A new metal-oxo-clusters-based inorganic framework[NaCo_(2)Mo_(2)O_(7)(OH)_(3)]_(n)(NaCoMo),named as 3D platelike ternary-oxo-cluster,has been hydrothermally synthesized and characterized by single-crystal X-ray diffr...A new metal-oxo-clusters-based inorganic framework[NaCo_(2)Mo_(2)O_(7)(OH)_(3)]_(n)(NaCoMo),named as 3D platelike ternary-oxo-cluster,has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction structure analysis,FT-IR spectroscopy,powder X-ray diffraction(PXRD),scanning electron microscope(SEM),energy-dispersive X-ray spectroscopy(EDS)analyses,X-ray photoelectron spectroscopy(XPS)and thermogravimetric analysis(TGA).Structure analysis reveals that there are no classical building units in NaCoMo,and the asymmetric units of NaCoMo are directly extended into a new platelike 3D structure.Density functional theory calculations(DFT)indicates that the crystal formation process is exothermic and the structure is extremely stable.In addition,the compound presents excellent catalytic activity in the condensation and cyclization reaction of sulfonyl hydrazides and 1,3-diketones to synthesize pyrazoles,and the yield of the desired product is up to 99%.The successful synthesis of NaCoMo represents the discovery of a new kind of non-classical polyoxometalates.展开更多
An aluminoborate,Na_(2.5)Rb[Al{B_(5)O_(10)}{B_(3)O_(5)}]·0.5NO_(3)·H_(2)O(1),was synthesized under hydrothermal condition,which was built by mixed oxoboron clusters and AlO_(4)tetrahedra.In the structure,the...An aluminoborate,Na_(2.5)Rb[Al{B_(5)O_(10)}{B_(3)O_(5)}]·0.5NO_(3)·H_(2)O(1),was synthesized under hydrothermal condition,which was built by mixed oxoboron clusters and AlO_(4)tetrahedra.In the structure,the[B_(5)O_(10)]^(5-)and[B_(3)O_(7)]^(5-)clusters are alternately connected to form 1D[B_(8)O_(15)]_(n)^(6n-)chains,which are further linked by AlO_(4)units to form a 2D monolayer with 7‑membered ring and 10‑membered ring windows.Two adjacent monolayers with opposite orientations further form a porous‑layered structure with six channels through B—O—Al bonds.Compound 1 was characterized by single crystal X‑ray diffraction,powder X‑ray diffraction(PXRD),IR spectroscopy,UV‑Vis diffuse reflection spectroscopy,and thermogravimetric analysis(TGA),respectively.UV‑Vis diffuse reflectance analysis indicates that compound 1 shows a wide transparency range with a short cutoff edge of 201 nm,suggesting it may have potential application in UV regions.CCDC:2383923.展开更多
Herein,we report the synthesis and third-order nonlinear optical(NLO)properties of a novel cage-based 2D metal-organic framework constructed from Ti_(4)L_(6)(L4-=embonate)cage combined with Mg^(2+)and tris[4-(1H-imida...Herein,we report the synthesis and third-order nonlinear optical(NLO)properties of a novel cage-based 2D metal-organic framework constructed from Ti_(4)L_(6)(L4-=embonate)cage combined with Mg^(2+)and tris[4-(1H-imidazol-1-yl)phenyl]amine(tipa)ligand,whose molecular formula is(Me_(2)CH_(2))_(2)[Mg_(3)(Ti_(4)L_(6))(tipa)(H_(2)O)_(12)](PTC‑378).The Ti_(4)L_(6)tetrahedral cages serve as robust building units,while the Mg^(2+)ions and tipa ligands provide structural stability and tunable optical properties.The resulting PTC‑378 film exhibited intriguing third-order NLO property,which was systematically investigated using Z-scan techniques.Our results demonstrate that the synergistic interaction between Ti_(4)L_(6)cages andπ-conjugated ligands significantly enhances the NLO performance of the materials.CCDC:2453909.展开更多
The chemistry of sulfur cycle contributes significantly to the atmospheric nucleation process,which is the first step of new particle formation(NPF).In the present study,cycloaddition reaction mechanism of sulfur trio...The chemistry of sulfur cycle contributes significantly to the atmospheric nucleation process,which is the first step of new particle formation(NPF).In the present study,cycloaddition reaction mechanism of sulfur trioxide(SO_(3))to hydrogen sulfide(H_(2)S)which is a typical air pollutant and toxic gas detrimental to the environment were comprehensively investigate through theoretical calculations and Atmospheric Cluster Dynamic Code simulations.Gas-phase stability and nucleation potential of the product thiosulfuric acid(H_(2)S_(2)O_(3),TSA)were further analyzed to evaluate its atmospheric impact.Without any catalysts,the H_(2)S+SO_(3)reaction is infeasible with a barrier of 24.2 kcal/mol.Atmospheric nucleation precursors formic acid(FA),sulfuric acid(SA),and water(H_(2)O)could effectively lower the reaction barriers as catalysts,even to a barrierless reaction with the efficiency of cis-SA>trans-FA>trans-SA>H_(2)O.Subsequently,the gas-phase stability of TSA was investigated.A hydrolysis reaction barrier of up to 61.4 kcal/mol alone with an endothermic isomerization reaction barrier of 5.1 kcal/mol under the catalytic effect of SA demonstrates the sufficient stability of TSA.Furthermore,topological and kinetic analysis were conducted to determine the nucleation potential of TSA.Atmospheric clusters formed by TSA and atmospheric nucleation precursors(SA,ammonia NH_(3),and dimethylamine DMA)were thermodynamically stable.Moreover,the gradually decreasing evaporation coefficients for TSA-base clusters,particularly for TSA-DMA,suggests that TSA may participate in NPF where the concentration of base molecules are relatively higher.The present new reaction mechanismmay contributes to a better understanding of atmospheric sulfur cycle and NPF.展开更多
Comparing to the conventional polyoxometalate(POM)-templated silver(Ag)clusters,asymmetrically covered POM-templated Ag clusters have been rarely reported.In this work,a new Ag cluster,H[Co(SiW_(11)O_(39))Co_(4)(OH)_(...Comparing to the conventional polyoxometalate(POM)-templated silver(Ag)clusters,asymmetrically covered POM-templated Ag clusters have been rarely reported.In this work,a new Ag cluster,H[Co(SiW_(11)O_(39))Co_(4)(OH)_(3)(NO_(3))_(2)(SiW_(9)O_(34))@Ag_(37)(^(t)BuC≡C)_(23)(NO_(3))_(2)(DMF)_(3)](Ag_(37)Co_(5)),has been successfully prepared using a facile solvothermal approach.Such a unique asymmetrical architecture is ascribed to the uneven charge distribution of the in situ generated[Co(SiW_(11)O_(39))]^(6-)and[Co_(4)(OH)_(3)(NO_(3))_(2)(SiW_(9)O_(34))]^(7-)moieties,leading to the asymmetrical coverage of alkynyl-protected Ag shell.Various physicochemical and catalytic studies revealed that the resulting solid-state Ag_(37)Co_(5) crystals exhibited interesting temperature-dependent photoluminescence property,efficient and recyclable photothermal conversion ability,and good catalytic activity towards the detoxication of 4-nitrophenol.展开更多
