Understanding the relationship between structure and properties is critical to the development of solidstate luminescence materials with desired characteristics and performance optimization. In this work, we elaborate...Understanding the relationship between structure and properties is critical to the development of solidstate luminescence materials with desired characteristics and performance optimization. In this work, we elaborately designed and synthesized a pair of mononuclear iridium(Ⅲ) complexes with similar structures but different degrees of cationization. [Ir2-f][2PF_(6)] with two counterions is obtained by simple Nmethylation of the ancillary ligand of [Ir1-f][PF_(6)] which is a classic cationic iridium(Ⅲ) complex. Such a tiny modification results in tremendously different optical properties in dilute solutions and powders.[Ir1-f][PF_(6)] exhibits weak light in solution but enhanced emission in solid-state as well as poly(methyl methacrylate) matrix, indicative of its aggregation-induced emission(AIE) activity. On the sharp contrary, [Ir2-f][2PF_(6)] is an aggregation-caused quenching(ACQ) emitter showing strong emission in the isolated state but nearly nonemissive in aggregation states. Benefiting from the appealing characteristics of mechanochromic luminescence and AIE behavior, [Ir1-f][PF_(6)] has been successfully applied in reversible re-writable data recording and cell imaging. These results might provide deep insights into AIE and ACQ phenomenon of iridium(Ⅲ) complexes and facilitate the development of phosphorescent materials with promising properties.展开更多
The rapid advancement of modern science and technology,coupled with the recent surge in new-energy electric vehicles,has significantly boosted the demand for lithium.This has promoted the development and efficient uti...The rapid advancement of modern science and technology,coupled with the recent surge in new-energy electric vehicles,has significantly boosted the demand for lithium.This has promoted the development and efficient utilization of lepidolite as a lithium source.Therefore,the processes for the flotation of lepidolite have been studied in depth,particularly the development and use of lepidolite flotation collectors and the action mechanism of the collectors on the lepidolite surface.Based on the crystal-structure characteristics of lepidolite minerals,this review focuses on the application of anionic collectors,amine cationic collectors(primary amines,quaternary ammonium salts,ether amines,and Gemini amines),and combined collectors to the flotation behavior of lepidolite as well as the adsorption mechanisms.New directions and technologies for the controllable flotation of lepidolite are proposed,including process improvement,reagent synthesis,and mechanistic research.This analysis demonstrates the need for the further study of the complex environment inside lepidolite and pulp.By using modern analytical detection methods and quantum chemical calculations,research on reagents for the flotation of lepidolite has expanded,providing new concepts and references for the efficient flotation recovery and utilization of lepidolite.展开更多
Formamidinium lead iodide(FAPbI_(3))perovskite exhibits an impressive X-ray absorption coefficient and a large carrier mobility-lifetime product(μτ),making it as a highly promising candidate for X-ray detection appl...Formamidinium lead iodide(FAPbI_(3))perovskite exhibits an impressive X-ray absorption coefficient and a large carrier mobility-lifetime product(μτ),making it as a highly promising candidate for X-ray detection application.However,the presence of larger FA^(+)cation induces to an expansion of the Pb-I octahedral framework,which unfortunately affects both the stability and charge carrier mobility of the corresponding devices.To address this challenge,we develop a novel low-dimensional(HtrzT)PbI_(3) perovskite featuring a conjugated organic cation(1H-1,2,4-Triazole-3-thiol,HtrzT^(+))which matches well with theα-FAPbI_(3) lattices in two-dimensional plane.Benefiting from the matched lattice between(HtrzT)PbI_(3) andα-FAPbI_(3),the anchored lattice enhances the Pb-I bond strength and effectively mitigates the inherent tensile strain of theα-FAPbI_(3) crystal lattice.The X-ray detector based on(HtrzT)PbI_(3)(1.0)/FAPbI_(3) device achieves a remarkable sensitivity up to 1.83×10^(5)μC Gy_(air)^(−1) cm^(−2),along with a low detection limit of 27.6 nGy_(air) s^(−1),attributed to the release of residual stress,and the enhancement in carrier mobility-lifetime product.Furthermore,the detector exhibits outstanding stability under X-ray irradiation with tolerating doses equivalent to nearly 1.17×10^(6) chest imaging doses.展开更多
Modal parameters can accurately characterize the structural dynamic properties and assess the physical state of the structure.Therefore,it is particularly significant to identify the structural modal parameters accordi...Modal parameters can accurately characterize the structural dynamic properties and assess the physical state of the structure.Therefore,it is particularly significant to identify the structural modal parameters according to the monitoring data information in the structural health monitoring(SHM)system,so as to provide a scientific basis for structural damage identification and dynamic model modification.In view of this,this paper reviews methods for identifying structural modal parameters under environmental excitation and briefly describes how to identify structural damages based on the derived modal parameters.The paper primarily introduces data-driven modal parameter recognition methods(e.g.,time-domain,frequency-domain,and time-frequency-domain methods,etc.),briefly describes damage identification methods based on the variations of modal parameters(e.g.,natural frequency,modal shapes,and curvature modal shapes,etc.)and modal validation methods(e.g.,Stability Diagram and Modal Assurance Criterion,etc.).The current status of the application of artificial intelligence(AI)methods in the direction of modal parameter recognition and damage identification is further discussed.Based on the pre-vious analysis,the main development trends of structural modal parameter recognition and damage identification methods are given to provide scientific references for the optimized design and functional upgrading of SHM systems.展开更多
In recent years, the research advancements have high-lighted the critical role of the A-site cation in determining the optoelectronic and physicochemical properties of organicinorganic lead halide perovskites. Mixed-c...In recent years, the research advancements have high-lighted the critical role of the A-site cation in determining the optoelectronic and physicochemical properties of organicinorganic lead halide perovskites. Mixed-cation perovskites(MCPs) have been extensively used as absorber thin films in perovskite solar cells(PSCs), achieving high power conversion efficiencies(PCE) over 26%^([1, 2]).展开更多
The recent commercialization of gene products has sparked significant interest in gene therapy,necessitating efficient and precise gene delivery via various vectors.Currently,viral vectors and lipid-based nanocarriers...The recent commercialization of gene products has sparked significant interest in gene therapy,necessitating efficient and precise gene delivery via various vectors.Currently,viral vectors and lipid-based nanocarriers are the predominant choices and have been extensively investigated and reviewed.Beyond these vectors,polymeric nanocarriers also hold the promise in therapeutic gene delivery owing to their versatile functionalities,such as improving the stability,cellar uptake and endosomal escape of nucleic acid drugs,along with precise delivery to targeted tissues.This review presents a brief overview of the status quo of the emerging polymeric nanocarriers for therapeutic gene delivery,focusing on key cationic polymers,nanocarrier types,and preparation methods.It also highlights targeted diseases,strategies to improve delivery efficiency,and potential future directions in this research area.The review is hoped to inspire the development,optimization,and clinical translation of highly efficient polymeric nanocarriers for therapeutic gene delivery.展开更多
