Halide perovskites have emerged as promising materials for X-ray detection with exceptional properties and reasonable costs.Among them,heterostructures between 3D perovskites and low-dimensional perovskites attract in...Halide perovskites have emerged as promising materials for X-ray detection with exceptional properties and reasonable costs.Among them,heterostructures between 3D perovskites and low-dimensional perovskites attract intensive studies of their advantages due to low-level ion migration and decent stability.However,there is still a lack of methods to precisely construct heterostructures and a fundamental understanding of their structure-dependent optoelectronic properties.Herein,a gas-phase method was developed to grow 2D perovskites directly on 3D perovskites with nanoscale accuracy.In addition,the larger steric hindrance of organic layers of 2D perovskites was proved to enable slower ion migration,which resulted in reduced trap states and better stability.Based on MAPbBr_(3)single crystals with the(PA)_(2)PbBr_(4)capping layer,the X-ray detector achieved a sensitivity of 22,245μC Gy_(air)^(−1)cm^(−2),a response speed of 240μs,and a dark current drift of 1.17.10^(–4)nA cm^(−1)s^(−1)V^(−1),which were among the highest reported for state-of-the-art perovskite-based X-ray detectors.This study presents a precise synthesis method to construct perovskite-based heterostructures.It also brings an in-depth understanding of the relationship between lattice structures and properties,which are beneficial for advancing high-performance and cost-effective X-ray detectors.展开更多
Metal halide perovskites(MHPs)with striking electrical and optical properties have appeared at the forefront of semiconductor materials for photocatalytic redox reactions but still suffer from some intrinsic drawbacks...Metal halide perovskites(MHPs)with striking electrical and optical properties have appeared at the forefront of semiconductor materials for photocatalytic redox reactions but still suffer from some intrinsic drawbacks such as inferior stability,severe charge-carrier recombination,and limited active sites.Heterojunctions have recently been widely constructed to improve light absorption,passivate surface for enhanced stability,and promote charge-carrier dynamics of MHPs.However,little attention has been paid to the review of MHPs-based heterojunctions for photocatalytic redox reactions.Here,recent advances of MHPs-based heterojunctions for photocatalytic redox reactions are highlighted.The structure,synthesis,and photophysical properties of MHPs-based heterojunctions are first introduced,including basic principles,categories(such as Schottky junction,type-I,type-II,Z-scheme,and S-scheme junction),and synthesis strategies.MHPs-based heterojunctions for photocatalytic redox reactions are then reviewed in four categories:H2evolution,CO_(2)reduction,pollutant degradation,and organic synthesis.The challenges and prospects in solar-light-driven redox reactions with MHPs-based heterojunctions in the future are finally discussed.展开更多
Halide perovskite materials have received considerable attention for solar cells,LEDs,lasers etc.owing to their controllable physicochemical properties and structural advantages.However,little research has focused on ...Halide perovskite materials have received considerable attention for solar cells,LEDs,lasers etc.owing to their controllable physicochemical properties and structural advantages.However,little research has focused on energy storage and conversion applications,such as use as anodes in lithium-ion batteries.In this paper,all-inorganic lead-free halide perovskite Cs_(3)Bi_(2)Cl_(9)powders were synthesized by the grinding method,and the lattice was successfully adjusted via introducing Mn^(2+).The characterization results show that Mn-ion substitution can cause local lattice distortion to restructure the lattice,which will cause a mixed arrangement of[BiCl_(6)]octahedra to improve the performance of the anode material.This new material can provide a feasible solution for solving the problem of low specific capacity anode materials caused by unstable crystal structures,and also indicates that such perovskites with unique crystal structures and lattice tunability have broad application prospects in lithium-ion batteries.展开更多
The relentless pursuit of advanced X-ray detection technologies has been significantly bolstered by the emergence of metal halides perovskites(MHPs)and their derivatives,which possess remarkable light yield and X-ray ...The relentless pursuit of advanced X-ray detection technologies has been significantly bolstered by the emergence of metal halides perovskites(MHPs)and their derivatives,which possess remarkable light yield and X-ray sensitivity.This comprehensive review delves into cutting-edge approaches for optimizing MHP scintillators performances by enhancing intrinsic physical properties and employing engineering radioluminescent(RL)light strategies,underscoring their potential for developing materials with superior high-resolution X-ray detection and imaging capabilities.We initially explore into recent research focused on strategies to effectively engineer the intrinsic physical properties of MHP scintillators,including light yield and response times.Additionally,we explore innovative engineering strategies involving stacked structures,waveguide effects,chiral circularly polarized luminescence,increased transparency,and the fabrication of flexile MHP scintillators,all of which effectively manage the RL light to achieve high-resolution and high-contrast X-ray imaging.Finally,we provide a roadmap for advancing next-generation MHP scintillators,highlighting their transformative potential in high-performance X-ray detection systems.展开更多
All-solid-state Li batteries(ASSLBs)using solid electrolytes(SEs)have gained significant attention in recent years considering the safety issue and their high energy density.Despite these advantages,the commercializat...All-solid-state Li batteries(ASSLBs)using solid electrolytes(SEs)have gained significant attention in recent years considering the safety issue and their high energy density.Despite these advantages,the commercialization of ASSLBs still faces challenges regarding the electrolyte/electrodes interfaces and growth of Li dendrites.Elemental doping is an effective and direct method to enhance the performance of SEs.Here,we report an Al-F co-doping strategy to improve the overall properties including ion conductivity,high voltage stability,and cathode and anode compatibility.Particularly,the Al-F co-doping enables the formation of a thin Li-Al alloy layer and fluoride interphases,thereby constructing a relatively stable interface and promoting uniform Li deposition.The similar merits of Al-F co-doping are also revealed in the Li-argyrodite series.ASSLBs assembled with these optimized electrolytes gain good electrochemical performance,demonstrating the universality of Al-F co-doping towards advanced SEs.展开更多
