The safety problems encountered with lithium–sulfur batteries(LSBs)hinder their development for practical applications.Herein,a highly thermally conductive separator was constructed by cross‐weaving super‐aligned c...The safety problems encountered with lithium–sulfur batteries(LSBs)hinder their development for practical applications.Herein,a highly thermally conductive separator was constructed by cross‐weaving super‐aligned carbon nanotubes(SA‐C)on super‐aligned boron nitride@carbon nanotubes(SA‐BC)to create a composite film(SA‐BC/SA‐C).This separator was used to fabricate safe LSBs with improved electrochemical performance.The highly aligned separator structure created a uniform thermal field that could rapidly dissipate heat accumulated during continuous operation due to internal resistance,which prevented the development of extremely high temperatures.The array of boron nitride nanosheets endowed the composite separator with a large number of adsorption sites,while the highly graphitized carbon nanotube skeleton accelerated the catalytic conversion of high‐valence polysulfides into low‐valence polysulfides.The arrayed molecular brush design enabled the regulation of local current density and ion flux,and considerably alleviated the growth of lithium dendrites,thus promoting the smooth deposition of Li metal.Consequently,a battery constructed with the SA‐BC/SA‐C separator showed a good discharge capacity of 685.2 mAh g−1 over 300 cycles(a capacity decay of 0.026%per cycle)at 2 C and 60°C.This“three‐in‐one”multifunctional separator design strategy constitutes a new path forward for overcoming the safety problems of LSBs.展开更多
Perovskite solar cells(PSCs)show great potential for next-generation photovoltaics,due to their excellent optical and electrical properties.However,defects existing inside the perovskite film impair both the performan...Perovskite solar cells(PSCs)show great potential for next-generation photovoltaics,due to their excellent optical and electrical properties.However,defects existing inside the perovskite film impair both the performance and stability of the device.Uncoordinated Pb^(2+),uncoordinated I^(-),and metallic Pb(Pb^(0))are the main defects occur during perovskite film preparation and device operation,due to the volatilization of organic cationic components.Passivating these defects is a desirable tas k,because they are non-radiative recombination centers that cause open-circuit voltage(VOC)loss and degradation of the perovskite layer.Herein,the multifunctional bioactive compound dopamine(DA)is introduced for the first time to control the perovskite film formation and passivate the uncoordinated Pb^(2+)defects via Lewis acid-base interactions.The Pb^(0) and I^(-)defects are effectively suppressed by the DA treatment.At the same time,the DA treatment results in a stronger crystal orientation along the(110)plane and upshifts the valence band of perovskite closer to the highest occupied molecular orbital(HOMO)of the hole transport layer(2,2’,7,7’-tetrakis(N,N’-di-pmethoxyphenylamine)-9,9’-spirobifluorene,spiro-OMeTAD),which is beneficial for charge separation and transport processes.Consequently,the stability of MAPbI_(3)(MA=CH_(3)NH_(3))PSCs prepared with the DA additive(especially the thermal stability)is effectively improved due to the better crystallinity and lower number of defect trap states of the perovskite film.The optimized MAPbI3 PSCs maintain approximately 90% of their original power conversion efficiency(PCE)upon annealing at 85℃ for 120 h.The best performance triple-cation perovskite(Cs_(0.05)(FA_(0.83)MA_(0.17))_(0.95)Pb(I_(0.83)Br_(0.17))_(3))(FA=formamidinium)solar cell with ITO/SnO_(2)/Cs_(0.05)(FA_(0.83)MA_(0.17))_(0.95)Pb(I_(0.83)Br_(0.17))_(3):DA/spiro-OMeTAD/MoO_(3)/Ag(ITO=indium tin oxide)structure shows a PCE of 21.03% with negligible hysteresis,which is dramatically enhanced compared to that of the control device(18.31%).Therefore,this work presents a simple and effective way to improve the efficiency and stability of PSCs by DA treatment.展开更多
Over the past few decades,photocatalysis technology has received extensive attention because of its potential to mitigate or solve energy and environmental pollution problems.Designing novel materials with outstanding...Over the past few decades,photocatalysis technology has received extensive attention because of its potential to mitigate or solve energy and environmental pollution problems.Designing novel materials with outstanding photocatalytic activities has become a research hotspot in this field.In this study,we prepared a series of photocatalysts in which BiOCl nanosheets were modified with carbon quantum dots(CQDs)to form CQDs/BiOCl composites by using a simple solvothermal method.The photocatalytic performance of the resulting CQDs/BiOCl composite photocatalysts was assessed by rhodamine B and tetracycline degradation under visible-light irradiation.Compared with bare BiOCl,the photocatalytic activity of the CQDs/BiOCl composites was significantly enhanced,and the 5 wt%CQDs/BiOCl composite exhibited the highest photocatalytic activity with a degradation efficiency of 94.5%after 30 min of irradiation.Moreover,photocatalytic N_(2)reduction performance was significantly improved after introducing CQDs.The 5 wt%CQDs/BiOCl composite displayed the highest photocatalytic N_(2)reduction performance to yield NH_3(346.25μmol/(g h)),which is significantly higher than those of 3 wt%CQDs/BiOCl(256.04μmol/(g h)),7 wt%CQDs/BiOCl(254.07μmol/(g h)),and bare BiOCl(240.19μmol/(g h)).Our systematic characterizations revealed that the key role of CQDs in improving photocatalytic performance is due to their increased light harvesting capacity,remarkable electron transfer ability,and higher photocatalytic activity sites.展开更多
The performance of proton exchange membrane fuel cells depends heavily on the oxygen reduction reaction(ORR)at the cathode,for which platinum-based catalysts are currently the standard.The high cost and limited availa...The performance of proton exchange membrane fuel cells depends heavily on the oxygen reduction reaction(ORR)at the cathode,for which platinum-based catalysts are currently the standard.The high cost and limited availability of platinum have driven the search for alternative catalysts.While FeN4 single-atom catalysts have shown promising potential,their ORR activity needs to be further enhanced.In contrast,dual-atom catalysts(DACs)offer not only higher metal loading but also the ability to break the ORR scaling relations.However,the diverse local structures and tunable coordination environments of DACs create a vast chemical space,making large-scale computational screening challenging.In this study,we developed a graph neural network(GNN)-based framework to predict the ORR activity of Fe-based DACs,effectively addressing the challenges posed by variations in local catalyst structures.Our model,trained on a dataset of 180 catalysts,accurately predicted the Gibbs free energy of ORR intermediates and overpotentials,and identified 32 DACs with superior catalytic activity compared to FeN4 SAC.This approach not only advances the design of high-performance DACs,but also offers a powerful computational tool that can significantly reduce the time and cost of catalyst development,thereby accelerating the commercialization of fuel cell technologies.展开更多
