直接Z-型立方/六方ZnIn2S4复合光催化剂的制备及其光催化性能

通过水热反应方法制备出立方相ZnIn₂S₄和六方相ZnIn₂S₄和系列不同摩尔比的复合相ZnIn₂S₄光催化剂,使用X射线衍射、扫描电子显微镜、电子能谱、透射电子显微镜、光致发光光谱、N₂吸附-脱附法及紫外-可见光漫反射等手段表征了样品的晶体结构、显微结构及吸光特性并在可见光照射下进行了甲基橙降解实验。结果表明,复合相ZnIn₂S₄样品都具有比立方相、六方相和机械混合的ZnIn₂S₄更好的可见光催化活性,当复合相ZnIn₂S₄样品中立方相与六方相摩尔比为3:7时体系的催化活性最高。这种样品被可见光照射30 min后,甲基橙的降解率达到95.2%。其降解机理与样品较大的比表面积以及样品中的立方相与六方相之间的密切接触而形成直接Z-型光催化过程有关。     

Reversible Stacking of 2D ZnIn2S4 Atomic Layers for Enhanced Photocatalytic Hydrogen Evolution

It is technically challenging to reversibly tune the layer number of 2D materials in the solution. Herein, a facile concentration modulation strategy is demonstrated to reversibly tailor the aggregation state of 2D ZnIn₂S₄ (ZIS) atomic layers, and they are implemented for effective photocatalytic hydrogen (H₂) evolution. By adjusting the colloidal concentration of ZIS (ZIS-X, X = 0.09, 0.25, or 3.0 mg mL⁻¹), ZIS atomic layers exhibit the significant aggregation of (006) facet stacking in the solution, leading to the bandgap shift from 3.21 to 2.66 eV. The colloidal stacked layers are further assembled into hollow microsphere after freeze-drying the solution into solid powders, which can be redispersed into colloidal solution with reversibility. The photocatalytic hydrogen evolution of ZIS-X colloids is evaluated, and the slightly aggregated ZIS-0.25 displays the enhanced photocatalytic H₂ evolution rates (1.11 µmol m⁻² h⁻¹). The charge-transfer/recombination dynamics are characterized by time-resolved photoluminescence (TRPL) spectroscopy, and ZIS-0.25 displays the longest lifetime (5.55 µs), consistent with the best photocatalytic performance. This work provides a facile, consecutive, and reversible strategy for regulating the photo-electrochemical properties of 2D ZIS, which is beneficial for efficient solar energy conversion.     

具有近红外吸收的二维/三维ZnIn2S4/氮掺杂石墨烯光催化剂的制备及其高效CO2捕获和光催化还原性能（英文）

具有宽光谱太阳能利用的分等级异质结光催化剂,正成为一种新兴的先进光催化材料,被应用于太阳能驱动二氧化碳转化为高附加值的化学原料.本工作通过水热法使二维硫化铟锌纳米墙垂直生长于三维氮掺杂石墨烯泡沫上,形成分等级异质结光催化剂.该催化剂展现出优异的光热转换效率、选择性捕获CO2和光催化还原CO2的能力.在273 K和1个大气压条件下,负载1 wt%氮掺杂石墨烯泡沫的复合催化剂表现出最优异的性能,其中对CO2和N2的吸附选择性为30.1,并且对CO2的等量吸附热为48.2 kJ mol^-1.在无助催化剂和牺牲剂的条件下,负载1 wt%氮掺杂石墨烯泡沫的复合催化剂,其光催化转化CO2为CH4、CO和CH3OH的效率分别是纯的硫化铟锌的9.1、3.5和5.9倍.该增强效应得益于三维石墨烯泡沫高度开放的网状结构,良好的CO2吸附能力和两种组份之间的强相互作用.此外,利用原位照射X射线光电子能谱仪和开尔文探针技术分析了电荷转移的方向,本工作为设计高效太阳能转化分等级异质结光催化剂开辟了新的思路.     

