Star-branched polyamide 6 was prepared via anionic ring-opening polymerization of ε-caprolactam in the presence of a simple benzene-centered trifunctional activator of N,N＇,N＂-trimesoyltricaprolactam. A high polyme...Star-branched polyamide 6 was prepared via anionic ring-opening polymerization of ε-caprolactam in the presence of a simple benzene-centered trifunctional activator of N,N＇,N＂-trimesoyltricaprolactam. A high polymer yields of above 95% were achieved at 160 ℃ for 15 min utilizing ε-caprolactam magnesium bromide as a catalyst. Compared with its linear counterpart, the resultant star-branched polyamide 6 showed smaller relative viscosity （1.51 ）, decreased melting temperature （218 ℃） and lower crystallinity （24.2%）. The specific properties demonstrated the existence of a star-branched structure and provided potential advantages in engineering applications.展开更多
Ischemia–reperfusion injury is a common pathophysiological mechanism in retinal degeneration.PANoptosis is a newly defined integral form of regulated cell death that combines the key features of pyroptosis,apoptosis,...Ischemia–reperfusion injury is a common pathophysiological mechanism in retinal degeneration.PANoptosis is a newly defined integral form of regulated cell death that combines the key features of pyroptosis,apoptosis,and necroptosis.Oligomerization of mitochondrial voltage-dependent anion channel 1 is an important pathological event in regulating cell death in retinal ischemia–reperfusion injury.However,its role in PANoptosis remains largely unknown.In this study,we demonstrated that voltage-dependent anion channel 1 oligomerization-mediated mitochondrial dysfunction was associated with PANoptosis in retinal ischemia–reperfusion injury.Inhibition of voltage-dependent anion channel 1 oligomerization suppressed mitochondrial dysfunction and PANoptosis in retinal cells subjected to ischemia–reperfusion injury.Mechanistically,mitochondria-derived reactive oxygen species played a central role in the voltagedependent anion channel 1-mediated regulation of PANoptosis by promoting PANoptosome assembly.Moreover,inhibiting voltage-dependent anion channel 1 oligomerization protected against PANoptosis in the retinas of rats subjected to ischemia–reperfusion injury.Overall,our findings reveal the critical role of voltage-dependent anion channel 1 oligomerization in regulating PANoptosis in retinal ischemia–reperfusion injury,highlighting voltage-dependent anion channel 1 as a promising therapeutic target.展开更多
A series of wear and flame resistant polyamide 6(PA6)composites were prepared using glass fiber(GF)and talc(T)as reinforcer,polytetrafluoroethylene(PTFE)and graphite(Gr)as solid lubricants,red phosphorus(RP)and zinc b...A series of wear and flame resistant polyamide 6(PA6)composites were prepared using glass fiber(GF)and talc(T)as reinforcer,polytetrafluoroethylene(PTFE)and graphite(Gr)as solid lubricants,red phosphorus(RP)and zinc borate(ZB)as flame retardant.The tribological property,mechanical property,flame retardant property and the flame retardant mechanism were investigated.The tests show that the formula of the wear resistant PA6 composite(WRPA 6)is PA6/GF/T/PTFE/Gr in the ratio of 100/15/5/10/5 by mass.Because this composite exhibits the lowest friction coefficient(0.1429)and no wear mass loss,the introduction of RP and ZB can increase the flame resistance of WRPA6,and the synergistic effect of RP and ZB is obtained.Detailedly,the composite with 4 parts of ZB and 12 parts of RP shows the best flame retardant property,achieving the highest limiting oxygen index(LOI)(30.2 vol%)and a UL94 V-0 rating,and the flame retardant mechanisms may be gas phase along with condense phase mechanism.展开更多
We report on the synthesis and characterizations of TiO2 nanoparticles embedded in polyamide-6composite nanofibers by using electrospinning technique. The influence of substrate on the electrical characteristics of po...We report on the synthesis and characterizations of TiO2 nanoparticles embedded in polyamide-6composite nanofibers by using electrospinning technique. The influence of substrate on the electrical characteristics of polyamide-6/TiO2 composite nanofibers was investigated. The resultant nanofibers exhibit good incorporation of TiO2 nanoparticles. The doping of TiO2 nanoparticles into the polyamide-6 nanofibers were confirmed by high resolution transmission electron microscopy and energy dispersive X-ray