Surface functionalization of Cu-based catalysts has demonstrated promising potential for enhancing the electrochemical CO_(2)reduction reaction(CO_(2)RR)toward multi-carbon(C2+)products,primarily by suppressing the pa...Surface functionalization of Cu-based catalysts has demonstrated promising potential for enhancing the electrochemical CO_(2)reduction reaction(CO_(2)RR)toward multi-carbon(C2+)products,primarily by suppressing the parasitic hydrogen evolution reaction and facilitating a localized CO_(2)/CO concentration at the electrode.Building upon this approach,we developed surface-functionalized catalysts with exceptional activity and selectivity for electrocatalytic CO_(2)RR to C_(2+)in a neutral electrolyte.Employing CuO nanoparticles coated with hexaethynylbenzene organic molecules(HEB-CuO NPs),a remarkable C_(2+)Faradaic efficiency of nearly 90%was achieved at an unprecedented current density of 300 mA cm^(-2),and a high FE(>80%)was maintained at a wide range of current densities(100-600 mA cm^(-2))in neutral environments using a flow cell.Furthermore,in a membrane electrode assembly(MEA)electrolyzer,86.14%FEC2+was achieved at a partial current density of 387.6 mA cm^(-2)while maintaining continuous operation for over 50 h at a current density of 200 mA cm^(-2).In-situ spectroscopy studies and molecular dynamics simulations reveal that reducing the coverage of coordinated K⋅H2O water increased the probability of intermediate reactants(CO)interacting with the surface,thereby promoting efficient C-C coupling and enhancing the yield of C_(2+)products.This advancement offers significant potential for optimizing local micro-environments for sustainable and highly efficient C_(2+)production.展开更多
Inhibiting the “shuttle effect” of soluble polysulfides and improving reaction kinetics are the key factors necessary for further exploration of high-performance Li-S batteries. Herein, an effective interface engine...Inhibiting the “shuttle effect” of soluble polysulfides and improving reaction kinetics are the key factors necessary for further exploration of high-performance Li-S batteries. Herein, an effective interface engineering strategy is reported, wherein nitriding of an Ni-based precursor is controlled to enhance Li-S cell regulation. The resulting in-situ formed NiO-Ni_(3)N heterostructure interface not only has a stronger polysulfide adsorption effect than that of monomeric NiO or Ni_(3)N but also has a faster Li ion diffusion ability than a simple physical mixture. More importantly, this approach couples the respective advantages of NiO and Ni_(3)N to reduce polarization and facilitate electron transfer during polysulfide reactions and synergistically catalyze polysulfide conversion. In addition, ultrafine nanoparticles are thought to effectively improve the use of additive materials. In summary, Li-S batteries based on this NiO-Ni_(3)N heterostructure have the features of long cycle stability, rapid charging-discharging, and good performance under high sulfur loading.展开更多
The use of carbon‐based materials is an appealing strategy to solve the issue of excessive CO_(2) emis‐sions.In particular,metal‐free nitrogen‐doped carbon materials(mf‐NCs)have the advantages of convenient synth...The use of carbon‐based materials is an appealing strategy to solve the issue of excessive CO_(2) emis‐sions.In particular,metal‐free nitrogen‐doped carbon materials(mf‐NCs)have the advantages of convenient synthesis,cost‐effectiveness,and high conductivity and are ideal electrocatalysts for the CO_(2) reduction reaction(CO_(2)RR).However,the unclear identification of the active N sites and the low intrinsic activity of mf‐NCs hinder the further development of high‐performance CO_(2)RR electrocat‐alysts.Achieving precise control over the synthesis of mf‐NC catalysts with well‐defined active N‐species sites is still challenging.To this end,we adopted a facile synthesis method to construct a set of mf‐NCs as robust catalysts for CO_(2)RR.The resulting best‐performing catalyst obtained a Far‐adaic efficiency of CO of approximately 90%at−0.55 V(vs.reversible hydrogen electrode)and good stability.The electrocatalytic performance and in situ attenuated total reflectance surface‐enhanced infrared absorption spectroscopy measurements collectively revealed that graphitic and pyridinic N can synergistically adsorb CO_(2) and H_(2)O and thus promote CO_(2) activation and protonation.展开更多
From the measured phase diagram data and experimental thermochemical properties, the DyCl3-KCl and DyCl3-CaCl2 phase diagrams were optimized and calculated by the CALPHAD technique. The Gibbs energies of liquid phase ...From the measured phase diagram data and experimental thermochemical properties, the DyCl3-KCl and DyCl3-CaCl2 phase diagrams were optimized and calculated by the CALPHAD technique. The Gibbs energies of liquid phase in the two systems has been optimized and calculated by new modified quasi-chemical model in the pair-approximation for short-range ordering, and a series of thermodynamic functions has also been optimized based on an interactive computer-assisted analysis. The results showed that the calculated phase diagrams and thermodynamic data were serf-consistent.展开更多
The complex DtbpNiCl2（Dtbp = 2,9-di-tert-butyl-1,10-phenanthroline） was synthe- sized and characterized by X-ray single-crystal structure analysis. For the complex： C20 H24 Cl2 N2 Ni CH2 Cl2, Mr = 506.95, monoclini...The complex DtbpNiCl2（Dtbp = 2,9-di-tert-butyl-1,10-phenanthroline） was synthe- sized and characterized by X-ray single-crystal structure analysis. For the complex： C20 H24 Cl2 N2 Ni CH2 Cl2, Mr = 506.95, monoclinic, space group P21 /c, a = 9.5905（3）, b = 13.7587（3）, c = 17.3364（5）, β = 94.244（2）°, V = 2281.31（11）3, Z = 4, Dc = 1.476 g/cm3, λ = 1.54184, μ = 5.606 mm-1, F（000） = 1048, S = 1.079, R = 0.0402 and wR = 0.1010 for 3223 observed reflections with I 〉 2σ（I）. In complex DtbpNiCl2, the nickel adopts a distorted tetrahedral geometry coordinated by two nitrogen atoms of Dtbp and two chlorine ions. The complex is connected by intermolecular C–H…Cl hydrogen bonds to form a 1D structure in the solid state.展开更多
