In-situ Synthesis of the Thinnest In2Se3/In2S3/In2Se3 Sandwich-Like Heterojunction for Photoelectrocatalytic Water Splitting

The efficient utilization of solar energy for photoelectrocatalytic (PEC) water splitting is a feasible solution for developing clean energy and alleviating environmental issues. However, as the core of PEC technology, the existing photoanode catalysts have disadvantages such as poor photoelectrocatalytic conversion efficiency, low conductivity of photogenerated carriers, and instability. Here, we report the ultrathin two-dimensional sandwich-like (SW) heterojunction of In₂Se₃/In₂S₃/In₂Se₃ (SW In₂S₃@In₂Se₃) for the first time for PEC water splitting. Our findings identify the efficient separation of electrons and holes by constructing SW In₂S₃@In₂Se₃ heterojunction. The in situ synthesis of ultrathin nanosheet arrays by using surface substitution of Se atom to epitaxially grow cell In₂Se₃ maximizes the contact area of heterogeneous interface and accelerates the transmission of charge carrier. Benefitting from the unique structure and composition characteristic, SW In₂S₃@In₂Se₃ displays excellent performance in PEC water splitting. The photocurrent density of SW In₂S₃@In₂Se₃ reaches 8.43 mA cm⁻² at 1.23 V_RHE. Compared with In₂S₃, the SW In₂S₃@In₂Se₃ photoanode has nearly 12 times higher PEC performance, which represents the best performance among the In₂S₃-based photoanode heterojunction reported so far. The evolution rate of O₂ reaches 78.8 μmol cm⁻² h⁻¹, and the photocurrent has no apparent variety within 24 h.     

A Hierarchical Nanostructured Carbon Nanofiber–In2S3 Photocatalyst with High Photodegradation and Disinfection Abilities Under Visible Light

Photocatalytic degradation of pollutants under visible light provides a new door to solve the water contamination problem by utilizing free and renewable sunlight. The search for highly efficient photocatalysts with hierarchical nanostructures remains crucial for accessing this new door. In this work, a new hierarchical nanostructured photocatalyst is designed and synthesized, for the first time, by anchoring In₂S₃ flower‐like nanostructures on non‐woven carbon nanofiber (CNF). The nanostructures of these CNF–In₂S₃ composites were fine‐tuned, with the aim of achieving the highest photocatalytic activity under visible light. The formation mechanism of the hierarchical nanostructure is also investigated. The results indicate that the optimized hierarchical CNF–In₂S₃ photocatalyst is superior in photodegradation and disinfection efficiency to that of pure In₂S₃ under visible‐light irradiation. The prominent photocatalytic activities of these hierarchical CNF–In₂S₃ photocatalysts can be attributed to the excellent properties of enhanced light absorption, large surface area, and efficient charge separation, which are all derived from the special three‐dimensional hierarchical nanostructures. Therefore, this work presents the great potential of this hierarchical nanostructured CNF–In₂S₃ photocatalyst in practical environmental remediation fields.     

Parallel Planar Heterojunction Strategy Enables Sb2S3 Solar Cells with Efficiency Exceeding 8 %

Solution-processed solar cells based on inorganic heterojunctions provide a potential approach to the efficient, stable and low-cost solar cells required for the terrestrial generation of photovoltaic energy. Antimony trisulfide (Sb₂S₃) is a promising photovoltaic absorber. Here, an easily solution-processed parallel planar heterojunction (PPHJ) strategy and related principle are developed to prepare efficient multiple planar heterojunction (PHJ) solar cells, and the PPHJ strategy boosts the efficiency of solution-processed Sb₂S₃ solar cells up to 8.32 % that is the highest amongst Sb₂S₃ devices. The Sb₂S₃-based PPHJ device consists of two kinds of conventional planar heterojunction (PHJ) subcells in a parallel connection: Sb₂S₃-based PHJ subcells dominating the absorption and charge generation and CH₃NH₃PbI₃-based PHJ subcells governing the electron transport towards collection electrode, but it belongs to an Sb₂S₃ device in nature. The resulting PPHJ device combines together the distinctive structural features of Sb₂S₃ absorbing layer as a main absorber and the duplexity of well-crystallized/oriented CH₃NH₃PbI₃ layer in charge transportation as an additional absorber, while the presence of perovskite does not affect device stability. The PPHJ strategy maintains the facile preparation by the conventional sequential depositions of multiple layers, but eliminates the normal complexity in both tandem and parallel tandem PHJ systems.     