Although the Mg-air battery with high theoretical energy density is desirable for the energy supply of marine engineering equipment,its applications remain limited due to the low actual discharge voltage and inferior ...Although the Mg-air battery with high theoretical energy density is desirable for the energy supply of marine engineering equipment,its applications remain limited due to the low actual discharge voltage and inferior Mg anode utilization rate.In addition to the microstructure of Mg alloy anodes,the properties of discharge product films are of great importance to the discharge performance.Herein,the discharge behaviors of Mg-Y-Zn alloys are first studied mainly from the perspective of film properties.Through contrastive analysis,it is found that the sufficient Y^(3+) produced during the discharge process can substitute Mg^(2+) in Mg(OH)_(2) to introduce effective cation vacancies.The Mg-Y-Zn anode with profuse cation vacancies in the product film shows a synergy of potential and efficiency,and this can be attributed to an increase in the migration pathway for Mg^(2+),reducing the diffusion over-potential caused by the protective product film.This study is expected to provide a new strategy from the perspective of cation vacancy design of discharge film for developing high-performance Mg-air batteries.展开更多
The development of flexible zinc-ion batteries(ZIBs)faces a threeway trade-off among the ionic conductivity,Zn^(2+)mobility,and the electrochemical stability of hydrogel electrolytes.To address this challenge,we desig...The development of flexible zinc-ion batteries(ZIBs)faces a threeway trade-off among the ionic conductivity,Zn^(2+)mobility,and the electrochemical stability of hydrogel electrolytes.To address this challenge,we designed a cationic hydrogel named PAPTMA to holistically improve the reversibility of ZIBs.The long cationic branch chains in the polymeric matrix construct express pathways for rapid Zn^(2+)transport through an ionic repulsion mechanism,achieving simultaneously high Zn^(2+)transference number(0.79)and high ionic conductivity(28.7 mS cm−1).Additionally,the reactivity of water in the PAPTMA hydrogels is significantly inhibited,thus possessing a strong resistance to parasitic reactions.Mechanical characterization further reveals the superior tensile and adhesion strength of PAPTMA.Leveraging these properties,symmetric batteries employing PAPTMA hydrogel deliver exceeding 6000 h of reversible cycling at 1 mA cm^(−2) and maintain stable operation for 1000 h with a discharge of depth of 71%.When applied in 4×4 cm2 pouch cells with MnO_(2) as the cathode material,the device demonstrates remarkable operational stability and mechanical robustness through 150 cycles.This work presents an eclectic strategy for designing advanced hydrogels that combine high ionic conductivity,enhanced Zn^(2+)mobility,and strong resistance to parasitic reactions,paving the way for long-lasting flexible ZIBs.展开更多
Hydrogen fuel cells are expected to play a central role in the next-generation energy paradigm.However,owing to practical limitations,hydrogen is supplied in the form of refined hydrocarbons or alcohols in industrial ...Hydrogen fuel cells are expected to play a central role in the next-generation energy paradigm.However,owing to practical limitations,hydrogen is supplied in the form of refined hydrocarbons or alcohols in industrial applications.Among them,methanol is widely used as a hydrogen source,and CO is inevitably generated during its oxidation process.Even a small amount of CO(∼20 ppm)strongly binds to Pt used as a catalyst,and deactivates it.In addition to CO,surface adsorption of organic cations by binder or ionomer use in alkaline fuel cells is also one of the poisoning issues to be overcome.Herein,we propose FePt bimetallic catalysts that can resist unavoidable CO and organic cation poisoning.Our synthetic strategy,including annealing and acid treatment,allows the catalysts to possess different alloying degrees and surface structures,which in turn induce different levels of resistance to CO and organic-cation poisonings.The correlation between the surface and bulk structures of the catalysts and poisoning resistance was elucidated through X-ray photoemission spectroscopy and electrochemical analysis.The results revealed that an FePt catalyst having an ordered atomic arrangement displayed a better poisoning resistance than that having a disordered arrangement.展开更多
Oxygen evolution reaction(OER)is often regarded as a crucial bottleneck in the field of renewable energy storage and conversion.To further accelerate the sluggish kinetics of OER,a cation and anion modulation strategy...Oxygen evolution reaction(OER)is often regarded as a crucial bottleneck in the field of renewable energy storage and conversion.To further accelerate the sluggish kinetics of OER,a cation and anion modulation strategy is reported here,which has been proven to be effective in preparing highly active electrocatalyst.For example,the cobalt,sulfur,and phosphorus modulated nickel hydroxide(denoted as NiCoPSOH)only needs an overpotential of 232 mV to reach a current density of 20 mA cm^(–2),demonstrating excellent OER performances.The cation and anion modulation facilitates the generation of high-valent Ni species,which would activate the lattice oxygen and switch the OER reaction pathway from conventional adsorbate evolution mechanism to lattice oxygen mechanism(LOM),as evidenced by the results of electrochemical measurements,Raman spectroscopy and differential electrochemical mass spectrometry.The LOM pathway of NiCoPSOH is further verified by the theoretical calculations,including the upshift of O 2p band center,the weakened Ni–O bond and the lowest energy barrier of rate-limiting step.Thus,the anion and cation modulated catalyst NiCoPSOH could effectively accelerate the sluggish OER kinetics.Our work provides a new insight into the cation and anion modulation,and broadens the possibility for the rational design of highly active electrocatalysts.展开更多
The implementation of ultrahigh-Ni cathodes in high-energy lithium-ion batteries(LIBs)is constrained by significant structural and interfacial degradation during cycling.In this study,doping-induced surface restructur...The implementation of ultrahigh-Ni cathodes in high-energy lithium-ion batteries(LIBs)is constrained by significant structural and interfacial degradation during cycling.In this study,doping-induced surface restructuring in ultrahigh-nickel cathode materials is rapidly facilitated through an ultrafast Joule heating method.Density functional theory(DFT)calculations,synchrotron X-ray absorption spectroscopy(XAS),and single-particle force test confirmed the establishment of a stable crystal framework and lattice oxygen,which mitigated H2-H3 phase transitions and improved structural reversibility.Additionally,the Sc doping process exhibits a pinning effect on the grain boundaries,as shown by scanning transmission electron microscopy(STEM),enhancing Li~+diffusion kinetics and decreasing mechanical strain during cycling.The in situ development of a cation-mixing layer at grain boundaries also creates a robust cathode/electrolyte interphase,effectively reducing interfacial parasitic reactions and transition metal dissolution,as validated by STEM and time-of-flight secondary ion mass spectrometry(TOF-SIMS).These synergistic modifications reduce particle cracking and surface/interface degradation,leading to enhanced rate capability,structural integrity,and thermal stability.Consequently,the optimized Sc-modified ultrahigh-Ni cathode(Sc-1)exhibits 93.99%capacity retention after 100 cycles at 1 C(25℃)and87.06%capacity retention after 100 cycles at 1 C(50℃),indicating excellent cycling and thermal stability.By presenting a one-step multifunctional modification approach,this research delivers an extensive analysis of the mechanisms governing the structure,microstructure,and interface properties of nickel-rich layered cathode materials(NCMs).These results underscore the potential of ultrahigh-Ni cathodes as viable candidates for advanced lithium-ion batteries(LIBs)in next-generation electric vehicles(EVs).展开更多