Fast,precise structure determination of unknown compounds has been the foundation but with a persistent challenge in the field of chemical research.Among various chemical characterization techniques,single-crystal X-r...Fast,precise structure determination of unknown compounds has been the foundation but with a persistent challenge in the field of chemical research.Among various chemical characterization techniques,single-crystal X-ray diffraction(SCXRD)stands out as the most straightforward and accurate method in modern structural chemistry.By precisely determining the three-dimensional arrangement of atoms within a crystal,it provides direct atomic-level evidence for understanding the relationship between material structure and properties[1].展开更多
Furfuryl ethyl ether(FEE)is considered as one of the most important candidates for biofuels due to its high-octane number.However,it is still challenging to produce FEE via the biomass-based route under mild condition...Furfuryl ethyl ether(FEE)is considered as one of the most important candidates for biofuels due to its high-octane number.However,it is still challenging to produce FEE via the biomass-based route under mild conditions.Here,we developed a photoinduced catalytic transfer hydrogenation(CTH)process for the efficient production of FEE through the reduction etherification of furfural(FF)using Na_(4)W_(10)O_(32)(NaDT),Pd/C,and ethanol as the hydrogen atom transfer(HAT)catalyst,hydrogenation catalyst,and the H donor,respectively.Notably,the introduction of brominated benzene(PhBr)as an additive significantly promoted the yield of FEE to 92.7%.A series of experiments and characterization results indicated that the attachment and detachment of Br atoms on Pd/C catalyst surface effectively regulate the balance between H^(+)sites and Pd sites in the NaDT+Pd/C catalytic system.The balance facilitates the preferential acetalization of FF catalyzed by H^(+)sites,followed by hydrogenation to efficiently produce FEE catalyzed by Pd sites.This photoinduced CTH process exhibits good stability and recyclability as well as universality for the transformation of various organic substrates under mild conditions.展开更多
In the original publication,incorrect version of Corresponding authors has been published.You-Yuan Huang and Bo Wang should be corresponding authors.The corrected Correspondingg authors are provided in this correction.
Plastics,renowned for their flexibility,stability,and cost-effectiveness,have become indispensable materials in modern life.However,their extensive use has led to a global environmental and health crisis.Especially,pl...Plastics,renowned for their flexibility,stability,and cost-effectiveness,have become indispensable materials in modern life.However,their extensive use has led to a global environmental and health crisis.Especially,plastic products infiltrate agroecosystems through atmospheric deposition,irrigation water,soil contamination,and the degradation of plastic mulch films,posing significant risks to vegetable quality and safety.Traditional disposal methods,such as incineration and landfilling,are energy-intensive and ecologically harmful,necessitating the development and application of innovative technologies for plastic removal.This paper reviews representative advanced(micro)plastic removal technologies,with a particular focus on frameworks-containing photocatalysis as a promising green method for processing(micro)plastics.First,we analyze and compare traditional,then discuss emerging removal technologies.Next,we elaborate on the principles of photocatalytic degradation of plastic products,discuss key influencing factors,and classify various photocatalysts.Additionally,we highlight the limitations of conventional photocatalysts,such as TiO_(2) and ZnO,and emphasize the advantages of frame-work materials(e.g.,MOFs,COFs,ZIFs)in photocatalytic degradation,including their structural tunability and development potential.Finally,based on the current progress and applications of framework photocatalysts,we identify existing limitations and propose future research directions.This review provides a theoretical foundation and innovative technological insights to address the global challenge of plastic pollution.展开更多
Developing high-voltage LiCoO_(2)(LCO)is essential in realizing practical all-solid-state lithium batteries(ASSLBs).However,high voltage-induced structural instability and oxygen evolution are crucial for the fast deg...Developing high-voltage LiCoO_(2)(LCO)is essential in realizing practical all-solid-state lithium batteries(ASSLBs).However,high voltage-induced structural instability and oxygen evolution are crucial for the fast degradation of layered metal oxide cathodes.This study reveals that the zirconization on the nearsurface region of LCO shows superior electrochemical performance at high voltage(≥4.5 V).Highangle annular dark field-scanning transmission electron microscopy firstly reveals the formation of sub-nanoscale Li_(2)CoZrO_(4)with disordered rock salt(a-LiFeO_(2))phase on the surface of LCO.Furthermore,zirconization could prevent the bending of the Co-O layers at high voltage,significantly inhibiting the formation of microcracks after many cycles and enhancing the structural stability of LCO,as further confirmed by high-resolution transmission electron microscopy.Further,Electron paramagnetic resonance and Electron energy loss spectroscopy provide direct experimental evidence that lattice oxygen on LCO at high voltage has greatly deactivated in sub-nanoscale zirconization(Li_(2)CoZrO_(4)).Density functional theory calculations reveal that Li_(2)CoZrO_(4)enhances the stability of lattice oxygen.Therefore,in ASSLBs,LZSO@LCO cathode exhibits impressive electrochemical cycling stability,e.g.,78.1% capacity retention after 1000 cycles at 0.5 C and 71.2% capacity retention over 100 cycles at 0.1 C at an extremely low temperature of -20℃.展开更多
