A novel precursor of nickel-cobalt alloy powders with an appropriate Ni to Co molar ratio was prepared under selectively synthetic conditions. The composition and morphology of the precursor were characterized by X-ra...A novel precursor of nickel-cobalt alloy powders with an appropriate Ni to Co molar ratio was prepared under selectively synthetic conditions. The composition and morphology of the precursor were characterized by X-ray diffractometry （XRD）, scanning electron microscopy （SEM）, Fourier transform infrared spectrometry （FT-IR） and energy dispersive spectrometry （EDS）. The effects of pH value, reaction temperature, metal ion concentrations and surfactant on the morphology and the dispersion of precursor were investigated. The results show that the morphology of precursor depends on ammonia content in the precursor. A fibriform precursor is a complicated ammonia-containing nickel-cobalt oxalate. The uniform shape-controlled fibrous precursor is obtained under the following optimum conditions： ammonia as complex agent as well as pH adjustor, oxalate as coprecipitator, 50-65 °C of reaction temperature, 0.5-0.8 mol/L of total concentration of Ni2＋ and Co2＋, PVP as dispersant, and pH 8.0-8.4.展开更多
Morphological evolution of Pd nanoparticles was studied in a solution-phase synthesis using cetyltrimethylammonium bromide （CTAB） and CTAB/sodium citrate mixture as capping agents, respectively. The morphological di...Morphological evolution of Pd nanoparticles was studied in a solution-phase synthesis using cetyltrimethylammonium bromide （CTAB） and CTAB/sodium citrate mixture as capping agents, respectively. The morphological diversity of Pd nanoparticles is the combined effect of different Pd twinned seeds formed in the nucleation stage and selectively enlarging one set of crystallographic facets in the growth stage, both of which can be affected by the concentrations of CTAB. Through changing the concentrations of CTAB and sodium ascorbate, Pd nanoparticles with different shapes were obtained. When citrate ions were introduced to manipulate the nucleation and growth process, star-shaped icosahedra and nanorods with pentagram cross-sections were obtained. Pd nanoparticles with different shapes have quite different surface plasmon resonance and surface-enhanced Raman scattering properties.展开更多
To achieve environmentally benign energy conversion with the carbon neutrality target via electrochemical reactions, the innovation of electrocatalysts plays a vital role in the enablement of renewable resources. Nowa...To achieve environmentally benign energy conversion with the carbon neutrality target via electrochemical reactions, the innovation of electrocatalysts plays a vital role in the enablement of renewable resources. Nowadays, Pt-based nanocrystals(NCs) have been identified as one class of the most promising candidates to efficiently catalyze both the half-reactions in hydrogen-and hydrocarbonbased fuel cells. Here, we thoroughly discuss the key achievement in developing shape-controlled Pt and Pt-based NCs, and their electrochemical applications in fuel cells. We begin with a mechanistic discussion on how the morphology can be precisely controlled in a colloidal system, followed by highlighting the advanced development of shape-controlled Pt, Pt-alloy, Pt-based core@shell NCs, Pt-based nanocages, and Pt-based intermetallic compounds. We then select some case studies on models of typical reactions(oxygen reduction reaction at the cathode and small molecular oxidation reaction at the anode) that are enhanced by the shape-controlled Pt-based nanocatalysts. Finally, we provide an outlook on the potential challenges of shape-controlled nanocatalysts and envision their perspective with suggestions.展开更多
A facile solution-phase route for the synthesis of shape-controlled ZnO nanocrystals in a polyol/water mixture system was developed. The obtained nanocrystals were characterized by X-ray diffraction, transmission elec...A facile solution-phase route for the synthesis of shape-controlled ZnO nanocrystals in a polyol/water mixture system was developed. The obtained nanocrystals were characterized by X-ray diffraction, transmission electron microscopy and UV-visible absorption spectroscopy. The results indicate that modulating the adding ways of water has a significant effect on the shape of the obtained nanocrystals. The addition of small quantity of water can increase the growth rate of crystals and leads to the formation of different shapes. The resulting shapes of the novel structures are diverse, including spheres, cones, and teardrops, all of which are obtained without any additional surfactants. These studies concerning the shape evolution of nanocrystals should be valuable for further design and for greater understanding of advanced nanoscale building-block architectures.展开更多
