State Key Laboratory of Crystal Materials

Abstract The ever‐growing demands for electrical energy storage have stimulated the pursuit of alternative advanced batteries. Zn‐ion batteries (ZIBs) are receiving increased attentions due to the low cost, high safety, and high eco‐efficiency. However, it is still a big challenge to develop suitable cathode materials for intercalation of Zn ions. This review provides a timely access for researchers to the recent activities regarding ZIBs. First, cathode materials including various manganese oxides, vanadium compounds, and Prussian blue analogs are summarized with details in crystal structures and Zn ion storage mechanisms. Then, the electrolytes and their influences on the electrochemical processes are discussed. Finally, opinions on the current challenge of ZIBs and perspective to future research directions are provided.

Transition metal carbides and nitrides (MXenes), a family of two-dimensional (2D) inorganic compounds, are materials composed of a few atomic layers of transition metal carbides, nitrides, or carbonitrides. Ti3C2, the first 2D layered MXene, was isolated in 2011. This material, which is a layered bulk material analogous to graphite, was derived from its 3D phase, Ti3AlC2 MAX. Since then, material scientists have either determined or predicted the stable phases of >200 different MXenes based on combinations of various transition metals such as Ti, Mo, V, Cr, and their alloys with C and N. Extensive experimental and theoretical studies have shown their exciting potential for energy conversion and electrochemical storage. To this end, we comprehensively summarize the current advances in MXene research. We begin by reviewing the structure types and morphologies and their fabrication routes. The review then discusses the mechanical, electrical, optical, and electrochemical properties of MXenes. The focus then turns to their exciting potential in energy storage and conversion. Energy storage applications include electrodes in rechargeable lithium- and sodium-ion batteries, lithium-sulfur batteries, and supercapacitors. In terms of energy conversion, photocatalytic fuel production, such as hydrogen evolution from water splitting, and carbon dioxide reduction are presented. The potential of MXenes for the photocatalytic degradation of organic pollutants in water, such as dye waste, is also addressed, along with their promise as catalysts for ammonium synthesis from nitrogen. Finally, their application potential is summarized.

Oxygen vacancies in crystal have important impacts on the electronic properties of ZnO. With ZnO(2) as precursors, we introduce a high concentration of oxygen vacancies into ZnO successfully. The obtained ZnO exhibits a yellow color, and the absorption edge shifts to longer wavelength. Raman and XPS spectra reveal that the concentration of oxygen vacancies in the ZnO decreased when the samples are annealed at higher temperature in air. It is consistent with the theory calculation. The increasing of oxygen vacancies results in a narrowing bandgap and increases the visible light absorption of the ZnO. The narrowing bandgap can be confirmed by the enhancement of the photocurrent response when the ZnO was irradiated with visible light. The ZnO with oxygen vacancies are found to be efficient for photodecomposition of 2,4-dichlorophenol under visible light irradiation.

Plasmonic photocatalyst [email protected], in which Ag nanoparticles are deposited on the surfaces of AgCl particles (SEM image depicted), was prepared by treating Ag2MoO4 with HCl to form AgCl powder and then reducing some Ag+ ions in the surface region of the AgCl particles to Ag0. This photocatalyst is highly efficient, for example in the degradation of organic dyes, and stable under visible light.

-chromen-2-one motif, as it is known according to IUPAC nomenclature. Coumarin derivatives are widely found in nature, especially in plants and are constituents of several essential oils. Up to now, thousands of coumarin derivatives have been isolated from nature or produced by chemists. More recently, the coumarin platform has been widely adopted in the design of small-molecule fluorescent chemosensors because of its excellent biocompatibility, strong and stable fluorescence emission, and good structural flexibility. This scaffold has found wide applications in the development of fluorescent chemosensors in the fields of molecular recognition, molecular imaging, bioorganic chemistry, analytical chemistry, materials chemistry, as well as in the biology and medical science communities. This review focuses on the important progress of coumarin-based small-molecule fluorescent chemosensors during the period of 2012-2018. This comprehensive and critical review may facilitate the development of more powerful fluorescent chemosensors for broad and exciting applications in the future.

