Based on the theoretical model of anion coordination polyhedron growth units, the growth mechanism of the basic magnesium chloride whisker was discussed in this paper.It was found that the basic magnesium chloride whi...Based on the theoretical model of anion coordination polyhedron growth units, the growth mechanism of the basic magnesium chloride whisker was discussed in this paper.It was found that the basic magnesium chloride whisker habits were related to the different environments in which anion coordination polyhedra grew. The growth units of basic magnesium chloride whiskers are [Mg - (OH) 4]2 -and [Mg - Cl 4]2 -. The growth process is the incorporation process of growth units. Growth units will have different incorporations and orientations caused by different system characters or heating. Furthermore, the formation mechanism of basic magnesium chloride whiskers was also interpreted using anion coordination polyhedron growth units.展开更多
Zinc-air batteries have recently attracted considerable interest owing to the larger storage capacity and lower cost compared to their lithium-ion counterparts. Electrode catalysts for the oxygen reduction reaction （...Zinc-air batteries have recently attracted considerable interest owing to the larger storage capacity and lower cost compared to their lithium-ion counterparts. Electrode catalysts for the oxygen reduction reaction （ORR） and oxygen evolution reaction （OER） play a critical role in the operation of rechargeable zinc-air batteries. Herein, we report a simple and scalable strategy to fabricate porous carbon polyhedra using Zn-doped Co-based zeolitic imidazolate frameworks （ZnCo-ZIFs） as precursors. Strikingly, Zn doping leads to smaller Co nanoparticles and higher nitrogen content, which in turn enhances the ORR and OER activities of the obtained porous carbon polyhedra. The synergistic effect of the N-doped carbon and cobalt nanoparticles in the composite, the improved conductivity resulting from the high graphitization of carbon, and the large surface area of the porous polyhedral structure resulted in porous carbon polyhedra with excellent ORR and OER electrocatalytic activity in alkaline media. More importantly, air cathodes based on the optimal porous carbon polyhedra further exhibited superior performance to Pt/C catalysts in primary and rechargeable zinc-air batteries.展开更多
A series of unique nanowire superstructures, Cu2O nanowire polyhedra, have been synthesized through a cost-effective hydrothermal route. Three types of nanowire polyhedra, namely octahedra, concave octahedra, and hexa...A series of unique nanowire superstructures, Cu2O nanowire polyhedra, have been synthesized through a cost-effective hydrothermal route. Three types of nanowire polyhedra, namely octahedra, concave octahedra, and hexapods, were formed in high morphological yields （90%） by reducing cupric acetate with o-anisidine or o-phenetidine in the presence of carboxylic acids. The architectures of these Cu2O nanowire polyhedra were examined by electron microscopy, which revealed ordered, highly aligned CU2O nanowires within the polyhedral outlines. The growth of the Cu2O nanowire polyhedra is controlled by the orientation and growth rates of the nanowire branches which are adjusted by addition of carboxylic acids. Compared to the Cu2O samples reported in the recent literature, the Cu2O nanowire octahedra exhibit notably enhanced photocatalytic activities for dye degradation in the presence of H202 under visible light, probably due to the high-density charge carriers photoexcited from the branched nanowires with their special structures. Additionally, the discussion in the recent literature of the photocatalytic activity of Cu2O in the absence of H2O2 for direct photodegradation of dyes seems questionable.展开更多
The growth units and formation mechanisms of quartz(SiO_2)and barium titanate (BaTiO_3)crystals under hydrothermal conditions have been investigated by means of cataphoretic experi- ments.It is proposed that the growt...The growth units and formation mechanisms of quartz(SiO_2)and barium titanate (BaTiO_3)crystals under hydrothermal conditions have been investigated by means of cataphoretic experi- ments.It is proposed that the growth units of the crystals in hydrothermal solutions have the structures of coordinative polyhedra of anions,which correspond to those of coordinative polyhedra in the crystals. The relationship between crystal morphology and physico-chemical conditions has been explained accord- ing to the modes of incorporation of the coordinative polyhedra of anions on the various faces of crystals. The dimensions of the growth units vary with the change of the growth condition.The incorporation rates on the various faces of the growth units with varied dimensions must be different,which leads to a satis- factory explanation for the variety of the crystal morphology.展开更多