To investigate the evolution of load-bearing characteristics of pre-stressed beams throughout their service life and to provide a basis for accurately assessing the actual working state of damaged pre-stressed concret...To investigate the evolution of load-bearing characteristics of pre-stressed beams throughout their service life and to provide a basis for accurately assessing the actual working state of damaged pre-stressed concrete T-beams,destructive tests were conducted on full-scale pre-stressed concrete beams.Based on the measurement and ana-lysis of beam deflection,strain,and crack development under various loading levels during the research tests,combined with the verification coefficient indicators specified in the codes,the verification coefficients of bridges at different stages of damage can be examined.The results indicate that the T-beams experience complete,incom-plete linear,and non-linear stages during the destructive test process.In the complete linear elastic stage,both the deflection and bottom strain verification coefficients comply with the specifications,indicating a good structural load-bearing capacity no longer adheres to the code’s requirements.In the non-linear stage,both coefficients exhi-bit a sharp increase,resulting in a further decrease in the structure’s load-bearing capacity.According to the pro-visions of the current code,the beam can be in the incomplete linear stage when both values fall within the code’s specified range.The strain verification coefficient sourced from the compression zone at the bottom of theflange is not recommended for assessing the bridge’s load-bearing capacity.展开更多
Posaconazole(PCZ)is a broad-spectrum anti-fungal drug approved by FDA and currently used off-label for the treatment of fungal keratitis(FK).Although ocular route serves as the most bioavailable route for treating FK,...Posaconazole(PCZ)is a broad-spectrum anti-fungal drug approved by FDA and currently used off-label for the treatment of fungal keratitis(FK).Although ocular route serves as the most bioavailable route for treating FK,delivery of PCZ to the eye remains a challenge due to poor permeation though the cornea and rapid elimination from the eye.Here we outline a comprehensive formulation development process,beginning with in silico studies,progressing through in vitro evaluations,and ultimately achieving therapeutic benefits in vivo.We report modified niosome-like surfactant vesicles,hereafter termed as NioTherms,formulated using a novel and simple heat-mix method,encapsulating PCZ for ocular administration in the form of an in situ gel.Excipient screening performed using in silico simulations highly correlate with in vitro studies(R^(2)=0.77),guiding optimization by Quality by Design(QbD)approach for encapsulating PCZ in NioTherms resulting in particles with an average size of 180.7±2.3 nm,zeta potential of +27.5±2.2 mV and entrapment efficiency of 87.6%±1.7%.A 2-fold increase in both mucin binding and cellular uptake indicates a functional role of positive surface charge in enhancingmucoadhesive properties of PCZ-NioTherms.In an in vivo murine ocular keratitis model,we demonstrate a 2-fold enhancement in trans-corneal permeability of PCZ-NioTherms and a 3-fold reduction in fungal burden compared to the control standard of care,the PCZ solution.Owing to a facile formulation process,we anticipate that PCZ-NioTherms would serve as a clinically translatable and patient compliant therapeutic intervention for treating FK.展开更多
Amidst environmental pollution and the energy crisis,photocatalytic technology has emerged as a potent tool for promoting clean energy and environmental preservation.However,the promotion and widespread adoption of ph...Amidst environmental pollution and the energy crisis,photocatalytic technology has emerged as a potent tool for promoting clean energy and environmental preservation.However,the promotion and widespread adoption of photocatalysis encounter the formidable challenge of synthesizing high-quality photocatalysts in a cost-effective and expedited manner.Thus,we have compiled an analysis elucidating the efficacy and heating mechanisms of microwaves,validating their superiority as a heat source.Furthermore,this review presents a comprehensive overview of microwave-assisted synthesis techniques for photocatalysts,marking the inaugural attempt to do so,and extensively discusses the merits of diverse microwave-based preparation methodologies.Moreover,we systematically examine approaches for modifying photocatalysts using microwave-assisted methods,providing insights into their pivotal role in photocatalyst enhancement.We aspire that this review will serve as a seminal reference,facilitating the judicious application of microwave-assisted synthesis techniques for the controlled and efficient production of photocatalysts,thereby advancing the dissemination and adoption of photocatalysis.展开更多
Conventional proton exchange membrane(PEM)electrolysis technology relies on ultrapure water,as cationic impurities(such as Na^(+),Ca^(2+) and Fe^(3+))can occupy H+transport sites in the membrane[1],leading to a sharp ...Conventional proton exchange membrane(PEM)electrolysis technology relies on ultrapure water,as cationic impurities(such as Na^(+),Ca^(2+) and Fe^(3+))can occupy H+transport sites in the membrane[1],leading to a sharp rise in cathode pH,catalyst deactivation,and membrane degradation[2].This forces the system to be equipped with complex water purification equipment and even necessitates the replacement of membrane electrode assemblies(MEAs),increasing the levelized cost of hydrogen(LCOH)[3].To address this,Tao Ling's group recently proposed a"local pH regulation"strategy in Nature Energy[4].展开更多
Herbicides are the most widely used class of pesticides in modern agriculture,while they are still problematic for their off-target hazards due to volatility,drift,and leaching.Nanoformulations appear to be a promisin...Herbicides are the most widely used class of pesticides in modern agriculture,while they are still problematic for their off-target hazards due to volatility,drift,and leaching.Nanoformulations appear to be a promising alternative to those traditional counterparts as herbicidal delivery systems in presenting equivalent control efficacy and higher biosafety profile,but there is no approach yet to dynamically track the release of herbicidal active ingredients in weeds.To bridge the gap between the visualization of herbicidal efficacy with nanoformulation and the mechanistic understanding of the active ingredient release in vivo,we present a proof-of-concept study on the development of a green nanoformulation of herbicide(nanoherbicide)delivering 2-methyl-4-chlorophenoxyacetic acid(MCPA)based on the co-assembly of MCPA and cationic carbon dot.The release of MCPA can be tracked in vivo via a fluorescence lighting-up strategy,due to the disassembly of the nanoherbicide in weeds and the liberation of carbon dot.Compared to active ingredient,the nanoherbicide exhibits reduced volatilization rate,improved foliar affinity,and retarded leaching effect in the soil,and the hazards on off-target organisms including farming plant,soil enzymes and microbiota are appreciably minimized.Due to the characteristics of carbon dot's fluorescence quenching and lightening as the nanoherbicide forms and disassembles,respectively,the entry,translocation,and disassembly of the nanoherbicide in weeds are recorded with fluorescent microscopy.Additionally,the timing to observe the disassembly state ex vivo and to visualize the early symptoms of weed wilting match,suggesting that the released MCPA retains mechanism of action against weeds.In contrast to other labelled nanoherbicides displaying stable fluorescence,this self-reportable fluorescence lighting-up nanoherbicide provides a viable solution to predict/correlate the herbicidal efficacy with fluorescence more realistically.展开更多