spectroscopy. Photoluminescence（PL） and cathodoluminescence（CL） spectroscopy were also used to characterize the samples.The PL and CL spectra reveal that the as-spun polyamide-6/TiO2 composite nanofibers consisted of overlapping of two broad emission bands due to the contribution of polyamide-6（centered at about 475 nm）, which might originate from organic functional groups of polyamide-6 and TiO2 nanoparticles（centered around 550 nm）. The electrical conductivity of the polyamide-6/TiO2 composite nanofibers on different substrates was carried out.It was found that the electrical conductivity of the polyamide-6/TiO2 composite nanofibers on silicon substrate was in the range of 13 μA, and about 1 to 20 p A for the paper and glass substrates.展开更多
The growth kinetics of microarc oxidation(MAO)coatings on Ti6Al4V alloy was studied by designing an electrolyte with low PO_(4)^(3−)content and high B_(4)O_(7)^(2−)content,using scanning electron microscopy,transmissi...The growth kinetics of microarc oxidation(MAO)coatings on Ti6Al4V alloy was studied by designing an electrolyte with low PO_(4)^(3−)content and high B_(4)O_(7)^(2−)content,using scanning electron microscopy,transmission electron microscopy,X-ray diffraction,and potentiodynamic polarization.The results showed that B_(4)O_(7)^(2−)increased the spark intensity and dissolved most of the oxides at high temperatures.Then,a thicker barrier layer at the coating/substrate interface was produced,which increased the polarization resistance of the coating.PO_(4)^(3−)at a low concentration also promoted the uniform growth of the MAO coating and the formation of hat-shaped holes in the outer deposition layer.The thickness of the MAO coatings obtained in Na_(2)B_(4)O_(7) electrolytes exhibited an exponential increase with time at spark discharge stage,while that of the MAO coating obtained in phosphate–tetraborate electrolytes showed a linear trend as the PO_(4)^(3−)content increased.展开更多
In this research, the morphologies, isothermal-crystallization kinetics, and spherulite growth of aliphatic polyketone/polyamide-6 blends were studied. A single glass-transition temperature （Tg） was determined, and ...In this research, the morphologies, isothermal-crystallization kinetics, and spherulite growth of aliphatic polyketone/polyamide-6 blends were studied. A single glass-transition temperature （Tg） was determined, and the composition dependence of Tg for these blends was well described by the Kwei equation. The strong intermolecular interaction between the two polymer components was confirmed by melting-point depression. The isothermal-crystallization kinetics were analyzed on the basis of the Avrami approach. A linear increase in the radii of the spherulites with time was observed for all compositions. All the spherulites continued to grow at nearly identical growth rates. With increasing polyamide-6 content, the size of the spherulites in the polyketone/polyamide-6 blends gradually decreased, and the number of spherulites in the blends increased.展开更多
The asymmetric polyamide-6 （PA6） membranes were prepared by thermally induced phase separation. From the scanning electron microscopy （SEM） images, it is observed that with the increase of silicon dioxide （SiO2）...The asymmetric polyamide-6 （PA6） membranes were prepared by thermally induced phase separation. From the scanning electron microscopy （SEM） images, it is observed that with the increase of silicon dioxide （SiO2） content the structure of obtained membranes gradually varied from cellular structure to large ball-shaped cluster aggregates. Subsequently, with the addition of SiO2, pure water flux increased first and then decreased, while rejection showed the opposite trend. Besides, raising the coagulation bath temperature was favorable to increase pure water flux. Consequently, different membrane morphologies and performance were obtained by changing SiO2 content and coagulation bath temperature.展开更多
