Since the discovery of the first drum-like CoB16- complex, metal-doped drum-like boron nanotubular structures have been investigated with various metal dopants and different tubular size, forming a new class of novel ...Since the discovery of the first drum-like CoB16- complex, metal-doped drum-like boron nanotubular structures have been investigated with various metal dopants and different tubular size, forming a new class of novel nanostructures. The CoB16- cluster was found to be composed of a central Co atom coordinated by two fused B8 rings in a tubular structure, representing the potential embryo of metal-filled boron nanotubes and providing opportunities to design one-dimensional metal-boron nanostructures. Here we report improved photoelectron spectroscopy and a more in-depth electronic structure analysis of CoB16-, providing further insight into the chemical bonding and stability of the drum-like doped boron tubular structures. Most interestingly, we find that the central Co atom has an unusually low oxidation state of ?1 and neutral CoB16 can be viewed as a charge transfer complex (Co-@BB16+), suggesting both covalent and electrostatic interactions between the dopant and the boron drum.展开更多
Catalysts for oxygen and hydrogen evolution reactions （OER/HER） are at the heart of renewable green energy sources such as water splitting. Although incredible efforts have been made to develop efficient catalysts f...Catalysts for oxygen and hydrogen evolution reactions （OER/HER） are at the heart of renewable green energy sources such as water splitting. Although incredible efforts have been made to develop efficient catalysts for OER and HER, great challenges still remain in the development of bifunctional catalysts. Here, we report a novel hybrid of Co3O4 embedded in tubular nanostructures of graphitic carbon nitride （GCN） and synthesized through a facile, large-scale chemical method at low temperature. Strong synergistic effects between Co3O4 and GCN resulted in excellent performance as a bifunctional catalyst for OER and HER. The high surface area, unique tubular nanostructure, and composition of the hybrid made all redox sites easily available for catalysis and provided faster ionic and electronic conduction. The Co3O4@GCN tubular nanostructured （TNS） hybrid exhibited the lowest overpotential （0.12 V） and excellent current density （147 mA/cm^2） in OER, better than benchmarks IrO2 and RuO2, and with superior durability in alkaline media. Furthermore, the Co3O4@GCN TNS hybrid demonstrated excellent performance in HER, with a much lower onset and overpotential, and a stable current density. It is expected that the Co3O4@GCN TNS hybrid developed in this study will be an attractive alternative to noble metals catalysts in large scale water splitting and fuel cells.展开更多
Incorporating pentagons and heptagons into the hexagonal networks of pristine carbon nanotubes （CNTs） can form various CNT-based nanostructures, as pentagons and heptagons will bend or twist the CNTs by introducing ...Incorporating pentagons and heptagons into the hexagonal networks of pristine carbon nanotubes （CNTs） can form various CNT-based nanostructures, as pentagons and heptagons will bend or twist the CNTs by introducing positive and negative curvature, respectively. Some typical so-made CNT-based nanostructures are reviewed in this article, including zero-dimensional toroidal CNTs, and one-dimensional kinked and coiled CNTs. Due to the presence of non-hexagonal rings and curved geometries, such nanostructures possess rather different structural, physical and chemical properties from their pristine CNT counterparts, which are reviewed comprehensively in this article. Additionally, their synthesis, modelling studies, and potential applications are discussed.展开更多
基金supported by the National Natural Science Foundation of China (No.21590792, No.91426302, and No.21433005)supported by the U.S. National Science Foundation (CHE-1763380)
文摘Since the discovery of the first drum-like CoB16- complex, metal-doped drum-like boron nanotubular structures have been investigated with various metal dopants and different tubular size, forming a new class of novel nanostructures. The CoB16- cluster was found to be composed of a central Co atom coordinated by two fused B8 rings in a tubular structure, representing the potential embryo of metal-filled boron nanotubes and providing opportunities to design one-dimensional metal-boron nanostructures. Here we report improved photoelectron spectroscopy and a more in-depth electronic structure analysis of CoB16-, providing further insight into the chemical bonding and stability of the drum-like doped boron tubular structures. Most interestingly, we find that the central Co atom has an unusually low oxidation state of ?1 and neutral CoB16 can be viewed as a charge transfer complex (Co-@BB16+), suggesting both covalent and electrostatic interactions between the dopant and the boron drum.
基金Acknowledgements Work at Beijing Institute of Technology was supported by the National Natural Science Foundation of China （Nos. 23171023 and 50972017） and Doctoral Program of the Ministry of Education of China （No. 20101101110026） Work at Peking University was supported by the NSFC-RGC Joint Research Scheme （No. 51361165201）, the National Natural Science Foundation of China （Nos. 51125001 and 51172005）, Beijing Natural Science Foundation （No. 2122022） and Doctoral Program of the Ministry of Education of China （No. 20120001110078）. Deanship of Scientific Research at King Saud University through Prolific Research Group Project （No. PRG-1436-25）.
文摘Catalysts for oxygen and hydrogen evolution reactions （OER/HER） are at the heart of renewable green energy sources such as water splitting. Although incredible efforts have been made to develop efficient catalysts for OER and HER, great challenges still remain in the development of bifunctional catalysts. Here, we report a novel hybrid of Co3O4 embedded in tubular nanostructures of graphitic carbon nitride （GCN） and synthesized through a facile, large-scale chemical method at low temperature. Strong synergistic effects between Co3O4 and GCN resulted in excellent performance as a bifunctional catalyst for OER and HER. The high surface area, unique tubular nanostructure, and composition of the hybrid made all redox sites easily available for catalysis and provided faster ionic and electronic conduction. The Co3O4@GCN tubular nanostructured （TNS） hybrid exhibited the lowest overpotential （0.12 V） and excellent current density （147 mA/cm^2） in OER, better than benchmarks IrO2 and RuO2, and with superior durability in alkaline media. Furthermore, the Co3O4@GCN TNS hybrid demonstrated excellent performance in HER, with a much lower onset and overpotential, and a stable current density. It is expected that the Co3O4@GCN TNS hybrid developed in this study will be an attractive alternative to noble metals catalysts in large scale water splitting and fuel cells.
文摘Incorporating pentagons and heptagons into the hexagonal networks of pristine carbon nanotubes （CNTs） can form various CNT-based nanostructures, as pentagons and heptagons will bend or twist the CNTs by introducing positive and negative curvature, respectively. Some typical so-made CNT-based nanostructures are reviewed in this article, including zero-dimensional toroidal CNTs, and one-dimensional kinked and coiled CNTs. Due to the presence of non-hexagonal rings and curved geometries, such nanostructures possess rather different structural, physical and chemical properties from their pristine CNT counterparts, which are reviewed comprehensively in this article. Additionally, their synthesis, modelling studies, and potential applications are discussed.