Ultrathin ZnIn2S4 Nanosheets Anchored on Ti3C2TX MXene for Photocatalytic H2 Evolution

Photocatalysts derived from semiconductor heterojunctions that harvest solar energy and catalyze reactions still suffer from low solar‐to‐hydrogen conversion efficiency. Now, MXene (Ti₃C₂T_X) nanosheets (MNs) are used to support the in situ growth of ultrathin ZnIn₂S₄ nanosheets (UZNs), producing sandwich‐like hierarchical heterostructures (UZNs‐MNs‐UZNs) for efficient photocatalytic H₂ evolution. Opportune lateral epitaxy of UZNs on the surface of MNs improves specific surface area, pore diameter, and hydrophilicity of the resulting materials, all of which could be beneficial to the photocatalytic activity. Owing to the Schottky junction and ultrathin 2D structures of UZNs and MNs, the heterostructures could effectively suppress photoexcited electron–hole recombination and boost photoexcited charge transfer and separation. The heterostructure photocatalyst exhibits improved photocatalytic H₂ evolution performance (6.6 times higher than pristine ZnIn₂S₄) and excellent stability.     

化学浴沉积方法制备硫化铟敏化太阳电池及其性能研究

硫化铟是一种稳定、低毒性的半导体材料. 本文采用低成本的化学浴沉积方法制备了硫化铟敏化太阳电池, X射线衍射(XRD)、光电子能谱(XPS)和扫描电镜(SEM)结果表明形成了硫化铟敏化的二氧化钛薄膜. 化学浴沉积温度对所得硫化铟敏化薄膜的形貌有显著的影响, 进而影响电池性能. 温度太低时, 化学浴沉积反应速率太低, 只发生少量沉积; 温度太高时, 化学浴沉积反应速率较快, 硫化铟来不及沉积到二氧化钛多孔薄膜内部. 当温度在40℃时, 硫化铟沉积均匀性最好, 薄膜的光吸收性能最佳, 电池的短路电流最大, 另外, 填充因子达到最佳, 为65%, 电池总体光电转换效率为0.32%.     

Band‐Edge Electronic Structure of β‐In2S3: The Role of s or p Orbitals of Atoms at Different Lattice Positions

As a promising solar‐energy material, the electronic structure and optical properties of Beta phase indium sulfide (β‐In₂S₃) are still not thoroughly understood. This paper devotes to solve these issues using density functional theory calculations. β‐In₂S₃ is found to be an indirect band gap semiconductor. The roles of its atoms at different lattice positions are not exactly identical because of the unique crystal structure. Additonally, a significant phenomenon of optical anisotropy was observed near the absorption edge. Owing to the low coordination numbers of the In3 and S2 atoms, the corresponding In3‐5s states and S2‐3p states are crucial for the composition of the band‐edge electronic structure, leading to special optical properties and excellent optoelectronic performances.     

Atomic‐Layer‐Confined Doping for Atomic‐Level Insights into Visible‐Light Water Splitting

A model of doping confined in atomic layers is proposed for atomic‐level insights into the effect of doping on photocatalysis. Co doping confined in three atomic layers of In₂S₃ was implemented with a lamellar hybrid intermediate strategy. Density functional calculations reveal that the introduction of Co ions brings about several new energy levels and increased density of states at the conduction band minimum, leading to sharply increased visible‐light absorption and three times higher carrier concentration. Ultrafast transient absorption spectroscopy reveals that the electron transfer time of about 1.6 ps from the valence band to newly formed localized states is due to Co doping. The 25‐fold increase in average recovery lifetime is believed to be responsible for the increased of electron–hole separation. The synthesized Co‐doped In₂S₃ (three atomic layers) yield a photocurrent of 1.17 mA cm^?2 at 1.5 V vs. RHE, nearly 10 and 17 times higher than that of the perfect In₂S₃ (three atomic layers) and the bulk counterpart, respectively.     

Phase diagram of the In3As2Se6-In3As2S3Se3 system

The In₃As₂Se₆-In₃As₂S₃Se₃ system has been investigated by methods of physicochemical analysis (DTA, X-ray powder diffraction, MSA) and by microhardness and density measurements. The phase diagram of the system, which is the quasi-binary section of the As-In-S-Se quaternary system, has been constructed. The region of the In₃As₂Se₆-based solid solutions is extended to 7 mol %, and the In ₃As₂S₃Se₃-based region to 15 mol %. A new quaternary compound In₆As₄S₃Se₉ is found in the system. Original Russian Text ? I.I. Aliev, R.S. Magammedragimova, A.A. Farzaliev, Dzh. Veliev, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 4, pp. 691–694.     