Metal halide perovskites have rapidly emerged as outstanding semiconductors for laser applications.Surface plasmon resonances of metals offer a platform for improving the perovskite lasing properties of metal halide p...Metal halide perovskites have rapidly emerged as outstanding semiconductors for laser applications.Surface plasmon resonances of metals offer a platform for improving the perovskite lasing properties of metal halide perovskites by accelerating radiative recombination.However,the constraint on degrees of freedom of perovskite-metal interactions in two dimensions keeps us from getting a full picture of plasmon-involved carrier dynamics and reaching the optimum perovskite lasing performance.Here we report a strategy of synthesizing quantitative coassemblies of perovskite and metal nanocrystals for studying the effect of surface plasmons on carrier dynamics in depth and exploring plasmon-enhanced perovskite lasing performance.Within the coassembly,each metal nanocrystal supports localized surface plasmon resonances capable of accelerating radiative recombination of all adjacent perovskite nanocrystals in three dimensions.The quantitative coassemblies disclose the evolution of radiative and nonradiative recombination processes in perovskite nanocrystals with the plasmon modes,identifying an optimal metal nanocrystal content for fulfilling the highest radiative efficiency in perovskite nanocrystals.By virtue of accelerated radiative recombination,the coassemblies of perovskite and metal nanocrystals allowed for the construction of microlaser arrays with enhanced performance including low thresholds and ultrafast outputs.This work fundamentally advances the perovskite-metal systems for plasmonically enhancing perovskite optoelectronic performance.展开更多
The recent research progress of structure- and size-controlled micro/nano-energetic materials is reviewed, which properties are fundamentally different from those of their corresponding bulk materials. The development...The recent research progress of structure- and size-controlled micro/nano-energetic materials is reviewed, which properties are fundamentally different from those of their corresponding bulk materials. The development of the construction strategies for achieving zero-dimensional (0D), one-dimensional (1D), two-dimensional (2D), and three-dimensional (3D) micro/nanostructures from energetic molecules is introduced. Also, an overview of the unique properties induced by micro/nanostructures and size effects is provided. Special emphasis is focused on the size-dependent properties that are different from those of the conventional micro-sized energetic materials, such as thermal decomposition, sensitivity, combustion and detonation, and compaction behaviors. A conclusion and our view of the future development of micro/nano-energetic materials and devices are given.展开更多
Covalent organic frameworks（COFs） as an emerging class of porous materials have achieved remarkable progress in recent years.Their high surface area,low mass densities,highly ordered periodic structures,and ease of ...Covalent organic frameworks（COFs） as an emerging class of porous materials have achieved remarkable progress in recent years.Their high surface area,low mass densities,highly ordered periodic structures,and ease of functionalization make COFs exhibit superior potential in gas storage and separation,optoelectronic device and catalysis.This mini review gives a brief introduction of COFs and highlights their applications in electronic and optical fields.展开更多
With the increasing concerns to energy shortage and environmental problems in modern society,the development of cheap,clean,and sustainable energy alternatives has been attracting tremendous attention globally.Among v...With the increasing concerns to energy shortage and environmental problems in modern society,the development of cheap,clean,and sustainable energy alternatives has been attracting tremendous attention globally.Among various strategies of renewable energy exploration,solar-driven water splitting into its compositional elements H2 and O2 is an ideal approach to convert and store renewable solar energy into chemical bonds.In recent few decades,as an emerging new type of catalysts,polyoxometalates(POMs)have been widely utilized for water splitting due to their versatile synthetic methodology and highly tunable physicochemical and photochemical properties.This critical review addresses the research advances of light-driven hydrogen evolution using polyoxometalate-based catalysts,including plenary POMs,transition-metal-substituted POMs,POM@MOF composites,and POM-semiconductor hybrids,under UV,near UV and visible light irradiation.In addition,the catalytic mechanism for each reaction system has been thoroughly discussed and summarized.Finally,a comprehensive outlook of this research area is also prospected.展开更多
The development of high-performance electrocatalysts for hydrogen evolution reaction(HER)is of great significance for green,sustainable,and renewable energy conversion.Herein,we report the synthesis of amorphous Ru cl...The development of high-performance electrocatalysts for hydrogen evolution reaction(HER)is of great significance for green,sustainable,and renewable energy conversion.Herein,we report the synthesis of amorphous Ru clusters on Co-doped defect-rich hollow carbon nanocage(a-Ru@Co-DHC)as an efficient electrocatalyst for HER in the basic media.Due to the advantages such as high surface area,rich edge defect,atomic Co doping and amorphous Ru clusters,the as-made a-Ru@Co-DHC displays an efficient HER performance with a near-zero onset overpotential,a low Tafel slope(62 mV dec^(−1)),a low overpotential of 40 mV at 10 mA cm^(−2) and high stability,outperforming the commercial Ru nanocrystal/C,commercial Pt/C,and other reported Ru-based catalysts.This work provides a new insight into designing new metal doped carbon nanocages catalysts supported by amorphous nanoclusters for achieving the enhanced electrocatalysis.展开更多
Due to the rapid development of portable,wearable and implantable electronics in the fields of mobile communications,biomonitoring,and aerospace or defense,there is an increasing demand for miniaturized and lightweigh...Due to the rapid development of portable,wearable and implantable electronics in the fields of mobile communications,biomonitoring,and aerospace or defense,there is an increasing demand for miniaturized and lightweight energy storage devices.Micro-supercapacitors(MSCs)possessing long lifetime,high power density,environment friendliness and safety,have attracted great attention recently.Since the performance of the MSCs is mainly related to the structure of the active electrode,there is a great need to explore the efficient fabricating strategies to deterministically coordinate the structure and functionality of microdevices.Considering that laser technology possesses many superior features of facility,high-precision,low-cost,high-efficiency,shape-adaptability and maneuverability,herein we summarize the development of laser technologies in MSCs manufacturing,along with their strengths and weaknesses.The current achievements and challenges are also highlighted and discussed,aiming to provide a valuable reference for the rational design and manufacture of MSCs in the future.展开更多