Porous SnO_2 nanostructures with controlled shapes were synthesized by a facile morphologically conserved transformation from Sn C_2O_4 precursor approach. Well-defined Sn C_2O_4 nanostructures can be obtained through...Porous SnO_2 nanostructures with controlled shapes were synthesized by a facile morphologically conserved transformation from Sn C_2O_4 precursor approach. Well-defined Sn C_2O_4 nanostructures can be obtained through a solution-based precipitation process at ambient conditions without any surfactant. The formation mechanism of such microstructures was tentatively proposed on the basis of intrinsic crystal structure and the reaction conditions. We found that the morphologies of precursor were well maintained while numerous pores were formed during the annealing process. The combined techniques of X-ray diffraction, nitrogen absorption–desorption, field emission scanning electron microscopy, and(high-resolution) transmission electron microscopy were used to characterize the as-prepared SnO_2 products. Moreover, cyclic voltammetry(CV) study shows that the shape of CV presents a current response like roughly rectangular mirror images with respect to the zero-current line without obvious redox peaks, which indicating an ideal capacitive behavior of the SnO_2 electrodes. The photoluminescence(PL) spectrum study suggests that the as-obtained porous SnO_2 nanostructures might have a large number of defects, vacancies of oxygen, and local lattice disorder at the interface, interior and exterior surfaces.展开更多
A SiO2-TiO2 template with ordered tubular mesochannels has been prepared by the sol-gel method. Au nanorods are deposited in the tubular mesochannels of the SiO2-TiO2 template, and the shape of Au is changed from nano...A SiO2-TiO2 template with ordered tubular mesochannels has been prepared by the sol-gel method. Au nanorods are deposited in the tubular mesochannels of the SiO2-TiO2 template, and the shape of Au is changed from nanorods to nanospheres by ultraviolet irradiation during thermal deposition. The photocatalytic activity of mesoporous SiO2-TiO2 with/without Au nanorods/nanospheres is evaluated. Deposition of Au in the mesoporous SiO2-TiO2 template enhances the photocatalysis of TiO2. Interestingly, the sample containing Au nanorods exhibits higher photocatalytic activity than that with Au nanospheres. Photocatalysis by exciting surface plasmon resonance is not detected in the composite samples regardless of the shape of the deposited Au nanoparticles.展开更多
The nanocubic Co3O4 was synthesized by hydrothermal oxidation method. The effects of cobalt salt, precipitating agent, surfactant, solvent, pH value of the suspension and the amount of oxidant H2O2 on the morphology a...The nanocubic Co3O4 was synthesized by hydrothermal oxidation method. The effects of cobalt salt, precipitating agent, surfactant, solvent, pH value of the suspension and the amount of oxidant H2O2 on the morphology and structure of Co3O4 were investigated. The Co3O4 powders were characterized by transmission electron microscope and X-ray diffraction. The results show that the morphology of Co3O4 is closely dependant on the anion in cobalt salts, but it is not so sensitive to the precipitating agents and solvents. The amount of H2O2 is the key factor to obtain Co3O4 with spinel crystal structure. The optimum synthetic conditions of uniform shape-controlled Co3O4 nanocubes are as follows: Co(CH3COO)2·4H2O as cobalt salt, KOH as precipitating agent, polyethylene glycol with relative molecular mass of about 20 000 as surfactant, water-n-butanol as solvent system, pH value of 8-9, the molar ratio of H2O2 to Co2+ above 2.5∶1.0, hydrothermal temperature of 160 ℃ and hydrothermal holding time of 10 h. The tap density and apparent density of nanocubic Co3O4 obtained with the average particle size of 20 nm are 1.01 g/cm3 and 0.70 g/cm3, respectively.展开更多
Gold nanoparticles （NPs） of various shapes were synthesized by a one-step method at ambient temperature in the presence of NaCl. 2-mercaptosuccinic acid （MSA） was used as both reducing agent and stabilizing agent....Gold nanoparticles （NPs） of various shapes were synthesized by a one-step method at ambient temperature in the presence of NaCl. 2-mercaptosuccinic acid （MSA） was used as both reducing agent and stabilizing agent. The shapes of gold NPs were controllable by simply tuning S/Au ratio （S is from MSA molecule, and S/Au ratio is controlled by tuning the volume of added MSA solution）, and triangle, polygonal and spherical nanoparticles were obtained. This result suggested a new way to consider the effects of MSA on the growth of nanoparticles, which showed that MSA is a strong capping agent and facilitates more uniform growth of nanoparticles in every dimension. And other important factors on nanoparticles growth including NaCl and temperature were discussed. Furthermore, a typical probe molecule, 4-aminothiophenol （4-ATP） was used to test the surface-enhanced Raman scattering （SERS） activity of these gold NPs and the results indicated good Raman activity on these substrates. And the enhancement factor （EF） at 1078 cm^- 1 （a1） was estimated to be as large as 6.3 × 10^4 and 5.5 × 10^4 for triangular plates and truncated particles, respectively.展开更多
