Fabing Su

Nitrogen-containing microporous carbon nanospheres with improved capacitive properties

We report the largely improved electrochemical capacitance of polypyrrole-derived microporous carbon nanospheres (MCNs, 80–100 nm in diameter) containing nitrogen functional groups. We have investigated the electrochemical properties of precursor polypyrrole nanospheres (PNs, with a high N/C ratio and low surface area) and as-derived carbon nanospheres (CNs, with a moderate N/C ratio and low surface area) prepared by carbonizing PNs at different temperatures, and MCNs (with a low N/C ratio and high surface area) obtained by chemical activation of CNs. The samples are thoroughly characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy, thermogravimetric analysis (TGA), nitrogen sorption, elemental analysis, and X-ray photoelectron spectroscopy (XPS). It is found that MCNs with a high surface area and N-doping species exhibit much better capacitive performance compared to the PNs and CNs, and commercial carbon blacks (XC-72 and BP2000) as well. The MCN sample gives a reversible specific capacitance of ∼240 F g−1 for 3000 cycles in aqueous media as a result of combined advantages of high electrochemical activity of doped heteroatoms (N and O) and accessible well-developed porosity, demonstrating the promising use in high-energy-density supercapacitors.

Hierarchically Ordered Macro−Mesoporous TiO2−Graphene Composite Films: Improved Mass Transfer, Reduced Charge Recombination, and Their Enhanced Photocatalytic Activities

Hierarchically ordered macro-mesoporous titania films have been produced through a confinement self-assembly method within the regular voids of a colloidal crystal with three-dimensional periodicity. Furthermore, graphene as an excellent electron-accepting and electron-transporting material has been incorporated into the hierarchically ordered macro-mesoporous titania frameworks by in situ reduction of graphene oxide added in the self-assembly system. Incorporation of interconnected macropores in mesoporous films improves the mass transport through the film, reduces the length of the mesopore channel, and increases the accessible surface area of the thin film, whereas the introduction of graphene effectively suppresses the charge recombination. Therefore, the significant enhancement of photocatalytic activity for degrading the methyl blue has been achieved. The apparent rate constants for macro-mesoporous titania films without and with graphene are up to 0.045 and 0.071 min(-1), respectively, almost 11 and 17 times higher than that for pure mesoporous titania films (0.0041 min(-1)).

General Synthesis and Gas-Sensing Properties of Multiple-Shell Metal Oxide Hollow Microspheres

Hollow spheres with nanometer-to-micrometer dimensions, controlled internal structure, and shell composition have attracted tremendous attention because of their potential application in catalysis, drug delivery, nanoreactors, energy conversion and storage systems, photonic devices, chemical sensors, and biotechnology. Single-shell and double-shell hollow spheres of various compositions have been synthesized by a number of methods, such as vesicles, emulsions, micelles, gas-bubble, and hard-templating methods. More recently, efforts have focused on the fabrication of hollow spheres with multiple shells, as these materials are expected to have better properties for applications such as drug release with prolonged release time, heterogeneous catalysis, lithiumion batteries, and photocatalysis. For example, multipleshell hollow microspheres of Cu2O have been prepared by vesicle templating and an intermediate-templating phasetransformation process. Multiple-shell azithromycin hollow microspheres were fabricated by hierarchical assembly. Cao and co-workers reported the synthesis of tripleshelled SnO2 hollow microspheres by chemically induced selfassembly in the hydrothermal environment which exhibited enhanced electrochemical performance. Yao and co-workers reported excellent cycle performance and enhanced lithium storage capacity of multiple-shell Co3O4 hollow microspheres synthesized by oriented self-assembly. These preparative methods, however, are suited for each specific material and cannot be applied generally to a wide range of materials. Currently, there is no general synthetic approach for fabricating multiple-shell hollow nanostructures of any desired material. Herein, we present a straightforward and general strategy to prepare metal oxide hollow microspheres with a controlled number of shells. Carbonaceous microspheres were used as sacrificial templates. The microspheres were saturated with a desired metal salt solution and then heated in air; the carbonaceous template evaporates and templates the formation of metal oxide shells. The number of shells is controlled by the metal ion loading and the process is general for a wide range of metal oxide materials. Scheme 1 illustrates the general process of fabricating multiple-shell hollow metal oxide microspheres. The key to this process is the use of carbonaceous particles rich with surface functional groups available for metal ion adsorption.

A thermodynamic analysis of methanation reactions of carbon oxides for the production of synthetic natural gas

Synthetic natural gas (SNG) can be obtained via methanation of synthesis gas (syngas). Many thermodynamic reaction details involved in this process are not yet fully understood. In this paper, a comprehensive thermodynamic analysis of reactions occurring in the methanation of carbon oxides (CO and CO2) is conducted using the Gibbs free energy minimization method. The equilibrium constants of eight reactions involved in the methanation reactions were calculated at different temperatures. The effects of temperature, pressure, ratio of H-2/CO (and H-2/CO2), and the addition of other compounds (H2O, O-2, CH4, and C2H4) in the feed gas (syngas) on the conversion of CO and CO2, CH4 selectivity and yield, as well as carbon deposition, were carefully investigated. In addition, experimental data obtained on commercial Ni-based catalysts for CO methanation and three cases adopted from the literature were compared with the thermodynamic calculations. It is found that low temperature, high pressure, and a large H-2/CO (and H-2/CO2) ratio are favourable for the methanation reactions. Adding steam into the feed gas could alleviate the carbon deposition to a large extent. Trace amounts of O-2 in syngas is unfavourable for SNG generation although it can lower carbon deposition. Additional CH4 in the feed gas almost has no influence on the CO conversion and CH4 yield, but it leads to the increase of carbon formed. Introduction of a small amount of C2H4, a representative of hydrocarbons in syngas, results in low CH4 yield and serious carbon deposition although it does not affect CO conversion. CO is relatively easy to hydrogenated compared to CO2 at the same reaction conditions. The comparison of thermodynamic calculations with experimental results demonstrated that the Gibbs free energy minimization method is significantly effective for understanding the reactions occurring in methanation and helpful for the development of catalysts and processes for the production of SNG.

