The degradation of antibiotics in wastewater poses a critical environmental challenge, necessitating the development of advanced photocatalysts capable of efficiently generating active species. Hence, a novel Zn3In2S6/Bi3O4Br (ZB) heterojunction enriched with oxygen vacancies (OVs) was designed. The optimized ZB-1 (mass percentage of Bi3O4Br to Zn3In2S6 = 1 %) exhibited the highest nitrofurazone (NFZ) degradation rate constant (k) of 0.24 min-1 after 20 min illumination, which was 6.6 and 26.3 folds of the original Zn3In2S6 and Bi3O4Br, respectively. ZB-1 also demonstrated excellent cycling durability and resistance to pH fluctuation. The OVs potentiated O2 adsorption and drew the photogenerated electrons for oxygen (O2) activation, thereby enhancing carrier mobility. Furthermore, the constructed heterojunction facilitated light absorption and carrier migration for O2 activation. The OVs and heterojunctions collaboratively meliorated carrier utilization and active species generation. As a result, abundant superoxide radicals (O2-) were generated and significantly contributed to eliminating NFZ. Meanwhile, the photocatalytic mechanism was clarified by theoretical calculation. The degradation pathway of NFZ and the biotoxicity of its intermediates were systematically conjectured. This research provides a new perspective for designing efficient, durable, and reproducible photocatalysts, which can help address environmental issues related to antibiotic contamination.

Herein, flower-like Zn3In2S6 (ZIS3) crystallites were grown onto acorn leaf-like CdS assemblies via a two-step hydrothermal approach. Under visible light irradiation, the Zn3In2S6-enriched heterostructures demonstrated an enhanced azo-dye degradation rate, with the majority of the organic analyte (Orange G) being degraded within 60 min. In contrast, the CdS-enriched hybrids showed poor photocatalytic performance. The optimized hybrid containing a nominal CdS content of 4 wt% was characterized by various physicochemical techniques, such as XRD, SEM, XPS and Raman. XPS analysis showed that the electron density around the Zn and In sites in Zn3In2S6 was slightly increased, implying a certain charge migration pattern. Complementary information from scavenging experiments suggested that hydroxy radicals were not the exclusive transient responsible for oxidative degradation of the organic azo-dye. This research provides new information about the development of metal chalcogenide-based heterostructures for efficient photocatalytic organic pollutant degradation.

Three-dimensional hollow tube-like structures have obtained considerable attention owing to their pronounced advantages in photocatalytic reactions. Herein, metal organic framework (MOF)-derived MnIn2S4@In2S3 with hollow tube-like structure was successfully synthesized through a facial hydrothermal combined solvothermal method. Electron spin resonance technology and radical scavengers verified that holes and superoxide anions are the primary reactive species in the photocatalytic reaction. The resulting hollow tube-like MnIn2S4@In2S3(MnIS) composite exhibits superior H2O2 yield and ofloxacin photodegradation performance, which are much higher than those of pure MnIn2S4 and In2S3 samples. The experimental results along with density functional theory (DFT) calculations indicate that the co-sharing of In and S elements in MnIn2S4 and In2S3 within the MnIS composites induces strong interface interactions. Additionally, the generation and decomposition of H2O2 provide more active sites, thereby facilitating the photodegradation of ofloxacin. Meanwhile, the formation of an S-scheme heterojunction between MnIn2S4 and In2S3 promotes swifter charge separation and transfer, leading to superior performance in terms of H2O2 evolution and ofloxacin degradation. This investigation offers a novel insight by co-constructing MOF-derived hollow nanotubes and heterojunctions for achieving highly efficient photocatalytic solar-to-fuels conversion.

Converting CO2 into CO, CH4, and other hydrocarbons using solar energy presents a viable approach for addressing energy shortages. In this study, photocatalysts with S-deficient WO3/Zn3In2S6 (WO3/VS-ZIS) S-scheme heterojunctions have been successfully synthesized. Under UV-vis light irradiation, 20 %WO3/VS-ZIS demonstrated significantly improved CO2 reduction activity and CH4 selectivity. Detailed characterization and density functional theory (DFT) calculations reveal that the enhanced performance is due to the synergistic optimization of the S-scheme heterojunction and sulfur vacancies (VS) for CO2 reduction. The presence of VS aids in the adsorption and activation of CO2 and enhances the separation of charge carriers. The 2D/2D S-scheme heterostructure assembled with WO3 nanosheets not only accelerates the migration and separation of photoexcited charge carriers but also improves the adsorption of H2O and the formation of VS, thereby increasing the adsorption and activation of CO2 and facilitating the protonation of CO* to produce CH4. This study clarifies the synergistic effect of VS and S-scheme heterostructures in improving photocatalytic performance, offering valuable insights into the photoactivation process of CO2 at VS in S-scheme heterojunctions.

