Gui-Li Tian

Unstacked double-layer templated graphene for high-rate lithium–sulphur batteries

Preventing the stacking of graphene is essential to exploiting its full potential in energy-storage applications. The introduction of spacers into graphene layers always results in a change in the intrinsic properties of graphene and/or induces complexity at the interfaces. Here we show the synthesis of an intrinsically unstacked double-layer templated graphene via template-directed chemical vapour deposition. The as-obtained graphene is composed of two unstacked graphene layers separated by a large amount of mesosized protuberances and can be used for high-power lithium-sulphur batteries with excellent high-rate performance. Even after 1,000 cycles, high reversible capacities of ca. 530 mA h g(-1) and 380 mA h g(-1) are retained at 5 C and 10 C, respectively. This type of double-layer graphene is expected to be an important platform that will enable the investigation of stabilized three-dimensional topological porous systems and demonstrate the potential of unstacked graphene materials for advanced energy storage, environmental protection, nanocomposite and healthcare applications.

Graphene/single-walled carbon nanotube hybrids: one-step catalytic growth and applications for high-rate Li-S batteries.

The theoretically proposed graphene/single-walled carbon nanotube (G/SWCNT) hybrids by placing SWCNTs among graphene planes through covalent C-C bonding are expected to have extraordinary physical properties and promising engineering applications. However, the G/CNT hybrids that have been fabricated differ greatly from the proposed G/SWCNT hybrids because either the covalent C-C bonding is not well constructed or only multiwalled CNTs/carbon nanofibers rather than SWCNTs are available in the hybrids. Herein, a novel G/SWCNT hybrid was successfully fabricated by a facile catalytic growth on layered double hydroxide (LDH) at a high temperature over 950 °C. The thermally stable Fe nanoparticles and the uniform structure of the calcined LDH flakes are essential for the simultaneously catalytic deposition of SWCNTs and graphene. The SWCNTs and the CVD-grown graphene, as well as the robust connection between the SWCNTs and graphene, facilitated the construction of a high electrical conductive pathway. The internal spaces between the two stacked graphene layers and among SWCNTs offer room for sulfur storage. Therefore, the as obtained G/SWCNT-S cathode exhibited excellent performance in Li-S batteries with a capacity as high as 650 mAh g(-1) after 100 cycles even at a high current rate of 5 C. Such a novel G/SWCNT hybrid can serve not only as a prototype to shed light on the chemical principle of G/CNT synthesis but also as a platform for their further applications in the area of nanocomposites, heterogeneous catalysis, drug delivery, electrochemical energy storage, and so on.

Nitrogen-doped graphene/carbon nanotube hybrids : in situ formation on bifunctional catalysts and their superior electrocatalytic activity for oxygen evolution/reduction reaction

There is a growing interest in oxygen electrode catalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), as they play a key role in a wide range of renewable energy technologies such as fuel cells, metal-air batteries, and water splitting. Nevertheless, the development of highly-active bifunctional catalysts at low cost for both ORR and OER still remains a huge challenge. Herein, we report a new N-doped graphene/single-walled carbon nanotube (SWCNT) hybrid (NGSH) material as an efficient noble-metal-free bifunctional electrocatalyst for both ORR and OER. NGSHs were fabricated by in situ doping during chemical vapor deposition growth on layered double hydroxide derived bifunctional catalysts. Our one-step approach not only provides simultaneous growth of graphene and SWCNTs, leading to the formation of three dimensional interconnected network, but also brings the intrinsic dispersion of graphene and carbon nanotubes and the dispersion of N-containing functional groups within a highly conductive scaffold. Thus, the NGSHs possess a large specific surface area of 812.9 m(2) g(-1) and high electrical conductivity of 53.8 S cm(-1) . Despite of relatively low nitrogen content (0.53 at%), the NGSHs demonstrate a high ORR activity, much superior to two constituent components and even comparable to the commercial 20 wt% Pt/C catalysts with much better durability and resistance to crossover effect. The same hybrid material also presents high catalytic activity towards OER, rendering them high-performance cheap catalysts for both ORR and OER. Our result opens up new avenues for energy conversion technologies based on earth-abundant, scalable, noble-metal-free catalysts.

Nitrogen‐Doped Aligned Carbon Nanotube/Graphene Sandwiches: Facile Catalytic Growth on Bifunctional Natural Catalysts and Their Applications as Scaffolds for High‐Rate Lithium‐Sulfur Batteries

Nitrogen-doped aligned CNT/graphene sandwiches are rationally designed and in-situ fabricated by a facile catalytic growth on bifunctional natural catalysts that exhibit high-rate performances as scaffolds for lithium-sulfur batteries, with a high initial capacity of 1152 mA h g(-1) at 1.0 C. A remarkable capacity of 770 mA h g(-1) can be achieved at 5.0 C. Such a design strategy for materials opens up new perspectives to novel advanced functional composites, especially interface-modified hierarchical nanocarbons for broad applications.

