Bimetallic selenide heterostructure with directional built-in electricfield confined in N-doped carbon nanofibers for superior sodium storage with ultralong lifespan

Constructing heterostructure is considered as an effective strategy to address the sluggish electronic and ionic kinetics of anode materials for sodium ion batteries(SIBs).However,realizing the orientated growth and uniform distribution of the heterostructure is still a great challenge.Herein,the regulated novel CoSe_(2)/NiSe_(2)heterostructure confined in N-doped carbon nanofibers(CoSe_(2)/NiSe_(2)@N-C)are prepared by using Co/Ni-ZIF template,in which,the CoSe_(2)/NiSe_(2)heterostructures realize uniform distribution on a micro level.Benefiting from the unique heterostructure and N-doped carbon nanofibers,the CoSe_(2)/NiSe_(2)@N-C deliveries superior rate capability and durable cycle lifespan with a reversible capacity of 400.5 mA h g^(-1)after 5000 cycles at 2 A g^(-1).The Na-ion full battery with CoSe_(2)/NiSe_(2)@N-C anode and layered oxide cathode displays a remarkable energy density of 563 W h kg^(-1)with 241.1 W kg^(-1)at 0.1 A g^(-1).The theoretical calculations disclose that the periodic and directional built-in electric-field along with the heterointerfaces of CoSe_(2)/NiSe_(2)@N-C can accelerate electrochemical reaction kinetics.The in(ex)situ experimental measurements reveal the reversible conversion reaction and stable structure of CoSe_(2)/NiSe_(2)@N-C during Na+insertion/extraction.The study highlights the potential ability of precisely controlled heterostructure to stimulate the electrochemical performances of advanced anode for SIBs.

Ultralong nitrogen/sulfur Co-doped carbon nano-hollowsphere chains with encapsulated cobalt nanoparticles for highly efficient oxygen electrocatalysis

The development of simple and effective strategies to prepare electrocatalysts,which possess unique and stable structures comprised of metal/nonmetallic atoms for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER),is currently an urgent issue.Herein,an efficient bifunctional electrocatalyst featured by ultralong N,S-doped carbon nano-hollow-sphere chains about 1300 nm with encapsulated Co nanoparticles(Co-CNHSCs)is developed.The multifunctional catalytic properties of Co together with the heteroatom-induced charge redistribution(i.e.,modulating the electronic structure of the active site)result in superior catalytic activities toward OER and ORR in alkaline media.The optimized catalyst Co-CNHSC-3 displays an outstanding electrocatalytic ability for ORR and OER,a high specific capacity of 1023.6 mAh gZn^(-1),and excellent reversibility after 80 h at 10mA cm^(-2)in a Zn-air battery system.This work presents a new strategy for the design and synthesis of efficient multifunctional carbon-based catalysts for energy storage and conversion devices.

Effect of aggregation on thermally activated delayed fluorescence and ultralong organic phosphorescence:QM/MM study

Aggregation-induced thermally activated delayed fluorescence(TADF)phenomena have attracted extensive attention recently.In this paper,several theoretical models including monomer,dimer,and complex are used for the explanation of the luminescent properties of(R)-5-(9H-carbazol-9-yl)-2-(1,2,3,4-tetrahydronaphthalen-1-yl)isoindoline-1,3-dione((R)-ImNCz),which was recently reported[Chemical Engineering Journal 418129167(2021)].The polarizable continuum model(PCM)and the combined quantum mechanics and molecular mechanics(QM/MM)method are adopted in simulation of the property of the molecule in the gas phase,solvated in acetonitrile and in aggregation states.It is found that large spin–orbit coupling(SOC)constants and a smaller energy gap between the first singlet excited state and the first triplet excited state(△E_(st))in prism-like single crystals(SC_(p)-form)are responsible for the TADF of(R)-lmNCz,while no TADF is found in block-like single crystals(SC_(b)-form)with a larger △E_(st).The multiple ultralong phosphorescence(UOP)peaks in the spectrum are of complex origins,and they are related not only to ImNCz but also to a minor amount of impurities(ImNBd)in the crystal prepared in the laboratory.The dimer has similar phosphorescence emission wavelengths to the(R)-lmNCz-SC_(p) monomers.The complex composed of(R)-lmNCz and(R)-lmNBd contributes to the phosphorescent emission peak at about 600 nm,and the phosphorescent emission peak at about 650 nm is generated by(R)-lmNBd.This indicates that the impurity could also contribute to emission in molecular crystals.The present calculations clarify the relationship between the molecular aggregation and the light-emitting properties of the TADF emitters and will therefore be helpful for the design of potentially more useful TADF emitters.