Transition metal carbonates(TMCs)hold great potential as high-performance electrodes for alkali metal-ion batteries,owing to multiple-ion storage mechanisms involving conversion process and electrocatalytic reaction.H...Transition metal carbonates(TMCs)hold great potential as high-performance electrodes for alkali metal-ion batteries,owing to multiple-ion storage mechanisms involving conversion process and electrocatalytic reaction.However,they still suffer from inferior electronic conductivity and volume variation during delithiation/lithiation.Heterostructure and heteroatoms doping offer immense promise in enhancing reaction kinetics and structural integrity,which unfortunately have not been achieved in TMCs.Herein,a unique TMCs heterostructure with Ni-doped MnCO_(3)as“core”and Mn-doped NiCO_(3)as“shell”,which is wrapped by graphene(NM@MN/RGO),is achieved by cations differentiation strategy.The formation process for core-shell NM@MN consists of epitaxial growth of NiCO_(3)from MnCO_(3)and synchronously mutual doping,owing to the similar crystal structures but different solubility product constant/formation energy of MnCO_(3)and NiCO_(3).In-situ electrochemical impedance spectroscopy,galvanostatic intermittent titration technique,differential capacity versus voltage plots,theoretical calculation and kinetic analysis reveal the superior electrochemical activity of the NM@MN/RGO to MnCO_(3)/RGO.The NM@MN/RGO shows excellent lithium storage properties(1013.4 mAh·g^(-1)at 0.1 A·g^(-1)and 760 mAh·g^(-1)after 1000 cycles at 2 A·g^(-1))and potassium storage properties(capacity decay rate of 0.114 mAh·g^(-1)per cycle).This work proposes an efficient cation differentiation strategy for constructing advanced TMC electrodes.展开更多
Developing cost-effective single-crystalline Ni-rich Co-poor cathodes operating at high-voltage is one of the most important ways to achieve higher energy Li-ion batteries. However, the Li/O loss and Li/Ni mixing unde...Developing cost-effective single-crystalline Ni-rich Co-poor cathodes operating at high-voltage is one of the most important ways to achieve higher energy Li-ion batteries. However, the Li/O loss and Li/Ni mixing under high-temperature lithiation result in electrochemical kinetic hysteresis and structural instability. Herein, we report a highly-ordered single-crystalline LiNi0.85Co0.05Mn0.10O2(NCM85) cathode by doping K+and F-ions. To be specific, the K-ion as a fluxing agent can remarkably decrease the solid-state lithiation temperature by ~30°C, leading to less Li/Ni mixing and oxygen vacancy. Meanwhile, the strong transitional metal(TM)-F bonds are helpful for enhancing de-/lithiation kinetics and limiting the lattice oxygen escape even at 4.5 V high-voltage. Their advantages synergistically endow the single-crystalline NCM85 cathode with a very high reversible capacity of 222.3 mAh g-1. A superior capacity retention of 91.3% is obtained after 500 times at 1 C in pouch-type full cells, and a prediction value of 75.3% is given after cycling for 5000 h. These findings are reckoned to expedite the exploitation and application of high-voltage single-crystalline Ni-rich cathodes for next-generation Li-ion batteries.展开更多
Incorporating organic bulky cations in the precursor or post-treatment to achieve two-dimensional/thr ee-dimensional(2D/3D)heterojunction is an effective strategy for enhancing the stability of perovskite materials.Ho...Incorporating organic bulky cations in the precursor or post-treatment to achieve two-dimensional/thr ee-dimensional(2D/3D)heterojunction is an effective strategy for enhancing the stability of perovskite materials.However,the issue of insufficient charge transport in 2D perovskites limits their development,and the fundamental mechanism of out-of-plane carrier transport remains unclear.This study designed and synthesized seven organic phenyl-core cations,differentiated at the 1-and 1,4-positions,and identified the impacts on the corresponding properties of the 2D crystalline perovskite.Shorter cations facilitated a more compact arrangement of adjacent inorganic layers,aligning to favor charge transport along the vertical direction.In addition,introducing high electronegativity led to increased intermolecular interactions,resulting in enhanced structural stability and improved phenyl ring π-orbital overlap and interlayer electron coupling,yielding efficient charge transport.Resilience to thermal stressing of the perovskite was strongly correlated with the carbon chain length of the spacer cations.The increase in cation length and the reduction in the rigidity of the amino-terminal both aided in the dispersion of thermal stress in the inorganic framework.Additional hydrogen bonding also contributed to mitigating structural disorder.展开更多
Directly occluding polymer nanoparticles into growing host crystals provides a versatile pathway for synthe sizing polymer-inorganic composite crystals,where vip nanoparticles are distributed within the crystal matr...Directly occluding polymer nanoparticles into growing host crystals provides a versatile pathway for synthe sizing polymer-inorganic composite crystals,where vip nanoparticles are distributed within the crystal matrix.However,systematically controlling the extent of nanoparticle occlusion within a host crystal remains a significant challenge.In this study,we employ a one-step,soap-free emulsion polymerization method to synthesize polyethyleneimine-functionalized poly(tert-butyl methacrylate)(PtBMA/PEI)nanoparticles.These cationic nanoparticles are subsequently modified using formaldehyde to systematically tune the content of surface amine group via the Eschweiler-Clarke reaction.This approach yields a series of model nanoparticles that allow us to investigate how surface chemistry influences the extent of nanoparticle occlusion within calcite crystals.Our findings reveal that the extent of nanoparticle occlusion within calcite crystals is proportional to the surface amine group content.This study offers a new design rule for creating composite crystals with tailored compositions through a nanoparticle occlusion strategy.展开更多
基金financial support from the National Natural Science Foundation of China(Nos.22175033 and 51902124).
文摘Understanding the relationship between structure and properties is critical to the development of solidstate luminescence materials with desired characteristics and performance optimization. In this work, we elaborately designed and synthesized a pair of mononuclear iridium(Ⅲ) complexes with similar structures but different degrees of cationization. [Ir2-f][2PF_(6)] with two counterions is obtained by simple Nmethylation of the ancillary ligand of [Ir1-f][PF_(6)] which is a classic cationic iridium(Ⅲ) complex. Such a tiny modification results in tremendously different optical properties in dilute solutions and powders.[Ir1-f][PF_(6)] exhibits weak light in solution but enhanced emission in solid-state as well as poly(methyl methacrylate) matrix, indicative of its aggregation-induced emission(AIE) activity. On the sharp contrary, [Ir2-f][2PF_(6)] is an aggregation-caused quenching(ACQ) emitter showing strong emission in the isolated state but nearly nonemissive in aggregation states. Benefiting from the appealing characteristics of mechanochromic luminescence and AIE behavior, [Ir1-f][PF_(6)] has been successfully applied in reversible re-writable data recording and cell imaging. These results might provide deep insights into AIE and ACQ phenomenon of iridium(Ⅲ) complexes and facilitate the development of phosphorescent materials with promising properties.