The challenge for single-atom catalysts in various C-C cross coupling reaction exists in the development of solid supporting materials.It has been desired tofind a supporting material designed in molecular level to an...The challenge for single-atom catalysts in various C-C cross coupling reaction exists in the development of solid supporting materials.It has been desired tofind a supporting material designed in molecular level to anchor a single-atom catalyst and provide high degree of dispersion and substrate access in aqueous media.Here,we prepared discrete cages of metal-organic polyhedra anchoring single Pd atom(MOP-BPY(Pd))and successfully performed a Suzuki-Miyaura cross coupling reaction with various substrates in aqueous media.It was revealed that each tetrahedral cage of MOP-BPY(Pd)has 4.5 Pd atoms on average and retained its high degree of dispersion up to 3 months in water.The coupling efficiencies of the Suzuki-Miyaura cross coupling reaction exhibited more than 90.0%for various substrates we have tested in the aqueous media,which is superior to those of the molecular Pd complex and metal-organic framework(MOF)anchoring Pd atoms.Moreover,MOP-BPY(Pd)was successfully recovered and recycled without performance degradation.展开更多
Photoresponsiveness of materials is critical to their tunability and efficiency in terminal applications.Photoresponsive metal-organic polyhedra(PMOPs)feature intrinsic pores and remote controllability,but aggregation...Photoresponsiveness of materials is critical to their tunability and efficiency in terminal applications.Photoresponsive metal-organic polyhedra(PMOPs)feature intrinsic pores and remote controllability,but aggregation of PMOPs in solid state hampers their photoresponsiveness seriously.Herein,we report the construction of a new PMOP(Cu_(24)(C_(16)H_(12)N_(2)O_(4))_(12)(C_(18)H_(22)O_(5))12,denoted as MOP-PR-LA),where long alkyl(LA)chains act as the intermolecular poles,propping against adjacent PMOP molecules to create individual microenvironment benefiting the isomerization of photoresponsive(PR)moieties.Upon ultraviolet(UV)-and visible-light irradiation,MOP-PR-LA is much easier to isomerize than the counterpart MOP-PR without LA.For propylene adsorption,MOP-PR has a low change of adsorption capacity(9.9%),while that of MOP-PR-LA reaches 58.6%.Density functional theory calculations revealed that PR in the cis state has a negative effect on adsorption,while the trans state of PR favors adsorption.This work might open an avenue for the construction of photoresponsive materials with high responsiveness and controllability.展开更多
Based on the generalized gauge function, a numerical criterion which specifies the topological rela-tionship between convex polyhedra is presented. It can be applied to detecting the overlap, just contact or separatio...Based on the generalized gauge function, a numerical criterion which specifies the topological rela-tionship between convex polyhedra is presented. It can be applied to detecting the overlap, just contact or separation between two sets of convex polyhedra. As the solution of a linear programming problem, the value of this criterion can be calculated easily. The presented criterion is available to provide heuristic information for generating intermediate configuration point as well as checking the hypothesized path for admissibility in flexible-trajectory path planning ap-proach.展开更多
Based on the concept of gauge function, the pseudo minimum translational distance (PMTD) between two convex objects is defined in this paper. PMTD not only provides a measure of the clearance between two separating ob...Based on the concept of gauge function, the pseudo minimum translational distance (PMTD) between two convex objects is defined in this paper. PMTD not only provides a measure of the clearance between two separating objects, but also quantifies the penetration of two objects intersecting each other. It is proved that the PMTD is differentiate almost everywhere w. r.t. the configuration variable of the objects. Algorithms for calculating PMTD and its derivative are also presented.展开更多
Convex polyhedral cuprate clusters are being formed through lateral frustration when the a and c lattice parameters of the tetragonal ACuO2 infinite layer structure will become identical by substitution of a large cat...Convex polyhedral cuprate clusters are being formed through lateral frustration when the a and c lattice parameters of the tetragonal ACuO2 infinite layer structure will become identical by substitution of a large cation (A = Ba2+). However, the corner-shared CuO2 plaquettes of the infinite network suffer a topotactic rearrangement forming edge-connected units, for instance Cu18O24 cages (polyhedron notation [4641238]) with 2 compound (space group P4/ nmm) will be discussed. The possibility to construct a cuprate super-cage with m3m symmetry (polyhedron notation [4641242438]) is being reported. This super-cage still consists of edge-connected CuO2 plaquettes when fully decorated