High-Power and Ultralong-Life Aqueous Zinc-Ion Hybrid Capacitors Based on Pseudocapacitive Charge Storage

Rechargeable aqueous zinc-ion hybrid capacitors and zincion batteries are promising safe energy storage systems.In this study,amorphous RuO2·H2O for the first time was employed to achieve fast and ultralong-life Zn2+storage based on a pseudocapacitive storage mechanism.In the RuO2·H2O||Zn zinc-ion hybrid capacitors with Zn(CF3SO3)2 aqueous electrolyte,the RuO2·H2O cathode can reversibly store Zn2+in a voltage window of 0.4-1.6 V(vs.Zn/Zn2+),delivering a high discharge capacity of 122 mAh g?1.In particular,the zinc-ion hybrid capacitors can be rapidly charged/discharged within 36 s with a very high power density of 16.74 kW kg?1 and a high energy density of 82 Wh kg?1.Besides,the zinc-ion hybrid capacitors demonstrate an ultralong cycle life(over 10,000 charge/discharge cycles).The kinetic analysis elucidates that the ultrafast Zn2+storage in the RuO2·H2O cathode originates from redox pseudocapacitive reactions.This work could greatly facilitate the development of high-power and safe electrochemical energy storage.

CNTs@S composite as cathode for all-solid-state lithium-sulfur batteries with ultralong cycle life

The main challenges in development of traditional liquid lithium-sulfur batteries are the shuttle effect at the cathode caused by the polysulfide and the safety concern at the Li metal anode arose from the dendrite formation.All-solid-state lithium-sulfur batteries have been proposed to solve the shuttle effect and prevent short circuits.However,solid-solid contacts between the electrodes and the electrolyte increase the interface resistance and stress/strain,which could result in the limited electrochemical performances.In this work,the cathode of all-solid-state lithium-sulfur batteries is prepared by depositing sulfur on the surface of the carbon nanotubes(CNTs@S)and further mixing with Li10GeP2S12 electrolyte and acetylene black agents.At 60℃,CNTs@S electrode exhibits superior electrochemical performance,delivering the reversible discharge capacities of 1193.3,959.5,813.1,569.6 and 395.5 mAhg^-1 at the rate of 0.1,0.5,1,2 and 5 C,respectively.Moreover,the CNTs@S is able to demonstrate superior high-rate capability of 660.3 mAhg^-1 and cycling stability of 400 cycles at a high rate of 1.0 C.Such uniform distribution of the CNTs,S and Li10GeP2S12 electrolyte increase the electronic and ionic conductivity between the cathode and the electrolyte hence improves the rate performance and capacity retention.

Synthesis of ultralong Si_3N_4 nanowires by a simple thermal evaporation method

Largescale vaporsolid synthesis of ultralong silicon nitride （Si3N4） nanowires was achieved by using simple thermal evaporation of mixture powders of active carbon and monoxide silicon. The products were charac terized by Xray diffraction, scanning electron microscopy, energydispersive Xray spectroscopy, and transmission electron microscopy. The results suggest that the silicon nitride nanowires have a smooth surface, with lengths of up to several hundreds of microns and diameters of 100300 nm. A detailed study of both the chemical and structural composition was performed. Such ultralong sil icon nitride nanowires demonstrate potential applications as materials for constructing nanoscale devices and as reinforcement in advanced composites.