Atomic radiative data such as excitation energies, transition wavelengths, radiative rates, and level lifetimes with high precision are the essential parameters for the abundance analysis, simulation, and diagnostics ...Atomic radiative data such as excitation energies, transition wavelengths, radiative rates, and level lifetimes with high precision are the essential parameters for the abundance analysis, simulation, and diagnostics in fusion and astrophysical plasmas. In this work, we mainly focus on reviewing our two projects performed in the past decade. One is about the ions with Z■30 that are generally of astrophysical interest, and the other one is about the highly charged krypton(Z = 36)and tungsten(Z = 74) ions that are relevant in research of magnetic confinement fusion. Two different and independent methods, namely, multiconfiguration Dirac–Hartree–Fock(MCDHF) and the relativistic many-body perturbation theory(RMBPT) are usually used in our studies. As a complement/extension to our previous works for highly charged tungsten ions with open M-shell and open N-shell, we also mainly focus on presenting and discussing our complete RMBPT and MCDHF calculations for the excitation energies, wavelengths, electric dipole(E1), magnetic dipole(M1), electric quadrupole(E2), and magnetic quadrupole(M2) transition properties, and level lifetimes for the lowest 148 levels belonging to the 3l3configurations in Al-like W61+. We also summarize the uncertainties of our systematical theoretical calculations, by cross-checking/validating our datasets from our RMBPT and MCDHF calculations, and by detailed comparisons with available accurate observations and other theoretical calculations. The data are openly available in Science Data Bank at https://doi.org/10.57760/sciencedb.10569.展开更多
It was found that silver nanoparticles could strongly enhance the chemiluminescence (CL) of the luminol-KIO4 system in the presence of Co2+. The most intensive CL signals were obtained with silver nanoparticles in dia...It was found that silver nanoparticles could strongly enhance the chemiluminescence (CL) of the luminol-KIO4 system in the presence of Co2+. The most intensive CL signals were obtained with silver nanoparticles in diameter of 22 nm. The studies of UV-visible spectra and CL spectra were carried out to explore the possible CL enhancement mechanism. Moreover, the influences of 17 amino acids and 25 organic compounds on the luminol-KIO4-Co2+-Ag NPs CL system were studied by a flow injection procedure, which led to an effective method to detect these compounds.展开更多
Taking advantage of the extremely small size of the gold nanodisk electrode,the single hydrogen nanobubble generated on the surface of the nanoelectrode was studied to evaluate its hydrogen evolution performance.It wa...Taking advantage of the extremely small size of the gold nanodisk electrode,the single hydrogen nanobubble generated on the surface of the nanoelectrode was studied to evaluate its hydrogen evolution performance.It was found that compared with the bare gold nanodisk electrode,the bubble formation potential of the gold nanodisk electrode modified with tungsten disulfide quantum dots(WS_(2)QDs)on the surface was more positive,indicating that its hydrogen evolution activity was higher.Microdynamic model analysis shows that the average standard rate constant of the rate-determining step of the hydrogen evolution reaction of gold nanoelectrodes modified with WS_(2)QDs is approximately 12 times larger than that of gold nanoelectrodes.This work based on the formation of nanobubbles provides new ideas for the design and performance evaluation of hydrogen evolution reaction catalysts.展开更多
The water-soluble CdS nanoparticles were synthesized in aqueous solution. A novel fluorescence resonance energy transfer （FP, ET） system with CdS nanoparticles as energy donors and 3,3＇-diethyl-oxadicarbocyanine io...The water-soluble CdS nanoparticles were synthesized in aqueous solution. A novel fluorescence resonance energy transfer （FP, ET） system with CdS nanoparticles as energy donors and 3,3＇-diethyl-oxadicarbocyanine iodide （DOCAI） dyes as energy accepter has been developed.展开更多
A soluble, poly（ethylene glycol）-supported piperazine catalyst was prepared. This soluble catalyst efficiently catalyzes the Knoevenagel condensation of various aromatic aldehydes with diethyl malonate or ethyl acet...A soluble, poly（ethylene glycol）-supported piperazine catalyst was prepared. This soluble catalyst efficiently catalyzes the Knoevenagel condensation of various aromatic aldehydes with diethyl malonate or ethyl acetoacetate in a homogeneous phase to afford the desired alkenes in good purity and yield with a facile work-up process. It was found that the polymer reagent could be repeatedly used at least four times without the too much loss of activity. The catalyst has shown a good activity, stability, and recycling capability.展开更多
Fluorescent dyes are heavily sought for their potentials applications in bioimaging, sensing, theranostic,and optoelectronic materials. Among them, BODIPY dyes are privileged fluorophores that are now widely used in h...Fluorescent dyes are heavily sought for their potentials applications in bioimaging, sensing, theranostic,and optoelectronic materials. Among them, BODIPY dyes are privileged fluorophores that are now widely used in highly diverse research fields. The increasing success of BODIPY dyes is closely associated with their excellent and tunable photophysical properties due to their rich functionalization chemistry.Recently, growing research efforts have been devoted to the direct functionalization of the BODIPY core,because it allows the facile installation of desired functional groups in a single atom economical step. The challenges of this direct C-H derivation come from the difficulties in finding suitable functionalization agents and proper control of the regioselectivity of the functionalization. The aim of this work is to provide an overview of BODIPY dyes and a summarization of the different synthetic methodologies reported for direct C–H functionalization of the BODIPY framework.展开更多
The reactions of neutral pyrrolyl-functionalized indole with rare-earth metal amides [(Me3Si)2N]3RE(μ-Cl)Li(THF)3 produced the rare-earth metal complexes [(Me3Si)2N]2RE([η1:μ-η2-3-(2-(N–CH3)C4H3NCH=N–CH2CH2)C8H5...The reactions of neutral pyrrolyl-functionalized indole with rare-earth metal amides [(Me3Si)2N]3RE(μ-Cl)Li(THF)3 produced the rare-earth metal complexes [(Me3Si)2N]2RE([η1:μ-η2-3-(2-(N–CH3)C4H3NCH=N–CH2CH2)C8H5N])(μ-Cl)Li(THF)(RE = Er, Y) having indolyl ligand η1 bonded to rare-earth metal ion and η2 bonded to lithium ion. The catalytic activities of these lanthanide amido complexes for addition of terminal alkynes to aromatic nitriles were explored. Results reveal that these complexes displayed a good catalytic activity for the addition reaction under mild conditions.展开更多