Self-trapping excitons(STEs) emission in metal halides has been a matter of interest, correlating with the strength of electron-phonon coupling in the lattice, which are usually caused by ions with ns~2 electronic str...Self-trapping excitons(STEs) emission in metal halides has been a matter of interest, correlating with the strength of electron-phonon coupling in the lattice, which are usually caused by ions with ns~2 electronic structure. In this work, Sb^(3+)/Te^(4+)ions doped Zn-based halide single crystals(SCs) with two STEs emissions have been synthesized and the possibility of its anti-counterfeiting application was explored.Further, the relationship between the strength of electron-phonon coupling and photoluminescence quantum yields(PLQYs) for STEs in a series of metal halides has been studied. And the semi-empirical range of the Huang-Rhys factors(S) for metal halides with excellent photoluminescence(PL) property has been summarized. This work provides ideas for further research into the relationship between luminescence performance and electron-phonon coupling of metal halides, and also provides a reference for designing the metal halides with high PLQYs.展开更多
Adopting high-voltage Ni-rich cathodes in halide and sulfide-based all-solid-state lithium batteries(ASSLBs)holds great promise for breaking through the 400 Wh kg^(-1)bottleneck.However,both cell configurations are co...Adopting high-voltage Ni-rich cathodes in halide and sulfide-based all-solid-state lithium batteries(ASSLBs)holds great promise for breaking through the 400 Wh kg^(-1)bottleneck.However,both cell configurations are confronted with intricate interfacial challenges in high-voltage regines(>4.5 V),resulting in inadequate cathode utilization and premature cell degradation.Moreover,contrary to previous studies,coupled with LiNi_(0.85)Co_(0.1)Mn_(0.05)O_(2)cathodes,typical halide(Li_(2)ZrCl_(6))-based cells at 4.5 V feature unlimited interfacial degradation and poor long cycle stability,while typical sulfide(Li_(6)PS_(5)Cl)-based cells feature self-limited interfacial degradation and poor initial cycle stability.Herein,this work addresses the high-voltage limitations of Li_(2)ZrCl_(6)and Li_(6)PS_(5)Cl catholyte-based cells by manipulating electrode mass fraction and tailoring interfacial composition,thereby effectively improving interfacial charge-transfer kinetics and(electro)chemical stability within cathodes.After appropriate interface design,both optimized cells at 4.5 V demonstrate remarkably increased initial discharge capacities(>195 mA h g^(-1)at0.1 C),improved cycle stabilities(>80%after 600 cycles at 0.5 C),and enhanced rate performances(>115 mA h g^(-1)at 1.0 C).This work deepens our understanding of high-voltage applications for halide/sulfide electrolytes and provides generalized interfacial design strategies for advancing high-voltage ASSLBs.展开更多
Mercury removal from coal combustion flue gas remains a significant challenge for environmental protection due to the lack of cost-effective sorbents.In this study,a series of red mud(RM)-based sorbents impregnated wi...Mercury removal from coal combustion flue gas remains a significant challenge for environmental protection due to the lack of cost-effective sorbents.In this study,a series of red mud(RM)-based sorbents impregnated with sodium halides(NaBr and NaI)are presented to capture elemental mercury(Hg^(0))from flue gas.The modified RM underwent comprehensive characterization,including analysis of its textural qualities,crystal structure,chemical composition,and thermal properties.The results indicate that the halide impregnation substantially impacts the surface area and pore size of the RM.Hg^(0) removal performance was evaluated on a fixed-bed reactor in simulated flue gas(consisting of N_(2),O_(2),CO_(2),NO and SO_(2),etc.)on a modified RM.At an optimal adsorption temperature of 160℃,NaI-modified sorbent(RMI5)offers a removal efficiency of 98%in a mixture of gas,including O_(2),NO and HCl.Furthermore,pseudo-second-order model fitting results demonstrate the chemisorption mechanism for the adsorption of Hg^(0) in kinetic investigations.展开更多
Polyfluoroarenes represent an essential group of compounds in the fields of medical and material chemistry.It is still a challenge to synthesize alkylated polyfluoroarenes.Herein,a Ni-catalyzed reductive alkylation of...Polyfluoroarenes represent an essential group of compounds in the fields of medical and material chemistry.It is still a challenge to synthesize alkylated polyfluoroarenes.Herein,a Ni-catalyzed reductive alkylation of polyfluoroarenes with alkyl halides under mild conditions is reported.Polyfluoroarenes(3~6 F)can reacted smoothly with a diverse range of alkyl halides,such as primary,secondary,and tertiary alkyl iodides.The efficient formation of C(sp2)—C(sp3)can be achieved through the combination of Ni catalysis and(Bpin)2/K2CO3 as terminal reductant.展开更多
Lithium halide solid-state electrolytes,with the general formula of Li_(3±m)M_(n)X_(6),are regarded as the promising families of electrolyte material for all solid-state lithium-ion batteries because of the relat...Lithium halide solid-state electrolytes,with the general formula of Li_(3±m)M_(n)X_(6),are regarded as the promising families of electrolyte material for all solid-state lithium-ion batteries because of the relatively good ionic conductivity,high oxidative stability against high-voltage oxide cathodes,and broad electrochemical stability window[1].Here,M stands for one or multiple metal elements and X for one or multiple halogen elements.展开更多
Herein,we have developed a sustainable linear paired electrolysis strategy for the redox-neutral benzylation of N-heteroarenes with benzyl halides using solid ion resin as the recyclable electrolyte.This method suffic...Herein,we have developed a sustainable linear paired electrolysis strategy for the redox-neutral benzylation of N-heteroarenes with benzyl halides using solid ion resin as the recyclable electrolyte.This method sufficiently utilizes both cathodic and anodic reactions to produce a variety of benzylated Nheteroarenes,features high atom-and step-economy,excellent energy efficiency,operational simplicity,good functional group tolerance,mild conditions and no requirement of sacrifice reagent and base additive.Importantly,the inexpensive and commercially available solid ion resin electrolyte was validated in both gram-scale synthesis and electrolyte cycling experiment.We hope this strategy not only provides a sustainable synthetic strategy for benzylated compounds but also develops the further utilization of ion resin in electrosynthesis as well as linear paired electrolysis.展开更多