Electronic waste (e-waste) has become a significant environmental concern worldwide due to the rapid advancement of technology and short product lifecycles. Waste-printed electronic boards (WPCBs) contain valuable metals and semiconductors; among them, tin can be recycled and repurposed for sustainable material production. This study presents a potential ecofriendly methodology for the recovery of tin from WPCBs in the form of tin oxide nanostructured powders. The soldering points in the WPCBs are extracted and dissolved in the dilute HNO3 solution, followed by the formation of metastannic acid, which is subsequently transformed into SnO2 nanoparticles. Different characterization techniques (XRD, XPS, FE-SEM, and TEM) are employed to confirm the morphology and composition of nanoparticles. The prepared SnO2 NPs, having a size range of <50 nm, show excellent photocatalytic degradation of cationic (methylene blue, MB) and anionic (eosin Y, EY) dyes for wastewater treatment. The as-synthesized SnO2 can degrade the mixed dyes (MB+EY) under the illumination of natural sunlight at rate constants of 0.0153 and 0.1103 min-1 for MB and EY, respectively. The positive zeta potential and smaller particle size of the SnO2 NPs possess the extra advantage of the adsorption of anionic over cationic dye, resulting in faster degradation of EY, which is further supported by DFT calculation. The synthesis of SnO2 from waste-printed electronic boards offers a dual benefit: It not only provides a sustainable solution for managing electronic waste but also contributes to the production of useful photocatalysts for wastewater treatment. By converting waste into valuable resources, this approach aligns with the principles of the circular economy and mitigates the environmental impact associated with e-waste disposal.

Density functional theory (DFT) is one of the most widely used methods in the field of computational materials and has become an important research method for photocatalytic heterojunctions. Based on the research progress of DFT in the field of photocatalytic heterojunctions, this review introduces three kinds of heterojunction modeling in detail as well as the problems encountered in the construction process and the solutions. It provides a comprehensive review of the calculation methods of important parameters related to photocatalytic heterojunctions. Comparison, analysis, and discussion were conducted on some functional selections and calculation results based on experimental data. Finally, the limitations and shortcomings of DFT in the field of photocatalytic heterojunctions are pointed out. This review will provide valuable guidance for the calculation and analysis of the performance of photocatalytic heterojunctions and help promote the wider application of DFT in the field of photocatalysis.

Crafting an inorganic semiconductor heterojunction with defect engineering and morphology modulation is a strategic approach to produce clean energy by the highly efficient light-driven splitting of water. In this paper, a novel Z-scheme sulfur-vacancy containing Zn3In2S6 (Vs-Zn3In2S6) nanosheets/In2O3 hollow hexagonal prisms heterostructrue (Vs-ZIS6INO) was firstly constructed by an oil bath method, in which Vs-Zn3In2S6 nanosheets grew on the surfaces of In2O3 hollow hexagonal prisms to form a hollow core-shell structure. The obtained Vs-ZIS6INO heterostructrue exhibited much enhanced activity of the production of H2 and H2O2 by the light-driven water splitting. In particular, under visible light irradiation (λ > 420 nm), the rate of generation of H2 of Vs-ZIS6INO sample containing 30 wt% Vs-Zn3In2S6 (30Vs-ZIS6INO) could reach 3721 μmol g-1h-1, which was 87 and 6 times higher than those of Zn3In2S6 (43 μmol g-1h-1) and Vs-Zn3In2S6 (586 μmol g-1h-1), respectively. Meanwhile, 30Vs-ZIS6INO could exhibit the rate of H2O2 production of 483 μmol g-1h-1 through the dual pathways of indirect 2e- oxygen reduction (ORR) and water oxidation (WOR) without adding any sacrifice agents, far exceeding In2O3 (7 μmol g-1h-1) and Vs-Zn3In2S6 (58 μmol g-1h-1). The excellent photocatalytic activities of H2 and H2O2 generations of Vs-ZIS6INO sample might result from the synergistic effect of the sulfur vacancy, hollow core-shell structure, and Z-scheme heterostructure, which accelerated the electron delocalization, enhanced the absorption and conversion of solar energy, reduced the carrier diffusion distance, and ensured high REDOX ability. In addition, the possible photocatalytic mechanisms for the production of H2 and H2O2 were discussed in detail. This study provided a new idea and reference for constructing the novel and efficient inorganic semiconductor heterostructures by coordinating vacancy defect and morphology design to adequately utilize water splitting for the production of clean energy.