Inorganic lead halide perovskite nanocrystals(NCs)with superior photoelectric properties are expected to have excellent performance in many fields.However,the anion exchange changes their features and is unfavorable f...Inorganic lead halide perovskite nanocrystals(NCs)with superior photoelectric properties are expected to have excellent performance in many fields.However,the anion exchange changes their features and is unfavorable for their applications in many fields.Hence,impeding anion exchange is important for improving the composition stability of inorganic lead halide perovskite NCs.Herein,CsPb X3(X=Cl,Br)NCs are coated with Cs4PbX6 shell to impede anion exchange and reduce anion mobility.The Cs4PbX6 shell is facily fabricated on CsPbX3 NCs through high temperature injection method.Anion exchange experiments demonstrate that the Cs4 PbX6 shell completely encapsulates CsPbX3 NCs and greatly improves the composition stability of CsPbX3 NCs.Moreover,our work also sheds light on the potential design approaches of various heterostructures to expand the application of CsPbM3(M=Cl,Br,I)NCs.展开更多
A statistical approach is developed, based on a Monte Carlo method, in order to determine the statistical composition of a polyamide-6 sample composed of caprolactam （an AB-type monomer） and of a di-acid （A2 type）...A statistical approach is developed, based on a Monte Carlo method, in order to determine the statistical composition of a polyamide-6 sample composed of caprolactam （an AB-type monomer） and of a di-acid （A2 type） or a tri- acid （A3 type） as coupling agents. For this composition, the linear theological behavior of these systems is predicted using a tube-based theory. This allows us to show that while coupling agents of type A2 can be seen as flow improver, the effect of branching agents of type A3, depending on the synthesis recipe and the conversion level, can lead either to an increase or to a decrease of the viscosity. By adding specific amount of these agents, we also show that it is possible to obtain materials with the same zero-shear viscosity but with different shear thinning behavior. Furthermore, the polydispersity of linear samples of the same average number molecular weight, Mn, is discussed in function of the amount of A2 monomers they contain. Ranging from 2 to 1.5, this difference in polydispersity is expected to have a significant influence on the processing behavior of such materials.展开更多
Photocatalytic ammonia generation via nitrogen reduction reaction(NRR)is a green and prospective nitrogen fixation technique.However,NRR is often hampered by the high N_(2) adsorption/activation energies and is accomp...Photocatalytic ammonia generation via nitrogen reduction reaction(NRR)is a green and prospective nitrogen fixation technique.However,NRR is often hampered by the high N_(2) adsorption/activation energies and is accompanied by a slow kinetics oxygen evolution reaction(OER).Herein,a robust Bi_(2)S_(3)/OVBi_(2)MoO_(6)S-scheme heterojunction is constructed using a simple in-situ anion exchange process,which enables oxygen vacancy(OVs)abundant Bi_(2)Mo O_(6) microspheres with surface deposited Bi_(2)S_(3).The asfabricated Bi_(2)S_(3)/OVBi_(2)MoO_(6) functioned as an effective photocatalyst to convert N_(2)-to-NH_(3) under mild conditions.The photocatalytic NH_(3)/NH_(4)^(+) production rate reached 126μmol g_(cat)^(-1)under visible light for2.5 h with 2%of Bi_(2)S_(3)/OVBi_(2)MoO_(6)photocatalyst,which was 8-fold higher than pristine Bi_(2)MoO_(6).Furthermore,the as-fabricated Bi_(2)S_(3)/Bi_(2)MoO_(6)heterojunction exhibited good selectivity,high stability and reproducibility.The excellent photocatalytic NRR performance was ascribed to the Bi_(2)S_(3)/Bi_(2)MoO_(6)heterojunction formed subsequent to the strong interaction between Bi_(2)S_(3)and Bi_(2)MoO_(6).The OVs facilitated the chemical adsorption process allowing activation of N_(2)molecule on the Bi_(2)S_(3)/Bi_(2)MoO_(6).Simultaneously,the S-scheme heterojunction prolonged the lifetime of photogenerated carriers,accelerated the electrons/holes spatial separation and accumulation on the Bi_(2)S_(3)(reduction)and Bi_(2)MoO_(6)side(oxidation),respectively,thus strengthening both OER and NRR half-reactions.This simple in-situ anion exchange method offers a novel technique for strengthening OER and NRR half-reactions in Bi-based photocatalysts for effective photocatalytic ammonia generation.展开更多
The [CdCl_4]^（2-） anion as a structure inducer has proved to be useful in the construction of cucurbit[n]urilmetal coordination architectures and materials. In order to better understand the role and influence of th...The [CdCl_4]^（2-） anion as a structure inducer has proved to be useful in the construction of cucurbit[n]urilmetal coordination architectures and materials. In order to better understand the role and influence of the structure inducer in Q[n] systems, we report herein the self-assembly of Q[6] solely in the presence of[CdCl_4]^（2-）anions and in the presence of both a linear cationic organic vip and [CdCl_4]^（2-）anions. X-ray diffraction analysis revealed that 1D Q[6] porous channels were formed by the noncovalent interactions between Q[6] and [CdCl_4]^（2-）anions, but the ＇＇honeycomb effect＇＇ was not observed in the present study.However, it seems that the ＇＇honeycomb effect＇＇ and the self-assembly of Q[6] with [CdCl_4]^（2-）anions can be significantly modified and switched in the presence of a linear cationic dibutylamine vip through some unusual noncovalent interactions.展开更多
