Five optimized geometries of F-?(H2O)n (n = 1, 2) were obtained with ab initio calculation at the B3LYP/6-311++G** level. The accurate intermonomer interaction energy was calculated using the MP2 electron correlation ...Five optimized geometries of F-?(H2O)n (n = 1, 2) were obtained with ab initio calculation at the B3LYP/6-311++G** level. The accurate intermonomer interaction energy was calculated using the MP2 electron correlation correction as well as the basis set superposition error correction by the Boys-Bernardi “counterpoise” protocol. Natural bond orbital (NBO) theory was applied to quantify the relative strength of these interactions and account for their effects on the stability, structural and vibrational parameters of Fˉ?(H2O)n (n = 1, 2). It is shown that the charge transferring from the lone pair of F-1 to the σ?OH(…F) antibonding orbital is important. The results indicate the occupancy of σ?OH(…F) is increased (denoted ?σ?OH(…F)) and the σOH(…F) bond is leng- thened (denoted ?ROH(…F)), leading to the red-shift and the red-shift values have linear correlation with both ?σ?OH(…F) and ?ROH(…F).展开更多
Driven by safety issues,environmental concerns,and high costs,rechargeable aqueous zinc-ion batteries(ZIBs)have received increasing attention in recent years owing to their unique advantages.However,the sluggish kinet...Driven by safety issues,environmental concerns,and high costs,rechargeable aqueous zinc-ion batteries(ZIBs)have received increasing attention in recent years owing to their unique advantages.However,the sluggish kinetics of divalent charge Zn^(2+)in the cathode materials caused by the strong electrostatic interaction and their unsatisfactory cycle life hinder the development of ZIBs.Herein,organic cations and Zn^(2+)ions co-pre-inserted vanadium oxide([N(CH_(3))_(4)]_(0.77),Zn_(0.23))V_(8)O_(20)·3.8H_(2)O are reported as the cathode for ultra-stable aqueous ZIBs,in which the weaker electrostatic interactions between Zn^(2+)and organic ion-pinned vanadium oxide can induce the high reversibility of Zn^(2+)insertion and extraction,thereby improving the cycle life.It is demonstrated that([N(CH_(3))_(4)]_(0.77),Zn_(0.23))V_(8)O_(20)·3.8H_(2)O cathodes deliver a discharge capacity of 181 mA h g^(-1)at8 A g^(-1)and ultra-long life span(99.5%capacity retention after 2000 cycles).A reversible Zn^(2+)/H^(+)ions(de)intercalation storage process and pseudocapacitive charge storage are characterized.The weaker interactions between organic ion and Zn^(2+)open a novel avenue for the design of highly reversible cathode materials with long-term cycling stability.展开更多
Flexible-robust hydrogen-bonded organic frameworks(HOFs)are attracting increasing interest due to their excellent separation performance for important industrial gases,but the construction remains challenging.Herein,a...Flexible-robust hydrogen-bonded organic frameworks(HOFs)are attracting increasing interest due to their excellent separation performance for important industrial gases,but the construction remains challenging.Herein,a sticked-layer strategy is first proposed to construct a flexible-robust HOF,HOFFJU-8,from a donor(D)–π–acceptor(A)molecule 4,4′,4″,4‴-(pyrrolo[3,2-b]pyrrole-1,2,4,5-tetrayl)tetrabenzonitrile(DP-4CN).HOF-FJU-8 is amicroporous three-dimensional framework composed of two kinds of DP-4CN molecules,one acting as building units for the two-dimensional layer via C≡N···H–C hydrogen bond dimers and another as the sticks to link the layers along channels through D–Aπ···πinteractions.The activated framework HOF-FJU-8a possesses flexible-robust pore characteristics,as determined by the gas adsorption and in situ gas-loaded powder X-ray diffraction.HOF-FJU-8a exhibits adaptive adsorption and stronger binding affinity to C_(2)H_(2)rather than CO_(2)due to the flexible-robust nature,which can effectively separate acetylene and carbon dioxide mixtures.展开更多