Photocatalysis is an effective technique to remove antibiotic residues from aquatic environments. Typical metal sulfides like Zn3In2S6 have been applied to a wide range of photocatalytic applications. However, there are currently no readily accessible methods to increase its antibiotic-degrading activity. Here, a facile hydrothermal approach is developed for the preparation of flower-like Zn3In2S6 with tunable sulfur lattice defects. Photogenerated carriers can be separated and transferred more easily when there is an adequate amount of lattice defects. Moreover, lattice defect-induced electronic modulation enhances light utilization and adsorption properties. The modified Zn3In2S6 demonstrates outstanding photocatalytic degradation activity for levofloxacin, ofloxacin, and tetracycline. This work sheds light on exploring metal sulfides with sulfur lattice defects for enhancing photocatalytic activity.

Graphitic phase carbon nitride (g-C3N5), as a novel n-type metal-free material, is employed as a visible light-receptive catalyst because of its narrow band gap and abundant nitrogen. To overcome the low carrier mobility efficiency of g-C3N5, its modification by K ions was adopted. In addition, In2S3 was selected to couple with modified g-C3N5 to overcome the recombination of photogenerated e-/h+. As a novel photocatalytic material, it was proven to possess a high visible light absorption capacity and a strong H2O2 production ability (up to 3.89 mmol⋅L-1 in 2 h). Moreover, a S-scheme heterojunction structure was successfully constructed between the two materials, which was tested and confirmed to be successful in raising the photogenerated e-/h+ separation efficiency. Ultimately, the primary processes of photocatalytic H2O2 production were summarized by superoxide radical and rotating disc electron measurements. This research provides a fresh perspective for the synthesis of C3N5-based S-scheme heterojunction photocatalysts for producing H2O2.

In this study, we synthesized nano zero-valent iron incorporated with a multifunctional molybdenum disulfide film (MoS2@nZVI). The material exhibited a 100.00 % removal efficiency for sulfamethoxazole (SMX) and achieved a kobs of 0.4485 min-1 within 10 min. The excellent degradation performance can be attributed to the incorporation of the MoS2 film, which facilitated Fe2+ regeneration. Simultaneously, the MoS2 film assisted in proton accumulation and electron transfer, thereby amplifying the efficiency of SMX degradation across a wide pH range. Comprehensive experimental examinations and characterizations confirmed the selectivity and stability of the MoS2@nZVI catalysts, encompassing both degradation efficiency and structural stability. Interestingly, the MoS2@nZVI/PMS system for SMX degradation significantly involved a non-radical mechanism (1O2), along with radicals (SO4·-, ·OH, and O2·-). The direct oxidation of PMS by Fe2+ not only facilitated the generation of ·OH and SO4·- but also actively engaged in a reaction with O2, leading to the production of O2·-. The primary pathway for 1O2 production was established through the interplay between Mo6+ and O2·-, in conjunction with the direct electron transfer (DET) mechanism between PMS and SMX. The contributions of these active species to SMX degradation occurred in the following precedence: SO4·- > 1O2 > ·OH > O2·-. Notably, the primary pathways for radicals and non-radicals were studied during separate reaction periods. This investigation proposed a promising approach for mitigating pharmaceutical pollutants using a transition metal sulfide-modified nZVI catalyst.

Finely modulated light-induced charge separation and transfer is a central challenge to achieve efficient photocatalysis. Although progress has been made in this field, most of the previous research works focused on the separation or migration of photogenerated carriers but did not build a bridge between the two. How to realize the strong driving and precise migration of carriers has become the focus of our work. We report an ingeniously designed ternary heterojunction. Taking NiFe-MOF as the "parent material", the FeP4/NixPy heterojunction is derived in situ while maintaining the frame structure through gas-solid reaction, and finally the Z-type electron transfer is realized. With Cu3P anchoring spindle matrix, an electron transport tunnel is opened up in Cu3P/FeP4/NixPy ternary heterojunction under the action of p-n heterojunction built-in electric field driving and accurate energy band matching. The strong driving force of the built-in electric field provides an inexhaustible power for the transmission of electrons, and the fine series of electron transmission channels realizes the precise transmission of electrons. The above fine design makes the perfect fit between the built-in electric field and the electron transfer channel, which not only effectively improves the embarrassing situation of insufficient electron driving force of hydrogen evolution reaction in the previous research, but also makes up for the weakening of semiconductor reduction ability caused by the construction of traditional p-n heterostructures. This research work provides a new idea for the construction of multiple heterostructures and the design of fine interface engineering in the future.

