Excitation-Dependent Long-Life Luminescent Polymeric Systems under Ambient Conditions

Organic room temperature luminescent materials present a unique phosphorescence emission with a long lifetime. However, many of these materials only emit single blue or green color in spite of external stimulation, and their color tunability is limited. Herein, we report a rational design to extend the emission color range from blue to red by controlling the doping of simple pyrene derivatives into a robust polymer matrix. The integration of these pyrene molecules into the polymer films enhances the intersystem crossing pathway, decreases the first triplet level of the system, and ensures the films show a sensitive response to excitation energy, finally yielding excitation-dependent long-life luminescent polymeric systems under ambient conditions. These materials were used to construct anti-counterfeiting patterns with multicolor interconversion, presenting a promising application potential in the field of information security.     

Indandione-Terminated Quinoids: Facile Synthesis by Alkoxide-Mediated Rearrangement Reaction and Semiconducting Properties

A series of 1,3-indandione-terminated π-conjugated quinoids were synthesized by alkoxide-mediated rearrangement reaction of the respective alkene precursors, followed by air oxidation. This new protocol allows access to quinoidal compounds with variable termini and cores. The resulting quinoids all show LUMO levels below −4.0 eV and molar extinction coefficients above 10⁵ L mol⁻¹ cm⁻¹. The optoelectronic properties of these compounds can be regulated by tuning the central cores as well as the aryl termini ascribed to the delocalized frontier molecular orbitals over the entire molecular skeleton involving aryl termini. n-Channel organic thin-film transistors with electron mobility of up to 0.38 cm² V⁻¹ s⁻¹ were fabricated, showing the potential of this new class of quinoids as organic semiconductors.     

Surface-Polarity-Induced Spatial Charge Separation Boosts Photocatalytic Overall Water Splitting on GaN Nanorod Arrays

Photocatalytic overall water splitting has been recognized as a promising approach to convert solar energy into hydrogen. However, most of the photocatalysts suffer from low efficiencies mainly because of poor charge separation. Herein, taking a model semiconductor gallium nitride (GaN) as an example, we uncovered that photogenerated electrons and holes can be spatially separated to the nonpolar and polar surfaces of GaN nanorod arrays, which is presumably ascribed to the different surface band bending induced by the surface polarity. The photogenerated charge separation efficiency of GaN can be enhanced significantly from about 8 % to more than 80 % via co-exposing polar and nonpolar surfaces. Furthermore, spatially assembling reduction and oxidation cocatalysts on the nonpolar and polar surfaces remarkably boosts photocatalytic overall water splitting, with the quantum efficiency increased from 0.9 % for the film photocatalyst to 6.9 % for the nanorod arrays photocatalyst.     

Crystallization-Induced Reversal from Dark to Bright Excited States for Construction of Solid-Emission-Tunable Squaraines

Squaraines (SQs) with tunable emission in the solid state is of great importance for various demands; however a remaining challenge is emission quenching upon aggregation. Herein, a unique SQ, named as CIEE-SQ, is designed to exhibit strong emission in crystal, undergoing crystallization-induced reverse from dark ¹(n+σ,π*) to bright ¹(π,π*) excited states. Such an excited state of CIEE-SQ can be subtly tuned by molecular conformation changes during the unexpected temperature-triggered single-crystal to single-crystal (SCSC) reversible transformation. Furthermore, co-crystallization between CIEE-SQ and chloroform largely stabilize the ¹(π,π*) state, enhancing the transition dipole moment and decreasing the reorganization energy to boost the fluorescence, which is promising in data encryption and decryption.     

Facile Synthesis of Hierarchical Nanosized Single-Crystal Aluminophosphate Molecular Sieves from Highly Homogeneous and Concentrated Precursors

The synthesis of hierarchical nanosized zeolite materials without growth modifiers and mesoporogens remains a substantial challenge. Herein, we report a general synthetic approach to produce hierarchical nanosized single-crystal aluminophosphate molecular sieves by preparing highly homogeneous and concentrated precursors and heating at elevated temperatures. Accordingly, aluminophosphate zeotypes of LTA (8-rings), AEL (10-rings), AFI (12-rings), and -CLO (20-rings) topologies, ranging from small to extra-large pores, were synthesized. These materials show exceptional properties, including small crystallites (30–150 nm), good monodispersity, abundant mesopores, and excellent thermal stability. A time-dependent study revealed a non-classical crystallization pathway by particle attachment. This work opens a new avenue for the development of hierarchical nanosized zeolite materials and understanding their crystallization mechanism.     

