Graphitic-C3N4/ZnCr-layered double hydroxide 2D/2D nanosheet heterojunction: Mesoporous photocatalyst for advanced oxidation of azo dyes with in situ produced H2O2

In this study the constructional modification of Graphitic carbon nitride nanosheet (GCN-ns) has been made with the aid of ZnCr layered double hydroxide (ZC-LDH) in a unique 2D-2D structure to enhance its visible light absorption. Optical and morphological study presents successful incorporation of ZC-LDH on the surface of GCN-ns. Through adjusting of GCN-ns by ZC-LDH lower recombination rate of e^?/h⁺ pairs, longer lifetimes and an increase in contamination reduction was brought out. The binary nanocomposite was employed to effectively degrade Rhodamine B under UV/vis light irradiation. The improvement in photocatalytic abilities was proven to be related to in situ self-production of H₂O₂ on GCN-ns/ZC-LDH surface by Xe light irradiation which in return accounts for additional hydroxide radical generation. Radical quenching experiments specified the main active species involved while the consequent step-scheme (S-scheme) charge transfer mechanism was proposed.     

Mo-Modified ZnIn2S4@NiTiO3 S-Scheme Heterojunction with Enhanced Interfacial Electric Field for Efficient Visible-Light-Driven Hydrogen Evolution

Designing and developing visible-light-responsive materials for solar to chemical energy is an efficient and promising approach to green and sustainable carbon-neutral energy systems. Herein, a facile in situ growth hydrothermal strategy using Mo-modified ZnIn₂S₄ (Mo-ZIS) nanosheets coupled with NiTiO₃ (NTO) microrods to synthesize multifunctional Mo-modified ZIS wrapped NTO microrods (Mo-ZIS@NTO) photocatalyst with enhanced interfacial electric field (IEF) effect and typical S-scheme heterojunction is reported. Mo-ZIS@NTO catalyst possesses wide-spectrum light absorption properties, excellent visible light-to-thermal energy effect, electron mobility, charges transfer, and strong IEF and exhibits excellent solar-to-chemical energy conversion for efficient visible-light-driven photocatalytic hydrogen evolution. Notably, the engineered Mo_1.4-ZIS@NTO catalyst exhibits superior performance with H₂ evolution rate of up to 14.06 mmol g⁻¹ h^{− 1} and the apparent quantum efficiency of 44.1% at 420 nm. The scientific explorations provide an in-depth understanding of microstructure, S-scheme heterojunction, enhanced IEF, Mo-dopant facilitation effect. Moreover, the theoretical simulations verify the critical role of Mo element in promoting the adsorption and activation of H₂O molecules, modulating the H adsorption behavior on active S sites, and thus accelerating the overall catalytic efficiency. The photocatalytic hydrogen evolution mechanism via S-scheme heterojunction with adjustable IEF regulation over Mo_1.4-ZIS@NTO is also demonstrated.     

S型异质结BiOBr/ZnMoO4的构建及光催化降解性能研究

光催化被广泛用于去除水中的难降解有机污染物,但是由于光生电子和空穴的复合率高,抑制了半导体光催化剂的催化活性。本研究通过简便的溶剂热法成功制备了一种BiOBr/ZnMoO₄复合材料。通过结构分析、原位XPS、功函数测试、自由基捕获及电子顺磁共振(ESR)实验等证实了BiOBr/ZnMoO₄复合材料形成了S型异质结。实验结果表明,适当ZnMoO₄含量的BiOBr/ZnMoO₄异质结可以显著提高BiOBr的光催化性能。与纯BiOBr、ZnMoO₄相比,质量分数15%BiOBr/ZnMoO₄在可见光下表现出最佳的光催化活性,双酚A的光催化降解率达到85.3%(90min),环丙沙星的光降解速率常数分别是BiOBr的2.6倍和ZnMoO₄的484倍。这可归因于BiOBr和ZnMoO₄之间形成了紧密的界面结合和S型异质结,使得光生载流子可以实现有效的空间分离和转移。这项工作为定向合成Bi基S型异质结复合光催化材料提供了一种...     

