Crystalline nanostructures possess defects/vacancies that affect their physical and chemical properties. In this regard, the electronic structure of materials can be effectively regulated through defect engineering; t...Crystalline nanostructures possess defects/vacancies that affect their physical and chemical properties. In this regard, the electronic structure of materials can be effectively regulated through defect engineering; therefore, the correlation between defects/vacancies and the properties of a material has attracted extensive attention. Here, we report the synthesis of Bi2S3 microspheres by nanorod assemblies with exposed {211} facets, and the investigation of the types and concentrations of defects/vacancies by means of positron annihilation spectrometry. Our studies revealed that an increase in the calcined temperature, from 350 to 400 ℃, led the predominant defect/vacancy densities to change from isolated bismuth vacancies （VBi） to septuple Bi3＋-sulfur vacancy associates （VBiBiBiSSSS）. Furthermore, the concentration of septuple BiB＋-sulfur vacancy associates increased as the calcined temperature was increased from 400 to 450 ℃. The characterized transient photocurrent spectrum demonstrates that the photocurrent values closely correlate with the types and concentrations of the predominant defects/vacancies. Our theoretical computation, through first principles, showed that VBiBiBiSSSS strongly absorbs I2（sol）, easily desorbs I-（sol）, and enhances the electrocatalytic activity of the nanostructures.展开更多
The presence of defects/vacancies in nanomaterials influences the electronic structure of materials, and thus, it is necessary to study the correlation between the optoelectronic properties of a nanomaterial and its d...The presence of defects/vacancies in nanomaterials influences the electronic structure of materials, and thus, it is necessary to study the correlation between the optoelectronic properties of a nanomaterial and its defects/vacancies. Herein, we report a facile solvothermal route to synthesize three-dimensional （3D） SnS nanostructures formed by {131} faceted nanosheet assembly. The 3D SnS nanostructures were calcined at temperatures of 350, 400, and 450 ~C and used as counter electrodes, before their photocurrent properties were investigated. First principle computation revealed the photocurrent properties depend on the defect/vacancy concentration within the samples. It is very interesting that characterization with positron annihilation spectrometry confirmed that the density of defects/vacancies increased with the calcination temperature, and a maximum photocurrent was realized after treatment at 400 ℃. Further, the defect/vacancy density decreased when the calcination temperature reached 450℃ as the higher calcination temperature enlarged the mesopores and densified the pore walls, which led to a lower photocurrent value at 450℃ than at 400℃.展开更多
Exploration of structure-property relationships as a function of dopant concentration is commonly based on mean field theories for solid solutions.However,such theories that work well for semiconductors tend to fail i...Exploration of structure-property relationships as a function of dopant concentration is commonly based on mean field theories for solid solutions.However,such theories that work well for semiconductors tend to fail in materials with strong correlations,either in electronic behavior or chemical segregation.In these cases,the details of atomic arrangements are generally not explored and analyzed.The knowledge of the generative physics and chemistry of the material can obviate this problem,since defect configuration libraries as stochastic representation of atomic level structures can be generated,or parameters of mesoscopic thermodynamic models can be derived.To obtain such information for improved predictions,we use data from atomically resolved microscopic images that visualize complex structural correlations within the system and translate them into statistical mechanical models of structure formation.Given the significant uncertainties about the microscopic aspects of the material’s processing history along with the limited number of available images,we combine model optimization techniques with the principles of statistical hypothesis testing.We demonstrate the approach on data from a series of atomically-resolved scanning transmission electron microscopy images of Mo_(x)Re_(1-x)S_(2) at varying ratios of Mo/Re stoichiometries,for which we propose an effective interaction model that is then used to generate atomic configurations and make testable predictions at a range of concentrations and formation temperatures.展开更多
文摘Crystalline nanostructures possess defects/vacancies that affect their physical and chemical properties. In this regard, the electronic structure of materials can be effectively regulated through defect engineering; therefore, the correlation between defects/vacancies and the properties of a material has attracted extensive attention. Here, we report the synthesis of Bi2S3 microspheres by nanorod assemblies with exposed {211} facets, and the investigation of the types and concentrations of defects/vacancies by means of positron annihilation spectrometry. Our studies revealed that an increase in the calcined temperature, from 350 to 400 ℃, led the predominant defect/vacancy densities to change from isolated bismuth vacancies （VBi） to septuple Bi3＋-sulfur vacancy associates （VBiBiBiSSSS）. Furthermore, the concentration of septuple BiB＋-sulfur vacancy associates increased as the calcined temperature was increased from 400 to 450 ℃. The characterized transient photocurrent spectrum demonstrates that the photocurrent values closely correlate with the types and concentrations of the predominant defects/vacancies. Our theoretical computation, through first principles, showed that VBiBiBiSSSS strongly absorbs I2（sol）, easily desorbs I-（sol）, and enhances the electrocatalytic activity of the nanostructures.
文摘The presence of defects/vacancies in nanomaterials influences the electronic structure of materials, and thus, it is necessary to study the correlation between the optoelectronic properties of a nanomaterial and its defects/vacancies. Herein, we report a facile solvothermal route to synthesize three-dimensional （3D） SnS nanostructures formed by {131} faceted nanosheet assembly. The 3D SnS nanostructures were calcined at temperatures of 350, 400, and 450 ~C and used as counter electrodes, before their photocurrent properties were investigated. First principle computation revealed the photocurrent properties depend on the defect/vacancy concentration within the samples. It is very interesting that characterization with positron annihilation spectrometry confirmed that the density of defects/vacancies increased with the calcination temperature, and a maximum photocurrent was realized after treatment at 400 ℃. Further, the defect/vacancy density decreased when the calcination temperature reached 450℃ as the higher calcination temperature enlarged the mesopores and densified the pore walls, which led to a lower photocurrent value at 450℃ than at 400℃.
文摘Exploration of structure-property relationships as a function of dopant concentration is commonly based on mean field theories for solid solutions.However,such theories that work well for semiconductors tend to fail in materials with strong correlations,either in electronic behavior or chemical segregation.In these cases,the details of atomic arrangements are generally not explored and analyzed.The knowledge of the generative physics and chemistry of the material can obviate this problem,since defect configuration libraries as stochastic representation of atomic level structures can be generated,or parameters of mesoscopic thermodynamic models can be derived.To obtain such information for improved predictions,we use data from atomically resolved microscopic images that visualize complex structural correlations within the system and translate them into statistical mechanical models of structure formation.Given the significant uncertainties about the microscopic aspects of the material’s processing history along with the limited number of available images,we combine model optimization techniques with the principles of statistical hypothesis testing.We demonstrate the approach on data from a series of atomically-resolved scanning transmission electron microscopy images of Mo_(x)Re_(1-x)S_(2) at varying ratios of Mo/Re stoichiometries,for which we propose an effective interaction model that is then used to generate atomic configurations and make testable predictions at a range of concentrations and formation temperatures.