Inorganic anions such as phosphates and carbonates are essential in the natural system and it is important for the detec-tion of such species.In this work,the fluorescence sensing capacity of Zr(IV)framework with an a...Inorganic anions such as phosphates and carbonates are essential in the natural system and it is important for the detec-tion of such species.In this work,the fluorescence sensing capacity of Zr(IV)framework with an amino-functional group,namely UiO-66-NH_(2),towards specific inorganic anions was investigated in aqueous media.The results revealed that the fluorescence emission intensity of UiO-66-NH2 could be strongly enhanced by phosphate and carbonate anions including HPO_(4)^(2-),H_(2)PO_(4)^(-),PO_(4)^(3-),P_(2)O_(7)^(4-),HCO_(3)^(-)and CO_(3)^(2-),implying its sensing capacity towards phosphate and carbonate anions.Furthermore,fluorescence titration experiments exhibit that the emission intensity enhancement ratio depends linearly on the concentration of anions,suggesting the possibility of quantitative detection of these anions.Further studies suggest that the sensing of UiO-66-NH,towards HPO_(4)^(2-)/PO_(4)^(3-)/P_(2)O_(4)^(-)/HCO_(3)^(-)/CO_(2)-could be ascribed to the collapse of the framework,while that for H_(2)PO_(4)-could be attributed to the adsorption of H,PO4-by UiO-66-NH2 with hydrogen bonding interactions between H,PO4-and the amino group of UiO-66-NH_(2) supported by the different fluorescence response of UiO-66 and UiO-66-NH,towards the anions.展开更多
Ligands play a key role in controlling activity of organometallic complexes so that development of new ligands to overcome the challenge is the main topic of modern chemistry.The first example of 1,1-hydride migratory...Ligands play a key role in controlling activity of organometallic complexes so that development of new ligands to overcome the challenge is the main topic of modern chemistry.The first example of 1,1-hydride migratory insertion and intramolecular redox reaction has been realized in this work by applying a new ligand in rare-earth metal chemistry.The novel rare-earth metal complexes L^(Mes)RECH2TMS(THF)(RE=Y(1a),Dy(1b),Er(1c),Yb(1d),L^(Mes)=1-(3-(2,6-iPr_(2)C_(6)H_(3)N=CH)C8H4N)-CH_(2)CH_(2)-3-(2-CH2–4,6-Me_(2)C_(6)H_(2))-(N(CH)_(2)NC),THF=tetrahydrofuran)bearing a ligand with imino,indolyl,NHC(N-heterocyclic carbene)multiple functionalities were synthesized and characterized.Treatment of complexes 1 with silanes(PhSiH3or PhSiH2Me or PhSiD3)selectively produced the unprecedented 1,1-hydride(or deuterated H)migratory insertion of the indolyl moiety of the novel unsymmetrical dinuclear rare-earth metal complexes 2.The complex 2a reacts with Ph_(2)C=O to give the selective C=O double bond insertion to the RE–Co-methylene-Mesbond product 3a which further reacts with another Ph_(2)C=O(or DMAP,4-N,N-dimethylaminopyridine)affording the novelμ-η^(2):η^(3)-dianionic 3-iminoindolyl dinuclear rare-earth metal complex 4a.The latter is formed through an unusual intramolecular redox reaction(through electron migration from the 2-carbanion of the indolyl ring to the imino motif)resulting in the re-aromatization of the indolyl ring.展开更多
The zinc complex with neutral organochalcogen ligand Mbit, [（Mbit）2Zn]（Cl O4）2（1, Mbit = 1,1＇-methylenebis（3-methyl-imidazole-2-thione））, has been synthesized and characterized. The complex has been character...The zinc complex with neutral organochalcogen ligand Mbit, [（Mbit）2Zn]（Cl O4）2（1, Mbit = 1,1＇-methylenebis（3-methyl-imidazole-2-thione））, has been synthesized and characterized. The complex has been characterized by elemental analysis, NMR and IR spectra. The molecular structure of 1 has been determined by X-ray crystallography. For the complex, C18H24Cl2N8O8S4 Zn, Mr = 744.96, triclinic, space group P1, a = 11.2923（18）, b = 11.9353（19）, c = 13.837（3） , α = 114.763（2）, β = 92.132（2）, γ = 116.039（2）°, V = 1464.6（5） 3, Z = 2, Dc = 1.689 g/cm3, λ = 1.54184 , μ = 1.363 mm-1, F（000） = 760, S = 1.098, the final R = 0.0554 and w R = 0.0.1579. Complex 1 exhibits photocatalytic activity for methyl orange（MO） degradation under UV light and shows good stability toward photocatalysis.展开更多
Aqueous zinc ion batteries(ZIBs) are attracting considerable attentions for practical energy storage because of their low cost and high safety.Nevertheless,the traditional manganese oxide cathode materials suffer from...Aqueous zinc ion batteries(ZIBs) are attracting considerable attentions for practical energy storage because of their low cost and high safety.Nevertheless,the traditional manganese oxide cathode materials suffer from the low intrinsic electronic conductivity,sluggish ions diffusion kinetics,and structural collapse,hindering their large-scale application.Herein,we successfully developed a latent amorphous Mn_(1.8)Fe_(1.2)O_(4) hollow nanocube(a-H-MnFeO) cathode material derived from Prussian blue analogue precursor.The amorphous nature endows the cathode with lower diffusion barrier and narrower band gap compared with crystalline counterpart,resulting in the superior Zn^(2+) ions and electrons transport kinetics.Hollow structure can furnish abundant surface sites and suppress the structural collapse during the repeated charge/discharge processes.By virtue of the multiple advantageous features,the a-H-MnFeO cathode exhibits exceptional electrochemical performance,in terms of high capacity,excellent rate capability,and prolonged cycle life.This strategy will pave the way for the structural design of emerging cathode materials.展开更多
基金National Key R&D Program of China,Grant/Award Number:2022YFE0206500。
文摘The safety problems encountered with lithium–sulfur batteries(LSBs)hinder their development for practical applications.Herein,a highly thermally conductive separator was constructed by cross‐weaving super‐aligned carbon nanotubes(SA‐C)on super‐aligned boron nitride@carbon nanotubes(SA‐BC)to create a composite film(SA‐BC/SA‐C).This separator was used to fabricate safe LSBs with improved electrochemical performance.The highly aligned separator structure created a uniform thermal field that could rapidly dissipate heat accumulated during continuous operation due to internal resistance,which prevented the development of extremely high temperatures.The array of boron nitride nanosheets endowed the composite separator with a large number of adsorption sites,while the highly graphitized carbon nanotube skeleton accelerated the catalytic conversion of high‐valence polysulfides into low‐valence polysulfides.The arrayed molecular brush design enabled the regulation of local current density and ion flux,and considerably alleviated the growth of lithium dendrites,thus promoting the smooth deposition of Li metal.Consequently,a battery constructed with the SA‐BC/SA‐C separator showed a good discharge capacity of 685.2 mAh g−1 over 300 cycles(a capacity decay of 0.026%per cycle)at 2 C and 60°C.This“three‐in‐one”multifunctional separator design strategy constitutes a new path forward for overcoming the safety problems of LSBs.