Carbon dioxide (CO2) cycloaddition not only produces highly valued cyclic carbonate but also utilizes CO2 as C1 resources with 100% atomic efficiency. However, traditional catalytic routes still suffer from inferior catalytic efficiency and harsh reaction conditions. Developing multienergy-field catalytic technology with expected efficiency offers great opportunity for satisfied yield under mild conditions. Herein, Zn3In2S6 with sulfur vacancies (Sv) was fabricated with the assistance of cetyltrimethylammonium bromide (CTAB), which is further employed for photothermally driven CO2 cycloaddition first. Photoluminescence spectroscopy and photoelectrochemical characterization demonstrated its superior separation kinetics of photoinduced carriers induced by defect engineering. The temperature-programmed desorption (TPD) technique indicated its excellent Lewis acidity-basicity characters. Due to the combination of above merits from photocatalysis and thermal catalysis, defective Zn3In2S6-Sv achieved a yield as high as 73.2% for cyclic carbonate at 80 °C under blue LED illumination within 2 h (apparent quantum yield of 0.468% under illumination of 380 nm monochromatic light at 36 mW·cm-2), which is 2.9, 2.0, and 6.9 times higher than that in dark conditions and those of pristine Zn3In2S6 and industrial representative tetrabutylammonium bromide (TBAB) thermal-catalysis process under the same conditions, respectively. The synergistic reaction path of photocatalysis and thermal catalysis was discriminated by theoretical calculation. This work provides new insights into the photothermal synergistic catalysis CO2 cycloaddition with defective ternary metal sulfides.

Due to the adverse effects of long-term oxytetracycline (OTC) residues in aquatic environments, an effective treatment is urgently needed. Immobilized microbial technology has been widely explored in the treatment of various organic pollutants in aquatic environments with its excellent environmental adaptability. Nevertheless, studies on its application in the removal of antibiotics are relatively scarce and not in sufficient depth. Only a few studies have further investigated the final fate of antibiotics in the immobilized bacteria system. In this study, a novel kind of OTC-degrading bacteria Mycolicibacterium sp. was immobilized on straw biochar and magnetic biochar, respectively. Magnetic biochar was proved to be a more satisfactory immobilization carrier due to its superior property and the advantage of easy recycling. Compared with free bacteria, immobilized bacteria had stronger environmental adaptability under different OTC concentrations, pH, and heavy metal ions. After 5 cycles, immobilized bacteria could still remove 71.8% of OTC, indicating that it had a stable recyclability. Besides, OTC in real swine wastewater was completely removed by immobilized bacteria within 2 days. The results of FTIR showed that bacteria were successfully immobilized on biochar and O-H, N-H, and C-N groups might be involved in the removal of OTC. The fate analysis indicated that OTC was removed by simultaneous adsorption and biodegradation, while biodegradation (92.8%) played a dominant role in the immobilized bacteria system. Meanwhile, the amount of adsorbed OTC (7.20%) was rather small, which could effectively decrease the secondary pollution of OTC. At last, new degradation pathways of OTC were proposed. This study provides an eco-friendly and effective approach to remedy OTC pollution in wastewater.

Metal sulfide based photocatalysts are considered to be economic, environmentally benign and renewable. The rapid recombination of photogenerated electrons and holes and low solar energy utilization efficiency, however, remain a huge bottleneck. Herein, two-dimensional/two-dimensional (2D/2D) S-scheme WS2/Zn3In2S6 heterostructure with ultrathin nanosheets intervening between neighboring component has been designed. The large and intimate S-scheme heterojunctions facilitate interfacial charge separation/transfer and optimize the available redox potential. Besides, the ultrathin 2D/2D heterostructure ensures large specific surface area, maximized interface synergistic interaction, and effective exposure of surface active sites. As a result, 2 wt% WS2/Zn3In2S6 exhibits a high photocatalytic hydrogen production rate of 30.21 mmol·g-1·h-1 under simulated solar light illumination with an apparent quantum efficiency of 56.1% at 370 nm monochromatic light, far exceeding pristine Zn3In2S6 (6.65 mmol·g-1·h-1). Our work underscores the significance of integrating morphology engineering and S-scheme heterojunctions design for high-efficient and low-cost photocatalysts.