Relationship of structure and enhanced photocatalytic activity of S-scheme BiOCl/g-C3N4 heterojunction for xanthate removal under visible light

Constructing heterojunctions is an excellent way to enhance the photocatalytic property of semiconductors. Herein, a range of S-scheme BiOCl/g-C₃N₄ heterojunctions with varying mass ratios were designed using a facile hydrothermal route, and their photocatalytic ability was assessed by degrading the ethyl xanthate (EX) under visible light (λ > 400 nm). The results showed that the degradation efficiency of BiOCl/g-C₃N₄-0.1 heterojunction for EX was up to 91.2 % within 180 min, and its apparent rate constants (K_app) were 4.3 and 11 times greater than those of BiOCl and g-C₃N₄, respectively. The experimental and characterization results revealed that the excellent photocatalytic property was ascribed to the construction of S-scheme heterojunctions. Such structure not only enhanced the visible light response but also facilitated the efficient separation of photoinduced carriers with the S-scheme transfer route, retaining strong redox-capable holes and electrons to participate in surface reactions. Furthermore, the cycling experiments indicated that the fabricated photocatalysts have great recyclability and stability. Based on the results of active substance capture, the S-scheme charge transfer model was proposed and the photodegradation mechanism of EX was reasonably elucidated. Overall, this work offers some theoretical direction for the design and construction of S-scheme heterojunctions with superior visible-light-driven photocatalytic performance.     

Bismuth oxycarbonate grafted NiFe-LDH supported on g-C3N4 as bifunctional catalyst for photoelectrochemical water splitting

In the present study, we report the synthesis of photoactive bismuth oxycarbonate (BOC, Bi₂O₂CO₃) grafted NiFe layered double hydroxide (LDH) supported on g-C₃N₄ (15 wt% of g-C₃N₄) by coprecipitation method. The band gap of this photoactive material is determined to be 1.7 eV. The Bi₂O₂CO₃ agglomerates are anchored on NiFe-LDH plates and g-C₃N₄ nanosheets intercalated between the LDH plates. This architecture helps in expediting electron transfer for hydrogen and oxygen evolution reactions. The pristine NiFe-LDH photoanode acquires bifunctional character because of Bi₂O₂CO₃ agglomerates and g-C₃N₄ embedded in the architecture of BOC/NiFe-LDH@g-C₃N₄. This is found to be an efficient photoanode for oxygen evolution and photocathode for hydrogen evolution reactions. The water splitting process occurs along the heterojunction formed between g-C₃N₄ nanosheets and Bi₂O₂CO₃ grafted NiFe-LDH. Further, an additional interfacial charge transfer aided by Bi₂O₂CO₃ results in S-scheme mechanism, which enhances the rate of photoelectrochemical hydrogen and oxygen evolution reactions.     

Construction of hierarchical FeIn2S4/BiOBr S-scheme heterojunction with enhanced visible-light photocatalytic performance for antibiotics degradation

Constructing heterojunction provides a promising tactic to improve the photocatalytic efficiency of catalysts. In this paper, hierarchical FeIn₂S₄/BiOBr heterostructure photocatalysts were prepared by facile two step methods and applied to effectively remove ciprofloxacin (CIP) and tetracycline (TC) under visible light. Compared to single catalyst, FeIn₂S₄/BiOBr hybrids display significantly improved photocatalytic activity. Among the series, 6 wt% FeIn₂S₄/BiOBr shows the optimal photocatalytic performance, where the degradation efficiencies of TC and CIP are 3.15 and 2.88 times greater than pure BiOBr, respectively. Such an improvement could arise from the S-scheme heterojunctions and unique hierarchical structures, which brings stronger light absorption, higher photoexcited charge separation efficiency and superior redox ability. Furthermore, 6 wt% FeIn₂S₄/BiOBr composite exhibits excellent stability and reusability. Radical capture experiments and EPR analyses uncover that O₂^–, h⁺ and OH are primarily reactive substances during photocatalytic removal of TC. The products of TC were detected by LC-MS analyses and possible decomposition paths are proposed. Eventually, a possible photodegradation mechanism over FeIn₂S₄/BiOBr S-scheme heterojunction is proposed. These findings supply new perspective for the simple synthesis of S-scheme photocatalysts with promising applications in environment remediation.     

Rational design of ZnO–CuO–Au S-scheme heterojunctions for photocatalytic hydrogen production under visible light

An integration of S-scheme heterojunction catalyst with surface plasmon resonance effect is the prime focus of current research activites in the field of visible light driven photocatalytic hydrogen (H₂) evolution. Herein, a sol-gel route is used to design a heterojunction of ZnO–CuO–Au. The effect of process parameters, including irradiation time, catalyst dose, and sacrificial reagents on the hydrogen evolution is studied. The S-scheme ZnO–CuO–Au heterojunction catalyst demonstrated high surface area, better optical absorption response in the visible part of light spectrum, and improved separation and transportion of charge carriers as verified by DRS, PL, and photoelectrochemical studies. The maximum H₂ evolution rateof ZnO–CuO–Au reaches 4655 μmolh⁻¹g⁻¹, which is 5 and 3.2 times higher than ZnO–CuO and Au–ZnO catalysts, respectively. A possible reason of this increase in H₂ evolution rate is inhibited recombination of charge carriers because of the S-scheme design to increase electrons with strong reduction potential and prolong lifetime, Au serves as an SPR source and conductive channel to swift the transfer of electrons and high density of active sites. This work offers innovative insight into designing plasmonic metals-modified S-scheme systems for solar fuel production.     