基金financially supported by the National Natural Science Foundation of China(No.61974045)the Natural Science Foundation of Guangdong Province(Nos.2019A1515012092 and 2017A030313)+2 种基金the Key Laboratory of Functional Molecular Solids,Ministry of Education(No.FMS201905)the Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development(No.Y909kp1001)a project funded by the Science and Technology Bureau of the Dongguan Government(No.2019622163008)。
文摘Perovskite solar cells(PSCs)show great potential for next-generation photovoltaics,due to their excellent optical and electrical properties.However,defects existing inside the perovskite film impair both the performance and stability of the device.Uncoordinated Pb^(2+),uncoordinated I^(-),and metallic Pb(Pb^(0))are the main defects occur during perovskite film preparation and device operation,due to the volatilization of organic cationic components.Passivating these defects is a desirable tas k,because they are non-radiative recombination centers that cause open-circuit voltage(VOC)loss and degradation of the perovskite layer.Herein,the multifunctional bioactive compound dopamine(DA)is introduced for the first time to control the perovskite film formation and passivate the uncoordinated Pb^(2+)defects via Lewis acid-base interactions.The Pb^(0) and I^(-)defects are effectively suppressed by the DA treatment.At the same time,the DA treatment results in a stronger crystal orientation along the(110)plane and upshifts the valence band of perovskite closer to the highest occupied molecular orbital(HOMO)of the hole transport layer(2,2’,7,7’-tetrakis(N,N’-di-pmethoxyphenylamine)-9,9’-spirobifluorene,spiro-OMeTAD),which is beneficial for charge separation and transport processes.Consequently,the stability of MAPbI_(3)(MA=CH_(3)NH_(3))PSCs prepared with the DA additive(especially the thermal stability)is effectively improved due to the better crystallinity and lower number of defect trap states of the perovskite film.The optimized MAPbI3 PSCs maintain approximately 90% of their original power conversion efficiency(PCE)upon annealing at 85℃ for 120 h.The best performance triple-cation perovskite(Cs_(0.05)(FA_(0.83)MA_(0.17))_(0.95)Pb(I_(0.83)Br_(0.17))_(3))(FA=formamidinium)solar cell with ITO/SnO_(2)/Cs_(0.05)(FA_(0.83)MA_(0.17))_(0.95)Pb(I_(0.83)Br_(0.17))_(3):DA/spiro-OMeTAD/MoO_(3)/Ag(ITO=indium tin oxide)structure shows a PCE of 21.03% with negligible hysteresis,which is dramatically enhanced compared to that of the control device(18.31%).Therefore,this work presents a simple and effective way to improve the efficiency and stability of PSCs by DA treatment.
基金financially suppor ted by Key Research and Development Project of Anhui Province(No.2023h11020002)Natural Science Research Project for Universities in Anhui Province(No.KJ2021ZD0006)+3 种基金Natural Science Foundation of Anhui Province(No.2208085MB21)Fundamental Research Funds for the Central Universities of China(No.PA2022GDSK0056)Anhui Laboratory of Molecule-Based Materials(No.fzj22009)National Natural Science Foundation of China(Nos.21725102,22205108)。
文摘Over the past few decades,photocatalysis technology has received extensive attention because of its potential to mitigate or solve energy and environmental pollution problems.Designing novel materials with outstanding photocatalytic activities has become a research hotspot in this field.In this study,we prepared a series of photocatalysts in which BiOCl nanosheets were modified with carbon quantum dots(CQDs)to form CQDs/BiOCl composites by using a simple solvothermal method.The photocatalytic performance of the resulting CQDs/BiOCl composite photocatalysts was assessed by rhodamine B and tetracycline degradation under visible-light irradiation.Compared with bare BiOCl,the photocatalytic activity of the CQDs/BiOCl composites was significantly enhanced,and the 5 wt%CQDs/BiOCl composite exhibited the highest photocatalytic activity with a degradation efficiency of 94.5%after 30 min of irradiation.Moreover,photocatalytic N_(2)reduction performance was significantly improved after introducing CQDs.The 5 wt%CQDs/BiOCl composite displayed the highest photocatalytic N_(2)reduction performance to yield NH_3(346.25μmol/(g h)),which is significantly higher than those of 3 wt%CQDs/BiOCl(256.04μmol/(g h)),7 wt%CQDs/BiOCl(254.07μmol/(g h)),and bare BiOCl(240.19μmol/(g h)).Our systematic characterizations revealed that the key role of CQDs in improving photocatalytic performance is due to their increased light harvesting capacity,remarkable electron transfer ability,and higher photocatalytic activity sites.
基金This work was supported by the National Natural Science Foundation of China(No.22473001)the Natural Science Funds for Distinguished Young Scholar of Anhui Province(1908085J08)the University An-nual Scientific Research Plan of Anhui Province(2022AH010013).