Microwave Synthesized In2S3@CNTs with Excellent Properties inLithium‐Ion Battery and Electromagnetic Wave Absorption

The three‐dimensional nanoflower‐like β‐In₂S₃ composited with carbon nanotubes (CNTs) has been synthesized by a single mode microwave‐assisted hydrothermal technique. The In₂S₃ and CNTs nanocomposites (In₂S₃@CNTs) were investigated as the anode materials of lithium batteries (LIBs) and the electromagnetic wave absorption materials. For LIBs applications, the In₂S₃@CNTs nanocomposite exhibited excellent cycling stability with a high reversible charge capacity of 575 mA⋅h⋅g^–1 after 300 cycles at 0.5 A⋅g^–1. In addition, the In₂S₃@CNTs used as electromagnetic wave absorber displayed a maximum reflection loss of –42.75 dB at 11.96 GHz with a thickness of 1.55 mm.     

In2O3敏化ZnO纳米棒阵列的性能及其光电催化活性

以掺氟SnO₂ (FTO)导电玻璃为基底, 采用水热法制备了ZnO纳米棒阵列. 通过In(NO₃)₃水溶液水洗的方法, 合成了In₂O₃敏化ZnO纳米棒阵列光催化剂. 采用场发射扫描电子显微镜(FESEM), X射线能谱(EDX), X射线衍射(XRD)及紫外-可见漫反射光谱(UV-Vis DRS)对样品的形貌、结构、组成、晶相等进行一系列的表征. 以罗丹明B (RhB)为目标降解物, 探究了In₂O₃敏化ZnO 纳米棒阵列光电催化活性. 采用场诱导表面光伏技术(FISPV)研究了不同含量的In₂O₃敏化ZnO纳米棒阵列在光照射下的光生电荷行为. 结合电化学工作站检测不同样品的光电流, 随着In₂O₃敏化量的改变, 光电流和开路电压也随之改变. 并探讨了In₂O₃敏化ZnO纳米棒阵列光生电荷行为与光电催化活性之间的关系. 结果表明, 适量In₂O₃敏化的ZnO光催化剂在可见光下2 h内对罗丹明B的降解效率达到95%, 是单纯ZnO纳米棒阵列的2.4倍.     

A facile preparation and visible light-induced photocatalysis of indium sulfide superstructure

β-In₂S₃ superstructure comprised of nanoflakes with the sizes of 200–450 nm has been synthesized by a facile reflux method with the assistance of the sodium dodecylsulfate at low temperature (80 °C). XRD, SEM, TEM, HRTEM, and UV–vis spectra were used to characterize the In₂S₃ superstructure. Prepared In₂S₃ superstructures exhibited high photocatalytic activities in the degradation of rhodamine B under visible light irradiation (λ > 420 nm), in which 97.5% RhB was photodegraded after 60 min.     

Recent status and future perspectives of ZnIn2S4 for energy conversion and environmental remediation

Zinc indium sulfide (ZnIn₂S₄), a novel photocatalyst, has attracted considerable attention and been extensively studied over the past few years owing to its various advantages such as nontoxicity, structural stability, easy availability, suitable band gap and fascinating photocatalytic activity. This review mainly focuses on the recent state-of-art progress of ZnIn₂S₄-based photocatalysts. First, we briefly introduced preparation methods of ZnIn₂S₄ with diverse morphological structures. Then, considering the photocatalytic activity of pristine ZnIn₂S₄ would be confined by rapid recombination of photo-generated electron-hole pairs and limited light absorption range, different modulation strategies such as layer and size control, doping, vacancy engineering and hetero-nanostructures were expounded in detail. Afterwards, the applications of ZnIn₂S₄ in various fields such as H₂ production, CO₂ reduction, value-added products synthesis, pollutant purification and N₂ fixation are clearly summarized. In the end, we sorted out the conclusions and outlook, aiming to provide some new insights for this fascinating material.     

Structural, textural and photocatalytic properties of quantum-sized In2S3-sensitized Ti-MCM-41 prepared by ion-exchange and sulfidation methods

In₂S₃ nanocrystallites were successfully encapsulated into the mesopores of Ti-MCM-41 by a two-step method involving ion-exchange and sulfidation. The X-ray diffraction (XRD) patterns, UV-vis absorption spectra (UV-Vis), high-resolution transmission electron microscopy (HRTEM) and N₂ adsorption-desorption isotherms were used to characterize the structure of the composite materials. It is found that the diameter of most In₂S₃ nanocrystallites is about 2.5 nm, less than the pore size of Ti-MCM-41. The In₂S₃ nanocrystallites inside the Ti-MCM-41 host show a significant blue-shift in the UV-vis absorption spectra. Under irradiation of visible light (), the composite material has much higher photocatalytic activity for hydrogen evolution than bulk In₂S₃. It can be explained by the effective charge-separation in the quantum-sized In₂S₃-sensitized Ti-MCM-41.     

