In the 21^(st)century,the rapid development of human society has made people’s demand for green energy more and more urgent.The high-energy-density hydrogen energy obtained by fully splitting water is not only enviro...In the 21^(st)century,the rapid development of human society has made people’s demand for green energy more and more urgent.The high-energy-density hydrogen energy obtained by fully splitting water is not only environmentally friendly,but also is expected to solve the problems caused by the intermittent nature of new energy.However,the slow kinetics and large overpotential of the oxygen evolution reaction(OER)limit its application.The introduction of Te element is expected to bring new breakthroughs.With the least electronegativity among the chalcogens,the Te element has many special properties,such as multivalent states,strong covalentity,and high electrical conductivity,which make it a promising candidate in electrocatalytic OER.In this review,we introduce the peculiarities of Te element,summarize Te doping and the extraordinary performance of its compounds in OER,with emphasis on the scientific mechanism behind Te element promoting the OER kinetic process.Finally,challenges and development prospects of the applications of Te element in OER are presented.展开更多
The electronic configuration of central metal atoms in single-atom catalysts(SACs)is pivotal in electrochemical CO_(2)reduction reaction(eCO_(2)RR).Herein,chalcogen heteroatoms(e.g.,S,Se,and Te)were incorporated into ...The electronic configuration of central metal atoms in single-atom catalysts(SACs)is pivotal in electrochemical CO_(2)reduction reaction(eCO_(2)RR).Herein,chalcogen heteroatoms(e.g.,S,Se,and Te)were incorporated into the symmetric nickel-nitrogen-carbon(Ni-N4-C)configuration to obtain Ni-X-N3-C(X:S,Se,and Te)SACs with asymmetric coordination presented for central Ni atoms.Among these obtained Ni-X-N3-C(X:S,Se,and Te)SACs,Ni-Se-N3-C exhibited superior eCO_(2)RR activity,with CO selectivity reaching~98%at-0.70 V versus reversible hydrogen electrode(RHE).The Zn-CO_(2)battery integrated with Ni-Se-N3-C as cathode and Zn foil as anode achieved a peak power density of 1.82 mW cm-2 and maintained remarkable rechargeable stability over 20 h.In-situ spectral investigations and theoretical calculations demonstrated that the chalcogen heteroatoms doped into the Ni-N4-C configuration would break coordination symmetry and trigger charge redistribution,and then regulate the intermediate behaviors and thermodynamic reaction pathways for eCO_(2)RR.Especially,for Ni-Se-N3-C,the introduced Se atoms could significantly raise the d-band center of central Ni atoms and thus remarkably lower the energy barrier for the rate-determining step of*COOH formation,contributing to the promising eCO_(2)RR performance for high selectivity CO production by competing with hydrogen evolution reaction.展开更多
Increasing risks of incidental and occupational exposures to two-dimensional transition metal dichalcogenides(2D TMDCs)due to their broad application in various areas raised their public health concerns.While the comp...Increasing risks of incidental and occupational exposures to two-dimensional transition metal dichalcogenides(2D TMDCs)due to their broad application in various areas raised their public health concerns.While the composition-dependent cytotoxicity of 2D TMDCs has been well-recognized,how the outer chalcogenide atoms and inner transition metal atoms differentially contribute to their perturbation on cell homeostasis at non-lethal doses remains to be identified.In the present work,we compared the autophagy induction and related mechanisms in response to WS_(2),NbS_(2),WSe_(2)and Nb Se_(2)nanosheets exposures in MH-S murine alveolar macrophages.All these 2D TMDCs had comparable physicochemical properties,overall cytotoxicity and capability in triggering autophagy in MH-S cells,but showed outer chalcogen-dependent subcellular localization and activation of autophagy pathways.Specifically,WS_(2)and NbS_(2)nanosheets adhered on the cell surface and internalized in the lysosomes,and triggered m TOR-dependent activation of autophagy.Meanwhile,WSe_(2)and Nb Se_(2)nanosheets had extensive distribution in cytoplasm of MH-S cells and induced autophagy in an m TOR-independent manner.Furthermore,the 2D TMDCs-induced perturbation on autophagy aggravated the cytotoxicity of respirable benzo[a]pyrene.These findings provide a deeper insight into the potential health risk of environmental 2D TMDCs from the perspective of homeostasis perturbation.展开更多
Catalyzed by commercially available(PhTe)2, molecular oxygen could be utilized as the mild, cheap and safe oxidant for oxidative deoximation reactions under solvent-free conditions. As the first report on organotellur...Catalyzed by commercially available(PhTe)2, molecular oxygen could be utilized as the mild, cheap and safe oxidant for oxidative deoximation reactions under solvent-free conditions. As the first report on organotellurium-catalyzed deoximation reaction, this work not only provides an efficient deoximation method, but also discloses new features of tellurium catalyst different from those of the organoselenium catalysts.展开更多