The capping agents for liquid metal (LM) nanodroplets in aqueous solutions are restricted to thiol-containing and positively-charged molecules or macromolecules.However,both thiolate-metal complex and electrostatic in...The capping agents for liquid metal (LM) nanodroplets in aqueous solutions are restricted to thiol-containing and positively-charged molecules or macromolecules.However,both thiolate-metal complex and electrostatic interaction are liable to detachment upon strong mechanical forces such as sonication,leading to limited stability and applications.To address this,we utilized ultrasmall water soluble melanin nanoparticles (MNPs) as the capping agent,which exhibited strong metal binding capability with the oxide layer of gallium based LMs and resulted in enhanced stability.Interestingly,shape-controlled synthesis of LM nanodroplets can be achieved by the incorporation of MNPs.Various EGaln nanostructures including nanorice,nanosphere and nanorod were obtained by simply tuning the feed ratio,sonication time,and suspension temperature.Among these shapes,EGaln nanorice has the best photothermal conversion efficiency,which could be leveraged for photothermal therapy.展开更多
A series of SrTiO3 polyhedral submicro/nanocrystals with systematic morphology evolution from cubic to edge-truncated cubic and truncated rhombic dodecahedra have been synthesized by using a series of alcohol molecule...A series of SrTiO3 polyhedral submicro/nanocrystals with systematic morphology evolution from cubic to edge-truncated cubic and truncated rhombic dodecahedra have been synthesized by using a series of alcohol molecules with different acidities as surfactants. The concentration and pKa value of the alcohols both play important roles in determining the size and shape of the SrTiO3 polyhedral submicro]nanocrystals. The adsorption energy of alcohol molecules on SrTiO3 [110] facets depends on their pKa values, which are therefore critical for morphology control. Using the same strategy, a series of BaTiO3 polyhedral submicro/nanocrystals with systematic morphology evolution have also been successfully prepared.展开更多
Synthesis of shape-controlled Pt nanocrystals is substantial and important for enhancing chemical and electrochemical reactions.However,the removal of capping agents,shape-controlling chemicals,on Pt surfaces is essen...Synthesis of shape-controlled Pt nanocrystals is substantial and important for enhancing chemical and electrochemical reactions.However,the removal of capping agents,shape-controlling chemicals,on Pt surfaces is essential prior to conducting the catalytic reactions.Here we report a facile one-pot synthesis of Pt nanocubes directly grown on carbon supports(Pt nanocubes/C) with modulating the kinetic reaction factors for shaping the nanocrystals,but without adding any capping agents for preserving the clean Pt surfaces.Well-dispersed Pt nanocubes/C shows enhanced activity and long-term stability toward methanol oxidation reaction compared to the commercial Pt/C catalyst.展开更多
In this paper,some engineering problems arising from hydraulics and the design of hy- draulic structures are proposed,in accordance with the viewpoint of cybernetics,as the shape-control problems for distributed param...In this paper,some engineering problems arising from hydraulics and the design of hy- draulic structures are proposed,in accordance with the viewpoint of cybernetics,as the shape-control problems for distributed parameter system(DPS),whose solution is obtained using BEM-Optimization technique.As a classical example,the problem of flow over a weir is converted first into a shape-con- trol problem,which is then converted into an optimization problem to be solved.Computational results show that the BEM-Optimization method is an efficient way to solve shape-control problems for DPS, which not only can avoid the tedious process of trial and error or iteration,but also has high accuracy and less CPU consumption.For the problem of flow over a weir,the stream function,the free surface profile and the unknown flow-rate can be found simultaneously.展开更多
基金Project (20090162120080) supported by Doctoral Fund of Ministry of Education, ChinaProject (20070410989) supported by China Postdoctoral Science FoundationProject(748310000) supported by Central South University Science Foundation for Youths, China
文摘A novel precursor of nickel-cobalt alloy powders with an appropriate Ni to Co molar ratio was prepared under selectively synthetic conditions. The composition and morphology of the precursor were characterized by X-ray diffractometry （XRD）, scanning electron microscopy （SEM）, Fourier transform infrared spectrometry （FT-IR） and energy dispersive spectrometry （EDS）. The effects of pH value, reaction temperature, metal ion concentrations and surfactant on the morphology and the dispersion of precursor were investigated. The results show that the morphology of precursor depends on ammonia content in the precursor. A fibriform precursor is a complicated ammonia-containing nickel-cobalt oxalate. The uniform shape-controlled fibrous precursor is obtained under the following optimum conditions： ammonia as complex agent as well as pH adjustor, oxalate as coprecipitator, 50-65 °C of reaction temperature, 0.5-0.8 mol/L of total concentration of Ni2＋ and Co2＋, PVP as dispersant, and pH 8.0-8.4.