with copper ions, but with different curvatures, arranged in circles of 9.39 ? of diameter with 139.2° Cu-O-Cu antiferromagnetic super-exchange interaction. On the one hand, the realization of such a quite stable cuprate super-cage as a candidate for high-Tc superconductivity depends on whether a template of suitable size such as the cation or C(CH3)4 enables its formation, and on the other hand the cage can further be stabilized by highly charged cations located along the [111] direction. Synthesis options will be proposed based on suggested cage formation pathways. An X-ray powder pattern was calculated for a less dense cluster structure of Im3m space group with a lattice parameter of a = 14.938 ? and two formula units of Cu46O51 to facilitate future identification. Characteristic X-ray scattering features as identification tool were obtained when the electron distribution of the hollow polyhedron was approximated with electron density in a spherical shell.展开更多
Silicon(Si)holds promise as an anode material for lithium-ion batteries(LIBs)as it is widely avail-able and characterized by high specific capacity and suitable working potential.However,the relatively low electrical ...Silicon(Si)holds promise as an anode material for lithium-ion batteries(LIBs)as it is widely avail-able and characterized by high specific capacity and suitable working potential.However,the relatively low electrical conductivity of Si and the significantly high extent of volume expansion realized dur-ing lithiation hinder its practical application.We prepared N-doped carbon polyhedral micro cage en-capsulated Si nanoparticles derived from Co-Mo bimetal metal-organic framework(MOFs)(denoted as Si/CoMo@NCP)and explored their lithium storage performance as anode materials to address these prob-lems.The Si/CoMo@NCP anode exhibited a high reversible lithium storage capacity(1013 mAh g^(−1)at 0.5 A g^(−1)after 100 cycles),stable cycle performance(745 mAh g^(−1)at 1 A g^(−1)after 400 cycles),and excellent rate performance(723 mAh g^(−1)at 2 A g^(−1)).Also,the constructed the full-cell NCM 811//Si/CoMo@NCP exhibited well reversible capacity.The excellent electrochemical performances of Si/CoMo@NCP were at-tributed to two unique properties.The encapsulation of NCP with doped nitrogen and porous structural carbon improves the electrical conductivity and cycling stability of the molecules.The introductions of metallic cobalt and its oxides help to improve the rate capability and lithiation capacity of the materials following multi-electron reaction mechanisms.展开更多
In the late phase of Bombyx mori nucleopolyhedrovirus(BmNPV)infection,a large amount of polyhedra appear in the infected cell nucleolus,these polyhedra being dense protein crystals protecting the incorporated virions ...In the late phase of Bombyx mori nucleopolyhedrovirus(BmNPV)infection,a large amount of polyhedra appear in the infected cell nucleolus,these polyhedra being dense protein crystals protecting the incorporated virions from the harsh environment.To investigate whether the foreign protein could be immobilized into the polyhedra of BmNPV,two recombinant baculoviruses were generated by a novel BmNPV polyhedrin-plus(polh +)Bac-to-Bac system,designated as vBmBac(polh +)-enhanced green fluorescent protein(EGFP)and vBmBac(polh +)-LacZ,which can express the polyhedrin and foreign protein simultaneously.Light microscopy analysis showed that all viruses produced polyhedra of normal appearance.Green fluorescence can be apparently detected on the surface of the vBmBac(polh +)-EGFP polyhedra,but not the BmNPV polyhedra.Fluorescence analysis and anti-desiccation testing confirmed that EGFP was embedded in the polyhedra.As expected,the vBmBac(polh +)-LacZ polyhedra contained an amount of LacZ and had a higherβ-galactosidase activity.Sodium dodecyl sulfate polyacrylamide gel electrophoresis(SDS-PAGE)and Western blotting were also performed to verify if the foreign proteins were immobilized into polyhedra.This study provides a new inspiration for efficient preservation of useful proteins and development of new pesticides with toxic proteins.展开更多
基金supported by the National Natural Science Foundation of China (Grant Nos. 40776071, 40976074)
文摘Based on the theoretical model of anion coordination polyhedron growth units, the growth mechanism of the basic magnesium chloride whisker was discussed in this paper.It was found that the basic magnesium chloride whisker habits were related to the different environments in which anion coordination polyhedra grew. The growth units of basic magnesium chloride whiskers are [Mg - (OH) 4]2 -and [Mg - Cl 4]2 -. The growth process is the incorporation process of growth units. Growth units will have different incorporations and orientations caused by different system characters or heating. Furthermore, the formation mechanism of basic magnesium chloride whiskers was also interpreted using anion coordination polyhedron growth units.