Engineering nonspherical hollow structures with complex interiors by template-engaged redox etching

Despite the significant advancement in making hollow structures, one unsolved challenge in the field is how to engineer hollow structures with specific shapes, tunable compositions, and desirable interior structures. In particular, top-down engineering the interiors inside preformed hollow structures is still a daunting task. In this work, we demonstrate a facile approach for the preparation of a variety of uniform hollow structures, including Cu(2)O@Fe(OH)(x) nanorattles and Fe(OH)(x) cages with various shapes and dimensions by template-engaged redox etching of shape-controlled Cu(2)O crystals. The composition can be readily modulated at different structural levels to generate other interesting structures such as Cu(2)O@Fe(2)O(3) and Cu@Fe(3)O(4) rattles, as well as Fe(2)O(3) and Fe(3)O(4) cages. More remarkably, this strategy enables top-down engineering the interiors of hollow structures as demonstrated by the fabrication of double-walled nanorattles and nanoboxes, and even box-in-box structures. In addition, this approach is also applied to form Au and MnO(x) based hollow structures.

Templating methods for preparation of porous structures

This article features recent research progress towards various templating methods for preparing porous structures with prescribed structural, surface, and morphological properties. It should be noted that this is not a comprehensive review article as such reviews are available in the literature. Instead, on the basis of our own research results we attempt to provide a brief summary of recent demonstrations of how templating strategies can be used to prepare porous architectures with desired properties to meet the specific requirements of new technological applications, such as environmentally friendly technology, nanotechnology, tissue engineering, and photonics.

Shape-Controlled Synthesis of Cobalt-based Nanocubes, Nanodiscs, and Nanoflowers and Their Comparative Lithium-Storage Properties

Facile hydrothermal methods have been developed to synthesize large Co3O4 nanocubes, β-Co(OH)2 hexagonal nanodiscs and nanoflowers. Samples are thoroughly characterized by field-emission scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Brunauer-Emmett-Teller method, and thermogravimetric analysis. The Co3O4 nanocubes have an average size of about 350 nm with a perfect cubic shape, and the β-Co(OH)2 nanodiscs are uniform hexagonal platelets, whereas the β-Co(OH)2 nanoflowers are assembled from large sheetlike subunits. After thermal annealing in air at a moderate temperature, the as-prepared β-Co(OH)2 samples can be converted into spinel Co3O4 without significant alterations in morphology. We have also investigated the comparative lithium storage properties of these three Co3O4 samples with distinct morphologies. The nanoflower sample shows highly reversible lithium storage capability after 100 charge-discharge cycles.

CuO nanostructures supported on Cu substrate as integrated electrodes for highly reversible lithium storage

Arrays of CuO nanostructures, including nanorods and nanosheets, supported on a Cu substrate have been rationally fabricated from their morphology-controlled Cu(2)(OH)(3)NO(3) precursors by thermal annealing. The as-prepared CuO samples can be directly used as integrated electrodes for lithium-ion batteries without the addition of other ancillary materials such as carbon black or a binder to enhance electrode conductivity and cycling stability. The unique nanostructural features endower them excellent electrochemical performance as demonstrated by high capacities of 450-650 mAh g(-1) at 0.5-2 C and almost 100% capacity retention over 100 cycles after the second cycle.

Recent advances in methanation catalysts for the production of synthetic natural gas

Methanation of coal-or biomass-derived carbon oxides for production of synthetic natural gas (SNG) is gaining considerable interest due to energy issues and the opportunity of reducing greenhouse gases by carbon dioxide conversion. The key component of the methanation process is the catalyst design. Ideally, the catalyst should show high activity at low temperatures (200-300 degrees C) and high stability at high temperatures (600-700 degrees C). In the past decades, various methanation catalysts have been investigated, among which transition metals including Ni, Fe, Co, Ru, Mo, etc. dispersed on metal oxide supports such as Al2O3, SiO2, TiO2, ZrO2, CeO2 etc. have received great attention due to their relatively high catalytic activity and selectivity. Furthermore, over the past few years, great efforts have been made both in methanation catalysts development and reaction mechanism investigation. Here we provide a comprehensive review to these most advancements, covering the reaction thermodynamics, mechanism and kinetics, the effects of catalyst active components, supports, promoters and preparation methods, hoping to outline the pathways for the future methanation catalysts design and development for SNG production.

Synthesis of network reduced graphene oxide in polystyrene matrix by a two-step reduction method for superior conductivity of the composite

Polymer/graphene composites have attracted much attention due to their unique organic–inorganic hybrid structure and exceptional properties. In this paper, we report the synthesis of polystyrene/reduced graphene oxide (PS/r-GO) composites by a two-step in situ reduction technique, which consists of a hydrazine hydrate reduction and a subsequent thermal reduction at 200 °C for 12 h. The structure and micromorphology of PS/r-GO composites were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis. The results show that the GO can be efficiently reduced by the two-step in situ reduction method, and the r-GO sheets are well dispersed and ultimately form a continuous network structure in the polymer matrix. PS/r-GO composite films (5 wt% GO) are prepared by the hot press molding method, possessing a conductivity as high as 22.68 S m−1. The superior conductivity arises from the high reduction degree of GO and its high dispersion and the formation of a network structure in the polymer matrix. These polymer/r-GO composites are expected to be applied in multiple electric devices. The techniques for preparing polymer/r-GO composite films could be further extended to other similar systems.