High MXene loading, nacre-inspired MXene/ANF electromagnetic interference shielding composite films with ultralong strain-tofailure and excellent Joule heating performance

The high power density and intelligence of next-generation flexible electronic devices bring many challenges to fabricate flexible composite films with electromagnetic interference(EMI)shielding effectiveness(SE)property and excellent toughness via a simple method.Herein,inspired by the layered structure and biopolymer matrix networks in natural nacre,nacre-like layered Ti_(3)C2TX(MXene)/aramid nanofiber(ANF)films were fabricated through sol-gel,vacuum-assisted filtration,and hot-pressing.Three-dimensional(3D)interconnected aramid nanofibers networks between adjacent layered MXene result in an ultralong strain-to-failure of the film.Even though the functional filler MXene contents are as high as 60 wt.%and 70 wt.%,the strain-to-failure of the films could reach astonishing values of 18.34%±1.86%and 14.43%±1.26%,respectively.And the tensile strength could maintain about 85 MPa.Excitingly,with such a high filler,the film can also withstand double folding and vigorous rubbing without damage,which could better adapt to a harsh application environment.The result means that this work provides a convenient way to prepare other high functional filler composite films with excellent mechanical performance.The EMI SE values could reach 45 and 52.15 dB at 60 wt.%and 70 wt.%MXene in 8.2–12.4 GHz.Meanwhile,the films have prominent Joule heating properties,high sensitivity(<15 s),small voltage operation(0.5 V),and high operation constancy(1300 s).Therefore,nacre-inspired MXene/ANF composite films in this work have ability to apply in many areas including communication technology,military,and aerospace.

Double-layered skeleton of Li alloy anchored on 3D metal foam enabling ultralong lifespan of Li anode under high rate

The high specific capacity and low negative electrochemical potential of lithium metal anodes(LMAs),may allow the energy density threshold of Li metal batteries(LMBs)to be pushed higher.However,the existing detrimental issues,such as dendritic growth and volume expansion,have hindered the practical implementation of LMBs.Introducing three-dimensional frameworks(e.g.,copper and nickel foam),have been regarded as one of the fundamental strategies to reduce the local current density,aiming to extend the Sand'time.Nevertheless,the local environment far from the skeleton is almost the same as the typical plane Li,due to macroporous space of metal foam.Herein,we built a double-layered 3D current collector of Li alloy anchored on the metal foam,with micropores interconnected macropores,via a viable thermal infiltration and cooling strategy.Due to the excellent electronic and ionic conductivity coupled with favorable lithiophilicity,the Li alloy can effectively reduce the nucleation barrier and enhance the Li^(+)transportation rate,while the metal foam can role as the primary promotor to enlarge the surface area and buffer the dimensional variation.Synergistically,the Li composite anode with hierarchical structure of primary and secondary scaffolds realized the even deposition behavior and minimum volume expansion,outputting preeminent prolonged cycling performances under high rate.

Matrix-Mediated Color-Tunable Ultralong Organic Room Temperature Phosphorescence of 7H-Benzo[c]carbazole Derivatives

Building on the recent systematic research on 1Hbenzo[f]indole(Bd),an important advancement in constructing ultralong organic room temperature(UORTP)materials with a universal strategy via a readily obtained unit(7H-Benzo[c]carbazole,BCz)is proposed in this work.Pure powders of BCz and its derivatives merely exhibit blue fluorescence at ambient condition.However,when BCz and its derivatives are dispersed into polymer or powder matrixes,strong photo-activated green UORTP can be observed from their doped systems at room temperature.Moreover,the UORTP color can be tuned between green and yellow depending on the matrix.The ultralong phosphorescence originates from the generation of charge-separated states via radicals.The matrixes play a key role in both stabilizing charge-separated states and controlling UORTP color.More interestingly,when using polymethyl methacrylate as matrix,the doped films achieve stronger photo-activated ultralong phosphorescence underwater than in air at room temperature.Comparedwith Bd,BCz achieves better performance not only in ultralong phosphorescence properties but also in practical applications.This work gains a deeper insight into the mechanism of UORTP and paves a new approach to applying organic phosphorescent materials to underwater coating and imaging.