MoS(2) nanosheet-coated TiO(2) nanobelt heterostructures--referred to as TiO(2)@MoS(2)--with a 3D hierarchical configuration are prepared via a hydrothermal reaction. The TiO(2) nanobelts used as a synthetic template inhibit the growth of MoS(2) crystals along the c-axis, resulting in a few-layer MoS(2) nanosheet coating on the TiO(2) nanobelts. The as-prepared TiO(2)@MoS(2) heterostructure shows a high photocatalytic hydrogen production even without the Pt co-catalyst. Importantly, the TiO(2)@MoS(2) heterostructure with 50 wt% of MoS(2) exhibits the highest hydrogen production rate of 1.6 mmol h(-1) g(-1). Moreover, such a heterostructure possesses a strong adsorption ability towards organic dyes and shows high performance in photocatalytic degradation of the dye molecules.

Heterogeneous photocatalysis that employs photo-excited semiconductor materials to reduce water and oxidize toxic pollutants upon solar light irradiation holds great prospects for renewable energy substitutes and environmental protection. To utilize solar light effectively, the quest for highly active photocatalysts working under visible light has always been the research focus. Layered BiOX (X = Cl, Br, I) are a kind of newly exploited efficient photocatalysts, and their light response can be tuned from UV to visible light range. The properties of semiconductors are dependent on their morphologies and compositions as well as structures, and this also offers the guidelines for design of highly-efficient photocatalysts. In this review, recent advances and emerging strategies in tailoring BiOX (X = Cl, Br, I) nanostructures to boost their photocatalytic properties are surveyed.

A Ni3S2 nanorods/Ni foam composite electrode is prepared as a high-performance catalyst for the oxygen evolution reaction (OER), which exhibits excellent OER activity with a small overpotential of ∼157 mV based on the onset of catalytic current.

First-principles calculations are performed to study the electronic and magnetic properties of VX(2) monolayers (X = S, Se). Our results unveil that VX(2) monolayers exhibit exciting ferromagnetic behavior, offering evidence of the existence of magnetic behavior in pristine 2D monolayers. Furthermore, interestingly, both the magnetic moments and strength of magnetic coupling increase rapidly with increasing isotropic strain from -5% to 5% for VX(2) monolayers. It is proposed that the strain-dependent magnetic moment is related to the strong ionic-covalent bonds, while both the ferromagnetism and the variation in strength of magnetic coupling with strain arise from the combined effects of both through-bond and through-space interactions. These findings suggest a new route to facilitate the design of nanoelectronic devices for complementing graphene.

One-dimensional TiO2 nanostructured surface heterostructures (1D TiO2NSHs) have been comprehensively studied during the past two decades because of the possible practical applications in various fields, including photocatalysis, dye-sensitized solar cells, sensors, lithium batteries, biomedicine, catalysis, and supercapacitors. Combining extensive advancements in materials science and nanotechnology, a 1D TiO2NSH material with well-controlled size, morphology, and composition has been designed and synthesized. More importantly, its superior properties, including a high aspect ratio structure, chemical stability, large specific surface area, excellent electronic or ionic charge transfer, and a specific interface effect, have attracted a great deal of interest in improving current performance and exploring new applications. In this tutorial review, we introduce the characteristics of 1D TiO2 nanostructures, the design principles for the fabrication of 1D TiO2NSHs, and we also summarize the recent progress in developing synthesis methods and applications of 1D TiO2NSHs in different fields. The relationship between the secondary phase and the 1D TiO2 nanostructure and between the performance in applications and the excellent physical properties of 1D TiO2NSHs are also discussed.