In Situ Formation ZnIn2S4/Mo2TiC2 Schottky Junction for Accelerating Photocatalytic Hydrogen Evolution Kinetics: Manipulation of Local Coordination and Electronic Structure

Regulating electronic structures of the active site by manipulating the local coordination is one of the advantageous means to improve photocatalytic hydrogen evolution (PHE) kinetics. Herein, the ZnIn₂S₄/Mo₂TiC₂ Schottky junctions are designed to be constructed through the interfacial local coordination of In³⁺ with the electronegative  O terminal group on Mo₂TiC₂ based on the different work functions. Kelvin probe force microscopy and charge density difference reveal that an electronic unidirectional transport channel across the Schottky interface from ZnIn₂S₄ to Mo₂TiC₂ is established by the formed local nucleophilic/electrophilic region. The increased local electron density of Mo₂TiC₂ inhibits the backflow of electrons, boosts the charge transfer and separation, and optimizes the hydrogen adsorption energy. Therefore, the ZnIn₂S₄/Mo₂TiC₂ photocatalyst exhibits a superior PHE rate of 3.12 mmol g⁻¹ h⁻¹ under visible light, reaching 3.03 times that of the pristine ZnIn₂S₄. This work provides some insights and inspiration for preparing MXene-based Schottky catalysts to accelerate PHE kinetics.     

Spatially Separating Redox Centers on Z‐Scheme ZnIn2S4/BiVO4 Hierarchical Heterostructure for Highly Efficient Photocatalytic Hydrogen Evolution

Photocatalysis technology using solar energy for hydrogen (H₂) production still faces great challenges to design and synthesize highly efficient photocatalysts, which should realize the precise regulation of reactive sites, rapid migration of photoinduced carriers and strong visible light harvest. Here, a facile hierarchical Z‐scheme system with ZnIn₂S₄/BiVO₄ heterojunction is proposed, which can precisely regulate redox centers at the ZnIn₂S₄/BiVO₄ hetero‐interface by accelerating the separation and migration of photoinduced charges, and then enhance the oxidation and reduction ability of holes and electrons, respectively. Therefore, the ZnIn₂S₄/BiVO₄ heterojunction exhibits excellent photocatalytic performance with a much higher H₂‐evolution rate of 5.944 mmol g^?1 h^?1, which is about five times higher than that of pure ZnIn₂S₄. Moreover, this heterojunction shows good stability and recycle ability, providing a promising photocatalyst for efficient H₂ production and a new strategy for the manufacture of remarkable photocatalytic materials.     

Supporting Ultrathin ZnIn2S4 Nanosheets on Co/N‐Doped Graphitic Carbon Nanocages for Efficient Photocatalytic H2 Generation

Ultrathin ZnIn₂S₄ nanosheets (NSs) are grown on Co/N‐doped graphitic carbon (NGC) nanocages, composed of Co nanoparticles surrounded by few‐layered NGC, to obtain hierarchical Co/NGC@ZnIn₂S₄ hollow heterostructures for photocatalytic H₂ generation with visible light. The photoredox functions of discrete Co, conductive NGC, and ZnIn₂S₄ NSs are precisely combined into hierarchical composite cages possessing strongly hybridized shell and ultrathin layered substructures. Such structural and compositional virtues can expedite charge separation and mobility, offer large surface area and abundant reactive sites for water photosplitting. The Co/NGC@ZnIn₂S₄ photocatalyst exhibits outstanding H₂ evolution activity (e.g., 11270 µmol h^?1 g^?1) and high stability without engaging any cocatalyst.     

Porous g-C3N4-encapsulated TiO2 hollow sphere as a high-performance Z-scheme hybrid for solar-induced photocatalytic abatement of environmentally toxic pharmaceuticals

Herein,we rationally constructed a hybrid heterostructure comprising porous g-C3N4(CN)-encapsulated anatase TiO2 hollow spheres(TOHS)via a synthesis method that involves hydrothermal and calcination treatments.The fabricated hybrid,termed CN/TOHS,demonstrated extraordinary activity toward the degradation of environmentally toxic pharmaceutical substances(acetaminophen and ciprofloxacin)in aqueous solutions under simulated sunlight irradiation;the activity of CN/TOHS was superior to that attained for individual TOHS and CN counterparts.In particular,the CN/TOHS hybrid containing 13.3 wt.％of CN on TOHS displayed the optimum degradation activity among the tested catalysts used in this study,and it also possessed exceptional recyclability and stability during consecutive degradation tests.The remarkable photocatalytic activity and stability of the hybrid were predominantly ascribed to the large solid interfacial contact between constituents,TOHS and CN,induced by effective hybrid structure,which boosted the interfacial charge transfer and impeded with the direct recombination of photo-induced charges.Notably,the results of the liquid chromatography-mass spectrometry analysis corroborated the effective mineralization of model pharmaceutical pollutants in the presence of the CN/TOHS hybrid.The simple interfacial engineering strategy presented in this study offers a potential route for the rational design of novel catalysts for application in environmental remediation and solar energy conversion.     