The hydrogen evolution reaction (HER) and dendrite growth associated with Zn anode have become the main bottlenecks for the further development of zinc ion batteries (ZIBs).In this work,the electrochemical activity of...The hydrogen evolution reaction (HER) and dendrite growth associated with Zn anode have become the main bottlenecks for the further development of zinc ion batteries (ZIBs).In this work,the electrochemical activity of H_(3)O^(+) is inhibited by the supramolecular host–guest complex composed of H_(3)O^(+) as guest and 18-crown-6 as host.The even Zn plating is induced by the host–guest complex electrostatic shielding layer on Zn anode,as detected by in-situ optical microscopy.The lamellar Zn is plated which profits from the improved Zn plating behavior.Density functional theory (DFT) calculation presents the stable structure of complex.The less produced H_(2) content is monitored online by a mass spectrometer during Zn plating/stripping,which indicates HER can be hampered by the host–guest behavior.Thus,the ZIBs with long life and high Coulombic efficiency are achieved via introducing 18-crown-6.The proposed host–guest supramolecular interaction is expected to facilitate the furthermore development of Zn batteries.展开更多
Hydrous minerals in the subducting slabs are potential water carriers into the deep mantle,and thus the synthesis of new hydrous phases is significant in our understanding of water circulation throughout the Earth’s ...Hydrous minerals in the subducting slabs are potential water carriers into the deep mantle,and thus the synthesis of new hydrous phases is significant in our understanding of water circulation throughout the Earth’s interior.In this study,we report the two new hydrous phases,Al_(2)SiO_(6)H_(2)and Al_(5.5)Si_(4)O_(18)H_(3.5)(hereafter referred to simply as phases Psi and Phi,respectively),which are synthesized in the Al_(2)O_(3)-SiO_(2)-H_(2)O system at 15.5 GPa,1400℃and 17.5 GPa,1600℃ by using Sakura2500-ton multi-anvil apparatus.The luminescence spectra of Cr3+show the phase Psi has characteristic peaks at 687,693 and705 nm,while phase Phi has characteristic peaks at 691,696 and 708 nm.Single-crystal X-ray diffraction (SCXRD) refinements yield a monoclinic structure of both phases (space group P2_(1)) with ideal chemical formulae of Al_(2)SiO6H2and Al5.5Si4O18H3.5respectively.The determined lattice parameters for phase Psi are a=9.4168±0.0016Å,b=4.3441±0.0007Å,c=9.4360±0.002Åand β=119.726±0.005°at ambient pressure and 300 K,while the phase Phi has a=7.2549±0.0018Å,b=4.3144±0.001Å,c=8.0520±0.002Å,and β=101.740±0.009°at ambient pressure and 250 K.Electron microprobe analyses (EPMA) show the chemical compositions of phases Psi and Phi to be Al_(1.99)Si_(0.85)O_(6)H_(2.62)and Al_(5.58)Si_(2.81)O_(18)H_(8.03),respectively,which slightly deviate from the ideal formulae inferred from SCXRD measurements.This may result from the disorder or substitution of Al and Si by H in the crystal structures under our synthesis conditions.Our study suggests that phases Psi and Phi are the two potential water carriers at the upper part of the mantle transitions zone,providing new insights into how deep water is stored in this region.展开更多
Nano-drug delivery systems with multiple stimulus-responsive capabilities have superior response performance and efficient drug release.Nevertheless,it is sophisticated to construct multiple stimulus-responsive system...Nano-drug delivery systems with multiple stimulus-responsive capabilities have superior response performance and efficient drug release.Nevertheless,it is sophisticated to construct multiple stimulus-responsive systems where the two or more functional groups need to be introduced simultaneously.Xanthate,one functional group with pH and H2O2 stimulus responsiveness,has significant potential applications for building dual-responsive drug delivery system.Herein,we present a novel dual stimuli-responsive supramolecular drug delivery system by using sodium xanthate derivative(SXD)as guest molecule and quaternary ammonium