Different from the classical configuration CuO/CeO2 catalyst,the inverse configuration CeO2 /CuO catalyst （atomic ratio of Ce/Cu=10/100） was prepared by impregnation method.Five calcination temperatures were selecte...Different from the classical configuration CuO/CeO2 catalyst,the inverse configuration CeO2 /CuO catalyst （atomic ratio of Ce/Cu=10/100） was prepared by impregnation method.Five calcination temperatures were selected to investigate the interaction between CeO2 and CuO support.It is found that as calcination temperature increased from 500 to 900 C,sintering of CeO2 particles on the support occurred together with the diffusion of a portion of Ce 4＋ ions into CuO crystals,forming solid solution.Formation of interface complex Ce-O-Cu was suggested by TPR measurements.The catalyst calcined at 700 C gives the highest activity for preferential oxidation of CO in excess H2 stream.展开更多
Efficient synthesis of transition metal hydroxides on conductive substrate is essential for enhancing their merits in industrialization of energy storage field.However,most of the synthetic routes at present mainly re...Efficient synthesis of transition metal hydroxides on conductive substrate is essential for enhancing their merits in industrialization of energy storage field.However,most of the synthetic routes at present mainly rely on traditional bottom-up method,which involves tedious steps,time-consuming treatments,or additional alkaline media,and is unfavorable for high-efficiency production.Herein,we present a facile,ultrafast and general avenue to synthesize transition metal hydroxides on carbon substrate within 13 s by Joule-heating method.With high reaction kinetics caused by the instantaneous high temperature,seven kinds of transition metal-layered hydroxides(TM-LDHs)are formed on carbon cloth.Therein,the fastest synthesis rate reaches~0.46 cm^(2)s^(-1).Density functional theory calculations further demonstrate the nucleation energy barriers and potential mechanism for the formation of metal-based hydroxides on carbon substrates.This efficient approach avoids the use of extra agents,multiple steps,and long production time and endows the LDHs@carbon cloth with outstanding flexibility and machinability,showing practical advantages in both common and micro-zinc ion-based energy storage devices.To prove its utility,as a cathode in rechargeable aqueous alkaline Zn(micro-)battery,the NiCo LDH@carbon cloth exhibits a high energy density,superior to most transition metal LDH materials reported so far.展开更多
A versatile heteropoly acid(H_(3)PMo_(12)O_(40))-catalyzed coupling of diarylmethanols with epoxides was established for the synthesis of polyaryl-substituted aldehydes.Furthermore,the catalytic system was also suitab...A versatile heteropoly acid(H_(3)PMo_(12)O_(40))-catalyzed coupling of diarylmethanols with epoxides was established for the synthesis of polyaryl-substituted aldehydes.Furthermore,the catalytic system was also suitable for the reaction of diarylmethanols and diols/aldehydes.The application of such an earthabundant,readily accessible,and nontoxic catalyst provides a green approach for the construction of polyaryl-substituted aldehydes.展开更多
The development of an inorganic electrochemical stable solid-state electrolyte is essentially responsible for future state-of-the-art all-solid-state lithium batteries(ASSLBs).Because of their advantages in safety,wor...The development of an inorganic electrochemical stable solid-state electrolyte is essentially responsible for future state-of-the-art all-solid-state lithium batteries(ASSLBs).Because of their advantages in safety,working temperature,high energy density,and packaging,ASSLBs can develop an ideal energy storage system for modern electric vehicles(EVs).A solid electrolyte(SE)model must have an economical synthesis approach,exhibit electrochemical and chemical stability,high ionic conductivity,and low interfacial resistance.Owing to its highest conductivity of 17 mS·cm^(-1),and deformability,the sulfide-based Li_(7)P_(3)S_(11) solid electrolyte is a promising contender for the high-performance bulk type of ASSLBs.Herein,we present a current glimpse of the progress of synthetic procedures,structural aspects,and ionic conductivity improvement strategies.Structural elucidation and mechanistic approaches have been extensively discussed by using various characterization techniques.The chemical stability of Li_(7)P_(3)S_(11) could be enhanced via oxide doping,and hard and soft acid/base(HSAB)concepts are also discussed.The issues to be undertaken for designing the ideal solid electrolytes,interfacial challenges,and high energy density have been discoursed.This review aims to provide a bird’s eye view of the recent development of Li_(7)P_(3)S_(11)-based solid-state electrolyte applications and explore the strategies for designing new solid electrolytes with a target-oriented approach to enhance the efficiency of high energy density allsolid-state lithium batteries.展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.22001034,21871026,21804019)the Open Fund of the Jiangxi Province Key Laboratory of Synthetic Chemistry(No.JXSC202008)the Research Found of East China University of Technology(Nos.DHBK2019264,DHBK2019265,DHBK2019267)。
文摘A new metal-oxo-clusters-based inorganic framework[NaCo_(2)Mo_(2)O_(7)(OH)_(3)]_(n)(NaCoMo),named as 3D platelike ternary-oxo-cluster,has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction structure analysis,FT-IR spectroscopy,powder X-ray diffraction(PXRD),scanning electron microscope(SEM),energy-dispersive X-ray spectroscopy(EDS)analyses,X-ray photoelectron spectroscopy(XPS)and thermogravimetric analysis(TGA).Structure analysis reveals that there are no classical building units in NaCoMo,and the asymmetric units of NaCoMo are directly extended into a new platelike 3D structure.Density functional theory calculations(DFT)indicates that the crystal formation process is exothermic and the structure is extremely stable.In addition,the compound presents excellent catalytic activity in the condensation and cyclization reaction of sulfonyl hydrazides and 1,3-diketones to synthesize pyrazoles,and the yield of the desired product is up to 99%.The successful synthesis of NaCoMo represents the discovery of a new kind of non-classical polyoxometalates.