Two new supramolecular architectures {（HC2O4）2^2- [C6H（18）N2^2＋ C（36）H（36）N（24）O（12）]} 12H2O（1） and{（C6H5SO3）22 [C6H（18）N22＋ C（36）H（36）N（24）O（12）]} 12H2O（2） were synthesized and character...Two new supramolecular architectures {（HC2O4）2^2- [C6H（18）N2^2＋ C（36）H（36）N（24）O（12）]} 12H2O（1） and{（C6H5SO3）22 [C6H（18）N22＋ C（36）H（36）N（24）O（12）]} 12H2O（2） were synthesized and characterized by singlecrystal X-ray diffraction, thermogravimetric analysis and X-ray powder diffraction. Compound 1contains infinite two dimensional（2D） L18（8）14（8）8（4） type anion–water aggregates [（HC2O4）4（H2O）（22）]^4- and results in the construction of sandwich-like three dimensional（3D） networks. In compound 2, honeycomb-like three dimensional（3D） networks are fabricated by one dimensional（1D）＂W＂-like T5（0）A2 type anion–water clusters [（C6H5SO3）（H2O）6]^-. These results indicate that anionic groups play a crucial role in modulating the structures of water clusters with their spatial structure and binding sites. In these two structures, the majority of interactions are O...H and H...H interactions on the Hirshfeld surface, which means that hydrogen bonding and hydrophobic interactions are the dominate drive forces in forming these supramolecular systems.展开更多
基金supported by a grant from the National High Technology Research and Development Program of China(No.2014AA021201)the National Basic Research Program of China(No.2012CB721104)+1 种基金China Postdoctoral Science Foundation(No.2014M551574)the Priority Academic Program Development of Jiangsu Higher Education Institutions
文摘Star-branched polyamide 6 was prepared via anionic ring-opening polymerization of ε-caprolactam in the presence of a simple benzene-centered trifunctional activator of N,N＇,N＂-trimesoyltricaprolactam. A high polymer yields of above 95% were achieved at 160 ℃ for 15 min utilizing ε-caprolactam magnesium bromide as a catalyst. Compared with its linear counterpart, the resultant star-branched polyamide 6 showed smaller relative viscosity （1.51 ）, decreased melting temperature （218 ℃） and lower crystallinity （24.2%）. The specific properties demonstrated the existence of a star-branched structure and provided potential advantages in engineering applications.
基金supported by the National Natural Science Foundation of China,Nos.82172196(to KX),82372507(to KX)the Natural Science Foundation of Hunan Province,China,No.2023JJ40804(to QZ)the Key Laboratory of Emergency and Trauma(Hainan Medical University)of the Ministry of Education,China,No.KLET-202210(to QZ)。
文摘Ischemia–reperfusion injury is a common pathophysiological mechanism in retinal degeneration.PANoptosis is a newly defined integral form of regulated cell death that combines the key features of pyroptosis,apoptosis,and necroptosis.Oligomerization of mitochondrial voltage-dependent anion channel 1 is an important pathological event in regulating cell death in retinal ischemia–reperfusion injury.However,its role in PANoptosis remains largely unknown.In this study,we demonstrated that voltage-dependent anion channel 1 oligomerization-mediated mitochondrial dysfunction was associated with PANoptosis in retinal ischemia–reperfusion injury.Inhibition of voltage-dependent anion channel 1 oligomerization suppressed mitochondrial dysfunction and PANoptosis in retinal cells subjected to ischemia–reperfusion injury.Mechanistically,mitochondria-derived reactive oxygen species played a central role in the voltagedependent anion channel 1-mediated regulation of PANoptosis by promoting PANoptosome assembly.Moreover,inhibiting voltage-dependent anion channel 1 oligomerization protected against PANoptosis in the retinas of rats subjected to ischemia–reperfusion injury.Overall,our findings reveal the critical role of voltage-dependent anion channel 1 oligomerization in regulating PANoptosis in retinal ischemia–reperfusion injury,highlighting voltage-dependent anion channel 1 as a promising therapeutic target.