Both molybdenum disulfide (MoS2) and nano zero-valent iron (nZVI) exhibit excellent adsorption abilities. However, the constrained conductivity of MoS2 and the lack of selectivity of nZVI for electron transfer still pose challenges. In this study, we designed a series of novel nano zero-valent iron supported by molybdenum disulfide composites (nZVI@MD) with multiple electron-rich active sites, including iron dopant replacement, iron atom intercalation and exposed Mo4+, for effective removal of Cr(VI). Results showed that preparation temperature and the amount of MoS2 added were identified as the two most significant factors affecting the reduction properties of nZVI@MD. Systematic experiments revealed that the nZVI@MD exhibited good anti-interference performance, stability and reusability due to its excellent electron selectivity. Characterization results exhibited that iron atoms replaced the sulfur vacancies in MoS2 and inserted into an intercalation of MoS2 during the preparation process. The mechanisms underlying the uptake of Cr(VI) by nZVI@MD can be proposed as follows: (i) electrostatic interactions, (ii) reduction reaction, and (iii) co-precipitation involving Fe-O-Cr. Furthermore, nZVI@MD exhibited excellent electron activity, hydrophilicity and oxidation resistance, confirmed by density functional theory (DFT) calculations. This work provided new strategies and mechanistic insights for the rational design of adsorbents.

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.

Photocatalytic water splitting has been identified as a promising solution to tackle the current environmental and energy crisis in the world. However, the challenge of this green technology is the inefficient separation and utilization of photogenerated electron-hole pairs in photocatalysts. To overcome this challenge in one system, a ternary ZnO/Zn₃In₂S₆/Pt material was prepared as a photocatalyst using a stepwise hydrothermal process and in-situ photoreduction deposition. The integrated S-scheme/Schottky heterojunction in the constructed ZnO/Zn₃In₂S₆/Pt photocatalyst enabled it to exhibit efficient photoexcited charge separation/transfer. The evolved H₂ reached up to 3.5 mmol g^-1h^-1. Meanwhile, the ternary composite possessed a high cyclic stability against photo-corrosion under irradiation. Practically, the ZnO/Zn₃In₂S₆/Pt photocatalyst also showed great potential for H₂ evolution while simultaneously degrading organic contaminants like bisphenol A. It is hoped in this work that the incorporation of Schottky junctions and S-scheme heterostructures in the construction of photocatalysts would lead to accelerated electron transfer and high photoinduced electron-hole pair separation, respectively, to synergistically enhance the performance of photocatalysts.

Converting solar energy into hydrogen energy is a feasible means to solve the current energy crisis. However, developing an excellent photocatalyst with high light utilization and stability for hydrogen production remains a great challenge. In this work, CoS₂ nanoparticles as cocatalysts are growth on Zn₃In₂S₆ nanosheets with abundant sulfur vacancies for hydrogen evolution, and the optimal rate of hydrogen evolution is as high as 5.69 mmol h^-1 g^-1 in the absence of noble metal co-catalyst Pt, which is 2.87 and 2.29 times that of CoS₂/Zn₃In₂S₆ (with few sulfur vacancies) and Zn₃In₂S₆ (with rich sulfur vacancies). In addition, the hydrogen production rate of CoS₂/Zn₃In₂S₆ composite (with rich sulfur vacancies and 1 wt% Pt) is 24.17 mmol h^-1 g^-1, which is 4.25 and 1.90 times that of CoS₂/Zn₃In₂S₆ (with rich sulfur vacancies) and 1%-Pt/Zn₃In₂S₆ (with rich sulfur vacancies), respectively. The apparent quantum efficiency (AQE) of CoS₂/Zn₃In₂S₆ composite (with rich sulfur vacancies and 1 wt% Pt) reaches 66.20% under light irradiation at the wavelength of 370 nm. Above all indicate that dual cocatalysts (CoS₂ and Pt) and sulfur vacancies can promote the efficient hydrogen evolution activity of Zn₃In₂S₆ nanosheets. This work will provide new ideas and insights for the development of photocatalytic hydrogen production technology.