文摘Zinc-air batteries have recently attracted considerable interest owing to the larger storage capacity and lower cost compared to their lithium-ion counterparts. Electrode catalysts for the oxygen reduction reaction （ORR） and oxygen evolution reaction （OER） play a critical role in the operation of rechargeable zinc-air batteries. Herein, we report a simple and scalable strategy to fabricate porous carbon polyhedra using Zn-doped Co-based zeolitic imidazolate frameworks （ZnCo-ZIFs） as precursors. Strikingly, Zn doping leads to smaller Co nanoparticles and higher nitrogen content, which in turn enhances the ORR and OER activities of the obtained porous carbon polyhedra. The synergistic effect of the N-doped carbon and cobalt nanoparticles in the composite, the improved conductivity resulting from the high graphitization of carbon, and the large surface area of the porous polyhedral structure resulted in porous carbon polyhedra with excellent ORR and OER electrocatalytic activity in alkaline media. More importantly, air cathodes based on the optimal porous carbon polyhedra further exhibited superior performance to Pt/C catalysts in primary and rechargeable zinc-air batteries.
基金This work was financially supported by the National Natural Science Foundation of China （No. 21071079）, the Research Fund of the State Key Laboratory of Materials-Oriented Chemical Engineering （2009）, and the Young Teachers Fund of Nanjing University of Technology.
文摘A series of unique nanowire superstructures, Cu2O nanowire polyhedra, have been synthesized through a cost-effective hydrothermal route. Three types of nanowire polyhedra, namely octahedra, concave octahedra, and hexapods, were formed in high morphological yields （90%） by reducing cupric acetate with o-anisidine or o-phenetidine in the presence of carboxylic acids. The architectures of these Cu2O nanowire polyhedra were examined by electron microscopy, which revealed ordered, highly aligned CU2O nanowires within the polyhedral outlines. The growth of the Cu2O nanowire polyhedra is controlled by the orientation and growth rates of the nanowire branches which are adjusted by addition of carboxylic acids. Compared to the Cu2O samples reported in the recent literature, the Cu2O nanowire octahedra exhibit notably enhanced photocatalytic activities for dye degradation in the presence of H202 under visible light, probably due to the high-density charge carriers photoexcited from the branched nanowires with their special structures. Additionally, the discussion in the recent literature of the photocatalytic activity of Cu2O in the absence of H2O2 for direct photodegradation of dyes seems questionable.
基金the key research project in Climbing Program from the State Science and Technology Commission of China
文摘The growth units and formation mechanisms of quartz(SiO_2)and barium titanate (BaTiO_3)crystals under hydrothermal conditions have been investigated by means of cataphoretic experi- ments.It is proposed that the growth units of the crystals in hydrothermal solutions have the structures of coordinative polyhedra of anions,which correspond to those of coordinative polyhedra in the crystals. The relationship between crystal morphology and physico-chemical conditions has been explained accord- ing to the modes of incorporation of the coordinative polyhedra of anions on the various faces of crystals. The dimensions of the growth units vary with the change of the growth condition.The incorporation rates on the various faces of the growth units with varied dimensions must be different,which leads to a satis- factory explanation for the variety of the crystal morphology.
基金the Basic Science Research Program(No.NRF-2019R1A2C4069764)by Convergent Technology R&D Program for Hum an Augm entation(No.2019M3C1B8077549)through the National Research Foundation of Korea(NRF)funded by Ministry of Science and ICT.
