and migration of photogenerated carriers. Total organic carbon (TOC) experiment proves that the two pollutants are effectively mineralized under the action of the prepared photocatalyst. The degradation path of m-Cresol degradation products was inferred based on the ion fragments. The capture experiment and Nitro-blue tetrazolium (NBT)-•O2- measurement show that superoxide radical plays a major role in photocatalytic degradation. The outstanding stability of the prepared flower-like heterojunction samples was examined by cyclic experiments. The S-scheme charge transfer mechanism has been proposed to explain the boosted activity of the flower-like heterojunction photocatalyst. This work provides a new idea for the design of efficient and stable g-C3N4-based photocatalyst for the photocatalytic degradation of refractory wastewater.

S-scheme heterojunction phthalocyanine/TiO2 photoelectrochemical sensor for innovative glutathione detection.

A novel photoelectrochemical sensor, employing an S-scheme heterojunction of phthalocyanine and TiO2 nanoparticles, has been developed to enable highly sensitive determination of glutathione. By integrating the favorable stability, environmental benignity, and electronic properties of the TiO2 matrix with the unique photoactivity of phthalocyanine species, the designed sensor presents a substantial linear dynamic range and a low detection limit for the quantification of glutathione. The sensitivity is attributed to efficient charge transfer and separation across the staggered heterojunction energy levels, which generates measurable photocurrent signals. Systematic variation of phthalocyanine content reveals an optimal composition that balances light harvesting capacity and electron-hole recombination rates. The incorporation of phosphotungstic acid (PTA) in sample preparation effectively minimizes interference from compounds like L-cysteine and others. Consequently, this leads to an improvement in accuracy through the reduction of impurity levels. Appreciable photocurrent enhancements are observed upon introduction of both oxidized and reduced glutathione at the optimized composite photoanode. Coupled with advantageous features of photoelectrochemical transduction such as simplicity, cost-effectiveness, and resistance to fouling, this sensor holds great promise for practical applications in complex biological media.

Photocatalytic adsorption/degradation of tetracycline by S-scheme BiOI/BiOIO3 p-n heterojunction from dissociation of BiOIO3in-situ solvothermal process.

The pollution of tetracycline (TC) had attracted more and more attention due to its unprecedented use and potential hazards. The S-scheme BiOI/BiOIO3 p-n heterojunction was successfully fabricated by in-situ solvothermal treatment of BiOIO3, and was used for the removal of TC from aqueous solutions. The results demonstrated that the construction of S-scheme p-n heterojunction could significantly improve the removal of TC by photocatalytic adsorption/degradation synergism. The removal rate of TC was significantly enhanced after solvothermal modification. The three main reasons for the enhanced removal efficiency were as follows: first, the light absorption range of the BiOIO3 was enhanced by solvothermal treatment; secondly, the construction of the heterojunction was beneficial to the valid separation and migration of the photo-generated carriers; finally, the adsorption of TC enhanced the speed of TC reaching the semiconductor interface and reacting with active species. Trapping tests were conducted to reveal that •O2- and 1O2 are the main reactive species for TC degradation. The nine degradation products were identified by the high performance liquid chromatography-mass spectrometry (HPLC-MS), and the three reaction pathways were deduced. A possible S-scheme p-n heterojunction photocatalytic mechanism was presented on the basis of band structures and active species capturing experiment.

In situ construction of Ag/Bi2O3/Bi5O7I heterojunction with Bi-MOF for enhance the photocatalytic efficiency of bisphenol A by facet-coupling and s-scheme structure.

In this study, Ag/Bi2O3/Bi5O7I with s-scheme heterostructures were successfully synthesized in situ by nano-silver modification of CUA-17 and halogenated hydrolysis.The growth rate of Bi2O3 crystals was effectively controlled by adjusting the doping amount of Ag, resulting in the formation of a facet-coupling heterojunctions. Through the investigation of the microstructure and compositional of catalysts, it has been confirmed that an intimate facet coupling between the Bi2O3 (120) facet and the Bi5O7I (312) facet, which provides robust support for charge transfer. Under visible light irradiation, the AgBOI.3 heterojunction photocatalyst exhibited an outstanding degradation rate of 98.2% for Bisphenol A (BPA) with excellent stability. Further characterization using optical, electrochemical, impedance spectroscopy, and electron spin resonance techniques revealed significantly enhanced efficiency in photogenerated charge separation and transfer, and confirming the s-scheme structure of the photocatalyst. Density functional theory calculations was employed to elucidate the mechanism of BPA degradation and the degradation pathway of BPA was investigated by LC-MS. Finally, the toxicity of the degradation intermediates was evaluated using T.E.S.T software.

Interface coupling to improve O2 adsorption and accelerate charge separation for boosting photocatalytic performance of ZnO/ZnIn2S4 composite in H2O2 production and environmental remediation.

The key to heterogeneous photo-Fenton technology lies in the efficient generation of hydrogen peroxide (H2O2). Herein, a newly-designed ZnO/ZnIn2S4 composite with heterostructure is synthesized. Benefiting from the formation of built-in electric field, the recombination of photoinduced electrons and holes is suppressed and interfacial charge transfer resistance is reduced. Importantly, the embedding of ZnO in ZnIn2S4 can improve the hydrophobicity and create microscopic three-phase interface, thereby boosting the capture capability for O2 and providing the convenience for the occurrence of O2 reduction reaction. More interestingly, the existence of ZnIn2S4 in the ZnO/ZnIn2S4 composite can reduce the Gibbs free energy (ΔG) of key intermediate (OOH*) formation, which will accelerate the generation of H2O2. As a result, the ZnO/ZnIn2S4 composite displays excellent performance in photocatalytic H2O2 production, and the highest yield was about 897.6 µmol/g/h within 60 min under visible light irradiation. The transfer of photoinduced carriers follows the S-scheme type mechanism. The photogenerated holes can be captured by drug residues (i.e., diclofenac sodium) to accelerate H2O2 production, while generated H2O2 can combine with Fe2+ to construct photo-Fenton system for achieving the advanced degradation of diclofenac sodium, which was mainly related to the formation of OH•. Furthermore, generated H2O2 can be applied for performing the inactivation of pathogenic bacteria. In short, current work will provide a valuable reference for future research.

Insights on the efficiency and contribution of single active species in photocatalytic degradation of tetracycline: Priority attack active sites, intermediate products and their toxicity evaluation.

Photocatalysis has been proven to be an excellent technology for treating antibiotic wastewater, but the impact of each active species involved in the process on antibiotic degradation is still unclear. Therefore, the S-scheme heterojunction photocatalyst Ti3C2/g-C3N4/TiO2 was successfully synthesized using melamine and Ti3C2 as precursors by a one-step calcination method using mechanical stirring and ultrasound assistance. Its formation mechanism was studied in detail through multiple characterizations and work function calculations. The heterojunction photocatalyst not only enabled it to retain active species with strong oxidation and reduction abilities, but also significantly promoted the separation and transfer of photo-generated carriers, exhibiting an excellent degradation efficiency of 94.19 % for tetracycline (TC) within 120 min. Importantly, the priority attack sites, degradation pathways, degradation intermediates and their ecological toxicity of TC under the action of each single active species (·O2-, h+, ·OH) were first positively explored and evaluated through design experiments, Fukui function theory calculations, HPLC-MS, Escherichia coli toxicity experiments, and ECOSAR program. The results indicated that the preferred attack sites of ·O2- on TC were O20, C7, C11, O21, and N25 atoms with high f+ value. The toxicity of intermediates produced by ·O2- was also lower than those produced by h+ and ·OH.