石墨烯-ZnIn2S4纳米复合微球的制备及光催化产氢活性

采用光催化还原法制备了石墨烯-ZnIn₂S₄纳米复合微球。采用XRD、SEM、TEM、FT-IR、XPS和DRS等手段对样品进行表征, 结果表明, 经过光催化还原处理后氧化石墨被还原成石墨烯, ZnIn₂S₄纳米微球负载在石墨烯表面。光催化产氢的实验结果表明, 当石墨烯含量为2.0wt%、光催化还原时间为24 h时, 石墨烯-ZnIn₂S₄纳米复合微球在模拟太阳光下产氢量达到1540.8 μmol, 是纯ZnIn₂S₄纳米微球的9.8倍。增强光催化性能的原因归结为石墨烯在复合光催化剂中起到了电子快速传输作用, 同时还对纳米复合微球光催化产氢反应机理进行了分析讨论。     

Synergistic Functionality of Dopants and Defects in Co-Phthalocyanine/B-CN Z-Scheme Photocatalysts for Promoting Photocatalytic CO2 Reduction Reactions

The realization of solar-light-driven CO₂ reduction reactions (CO₂ RR) is essential for the commercial development of renewable energy modules and the reduction of global CO₂ emissions. Combining experimental measurements and theoretical calculations, to introduce boron dopants and nitrogen defects in graphitic carbon nitride (g-C₃N₄), sodium borohydride is simply calcined with the mixture of g-C₃N₄ (CN), followed by the introduction of ultrathin Co phthalocyanine through phosphate groups. By strengthening H-bonding interactions, the resultant CoPc/P-BNDCN nanocomposite showed excellent photocatalytic CO₂ reduction activity, releasing 197.76 and 130.32 µmol h⁻¹ g⁻¹ CO and CH₄, respectively, and conveying an unprecedented 10-26-time improvement under visible-light irradiation. The substantial tuning is performed towards the conduction and valance band locations by B-dopants and N-defects to modulate the band structure for significantly accelerated CO₂ RR. Through the use of ultrathin metal phthalocyanine assemblies that have a lot of single-atom sites, this work demonstrates a sustainable approach for achieving effective photocatalytic CO₂ activation. More importantly, the excellent photoactivity is attributed to the fast charge separation via Z-scheme transfer mechanism formed by the universally facile strategy of dimension-matched ultrathin (≈4 nm) metal phthalocyanine-assisted nanocomposites.     

Facile construction of highly efficient MOF-based Pd@UiO-66-NH2@ZnIn2S4 flower-like nanocomposites for visible-light-driven photocatalytic hydrogen production

Construction of metal-organic-frameworks-based composite photocatalysts has attracted much atten-tion for the reasonable band gap and high surface areas to improve the photocatalytic activity.In this study,the ternary heterojunction Pd@UiO-66-NH2@Znln2S4 nanocomposites were facilely prepared for the first time by a two-step method.The visible-light-promoted hydrogen production rate of 0.3％ Pd@UiO-66-NH2@Znln2S4 reaches up to 5.26 mmol g-1 h-1,which is evidently much higher than pure UiO-66-NH2,ZnIn2S4 and binary UiO-66-NH2/ZnIn2S4 composites.Such a huge improvement in the pho-tocatalytic performance is mainly attributed to the matched band gap of ZnIn2S4 and UiO-66-NH2,and the introduction of Pd NPs into photocatalysts that broaden spectral response range and promote the photon induced charge carrier separation.This work may provide a feasible approach for the design and construction of metal-organic-frameworks-based photocatalytic materials.     

Mechanism of energy transfer in Sr2CeO4:Eu phosphor

Blue–white phosphor Sr₂CeO₄ belongs to a particular class of optical materials whose luminescence is governed by optical transitions associated with the electron charge transfer. The originality of its crystallographic structure, a chain-like sequence of luminescent centers, permits an effective transfer of the electronic excitation energy from the host to doped centers. Sr₂CeO₄, рure and doped with Eu³⁺-ions of different concentrations, was synthesized by the Pechini citrate-gel method. The luminescence spectra and luminescence decay curves of Sr₂CeO₄ and Sr₂CeO₄:Eu³⁺ at 300 and 80 K were investigated. The performed experiments revealed the Förster nonradiative energy transfer under the energy migration condition from the crystal host to the doped europium ions.     