基金Project(149929)supported by the Postdoctoral Fund of Central South University,ChinaProject(16C0292)supported by the Hunan Education Department,ChinaProject(2016TP1022)supported by the Hunan Provincial Key Lab of Dark Tea and Jin-hua,China
文摘A series of wear and flame resistant polyamide 6(PA6)composites were prepared using glass fiber(GF)and talc(T)as reinforcer,polytetrafluoroethylene(PTFE)and graphite(Gr)as solid lubricants,red phosphorus(RP)and zinc borate(ZB)as flame retardant.The tribological property,mechanical property,flame retardant property and the flame retardant mechanism were investigated.The tests show that the formula of the wear resistant PA6 composite(WRPA 6)is PA6/GF/T/PTFE/Gr in the ratio of 100/15/5/10/5 by mass.Because this composite exhibits the lowest friction coefficient(0.1429)and no wear mass loss,the introduction of RP and ZB can increase the flame resistance of WRPA6,and the synergistic effect of RP and ZB is obtained.Detailedly,the composite with 4 parts of ZB and 12 parts of RP shows the best flame retardant property,achieving the highest limiting oxygen index(LOI)(30.2 vol%)and a UL94 V-0 rating,and the flame retardant mechanisms may be gas phase along with condense phase mechanism.
基金supported by a grant from the Korean Ministry of Education,Science and Technology(The Regional Core Research Program/Center for Healthcare Technology&Development,Chonbuk National University,Jeonju 561-756 Republic of Korea)
文摘We report on the synthesis and characterizations of TiO2 nanoparticles embedded in polyamide-6composite nanofibers by using electrospinning technique. The influence of substrate on the electrical characteristics of polyamide-6/TiO2 composite nanofibers was investigated. The resultant nanofibers exhibit good incorporation of TiO2 nanoparticles. The doping of TiO2 nanoparticles into the polyamide-6 nanofibers were confirmed by high resolution transmission electron microscopy and energy dispersive X-ray spectroscopy. Photoluminescence（PL） and cathodoluminescence（CL） spectroscopy were also used to characterize the samples.The PL and CL spectra reveal that the as-spun polyamide-6/TiO2 composite nanofibers consisted of overlapping of two broad emission bands due to the contribution of polyamide-6（centered at about 475 nm）, which might originate from organic functional groups of polyamide-6 and TiO2 nanoparticles（centered around 550 nm）. The electrical conductivity of the polyamide-6/TiO2 composite nanofibers on different substrates was carried out.It was found that the electrical conductivity of the polyamide-6/TiO2 composite nanofibers on silicon substrate was in the range of 13 μA, and about 1 to 20 p A for the paper and glass substrates.
文摘The growth kinetics of microarc oxidation(MAO)coatings on Ti6Al4V alloy was studied by designing an electrolyte with low PO_(4)^(3−)content and high B_(4)O_(7)^(2−)content,using scanning electron microscopy,transmission electron microscopy,X-ray diffraction,and potentiodynamic polarization.The results showed that B_(4)O_(7)^(2−)increased the spark intensity and dissolved most of the oxides at high temperatures.Then,a thicker barrier layer at the coating/substrate interface was produced,which increased the polarization resistance of the coating.PO_(4)^(3−)at a low concentration also promoted the uniform growth of the MAO coating and the formation of hat-shaped holes in the outer deposition layer.The thickness of the MAO coatings obtained in Na_(2)B_(4)O_(7) electrolytes exhibited an exponential increase with time at spark discharge stage,while that of the MAO coating obtained in phosphate–tetraborate electrolytes showed a linear trend as the PO_(4)^(3−)content increased.