Aggregation-induced emission (AIE) has been harnessed in many systems through the principle of restriction of intramolecular rotations (RIR) based on mechanistic understanding from archetypal AIE molecules such as tetraphenylethene (TPE). However, as the family of AIE-active molecules grows, the RIR model cannot fully explain some AIE phenomena. Here, we report a broadening of the AIE mechanism through analysis of 10,10',11,11'-tetrahydro-5,5'-bidibenzo[a,d][7]annulenylidene (THBDBA), and 5,5'-bidibenzo[a,d][7]annulenylidene (BDBA). Analyses of the computational QM/MM model reveal that the novel mechanism behind the AIE of THBDBA and BDBA is the restriction of intramolecular vibration (RIV). A more generalized mechanistic understanding of AIE results by combining RIR and RIV into the principle of restriction of intramolecular motions (RIM).

The bandgaps of monolayer and bulk molybdenum sulfide (MoS2 ) result in that they are far from suitable for application as a saturable absorption device. In this paper, the operation of a broadband MoS2 saturable absorber is demonstrated by the introduction of suitable defects. It is believed that the results provide some inspiration in the investigation of two-dimensional optoelectronic materials.

Abstract Femtosecond‐laser micromachining (also known as inscription or writing) has been developed as one of the most efficient techniques for direct three‐dimensional microfabrication of transparent optical materials. In integrated photonics, by using direct writing of femtosecond/ultrafast laser pulses, optical waveguides can be produced in a wide variety of optical materials. With diverse parameters, the formed waveguides may possess different configurations. This paper focuses on crystalline dielectric materials, and is a review of the state‐of‐the‐art in the fabrication, characterization and applications of femtosecond‐laser micromachined waveguiding structures in optical crystals and ceramics. A brief outlook is presented by focusing on a few potential spotlights.

Renewable, cost-effective and eco-friendly electrode materials have attracted much attention in the energy conversion and storage fields. Bagasse, the waste product from sugarcane that mainly contains cellulose derivatives, can be a promising candidate to manufacture supercapacitor electrode materials. This study demonstrates the fabrication and characterization of highly porous carbon aerogels by using bagasse as a raw material. Macro and mesoporous carbon was first prepared by carbonizing the freeze-dried bagasse aerogel; consequently, microporous structure was created on the walls of the mesoporous carbon by chemical activation. Interestingly, it was observed that the specific surface area, the pore size and distribution of the hierarchical porous carbon were affected by the activation temperature. In order to evaluate the ability of the hierarchical porous carbon towards the supercapacitor electrode performance, solid state symmetric supercapacitors were assembled, and a comparable high specific capacitance of 142.1 F g(-1) at a discharge current density of 0.5 A g(-1) was demonstrated. The fabricated solid state supercapacitor displayed excellent capacitance retention of 93.9% over 5000 cycles. The high energy storage ability of the hierarchical porous carbon was attributed to the specially designed pore structures, i.e., co-existence of the micropores and mesopores. This research has demonstrated that utilization of sustainable biopolymers as the raw materials for high performance supercapacitor electrode materials is an effective way to fabricate low-cost energy storage devices.

Lead-free piezoelectric ceramics, with the nominal composition of 0.948(K0.5Na0.5)NbO3–0.052LiSbO3 (KNN-LS5.2), were synthesized by conventional solid-state sintering, and the piezoelectric and electromechanical properties were characterized as a function of temperature. The Curie temperature of the KNN based perovskite material was found to be 368°C with an orthorhombic-tetragonal polymorphic phase transition (TO-T) temperature at approximately ∼35°C. The room temperature dielectric permittivity (ε33T∕ε0) and loss were found to be 1380 and 2%, respectively, with piezoelectric properties of k33∼62% and d33∼265pC∕N and k31∼30% and d31∼−116pC∕N. The temperature dependence of the properties mimicked the compositional variation seen in the proximity of a morphotropic phase boundary [e.g., lead zirconate titanate (PZT)], with a maxima in the dielectric and piezoelectric properties and a corresponding “softening” of the elastic properties. Unlike that found for PZT-type materials, the modified KNN material exhibited characteristics of both “soft” and “hard” piezoelectricities owing to the distinctly different domain states associated with orthorhombic and tetragonal phases.