Gas phase carbonylation of methane is studied in the presence of molecular oxygen over pure carbon carriers and carbon supported rhodium chalcogen halides. Activated carbons and fullerene blacks have been used as carb...Gas phase carbonylation of methane is studied in the presence of molecular oxygen over pure carbon carriers and carbon supported rhodium chalcogen halides. Activated carbons and fullerene blacks have been used as carbon supports. XPS and IR-spectroscopy data show the formation of rhodium chalcogen halides in solids prepared by different methods. We have found that the productivity of acetic acid by carbon supported rhodium chalcogen halides depends strongly on the carbon carrier and the method of the catalyst preparation. Namely, the catalyst with highest productivity for the acetic acid is prepared by synthesizing the rhodium chalcogen halide over the carbon support followed by thermal destruction. We have also found that rhodium chalcogen halides over activated carbons are more active compared with fullerene supported catalysts.展开更多
Luminescent open-shell organic radicals have recently been regarded as one of the most potential materials in organic light-emitting diodes(OLEDs).Herein,we have synthesized two new organic radicals,namely tris{4-[4-(...Luminescent open-shell organic radicals have recently been regarded as one of the most potential materials in organic light-emitting diodes(OLEDs).Herein,we have synthesized two new organic radicals,namely tris{4-[4-(tert-butyl)phenoxy]-2,6-dichlorophenyl}methane radical(TTM-O)and tris(4-{[4-(tert-butyl)-phenyl]thio}-2,6-dichlorophenyl)methane radical(TTM-S),by the substitution of chalcogen atom elements at the para position of conventional tris(2,4,6-trichlorophenyl)methyl(TTM)radical moiety.Interestingly,both TTM-O and TTM-S exhibited significantly enhanced photostability compared with the unsubstituted TTM radical parent.Moreover,the chalcogen atom also had a crucial impact on the photoluminescence quantum yield(PLQY)of the radicals,i.e.,the PLQY of TTM-S was greatly enhanced compared to TTM radical while TTM-O was nearly non-emissive.Particularly,TTM-S showed intense PLQY of 37.54%and 185-fold longer photostability than that in cyclohexane solution of TTM.展开更多
Growing interest in non-covalent interactions involving chalcogen atoms has been ascribed to their importance in crystal engineering, molecular recognition and macromolecular edifices. The present study is dealing wit...Growing interest in non-covalent interactions involving chalcogen atoms has been ascribed to their importance in crystal engineering, molecular recognition and macromolecular edifices. The present study is dealing with chalcogen bonds involving divalent Sulphur, Selenium and Tellurium atoms, acting as sigma-hole donors, in small-molecule compounds using the Cambridge Structural Database (CSD) in conjunction with ab initio calculations. Results derived from CSD surveys and computational study revealed that nucleophiles formed complexes with the chalcogen-bond donors R1-X-R2 (X = S, Se or Te). The main forces stabilizing the complexes were chalcogen bonds, enhanced by dispersion interactions. Complexation pattern and energetics show that nucleophile bonding at divalent S, Se and Te atoms is a relatively strong and directed interaction. The bond consists of a charge transfer from a nucleophile atom lone pair to an X-R1 or X-R2 antibonding orbital.展开更多
This paper presents a versatile method for synthesizing electron-rich polynuclear transition metal clusters with chalcogen bridges and phosphine ligands.The reactions of transition metal complexes(R3P)2MX2(M=Co,Ni;R=P...This paper presents a versatile method for synthesizing electron-rich polynuclear transition metal clusters with chalcogen bridges and phosphine ligands.The reactions of transition metal complexes(R3P)2MX2(M=Co,Ni;R=Ph,Bu,Et;X=Cl,Br) with bridging reagents Na2Ex (E=S,Se;x=1.2) are described.The geometric and electronic structures of a series of polynuclear transition metal clusters with trianglar M3 units are also discussed.展开更多
The gas phase methane oxidative carbonylation was studied in the presence of molecular oxygen over silica materials including their mechanical mixtures with rhodium chalcogen chlorides obtained in non-aqueous inorgani...The gas phase methane oxidative carbonylation was studied in the presence of molecular oxygen over silica materials including their mechanical mixtures with rhodium chalcogen chlorides obtained in non-aqueous inorganic media. The formation of Rh4SCl7, Rh4S9Cl2, Rh4SesCl3 and Rh3Se3Cl solids was confirmed by elemental analysis, IR absorption spectroscopy, XPS and X-ray diffraction. Silica, vanadium-, and molybdenum-containing mesoporous molecular sieves have been used as supports. It was found that productivity of oxygenates （methanol, methyl acetate and acetic acid） depends mainly on the method of the catalyst preparation and the type of the support.展开更多