文摘An aluminoborate,Na_(2.5)Rb[Al{B_(5)O_(10)}{B_(3)O_(5)}]·0.5NO_(3)·H_(2)O(1),was synthesized under hydrothermal condition,which was built by mixed oxoboron clusters and AlO_(4)tetrahedra.In the structure,the[B_(5)O_(10)]^(5-)and[B_(3)O_(7)]^(5-)clusters are alternately connected to form 1D[B_(8)O_(15)]_(n)^(6n-)chains,which are further linked by AlO_(4)units to form a 2D monolayer with 7‑membered ring and 10‑membered ring windows.Two adjacent monolayers with opposite orientations further form a porous‑layered structure with six channels through B—O—Al bonds.Compound 1 was characterized by single crystal X‑ray diffraction,powder X‑ray diffraction(PXRD),IR spectroscopy,UV‑Vis diffuse reflection spectroscopy,and thermogravimetric analysis(TGA),respectively.UV‑Vis diffuse reflectance analysis indicates that compound 1 shows a wide transparency range with a short cutoff edge of 201 nm,suggesting it may have potential application in UV regions.CCDC:2383923.
文摘Herein,we report the synthesis and third-order nonlinear optical(NLO)properties of a novel cage-based 2D metal-organic framework constructed from Ti_(4)L_(6)(L4-=embonate)cage combined with Mg^(2+)and tris[4-(1H-imidazol-1-yl)phenyl]amine(tipa)ligand,whose molecular formula is(Me_(2)CH_(2))_(2)[Mg_(3)(Ti_(4)L_(6))(tipa)(H_(2)O)_(12)](PTC‑378).The Ti_(4)L_(6)tetrahedral cages serve as robust building units,while the Mg^(2+)ions and tipa ligands provide structural stability and tunable optical properties.The resulting PTC‑378 film exhibited intriguing third-order NLO property,which was systematically investigated using Z-scan techniques.Our results demonstrate that the synergistic interaction between Ti_(4)L_(6)cages andπ-conjugated ligands significantly enhances the NLO performance of the materials.CCDC:2453909.
基金supported by the Budget Surplus of Central Financial Science and Technology Plan (No.2021-JY-14)the Project funded by China Postdoctoral Science Foundation (No.2020M680636)+3 种基金the Fundamental Research Funds for Central Public Welfare Scientific Research Institutes of China,Chinese Research Academy of Environmental Sciences (Nos.2022YSKY-21 and 2022YSKY-27)the National Natural Science Foundation of China (No.41375133)the Science Foundation of Chinese Research Academy of Environmental Sciences (No.JY-41375133)Tian He Qingsuo Project-special fund project.
文摘The chemistry of sulfur cycle contributes significantly to the atmospheric nucleation process,which is the first step of new particle formation(NPF).In the present study,cycloaddition reaction mechanism of sulfur trioxide(SO_(3))to hydrogen sulfide(H_(2)S)which is a typical air pollutant and toxic gas detrimental to the environment were comprehensively investigate through theoretical calculations and Atmospheric Cluster Dynamic Code simulations.Gas-phase stability and nucleation potential of the product thiosulfuric acid(H_(2)S_(2)O_(3),TSA)were further analyzed to evaluate its atmospheric impact.Without any catalysts,the H_(2)S+SO_(3)reaction is infeasible with a barrier of 24.2 kcal/mol.Atmospheric nucleation precursors formic acid(FA),sulfuric acid(SA),and water(H_(2)O)could effectively lower the reaction barriers as catalysts,even to a barrierless reaction with the efficiency of cis-SA>trans-FA>trans-SA>H_(2)O.Subsequently,the gas-phase stability of TSA was investigated.A hydrolysis reaction barrier of up to 61.4 kcal/mol alone with an endothermic isomerization reaction barrier of 5.1 kcal/mol under the catalytic effect of SA demonstrates the sufficient stability of TSA.Furthermore,topological and kinetic analysis were conducted to determine the nucleation potential of TSA.Atmospheric clusters formed by TSA and atmospheric nucleation precursors(SA,ammonia NH_(3),and dimethylamine DMA)were thermodynamically stable.Moreover,the gradually decreasing evaporation coefficients for TSA-base clusters,particularly for TSA-DMA,suggests that TSA may participate in NPF where the concentration of base molecules are relatively higher.The present new reaction mechanismmay contributes to a better understanding of atmospheric sulfur cycle and NPF.