S-scheme bimetallic sulfide ZnCo2S4/g-C3N4 heterojunction for photocatalytic H2 evolution

Transition bimetallic sulfides have attracted widespread attention because of their superior electrochemical characteristics compared to their parent materials. Herein, ternary ZnCo₂S₄ was deposited on g-C₃N₄ (CN) to enhance the photocatalytic water splitting reactivity of CN. The hydrogen (H₂) evolution rate of 25 wt%-ZnCo₂S₄/CN reached 6619 μmol h⁻¹ g⁻¹, which was 55.2 times higher than that of CN alone. Under the same conditions, ZnS/CN and Co₃S₄/CN were also synthesized, and their H₂ evolution rates were both inferior to that of ZnCo₂S₄/CN. Investigations showed that the presence of both zinc and cobalt ions in ZnCo₂S₄ lowered the H₂ evolution overpotential and charge recombination rate, leading to excellent H₂ release activity. In addition, the composite maintained its activity even after reacting for 20 h, and the charge transfer mechanism between ZnCo₂S₄ and CN was subject to the S-scheme charge transfer route according to trapping experiments for active species. This work revealed a promising and efficient bimetallic sulfide heterojunction to enhance H₂ evolution during water splitting and thus achieved improved conversion efficiency for solar energy applications.     

Super-Photothermal Effect-Mediated Fast Reaction Kinetic in S-Scheme Organic/Inorganic Heterojunction Hollow Spheres Toward Optimized Photocatalytic Performance

Using full solar spectrum for energy conversion and environmental remediation is a major challenge, and solar-driven photothermal chemistry is a promising route to achieve this goal. Herein, this work reports a photothermal nano-constrained reactor based on hollow structured g-C₃N₄@ZnIn₂S₄ core–shell S-scheme heterojunction, where the synergistic effect of super-photothermal effect and S-scheme heterostructure significantly improve the photocatalytic performance of g-C₃N₄. The formation mechanism of g-C₃N₄@ZnIn₂S₄ is predicted in advance by theoretical calculations and advanced techniques, and the super-photothermal effect of g-C₃N₄@ZnIn₂S₄ and its contribution to the near-field chemical reaction is confirmed by numerical simulations and infrared thermography. Consequently, the photocatalytic degradation rate of g-C₃N₄@ZnIn₂S₄ for tetracycline hydrochloride is 99.3%, and the photocatalytic hydrogen production is up to 4075.65 µmol h⁻¹ g⁻¹, which are 6.94 and 30.87 times those of pure g-C₃N₄, respectively. The combination of S-scheme heterojunction and thermal synergism provides a promising insight for the design of an efficient photocatalytic reaction platform.     

Regular octahedron Cu-MOFs modifies Mn0.05Cd0.95S nanoparticles to form a S-scheme heterojunction for photocatalytic hydrogen evolution

Structured efficient and effective photocatalysts was crucial to improve photocatalytic efficiency. In this work, regular octahedron Cu-MOFs and Mn_0.05Cd_0.95S nanoparticles were adopted to constitute a S-scheme heterojunction. The Cu-MOFs/Mn_0.05Cd_0.95S (5 wt%) composite exhibited powerful photocatalytic hydrogen evolution activity of 547.5 μmol after 5 h under visible light irradiation (λ > 420 nm), which was ascribed to structure a S-scheme heterojunction brought great redox capacity and efficient separation and transfer of electrons and holes. The SEM and HRTEM results presented close contact of the Cu-MOFs and Mn_0.05Cd_0.95S. The PL, TRPL, and electrochemical properties further indicated that the composite photocatalysts had competent photocatalytic performance. The UV–vis DRS indicated that the composite catalyst had excellent light absorption capacity. It was confirmed that the composite photocatalysts owned excellent chemical stability by the XPS, FT-TR, and XRD. The S-scheme process can eliminate useless electrons and holes and provide more electrons to participate H₂ evolution reduction. This work contributed new strategy to rational structure heterojunction photocatalysts for hydrogen evolution.