基金ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China （No.i0574122, No.50772110, and No.50721091）, the National Basic Research Program of China （No.2006CB922000, No.2007CB925202, and No.2009CB939901）, and the Fund of the Chinese Academy of Sciences for Key Topics in Innovation Engineering （KJCX2.YW.W06-3）
文摘Morphological evolution of Pd nanoparticles was studied in a solution-phase synthesis using cetyltrimethylammonium bromide （CTAB） and CTAB/sodium citrate mixture as capping agents, respectively. The morphological diversity of Pd nanoparticles is the combined effect of different Pd twinned seeds formed in the nucleation stage and selectively enlarging one set of crystallographic facets in the growth stage, both of which can be affected by the concentrations of CTAB. Through changing the concentrations of CTAB and sodium ascorbate, Pd nanoparticles with different shapes were obtained. When citrate ions were introduced to manipulate the nucleation and growth process, star-shaped icosahedra and nanorods with pentagram cross-sections were obtained. Pd nanoparticles with different shapes have quite different surface plasmon resonance and surface-enhanced Raman scattering properties.
基金supported by the National Science Foundation (DMR 1808383)partially supported by S3IP at the State University of New York at Binghamton。
文摘To achieve environmentally benign energy conversion with the carbon neutrality target via electrochemical reactions, the innovation of electrocatalysts plays a vital role in the enablement of renewable resources. Nowadays, Pt-based nanocrystals(NCs) have been identified as one class of the most promising candidates to efficiently catalyze both the half-reactions in hydrogen-and hydrocarbonbased fuel cells. Here, we thoroughly discuss the key achievement in developing shape-controlled Pt and Pt-based NCs, and their electrochemical applications in fuel cells. We begin with a mechanistic discussion on how the morphology can be precisely controlled in a colloidal system, followed by highlighting the advanced development of shape-controlled Pt, Pt-alloy, Pt-based core@shell NCs, Pt-based nanocages, and Pt-based intermetallic compounds. We then select some case studies on models of typical reactions(oxygen reduction reaction at the cathode and small molecular oxidation reaction at the anode) that are enhanced by the shape-controlled Pt-based nanocatalysts. Finally, we provide an outlook on the potential challenges of shape-controlled nanocatalysts and envision their perspective with suggestions.
基金Funded by the National Natural Science Foundation of China (No.50572039)the Postdoctoral Foundation of China (No. 20060390284)Jiangsu Planned Projects for Postdoctoral Research Funds
文摘A facile solution-phase route for the synthesis of shape-controlled ZnO nanocrystals in a polyol/water mixture system was developed. The obtained nanocrystals were characterized by X-ray diffraction, transmission electron microscopy and UV-visible absorption spectroscopy. The results indicate that modulating the adding ways of water has a significant effect on the shape of the obtained nanocrystals. The addition of small quantity of water can increase the growth rate of crystals and leads to the formation of different shapes. The resulting shapes of the novel structures are diverse, including spheres, cones, and teardrops, all of which are obtained without any additional surfactants. These studies concerning the shape evolution of nanocrystals should be valuable for further design and for greater understanding of advanced nanoscale building-block architectures.