文摘The performance of proton exchange membrane fuel cells depends heavily on the oxygen reduction reaction(ORR)at the cathode,for which platinum-based catalysts are currently the standard.The high cost and limited availability of platinum have driven the search for alternative catalysts.While FeN4 single-atom catalysts have shown promising potential,their ORR activity needs to be further enhanced.In contrast,dual-atom catalysts(DACs)offer not only higher metal loading but also the ability to break the ORR scaling relations.However,the diverse local structures and tunable coordination environments of DACs create a vast chemical space,making large-scale computational screening challenging.In this study,we developed a graph neural network(GNN)-based framework to predict the ORR activity of Fe-based DACs,effectively addressing the challenges posed by variations in local catalyst structures.Our model,trained on a dataset of 180 catalysts,accurately predicted the Gibbs free energy of ORR intermediates and overpotentials,and identified 32 DACs with superior catalytic activity compared to FeN4 SAC.This approach not only advances the design of high-performance DACs,but also offers a powerful computational tool that can significantly reduce the time and cost of catalyst development,thereby accelerating the commercialization of fuel cell technologies.
基金supported by the National Natural Science Foundation of China(22101182)the Shenzhen Science and Technology Program(Nos.JCYJ20210324095202006,JCYJ20220531095813031,and JCYJ20230807140700001)Guangdong Basic and Applied Basic Research Foundation(2022A1515010318).
文摘Surface functionalization of Cu-based catalysts has demonstrated promising potential for enhancing the electrochemical CO_(2)reduction reaction(CO_(2)RR)toward multi-carbon(C2+)products,primarily by suppressing the parasitic hydrogen evolution reaction and facilitating a localized CO_(2)/CO concentration at the electrode.Building upon this approach,we developed surface-functionalized catalysts with exceptional activity and selectivity for electrocatalytic CO_(2)RR to C_(2+)in a neutral electrolyte.Employing CuO nanoparticles coated with hexaethynylbenzene organic molecules(HEB-CuO NPs),a remarkable C_(2+)Faradaic efficiency of nearly 90%was achieved at an unprecedented current density of 300 mA cm^(-2),and a high FE(>80%)was maintained at a wide range of current densities(100-600 mA cm^(-2))in neutral environments using a flow cell.Furthermore,in a membrane electrode assembly(MEA)electrolyzer,86.14%FEC2+was achieved at a partial current density of 387.6 mA cm^(-2)while maintaining continuous operation for over 50 h at a current density of 200 mA cm^(-2).In-situ spectroscopy studies and molecular dynamics simulations reveal that reducing the coverage of coordinated K⋅H2O water increased the probability of intermediate reactants(CO)interacting with the surface,thereby promoting efficient C-C coupling and enhancing the yield of C_(2+)products.This advancement offers significant potential for optimizing local micro-environments for sustainable and highly efficient C_(2+)production.
基金financial support of the Youth Project of the Provincial Natural Science Foundation of Anhui(No. 2008085QE267)the Doctoral Research Initiation Foundation of Anhui Normal University (No. 751973)+2 种基金the National Natural Science Foundation of China (No. 51972162)the Fundamental Research Funds for the Central Universities (No. 0213-14380196)the Science and Technology Project of Nanchang (No. 2017-SJSYS-008)。
文摘Inhibiting the “shuttle effect” of soluble polysulfides and improving reaction kinetics are the key factors necessary for further exploration of high-performance Li-S batteries. Herein, an effective interface engineering strategy is reported, wherein nitriding of an Ni-based precursor is controlled to enhance Li-S cell regulation. The resulting in-situ formed NiO-Ni_(3)N heterostructure interface not only has a stronger polysulfide adsorption effect than that of monomeric NiO or Ni_(3)N but also has a faster Li ion diffusion ability than a simple physical mixture. More importantly, this approach couples the respective advantages of NiO and Ni_(3)N to reduce polarization and facilitate electron transfer during polysulfide reactions and synergistically catalyze polysulfide conversion. In addition, ultrafine nanoparticles are thought to effectively improve the use of additive materials. In summary, Li-S batteries based on this NiO-Ni_(3)N heterostructure have the features of long cycle stability, rapid charging-discharging, and good performance under high sulfur loading.
文摘The use of carbon‐based materials is an appealing strategy to solve the issue of excessive CO_(2) emis‐sions.In particular,metal‐free nitrogen‐doped carbon materials(mf‐NCs)have the advantages of convenient synthesis,cost‐effectiveness,and high conductivity and are ideal electrocatalysts for the CO_(2) reduction reaction(CO_(2)RR).However,the unclear identification of the active N sites and the low intrinsic activity of mf‐NCs hinder the further development of high‐performance CO_(2)RR electrocat‐alysts.Achieving precise control over the synthesis of mf‐NC catalysts with well‐defined active N‐species sites is still challenging.To this end,we adopted a facile synthesis method to construct a set of mf‐NCs as robust catalysts for CO_(2)RR.The resulting best‐performing catalyst obtained a Far‐adaic efficiency of CO of approximately 90%at−0.55 V(vs.reversible hydrogen electrode)and good stability.The electrocatalytic performance and in situ attenuated total reflectance surface‐enhanced infrared absorption spectroscopy measurements collectively revealed that graphitic and pyridinic N can synergistically adsorb CO_(2) and H_(2)O and thus promote CO_(2) activation and protonation.
基金Project supported by Key Item Faundation of Anhui MunicipalCommission of Education (Grant No .2005KJ016ZD)
文摘From the measured phase diagram data and experimental thermochemical properties, the DyCl3-KCl and DyCl3-CaCl2 phase diagrams were optimized and calculated by the CALPHAD technique. The Gibbs energies of liquid phase in the two systems has been optimized and calculated by new modified quasi-chemical model in the pair-approximation for short-range ordering, and a series of thermodynamic functions has also been optimized based on an interactive computer-assisted analysis. The results showed that the calculated phase diagrams and thermodynamic data were serf-consistent.