Low-dimensional hybrid metal halides exhibit broadband emission and high photoluminescence quantum yield(PLQY), making them promising candidates for the next-generation luminescent materials in lighting applications. ...Low-dimensional hybrid metal halides exhibit broadband emission and high photoluminescence quantum yield(PLQY), making them promising candidates for the next-generation luminescent materials in lighting applications. Here,the emission intensity of(C_(12)H_(24)O_(6))_(2)Na_(2)(H_(2)O)_(3)Cu_(4)I_(6) was strengthened between 9.3 GPa and 17.2 GPa, accompanied by the redshift of emission wavelength. The photoluminescence(PL) of Cu(Ⅰ)-based organometallic halides originates from multiple emission states, which are a metal-to-ligand charge transfer or a halide-to-ligand charge transfer(MLCT/HLCT)excited state and a cluster-centered(CC) excited state. MLCT/HLCT-related emission wavelength redshifts while CCrelated emission wavelength remains unchanged, indicating that the rearrangement of different emission states plays a critical role in the changes of luminescence wavelength. This study not only deepens the understanding of the influence of high pressure on(C_(12)H_(24)O_(6))_(2)Na_(2)(H_(2)O)_(3)Cu_(4)I_(6), but also provides valuable insights into the structure–property relationship of zero-dimensional Cu(Ⅰ)-based organometallic halides.展开更多
Existing organic halide synthesis routes typically employ elemental halogens(X_(2),X=Cl or Br),leading to low atom economy and significant environmental pollution.In this work,we developed an atom efficient electrosyn...Existing organic halide synthesis routes typically employ elemental halogens(X_(2),X=Cl or Br),leading to low atom economy and significant environmental pollution.In this work,we developed an atom efficient electrosynthesis and separation strategy for halogenation reagents—N-chlorosuccinimide(NCS)and N-bromosuccinimide(NBS)—at high current densities.Faradic efficiency(FE)of 91.0%and 81.3%was achieved for NCS and NBS generation on RuO_(x)/TiO_(2)/Ti in a batch cell,respectively.Electrosynthesis of NCS likely involves both heterogeneous catalytic and homogeneous tandem pathways,while NBS is likely formed in a Langmuir-Hinshelwood mechanism with a proton-coupled electron transfer as the rate-determining step.A coupled continuous electrocatalytic synthesis and in situ separation setup was developed for the efficient production of NCS and NBS,which yielded 0.77 g of NCS in 12000 s and 0.81 g of NBS in 15000 s,both with relative purity exceeding 95%.The halogenation of acetone using NCS and NBS enabled gram-scale production of the key intermediate in organic synthesis,1-halogenacetone,with over 95%recovery of succinimide.展开更多
Two-dimensional(2D)chiral halide perovskites(CHPs)have attracted broad interest due to their distinct spin-dependent properties and promising applications in chiroptics and spintronics.Here,we report a new type of 2D ...Two-dimensional(2D)chiral halide perovskites(CHPs)have attracted broad interest due to their distinct spin-dependent properties and promising applications in chiroptics and spintronics.Here,we report a new type of 2D CHP single crystals,namely R/S-3BrMBA_(2)PbBr_(4).The chirality of the as-prepared samples is confirmed by exploiting circular dichroism spectroscopy,indicating a successful chirality transfer from chiral organic cations to their inorganic perovskite sublattices.Furthermore,we observed bright photoluminescence spanning from 380 to 750 nm in R/S-3BrMBA_(2)PbBr_(4)crystals at room temperature.Such broad photoluminescence originates from free excitons and self-trapped excitons.In addition,efficient second-harmonic generation(SHG)performance was observed in chiral perovskite single crystals with high circular polarization ratios and non-linear optical circular dichroism.This demonstrates that R/S-3BrMBA_(2)PbBr_(4)crystals can be used to detect and generate left-and righthanded circularly polarized light.Our study provides a new platform to develop high-performance chiroptical and spintronic devices.展开更多
Recent advancements in lead halide perovskites opened up an avenue for vast optoelectronic applications.However,lead toxicity and the complicated synthesis process posed major obstacles to their further practical appl...Recent advancements in lead halide perovskites opened up an avenue for vast optoelectronic applications.However,lead toxicity and the complicated synthesis process posed major obstacles to their further practical applications.To address these issues,a facile and robust mechanochemical synthesis of cesium manganese halide(Cs_(3)MnX_(5),X=halide element)was developed via a highly efficient solvent-free ball milling strategy.展开更多
Lead-free halide double perovskites have recently attracted significant attention due to their exceptional stability and favorable band gaps,making them promising candidates for solar cell applications.However,the rel...Lead-free halide double perovskites have recently attracted significant attention due to their exceptional stability and favorable band gaps,making them promising candidates for solar cell applications.However,the relationship between their structural characteristics and intrinsic band gap remains under-explored.This study presents a method to investigate the structure-band gap correlation in a typical halide double perovskite,MA_(2)Pt_(6)(MA^(+)=CH_(3)NH_(3)^(+)),using high pressure techniques.The band gap of MA_(2)PtI_(6)is effectively reduced at two different rates of 0.063 eV/GPa and 0.079 eV/GPa before and after 1.2 GPa,and progressively closes as pressure further increases.These optical changes are closely related to the pressure induced structural evolution of MA_(2)PtI_(6).Moreover,a phase transition from trigonal(R-3m)to monoclinic(P2/m)occurs at 1.2 GPa and completes by 2.0 GPa,driven by pressure-induced distortion of the[PtI_(6)]^(2-)octahedra,which is responsible for the variation of the band gap.These promising findings pave the way for potential applications in the structural and band gap tuning of halide double perovskites.展开更多