Manipulating intermolecular interactions for ultralong organic phosphorescence

Ultralong organic phosphorescence(UOP)materials have received considerable attention in the field of organic optoelectronics due to their long lifetime,high exciton utilization,large Stokes shift,and so on.Great advancements have been achieved through manipulating intermolecular interactions for high-performance UOP materials in recent years.This review will discuss the influence of various intermolecular interactions,includingπ-πinteractions,n-πinteractions,halogen bonding,hydrogen bonding,coordinative bonding,and ionic bonding on phosphorescent properties at room temperature,respectively.We summarize the rule of manipulating intermolecular interactions for UOP materials with superior phosphorescent properties.This review will provide a guideline for developing new UOP materials with superior phosphorescent properties for potential applications in organic electronics and bioelectronics.

Ultralong room temperature phosphorescence via the charge transfer-separation-recombination mechanism based on organic small molecule doping strategy

Ultra-long room temperature phosphorescence(URTP) has been increasingly recognized in pure organic luminophor in recent years. Through a simpler molecular design and charge separation-recombination pathway, organic luminophor can achieve even better URTP properties. In this work, we achieved URTP in a system of host-guest doped benzophenone derivatives whose phosphorescence is visible to the naked eye. The differences in the wavelength lifetimes of luminescent emission correspond to different photophysical mechanisms. Through a combination of theoretical calculations and experiments, the host acts as a powerful substrate that restricts the motion of the guest and inhibits the non-radiative transitions of the guest, accompanied by a charge transfer separation-recombination process between the host and the guest, resulting in an URTP phenomenon. Transient absorption results demonstrate the existence of a charge-separated state. The design strategy via charge separation is generic and easy to implement,providing a direction for the future design of doped URTP.

A universal strategy for achieving dual cross-linked networks to obtain ultralong polymeric room temperature phosphorescence

Efficient polymeric room-temperature phosphorescence(PRTP)with excellent processability and flexibility is highly desirable but still faces formidable challenge.Herein,a general strategy is developed for efficient PRTP through photo-polymerization of phosphor monomers and N-isopropylacrylamide(NIPAM)spontaneously without a crosslinker.Remarkably ultralong lifetime of 3.54 s with afterglow duration time of 25 s and decent phosphorescent quantum efficiency of 13%are achieved.This efficient PRTP has been demonstrated to be derived from the synergistic effect of the covalent and hydrogen bonds networks formed through photo-polymerization of NIPAM.The electron paramagnetic resonance(EPR)spectra confirmed that methyl radicals are generated under the irradiation of ultraviolet light and promote the formation of covalent cross-linking networks.This strategy has also been proved to be generalizable to several other phosphor monomers.Interestingly,the polymer films display ultrahigh temperature resistance with long afterglows even at 140℃ and unexampled ultralong lifetime of 2.45 s in aqueous solutions.This work provides a simple and feasible avenue to obtain efficient PRTP.

Ultralong afterglow and unity quantum yield from a transparent CsCdCl_(3):Mn crystal

Transparent afterglow crystals are keenly desired for three-dimensional information storage.Herein,CsCdCl3 perovskite crystals were grown by a programmable cool-ing procedure in a hydrothermal reactor.The pristine crystal showed an abnormal optical behavior where the absorption increased by 2.3 folds at high temperature,leading to a fourfold boost of photoluminescence(PL)intensity.After Mn2+dop-ing,the PL quantum yield was improved to nearly unity.Importantly,the doped crystals exhibited an ultralong afterglow up to 12 h after ceasing UV excitation and a high transmittance up to 75%in the visible region.This work brought a new mem-ber to the library of transparent afterglow crystal,opening up many possibilities to advanced applications such as volumetric display and three-dimensional information encryption.