文摘The challenge for single-atom catalysts in various C-C cross coupling reaction exists in the development of solid supporting materials.It has been desired tofind a supporting material designed in molecular level to anchor a single-atom catalyst and provide high degree of dispersion and substrate access in aqueous media.Here,we prepared discrete cages of metal-organic polyhedra anchoring single Pd atom(MOP-BPY(Pd))and successfully performed a Suzuki-Miyaura cross coupling reaction with various substrates in aqueous media.It was revealed that each tetrahedral cage of MOP-BPY(Pd)has 4.5 Pd atoms on average and retained its high degree of dispersion up to 3 months in water.The coupling efficiencies of the Suzuki-Miyaura cross coupling reaction exhibited more than 90.0%for various substrates we have tested in the aqueous media,which is superior to those of the molecular Pd complex and metal-organic framework(MOF)anchoring Pd atoms.Moreover,MOP-BPY(Pd)was successfully recovered and recycled without performance degradation.
基金the National Key R&D Program of China(No.2022YFB3806800)the National Science Fund for Distinguished Young Scholars(No.22125804)+1 种基金the National Natural Science Foundation of China(No.22078155)the Project of Priority Academic Program Development of Jiangsu Higher Education Institutions.
文摘Photoresponsiveness of materials is critical to their tunability and efficiency in terminal applications.Photoresponsive metal-organic polyhedra(PMOPs)feature intrinsic pores and remote controllability,but aggregation of PMOPs in solid state hampers their photoresponsiveness seriously.Herein,we report the construction of a new PMOP(Cu_(24)(C_(16)H_(12)N_(2)O_(4))_(12)(C_(18)H_(22)O_(5))12,denoted as MOP-PR-LA),where long alkyl(LA)chains act as the intermolecular poles,propping against adjacent PMOP molecules to create individual microenvironment benefiting the isomerization of photoresponsive(PR)moieties.Upon ultraviolet(UV)-and visible-light irradiation,MOP-PR-LA is much easier to isomerize than the counterpart MOP-PR without LA.For propylene adsorption,MOP-PR has a low change of adsorption capacity(9.9%),while that of MOP-PR-LA reaches 58.6%.Density functional theory calculations revealed that PR in the cis state has a negative effect on adsorption,while the trans state of PR favors adsorption.This work might open an avenue for the construction of photoresponsive materials with high responsiveness and controllability.
基金Project supported by the National Natural Science Foundation of China.
文摘Based on the generalized gauge function, a numerical criterion which specifies the topological rela-tionship between convex polyhedra is presented. It can be applied to detecting the overlap, just contact or separation between two sets of convex polyhedra. As the solution of a linear programming problem, the value of this criterion can be calculated easily. The presented criterion is available to provide heuristic information for generating intermediate configuration point as well as checking the hypothesized path for admissibility in flexible-trajectory path planning ap-proach.
基金the National Natural Science Foundation of China (Grant Nos. 59805004, 59990470) the National Distinguished Youth Foundation (Grant No. 59725514).
文摘Based on the concept of gauge function, the pseudo minimum translational distance (PMTD) between two convex objects is defined in this paper. PMTD not only provides a measure of the clearance between two separating objects, but also quantifies the penetration of two objects intersecting each other. It is proved that the PMTD is differentiate almost everywhere w. r.t. the configuration variable of the objects. Algorithms for calculating PMTD and its derivative are also presented.