文摘In this research, the morphologies, isothermal-crystallization kinetics, and spherulite growth of aliphatic polyketone/polyamide-6 blends were studied. A single glass-transition temperature （Tg） was determined, and the composition dependence of Tg for these blends was well described by the Kwei equation. The strong intermolecular interaction between the two polymer components was confirmed by melting-point depression. The isothermal-crystallization kinetics were analyzed on the basis of the Avrami approach. A linear increase in the radii of the spherulites with time was observed for all compositions. All the spherulites continued to grow at nearly identical growth rates. With increasing polyamide-6 content, the size of the spherulites in the polyketone/polyamide-6 blends gradually decreased, and the number of spherulites in the blends increased.
基金supported by the National Natural Science Foundation of China(No.20874073)National 863(high-tech research and development) Program of China(No.2007AA030304)Tianjin Science and Technology Key Support Plan (No.08ZCGYGX03700).
文摘The asymmetric polyamide-6 （PA6） membranes were prepared by thermally induced phase separation. From the scanning electron microscopy （SEM） images, it is observed that with the increase of silicon dioxide （SiO2） content the structure of obtained membranes gradually varied from cellular structure to large ball-shaped cluster aggregates. Subsequently, with the addition of SiO2, pure water flux increased first and then decreased, while rejection showed the opposite trend. Besides, raising the coagulation bath temperature was favorable to increase pure water flux. Consequently, different membrane morphologies and performance were obtained by changing SiO2 content and coagulation bath temperature.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11474018,61704007,and 61575019)the National Key Research and Development Program of China(Grant No.2017YFB0404501)+1 种基金the Fundamental Research Funds for the Central Universities,China(Grant No.2017RC034)the Shenzhen China Star Optoelectronics Technology Co.,Ltd
文摘Inorganic lead halide perovskite nanocrystals(NCs)with superior photoelectric properties are expected to have excellent performance in many fields.However,the anion exchange changes their features and is unfavorable for their applications in many fields.Hence,impeding anion exchange is important for improving the composition stability of inorganic lead halide perovskite NCs.Herein,CsPb X3(X=Cl,Br)NCs are coated with Cs4PbX6 shell to impede anion exchange and reduce anion mobility.The Cs4PbX6 shell is facily fabricated on CsPbX3 NCs through high temperature injection method.Anion exchange experiments demonstrate that the Cs4 PbX6 shell completely encapsulates CsPbX3 NCs and greatly improves the composition stability of CsPbX3 NCs.Moreover,our work also sheds light on the potential design approaches of various heterostructures to expand the application of CsPbM3(M=Cl,Br,I)NCs.
文摘A statistical approach is developed, based on a Monte Carlo method, in order to determine the statistical composition of a polyamide-6 sample composed of caprolactam （an AB-type monomer） and of a di-acid （A2 type） or a tri- acid （A3 type） as coupling agents. For this composition, the linear theological behavior of these systems is predicted using a tube-based theory. This allows us to show that while coupling agents of type A2 can be seen as flow improver, the effect of branching agents of type A3, depending on the synthesis recipe and the conversion level, can lead either to an increase or to a decrease of the viscosity. By adding specific amount of these agents, we also show that it is possible to obtain materials with the same zero-shear viscosity but with different shear thinning behavior. Furthermore, the polydispersity of linear samples of the same average number molecular weight, Mn, is discussed in function of the amount of A2 monomers they contain. Ranging from 2 to 1.5, this difference in polydispersity is expected to have a significant influence on the processing behavior of such materials.