An aqueous BiI_(3)-Zn battery with dual mechanisms of Zn^(2+)(de)intercalation and I^(-)/I_(2)redox

The development of aqueous battery with dual mechanisms is now arousing more and more interest.The dual mechanisms of Zn^(2+)(de)intercalation and I^(-)/I_(2)redox bring unexpected effects.Herein,differing from previous studies using Zn I_(2)additive,this work designs an aqueous Bi I_(3)-Zn battery with selfsupplied I^(-).Ex situ tests reveal the conversion of Bi I_(3)into Bi(discharge)and Bi OI(charge)at the 1st cycle and the dissolved I^(-)in electrolyte.The active I^(-)species enhances the specific capacity and discharge medium voltage of electrode as well as improves the generation of Zn dendrite and by-product.Furthermore,the porous hard carbon is introduced to enhance the electronic/ionic conductivity and adsorb iodine species,proven by experimental and theoretical studies.Accordingly,the well-designed Bi I_(3)-Zn battery delivers a high reversible capacity of 182 m A h g^(-1)at 0.2 A g^(-1),an excellent rate capability with 88 m A h g^(-1)at 10 A g^(-1),and an impressive cyclability with 63%capacity retention over 20 K cycles at 10 A g^(-1).An excellent electrochemical performance is obtained even at a high mass loading of 6 mg cm^(-2).Moreover,a flexible quasi-solid-state Bi I_(3)-Zn battery exhibits satisfactory battery performances.This work provides a new idea for designing high-performance aqueous battery with dual mechanisms.

长大海底盾构隧道施工期环境温度分布实测分析及影响因素研究

为开展长大海底盾构隧道施工期独头通风流场分布及参数优化后环境降温效果研究,通过现场监测数据明确隧道沿程环境温度和风速特征,并对海底盾构隧道主要热源进行统计,建立长大海底盾构隧道施工期的温度场三维数值计算模型,探究盾构掘进长度、通风量和入口风温等因素对隧道环境温度场和通风死区分布的影响。研究结果表明:1)盾构主机和1号台架下层和中层设备为主要的散热源,设备后方的大范围通风死区处有局部异常高温;2)从盾构主机至始发井,隧道内回风风速先骤减再略微增加后基本保持稳定,通风量损失主要在盾构刀盘后配套作业区;3)隧道沿程环境温度呈骤降—缓降—缓升的变化规律;4)在盾构掘进长度小于6 km时,盾构主机处温度呈快速线性增大随后增速放缓的变化特征;5)通风死区范围随着盾构掘进长度和通风量的增加分别呈指数上升和指数衰减的趋势,加大通风量能有效消除隧道内通风死区。

Tunable and switchable harmonic h-shaped pulse generation in a 3.03 km ultralong mode-locked thulium-doped fiber laser

We experimentally demonstrated a type of tunable and switchable harmonic h-shaped pulse generation in a thulium-doped fiber(TDF) laser passively mode locked by using an ultralong nonlinear optical loop mirror.The total cavity length was ～3.03 km, the longest ever built for a TDF laser to our best knowledge, which resulted in an ultralarge anomalous dispersion over -200 ps^2 around the emission wavelength. The produced h-shaped pulse can operate either in a fundamental or in a high-order harmonic mode-locking(HML) state depending on pump power and intra-cavity polarization state(PS). The pulse duration, no matter of the operation state, was tunable with pump power. However, pulse breaking and self-organizing occurred, resulting in high-order HML,when the pump power increased above a threshold. At a fixed pump power, the order of HML was switchable from one to another by manipulating the PS. Switching from the 8 th up to the 48 th order of HML was achieved with a fixed pump power of ～4.15 W. Our results revealed the detailed evolution and switching characteristics of the HML and individual pulse envelope with respect to both the pump power and PS. We have also discussed in detail the mechanisms of both the h-shaped pulse generation and the switching of its HML. This contribution would be helpful for further in-depth study on the underlying dynamics of long-duration particular-envelope pulses with ultralarge anomalous dispersion and ultralong roundtrip time.