基金financially supported by the National Natural Science Foundation of China(Nos.21871025,21831001)the Recruitment Program of Global Experts(Young Talents)Beijing Institute of Technology(BIT)Excellent Young Scholars Research Fund.
文摘Comparing to the conventional polyoxometalate(POM)-templated silver(Ag)clusters,asymmetrically covered POM-templated Ag clusters have been rarely reported.In this work,a new Ag cluster,H[Co(SiW_(11)O_(39))Co_(4)(OH)_(3)(NO_(3))_(2)(SiW_(9)O_(34))@Ag_(37)(^(t)BuC≡C)_(23)(NO_(3))_(2)(DMF)_(3)](Ag_(37)Co_(5)),has been successfully prepared using a facile solvothermal approach.Such a unique asymmetrical architecture is ascribed to the uneven charge distribution of the in situ generated[Co(SiW_(11)O_(39))]^(6-)and[Co_(4)(OH)_(3)(NO_(3))_(2)(SiW_(9)O_(34))]^(7-)moieties,leading to the asymmetrical coverage of alkynyl-protected Ag shell.Various physicochemical and catalytic studies revealed that the resulting solid-state Ag_(37)Co_(5) crystals exhibited interesting temperature-dependent photoluminescence property,efficient and recyclable photothermal conversion ability,and good catalytic activity towards the detoxication of 4-nitrophenol.
基金the National Natural Science Foundation of China(Nos.22471014 and 22271013)the Beijing Natural Science Foundation(No.2232024)for financial support.
文摘Fast,precise structure determination of unknown compounds has been the foundation but with a persistent challenge in the field of chemical research.Among various chemical characterization techniques,single-crystal X-ray diffraction(SCXRD)stands out as the most straightforward and accurate method in modern structural chemistry.By precisely determining the three-dimensional arrangement of atoms within a crystal,it provides direct atomic-level evidence for understanding the relationship between material structure and properties[1].
文摘Furfuryl ethyl ether(FEE)is considered as one of the most important candidates for biofuels due to its high-octane number.However,it is still challenging to produce FEE via the biomass-based route under mild conditions.Here,we developed a photoinduced catalytic transfer hydrogenation(CTH)process for the efficient production of FEE through the reduction etherification of furfural(FF)using Na_(4)W_(10)O_(32)(NaDT),Pd/C,and ethanol as the hydrogen atom transfer(HAT)catalyst,hydrogenation catalyst,and the H donor,respectively.Notably,the introduction of brominated benzene(PhBr)as an additive significantly promoted the yield of FEE to 92.7%.A series of experiments and characterization results indicated that the attachment and detachment of Br atoms on Pd/C catalyst surface effectively regulate the balance between H^(+)sites and Pd sites in the NaDT+Pd/C catalytic system.The balance facilitates the preferential acetalization of FF catalyzed by H^(+)sites,followed by hydrogenation to efficiently produce FEE catalyzed by Pd sites.This photoinduced CTH process exhibits good stability and recyclability as well as universality for the transformation of various organic substrates under mild conditions.
文摘In the original publication,incorrect version of Corresponding authors has been published.You-Yuan Huang and Bo Wang should be corresponding authors.The corrected Correspondingg authors are provided in this correction.
基金supported by Key Laboratory of Vegetables Quality and Safety Control,Ministry of Agriculture and Rural Affairs,grants from The Agricultural Science and Technology Innovation Program(ASTIP),Development Program of China(2022YFF0606800)the Special Fund for the Industrial System Construction of Modern Agriculture of China(CARS-23-E03)National Center of Technology Innovation for Comprehensive Utilization of Saline-Alkali(GYJ2023004).
文摘Plastics,renowned for their flexibility,stability,and cost-effectiveness,have become indispensable materials in modern life.However,their extensive use has led to a global environmental and health crisis.Especially,plastic products infiltrate agroecosystems through atmospheric deposition,irrigation water,soil contamination,and the degradation of plastic mulch films,posing significant risks to vegetable quality and safety.Traditional disposal methods,such as incineration and landfilling,are energy-intensive and ecologically harmful,necessitating the development and application of innovative technologies for plastic removal.This paper reviews representative advanced(micro)plastic removal technologies,with a particular focus on frameworks-containing photocatalysis as a promising green method for processing(micro)plastics.First,we analyze and compare traditional,then discuss emerging removal technologies.Next,we elaborate on the principles of photocatalytic degradation of plastic products,discuss key influencing factors,and classify various photocatalysts.Additionally,we highlight the limitations of conventional photocatalysts,such as TiO_(2) and ZnO,and emphasize the advantages of frame-work materials(e.g.,MOFs,COFs,ZIFs)in photocatalytic degradation,including their structural tunability and development potential.Finally,based on the current progress and applications of framework photocatalysts,we identify existing limitations and propose future research directions.This review provides a theoretical foundation and innovative technological insights to address the global challenge of plastic pollution.