Efficient Decomposition of Organic Pollutants Over In2O3/TiO2 Nanocomposite Photocatalyst Under Visible Light Irradiation

The heterojunction structures of In₂O₃/TiO₂, exhibiting visible light photocatalytic efficiency, has been synthesized by utilizing maleic acid as an organic linker to combine In₂O₃ and Degussa P25 (TiO₂) nanoparticles. The prepared nanocomposite has been characterized by FESEM, TEM, XRD and UV?CVisible reflectance spectra. The photocatalytic efficiency of the composite photocatalyst has been investigated based on the decomposition of 2-propanol (IP) in gas phase and 1,4-dichlorobenzene (DCB) in aqueous phase under visible light (??????420?nm) irradiation. The results reveal that the In₂O₃/TiO₂ composite photocatalyst with 7?wt% In₂O₃ demonstrated 6.3 times of efficiency in evolving CO₂ from gaseous IP and 8.7 times of efficiency in removing aqueous DCB in compare with Degussa P25. In this In₂O₃/TiO₂ composite system, TiO₂ seems to be the principal photocatalyst whereas the function of In₂O₃ is to sensitize TiO₂ by absorbing visible light (??????420?nm). The extraordinary high photocatalytic efficiency of this composite In₂O₃/TiO₂ under visible light has been explained on the basis of relative energy band positions of the component semiconductors.     

Photoluminescence and photocatalytic properties of Er<Superscript>3+</Superscript>-doped In<Subscript>2</Subscript>O<Subscript>3</Subscript> thin films prepared by sol–gel: application to Rhodamine B degradation under solar light

The effect of Er³⁺ doping (1%) on the structural, optical and photocatalytic properties of In₂O₃ thin films deposited on quartz substrates by spin coating was investigated. The In₂O₃:1% Er³⁺ films, annealed in the temperature range 800–1000 °C, were characterized by X-ray diffraction, scanning electron microscopy (SEM), atomic force microscopy, UV–Vis spectroscopy, ellipsometry and photoluminescence (PL). The films are polycrystalline with a cubic structure and the lattice parameter increases with the incorporation of Er³⁺ owing to its larger radius. The SEM images of the film show a granular morphology with large grains (~ 200 nm). The doped In₂O₃ film exhibits less transparency than In₂O₃ in the UV–visible region with band gaps of 3.42 and 3.60 eV, respectively. PL shows strong lines at 548 and 567 nm, assigned to Er³⁺ under direct excitation at 532 nm. The energy diagram of the junction In₂O₃:1% Er³⁺/Na₂SO₄ (0.1 M) solution plotted from physical and photoelectrochemical characterizations shows the feasibility of the films for Rhodamine B (RhB) degradation under solar light. The conduction band at 2.22 V deriving from the In³⁺:5s orbital is suitably positioned with respect to the O₂/O ₂ ^· level (~ 1.40 V_SCE), leading to oxidation of 32% of 10 ppm RhB within 40 min of solar irradiation.     

Discrete Supertetrahedral T5 Selenide Clusters and Their Se/S Solid Solutions: Ionic-Liquid-Assisted Precursor Route Syntheses and Photocatalytic Properties

Although supertetrahedral Tn sulfide clusters (n=2–6) have been extensively explored, the synthesis of Tn selenide clusters with n>4 has not been achieved thus far. Reported here are ionic-liquid (IL)-assisted precursor route syntheses, characterizations, and the photocatalytic properties of six new M-In-Q (M=Cu or Cd; Q=Se or Se/S) chalcogenide compounds, namely [Bmmim]₁₂Cu₅In₃₀Q₅₂Cl₃(Im) (Q=Se ( T5-1 ), Se_48.5S_3.5 ( T5-2 ); Bmmim=1-butyl-2,3-dimethylimidazolium, Im=imidazole), [Bmmim]₁₁Cd₆In₂₈Q₅₂Cl₃(MIm) (Q=Se ( T5-3 ), Se_28.5S_23.5 ( T5-4 ), Se₁₆S₃₆ ( T5-5 ); MIm=1-methylimidazole), and [Bmmim]₉Cd₆In₂₈Se₈S₄₄Cl(MIm)₃ ( T5-6 ). The cluster compounds T5-1 and T5-3 represent the largest molecular supertetrahedral Tn selenide clusters to date. Under visible-light illumination, the Cu-In-Q compounds showed photocatalytic activity towards the decomposition of crystal violet, whereas the Cd-In-Q compounds exhibited good photocatalytic H₂ evolution activity. Interestingly, the experimental results show that the photocatalytic performances of the selenide/sulfide solid solutions were significantly better than those of their selenide analogues, for example, the degradation time of the organic dye with T5-2 was much shorter than that with T5-1 , whereas the photocatalytic H₂ evolution efficiencies with T5-3 – T5-6 improved significantly with increasing sulfur content. This work highlights the significance of IL-assisted precursor route synthesis and the tuning of photocatalytic properties through the formation of solid solutions.     