基金financially supported by the Excellent Youth Scholars Program of State Key Laboratory of Complex Nonferrous Metal Resource Clean Utilization,Kunming University of Science and Technology,China(No.YXQN-2024003)the Central Government-Guided Local Science and Technology Development Fund Project,China(No.202407AB110022)。
文摘The rapid advancement of modern science and technology,coupled with the recent surge in new-energy electric vehicles,has significantly boosted the demand for lithium.This has promoted the development and efficient utilization of lepidolite as a lithium source.Therefore,the processes for the flotation of lepidolite have been studied in depth,particularly the development and use of lepidolite flotation collectors and the action mechanism of the collectors on the lepidolite surface.Based on the crystal-structure characteristics of lepidolite minerals,this review focuses on the application of anionic collectors,amine cationic collectors(primary amines,quaternary ammonium salts,ether amines,and Gemini amines),and combined collectors to the flotation behavior of lepidolite as well as the adsorption mechanisms.New directions and technologies for the controllable flotation of lepidolite are proposed,including process improvement,reagent synthesis,and mechanistic research.This analysis demonstrates the need for the further study of the complex environment inside lepidolite and pulp.By using modern analytical detection methods and quantum chemical calculations,research on reagents for the flotation of lepidolite has expanded,providing new concepts and references for the efficient flotation recovery and utilization of lepidolite.
基金supports from the National Natural Science Foundation of China(22375220,U2001214,22471302)the Guangdong Basic and Applied Basic Research Foundation(2024B1515020101)Open Project Fund from State Key Laboratory of Optoelectronic Materials and Technologies(OEMT-2024-KF-08).
文摘Formamidinium lead iodide(FAPbI_(3))perovskite exhibits an impressive X-ray absorption coefficient and a large carrier mobility-lifetime product(μτ),making it as a highly promising candidate for X-ray detection application.However,the presence of larger FA^(+)cation induces to an expansion of the Pb-I octahedral framework,which unfortunately affects both the stability and charge carrier mobility of the corresponding devices.To address this challenge,we develop a novel low-dimensional(HtrzT)PbI_(3) perovskite featuring a conjugated organic cation(1H-1,2,4-Triazole-3-thiol,HtrzT^(+))which matches well with theα-FAPbI_(3) lattices in two-dimensional plane.Benefiting from the matched lattice between(HtrzT)PbI_(3) andα-FAPbI_(3),the anchored lattice enhances the Pb-I bond strength and effectively mitigates the inherent tensile strain of theα-FAPbI_(3) crystal lattice.The X-ray detector based on(HtrzT)PbI_(3)(1.0)/FAPbI_(3) device achieves a remarkable sensitivity up to 1.83×10^(5)μC Gy_(air)^(−1) cm^(−2),along with a low detection limit of 27.6 nGy_(air) s^(−1),attributed to the release of residual stress,and the enhancement in carrier mobility-lifetime product.Furthermore,the detector exhibits outstanding stability under X-ray irradiation with tolerating doses equivalent to nearly 1.17×10^(6) chest imaging doses.
基金supported by the Innovation Foundation of Provincial Education Department of Gansu(2024B-005)the Gansu Province National Science Foundation(22YF7GA182)the Fundamental Research Funds for the Central Universities(No.lzujbky2022-kb01)。
文摘Modal parameters can accurately characterize the structural dynamic properties and assess the physical state of the structure.Therefore,it is particularly significant to identify the structural modal parameters according to the monitoring data information in the structural health monitoring(SHM)system,so as to provide a scientific basis for structural damage identification and dynamic model modification.In view of this,this paper reviews methods for identifying structural modal parameters under environmental excitation and briefly describes how to identify structural damages based on the derived modal parameters.The paper primarily introduces data-driven modal parameter recognition methods(e.g.,time-domain,frequency-domain,and time-frequency-domain methods,etc.),briefly describes damage identification methods based on the variations of modal parameters(e.g.,natural frequency,modal shapes,and curvature modal shapes,etc.)and modal validation methods(e.g.,Stability Diagram and Modal Assurance Criterion,etc.).The current status of the application of artificial intelligence(AI)methods in the direction of modal parameter recognition and damage identification is further discussed.Based on the pre-vious analysis,the main development trends of structural modal parameter recognition and damage identification methods are given to provide scientific references for the optimized design and functional upgrading of SHM systems.
基金financially supported by the National Natural Science Foundation of China (52462032, 62274018, 52462031)Natural Science Foundation of Yunnan Province (202501AT070353, 202101BE070001-049)+2 种基金the Xinjiang Construction Corps Key Areas of Science and Technology Research Project (2023AB029)the Tianchi Talent Program of Xinjiang Uygur Autonomous Region (2024, Jiangzhao Chen)the Key Project of Chongqing Overseas Students Returning to China Entrepreneurship and Innovation Support Plan (cx2023006)。
文摘In recent years, the research advancements have high-lighted the critical role of the A-site cation in determining the optoelectronic and physicochemical properties of organicinorganic lead halide perovskites. Mixed-cation perovskites(MCPs) have been extensively used as absorber thin films in perovskite solar cells(PSCs), achieving high power conversion efficiencies(PCE) over 26%^([1, 2]).
基金supported by National Natural Science Foundation of China(82104082)Natural Science Foundation of Qinghai Province(2024-ZJ-911).
文摘The recent commercialization of gene products has sparked significant interest in gene therapy,necessitating efficient and precise gene delivery via various vectors.Currently,viral vectors and lipid-based nanocarriers are the predominant choices and have been extensively investigated and reviewed.Beyond these vectors,polymeric nanocarriers also hold the promise in therapeutic gene delivery owing to their versatile functionalities,such as improving the stability,cellar uptake and endosomal escape of nucleic acid drugs,along with precise delivery to targeted tissues.This review presents a brief overview of the status quo of the emerging polymeric nanocarriers for therapeutic gene delivery,focusing on key cationic polymers,nanocarrier types,and preparation methods.It also highlights targeted diseases,strategies to improve delivery efficiency,and potential future directions in this research area.The review is hoped to inspire the development,optimization,and clinical translation of highly efficient polymeric nanocarriers for therapeutic gene delivery.
基金support of the Natural Science Foundation of Heilongjiang Province of China(No.LH2023E059)the National Natural Science Foundation of China(No.52071093)the Opening Project of Jiangsu Key Laboratory of Advanced Structural Materials and Application Technology(No.ASMA202205).