基金supported by the National Natural Science Foundation of China(no.21203008,21975025,12274025,and 22372008)Hainan Province Science and Technology Special Fund(ZDYF2021SHFZ232 and ZDYF2023GXJS022)Hainan Province Postdoctoral Science Foundation(No.300333)。
文摘Developing high-voltage LiCoO_(2)(LCO)is essential in realizing practical all-solid-state lithium batteries(ASSLBs).However,high voltage-induced structural instability and oxygen evolution are crucial for the fast degradation of layered metal oxide cathodes.This study reveals that the zirconization on the nearsurface region of LCO shows superior electrochemical performance at high voltage(≥4.5 V).Highangle annular dark field-scanning transmission electron microscopy firstly reveals the formation of sub-nanoscale Li_(2)CoZrO_(4)with disordered rock salt(a-LiFeO_(2))phase on the surface of LCO.Furthermore,zirconization could prevent the bending of the Co-O layers at high voltage,significantly inhibiting the formation of microcracks after many cycles and enhancing the structural stability of LCO,as further confirmed by high-resolution transmission electron microscopy.Further,Electron paramagnetic resonance and Electron energy loss spectroscopy provide direct experimental evidence that lattice oxygen on LCO at high voltage has greatly deactivated in sub-nanoscale zirconization(Li_(2)CoZrO_(4)).Density functional theory calculations reveal that Li_(2)CoZrO_(4)enhances the stability of lattice oxygen.Therefore,in ASSLBs,LZSO@LCO cathode exhibits impressive electrochemical cycling stability,e.g.,78.1% capacity retention after 1000 cycles at 0.5 C and 71.2% capacity retention over 100 cycles at 0.1 C at an extremely low temperature of -20℃.
基金supported by the National Natural Science Foundation of China(Nos.52272186,22090023 and 22375207)Beijing Institute of Technology Research Fund Program for Young Scholars(No.XSQD-6120220081)
文摘Metal halide perovskites have rapidly emerged as outstanding semiconductors for laser applications.Surface plasmon resonances of metals offer a platform for improving the perovskite lasing properties of metal halide perovskites by accelerating radiative recombination.However,the constraint on degrees of freedom of perovskite-metal interactions in two dimensions keeps us from getting a full picture of plasmon-involved carrier dynamics and reaching the optimum perovskite lasing performance.Here we report a strategy of synthesizing quantitative coassemblies of perovskite and metal nanocrystals for studying the effect of surface plasmons on carrier dynamics in depth and exploring plasmon-enhanced perovskite lasing performance.Within the coassembly,each metal nanocrystal supports localized surface plasmon resonances capable of accelerating radiative recombination of all adjacent perovskite nanocrystals in three dimensions.The quantitative coassemblies disclose the evolution of radiative and nonradiative recombination processes in perovskite nanocrystals with the plasmon modes,identifying an optimal metal nanocrystal content for fulfilling the highest radiative efficiency in perovskite nanocrystals.By virtue of accelerated radiative recombination,the coassemblies of perovskite and metal nanocrystals allowed for the construction of microlaser arrays with enhanced performance including low thresholds and ultrafast outputs.This work fundamentally advances the perovskite-metal systems for plasmonically enhancing perovskite optoelectronic performance.
基金Sponsored by National Natural Science Foundation of China (21231002,21276026,21271023,21173021,91022006,11202193,11172276,and 11072225)the 111 Project ( B07012)+1 种基金the Program of Cooperation of the Beijing Education Commission ( 20091739006)Specialized Research Fund for the Doctoral Program of Higher Education ( 20101101110031)
文摘The recent research progress of structure- and size-controlled micro/nano-energetic materials is reviewed, which properties are fundamentally different from those of their corresponding bulk materials. The development of the construction strategies for achieving zero-dimensional (0D), one-dimensional (1D), two-dimensional (2D), and three-dimensional (3D) micro/nanostructures from energetic molecules is introduced. Also, an overview of the unique properties induced by micro/nanostructures and size effects is provided. Special emphasis is focused on the size-dependent properties that are different from those of the conventional micro-sized energetic materials, such as thermal decomposition, sensitivity, combustion and detonation, and compaction behaviors. A conclusion and our view of the future development of micro/nano-energetic materials and devices are given.
基金the 973 Program(No.2013CB834704)the National Natural Science Foundation of China(Nos.21471018,21201018,21404010)1000 Plan (Youth) for financial support
文摘Covalent organic frameworks（COFs） as an emerging class of porous materials have achieved remarkable progress in recent years.Their high surface area,low mass densities,highly ordered periodic structures,and ease of functionalization make COFs exhibit superior potential in gas storage and separation,optoelectronic device and catalysis.This mini review gives a brief introduction of COFs and highlights their applications in electronic and optical fields.
文摘With the increasing concerns to energy shortage and environmental problems in modern society,the development of cheap,clean,and sustainable energy alternatives has been attracting tremendous attention globally.Among various strategies of renewable energy exploration,solar-driven water splitting into its compositional elements H2 and O2 is an ideal approach to convert and store renewable solar energy into chemical bonds.In recent few decades,as an emerging new type of catalysts,polyoxometalates(POMs)have been widely utilized for water splitting due to their versatile synthetic methodology and highly tunable physicochemical and photochemical properties.This critical review addresses the research advances of light-driven hydrogen evolution using polyoxometalate-based catalysts,including plenary POMs,transition-metal-substituted POMs,POM@MOF composites,and POM-semiconductor hybrids,under UV,near UV and visible light irradiation.In addition,the catalytic mechanism for each reaction system has been thoroughly discussed and summarized.Finally,a comprehensive outlook of this research area is also prospected.
文摘The development of high-performance electrocatalysts for hydrogen evolution reaction(HER)is of great significance for green,sustainable,and renewable energy conversion.Herein,we report the synthesis of amorphous Ru clusters on Co-doped defect-rich hollow carbon nanocage(a-Ru@Co-DHC)as an efficient electrocatalyst for HER in the basic media.Due to the advantages such as high surface area,rich edge defect,atomic Co doping and amorphous Ru clusters,the as-made a-Ru@Co-DHC displays an efficient HER performance with a near-zero onset overpotential,a low Tafel slope(62 mV dec^(−1)),a low overpotential of 40 mV at 10 mA cm^(−2) and high stability,outperforming the commercial Ru nanocrystal/C,commercial Pt/C,and other reported Ru-based catalysts.This work provides a new insight into designing new metal doped carbon nanocages catalysts supported by amorphous nanoclusters for achieving the enhanced electrocatalysis.