capped pillar[5]arene(QAP5)as host molecule through host-guest interaction on the basis of electrostatic interaction.The amphiphile QAP5⊃SXD could self-assemble into vesicles to efficiently load the anti-cancer drug DOX.The experimental results showed that QAP5⊃SXD nanoparticles could achieve efficient drug delivery and controlled release in the tumor microenvironment.Cytotoxicity experiments proved that DOX@QAP5⊃SXD nanoparticles could significantly improve the anticancer efficiency of free DOX on cancer cells.The present study provides an efficient strategy to develop supramolecular nanocarriers with dual-responsiveness in one functional group for controlled drug release.展开更多
In order to create effective combustion technologies and fuels with low or no carbon emissions,the research was conducted to assess the coupled interactive effects of NH_(3) and H_(2) additions on ethylene counterflow...In order to create effective combustion technologies and fuels with low or no carbon emissions,the research was conducted to assess the coupled interactive effects of NH_(3) and H_(2) additions on ethylene counterflow diffusion flames from a kinetic perspective.The effects of the NH_(3)/H_(2) combination on flame temperatures,major species,key radicals,important intermediate species,representative oxygenated species and NO_xwere examined.The results of the study utilizing fictitious inert NH_(3) and/or H_(2) revealed the chemical effects of the two components.It was found that the NH_(3)/H_(2) coupled effects had a more effective inhibitory effect on soot precursors than the effects of corresponding sum of single NH_(3) or H_(2) addition.The production of soot precursors was promoted by the coupled chemical effects of NH_(3) and H_(2),but the coupled dilution and thermal effects were observed to have a greater impact,resulting in a decrease of the mole fractions of soot precursors.As for the interaction of NH_(3) and H_(2) effects,the presence of H_(2) decreased the chemical effects of NH_(3) on the augmentation of C_(2)H_(2),A1,A2,and CH_(3)CHO mole fractions.The NH_(3) addition alleviated the H_(2) chemical effects on increasing C_(2)H_(2),C_(3)H_(3),A1 and A2 concentrations.Conversely,the NH_(3)chemical effects on C_(3)H_(3),OH and CH_(3)CHO were enhanced when H_(2) was added.The presence of NH_(3) augmented the chemical effects of H_(2) on the growth of OH mole fraction.Moreover,the H_(2) chemical effects hindered the production of NO and NO_(2) in the presence of NH_(3).展开更多
Owing to the exorbitant overpotential and serious carrier recombination of graphitic carbon nitride(gC_(3)N_(4)),noble metal(NM)is usually served as the H_(2)evolution co-catalyst.Although the NM(such as Pt)nanopartic...Owing to the exorbitant overpotential and serious carrier recombination of graphitic carbon nitride(gC_(3)N_(4)),noble metal(NM)is usually served as the H_(2)evolution co-catalyst.Although the NM(such as Pt)nanoparticles can reduce the H_(2)evolution overpotential,the weak van der Waals interaction between Pt and g-C_(3)N_(4)makes against the charge transfer.Herein,the solvothermal method is developed to achieve semi-chemical interaction between Pt and g-C_(3)N_(4)nanotube(Pt-CNNT)for fast charge transfer.Moreover,the generated in-plane homojunction of CNNT can accelerate charge separation and restrain recombination.Meanwhile,the metallic Pt is an excellent H_(2)evolution co-catalyst.Photo/electrochemical tests verify that the semi-chemical interaction can improve photogenerated charge separation and transferability of CNNT.As a result,the photocatalytic H_(2)evolution turnover frequency(TOF)of Pt-CNNT under visible light irradiation reaches up to 918 h^(-1),which is one of the highest in the g-C_(3)N_(4)-based photocatalysts.This work provides a new idea to improve the charge transfer for efficient photocatalytic H_(2)evolution.展开更多
基金This work was supported by the Foundation of Education Committee of Gansu Province (021-227).