Aluminum batteries are attractive in electrochemical energy storage due to high energy density and lowcost aluminum,while the energy density is limited for the lack of favorable positive electrode materials to match a...Aluminum batteries are attractive in electrochemical energy storage due to high energy density and lowcost aluminum,while the energy density is limited for the lack of favorable positive electrode materials to match aluminum negative electrodes.Tellurium positive electrode is intrinsically electrically conductive among chalcogen and holds high theoretical specific capacity(1260.27 mAh g^(-1)) and discharge voltage plateau(~1,5 V).However,the chemical and electrochemical dissolution of Te active materials results in the low material utilization and poor cycling stability.To enhance the electrochemical performance,herein a nitrogen doped porous carbon(N-PC) is derived from zeolite imidazolate framework(ZIF-67)as an effective tellurium host to suppress the undesired shuttle effect.In order to inhibit the volume expansion of N-PC during the charge/discharge process,the reduced graphene oxide(rGO) nanosheets are introduced to form a stable host materials(N-PC-rGO) for stabilizing Te.The physical encapsulation and chemical confinement to soluble tellurium species are achieved.N-PC-rGO-Te positive electrode exhibits an improved initial specific capacity and long-term cycling performance at a current density of 500 mA g^(-1)(initial specific capacity:935.5 mAh g^(-1);after 150 cycles:467.5 mAh g^(-1)), highlighting a promising design strategy for inhibiting chemical and electrochemical dissolution of Te.展开更多
To understand the effects of chalcogen atoms on the crystal structure of the series of 3,7-bis(methylchalcogeno)benzo[1,2-b:4,5-b′]dichalcogenophene-based organic semiconductors,three benzodifuran derivatives(1—3)an...To understand the effects of chalcogen atoms on the crystal structure of the series of 3,7-bis(methylchalcogeno)benzo[1,2-b:4,5-b′]dichalcogenophene-based organic semiconductors,three benzodifuran derivatives(1—3)and dimethoxy derivatives of benzodithiophene and benzodiselenophene(4 and 7)were newly synthesized to complete the“3×3 matrix”of the oxygen-,sulfur-,and selenium-derivatives(1—9).The crystal structures of 1—9 were classified into four classes,sandwich pitchedπ-stack(1),dimeric(2 and 3),pitchedπ-stack(4,5,7,8,9),and brickwork structure(6 and 9).The causes for the different crystal structures depending on the chalcogen atoms were investigated by the theoretical calculations,indicating that the chalcogen atoms in the core and substituents primarily affected the packing structures.Although the crystal growth in the vapor phase afforded different polymorphs,the relationship between the crystal structure and the carrier transport property was carefully investigated.展开更多
Artificial membrane transporters that either use chalcogen bonds to facilitate transmembrane flux of anions or show high selectivity toward perchlorate anions are rare.In this work,we report on one such novel monopept...Artificial membrane transporters that either use chalcogen bonds to facilitate transmembrane flux of anions or show high selectivity toward perchlorate anions are rare.In this work,we report on one such novel monopeptide-based transporter system,featuring both chalcogen bonds for highly efficient anion transport and high transport selectivity toward ClO_(4)^(-) anions.Structurally,these monopeptide molecules associate with each other via H-bonds to produce H-bonded 1D stack that not only one dimensionally but also directionally aligns the terminal bicyclic thiophene motifs to the same side.Functionally,these well-aligned thiophenes create a sulfur-rich transmembrane pathway,combinatorially fine-tunable to enable anions to efficiently cross the membrane in the increasing activity of Cl^(-)<Br^(-)<NO_(3)^(-)<ClO_(4)^(-) via chalcogen bonds,with EC_(50)values of 0.75,0.40,0.37 and 0.093μmol/L(0.3 mol%relative to lipid molecules),respectively.展开更多