In past decades,ABX_(3) halide perovskites have attracted great interest in solar cells due to excellent opto-electronic properties,such as high carrier mobility.However,instability and toxicity are obstacles on the c...In past decades,ABX_(3) halide perovskites have attracted great interest in solar cells due to excellent opto-electronic properties,such as high carrier mobility.However,instability and toxicity are obstacles on the commercial route for perovskites.Many studies have turned to exploring A_(2) BX_(6) and A_(3) B_(2) X_(9) for better stability.Unfortunately,the carrier mobilities of these two types are inferior to ABX_(3),lower by an order of magnitude.Furthermore,the mobility of ABX_(3) is distributed over a large range of 1.78-4500 cm^(2) V^(−1) s^(−1) in experiments,which contributes to another diversity of mobilities.In this paper,we aim at reveal-ing the physical origin of the above-mentioned diversities by theoretical studies on CsBX_(3),Cs_(2) BX_(6),and Cs_(3) B_(2) X_(9)(B=Sn,Pb,Sb,Bi,X=Br,Cl).The difference in group velocities is the major reason responsible for the variation in these types.The unique three-dimensional connected conductive network of CsBX_(3) determines its large group velocity.As for carrier scattering,ionized impurity scattering dominates at low carrier and high ionized impurity concentrations.Detailed analysis reveals that band degeneracy is strongly related to the impurity scattering rate,while dielectric constant is almost immune.Our study provides a better understanding of the relationship between electronic structures and mobilities for po-tential applications in photovoltaics.展开更多
A dual-halide solid electrolyte,Li_(3)YCl_(3)Br_(3),was synthesized using a wet-chemistry route instead of the conventional mechanical ball-milling route.Li_(3)YCl_(3)Br_(3) exhibits an ion conductivity of 2.08 mS/cm ...A dual-halide solid electrolyte,Li_(3)YCl_(3)Br_(3),was synthesized using a wet-chemistry route instead of the conventional mechanical ball-milling route.Li_(3)YCl_(3)Br_(3) exhibits an ion conductivity of 2.08 mS/cm and an electro-chemical stability window of 3.8 V.Additionally,an all-solid-state lithium-ion battery using Li_(3)YCl_(3)Br_(3) and LiNi_(0.83)Co_(0.11)Mn_(0.06)O_(2)(NCM811)as the cathode material achieves a capacity retention of 93%after 200 cycles at 0.3C and maintains a specific capacity of 115 mA·h/g during 2C cycling.This exceptional performance is attributed to the high oxidative stability of Li_(3)YCl_(3)Br_(3) and the in-situ formation of Y_(2)O_(3) inert protective layer on the NCM811 surface under high voltage.Consequently,the study demonstrates the feasibility of a simple,cost-effective wet-chemistry route for synthesizing multi-component halides,highlighting its potential for large-scale production of halide solid electrolytes for practical applications.展开更多
Despite the rapid efficiency increase,tin halide perovskite solar cells are significantly behind their lead-based counterpart,with the highest reported efficiency of 15.38%.The main reason for this large difference is...Despite the rapid efficiency increase,tin halide perovskite solar cells are significantly behind their lead-based counterpart,with the highest reported efficiency of 15.38%.The main reason for this large difference is attributed to the instability of Sn^(2+),which easily oxidizes to Sn^(4+),creating Sn vacancies and increasing the open-circuit voltage loss.In this work,we implemented tin thiocyanate(Sn(SCN)_(2))as an additive for passivating the bulk defects of a germanium-doped tin halide perovskite film.Adding Sn^(2+)and SCN-ions reduces the Sn and iodine vacancies,limiting non-radiative recombination and favoring longer charge-carrier dynamics.Moreover,the addition of Sn(SCN)_(2) induces a higher film crystallinity and preferential orientation of the(l00)planes parallel to the substrate.The passivated devices showed improved photovoltaic parameters with the best open-circuit voltage of 0.716 V and the best efficiency of 12.22%,compared to 0.647 V and 10.2%for the reference device.In addition,the passivated solar cell retains 88.7%of its initial efficiency after 80 min of illumination under 100 mW cm^(-2) and is substantially better than the control device,which reaches 82.6%of its initial power conversion efficiency only after 30 min.This work demonstrates the passivation potential of tin-based additives,which combined with different counterions give a relatively large space of choices for passivation of Sn-based perovskites.展开更多
Organic metal halides with white-light emissions have shown significant application prospects in the fields of solid-state lighting and displays, but their structural design and synthesis remain a major challenge. Her...Organic metal halides with white-light emissions have shown significant application prospects in the fields of solid-state lighting and displays, but their structural design and synthesis remain a major challenge. Here, the material design concept of functional units has been applied to prepare a zero-dimensional (oD) organic anti-mony halide (1-BMP)_(5)(SbCl_(5))_(2)SbCl_(4) with two luminescent centers from the inorganic units and the organic units, emitting red emission about 670 nm and cyan emission about 508 nm respectively, combined to form white light. Based on the photoluminescence (PL), the time-resolved PL analysis and density functional theory (DFT) calculation, it is shown that the red and cyan emission comes from STEs related to inorganic units [SbCl_(5)]^(2-) and the fluorescence of organic cations 1-BMP^(+), respectively. This work provides new methods and ideas for the development of low-cost and eco-friendly white emission phosphors for single-component solid-state WLEDs.展开更多
基金support from National Key Research and Development Program of China(2024YFE0217100)the National Natural Science Foundation of China(21905006,22261160370,and 62105075)+7 种基金the Guangdong Provincial Science and Technology Plan(2021A0505110003)the Natural Science Foundation of Hunan Province,China(2023JJ50132)Guangxi Department of Science and Technology(2020GXNSFBA159049 and AD19110030)the Shenzhen Science and Technology Program(SGDX20230116093205009,JCYJ20220818100211025 and 2022378670)the Natural Science Foundation of Top Talent of SZTU(GDRC202343)financial support of Innovation and Technology Fund(#GHP/245/22SZ)The University Grant Council of the University of Hong Kong(grant No.2302101786)General Research Fund(grant Nos.17200823 and 17310624)from the Research Grants Council.