文摘Although the Mg-air battery with high theoretical energy density is desirable for the energy supply of marine engineering equipment,its applications remain limited due to the low actual discharge voltage and inferior Mg anode utilization rate.In addition to the microstructure of Mg alloy anodes,the properties of discharge product films are of great importance to the discharge performance.Herein,the discharge behaviors of Mg-Y-Zn alloys are first studied mainly from the perspective of film properties.Through contrastive analysis,it is found that the sufficient Y^(3+) produced during the discharge process can substitute Mg^(2+) in Mg(OH)_(2) to introduce effective cation vacancies.The Mg-Y-Zn anode with profuse cation vacancies in the product film shows a synergy of potential and efficiency,and this can be attributed to an increase in the migration pathway for Mg^(2+),reducing the diffusion over-potential caused by the protective product film.This study is expected to provide a new strategy from the perspective of cation vacancy design of discharge film for developing high-performance Mg-air batteries.
基金financially supported by the General Research Fund(CityU 11315622 and CityU 11310123)National Natural Science Foundation(NSFC 52372229 and NSFC 52172241)+3 种基金Green Tech Fund(GTF202220105)Guangdong Basic and Applied Basic Research Foundation(2024A1515011008)City University of Hong Kong(No.9020002)the Shenzhen Research Institute of City University of Hong Kong.
文摘The development of flexible zinc-ion batteries(ZIBs)faces a threeway trade-off among the ionic conductivity,Zn^(2+)mobility,and the electrochemical stability of hydrogel electrolytes.To address this challenge,we designed a cationic hydrogel named PAPTMA to holistically improve the reversibility of ZIBs.The long cationic branch chains in the polymeric matrix construct express pathways for rapid Zn^(2+)transport through an ionic repulsion mechanism,achieving simultaneously high Zn^(2+)transference number(0.79)and high ionic conductivity(28.7 mS cm−1).Additionally,the reactivity of water in the PAPTMA hydrogels is significantly inhibited,thus possessing a strong resistance to parasitic reactions.Mechanical characterization further reveals the superior tensile and adhesion strength of PAPTMA.Leveraging these properties,symmetric batteries employing PAPTMA hydrogel deliver exceeding 6000 h of reversible cycling at 1 mA cm^(−2) and maintain stable operation for 1000 h with a discharge of depth of 71%.When applied in 4×4 cm2 pouch cells with MnO_(2) as the cathode material,the device demonstrates remarkable operational stability and mechanical robustness through 150 cycles.This work presents an eclectic strategy for designing advanced hydrogels that combine high ionic conductivity,enhanced Zn^(2+)mobility,and strong resistance to parasitic reactions,paving the way for long-lasting flexible ZIBs.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(Nos.2022M3J1A1063917 and 2021M3H4A3A02086681).
文摘Hydrogen fuel cells are expected to play a central role in the next-generation energy paradigm.However,owing to practical limitations,hydrogen is supplied in the form of refined hydrocarbons or alcohols in industrial applications.Among them,methanol is widely used as a hydrogen source,and CO is inevitably generated during its oxidation process.Even a small amount of CO(∼20 ppm)strongly binds to Pt used as a catalyst,and deactivates it.In addition to CO,surface adsorption of organic cations by binder or ionomer use in alkaline fuel cells is also one of the poisoning issues to be overcome.Herein,we propose FePt bimetallic catalysts that can resist unavoidable CO and organic cation poisoning.Our synthetic strategy,including annealing and acid treatment,allows the catalysts to possess different alloying degrees and surface structures,which in turn induce different levels of resistance to CO and organic-cation poisonings.The correlation between the surface and bulk structures of the catalysts and poisoning resistance was elucidated through X-ray photoemission spectroscopy and electrochemical analysis.The results revealed that an FePt catalyst having an ordered atomic arrangement displayed a better poisoning resistance than that having a disordered arrangement.
文摘Oxygen evolution reaction(OER)is often regarded as a crucial bottleneck in the field of renewable energy storage and conversion.To further accelerate the sluggish kinetics of OER,a cation and anion modulation strategy is reported here,which has been proven to be effective in preparing highly active electrocatalyst.For example,the cobalt,sulfur,and phosphorus modulated nickel hydroxide(denoted as NiCoPSOH)only needs an overpotential of 232 mV to reach a current density of 20 mA cm^(–2),demonstrating excellent OER performances.The cation and anion modulation facilitates the generation of high-valent Ni species,which would activate the lattice oxygen and switch the OER reaction pathway from conventional adsorbate evolution mechanism to lattice oxygen mechanism(LOM),as evidenced by the results of electrochemical measurements,Raman spectroscopy and differential electrochemical mass spectrometry.The LOM pathway of NiCoPSOH is further verified by the theoretical calculations,including the upshift of O 2p band center,the weakened Ni–O bond and the lowest energy barrier of rate-limiting step.Thus,the anion and cation modulated catalyst NiCoPSOH could effectively accelerate the sluggish OER kinetics.Our work provides a new insight into the cation and anion modulation,and broadens the possibility for the rational design of highly active electrocatalysts.
基金supported by the National Key R&D Program of China(2022YFB3803501)the National Natural Science Foundation of China(22179008,22209156)+5 种基金support from the Beijing Nova Program(20230484241)support from the China Postdoctoral Science Foundation(2024M754084)the Postdoctoral Fellowship Program of CPSF(GZB20230931)support from beamline BL08U1A of Shanghai Synchrotron Radiation Facility(2024-SSRF-PT-506950)beamline 1W1B of the Beijing Synchrotron Radiation Facility(2021-BEPC-PT-006276)support from Initial Energy Science&Technology Co.,Ltd(IEST)。
文摘The implementation of ultrahigh-Ni cathodes in high-energy lithium-ion batteries(LIBs)is constrained by significant structural and interfacial degradation during cycling.In this study,doping-induced surface restructuring in ultrahigh-nickel cathode materials is rapidly facilitated through an ultrafast Joule heating method.Density functional theory(DFT)calculations,synchrotron X-ray absorption spectroscopy(XAS),and single-particle force test confirmed the establishment of a stable crystal framework and lattice oxygen,which mitigated H2-H3 phase transitions and improved structural reversibility.Additionally,the Sc doping process exhibits a pinning effect on the grain boundaries,as shown by scanning transmission electron microscopy(STEM),enhancing Li~+diffusion kinetics and decreasing mechanical strain during cycling.The in situ development of a cation-mixing layer at grain boundaries also creates a robust cathode/electrolyte interphase,effectively reducing interfacial parasitic reactions and transition metal dissolution,as validated by STEM and time-of-flight secondary ion mass spectrometry(TOF-SIMS).These synergistic modifications reduce particle cracking and surface/interface degradation,leading to enhanced rate capability,structural integrity,and thermal stability.Consequently,the optimized Sc-modified ultrahigh-Ni cathode(Sc-1)exhibits 93.99%capacity retention after 100 cycles at 1 C(25℃)and87.06%capacity retention after 100 cycles at 1 C(50℃),indicating excellent cycling and thermal stability.By presenting a one-step multifunctional modification approach,this research delivers an extensive analysis of the mechanisms governing the structure,microstructure,and interface properties of nickel-rich layered cathode materials(NCMs).These results underscore the potential of ultrahigh-Ni cathodes as viable candidates for advanced lithium-ion batteries(LIBs)in next-generation electric vehicles(EVs).