基金the financial support of the National Science Foundation for Distinguished Young Scholars of China(Grant No.51025517)the Innovative Group Foundation of NSFC(Grant No.50721062)the financial support of the National 973 project of China(2007CB607606)
文摘Porous SnO_2 nanostructures with controlled shapes were synthesized by a facile morphologically conserved transformation from Sn C_2O_4 precursor approach. Well-defined Sn C_2O_4 nanostructures can be obtained through a solution-based precipitation process at ambient conditions without any surfactant. The formation mechanism of such microstructures was tentatively proposed on the basis of intrinsic crystal structure and the reaction conditions. We found that the morphologies of precursor were well maintained while numerous pores were formed during the annealing process. The combined techniques of X-ray diffraction, nitrogen absorption–desorption, field emission scanning electron microscopy, and(high-resolution) transmission electron microscopy were used to characterize the as-prepared SnO_2 products. Moreover, cyclic voltammetry(CV) study shows that the shape of CV presents a current response like roughly rectangular mirror images with respect to the zero-current line without obvious redox peaks, which indicating an ideal capacitive behavior of the SnO_2 electrodes. The photoluminescence(PL) spectrum study suggests that the as-obtained porous SnO_2 nanostructures might have a large number of defects, vacancies of oxygen, and local lattice disorder at the interface, interior and exterior surfaces.
基金supported by Grants-in-Aid for Young Scientists(Start-up)21860045Young Scientists(B)22760539 from the Japan Society for the Promotion of Science(JSPS)
文摘A SiO2-TiO2 template with ordered tubular mesochannels has been prepared by the sol-gel method. Au nanorods are deposited in the tubular mesochannels of the SiO2-TiO2 template, and the shape of Au is changed from nanorods to nanospheres by ultraviolet irradiation during thermal deposition. The photocatalytic activity of mesoporous SiO2-TiO2 with/without Au nanorods/nanospheres is evaluated. Deposition of Au in the mesoporous SiO2-TiO2 template enhances the photocatalysis of TiO2. Interestingly, the sample containing Au nanorods exhibits higher photocatalytic activity than that with Au nanospheres. Photocatalysis by exciting surface plasmon resonance is not detected in the composite samples regardless of the shape of the deposited Au nanoparticles.
基金Project(50542004) supported by the National Natural Science Foundation of ChinaProject(ZE097) supported by Creative Program of Central South University, China
文摘The nanocubic Co3O4 was synthesized by hydrothermal oxidation method. The effects of cobalt salt, precipitating agent, surfactant, solvent, pH value of the suspension and the amount of oxidant H2O2 on the morphology and structure of Co3O4 were investigated. The Co3O4 powders were characterized by transmission electron microscope and X-ray diffraction. The results show that the morphology of Co3O4 is closely dependant on the anion in cobalt salts, but it is not so sensitive to the precipitating agents and solvents. The amount of H2O2 is the key factor to obtain Co3O4 with spinel crystal structure. The optimum synthetic conditions of uniform shape-controlled Co3O4 nanocubes are as follows: Co(CH3COO)2·4H2O as cobalt salt, KOH as precipitating agent, polyethylene glycol with relative molecular mass of about 20 000 as surfactant, water-n-butanol as solvent system, pH value of 8-9, the molar ratio of H2O2 to Co2+ above 2.5∶1.0, hydrothermal temperature of 160 ℃ and hydrothermal holding time of 10 h. The tap density and apparent density of nanocubic Co3O4 obtained with the average particle size of 20 nm are 1.01 g/cm3 and 0.70 g/cm3, respectively.