Two-dimensional polymeric carbon nitride: structural engineering for optimizing photocatalysis

As a two-dimensional (2D) material, polymeric carbon nitride (g-C₃N₄) nanosheet holds great potentials in environmental purification and solar energy conversion. In this review, we summarized latest progress in the optimization of photocatalytic performance in 2D g-C₃N₄. Some of the latest structural engineering methods were summed up, where the relevant influences on the behaviors of photoinduced species were emphasized. Furthermore, the construction strategies for band structure modulation and charge separation promotion were then discussed in detail. A brief discussion on the opportunity and challenge of 2D g-C₃N₄-based photocatalysis are presented as the conclusion of this review.     

Cube‐in‐Cube Hollow Cu9S5 Nanostructures with Enhanced Photocatalytic Activities in Solar H2 Evolution

Hydrogen produced from water under solar energy is an ideal clean energy source, and the efficiency of hydrogen production usually depends on the catalytic systems based on new compounds and/or a unique nanostructure. Herein, well‐defined cube‐in‐cube hollow Cu₉S₅ nanostructures have been successfully prepared with Cu₂O nanocubes and CS₂ as precursors, and single‐shell hollow Cu₉S₅ nanocubes could be obtained by replacing CS₂ with Na₂S. The formation mechanism of cube‐in‐cube hollow nanostructures has been proposed based on the Kirkendell effect and an outward self‐assembly process. Further studies revealed that the cube‐in‐cube hollow Cu₉S₅ nanostructures exhibited better photocatalytic activity toward solar H₂ evolution and would be a promising photocatalyst in the solar hydrogen industry.     

Z-Scheme In2S3/NU-1000 Heterojunction for Boosting Photo-Oxidation of Sulfide into Sulfoxide under Ambient Conditions

Photocatalytic oxidation of sulfide into sulfoxide has attracted extensive attention as an environmentally friendly strategy for chemical transformations or toxic chemicals degradation. Herein, we construct a series of In₂S₃/NU-1000 heterojunction photocatalysts, which can efficiently catalyze the oxidation of sulfides to form sulfoxides as the sole product under LED lamp (full-spectrum) illumination in air at room temperature. Especially, the sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES), can also be photocatalytically oxidized with In₂S₃/NU-1000 to afford nontoxic 2-chloroethyl ethyl sulfoxide (CEESO) selectively and effectively. In contrast, individual NU-1000 and In₂S₃ show very low catalytic activity on this reaction. The significantly improved photocatalytic activity is ascribed to the constructing of an efficient Z-scheme photocatalysts In₂S₃/NU-1000, which exhibits the enhancement of light harvesting, the promotion of photogenerated electron-hole separation, and the retention of high porosity of the parent MOF. Moreover, mechanism studies in photocatalytic oxidation reveal that the superoxide radical (^.O₂⁻) and singlet oxygen (¹O₂) are the main oxidative species in the oxidation system. This work exploits the opportunities for the construction of porous Z-scheme photocatalysts based on the photoactive MOFs materials and inorganic semiconductors for promoting catalytic organic transformations. More importantly, it provides a route to the rational design of efficient photocatalysts for the detoxification of mustard gas.     

Preparation and characterization of In<Subscript>2</Subscript>S<Subscript>3</Subscript> semiconductor thin films using the sol–gel method

This study describes the In₂S₃ semiconductor thin film coating on glass substrate by sol–gel method. The In₂S₃ thin film samples were prepared and examined by the X-ray diffraction (XRD), the UV–visible optical absorption and transmission study, and the Scanning Electron Microscope (SEM) image analyses. The XRD analysis results show that the In₂S₃ semiconductor thin films prepared by sol–gel method is formed at T~360–520 °C temperature interval. Band gap energy and optical absorption spectrum analysis of the In₂S₃ thin films reveal that Eg~2.51 eV for the In₂S₃ thin films. According to the EDX result the film was In-rich with the In/S = 1.42 ratio. The thickness of prepared In₂S₃ layer is about 400 nm.