文摘To investigate the evolution of load-bearing characteristics of pre-stressed beams throughout their service life and to provide a basis for accurately assessing the actual working state of damaged pre-stressed concrete T-beams,destructive tests were conducted on full-scale pre-stressed concrete beams.Based on the measurement and ana-lysis of beam deflection,strain,and crack development under various loading levels during the research tests,combined with the verification coefficient indicators specified in the codes,the verification coefficients of bridges at different stages of damage can be examined.The results indicate that the T-beams experience complete,incom-plete linear,and non-linear stages during the destructive test process.In the complete linear elastic stage,both the deflection and bottom strain verification coefficients comply with the specifications,indicating a good structural load-bearing capacity no longer adheres to the code’s requirements.In the non-linear stage,both coefficients exhi-bit a sharp increase,resulting in a further decrease in the structure’s load-bearing capacity.According to the pro-visions of the current code,the beam can be in the incomplete linear stage when both values fall within the code’s specified range.The strain verification coefficient sourced from the compression zone at the bottom of theflange is not recommended for assessing the bridge’s load-bearing capacity.
文摘Posaconazole(PCZ)is a broad-spectrum anti-fungal drug approved by FDA and currently used off-label for the treatment of fungal keratitis(FK).Although ocular route serves as the most bioavailable route for treating FK,delivery of PCZ to the eye remains a challenge due to poor permeation though the cornea and rapid elimination from the eye.Here we outline a comprehensive formulation development process,beginning with in silico studies,progressing through in vitro evaluations,and ultimately achieving therapeutic benefits in vivo.We report modified niosome-like surfactant vesicles,hereafter termed as NioTherms,formulated using a novel and simple heat-mix method,encapsulating PCZ for ocular administration in the form of an in situ gel.Excipient screening performed using in silico simulations highly correlate with in vitro studies(R^(2)=0.77),guiding optimization by Quality by Design(QbD)approach for encapsulating PCZ in NioTherms resulting in particles with an average size of 180.7±2.3 nm,zeta potential of +27.5±2.2 mV and entrapment efficiency of 87.6%±1.7%.A 2-fold increase in both mucin binding and cellular uptake indicates a functional role of positive surface charge in enhancingmucoadhesive properties of PCZ-NioTherms.In an in vivo murine ocular keratitis model,we demonstrate a 2-fold enhancement in trans-corneal permeability of PCZ-NioTherms and a 3-fold reduction in fungal burden compared to the control standard of care,the PCZ solution.Owing to a facile formulation process,we anticipate that PCZ-NioTherms would serve as a clinically translatable and patient compliant therapeutic intervention for treating FK.
基金supported by the National Natural Science Foundation of China(Grant Nos.52370109,52401227 and 52200122)the Natural Science Foundation of Chongqing(Grant No.CSTB2025NSCQ-GPX0827,CSTB2023NSCQ-MSX0096 and CSTB2024NSCQMSX1045)+3 种基金Research Project of Chongqing Education Commission Foundation(No.KJQN201800826 and KJQN202200806)Science and Technology Research Program of Chongqing Municipal Education Commission of China(No.KJZD-K202100801 and KJZD-M202400802)Post-doctoral Program Funded by Chongqing,and Chongqing University Innovation Research Group project(No.CXQT21023)the Startup Research Grant(No.F1240093)from Chongqing Jiaotong University.
文摘Amidst environmental pollution and the energy crisis,photocatalytic technology has emerged as a potent tool for promoting clean energy and environmental preservation.However,the promotion and widespread adoption of photocatalysis encounter the formidable challenge of synthesizing high-quality photocatalysts in a cost-effective and expedited manner.Thus,we have compiled an analysis elucidating the efficacy and heating mechanisms of microwaves,validating their superiority as a heat source.Furthermore,this review presents a comprehensive overview of microwave-assisted synthesis techniques for photocatalysts,marking the inaugural attempt to do so,and extensively discusses the merits of diverse microwave-based preparation methodologies.Moreover,we systematically examine approaches for modifying photocatalysts using microwave-assisted methods,providing insights into their pivotal role in photocatalyst enhancement.We aspire that this review will serve as a seminal reference,facilitating the judicious application of microwave-assisted synthesis techniques for the controlled and efficient production of photocatalysts,thereby advancing the dissemination and adoption of photocatalysis.
基金the Natural Science Foundation of Guangxi,China(No.2021GXNSFBA220058)the National Natural Science Foundation of China(Nos.22272036, 22362008)Guangxi Normal University Research Grant,China(No.2022TD).
文摘Conventional proton exchange membrane(PEM)electrolysis technology relies on ultrapure water,as cationic impurities(such as Na^(+),Ca^(2+) and Fe^(3+))can occupy H+transport sites in the membrane[1],leading to a sharp rise in cathode pH,catalyst deactivation,and membrane degradation[2].This forces the system to be equipped with complex water purification equipment and even necessitates the replacement of membrane electrode assemblies(MEAs),increasing the levelized cost of hydrogen(LCOH)[3].To address this,Tao Ling's group recently proposed a"local pH regulation"strategy in Nature Energy[4].
基金the National Natural Science Foundation of China(No.22278414)the National Key Research and Development Program of China(No.2023YFD1702100)+1 种基金the Science and Technology Major Project of Anhui Province(No.202203a06020001)Prof.Jian Luo at Anhui Agricultural University。
文摘Herbicides are the most widely used class of pesticides in modern agriculture,while they are still problematic for their off-target hazards due to volatility,drift,and leaching.Nanoformulations appear to be a promising alternative to those traditional counterparts as herbicidal delivery systems in presenting equivalent control efficacy and higher biosafety profile,but there is no approach yet to dynamically track the release of herbicidal active ingredients in weeds.To bridge the gap between the visualization of herbicidal efficacy with nanoformulation and the mechanistic understanding of the active ingredient release in vivo,we present a proof-of-concept study on the development of a green nanoformulation of herbicide(nanoherbicide)delivering 2-methyl-4-chlorophenoxyacetic acid(MCPA)based on the co-assembly of MCPA and cationic carbon dot.The release of MCPA can be tracked in vivo via a fluorescence lighting-up strategy,due to the disassembly of the nanoherbicide in weeds and the liberation of carbon dot.Compared to active ingredient,the nanoherbicide exhibits reduced volatilization rate,improved foliar affinity,and retarded leaching effect in the soil,and the hazards on off-target organisms including farming plant,soil enzymes and microbiota are appreciably minimized.Due to the characteristics of carbon dot's fluorescence quenching and lightening as the nanoherbicide forms and disassembles,respectively,the entry,translocation,and disassembly of the nanoherbicide in weeds are recorded with fluorescent microscopy.Additionally,the timing to observe the disassembly state ex vivo and to visualize the early symptoms of weed wilting match,suggesting that the released MCPA retains mechanism of action against weeds.In contrast to other labelled nanoherbicides displaying stable fluorescence,this self-reportable fluorescence lighting-up nanoherbicide provides a viable solution to predict/correlate the herbicidal efficacy with fluorescence more realistically.