文摘Five optimized geometries of F-?(H2O)n (n = 1, 2) were obtained with ab initio calculation at the B3LYP/6-311++G** level. The accurate intermonomer interaction energy was calculated using the MP2 electron correlation correction as well as the basis set superposition error correction by the Boys-Bernardi “counterpoise” protocol. Natural bond orbital (NBO) theory was applied to quantify the relative strength of these interactions and account for their effects on the stability, structural and vibrational parameters of Fˉ?(H2O)n (n = 1, 2). It is shown that the charge transferring from the lone pair of F-1 to the σ?OH(…F) antibonding orbital is important. The results indicate the occupancy of σ?OH(…F) is increased (denoted ?σ?OH(…F)) and the σOH(…F) bond is leng- thened (denoted ?ROH(…F)), leading to the red-shift and the red-shift values have linear correlation with both ?σ?OH(…F) and ?ROH(…F).
基金supported by the funding from the National Natural Science Foundation of China(grant nos.51902187,52072224,and 51732007)the Natural Science Foundation of Shandong Province(ZR2018BEM010)+3 种基金the Science Fund for Distinguished Young Scholars of Shandong Province(ZR2019JQ16)the Fundamental Research Funds of Shandong UniversityYoung Elite Scientist Sponsorship Program by CAST(YESS)the support from Collaborative Innovation Center of Technology and Equipment for Biological Diagnosis and Therapy in Universities of Shandong
文摘Driven by safety issues,environmental concerns,and high costs,rechargeable aqueous zinc-ion batteries(ZIBs)have received increasing attention in recent years owing to their unique advantages.However,the sluggish kinetics of divalent charge Zn^(2+)in the cathode materials caused by the strong electrostatic interaction and their unsatisfactory cycle life hinder the development of ZIBs.Herein,organic cations and Zn^(2+)ions co-pre-inserted vanadium oxide([N(CH_(3))_(4)]_(0.77),Zn_(0.23))V_(8)O_(20)·3.8H_(2)O are reported as the cathode for ultra-stable aqueous ZIBs,in which the weaker electrostatic interactions between Zn^(2+)and organic ion-pinned vanadium oxide can induce the high reversibility of Zn^(2+)insertion and extraction,thereby improving the cycle life.It is demonstrated that([N(CH_(3))_(4)]_(0.77),Zn_(0.23))V_(8)O_(20)·3.8H_(2)O cathodes deliver a discharge capacity of 181 mA h g^(-1)at8 A g^(-1)and ultra-long life span(99.5%capacity retention after 2000 cycles).A reversible Zn^(2+)/H^(+)ions(de)intercalation storage process and pseudocapacitive charge storage are characterized.The weaker interactions between organic ion and Zn^(2+)open a novel avenue for the design of highly reversible cathode materials with long-term cycling stability.
基金supported by the National Natural Science Foundation of China(grant nos.22271046,21971038,and 21975044)the Fujian Provincial Department of Science and Technology(grant no.2019L3004).
文摘Flexible-robust hydrogen-bonded organic frameworks(HOFs)are attracting increasing interest due to their excellent separation performance for important industrial gases,but the construction remains challenging.Herein,a sticked-layer strategy is first proposed to construct a flexible-robust HOF,HOFFJU-8,from a donor(D)–π–acceptor(A)molecule 4,4′,4″,4‴-(pyrrolo[3,2-b]pyrrole-1,2,4,5-tetrayl)tetrabenzonitrile(DP-4CN).HOF-FJU-8 is amicroporous three-dimensional framework composed of two kinds of DP-4CN molecules,one acting as building units for the two-dimensional layer via C≡N···H–C hydrogen bond dimers and another as the sticks to link the layers along channels through D–Aπ···πinteractions.The activated framework HOF-FJU-8a possesses flexible-robust pore characteristics,as determined by the gas adsorption and in situ gas-loaded powder X-ray diffraction.HOF-FJU-8a exhibits adaptive adsorption and stronger binding affinity to C_(2)H_(2)rather than CO_(2)due to the flexible-robust nature,which can effectively separate acetylene and carbon dioxide mixtures.
