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
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
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
The demand for neodymium(NdFeB) permanent magnets for electric vehicles and eco-friendly generators is increasing.However,NdFeB magnets contain rare earth elements(REEs),which are limited in supply.In this study,we pe...The demand for neodymium(NdFeB) permanent magnets for electric vehicles and eco-friendly generators is increasing.However,NdFeB magnets contain rare earth elements(REEs),which are limited in supply.In this study,we performed an exchange reaction between magnesium halides(fluoride and chloride) and waste NdFeB scrap and then compared the characteristics of the extracted halides salts.The compositions of the ternary Mg fluoride(LiF:NaF:MgF_(2)=50:40:10 in mole ratio) and chloride(LiCl:NaCl:MgCl_(2)=10:50:40 in mole ratio) salts were thermodynamically determined for achieving low eutectic temperatures.The reactions between the NdFeB scrap powder(1-2 mm) and Mg halide salts were carried out at 1073 and 873 K for the fluoride and chloride systems,respectively,in an argon atmosphere.After the reaction,we separated Nd halide from the residual salt and evaluated the Ndextraction rate.The phase formation of the salt was analyzed using X-ray diffraction(XRD),and the extraction rate of Nd was analyzed using inductively coupled plasma optical emission spectroscopy(ICPOES).Nd was extracted in the form of Nd halide(NdF_(3) or NdCl_(3)),and the extraction rates in the fluoride and chloride systems are 98.64% and 84.59%,respectively.Thus,the fluoride system is more effective than the chloride system for Nd extraction.Our study provides a comprehensive comparative analysis of the effectiveness of fluo ride and chlo ride systems in extracting REEs from NdFeB magnet scrap.Our study findings can be used to develop an effective method for recycling magnet scraps.展开更多
Low-dimensional lead-free metal halides have emerged as promising candidates for anti-counterfeiting applications,characterized by their low toxicity,diverse crystal structures,and exceptional optical properties.Conve...Low-dimensional lead-free metal halides have emerged as promising candidates for anti-counterfeiting applications,characterized by their low toxicity,diverse crystal structures,and exceptional optical properties.Conventional anti-counterfeiting technologies based on low-dimensional metal halides are often constrained by complex and time-consuming heating and solvent treatments that may insufficiently modify the luminescent characteristics of emitters,thus hindering their practical implementation in effective anti-counterfeiting strategies.In this study,we employ an innovative alloying strategy in low-dimensional zinc halides Cs_(2)ZnCl_(4) to enhance their luminescent performance.By introducing self-trapped exciton(STE)states through the alloying of Cu^(+)and Sb^(3+)ions in Cs_(2)ZnCl_(4),we achieve bright blue and red photoluminescence(PL)centered at 492 nm and 744 nm,respectively,under 266 nm excitation,with only red emission observed under 365 nm excitation.This approach enables instant and reliable anti-counterfeiting applications.This work presents new opportunities for developing robust anti-counterfeiting and information encryption/decryption technologies.展开更多
The research of long persistent luminescence(LPL)materials has yield brilliant results in many fields.However,the efforts are still needed for the regulation of the LPL performance.In this work,a series of LPL metal o...The research of long persistent luminescence(LPL)materials has yield brilliant results in many fields.However,the efforts are still needed for the regulation of the LPL performance.In this work,a series of LPL metal organic halides with rich halogen-bond interactions,Py-CdX_(2)(X=Cl,Br,I)were synthesized through self-assembly by Cd X_(2)and pyridine solvent.The steady-state emission redshifted and phosphorescence lifetime declined as the halogen atoms are aggravated.Three halides exhibit adjustable emission from blue to green and multiple phosphorescence from green to yellow at room temperature by changing the excitation wavelengths.Surprisingly,Py-CdX_(2)can emit the visible color-tunable LPL from green to yellow after removing different excitation sources at ambient conditions.Combing the results of theoretical calculation and experimental analysis,it is found that heavy atom effect and the rich intermolecular halogen bond help realize LPL and multiple triplet states originated from the pyridine ring and the halogens.展开更多
Methyl halides are crucial trace greenhouse gases in the atmosphere,playing a significant role in global climate change and the atmospheric environment.This study investigated the photochemical production of methyl ha...Methyl halides are crucial trace greenhouse gases in the atmosphere,playing a significant role in global climate change and the atmospheric environment.This study investigated the photochemical production of methyl halides in an artificial seawater system using guaiacol as a precursor through laboratory simulation experiments.The influences of various environmental factors,including illumination time,radiation wavebands,illumination intensity,concentrations of guaiacol and halide ions(X^(-)),Fe^(3+),salinity,dissolved oxygen(DO),and pH value on the photochemical production of methyl halides were examined.We demonstrated that increased illumination intensity and duration promote the photochemical production of methyl halides,with a notable enhancement under UV-B radiation.Guaiacol and halide ions were identified as key precursors,and their high