文摘Halide perovskites have emerged as promising materials for X-ray detection with exceptional properties and reasonable costs.Among them,heterostructures between 3D perovskites and low-dimensional perovskites attract intensive studies of their advantages due to low-level ion migration and decent stability.However,there is still a lack of methods to precisely construct heterostructures and a fundamental understanding of their structure-dependent optoelectronic properties.Herein,a gas-phase method was developed to grow 2D perovskites directly on 3D perovskites with nanoscale accuracy.In addition,the larger steric hindrance of organic layers of 2D perovskites was proved to enable slower ion migration,which resulted in reduced trap states and better stability.Based on MAPbBr_(3)single crystals with the(PA)_(2)PbBr_(4)capping layer,the X-ray detector achieved a sensitivity of 22,245μC Gy_(air)^(−1)cm^(−2),a response speed of 240μs,and a dark current drift of 1.17.10^(–4)nA cm^(−1)s^(−1)V^(−1),which were among the highest reported for state-of-the-art perovskite-based X-ray detectors.This study presents a precise synthesis method to construct perovskite-based heterostructures.It also brings an in-depth understanding of the relationship between lattice structures and properties,which are beneficial for advancing high-performance and cost-effective X-ray detectors.
基金financially supported by National Natural Science Foundation of China(No.22302155)the Fundamental Research Funds of the Center Universities(No.D5000240188)the research program of ZJUT(YJY-ZS-20240001)。
文摘Metal halide perovskites(MHPs)with striking electrical and optical properties have appeared at the forefront of semiconductor materials for photocatalytic redox reactions but still suffer from some intrinsic drawbacks such as inferior stability,severe charge-carrier recombination,and limited active sites.Heterojunctions have recently been widely constructed to improve light absorption,passivate surface for enhanced stability,and promote charge-carrier dynamics of MHPs.However,little attention has been paid to the review of MHPs-based heterojunctions for photocatalytic redox reactions.Here,recent advances of MHPs-based heterojunctions for photocatalytic redox reactions are highlighted.The structure,synthesis,and photophysical properties of MHPs-based heterojunctions are first introduced,including basic principles,categories(such as Schottky junction,type-I,type-II,Z-scheme,and S-scheme junction),and synthesis strategies.MHPs-based heterojunctions for photocatalytic redox reactions are then reviewed in four categories:H2evolution,CO_(2)reduction,pollutant degradation,and organic synthesis.The challenges and prospects in solar-light-driven redox reactions with MHPs-based heterojunctions in the future are finally discussed.
基金supported by the Foundation of Yunnan Province(Nos.202301AU070021,202201BE070001-027)the Test Foundation of KUST(No.2022T20210208).
文摘Halide perovskite materials have received considerable attention for solar cells,LEDs,lasers etc.owing to their controllable physicochemical properties and structural advantages.However,little research has focused on energy storage and conversion applications,such as use as anodes in lithium-ion batteries.In this paper,all-inorganic lead-free halide perovskite Cs_(3)Bi_(2)Cl_(9)powders were synthesized by the grinding method,and the lattice was successfully adjusted via introducing Mn^(2+).The characterization results show that Mn-ion substitution can cause local lattice distortion to restructure the lattice,which will cause a mixed arrangement of[BiCl_(6)]octahedra to improve the performance of the anode material.This new material can provide a feasible solution for solving the problem of low specific capacity anode materials caused by unstable crystal structures,and also indicates that such perovskites with unique crystal structures and lattice tunability have broad application prospects in lithium-ion batteries.
基金supported by the National Nature Science Foundation of China(NSFC)(U2241236,1220041913,52473253)the National Key Research and Development Program of China(2022ZDZX0007)+1 种基金Fundamental Research Open Subject Grant Program of Yantai Advanced Materials and Green Manufacturing Laboratory of Shandong Province(AMGM2024F15)Yunnan Major Scientific and Technological Projects(202402AB080011).
文摘The relentless pursuit of advanced X-ray detection technologies has been significantly bolstered by the emergence of metal halides perovskites(MHPs)and their derivatives,which possess remarkable light yield and X-ray sensitivity.This comprehensive review delves into cutting-edge approaches for optimizing MHP scintillators performances by enhancing intrinsic physical properties and employing engineering radioluminescent(RL)light strategies,underscoring their potential for developing materials with superior high-resolution X-ray detection and imaging capabilities.We initially explore into recent research focused on strategies to effectively engineer the intrinsic physical properties of MHP scintillators,including light yield and response times.Additionally,we explore innovative engineering strategies involving stacked structures,waveguide effects,chiral circularly polarized luminescence,increased transparency,and the fabrication of flexile MHP scintillators,all of which effectively manage the RL light to achieve high-resolution and high-contrast X-ray imaging.Finally,we provide a roadmap for advancing next-generation MHP scintillators,highlighting their transformative potential in high-performance X-ray detection systems.
基金supported by the National Natural Science Foundation of China(Nos.52172243,52371215)。
文摘All-solid-state Li batteries(ASSLBs)using solid electrolytes(SEs)have gained significant attention in recent years considering the safety issue and their high energy density.Despite these advantages,the commercialization of ASSLBs still faces challenges regarding the electrolyte/electrodes interfaces and growth of Li dendrites.Elemental doping is an effective and direct method to enhance the performance of SEs.Here,we report an Al-F co-doping strategy to improve the overall properties including ion conductivity,high voltage stability,and cathode and anode compatibility.Particularly,the Al-F co-doping enables the formation of a thin Li-Al alloy layer and fluoride interphases,thereby constructing a relatively stable interface and promoting uniform Li deposition.The similar merits of Al-F co-doping are also revealed in the Li-argyrodite series.ASSLBs assembled with these optimized electrolytes gain good electrochemical performance,demonstrating the universality of Al-F co-doping towards advanced SEs.