Air stable diradicaloid polycyclic aromatic hydrocarbon(PAH)materials possess unique electronic and magnetic properties for various applications.In general,long conjugated distances between two radical centers are req...Air stable diradicaloid polycyclic aromatic hydrocarbon(PAH)materials possess unique electronic and magnetic properties for various applications.In general,long conjugated distances between two radical centers are required to improve the air stability,thereby complicating the synthetic procedures.Herein,the chalcogen containing rubicenes(O-,S-,and Se-rubicenes)were systematically investigated to understand the chalcogen effects on chalcogen-rubicene physicochemical properties.Impressively,these rubicenes presented unprecedented diradical characterwithin one simple benzene ring and excellent air stabilities.Theirdiradicalcharacterweremanifested by single-crystal X-ray studies,variable-temperature nuclear magnetic resonance,and electron spin resonance.Furthermore,the nucleus independent chemical shifts andthe anisotropy of the induced currentdensity calculations revealed that the formation of diradical was caused by a pro-aromaticity driving force.Importantly,the diradical character of rubicenes are visualizedbyFractionalOccupationNumberWeighted Electron Density(FOD)plots,which present high NFOD values from 1.651 to 1.830.This contribution provided distinctive insights into the structure and property relationship of PAH diradicals.展开更多
The electroactive materials used in the counter electrode(CE)are of great concern as they influence the photovoltaic performances of dye-sensitized solar cells.The main functions of CE materials are collecting electro...The electroactive materials used in the counter electrode(CE)are of great concern as they influence the photovoltaic performances of dye-sensitized solar cells.The main functions of CE materials are collecting electrons from the external circuit and transferring them to the electrolyte and realizing the catalytic reduction of the redox species(I3^– or Co^3+)present in the electrolyte.The research hotspot of CE materials is seeking functional materials that display high efficiency,low cost,and good electrochemical stability and can substitute the benchmark platinum electrode.Chalcogen compounds of cobalt,nickel,and iron have been widely applied as CE materials and exhibit excellent electrocatalytic performances owing to their unique electrical properties,similar energies of adsorption of I atoms as platinum,excellent catalytic activities,and good chemical stabilities.In this review,we trace the developments and performances of chalcogen compounds of iron,cobalt,and nickel as CE materials and present the latest research directions for improving the electrocatalytic performances.We then highlight the optimization strategies for further improving their performances,such as fabrication of architectures,regulation of the components,synthesis of composites containing carbon materials,and elemental doping.展开更多
Using ethylene glycol as solvent and reductant, CuCl2-2H2O, （NH2）2CS and self-prepared GaCl3 as the starting materials, CuGaS2 nanostrucutures were synthesized on a large scale at 220℃. Powder X-ray diffraction. tr...Using ethylene glycol as solvent and reductant, CuCl2-2H2O, （NH2）2CS and self-prepared GaCl3 as the starting materials, CuGaS2 nanostrucutures were synthesized on a large scale at 220℃. Powder X-ray diffraction. transmission electron microscopy, field-emission scanning electron microscope, high-resolution transmission electron microscopy＂ and X-ray＂ photoelectron spectroscopy were used to characterize the products. It demonstrated the evolution of the CuGaS2 particles from spherical assemblies to flowerlike morphology, over time, at 220℃. Simultaneously, we elucidated the specific roles of reaction temperature, reaction time and solvent in the formation of the final CuGaS2 nanostructures. A possible formation mechanism of CuGaS2 nanostrucutures was also discussed. The room temperature photoluminescence spectrum showed blue-shift and an increase of intensity, with a decrease in the sizes of CuGaS2 particles.展开更多
Chalcogen elements,such as sulfur(S),selenium(Se),tellurium(Te)and the interchalcogen compounds,have been studied extensively as cathode materials for the next-generation rechargeable lithium/sodium(Li/Na)batteries.Th...Chalcogen elements,such as sulfur(S),selenium(Se),tellurium(Te)and the interchalcogen compounds,have been studied extensively as cathode materials for the next-generation rechargeable lithium/sodium(Li/Na)batteries.The high energy output of the Li/Na-chalcogen battery originates from the two-electron conversion reaction between chalcogen cathode and alkali metal anode,through which both electrodes are able to deliver high theoretical capacities.The reaction also leads to parasitic reactions that deteriorate the chemical environment in the battery,and different cathode-anode combinations show their own features.In this article,we intend to discuss the fundamental conversion electrochemistry between chalcogen elements and alkali metals and its potential influence,either positive or negative,on the performance of batteries.The strategies to improve the conversion electrochemistry of chalcogen cathode are also reviewed to offer insights into the reasonable design of rechargeable Li/Nachalcogen batteries.展开更多
基金support from the National Natural Science Foundation of China(No.21905317)the Young Elite Scientists Sponsorship Program by CAST(No.2019QNRC001).