The ternary strategy has been widely identified as an effective approach to obtain high-efficiency organic solar cells (OSCs). However, for most ternary OSCs, the nonradiative voltage loss lies between those of the two binary devices, which limits further efficiency improvements. Herein, an asymmetric guest acceptor BTP-2F2Cl is designed and incorporated into a PM1:L8-BO host blend. Compared with the L8-BO neat film, the L8-BO:BTP-2F2Cl blend film shows higher photoluminescence quantum yield and larger exciton diffusion length. Introducing BTP-2F2Cl into the host blend extends its absorption spectrum, improves the molecular packing of host materials, and suppresses the nonradiative charge recombination of the ternary OSCs. Consequently, the power conversion efficiency is improved up to 19.17% (certified value 18.7%), which represents the highest efficiency value reported for single-junction OSCs so far. The results show that improving the exciton behaviors is a promising approach to reducing the nonradiative voltage loss and realizing high-performance OSCs.

Nanocrystalline SnO2 particles have been synthesized by a simple sol−gel method. The structural and optical properties of these SnO2 particles are investigated using X-ray powder diffraction, transmission electron microscopy, UV−visible absorption, and photoluminescence spectroscopy. The oxygen-vacancies-related photoluminescence of pure, cerium-, and manganese-doped SnO2 nanoparticles was systematically investigated. The origin of the luminescence is assigned to the recombination of electrons in a conduction band with holes in the center. Experimental results reveal that increasing calcining temperature can decrease the oxygen-vacancies-related luminescence intensity of the sample. After introducing Ce3+/Mn2+ ions into the host, the oxygen-vacancies-related luminescence has been enhanced remarkably resulting from the formation of many more oxygen vacancies. The dependence of the oxygen-vacancies-related luminescence intensity on the Ce3+/Mn2+ concentration is also discussed.

Near-infrared active photocatalytic properties of Bi2 WO6 nanosheets owing to the oxygen vacancies of the Bi2 WO6 nanosheets are reported. The broad spectrum photocatalyst, Bi2 WO6 -TiO2 nanobelt heterostructures, are obtained by assembling Bi2 WO6 nanocrystals on TiO2 nanobelts. The active light band of the novel hybrid photocatalyst with high photocatalytic activity covers full-spectrum solar light including the UV, visible, and near-infrared ranges.

Visible improvements: Owing to the plasmon resonance of silver nanoparticles deposited on the surface of AgBr, the newly-prepared plasmonic photocatalyst Ag section signAgBr has a strong absorption in the visible region (see picture) and shows high efficiency in the photodegradation of organic pollutants under visible light.

A three-dimensional graphene network (3DGN) grown on nickel foam is an excellent template for the synthesis of graphene-based composite electrodes for use in supercapacitors. Ni(OH)2nanosheets coated onto single-crystal Ni3S2nanorods grown on the surface of the 3DGN (referred to as the Ni3S2@Ni(OH)2/3DGN) are synthesized using a one-step hydrothermal reaction. SEM, TEM, XRD and Raman spectroscopy are used to investigate the morphological and structural evolution of the Ni3S2@Ni(OH)2/3DGN. Detailed electrochemical characterization shows that the Ni3S2@Ni(OH)2/3DGN exhibits high specific capacitance (1277 F g−1 at 2 mV s−1 and 1037.5 F g−1 at 5.1 A g−1) and areal capacitance (4.7 F cm−2 at 2 mV s−1 and 3.85 F cm−2 at 19.1 mA cm−2) with good cycling performance (99.1% capacitance retention after 2000 cycles).