基金supported by the financial aid from the National Natural Science Foundation of China (No. 22271273)International Partnership Program of Chinese Academy of Sciences (No. 121522KYSB20190022)。
文摘Self-trapping excitons(STEs) emission in metal halides has been a matter of interest, correlating with the strength of electron-phonon coupling in the lattice, which are usually caused by ions with ns~2 electronic structure. In this work, Sb^(3+)/Te^(4+)ions doped Zn-based halide single crystals(SCs) with two STEs emissions have been synthesized and the possibility of its anti-counterfeiting application was explored.Further, the relationship between the strength of electron-phonon coupling and photoluminescence quantum yields(PLQYs) for STEs in a series of metal halides has been studied. And the semi-empirical range of the Huang-Rhys factors(S) for metal halides with excellent photoluminescence(PL) property has been summarized. This work provides ideas for further research into the relationship between luminescence performance and electron-phonon coupling of metal halides, and also provides a reference for designing the metal halides with high PLQYs.
基金supported by the National Key R&D Program of China(2022YFB3803505)National Natural Scientific Foundation of China(U21A2080&22479009)National Related Project and the Fundamental Research Funds for the Central Universities(FRF-TP-22-01C2)。
文摘Adopting high-voltage Ni-rich cathodes in halide and sulfide-based all-solid-state lithium batteries(ASSLBs)holds great promise for breaking through the 400 Wh kg^(-1)bottleneck.However,both cell configurations are confronted with intricate interfacial challenges in high-voltage regines(>4.5 V),resulting in inadequate cathode utilization and premature cell degradation.Moreover,contrary to previous studies,coupled with LiNi_(0.85)Co_(0.1)Mn_(0.05)O_(2)cathodes,typical halide(Li_(2)ZrCl_(6))-based cells at 4.5 V feature unlimited interfacial degradation and poor long cycle stability,while typical sulfide(Li_(6)PS_(5)Cl)-based cells feature self-limited interfacial degradation and poor initial cycle stability.Herein,this work addresses the high-voltage limitations of Li_(2)ZrCl_(6)and Li_(6)PS_(5)Cl catholyte-based cells by manipulating electrode mass fraction and tailoring interfacial composition,thereby effectively improving interfacial charge-transfer kinetics and(electro)chemical stability within cathodes.After appropriate interface design,both optimized cells at 4.5 V demonstrate remarkably increased initial discharge capacities(>195 mA h g^(-1)at0.1 C),improved cycle stabilities(>80%after 600 cycles at 0.5 C),and enhanced rate performances(>115 mA h g^(-1)at 1.0 C).This work deepens our understanding of high-voltage applications for halide/sulfide electrolytes and provides generalized interfacial design strategies for advancing high-voltage ASSLBs.
基金supported by the National Natural Science Foundation of China(22278066,21776039)the National Key R&D Program of China(2023YFB4103001)The Fundamental Research Funds for the Central Universities(DUT2021TB03).
文摘Mercury removal from coal combustion flue gas remains a significant challenge for environmental protection due to the lack of cost-effective sorbents.In this study,a series of red mud(RM)-based sorbents impregnated with sodium halides(NaBr and NaI)are presented to capture elemental mercury(Hg^(0))from flue gas.The modified RM underwent comprehensive characterization,including analysis of its textural qualities,crystal structure,chemical composition,and thermal properties.The results indicate that the halide impregnation substantially impacts the surface area and pore size of the RM.Hg^(0) removal performance was evaluated on a fixed-bed reactor in simulated flue gas(consisting of N_(2),O_(2),CO_(2),NO and SO_(2),etc.)on a modified RM.At an optimal adsorption temperature of 160℃,NaI-modified sorbent(RMI5)offers a removal efficiency of 98%in a mixture of gas,including O_(2),NO and HCl.Furthermore,pseudo-second-order model fitting results demonstrate the chemisorption mechanism for the adsorption of Hg^(0) in kinetic investigations.
文摘Polyfluoroarenes represent an essential group of compounds in the fields of medical and material chemistry.It is still a challenge to synthesize alkylated polyfluoroarenes.Herein,a Ni-catalyzed reductive alkylation of polyfluoroarenes with alkyl halides under mild conditions is reported.Polyfluoroarenes(3~6 F)can reacted smoothly with a diverse range of alkyl halides,such as primary,secondary,and tertiary alkyl iodides.The efficient formation of C(sp2)—C(sp3)can be achieved through the combination of Ni catalysis and(Bpin)2/K2CO3 as terminal reductant.
文摘Lithium halide solid-state electrolytes,with the general formula of Li_(3±m)M_(n)X_(6),are regarded as the promising families of electrolyte material for all solid-state lithium-ion batteries because of the relatively good ionic conductivity,high oxidative stability against high-voltage oxide cathodes,and broad electrochemical stability window[1].Here,M stands for one or multiple metal elements and X for one or multiple halogen elements.
基金financial support from University of South China。
文摘Herein,we have developed a sustainable linear paired electrolysis strategy for the redox-neutral benzylation of N-heteroarenes with benzyl halides using solid ion resin as the recyclable electrolyte.This method sufficiently utilizes both cathodic and anodic reactions to produce a variety of benzylated Nheteroarenes,features high atom-and step-economy,excellent energy efficiency,operational simplicity,good functional group tolerance,mild conditions and no requirement of sacrifice reagent and base additive.Importantly,the inexpensive and commercially available solid ion resin electrolyte was validated in both gram-scale synthesis and electrolyte cycling experiment.We hope this strategy not only provides a sustainable synthetic strategy for benzylated compounds but also develops the further utilization of ion resin in electrosynthesis as well as linear paired electrolysis.