文摘In the 21^(st)century,the rapid development of human society has made people’s demand for green energy more and more urgent.The high-energy-density hydrogen energy obtained by fully splitting water is not only environmentally friendly,but also is expected to solve the problems caused by the intermittent nature of new energy.However,the slow kinetics and large overpotential of the oxygen evolution reaction(OER)limit its application.The introduction of Te element is expected to bring new breakthroughs.With the least electronegativity among the chalcogens,the Te element has many special properties,such as multivalent states,strong covalentity,and high electrical conductivity,which make it a promising candidate in electrocatalytic OER.In this review,we introduce the peculiarities of Te element,summarize Te doping and the extraordinary performance of its compounds in OER,with emphasis on the scientific mechanism behind Te element promoting the OER kinetic process.Finally,challenges and development prospects of the applications of Te element in OER are presented.
文摘The electronic configuration of central metal atoms in single-atom catalysts(SACs)is pivotal in electrochemical CO_(2)reduction reaction(eCO_(2)RR).Herein,chalcogen heteroatoms(e.g.,S,Se,and Te)were incorporated into the symmetric nickel-nitrogen-carbon(Ni-N4-C)configuration to obtain Ni-X-N3-C(X:S,Se,and Te)SACs with asymmetric coordination presented for central Ni atoms.Among these obtained Ni-X-N3-C(X:S,Se,and Te)SACs,Ni-Se-N3-C exhibited superior eCO_(2)RR activity,with CO selectivity reaching~98%at-0.70 V versus reversible hydrogen electrode(RHE).The Zn-CO_(2)battery integrated with Ni-Se-N3-C as cathode and Zn foil as anode achieved a peak power density of 1.82 mW cm-2 and maintained remarkable rechargeable stability over 20 h.In-situ spectral investigations and theoretical calculations demonstrated that the chalcogen heteroatoms doped into the Ni-N4-C configuration would break coordination symmetry and trigger charge redistribution,and then regulate the intermediate behaviors and thermodynamic reaction pathways for eCO_(2)RR.Especially,for Ni-Se-N3-C,the introduced Se atoms could significantly raise the d-band center of central Ni atoms and thus remarkably lower the energy barrier for the rate-determining step of*COOH formation,contributing to the promising eCO_(2)RR performance for high selectivity CO production by competing with hydrogen evolution reaction.
基金supported by the Special Scientific Research Fund for Talents Introduced of Hebei Agricultural University (No.YJ2019030)the National Natural Science Foundation of China (Nos.22276042,21906035)the Pearl River Young Talents Program of Guangdong Province (No.2017GC010269)。
文摘Increasing risks of incidental and occupational exposures to two-dimensional transition metal dichalcogenides(2D TMDCs)due to their broad application in various areas raised their public health concerns.While the composition-dependent cytotoxicity of 2D TMDCs has been well-recognized,how the outer chalcogenide atoms and inner transition metal atoms differentially contribute to their perturbation on cell homeostasis at non-lethal doses remains to be identified.In the present work,we compared the autophagy induction and related mechanisms in response to WS_(2),NbS_(2),WSe_(2)and Nb Se_(2)nanosheets exposures in MH-S murine alveolar macrophages.All these 2D TMDCs had comparable physicochemical properties,overall cytotoxicity and capability in triggering autophagy in MH-S cells,but showed outer chalcogen-dependent subcellular localization and activation of autophagy pathways.Specifically,WS_(2)and NbS_(2)nanosheets adhered on the cell surface and internalized in the lysosomes,and triggered m TOR-dependent activation of autophagy.Meanwhile,WSe_(2)and Nb Se_(2)nanosheets had extensive distribution in cytoplasm of MH-S cells and induced autophagy in an m TOR-independent manner.Furthermore,the 2D TMDCs-induced perturbation on autophagy aggravated the cytotoxicity of respirable benzo[a]pyrene.These findings provide a deeper insight into the potential health risk of environmental 2D TMDCs from the perspective of homeostasis perturbation.