基金the partial financial support from the National Natural Science Foundation of China (22075171)。
文摘The hydrogen evolution reaction (HER) and dendrite growth associated with Zn anode have become the main bottlenecks for the further development of zinc ion batteries (ZIBs).In this work,the electrochemical activity of H_(3)O^(+) is inhibited by the supramolecular host–guest complex composed of H_(3)O^(+) as guest and 18-crown-6 as host.The even Zn plating is induced by the host–guest complex electrostatic shielding layer on Zn anode,as detected by in-situ optical microscopy.The lamellar Zn is plated which profits from the improved Zn plating behavior.Density functional theory (DFT) calculation presents the stable structure of complex.The less produced H_(2) content is monitored online by a mass spectrometer during Zn plating/stripping,which indicates HER can be hampered by the host–guest behavior.Thus,the ZIBs with long life and high Coulombic efficiency are achieved via introducing 18-crown-6.The proposed host–guest supramolecular interaction is expected to facilitate the furthermore development of Zn batteries.
基金supported by the Special Research Fund for the Doctoral Program of Tongren University(Grant No.trxyDH2201)the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB42000000)the National Key Research and Development Program of China(Grant No.2019YFA0708502)。
文摘Hydrous minerals in the subducting slabs are potential water carriers into the deep mantle,and thus the synthesis of new hydrous phases is significant in our understanding of water circulation throughout the Earth’s interior.In this study,we report the two new hydrous phases,Al_(2)SiO_(6)H_(2)and Al_(5.5)Si_(4)O_(18)H_(3.5)(hereafter referred to simply as phases Psi and Phi,respectively),which are synthesized in the Al_(2)O_(3)-SiO_(2)-H_(2)O system at 15.5 GPa,1400℃and 17.5 GPa,1600℃ by using Sakura2500-ton multi-anvil apparatus.The luminescence spectra of Cr3+show the phase Psi has characteristic peaks at 687,693 and705 nm,while phase Phi has characteristic peaks at 691,696 and 708 nm.Single-crystal X-ray diffraction (SCXRD) refinements yield a monoclinic structure of both phases (space group P2_(1)) with ideal chemical formulae of Al_(2)SiO6H2and Al5.5Si4O18H3.5respectively.The determined lattice parameters for phase Psi are a=9.4168±0.0016Å,b=4.3441±0.0007Å,c=9.4360±0.002Åand β=119.726±0.005°at ambient pressure and 300 K,while the phase Phi has a=7.2549±0.0018Å,b=4.3144±0.001Å,c=8.0520±0.002Å,and β=101.740±0.009°at ambient pressure and 250 K.Electron microprobe analyses (EPMA) show the chemical compositions of phases Psi and Phi to be Al_(1.99)Si_(0.85)O_(6)H_(2.62)and Al_(5.58)Si_(2.81)O_(18)H_(8.03),respectively,which slightly deviate from the ideal formulae inferred from SCXRD measurements.This may result from the disorder or substitution of Al and Si by H in the crystal structures under our synthesis conditions.Our study suggests that phases Psi and Phi are the two potential water carriers at the upper part of the mantle transitions zone,providing new insights into how deep water is stored in this region.
基金supported by the National Natural Science Foundation of China(Nos.21877088.22171230)China Postdoctoral Science Foundation(No.2016M602861).