An Extra-Large-Pore Pure Silica Zeolite with 16×8×8-Membered Ring Pore Channels Synthesized using an Aromatic Organic Directing Agent

Extra-large-pore zeolites for processing large molecules have long been sought after by both the academia and industry. However, the synthesis of these materials, particularly extra-large-pore pure silica zeolites, remains a big challenge. Herein we report the synthesis of a new extra-large-pore silica zeolite, designated NUD-6, by using an easily synthesized aromatic organic cation as structure-directing agent. NUD-6 possesses an intersecting 16×8×8-membered ring pore channel system constructed by four-connected (Q⁴) and unusual three-connected (Q³) silicon species. The organic cations in NUD-6 can be removed in nitric acid to yield a porous material with high surface area and pore volume. The synthesis of NUD-6 presents a feasible means to prepare extra-large pore silica zeolites by using assembled aromatic organic cations as structure-directing agents.     

Rationally Designed Three-Layered Cu2S@Carbon@MoS2 Hierarchical Nanoboxes for Efficient Sodium Storage

Hybrid materials, integrating the merits of individual components, are ideal structures for efficient sodium storage. However, the construction of hybrid structures with decent physical/electrochemical properties is still challenging. Now, the elaborate design and synthesis of hierarchical nanoboxes composed of three-layered Cu₂S@carbon@MoS₂ as anode materials for sodium-ion batteries is reported. Through a facile multistep template-engaged strategy, ultrathin MoS₂ nanosheets are grown on nitrogen-doped carbon-coated Cu₂S nanoboxes to realize the Cu₂S@carbon@MoS₂ configuration. The design shortens the diffusion path of electrons/Na⁺ ions, accommodates the volume change of electrodes during cycling, enhances the electric conductivity of the hybrids, and offers abundant active sites for sodium uptake. By virtue of these advantages, these three-layered Cu₂S@carbon@MoS₂ hierarchical nanoboxes show excellent electrochemical properties in terms of decent rate capability and stable cycle life.     

两种形貌纳米Fe2O3对TKX-50热分解的催化性能研究

Energy components used in solid rocket propellants are beneficial for improving the energy performance, and their thermal decomposition characteristics significantly affect the combustion properties of the propellants. As a kind of energetic material with both high energy and low sensitivity (impact and friction), 5, 5'-bistetrazole-1, 1'-diolate (TKX-50) can effectively improve the energy and safety characteristics of solid propellants. Burning catalyst is another important component of solid propellants, which can significantly improve the burning rate of the propellant and reduce the pressure exponent. Among various burning catalysts, nanoscale transition metal oxides can promote the thermal decomposition of the energetic component, thus enhancing the combustion properties of the solid propellant. However, the catalytic effects of nanoscale transition metal oxides with different morphologies on the thermal decomposition of TKX-50 have rarely been studied. Based on the excellent catalytic activity of Fe₂O₃ for TKX-50 thermal decomposition, nano-Fe₂O₃ particles with spherical and tubular microstructures were used for TKX-50 thermal decomposition. The Fe₂O₃ nanoparticles were successfully fabricated via the solvothermal method and characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS) analyses. The XRD, FT-IR, and XPS results confirmed the successful fabrication of spherical and tubular Fe₂O₃ samples. The SEM and TEM images showed that the spherical Fe₂O₃ samples are composed of agglomerated Fe₂O₃ nanoparticles with an average particle size of 110 nm. In addition, the average diameter and length of hollow tubular Fe₂O₃ nanoparticles are 120 nm and 200 nm, respectively. The catalytic activities of spherical and tubular Fe₂O₃ for TKX-50 decomposition were studied by thermogravimetric analysis (TG) and differential scanning calorimetry (DSC) methods. The DSC and TG-DTG curves showed that both tubular and spherical Fe₂O₃ could effectively promote TKX-50 thermal decomposition. The first thermal decomposition peak temperature (T_FDP) of TKX-50 was reduced by 36.5 K and 26.3 K in the presence of tubular and spherical Fe₂O₃, respectively, at 10 K·min⁻¹. The activation energy (E_a) of TKX-50, determined by the iso-conversional method, was significantly reduced in the presence of both tubular and spherical Fe₂O₃. The results indicated that the microstructure of the catalyst has a significant effect on its catalytic performance for TKX-50 thermal decomposition, and that tubular Fe₂O₃ with hollow microstructure possesses better catalytic activity than spherical Fe₂O₃. The excellent catalytic activity of tubular Fe₂O₃ can be attributed to the hollow microstructure, which has more active sites for TKX-50 thermal decomposition.     

全固态钠离子电池硫系化合物电解质

全固态钠离子电池具有资源丰富、安全性高等优势,作为未来大规模储能的重要选择而成为近年来先进二次电池前沿研究热点。钠离子硫系化合物电解质室温离子电导率高、弹性模量高、容易冷压成型,能增强电极/电解质界面接触、减小界面阻抗、缓冲电极材料在充放电过程中的应力/应变,是全固态钠离子电池的研究重点。本文对钠离子硫系化合物固态电解质的结构及性质进行了总结,讨论了硫系化合物电解质的本征特性、与电极的界面稳定性,并介绍了硫系化合物全固态钠离子电池的研究现状,最后分析了硫系化合物电解质面临的挑战及今后的发展方向。