Electrolyte Engineering on Performance Enhancement of NiCo2S4 Anode for Sodium Storage

NiCo₂S₄ is an attractive anode for sodium-ion batteries (SIBs) due to its high capacity and excellent redox reversibility. Practical deployment of NiCo₂S₄ electrode in SIBs, however, is still hindered by the inferior capacity and unsatisfactory cycling performance, which result from the mismatch between the electrolyte chemistry and electrode. Herein, a functional electrolyte containing 1.0 m NaCF₃SO₃ in diethylene glycol dimethyl ether (DEGDME) (1.0 m NaCF₃SO₃-DEGDME) is developed, which can be readily used for NiCo₂S₄ anode with high initial coulomb efficiency (96.2%), enhanced cycling performance, and boosted capacities (341.7 mA h g⁻¹ after 250 continuous cycles at the current density of 200 mA g⁻¹). The electrochemical tests and related phase characterization combined with density functional theory (DFT) calculation indicate the ether-based electrolyte is more suitable for the NiCo₂S₄ anode in SIBs due to the formation of a stable electrode–electrolyte interface. Additionally, the importance of the voltage window is also demonstrated to further optimize the electrochemical performance of the NiCo₂S₄ electrode. The formation of sulfide intermediates during charging and discharging is predicted by combining DFT and verified by in situ XRD and HRTEM. The findings indicate that electrolyte engineering would be an effective way of performance enhancement for sulfides in practical SIBs.     

Z-scheme mechanism for methylene blue degradation over Fe2O3/g-C3N4 nanocomposite prepared via one-pot exfoliation and magnetization of g-C3N4

The low surface area, high recombination rate of photogenerated charge carriers, narrow visible range activity, and difficulty in the separation from cleaned solutions limit the wide application of g-C₃N₄ as a photocatalyst. Herein, we have succeeded in developing a one-pot strategy to overcome the above-mentioned difficulties of g-C₃N₄. The broadening of the visible-light response range and inducing magnetic nature to g-C₃N₄ was succeeded by preparing a nanocomposite with Fe₂O₃ via a facile solvothermal method. The preparation method additionally imparted layer exfoliation of g-C₃N₄ as evident from the XRD patterns and TEM images. The strong interaction between the components is revealed from the XPS analysis. The broadened visible-light absorbance of Fe₂O₃/g-C₃N₄ with a Z-scheme photocatalytic degradation mechanism is well evident from the UV‒Vis DRS analysis and PL measurement of the composite with terephthalic acid. The active species of photocatalysis were further investigated using scavenging studies in methylene blue degradation that revealed hydroxyl radicals and holes as the major contributors to the activity of Fe₂O₃/g-C₃N₄.     

SnS2/Co3S4 Hollow Nanocubes Anchored on S‐Doped Graphene for Ultrafast and Stable Na‐Ion Storage

SnS₂ has been widely studied as an anode material for sodium‐ion batteries (SIBs) based on the high theoretical capacity and layered structure. Unfortunately, rapid capacity decay associated with volume variation during cycling limits practical application. Herein, SnS₂/Co₃S₄ hollow nanocubes anchored on S‐doped graphene are synthesized for the first time via coprecipitation and hydrothermal methods. When applied as the anode for SIBs, the sample delivers a distinguished charge specific capacity of 1141.8 mAh g^?1 and there is no significant capacity decay (0.1 A g^?1 for 50 cycles). When the rate is increased to 0.5 A g^?1, it presents 845.7 mAh g^?1 after cycling 100 times. Furthermore, the composite also exhibits an ultrafast sodium storage capability where 392.9 mAh g^?1 can be obtained at 10 A g^?1 and the charging time is less than 3 min. The outstanding electrochemical properties can be ascribed to the enhancement of conductivity for the addition of S‐doped graphene and the existence of p–n junctions in the SnS₂/Co₃S₄ heterostructure. Moreover, the presence of mesopores between nanosheets can alleviate volume expansion during cycling as well as being beneficial for the migration of Na⁺.     

Magnesium Storage Performance and Mechanism of 2D‐Ultrathin Nanosheet‐Assembled Spinel MgIn2S4 Cathode for High‐Temperature Mg Batteries

Magnesium batteries have the potential to be a next generation battery with large capability and high safety, owing to the high abundance, great volumetric energy density, and reversible dendrite‐free capability of Mg anodes. However, the lack of a stable high‐voltage electrolyte, and the sluggish Mg‐ion diffusion in lattices and through interfaces limit the practical uses of Mg batteries. Herein, a spinel MgIn₂S₄ microflower‐like material assembled by 2D‐ultrathin (≈5.0 nm) nanosheets is reported and first used as a cathode material for high‐temperature Mg batteries with an ionic liquid electrolyte. The nonflammable ionic liquid electrolyte ensure the safety under high temperatures. As prepared MgIn₂S₄ exhibits wide‐temperature‐range adaptability (50–150 °C), ultrahigh capacity (≈500 mAh g^?1 under 1.2 V vs Mg/Mg²⁺), fast Mg²⁺ diffusibility (≈2.0 × 10^?8 cm² s^?1), and excellent cyclability (without capacity decay after 450 cycles). These excellent electrochemical properties are due to the fast kinetics of magnesium by the 2D nanosheets spinel structure and safe high‐temperature operation environment. From ex situ X‐ray diffraction and transmission electron microscopy measurements, a conversion reaction of the Mg²⁺ storage mechanism is found. The excellent performance and superior security make it promising in high‐temperature batteries for practical applications.     