文摘Convex polyhedral cuprate clusters are being formed through lateral frustration when the a and c lattice parameters of the tetragonal ACuO2 infinite layer structure will become identical by substitution of a large cation (A = Ba2+). However, the corner-shared CuO2 plaquettes of the infinite network suffer a topotactic rearrangement forming edge-connected units, for instance Cu18O24 cages (polyhedron notation [4641238]) with 2 compound (space group P4/ nmm) will be discussed. The possibility to construct a cuprate super-cage with m3m symmetry (polyhedron notation [4641242438]) is being reported. This super-cage still consists of edge-connected CuO2 plaquettes when fully decorated with copper ions, but with different curvatures, arranged in circles of 9.39 ? of diameter with 139.2° Cu-O-Cu antiferromagnetic super-exchange interaction. On the one hand, the realization of such a quite stable cuprate super-cage as a candidate for high-Tc superconductivity depends on whether a template of suitable size such as the cation or C(CH3)4 enables its formation, and on the other hand the cage can further be stabilized by highly charged cations located along the [111] direction. Synthesis options will be proposed based on suggested cage formation pathways. An X-ray powder pattern was calculated for a less dense cluster structure of Im3m space group with a lattice parameter of a = 14.938 ? and two formula units of Cu46O51 to facilitate future identification. Characteristic X-ray scattering features as identification tool were obtained when the electron distribution of the hollow polyhedron was approximated with electron density in a spherical shell.
基金the National Natural Science Foundation of China(NSFC,No.21203116)the Innovation Capability Support Plan of Shaanxi Province(Grant No.2022WGZJ-25)the Foundation of Shaanxi University of Science and Tech-nology(Grant No.210210031 and 210210032).
文摘Silicon(Si)holds promise as an anode material for lithium-ion batteries(LIBs)as it is widely avail-able and characterized by high specific capacity and suitable working potential.However,the relatively low electrical conductivity of Si and the significantly high extent of volume expansion realized dur-ing lithiation hinder its practical application.We prepared N-doped carbon polyhedral micro cage en-capsulated Si nanoparticles derived from Co-Mo bimetal metal-organic framework(MOFs)(denoted as Si/CoMo@NCP)and explored their lithium storage performance as anode materials to address these prob-lems.The Si/CoMo@NCP anode exhibited a high reversible lithium storage capacity(1013 mAh g^(−1)at 0.5 A g^(−1)after 100 cycles),stable cycle performance(745 mAh g^(−1)at 1 A g^(−1)after 400 cycles),and excellent rate performance(723 mAh g^(−1)at 2 A g^(−1)).Also,the constructed the full-cell NCM 811//Si/CoMo@NCP exhibited well reversible capacity.The excellent electrochemical performances of Si/CoMo@NCP were at-tributed to two unique properties.The encapsulation of NCP with doped nitrogen and porous structural carbon improves the electrical conductivity and cycling stability of the molecules.The introductions of metallic cobalt and its oxides help to improve the rate capability and lithiation capacity of the materials following multi-electron reaction mechanisms.
基金supported by the National Science Fund for Distinguished Young Scholars(22125804)the National Natural Science Foundation of China(22078155)the Project of Priority Academic Program Development of Jiangsu Higher Education Institutions。
基金supported by the National Basic Research Program(973)of China(No.2012CB114600)the Zhejiang Provincial Natural Science Foundation(No.Y3110058)the Public Agricultural Program of Zhejiang Province(No.2012C32G2010076),China
文摘In the late phase of Bombyx mori nucleopolyhedrovirus(BmNPV)infection,a large amount of polyhedra appear in the infected cell nucleolus,these polyhedra being dense protein crystals protecting the incorporated virions from the harsh environment.To investigate whether the foreign protein could be immobilized into the polyhedra of BmNPV,two recombinant baculoviruses were generated by a novel BmNPV polyhedrin-plus(polh +)Bac-to-Bac system,designated as vBmBac(polh +)-enhanced green fluorescent protein(EGFP)and vBmBac(polh +)-LacZ,which can express the polyhedrin and foreign protein simultaneously.Light microscopy analysis showed that all viruses produced polyhedra of normal appearance.Green fluorescence can be apparently detected on the surface of the vBmBac(polh +)-EGFP polyhedra,but not the BmNPV polyhedra.Fluorescence analysis and anti-desiccation testing confirmed that EGFP was embedded in the polyhedra.As expected,the vBmBac(polh +)-LacZ polyhedra contained an amount of LacZ and had a higherβ-galactosidase activity.Sodium dodecyl sulfate polyacrylamide gel electrophoresis(SDS-PAGE)and Western blotting were also performed to verify if the foreign proteins were immobilized into polyhedra.This study provides a new inspiration for efficient preservation of useful proteins and development of new pesticides with toxic proteins.