基金supported by the National Natural Science Foundation of China(21102004)the Natural Science Foundation of Anhui Higher Education Institutions of China(KJ2011A146)
文摘The complex DtbpNiCl2（Dtbp = 2,9-di-tert-butyl-1,10-phenanthroline） was synthe- sized and characterized by X-ray single-crystal structure analysis. For the complex： C20 H24 Cl2 N2 Ni CH2 Cl2, Mr = 506.95, monoclinic, space group P21 /c, a = 9.5905（3）, b = 13.7587（3）, c = 17.3364（5）, β = 94.244（2）°, V = 2281.31（11）3, Z = 4, Dc = 1.476 g/cm3, λ = 1.54184, μ = 5.606 mm-1, F（000） = 1048, S = 1.079, R = 0.0402 and wR = 0.1010 for 3223 observed reflections with I 〉 2σ（I）. In complex DtbpNiCl2, the nickel adopts a distorted tetrahedral geometry coordinated by two nitrogen atoms of Dtbp and two chlorine ions. The complex is connected by intermolecular C–H…Cl hydrogen bonds to form a 1D structure in the solid state.
基金the support from the National Natural Science Foundation of China (Grant Nos. 12074081 and 12104095)。
文摘Atomic radiative data such as excitation energies, transition wavelengths, radiative rates, and level lifetimes with high precision are the essential parameters for the abundance analysis, simulation, and diagnostics in fusion and astrophysical plasmas. In this work, we mainly focus on reviewing our two projects performed in the past decade. One is about the ions with Z■30 that are generally of astrophysical interest, and the other one is about the highly charged krypton(Z = 36)and tungsten(Z = 74) ions that are relevant in research of magnetic confinement fusion. Two different and independent methods, namely, multiconfiguration Dirac–Hartree–Fock(MCDHF) and the relativistic many-body perturbation theory(RMBPT) are usually used in our studies. As a complement/extension to our previous works for highly charged tungsten ions with open M-shell and open N-shell, we also mainly focus on presenting and discussing our complete RMBPT and MCDHF calculations for the excitation energies, wavelengths, electric dipole(E1), magnetic dipole(M1), electric quadrupole(E2), and magnetic quadrupole(M2) transition properties, and level lifetimes for the lowest 148 levels belonging to the 3l3configurations in Al-like W61+. We also summarize the uncertainties of our systematical theoretical calculations, by cross-checking/validating our datasets from our RMBPT and MCDHF calculations, and by detailed comparisons with available accurate observations and other theoretical calculations. The data are openly available in Science Data Bank at https://doi.org/10.57760/sciencedb.10569.
文摘It was found that silver nanoparticles could strongly enhance the chemiluminescence (CL) of the luminol-KIO4 system in the presence of Co2+. The most intensive CL signals were obtained with silver nanoparticles in diameter of 22 nm. The studies of UV-visible spectra and CL spectra were carried out to explore the possible CL enhancement mechanism. Moreover, the influences of 17 amino acids and 25 organic compounds on the luminol-KIO4-Co2+-Ag NPs CL system were studied by a flow injection procedure, which led to an effective method to detect these compounds.
基金financial support from the National Natural Science Foundation of China(No.21775003)Anhui Provincial Natural Science Foundation(No.2308085MB56)the Key Project of Anhui Provincial Department of Education Scientific Research Project(No.2023AH040032).
文摘Taking advantage of the extremely small size of the gold nanodisk electrode,the single hydrogen nanobubble generated on the surface of the nanoelectrode was studied to evaluate its hydrogen evolution performance.It was found that compared with the bare gold nanodisk electrode,the bubble formation potential of the gold nanodisk electrode modified with tungsten disulfide quantum dots(WS_(2)QDs)on the surface was more positive,indicating that its hydrogen evolution activity was higher.Microdynamic model analysis shows that the average standard rate constant of the rate-determining step of the hydrogen evolution reaction of gold nanoelectrodes modified with WS_(2)QDs is approximately 12 times larger than that of gold nanoelectrodes.This work based on the formation of nanobubbles provides new ideas for the design and performance evaluation of hydrogen evolution reaction catalysts.
基金This work was supported by the National Natural Science Foundation of China(No.20575001)the Fund of the Education Department of Anhui Province(No.2006KJ006TD)+1 种基金the education Commission Natural Science Foundation of Anhui Province(No.2005KJ017ZD)the Science Foundation of the Education Department of Anhui Province for Young Teacher(No.2006jq1050zd).
文摘The water-soluble CdS nanoparticles were synthesized in aqueous solution. A novel fluorescence resonance energy transfer （FP, ET） system with CdS nanoparticles as energy donors and 3,3＇-diethyl-oxadicarbocyanine iodide （DOCAI） dyes as energy accepter has been developed.
基金Supported by the National Natural Science Foundation of China(No.20872001)the Natural Science Foundation of Education Administration of Anhui Province,China(No.KJ2008A064)
文摘A soluble, poly（ethylene glycol）-supported piperazine catalyst was prepared. This soluble catalyst efficiently catalyzes the Knoevenagel condensation of various aromatic aldehydes with diethyl malonate or ethyl acetoacetate in a homogeneous phase to afford the desired alkenes in good purity and yield with a facile work-up process. It was found that the polymer reagent could be repeatedly used at least four times without the too much loss of activity. The catalyst has shown a good activity, stability, and recycling capability.
基金supported by the National Nature Science Foundation of China (Nos. 21672006, 21672007 and 21871006)
文摘Fluorescent dyes are heavily sought for their potentials applications in bioimaging, sensing, theranostic,and optoelectronic materials. Among them, BODIPY dyes are privileged fluorophores that are now widely used in highly diverse research fields. The increasing success of BODIPY dyes is closely associated with their excellent and tunable photophysical properties due to their rich functionalization chemistry.Recently, growing research efforts have been devoted to the direct functionalization of the BODIPY core,because it allows the facile installation of desired functional groups in a single atom economical step. The challenges of this direct C-H derivation come from the difficulties in finding suitable functionalization agents and proper control of the regioselectivity of the functionalization. The aim of this work is to provide an overview of BODIPY dyes and a summarization of the different synthetic methodologies reported for direct C–H functionalization of the BODIPY framework.
基金supported by the National Natural Science Foundation of China (21202002, 21372010)the National Basic Research Program of China (2012CB821600)grants from the Ministry of Education (20103424110001) and Anhui Province (KJ2012A138)
文摘The reactions of neutral pyrrolyl-functionalized indole with rare-earth metal amides [(Me3Si)2N]3RE(μ-Cl)Li(THF)3 produced the rare-earth metal complexes [(Me3Si)2N]2RE([η1:μ-η2-3-(2-(N–CH3)C4H3NCH=N–CH2CH2)C8H5N])(μ-Cl)Li(THF)(RE = Er, Y) having indolyl ligand η1 bonded to rare-earth metal ion and η2 bonded to lithium ion. The catalytic activities of these lanthanide amido complexes for addition of terminal alkynes to aromatic nitriles were explored. Results reveal that these complexes displayed a good catalytic activity for the addition reaction under mild conditions.