基金financially supported by the National Key Research and Development Program of China (2018YFD0200100)Natural Science Foundation of Jiangsu Province (BK20181449)+2 种基金Zhejiang Provincial Natural Science Foundation (LY19B020004)Jiangsu Provincial Six Talent Peaks Project (XCL-090)Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)
文摘Catalyzed by commercially available(PhTe)2, molecular oxygen could be utilized as the mild, cheap and safe oxidant for oxidative deoximation reactions under solvent-free conditions. As the first report on organotellurium-catalyzed deoximation reaction, this work not only provides an efficient deoximation method, but also discloses new features of tellurium catalyst different from those of the organoselenium catalysts.
文摘Gas phase carbonylation of methane is studied in the presence of molecular oxygen over pure carbon carriers and carbon supported rhodium chalcogen halides. Activated carbons and fullerene blacks have been used as carbon supports. XPS and IR-spectroscopy data show the formation of rhodium chalcogen halides in solids prepared by different methods. We have found that the productivity of acetic acid by carbon supported rhodium chalcogen halides depends strongly on the carbon carrier and the method of the catalyst preparation. Namely, the catalyst with highest productivity for the acetic acid is prepared by synthesizing the rhodium chalcogen halide over the carbon support followed by thermal destruction. We have also found that rhodium chalcogen halides over activated carbons are more active compared with fullerene supported catalysts.
基金National Natural Science Foundation of China(No.52003081)Shanghai Natural Science Foundation,China(No.22ZR1420600).
文摘Luminescent open-shell organic radicals have recently been regarded as one of the most potential materials in organic light-emitting diodes(OLEDs).Herein,we have synthesized two new organic radicals,namely tris{4-[4-(tert-butyl)phenoxy]-2,6-dichlorophenyl}methane radical(TTM-O)and tris(4-{[4-(tert-butyl)-phenyl]thio}-2,6-dichlorophenyl)methane radical(TTM-S),by the substitution of chalcogen atom elements at the para position of conventional tris(2,4,6-trichlorophenyl)methyl(TTM)radical moiety.Interestingly,both TTM-O and TTM-S exhibited significantly enhanced photostability compared with the unsubstituted TTM radical parent.Moreover,the chalcogen atom also had a crucial impact on the photoluminescence quantum yield(PLQY)of the radicals,i.e.,the PLQY of TTM-S was greatly enhanced compared to TTM radical while TTM-O was nearly non-emissive.Particularly,TTM-S showed intense PLQY of 37.54%and 185-fold longer photostability than that in cyclohexane solution of TTM.
文摘Growing interest in non-covalent interactions involving chalcogen atoms has been ascribed to their importance in crystal engineering, molecular recognition and macromolecular edifices. The present study is dealing with chalcogen bonds involving divalent Sulphur, Selenium and Tellurium atoms, acting as sigma-hole donors, in small-molecule compounds using the Cambridge Structural Database (CSD) in conjunction with ab initio calculations. Results derived from CSD surveys and computational study revealed that nucleophiles formed complexes with the chalcogen-bond donors R1-X-R2 (X = S, Se or Te). The main forces stabilizing the complexes were chalcogen bonds, enhanced by dispersion interactions. Complexation pattern and energetics show that nucleophile bonding at divalent S, Se and Te atoms is a relatively strong and directed interaction. The bond consists of a charge transfer from a nucleophile atom lone pair to an X-R1 or X-R2 antibonding orbital.
文摘This paper presents a versatile method for synthesizing electron-rich polynuclear transition metal clusters with chalcogen bridges and phosphine ligands.The reactions of transition metal complexes(R3P)2MX2(M=Co,Ni;R=Ph,Bu,Et;X=Cl,Br) with bridging reagents Na2Ex (E=S,Se;x=1.2) are described.The geometric and electronic structures of a series of polynuclear transition metal clusters with trianglar M3 units are also discussed.
基金supported by funds from scientific research programs of National Academy of Sciences of Ukraine and Ministry of Education and Science of Ukraine
文摘The gas phase methane oxidative carbonylation was studied in the presence of molecular oxygen over silica materials including their mechanical mixtures with rhodium chalcogen chlorides obtained in non-aqueous inorganic media. The formation of Rh4SCl7, Rh4S9Cl2, Rh4SesCl3 and Rh3Se3Cl solids was confirmed by elemental analysis, IR absorption spectroscopy, XPS and X-ray diffraction. Silica, vanadium-, and molybdenum-containing mesoporous molecular sieves have been used as supports. It was found that productivity of oxygenates （methanol, methyl acetate and acetic acid） depends mainly on the method of the catalyst preparation and the type of the support.