文摘Nano-drug delivery systems with multiple stimulus-responsive capabilities have superior response performance and efficient drug release.Nevertheless,it is sophisticated to construct multiple stimulus-responsive systems where the two or more functional groups need to be introduced simultaneously.Xanthate,one functional group with pH and H2O2 stimulus responsiveness,has significant potential applications for building dual-responsive drug delivery system.Herein,we present a novel dual stimuli-responsive supramolecular drug delivery system by using sodium xanthate derivative(SXD)as guest molecule and quaternary ammonium capped pillar[5]arene(QAP5)as host molecule through host-guest interaction on the basis of electrostatic interaction.The amphiphile QAP5⊃SXD could self-assemble into vesicles to efficiently load the anti-cancer drug DOX.The experimental results showed that QAP5⊃SXD nanoparticles could achieve efficient drug delivery and controlled release in the tumor microenvironment.Cytotoxicity experiments proved that DOX@QAP5⊃SXD nanoparticles could significantly improve the anticancer efficiency of free DOX on cancer cells.The present study provides an efficient strategy to develop supramolecular nanocarriers with dual-responsiveness in one functional group for controlled drug release.
基金supported by the National Natural Science Foundation of China(Grant Nos. 52076110 and 52106160)Jiangsu Provincial Natural Science Foundation of China(Grant Nos. BK20200490 and BK20220955)the Fundamental Research Funds for the Central Universities(Grant No. 30920031103)。
文摘In order to create effective combustion technologies and fuels with low or no carbon emissions,the research was conducted to assess the coupled interactive effects of NH_(3) and H_(2) additions on ethylene counterflow diffusion flames from a kinetic perspective.The effects of the NH_(3)/H_(2) combination on flame temperatures,major species,key radicals,important intermediate species,representative oxygenated species and NO_xwere examined.The results of the study utilizing fictitious inert NH_(3) and/or H_(2) revealed the chemical effects of the two components.It was found that the NH_(3)/H_(2) coupled effects had a more effective inhibitory effect on soot precursors than the effects of corresponding sum of single NH_(3) or H_(2) addition.The production of soot precursors was promoted by the coupled chemical effects of NH_(3) and H_(2),but the coupled dilution and thermal effects were observed to have a greater impact,resulting in a decrease of the mole fractions of soot precursors.As for the interaction of NH_(3) and H_(2) effects,the presence of H_(2) decreased the chemical effects of NH_(3) on the augmentation of C_(2)H_(2),A1,A2,and CH_(3)CHO mole fractions.The NH_(3) addition alleviated the H_(2) chemical effects on increasing C_(2)H_(2),C_(3)H_(3),A1 and A2 concentrations.Conversely,the NH_(3)chemical effects on C_(3)H_(3),OH and CH_(3)CHO were enhanced when H_(2) was added.The presence of NH_(3) augmented the chemical effects of H_(2) on the growth of OH mole fraction.Moreover,the H_(2) chemical effects hindered the production of NO and NO_(2) in the presence of NH_(3).
基金the National Natural Science Foundation of China(Nos.51868050,51938007,51878325,51868052,52100186,52170082,and 52063024)the Natural Science Foundation of Jiangxi Province(Nos.20202BAB213011 and 20181BBG78034)the Scientific Research Foundation of Nanchang Hangkong University(No.EA201902377)。
文摘Owing to the exorbitant overpotential and serious carrier recombination of graphitic carbon nitride(gC_(3)N_(4)),noble metal(NM)is usually served as the H_(2)evolution co-catalyst.Although the NM(such as Pt)nanoparticles can reduce the H_(2)evolution overpotential,the weak van der Waals interaction between Pt and g-C_(3)N_(4)makes against the charge transfer.Herein,the solvothermal method is developed to achieve semi-chemical interaction between Pt and g-C_(3)N_(4)nanotube(Pt-CNNT)for fast charge transfer.Moreover,the generated in-plane homojunction of CNNT can accelerate charge separation and restrain recombination.Meanwhile,the metallic Pt is an excellent H_(2)evolution co-catalyst.Photo/electrochemical tests verify that the semi-chemical interaction can improve photogenerated charge separation and transferability of CNNT.As a result,the photocatalytic H_(2)evolution turnover frequency(TOF)of Pt-CNNT under visible light irradiation reaches up to 918 h^(-1),which is one of the highest in the g-C_(3)N_(4)-based photocatalysts.This work provides a new idea to improve the charge transfer for efficient photocatalytic H_(2)evolution.