concentrations facilitated the formation of methyl halides.Additionally,different types of halide ions exhibited a competitive relationship in producing methyl halides.The study found that an increase in pH inhibited the photochemical formation of CH_(3)I due to the reaction between OH^(-)and·CH_(3).Dissolved oxygen was found to inhibit the photochemical formation of CH3I while promoting the formation of CH_(3)Cl.Conversely,an appropriate concentration of Fe^(3+)enhanced the photochemical production of methyl halides.Field observations indicated a high photochemical production of methyl halides in the natural waters near Qingdao’s coastal area,likely due to the high concentration of dissolved organic matter(DOM),which supports photochemical reactions.Furthermore,the photochemical production of methyl halides in natural seawater was significantly higher than in dark conditions,underscoring the importance of illumination in promoting these photochemical processes in seawater.展开更多
Ternary metal halides based on Cu(I)and Ag(I)have attracted intensive attention in optoelectronic applications due to their excellent luminescent properties,low toxicity,and robust stability.While the self-trapped exc...Ternary metal halides based on Cu(I)and Ag(I)have attracted intensive attention in optoelectronic applications due to their excellent luminescent properties,low toxicity,and robust stability.While the self-trapped excitons(STEs)emission mechanisms of Cu(I)halides are well understood,the STEs in Ag(I)halides remain less thoroughly explored.This study explores the STE emission efficiency within the A_(2)AgX_(3)(A=Rb,Cs;X=Cl,Br,I)system by identifying three distinct STE states in each material and calculating their configuration coordinate diagrams.We find that the STE emission efficiency in this system is mainly determined by STE stability and influenced by self-trapping and quenching barriers.Moreover,we investigate the impact of structural compactness on emission efficiency and find that the excessive electron–phonon coupling in this system can be reduced by increasing the structural compactness.The atomic packing factor is identified as a low-cost and effective descriptor for predicting STE emission efficiency in both Cs_(2)AgX_(3) and Rb_(2)AgX_(3) systems.These findings can deepen our understanding of STE behavior in metal halide materials and offer valuable insights for the design of efficient STE luminescent materials.The datasets presented in this paper are openly available in Science Data Bank at https://doi.org/10.57760/sciencedb.12094.展开更多
Recently,organic-inorganic hybrid metal halides(HMHs)have attracted extensive attention as promis-ing multifunctional materials by virtue of their structural diversity and tunable photophysical properties.However,it r...Recently,organic-inorganic hybrid metal halides(HMHs)have attracted extensive attention as promis-ing multifunctional materials by virtue of their structural diversity and tunable photophysical properties.However,it remains a challenge to design HMHs with specific functions on demand.Herein,by introduc-ing R/S-methylbenzylamine(R/S-MBA)and doping Sb^(3+),we have achieved both second harmonic gen-eration(SHG)and circularly polarized luminescence(CPL)properties in lead-free indium halides.The introduction of chiral organic cations can break the symmetry and induce the indium halides to crys-tallize in the chiral space group.The Sb^(3+)with ns2 electronic configuration can serve as the dopants to promote the formation of self-trapped excitons,so as to activate highly efficient luminescence.As a re-sult,the as-prepared Sb3+doped(R/S-MBA)3 InCl6 show not only SHG responses but also CPL signals with luminescence dissymmetry factor of−5.3×10^(−3) and 4.7×10^(−3).This work provides a new inspiration for the exploitation of chiral multifunctional materials.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
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
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
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
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
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
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
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
Halide solid-state electrolytes(SSEs)have become a new research focus for all-solid-state batteries because of their significant safety advantages,high ionic conductivity,high-voltage stability,and good ductility.None...Halide solid-state electrolytes(SSEs)have become a new research focus for all-solid-state batteries because of their significant safety advantages,high ionic conductivity,high-voltage stability,and good ductility.Nonetheless,stability issues are a key barrier to their practical application.In past reports,the analysis of halide electrolyte stability and its enhancement methods lacked relevance,which limited the design and optimization of halide solid electrolytes.This review focus on stability issues from a chemical,electrochemical,and interfacial point of view,with particular emphasis on the interaction of halide SSEs with anode and cathode interfaces.By focusing on innovative strategies to address the stability issue,this paper aims to further deepen the understanding and development of halide all-solid-state batteries by proposing to focus research efforts on improving their stability in order to address their inherent challenges and match higher voltage cathodes,paving the way for their wider application in the next generation of energy storage technologies.展开更多
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 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.