基金supported by the National Natural Science Foundation of China under Grant No.21101146
文摘Gold nanoparticles （NPs） of various shapes were synthesized by a one-step method at ambient temperature in the presence of NaCl. 2-mercaptosuccinic acid （MSA） was used as both reducing agent and stabilizing agent. The shapes of gold NPs were controllable by simply tuning S/Au ratio （S is from MSA molecule, and S/Au ratio is controlled by tuning the volume of added MSA solution）, and triangle, polygonal and spherical nanoparticles were obtained. This result suggested a new way to consider the effects of MSA on the growth of nanoparticles, which showed that MSA is a strong capping agent and facilitates more uniform growth of nanoparticles in every dimension. And other important factors on nanoparticles growth including NaCl and temperature were discussed. Furthermore, a typical probe molecule, 4-aminothiophenol （4-ATP） was used to test the surface-enhanced Raman scattering （SERS） activity of these gold NPs and the results indicated good Raman activity on these substrates. And the enhancement factor （EF） at 1078 cm^- 1 （a1） was estimated to be as large as 6.3 × 10^4 and 5.5 × 10^4 for triangular plates and truncated particles, respectively.
基金the Alfred P. Sloan Foundation (Sloan Research Fellowship)the National Natural Science Foundation of China (Nos.21504034,31671035,and 51473071)+3 种基金the National Key Research and Development Program of China (No. 2017ZX09304021 )the Jiangsu Provincial Medical Innovation Team (No.CXTDA2017024)Natural Science Foundation of Jiangsu Province (Nos.BK2016U37,BK20170204,and BE2016632). This work was performed in part at the Analytical Instrumentation Facility (AIF) at North Carolina State Universitywhich is supported by the State of North Carolina and the National Science Foundation (award number ECCS-1542015).
文摘The capping agents for liquid metal (LM) nanodroplets in aqueous solutions are restricted to thiol-containing and positively-charged molecules or macromolecules.However,both thiolate-metal complex and electrostatic interaction are liable to detachment upon strong mechanical forces such as sonication,leading to limited stability and applications.To address this,we utilized ultrasmall water soluble melanin nanoparticles (MNPs) as the capping agent,which exhibited strong metal binding capability with the oxide layer of gallium based LMs and resulted in enhanced stability.Interestingly,shape-controlled synthesis of LM nanodroplets can be achieved by the incorporation of MNPs.Various EGaln nanostructures including nanorice,nanosphere and nanorod were obtained by simply tuning the feed ratio,sonication time,and suspension temperature.Among these shapes,EGaln nanorice has the best photothermal conversion efficiency,which could be leveraged for photothermal therapy.
文摘A series of SrTiO3 polyhedral submicro/nanocrystals with systematic morphology evolution from cubic to edge-truncated cubic and truncated rhombic dodecahedra have been synthesized by using a series of alcohol molecules with different acidities as surfactants. The concentration and pKa value of the alcohols both play important roles in determining the size and shape of the SrTiO3 polyhedral submicro]nanocrystals. The adsorption energy of alcohol molecules on SrTiO3 [110] facets depends on their pKa values, which are therefore critical for morphology control. Using the same strategy, a series of BaTiO3 polyhedral submicro/nanocrystals with systematic morphology evolution have also been successfully prepared.
基金supported by Basic Science Research Program through the National Research Foundation of Korea(NRF) funded by the Ministry of Education(NRF-2015R1D1A3A01019467,NRF2017R1D1A1B03031892) and KBSI(D37614)
文摘Synthesis of shape-controlled Pt nanocrystals is substantial and important for enhancing chemical and electrochemical reactions.However,the removal of capping agents,shape-controlling chemicals,on Pt surfaces is essential prior to conducting the catalytic reactions.Here we report a facile one-pot synthesis of Pt nanocubes directly grown on carbon supports(Pt nanocubes/C) with modulating the kinetic reaction factors for shaping the nanocrystals,but without adding any capping agents for preserving the clean Pt surfaces.Well-dispersed Pt nanocubes/C shows enhanced activity and long-term stability toward methanol oxidation reaction compared to the commercial Pt/C catalyst.
文摘In this paper,some engineering problems arising from hydraulics and the design of hy- draulic structures are proposed,in accordance with the viewpoint of cybernetics,as the shape-control problems for distributed parameter system(DPS),whose solution is obtained using BEM-Optimization technique.As a classical example,the problem of flow over a weir is converted first into a shape-con- trol problem,which is then converted into an optimization problem to be solved.Computational results show that the BEM-Optimization method is an efficient way to solve shape-control problems for DPS, which not only can avoid the tedious process of trial and error or iteration,but also has high accuracy and less CPU consumption.For the problem of flow over a weir,the stream function,the free surface profile and the unknown flow-rate can be found simultaneously.