Multidimensional CdS nanowire/CdIn<Subscript>2</Subscript>S<Subscript>4</Subscript> nanosheet heterostructure for photocatalytic and photoelectrochemical applications

Nanomaterial shapes can have profound effects on material properties,and therefore offer an efficient way to improve the performances of designed materials and devices.The rational fabrication of multidimensional architectures such as one dimensional (1D)-two dimensional (2D) hybrid nanomaterials can integrate the merits of individual components and provide enhanced functionality.However,it is still very challenging to fabricate 1D/2D architectures because of the different growth mechanisms of the nanostructures.Here,we present a new solventmediated,surface reaction-driven growth route for synthesis of CdS nanowire (NW)/CdIn2S4 nanosheet (NS) 1D/2D architectures.The as-obtained CdS NW/CdIn2S4 NS structures exhibit much higher visible-light-responsive photocatalytic activities for water splitting than the individual components.The CdS NW/CdIn2S4 NS heterostructure was further fabricated into photoelectrodes,which achieved a considerable photocurrent density of 2.85 mA.cm-2 at 0 V vs.the reversible hydrogen electrode (RHE) without use of any co-catalysts.This represents one of the best results from a CdS-based photoelectrochemical (PEC) cell.Both the multidimensional nature and type Ⅱ band alignment of the 1D/2D CdS/CdIn2S4 heterostructure contribute to the enhanced photocatalytic and photoelectrochemical activity.The present work not only provides a new strategy for designing multidimensional 1D/2D heterostructures,but also documents the development of highly efficient energy conversion catalysts.     

Freestanding 1T‐MnxMo1–xS2–ySey and MoFe2S4–zSez Ultrathin Nanosheet‐Structured Electrodes for Highly Efficient Flexible Solid‐State Asymmetric Supercapacitors

Fabrication of hierarchical nanosheet arrays of 1T phase of transition‐metal dichalcogenides is indeed a critical task, but it holds immense potential for energy storage. A single‐step strategy is employed for the fabrication of stable 1T‐Mn_xMo_1–xS_2–ySe_y and MoFe₂S_4–zSe_z hierarchical nanosheet arrays on carbon cloth as positive and negative electrodes, respectively. The flexible asymmetric supercapacitor constructed with these two electrodes exhibits an excellent electrochemical performance (energy density of ≈69 Wh kg^?1 at a power density of 0.985 kW kg^?1) with ultralong cyclic stability of ≈83.5% capacity retention, after 10 000 consecutive cycles. Co‐doping of the metal and nonmetal boosts the charge storage ability of the transition‐metal chalcogenides following enrichment in the metallic 1T phase, improvement in the surface area, and expansion in the interlayer spacing in tandem, which is the key focus of the present study. This study explicitly demonstrates the exponential enhancement of specific capacity of MoS₂ following intercalation and doping of Mn and Se, and Fe₂S₃ following doping of Mo and Se could be an ideal direction for the fabrication of novel energy‐storage materials with high‐energy storage ability.     

发光二极管用荧光材料Sr2CeO4:Sm3+的合成及其发光特性

以具有一维结构的Sr2CeO4化合物为研究对象、Sm3 作为发光中心,探索了其作为LED用荧光材料的可能性.用高温固相法于1200℃、6h合成了Sr2CeO4:Sm3 系列单相粉末样品,并研究了其发光性质.结果表明,在365nm激发下,从荧光光谱中可以看出存在从基质向稀土离子的能量转移.通过调节荧光材料Sr2CeO4:Sm3 中稀土离子Sm3 的掺杂浓度,可以调谐发光体的发光颜色,当Sm3 离子浓度较小(<3%)时,体系发出很强的白光;当Sm3 离子浓度较大(3%～15%)时,体系发出红光.测量了荧光材料的色坐标,发现Sr2CeO4:1%Sm3 的色坐标是(0.334,0.320),接近于纯白色(0.33,0.33),可以作为一种新型的UV-LED用单一白色荧光材料.