基金Project supported by the National Key R&D Program of China (Grant No. 2023YFA1406200)the National Natural Science Foundation of China (Grant Nos. 12174144 and 12474009)the Graduate Innovation Fund of Jilin University (Grant No. 2024CX201)。
文摘Low-dimensional hybrid metal halides exhibit broadband emission and high photoluminescence quantum yield(PLQY), making them promising candidates for the next-generation luminescent materials in lighting applications. Here,the emission intensity of(C_(12)H_(24)O_(6))_(2)Na_(2)(H_(2)O)_(3)Cu_(4)I_(6) was strengthened between 9.3 GPa and 17.2 GPa, accompanied by the redshift of emission wavelength. The photoluminescence(PL) of Cu(Ⅰ)-based organometallic halides originates from multiple emission states, which are a metal-to-ligand charge transfer or a halide-to-ligand charge transfer(MLCT/HLCT)excited state and a cluster-centered(CC) excited state. MLCT/HLCT-related emission wavelength redshifts while CCrelated emission wavelength remains unchanged, indicating that the rearrangement of different emission states plays a critical role in the changes of luminescence wavelength. This study not only deepens the understanding of the influence of high pressure on(C_(12)H_(24)O_(6))_(2)Na_(2)(H_(2)O)_(3)Cu_(4)I_(6), but also provides valuable insights into the structure–property relationship of zero-dimensional Cu(Ⅰ)-based organometallic halides.
文摘Existing organic halide synthesis routes typically employ elemental halogens(X_(2),X=Cl or Br),leading to low atom economy and significant environmental pollution.In this work,we developed an atom efficient electrosynthesis and separation strategy for halogenation reagents—N-chlorosuccinimide(NCS)and N-bromosuccinimide(NBS)—at high current densities.Faradic efficiency(FE)of 91.0%and 81.3%was achieved for NCS and NBS generation on RuO_(x)/TiO_(2)/Ti in a batch cell,respectively.Electrosynthesis of NCS likely involves both heterogeneous catalytic and homogeneous tandem pathways,while NBS is likely formed in a Langmuir-Hinshelwood mechanism with a proton-coupled electron transfer as the rate-determining step.A coupled continuous electrocatalytic synthesis and in situ separation setup was developed for the efficient production of NCS and NBS,which yielded 0.77 g of NCS in 12000 s and 0.81 g of NBS in 15000 s,both with relative purity exceeding 95%.The halogenation of acetone using NCS and NBS enabled gram-scale production of the key intermediate in organic synthesis,1-halogenacetone,with over 95%recovery of succinimide.
基金supported by Natural Science Foundation of Jiangsu Province,Major Project(BK20222007).
文摘Two-dimensional(2D)chiral halide perovskites(CHPs)have attracted broad interest due to their distinct spin-dependent properties and promising applications in chiroptics and spintronics.Here,we report a new type of 2D CHP single crystals,namely R/S-3BrMBA_(2)PbBr_(4).The chirality of the as-prepared samples is confirmed by exploiting circular dichroism spectroscopy,indicating a successful chirality transfer from chiral organic cations to their inorganic perovskite sublattices.Furthermore,we observed bright photoluminescence spanning from 380 to 750 nm in R/S-3BrMBA_(2)PbBr_(4)crystals at room temperature.Such broad photoluminescence originates from free excitons and self-trapped excitons.In addition,efficient second-harmonic generation(SHG)performance was observed in chiral perovskite single crystals with high circular polarization ratios and non-linear optical circular dichroism.This demonstrates that R/S-3BrMBA_(2)PbBr_(4)crystals can be used to detect and generate left-and righthanded circularly polarized light.Our study provides a new platform to develop high-performance chiroptical and spintronic devices.
基金inancially supported by the National Science Foundation of China(52273217,52173209,51973201,52203051)the National Science Foundation for Young Scientists of Henan Province(232300421068,to Y.H.)+2 种基金the Key Scientific Research Projects of Col eges and Universities in Henan Province(Fundamental Research Project 2022,Grant 22ZX001,to X.P.)Postdoctoral Foundation of Henan Province(304348,G.S.)Postgraduate Education Reform and Quality Improvement Project of Henan Province(No.YJS2025GZZ03)。
文摘Recent advancements in lead halide perovskites opened up an avenue for vast optoelectronic applications.However,lead toxicity and the complicated synthesis process posed major obstacles to their further practical applications.To address these issues,a facile and robust mechanochemical synthesis of cesium manganese halide(Cs_(3)MnX_(5),X=halide element)was developed via a highly efficient solvent-free ball milling strategy.
基金supported by the National Natural Science Foundation of China(Grant No.12474414)the Natural Science Foundation of Henan(Grant No.242300421157)the ADXRD measurement was performed at the 4W2 beamline,the Beijing Synchrotron Radiation Facility(BSRF).
文摘Lead-free halide double perovskites have recently attracted significant attention due to their exceptional stability and favorable band gaps,making them promising candidates for solar cell applications.However,the relationship between their structural characteristics and intrinsic band gap remains under-explored.This study presents a method to investigate the structure-band gap correlation in a typical halide double perovskite,MA_(2)Pt_(6)(MA^(+)=CH_(3)NH_(3)^(+)),using high pressure techniques.The band gap of MA_(2)PtI_(6)is effectively reduced at two different rates of 0.063 eV/GPa and 0.079 eV/GPa before and after 1.2 GPa,and progressively closes as pressure further increases.These optical changes are closely related to the pressure induced structural evolution of MA_(2)PtI_(6).Moreover,a phase transition from trigonal(R-3m)to monoclinic(P2/m)occurs at 1.2 GPa and completes by 2.0 GPa,driven by pressure-induced distortion of the[PtI_(6)]^(2-)octahedra,which is responsible for the variation of the band gap.These promising findings pave the way for potential applications in the structural and band gap tuning of halide double perovskites.