Spatially Confined Hybridization of Nanometer-Sized NiFe Hydroxides into Nitrogen-Doped Graphene Frameworks Leading to Superior Oxygen Evolution Reactivity

Nanometer-sized hydroxide active centers are uniformly and strongly hybridized into a graphene framework by means of defect-anchored nucleation and spatially confined growth, resulting in a superior electrocatalyst for oxygen evolution reaction. This family of strongly coupled complexes and the topology-assisted fabrication strategy is expected to open up new avenues of research. It sheds light on a novel branch of advanced nano-architectured materials.

Hierarchical Vine-Tree-Like Carbon Nanotube Architectures: In-Situ CVD Self-Assembly and Their Use as Robust Scaffolds for Lithium-Sulfur Batteries

Hierarchical vine-tree-like carbon nanotube architectures composed of vine-like single-walled carbon nanotubes wrapping around the tree-like multi-walled carbon nanotubes are fabricated through in-situ chemical vapor deposition self-assembly. The vine-tree-like nanoarchitectures exhibit excellent cycling stability and rate performance when employed as the cathode scaffolds for lithium-sulfur batteries.

The Catalytic Pathways of Hydrohalogenation over Metal‐Free Nitrogen‐Doped Carbon Nanotubes

Nitrogen-doped carbon nanotubes (N-CNTs) are found to be active as one novel heterogeneous catalyst for acetylene hydrochlorination reaction, possessing good activity (TOF=2.3×10(-3)  s(-1) ) and high selectivity (>98 %). Compared to toxic and energy-consuming conventional catalysts, such as HgCl2 , N-CNTs are more favorable in terms of sustainability, because of their thermo-stability, metal-free make up, and the wide availability of bulk CNT. Coupling X-ray photoelectron spectroscopy and density functional theory computations (DFT), the main active source and reaction pathway are shown. Good linearity between the quaternary nitrogen content and conversion is revealed. DFT study shows that the nitrogen doping enhanced the formation of the covalent bond between C2 H2 and NCNT compared with the undoped CNT, and therefore promoted the addition reaction of the C2 H2 and HCl into C2 H3 Cl.

Space confinement and rotation stress induced self-organization of double-helix nanostructure: a nanotube twist with a moving catalyst head.

Inorganic materials with double-helix structure have attracted intensive attention due to not only their elegant morphology but also their amazing morphology-related potential applications. The investigation on the formation mechanism of the inorganic double-helix nanostructure is the first step for the fundamental studies of their materials or physical properties. Herein, we demonstrated the space confinement and rotation stress induced self-organization mechanism of the carbon nanotube (CNT)-array double helices under scanning electron microscopy by directly observing their formation process from individual layered double hydroxide flakes, which is a kind of hydrotalcite-like material composed of positively charged layers and charge-balancing interlayer anions. Space confinement is considered to be the most important extrinsic factor for the formation of CNT-array double helices. Synchronous growth of the CNT arrays oppositely from LDH flakes with space confinement on both sides at the same time is essential for the growth of CNT-array double helices. Coiling of the as-grown CNT arrays into double helices will proceed by self-organization, tending to the most stable morphology in order to release their internal rotation stress. Based on the demonstrated mechanism, effective routes were carried out to improve the selectivity for CNT-array double helices. The work provides a promising method for the fabrication of double-helix nanostructures with their two helices connected at the end by self-assembly.

Carbon nanotubes for supercapacitors： Consideration of cost and chemical vapor deposition techniques

Abstract In this topic, we first discussed the requirement and performance of supercapacitors using carbon nanotubes (CNTs) as the electrode, including specific surface area, purity and cost. Then we reviewed the preparation technique of single walled CNTs (SWNTs) in relatively large scale by chemical vapor deposition method. Its catalysis on the decomposition of methane and other carbon source, the reactor type and the process control strategies were discussed. Special focus was concentrated on how to increase the yield, selectivity, and purity of SWNTs and how to inhibit the formation of impurities, including amorphous carbon, multiwalled CNTs and the carbon encapsulated metal particles, since these impurities seriously influenced the performance of SWNTs in supercapacitors. Wish it be helpful to further decrease its product cost and for the commercial use in supercapacitors.

Flux and surfactant directed facile thermal conversion synthesis of hierarchical porous MgO for efficient adsorption and catalytic growth of carbon nanotubes

Three-dimensional (3D) hierarchical porous structures have attracted extensive attention owing to their versatile applications. Herein, 3D hierarchical porous MgO superstructures with a well faceted profile and high crystallinity were successfully obtained via a facile flux and surfactant directed decomposition of metal oxalates. As a nonionic surfactant, NP-9 served as the dispersing agent and prevented the porous MgO particles from aggregating with each other. The flux NaCl induced vapor migration through the porous structure, favoring the in situ crystallization of MgO after the phase conversion from the oxalate precursor, enhancing the toughness of the backbone and further realizing the preservation of the polyhedron-like morphology. The as-obtained hierarchical porous MgO superstructures were very efficient and effective as adsorbents for methylene blue (MB) and a catalyst support for single-walled carbon nanotube (SWCNTs) growth. The as-obtained SWCNTs afford an ultrahigh surface area of 1232 m2 g−1. Such superstructures could be employed as great potential candidates in dye-containing water treatment as well as heterogeneous catalysis.