基金supported by the National Key R&D Program of China(2017YFB1104300)NSFC(22075019,21604003)+1 种基金the Beijing Natural Science Foundation(2152028,2164070)the Beijing Municipal Science and Technology Commission(Z161100002116022)。
文摘Due to the rapid development of portable,wearable and implantable electronics in the fields of mobile communications,biomonitoring,and aerospace or defense,there is an increasing demand for miniaturized and lightweight energy storage devices.Micro-supercapacitors(MSCs)possessing long lifetime,high power density,environment friendliness and safety,have attracted great attention recently.Since the performance of the MSCs is mainly related to the structure of the active electrode,there is a great need to explore the efficient fabricating strategies to deterministically coordinate the structure and functionality of microdevices.Considering that laser technology possesses many superior features of facility,high-precision,low-cost,high-efficiency,shape-adaptability and maneuverability,herein we summarize the development of laser technologies in MSCs manufacturing,along with their strengths and weaknesses.The current achievements and challenges are also highlighted and discussed,aiming to provide a valuable reference for the rational design and manufacture of MSCs in the future.
文摘Different from the classical configuration CuO/CeO2 catalyst,the inverse configuration CeO2 /CuO catalyst （atomic ratio of Ce/Cu=10/100） was prepared by impregnation method.Five calcination temperatures were selected to investigate the interaction between CeO2 and CuO support.It is found that as calcination temperature increased from 500 to 900 C,sintering of CeO2 particles on the support occurred together with the diffusion of a portion of Ce 4＋ ions into CuO crystals,forming solid solution.Formation of interface complex Ce-O-Cu was suggested by TPR measurements.The catalyst calcined at 700 C gives the highest activity for preferential oxidation of CO in excess H2 stream.
基金the NSFC(22075019)National Key R&D Program of China(2017YFB1104300)。
文摘Efficient synthesis of transition metal hydroxides on conductive substrate is essential for enhancing their merits in industrialization of energy storage field.However,most of the synthetic routes at present mainly rely on traditional bottom-up method,which involves tedious steps,time-consuming treatments,or additional alkaline media,and is unfavorable for high-efficiency production.Herein,we present a facile,ultrafast and general avenue to synthesize transition metal hydroxides on carbon substrate within 13 s by Joule-heating method.With high reaction kinetics caused by the instantaneous high temperature,seven kinds of transition metal-layered hydroxides(TM-LDHs)are formed on carbon cloth.Therein,the fastest synthesis rate reaches~0.46 cm^(2)s^(-1).Density functional theory calculations further demonstrate the nucleation energy barriers and potential mechanism for the formation of metal-based hydroxides on carbon substrates.This efficient approach avoids the use of extra agents,multiple steps,and long production time and endows the LDHs@carbon cloth with outstanding flexibility and machinability,showing practical advantages in both common and micro-zinc ion-based energy storage devices.To prove its utility,as a cathode in rechargeable aqueous alkaline Zn(micro-)battery,the NiCo LDH@carbon cloth exhibits a high energy density,superior to most transition metal LDH materials reported so far.
基金the financial support from the National Natural Science Foundation of China(Nos.21871026,21971224)Research Found of East China University of Technology(Nos.DHBK2019265,DHBK2019267,DHBK2019264)。
文摘A versatile heteropoly acid(H_(3)PMo_(12)O_(40))-catalyzed coupling of diarylmethanols with epoxides was established for the synthesis of polyaryl-substituted aldehydes.Furthermore,the catalytic system was also suitable for the reaction of diarylmethanols and diols/aldehydes.The application of such an earthabundant,readily accessible,and nontoxic catalyst provides a green approach for the construction of polyaryl-substituted aldehydes.
基金the National Natural Science Foundation of China(51772030,21203008,21975025)the Natural Science Foundation of Beijing(2172051)+1 种基金Beijing Outstanding Young Scientists Program(BJJWZYJH01201910007023)the State Key Laboratory funding by the project for Modification of Chemical Fibers and Polymer Materials,Donghou University.
文摘The development of an inorganic electrochemical stable solid-state electrolyte is essentially responsible for future state-of-the-art all-solid-state lithium batteries(ASSLBs).Because of their advantages in safety,working temperature,high energy density,and packaging,ASSLBs can develop an ideal energy storage system for modern electric vehicles(EVs).A solid electrolyte(SE)model must have an economical synthesis approach,exhibit electrochemical and chemical stability,high ionic conductivity,and low interfacial resistance.Owing to its highest conductivity of 17 mS·cm^(-1),and deformability,the sulfide-based Li_(7)P_(3)S_(11) solid electrolyte is a promising contender for the high-performance bulk type of ASSLBs.Herein,we present a current glimpse of the progress of synthetic procedures,structural aspects,and ionic conductivity improvement strategies.Structural elucidation and mechanistic approaches have been extensively discussed by using various characterization techniques.The chemical stability of Li_(7)P_(3)S_(11) could be enhanced via oxide doping,and hard and soft acid/base(HSAB)concepts are also discussed.The issues to be undertaken for designing the ideal solid electrolytes,interfacial challenges,and high energy density have been discoursed.This review aims to provide a bird’s eye view of the recent development of Li_(7)P_(3)S_(11)-based solid-state electrolyte applications and explore the strategies for designing new solid electrolytes with a target-oriented approach to enhance the efficiency of high energy density allsolid-state lithium batteries.