基金supported by the National Key Research and Development Program of China(No.2021YFB3502200)the National Natural Science Foundation of China(Nos.52172216 and 92163212)+1 种基金support from the Shanghai Engi-neering Research Center for Integrated Circuits and Advanced Dis-play Materialssupported by Shanghai Techni-cal Service Center of Science and Engineering Computing,Shanghai University and Hefei Advanced Computing Center.
文摘In past decades,ABX_(3) halide perovskites have attracted great interest in solar cells due to excellent opto-electronic properties,such as high carrier mobility.However,instability and toxicity are obstacles on the commercial route for perovskites.Many studies have turned to exploring A_(2) BX_(6) and A_(3) B_(2) X_(9) for better stability.Unfortunately,the carrier mobilities of these two types are inferior to ABX_(3),lower by an order of magnitude.Furthermore,the mobility of ABX_(3) is distributed over a large range of 1.78-4500 cm^(2) V^(−1) s^(−1) in experiments,which contributes to another diversity of mobilities.In this paper,we aim at reveal-ing the physical origin of the above-mentioned diversities by theoretical studies on CsBX_(3),Cs_(2) BX_(6),and Cs_(3) B_(2) X_(9)(B=Sn,Pb,Sb,Bi,X=Br,Cl).The difference in group velocities is the major reason responsible for the variation in these types.The unique three-dimensional connected conductive network of CsBX_(3) determines its large group velocity.As for carrier scattering,ionized impurity scattering dominates at low carrier and high ionized impurity concentrations.Detailed analysis reveals that band degeneracy is strongly related to the impurity scattering rate,while dielectric constant is almost immune.Our study provides a better understanding of the relationship between electronic structures and mobilities for po-tential applications in photovoltaics.
基金financially supported by Hunan Provincial Science and Technology Department,China(No.2021JJ10058)Key Research and Development Program of Hunan Province,China(No.2023GK2016)。
文摘A dual-halide solid electrolyte,Li_(3)YCl_(3)Br_(3),was synthesized using a wet-chemistry route instead of the conventional mechanical ball-milling route.Li_(3)YCl_(3)Br_(3) exhibits an ion conductivity of 2.08 mS/cm and an electro-chemical stability window of 3.8 V.Additionally,an all-solid-state lithium-ion battery using Li_(3)YCl_(3)Br_(3) and LiNi_(0.83)Co_(0.11)Mn_(0.06)O_(2)(NCM811)as the cathode material achieves a capacity retention of 93%after 200 cycles at 0.3C and maintains a specific capacity of 115 mA·h/g during 2C cycling.This exceptional performance is attributed to the high oxidative stability of Li_(3)YCl_(3)Br_(3) and the in-situ formation of Y_(2)O_(3) inert protective layer on the NCM811 surface under high voltage.Consequently,the study demonstrates the feasibility of a simple,cost-effective wet-chemistry route for synthesizing multi-component halides,highlighting its potential for large-scale production of halide solid electrolytes for practical applications.
基金support from the Focus Group‘Next Generation Organic Photovoltaics’participating with the Dutch Institute for Fundamental Energy Research(DIFFER)(FOM130)Advanced Materials research program of the Zernike National Research Centre under the Bonus Incentive Scheme(BIS)of the Dutch Ministry for Education,Culture and Science.
文摘Despite the rapid efficiency increase,tin halide perovskite solar cells are significantly behind their lead-based counterpart,with the highest reported efficiency of 15.38%.The main reason for this large difference is attributed to the instability of Sn^(2+),which easily oxidizes to Sn^(4+),creating Sn vacancies and increasing the open-circuit voltage loss.In this work,we implemented tin thiocyanate(Sn(SCN)_(2))as an additive for passivating the bulk defects of a germanium-doped tin halide perovskite film.Adding Sn^(2+)and SCN-ions reduces the Sn and iodine vacancies,limiting non-radiative recombination and favoring longer charge-carrier dynamics.Moreover,the addition of Sn(SCN)_(2) induces a higher film crystallinity and preferential orientation of the(l00)planes parallel to the substrate.The passivated devices showed improved photovoltaic parameters with the best open-circuit voltage of 0.716 V and the best efficiency of 12.22%,compared to 0.647 V and 10.2%for the reference device.In addition,the passivated solar cell retains 88.7%of its initial efficiency after 80 min of illumination under 100 mW cm^(-2) and is substantially better than the control device,which reaches 82.6%of its initial power conversion efficiency only after 30 min.This work demonstrates the passivation potential of tin-based additives,which combined with different counterions give a relatively large space of choices for passivation of Sn-based perovskites.
基金the National Natural Science Foundation of China(22476220,22336007)the China Postdoctoral Science Foundation(2024M753736)the Guangdong Basic Research Center of Excellence for Functional Molecular Engineering(31000-42080002).
文摘Organic metal halides with white-light emissions have shown significant application prospects in the fields of solid-state lighting and displays, but their structural design and synthesis remain a major challenge. Here, the material design concept of functional units has been applied to prepare a zero-dimensional (oD) organic anti-mony halide (1-BMP)_(5)(SbCl_(5))_(2)SbCl_(4) with two luminescent centers from the inorganic units and the organic units, emitting red emission about 670 nm and cyan emission about 508 nm respectively, combined to form white light. Based on the photoluminescence (PL), the time-resolved PL analysis and density functional theory (DFT) calculation, it is shown that the red and cyan emission comes from STEs related to inorganic units [SbCl_(5)]^(2-) and the fluorescence of organic cations 1-BMP^(+), respectively. This work provides new methods and ideas for the development of low-cost and eco-friendly white emission phosphors for single-component solid-state WLEDs.