基金financially supported by the National Natural Science Foundation of China(Nos.22168040,21666039,21663030)the Open Project of State Key Laboratory of Organic-Inorganic Composites Beijing Key Laboratory,Beijing University of Chemical Technology Beijing(No.oic-201901009)+3 种基金the Project of Science&Technology Office of Shaanxi Province(Nos.2018TSCXL-NY-02–01,2020JQ-791)the Project of Yan’an Science and Technology Bureau(No.2018KG-04)the Graduate Innovation Project of Yan’an University(No.YCX2020005)the Open Project of Chongqing Key Laboratory of Inorganic Special Functional Materials,Yangtze Normal University(No.KFKT202001)。
文摘Photocatalytic ammonia generation via nitrogen reduction reaction(NRR)is a green and prospective nitrogen fixation technique.However,NRR is often hampered by the high N_(2) adsorption/activation energies and is accompanied by a slow kinetics oxygen evolution reaction(OER).Herein,a robust Bi_(2)S_(3)/OVBi_(2)MoO_(6)S-scheme heterojunction is constructed using a simple in-situ anion exchange process,which enables oxygen vacancy(OVs)abundant Bi_(2)Mo O_(6) microspheres with surface deposited Bi_(2)S_(3).The asfabricated Bi_(2)S_(3)/OVBi_(2)MoO_(6) functioned as an effective photocatalyst to convert N_(2)-to-NH_(3) under mild conditions.The photocatalytic NH_(3)/NH_(4)^(+) production rate reached 126μmol g_(cat)^(-1)under visible light for2.5 h with 2%of Bi_(2)S_(3)/OVBi_(2)MoO_(6)photocatalyst,which was 8-fold higher than pristine Bi_(2)MoO_(6).Furthermore,the as-fabricated Bi_(2)S_(3)/Bi_(2)MoO_(6)heterojunction exhibited good selectivity,high stability and reproducibility.The excellent photocatalytic NRR performance was ascribed to the Bi_(2)S_(3)/Bi_(2)MoO_(6)heterojunction formed subsequent to the strong interaction between Bi_(2)S_(3)and Bi_(2)MoO_(6).The OVs facilitated the chemical adsorption process allowing activation of N_(2)molecule on the Bi_(2)S_(3)/Bi_(2)MoO_(6).Simultaneously,the S-scheme heterojunction prolonged the lifetime of photogenerated carriers,accelerated the electrons/holes spatial separation and accumulation on the Bi_(2)S_(3)(reduction)and Bi_(2)MoO_(6)side(oxidation),respectively,thus strengthening both OER and NRR half-reactions.This simple in-situ anion exchange method offers a novel technique for strengthening OER and NRR half-reactions in Bi-based photocatalysts for effective photocatalytic ammonia generation.
基金supported by the National Natural Science Foundation of China (No. 21361006)‘‘Chun-Hui’’ Fund of Chinese Ministry of Education (No. Z2011037)Guizhou University (No. 20127027)
文摘The [CdCl_4]^（2-） anion as a structure inducer has proved to be useful in the construction of cucurbit[n]urilmetal coordination architectures and materials. In order to better understand the role and influence of the structure inducer in Q[n] systems, we report herein the self-assembly of Q[6] solely in the presence of[CdCl_4]^（2-）anions and in the presence of both a linear cationic organic vip and [CdCl_4]^（2-）anions. X-ray diffraction analysis revealed that 1D Q[6] porous channels were formed by the noncovalent interactions between Q[6] and [CdCl_4]^（2-）anions, but the ＇＇honeycomb effect＇＇ was not observed in the present study.However, it seems that the ＇＇honeycomb effect＇＇ and the self-assembly of Q[6] with [CdCl_4]^（2-）anions can be significantly modified and switched in the presence of a linear cationic dibutylamine vip through some unusual noncovalent interactions.
基金the financial support by the National Natural Science Foundation of China(Nos.21202037and 21401044)Doctor Fund of Henan University of Technology(No.2013BS066)
文摘Two new supramolecular architectures {（HC2O4）2^2- [C6H（18）N2^2＋ C（36）H（36）N（24）O（12）]} 12H2O（1） and{（C6H5SO3）22 [C6H（18）N22＋ C（36）H（36）N（24）O（12）]} 12H2O（2） were synthesized and characterized by singlecrystal X-ray diffraction, thermogravimetric analysis and X-ray powder diffraction. Compound 1contains infinite two dimensional（2D） L18（8）14（8）8（4） type anion–water aggregates [（HC2O4）4（H2O）（22）]^4- and results in the construction of sandwich-like three dimensional（3D） networks. In compound 2, honeycomb-like three dimensional（3D） networks are fabricated by one dimensional（1D）＂W＂-like T5（0）A2 type anion–water clusters [（C6H5SO3）（H2O）6]^-. These results indicate that anionic groups play a crucial role in modulating the structures of water clusters with their spatial structure and binding sites. In these two structures, the majority of interactions are O...H and H...H interactions on the Hirshfeld surface, which means that hydrogen bonding and hydrophobic interactions are the dominate drive forces in forming these supramolecular systems.