基金supported by the National Natural Science Foundation of China(No.51725401 and 51874019)the Fundamental Research Funds for the Central Universities(FRF-TP-17-002C2)。
文摘Aluminum batteries are attractive in electrochemical energy storage due to high energy density and lowcost aluminum,while the energy density is limited for the lack of favorable positive electrode materials to match aluminum negative electrodes.Tellurium positive electrode is intrinsically electrically conductive among chalcogen and holds high theoretical specific capacity(1260.27 mAh g^(-1)) and discharge voltage plateau(~1,5 V).However,the chemical and electrochemical dissolution of Te active materials results in the low material utilization and poor cycling stability.To enhance the electrochemical performance,herein a nitrogen doped porous carbon(N-PC) is derived from zeolite imidazolate framework(ZIF-67)as an effective tellurium host to suppress the undesired shuttle effect.In order to inhibit the volume expansion of N-PC during the charge/discharge process,the reduced graphene oxide(rGO) nanosheets are introduced to form a stable host materials(N-PC-rGO) for stabilizing Te.The physical encapsulation and chemical confinement to soluble tellurium species are achieved.N-PC-rGO-Te positive electrode exhibits an improved initial specific capacity and long-term cycling performance at a current density of 500 mA g^(-1)(initial specific capacity:935.5 mAh g^(-1);after 150 cycles:467.5 mAh g^(-1)), highlighting a promising design strategy for inhibiting chemical and electrochemical dissolution of Te.
基金financially supported by JSPS KAKENHI Grant Numbers JP19H00906,JP20K22421,and JP20H05865,and the Mitsubishi Foundation.
文摘To understand the effects of chalcogen atoms on the crystal structure of the series of 3,7-bis(methylchalcogeno)benzo[1,2-b:4,5-b′]dichalcogenophene-based organic semiconductors,three benzodifuran derivatives(1—3)and dimethoxy derivatives of benzodithiophene and benzodiselenophene(4 and 7)were newly synthesized to complete the“3×3 matrix”of the oxygen-,sulfur-,and selenium-derivatives(1—9).The crystal structures of 1—9 were classified into four classes,sandwich pitchedπ-stack(1),dimeric(2 and 3),pitchedπ-stack(4,5,7,8,9),and brickwork structure(6 and 9).The causes for the different crystal structures depending on the chalcogen atoms were investigated by the theoretical calculations,indicating that the chalcogen atoms in the core and substituents primarily affected the packing structures.Although the crystal growth in the vapor phase afforded different polymorphs,the relationship between the crystal structure and the carrier transport property was carefully investigated.
基金supported by the construct program of applied characteristic discipline in Hunan University of Science and Engineering,the Technology Plan of Guangdong Province(No. 2019A050510042)the Natural Science Foundation of Hunan Province of China (No. 2021JJ30291)Northwestern Polytechnical University。
文摘Artificial membrane transporters that either use chalcogen bonds to facilitate transmembrane flux of anions or show high selectivity toward perchlorate anions are rare.In this work,we report on one such novel monopeptide-based transporter system,featuring both chalcogen bonds for highly efficient anion transport and high transport selectivity toward ClO_(4)^(-) anions.Structurally,these monopeptide molecules associate with each other via H-bonds to produce H-bonded 1D stack that not only one dimensionally but also directionally aligns the terminal bicyclic thiophene motifs to the same side.Functionally,these well-aligned thiophenes create a sulfur-rich transmembrane pathway,combinatorially fine-tunable to enable anions to efficiently cross the membrane in the increasing activity of Cl^(-)<Br^(-)<NO_(3)^(-)<ClO_(4)^(-) via chalcogen bonds,with EC_(50)values of 0.75,0.40,0.37 and 0.093μmol/L(0.3 mol%relative to lipid molecules),respectively.
基金The work was supported by the NSFC(grant nos.51925306,21774130,and 21905277)National Key R&D Program of China(grant no.2018FYA 0305800)+2 种基金Key Research Program of the Chinese Academy of Sciences(grant no.XDPB08-2)the Strategic Priority Research Program of Chinese Academy of Sciences(grant no.XDB28000000)Fundamental Research Funds for the Central University.DFT results described in this short communication are obtained on the National Super-computing Center in Shenzhen(Shenzhen Cloud Computing Center).