Regioisomerism effect(RIE) on optimizing ultralong organic phosphorescence lifetimes

Organic phosphorescence materials demonstrate potential optoelectronic applications due to their remarkably ultralong organic phosphorescence(UOP)lifetime and abundant optical characteristics prior to the fluorescence materials.For a better insight into the intrinsic relationship among regioisomeric molecules,crystalline interactions,and phosphorescence properties,three crystalline dicarbazol-9-yl pyrazine-based regioisomers with para-,meta-and ortho-convergent substitutions(p-DCzP,m-DCzP,and o-DCzP)were designed and presented gradually increased UOP lifetimes prolonging from 63.14,127.93 to 350.46 ms,respectively,due to the regioisomerism effect(RIE)which would be an effective strategy for better understanding of structure-property of UOP materials.

A Single-Component Supramolecular Organic Framework with Efficient Ultralong Phosphorescence

Supramolecular organic frameworks(SOFs),due to the atomically precise integration of the repeated building units,exhibit intriguing properties and consequently potential applications in chemical and materials science communities.However,it remains a great challenge to achieve SOFs with ultralong organic phosphorescence(UOP)in a singlecomponent system.Herein,we report metal-free organic compound 9,9′-(6-(2-bromophenethoxy)-1,3,5-triazine-2,4-diyl)bis(9H-carbazole)(DCzPO)with UOP behavior.Owing to the combination of multiple supramolecular interactions,DCzPO formed a SOF structure with regular hexagonal holes,which shows an ultralong emission lifetime of 398 ms and a phosphorescence efficiency of 3%.So far as we know,among the reported luminescent SOFs,this one is the most highly efficient.This single-component SOF with ultralong phosphorescence will provide a new platform to rationally combine UOP and porous materials.

Ultralong Room-Temperature Phosphorescence of Silicon-Based Pure Organic Crystal for Oxygen Sensing

Quantitative oxygen detection is of great importance in biological fields,complex environments,and chemical process engineering.Due to the high sensitivity and rapid response of long-lived phosphorescence to oxygen,pure organic room-temperature phosphorescence(RTP)for oxygen detection has recently attracted considerable interest.However,to simultaneously achieve ultralong phosphorescence at room temperature and quantitative oxygen detection from pure organic crystals is difficult.Tight packing to restrict nonradiative decay is not apt to allow oxygen diffusion for sensing.Reported herein is an exceptional example,that is,a crystal of simple carbazole molecules that bridges with an ethoxysilane(DCzC2OSi)and is capable of oxygen sensing with remarkable sensitivity.Photophysical studies and single-crystal structure analysis reveal that DCzC2OSi crystals display ultralong RTP and suitable oxygen diffusion channels from its butterfly-like tetrahedron geometry.Further comparisons with the crystals of CzC2OH and DCzSi verify the important roles of silicon and ethoxy groups of DCzC2OSi for both enhanced phosphorescence lifetime and oxygen sensitivity.When the crystals of DCzC2OSi were doped into polymer,the lifetime-based oxygen sensor exhibited high KSV(5.308 kPa^(−1))with full reversibility,which is attractive for the development of practical oxygen sensors from pure organic crystals.

高密度超长碳纳米管的可控制备:进展与展望

碳纳米管因其优异的力学、电学、热学和光学性能,在碳基集成电路、超强超韧纤维、机械储能、柔性可穿戴设备等众多尖端领域拥有广阔的应用前景。碳纳米管的单体结构和微观形貌(如长度、取向度、缺陷浓度、洁净程度等)对其基础物理性质有显著的影响。在各类碳纳米管中,只有具有宏观长度、低缺陷浓度和高取向度的超长碳纳米管才能充分体现和发挥其本征的性能优势并满足很多尖端领域对其结构和性能的严格要求。实现超长碳纳米管实际应用的关键在于实现其大规模制备,然而其目前的产率远远无法满足应用需求,因而其在高密度、高产率制备方面依然面临很多挑战。深入讨论了超长碳纳米管的生长机理,分析了超长碳纳米管产率低的原因,系统总结了高密度超长碳纳米管的制备方法,并介绍了目前在超长碳纳米管实际应用方面的最新进展。另外,还总结了超长碳纳米管制备领域所面临的科学和技术挑战,并对未来的发展方向进行了深入的讨论。