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 the Technology Innovation (20010817,Technology for the ecofriendly rare earth refining from used motors and manufacture of permanent magnet materials) funded by the Ministry of Trade,Industry & Energy (MOTIE),Korea。
文摘The demand for neodymium(NdFeB) permanent magnets for electric vehicles and eco-friendly generators is increasing.However,NdFeB magnets contain rare earth elements(REEs),which are limited in supply.In this study,we performed an exchange reaction between magnesium halides(fluoride and chloride) and waste NdFeB scrap and then compared the characteristics of the extracted halides salts.The compositions of the ternary Mg fluoride(LiF:NaF:MgF_(2)=50:40:10 in mole ratio) and chloride(LiCl:NaCl:MgCl_(2)=10:50:40 in mole ratio) salts were thermodynamically determined for achieving low eutectic temperatures.The reactions between the NdFeB scrap powder(1-2 mm) and Mg halide salts were carried out at 1073 and 873 K for the fluoride and chloride systems,respectively,in an argon atmosphere.After the reaction,we separated Nd halide from the residual salt and evaluated the Ndextraction rate.The phase formation of the salt was analyzed using X-ray diffraction(XRD),and the extraction rate of Nd was analyzed using inductively coupled plasma optical emission spectroscopy(ICPOES).Nd was extracted in the form of Nd halide(NdF_(3) or NdCl_(3)),and the extraction rates in the fluoride and chloride systems are 98.64% and 84.59%,respectively.Thus,the fluoride system is more effective than the chloride system for Nd extraction.Our study provides a comprehensive comparative analysis of the effectiveness of fluo ride and chlo ride systems in extracting REEs from NdFeB magnet scrap.Our study findings can be used to develop an effective method for recycling magnet scraps.
基金supported by Chongqing Natural Science Foundation Innovation and Development Joint Fund(CSTB2025NSCQ-LZX0001)Ongoing Research Funding Program,(ORF-2025-762)King Saud University,Riyadh,Saudi Arabia,National Natural Science Foundationof China(11974063).
文摘Low-dimensional lead-free metal halides have emerged as promising candidates for anti-counterfeiting applications,characterized by their low toxicity,diverse crystal structures,and exceptional optical properties.Conventional anti-counterfeiting technologies based on low-dimensional metal halides are often constrained by complex and time-consuming heating and solvent treatments that may insufficiently modify the luminescent characteristics of emitters,thus hindering their practical implementation in effective anti-counterfeiting strategies.In this study,we employ an innovative alloying strategy in low-dimensional zinc halides Cs_(2)ZnCl_(4) to enhance their luminescent performance.By introducing self-trapped exciton(STE)states through the alloying of Cu^(+)and Sb^(3+)ions in Cs_(2)ZnCl_(4),we achieve bright blue and red photoluminescence(PL)centered at 492 nm and 744 nm,respectively,under 266 nm excitation,with only red emission observed under 365 nm excitation.This approach enables instant and reliable anti-counterfeiting applications.This work presents new opportunities for developing robust anti-counterfeiting and information encryption/decryption technologies.
基金financially supported by National Natural Science Foundation of China(No.22101162)Start-up Foundation of Shaanxi University of Science&Technology(No.126022036)。
文摘The research of long persistent luminescence(LPL)materials has yield brilliant results in many fields.However,the efforts are still needed for the regulation of the LPL performance.In this work,a series of LPL metal organic halides with rich halogen-bond interactions,Py-CdX_(2)(X=Cl,Br,I)were synthesized through self-assembly by Cd X_(2)and pyridine solvent.The steady-state emission redshifted and phosphorescence lifetime declined as the halogen atoms are aggravated.Three halides exhibit adjustable emission from blue to green and multiple phosphorescence from green to yellow at room temperature by changing the excitation wavelengths.Surprisingly,Py-CdX_(2)can emit the visible color-tunable LPL from green to yellow after removing different excitation sources at ambient conditions.Combing the results of theoretical calculation and experimental analysis,it is found that heavy atom effect and the rich intermolecular halogen bond help realize LPL and multiple triplet states originated from the pyridine ring and the halogens.
基金funded by the Natural Science Foundation of Shandong Province,China(No.ZR2021MD034)the National Natural Science Foundation of China(No.42276039).