文摘Air stable diradicaloid polycyclic aromatic hydrocarbon(PAH)materials possess unique electronic and magnetic properties for various applications.In general,long conjugated distances between two radical centers are required to improve the air stability,thereby complicating the synthetic procedures.Herein,the chalcogen containing rubicenes(O-,S-,and Se-rubicenes)were systematically investigated to understand the chalcogen effects on chalcogen-rubicene physicochemical properties.Impressively,these rubicenes presented unprecedented diradical characterwithin one simple benzene ring and excellent air stabilities.Theirdiradicalcharacterweremanifested by single-crystal X-ray studies,variable-temperature nuclear magnetic resonance,and electron spin resonance.Furthermore,the nucleus independent chemical shifts andthe anisotropy of the induced currentdensity calculations revealed that the formation of diradical was caused by a pro-aromaticity driving force.Importantly,the diradical character of rubicenes are visualizedbyFractionalOccupationNumberWeighted Electron Density(FOD)plots,which present high NFOD values from 1.651 to 1.830.This contribution provided distinctive insights into the structure and property relationship of PAH diradicals.
基金supported by the National Science Fund for Distinguished Young Scholars(21425729)from the National Natural Science Foundation of Chinathe National Special S&T Project on Water Pollution Control and Treatment(2017ZX07107002)+1 种基金China Postdoctoral Science Foundation(2018M640209)the Tianjin Science and Technology Support Key Projects(18YFZCSF00500)~~
文摘The electroactive materials used in the counter electrode(CE)are of great concern as they influence the photovoltaic performances of dye-sensitized solar cells.The main functions of CE materials are collecting electrons from the external circuit and transferring them to the electrolyte and realizing the catalytic reduction of the redox species(I3^– or Co^3+)present in the electrolyte.The research hotspot of CE materials is seeking functional materials that display high efficiency,low cost,and good electrochemical stability and can substitute the benchmark platinum electrode.Chalcogen compounds of cobalt,nickel,and iron have been widely applied as CE materials and exhibit excellent electrocatalytic performances owing to their unique electrical properties,similar energies of adsorption of I atoms as platinum,excellent catalytic activities,and good chemical stabilities.In this review,we trace the developments and performances of chalcogen compounds of iron,cobalt,and nickel as CE materials and present the latest research directions for improving the electrocatalytic performances.We then highlight the optimization strategies for further improving their performances,such as fabrication of architectures,regulation of the components,synthesis of composites containing carbon materials,and elemental doping.
文摘Using ethylene glycol as solvent and reductant, CuCl2-2H2O, （NH2）2CS and self-prepared GaCl3 as the starting materials, CuGaS2 nanostrucutures were synthesized on a large scale at 220℃. Powder X-ray diffraction. transmission electron microscopy, field-emission scanning electron microscope, high-resolution transmission electron microscopy＂ and X-ray＂ photoelectron spectroscopy were used to characterize the products. It demonstrated the evolution of the CuGaS2 particles from spherical assemblies to flowerlike morphology, over time, at 220℃. Simultaneously, we elucidated the specific roles of reaction temperature, reaction time and solvent in the formation of the final CuGaS2 nanostructures. A possible formation mechanism of CuGaS2 nanostrucutures was also discussed. The room temperature photoluminescence spectrum showed blue-shift and an increase of intensity, with a decrease in the sizes of CuGaS2 particles.
基金supported by the National Key R&D Program of China(2019YFA0705700)the National Natural Science Foundation of China(21975266,21805062)+1 种基金the Beijing National Laboratory for Molecular Sciences(BNLMS-CXXM-201906)support from the Start-up Funds from the Chinese Academy of Sciences。
文摘Chalcogen elements,such as sulfur(S),selenium(Se),tellurium(Te)and the interchalcogen compounds,have been studied extensively as cathode materials for the next-generation rechargeable lithium/sodium(Li/Na)batteries.The high energy output of the Li/Na-chalcogen battery originates from the two-electron conversion reaction between chalcogen cathode and alkali metal anode,through which both electrodes are able to deliver high theoretical capacities.The reaction also leads to parasitic reactions that deteriorate the chemical environment in the battery,and different cathode-anode combinations show their own features.In this article,we intend to discuss the fundamental conversion electrochemistry between chalcogen elements and alkali metals and its potential influence,either positive or negative,on the performance of batteries.The strategies to improve the conversion electrochemistry of chalcogen cathode are also reviewed to offer insights into the reasonable design of rechargeable Li/Nachalcogen batteries.