基金supported by the National Natural Science Foundation of China(NSFC)(Nos.52202371 and 51902102)the Natural Science Foundation of Shandong Province(Nos.ZR202211230173,ZR2020QE066 and ZR2021QE200)+2 种基金the Opening Project of State Key Laboratory of Advanced Technology for Float Glass(No.2020KF08)the SDUT&Zibo City Integration Development Project(No.2021SNPT0045)the fellowship of China Postdoctoral Science Foundation(No.2020M672081).
文摘Transition metal carbonates(TMCs)hold great potential as high-performance electrodes for alkali metal-ion batteries,owing to multiple-ion storage mechanisms involving conversion process and electrocatalytic reaction.However,they still suffer from inferior electronic conductivity and volume variation during delithiation/lithiation.Heterostructure and heteroatoms doping offer immense promise in enhancing reaction kinetics and structural integrity,which unfortunately have not been achieved in TMCs.Herein,a unique TMCs heterostructure with Ni-doped MnCO_(3)as“core”and Mn-doped NiCO_(3)as“shell”,which is wrapped by graphene(NM@MN/RGO),is achieved by cations differentiation strategy.The formation process for core-shell NM@MN consists of epitaxial growth of NiCO_(3)from MnCO_(3)and synchronously mutual doping,owing to the similar crystal structures but different solubility product constant/formation energy of MnCO_(3)and NiCO_(3).In-situ electrochemical impedance spectroscopy,galvanostatic intermittent titration technique,differential capacity versus voltage plots,theoretical calculation and kinetic analysis reveal the superior electrochemical activity of the NM@MN/RGO to MnCO_(3)/RGO.The NM@MN/RGO shows excellent lithium storage properties(1013.4 mAh·g^(-1)at 0.1 A·g^(-1)and 760 mAh·g^(-1)after 1000 cycles at 2 A·g^(-1))and potassium storage properties(capacity decay rate of 0.114 mAh·g^(-1)per cycle).This work proposes an efficient cation differentiation strategy for constructing advanced TMC electrodes.
基金supported by the National Natural Science Foundation of China(U22A20429 and 22308103)Shanghai Pilot Program for Basic Research(22TQ1400100-13)+2 种基金Postdoctoral Fellowship Program of CPSF(GZB20230214)China Postdoctoral Science Foundation(2023M731083)the Fundamental Research Funds for the Central Universities.
文摘Developing cost-effective single-crystalline Ni-rich Co-poor cathodes operating at high-voltage is one of the most important ways to achieve higher energy Li-ion batteries. However, the Li/O loss and Li/Ni mixing under high-temperature lithiation result in electrochemical kinetic hysteresis and structural instability. Herein, we report a highly-ordered single-crystalline LiNi0.85Co0.05Mn0.10O2(NCM85) cathode by doping K+and F-ions. To be specific, the K-ion as a fluxing agent can remarkably decrease the solid-state lithiation temperature by ~30°C, leading to less Li/Ni mixing and oxygen vacancy. Meanwhile, the strong transitional metal(TM)-F bonds are helpful for enhancing de-/lithiation kinetics and limiting the lattice oxygen escape even at 4.5 V high-voltage. Their advantages synergistically endow the single-crystalline NCM85 cathode with a very high reversible capacity of 222.3 mAh g-1. A superior capacity retention of 91.3% is obtained after 500 times at 1 C in pouch-type full cells, and a prediction value of 75.3% is given after cycling for 5000 h. These findings are reckoned to expedite the exploitation and application of high-voltage single-crystalline Ni-rich cathodes for next-generation Li-ion batteries.
基金financially supported by the Key Fund Project of Tianjin Natural Science Foundation(24JCZDJC00510)the Fundamental Research Funds for the Central Universitiespartially supported by the U.S.Department of Energy under Contract No.DE-AC3608GO28308 with Alliance for Sustainable Energy,Limited Liability Company(LLC),the Manager and Operator of the National Renewable Energy Laboratory,through Grant No.DE-SC0020718。
文摘Incorporating organic bulky cations in the precursor or post-treatment to achieve two-dimensional/thr ee-dimensional(2D/3D)heterojunction is an effective strategy for enhancing the stability of perovskite materials.However,the issue of insufficient charge transport in 2D perovskites limits their development,and the fundamental mechanism of out-of-plane carrier transport remains unclear.This study designed and synthesized seven organic phenyl-core cations,differentiated at the 1-and 1,4-positions,and identified the impacts on the corresponding properties of the 2D crystalline perovskite.Shorter cations facilitated a more compact arrangement of adjacent inorganic layers,aligning to favor charge transport along the vertical direction.In addition,introducing high electronegativity led to increased intermolecular interactions,resulting in enhanced structural stability and improved phenyl ring π-orbital overlap and interlayer electron coupling,yielding efficient charge transport.Resilience to thermal stressing of the perovskite was strongly correlated with the carbon chain length of the spacer cations.The increase in cation length and the reduction in the rigidity of the amino-terminal both aided in the dispersion of thermal stress in the inorganic framework.Additional hydrogen bonding also contributed to mitigating structural disorder.
基金financial supports from the National Natural Science Foundation of China(Nos.22475084 and 22101100)Guangdong Basic and Applied Basic Research Foundation(Nos.2024A1515012114 and 2025A1515012931)College Students’Innovation and Entrepreneurship Training Program.
文摘Directly occluding polymer nanoparticles into growing host crystals provides a versatile pathway for synthe sizing polymer-inorganic composite crystals,where vip nanoparticles are distributed within the crystal matrix.However,systematically controlling the extent of nanoparticle occlusion within a host crystal remains a significant challenge.In this study,we employ a one-step,soap-free emulsion polymerization method to synthesize polyethyleneimine-functionalized poly(tert-butyl methacrylate)(PtBMA/PEI)nanoparticles.These cationic nanoparticles are subsequently modified using formaldehyde to systematically tune the content of surface amine group via the Eschweiler-Clarke reaction.This approach yields a series of model nanoparticles that allow us to investigate how surface chemistry influences the extent of nanoparticle occlusion within calcite crystals.Our findings reveal that the extent of nanoparticle occlusion within calcite crystals is proportional to the surface amine group content.This study offers a new design rule for creating composite crystals with tailored compositions through a nanoparticle occlusion strategy.