基金the National Natural Science Foundation of China (grant No.22171131) for financial support of this worksupported by a Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions
文摘Inorganic anions such as phosphates and carbonates are essential in the natural system and it is important for the detec-tion of such species.In this work,the fluorescence sensing capacity of Zr(IV)framework with an amino-functional group,namely UiO-66-NH_(2),towards specific inorganic anions was investigated in aqueous media.The results revealed that the fluorescence emission intensity of UiO-66-NH2 could be strongly enhanced by phosphate and carbonate anions including HPO_(4)^(2-),H_(2)PO_(4)^(-),PO_(4)^(3-),P_(2)O_(7)^(4-),HCO_(3)^(-)and CO_(3)^(2-),implying its sensing capacity towards phosphate and carbonate anions.Furthermore,fluorescence titration experiments exhibit that the emission intensity enhancement ratio depends linearly on the concentration of anions,suggesting the possibility of quantitative detection of these anions.Further studies suggest that the sensing of UiO-66-NH,towards HPO_(4)^(2-)/PO_(4)^(3-)/P_(2)O_(4)^(-)/HCO_(3)^(-)/CO_(2)-could be ascribed to the collapse of the framework,while that for H_(2)PO_(4)-could be attributed to the adsorption of H,PO4-by UiO-66-NH2 with hydrogen bonding interactions between H,PO4-and the amino group of UiO-66-NH_(2) supported by the different fluorescence response of UiO-66 and UiO-66-NH,towards the anions.
基金supported by the National Natural Science Foundation of China(22031001,21871004,21861162009,22171004)the grants from the Education Department of Anhui Province(GXXT-2021-052)。
文摘Ligands play a key role in controlling activity of organometallic complexes so that development of new ligands to overcome the challenge is the main topic of modern chemistry.The first example of 1,1-hydride migratory insertion and intramolecular redox reaction has been realized in this work by applying a new ligand in rare-earth metal chemistry.The novel rare-earth metal complexes L^(Mes)RECH2TMS(THF)(RE=Y(1a),Dy(1b),Er(1c),Yb(1d),L^(Mes)=1-(3-(2,6-iPr_(2)C_(6)H_(3)N=CH)C8H4N)-CH_(2)CH_(2)-3-(2-CH2–4,6-Me_(2)C_(6)H_(2))-(N(CH)_(2)NC),THF=tetrahydrofuran)bearing a ligand with imino,indolyl,NHC(N-heterocyclic carbene)multiple functionalities were synthesized and characterized.Treatment of complexes 1 with silanes(PhSiH3or PhSiH2Me or PhSiD3)selectively produced the unprecedented 1,1-hydride(or deuterated H)migratory insertion of the indolyl moiety of the novel unsymmetrical dinuclear rare-earth metal complexes 2.The complex 2a reacts with Ph_(2)C=O to give the selective C=O double bond insertion to the RE–Co-methylene-Mesbond product 3a which further reacts with another Ph_(2)C=O(or DMAP,4-N,N-dimethylaminopyridine)affording the novelμ-η^(2):η^(3)-dianionic 3-iminoindolyl dinuclear rare-earth metal complex 4a.The latter is formed through an unusual intramolecular redox reaction(through electron migration from the 2-carbanion of the indolyl ring to the imino motif)resulting in the re-aromatization of the indolyl ring.
基金financially supported by the National Natural Science Foundation of China(21102004)National Training Programs of Innovation and Entrepreneurship for Undergraduates(201410370040)Training Programs of Innovation and Entrepreneurship of Anhui Province for Undergraduates(AH201410370040)
文摘The zinc complex with neutral organochalcogen ligand Mbit, [（Mbit）2Zn]（Cl O4）2（1, Mbit = 1,1＇-methylenebis（3-methyl-imidazole-2-thione））, has been synthesized and characterized. The complex has been characterized by elemental analysis, NMR and IR spectra. The molecular structure of 1 has been determined by X-ray crystallography. For the complex, C18H24Cl2N8O8S4 Zn, Mr = 744.96, triclinic, space group P1, a = 11.2923（18）, b = 11.9353（19）, c = 13.837（3） , α = 114.763（2）, β = 92.132（2）, γ = 116.039（2）°, V = 1464.6（5） 3, Z = 2, Dc = 1.689 g/cm3, λ = 1.54184 , μ = 1.363 mm-1, F（000） = 760, S = 1.098, the final R = 0.0554 and w R = 0.0.1579. Complex 1 exhibits photocatalytic activity for methyl orange（MO） degradation under UV light and shows good stability toward photocatalysis.
基金funding supported by the National Natural Science Foundation of China (52101246)the Fundamental Research Funds for the Central Universities+1 种基金the Natural Science Foundation of Heilongjiang Province, China (YQ2022B006)the funding supported by the Natural Science Foundation of Anhui Province (2208085MB21)。
文摘Aqueous zinc ion batteries(ZIBs) are attracting considerable attentions for practical energy storage because of their low cost and high safety.Nevertheless,the traditional manganese oxide cathode materials suffer from the low intrinsic electronic conductivity,sluggish ions diffusion kinetics,and structural collapse,hindering their large-scale application.Herein,we successfully developed a latent amorphous Mn_(1.8)Fe_(1.2)O_(4) hollow nanocube(a-H-MnFeO) cathode material derived from Prussian blue analogue precursor.The amorphous nature endows the cathode with lower diffusion barrier and narrower band gap compared with crystalline counterpart,resulting in the superior Zn^(2+) ions and electrons transport kinetics.Hollow structure can furnish abundant surface sites and suppress the structural collapse during the repeated charge/discharge processes.By virtue of the multiple advantageous features,the a-H-MnFeO cathode exhibits exceptional electrochemical performance,in terms of high capacity,excellent rate capability,and prolonged cycle life.This strategy will pave the way for the structural design of emerging cathode materials.