文摘Methyl halides are crucial trace greenhouse gases in the atmosphere,playing a significant role in global climate change and the atmospheric environment.This study investigated the photochemical production of methyl halides in an artificial seawater system using guaiacol as a precursor through laboratory simulation experiments.The influences of various environmental factors,including illumination time,radiation wavebands,illumination intensity,concentrations of guaiacol and halide ions(X^(-)),Fe^(3+),salinity,dissolved oxygen(DO),and pH value on the photochemical production of methyl halides were examined.We demonstrated that increased illumination intensity and duration promote the photochemical production of methyl halides,with a notable enhancement under UV-B radiation.Guaiacol and halide ions were identified as key precursors,and their high concentrations facilitated the formation of methyl halides.Additionally,different types of halide ions exhibited a competitive relationship in producing methyl halides.The study found that an increase in pH inhibited the photochemical formation of CH_(3)I due to the reaction between OH^(-)and·CH_(3).Dissolved oxygen was found to inhibit the photochemical formation of CH3I while promoting the formation of CH_(3)Cl.Conversely,an appropriate concentration of Fe^(3+)enhanced the photochemical production of methyl halides.Field observations indicated a high photochemical production of methyl halides in the natural waters near Qingdao’s coastal area,likely due to the high concentration of dissolved organic matter(DOM),which supports photochemical reactions.Furthermore,the photochemical production of methyl halides in natural seawater was significantly higher than in dark conditions,underscoring the importance of illumination in promoting these photochemical processes in seawater.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.62125402 and 62321166653).
文摘Ternary metal halides based on Cu(I)and Ag(I)have attracted intensive attention in optoelectronic applications due to their excellent luminescent properties,low toxicity,and robust stability.While the self-trapped excitons(STEs)emission mechanisms of Cu(I)halides are well understood,the STEs in Ag(I)halides remain less thoroughly explored.This study explores the STE emission efficiency within the A_(2)AgX_(3)(A=Rb,Cs;X=Cl,Br,I)system by identifying three distinct STE states in each material and calculating their configuration coordinate diagrams.We find that the STE emission efficiency in this system is mainly determined by STE stability and influenced by self-trapping and quenching barriers.Moreover,we investigate the impact of structural compactness on emission efficiency and find that the excessive electron–phonon coupling in this system can be reduced by increasing the structural compactness.The atomic packing factor is identified as a low-cost and effective descriptor for predicting STE emission efficiency in both Cs_(2)AgX_(3) and Rb_(2)AgX_(3) systems.These findings can deepen our understanding of STE behavior in metal halide materials and offer valuable insights for the design of efficient STE luminescent materials.The datasets presented in this paper are openly available in Science Data Bank at https://doi.org/10.57760/sciencedb.12094.
基金supported by the National Funds for Distinguished Young Scientists(No.61825503)the National Natural Science Foundation of China(Nos.62288102,62375142,22161160318).
文摘Recently,organic-inorganic hybrid metal halides(HMHs)have attracted extensive attention as promis-ing multifunctional materials by virtue of their structural diversity and tunable photophysical properties.However,it remains a challenge to design HMHs with specific functions on demand.Herein,by introduc-ing R/S-methylbenzylamine(R/S-MBA)and doping Sb^(3+),we have achieved both second harmonic gen-eration(SHG)and circularly polarized luminescence(CPL)properties in lead-free indium halides.The introduction of chiral organic cations can break the symmetry and induce the indium halides to crys-tallize in the chiral space group.The Sb^(3+)with ns2 electronic configuration can serve as the dopants to promote the formation of self-trapped excitons,so as to activate highly efficient luminescence.As a re-sult,the as-prepared Sb3+doped(R/S-MBA)3 InCl6 show not only SHG responses but also CPL signals with luminescence dissymmetry factor of−5.3×10^(−3) and 4.7×10^(−3).This work provides a new inspiration for the exploitation of chiral multifunctional materials.
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.
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supported by the National Natural Science Foundation of China(nos.22309027 and 52374301)the Shijiazhuang Basic Research Project(nos.241790667A and 241790907A)+3 种基金the Fundamental Research Funds for the Central Universities(no.N2523050)the Natural Science Foundation of Hebei Province(no.E2024501010)the Performance subsidy fund for Key Laboratory of Dielectric and Electrolyte Functional Material Hebei Province(no.22567627H)the 2024 Hebei Provincial Postgraduate Student Innovation Ability Training Funding Project(no.CXZZSS2025162)。
文摘Halide solid-state electrolytes(SSEs)have become a new research focus for all-solid-state batteries because of their significant safety advantages,high ionic conductivity,high-voltage stability,and good ductility.Nonetheless,stability issues are a key barrier to their practical application.In past reports,the analysis of halide electrolyte stability and its enhancement methods lacked relevance,which limited the design and optimization of halide solid electrolytes.This review focus on stability issues from a chemical,electrochemical,and interfacial point of view,with particular emphasis on the interaction of halide SSEs with anode and cathode interfaces.By focusing on innovative strategies to address the stability issue,this paper aims to further deepen the understanding and development of halide all-solid-state batteries by proposing to focus research efforts on improving their stability in order to address their inherent challenges and match higher voltage cathodes,paving the way for their wider application in the next generation of energy storage technologies.
