Zexiang Shen

Exploration of the active center structure of nitrogen-doped graphene-based catalysts for oxygen reduction reaction

We present two different ways to fabricate nitrogen-doped graphene (N-graphene) and demonstrate its use as a metal-free catalyst to study the catalytic active center for the oxygen reduction reaction (ORR). N-graphene was produced by annealing of graphene oxide (G-O) under ammonia or by annealing of a N-containing polymer/reduced graphene oxide (RG-O) composite (polyaniline/RG-O or polypyrrole/RG-O). The effects of the N precursors and annealing temperature on the performance of the catalyst were investigated. The bonding state of the N atom was found to have a significant effect on the selectivity and catalytic activity for ORR. Annealing of G-O with ammonia preferentially formed graphitic N and pyridinic N centers, while annealing of polyaniline/RG-O and polypyrrole/RG-O tended to generate pyridinic and pyrrolic N moieties, respectively. Most importantly, the electrocatalytic activity of the catalyst was found to be dependent on the graphitic N content which determined the limiting current density, while the pyridinic N content improved the onset potential for ORR. However, the total N content in the graphene-based non-precious metal catalyst does not play an important role in the ORR process.

Uniaxial Strain on Graphene: Raman Spectroscopy Study and Band-Gap Opening

Graphene was deposited on a transparent and flexible substrate, and tensile strain up to approximately 0.8% was loaded by stretching the substrate in one direction. Raman spectra of strained graphene show significant red shifts of 2D and G band (-27.8 and -14.2 cm(-1) per 1% strain, respectively) because of the elongation of the carbon-carbon bonds. This indicates that uniaxial strain has been successfully applied on graphene. We also proposed that, by applying uniaxial strain on graphene, tunable band gap at K point can be realized. First-principle calculations predicted a band-gap opening of approximately 300 meV for graphene under 1% uniaxial tensile strain. The strained graphene provides an alternative way to experimentally tune the band gap of graphene, which would be more efficient and more controllable than other methods that are used to open the band gap in graphene. Moreover, our results suggest that the flexible substrate is ready for such a strain process, and Raman spectroscopy can be used as an ultrasensitive method to determine the strain.

Three-Dimensional Graphene Foam Supported Fe3O4 Lithium Battery Anodes with Long Cycle Life and High Rate Capability

Fe3O4 has long been regarded as a promising anode material for lithium ion battery due to its high theoretical capacity, earth abundance, low cost, and nontoxic properties. However, up to now no effective and scalable method has been realized to overcome the bottleneck of poor cyclability and low rate capability. In this article, we report a bottom-up strategy assisted by atomic layer deposition to graft bicontinuous mesoporous nanostructure Fe3O4 onto three-dimensional graphene foams and directly use the composite as the lithium ion battery anode. This electrode exhibits high reversible capacity and fast charging and discharging capability. A high capacity of 785 mAh/g is achieved at 1C rate and is maintained without decay up to 500 cycles. Moreover, the rate of up to 60C is also demonstrated, rendering a fast discharge potential. To our knowledge, this is the best reported rate performance for Fe3O4 in lithium ion battery to date.

Pyridinic N doped graphene: synthesis, electronic structure, and electrocatalytic property

Different C–N bonding configurations in nitrogen (N) doped carbon materials have different electronic structures. Carbon materials doped with only one kind of C–N bonding configuration are an excellent platform for studying doping effects on the electronic structure and physical/chemical properties. Here we report synthesis of single layer graphene doped with pure pyridinic N by thermal chemical vapour deposition of hydrogen and ethylene on Cu foils in the presence of ammonia. By adjusting the flow rate of ammonia, the atomic ratio of N and C can be modulated from 0 to 16%. The domain like distribution of N incorporated in graphene was revealed by the imaging of Raman spectroscopy and time-of-flight secondary ion mass spectrometry. The ultraviolet photoemission spectroscopy investigation demonstrated that the pyridinic N efficiently changed the valence band structure of graphene, including the raising of density of π states near the Fermi level and the reduction of work function. Such pyridinic N doping in carbon materials was generally considered to be responsible for their oxygen reduction reaction (ORR) activity. The 2e reduction mechanism of ORR on our CNxgraphene revealed by rotating disk electrode voltammetry indicated that the pyridinic N may not be an effective promoter for ORR activity of carbon materials as previously expected.

High-performance flexible asymmetric supercapacitors based on a new graphene foam/carbon nanotube hybrid film

In this work, we report the fabrication of a new 3D graphene foam (GF)/carbon nanotube (CNT) hybrid film with high flexibility and robustness as the ideal support for deposition of large amounts of electrochemically active materials per unit area. To demonstrate the concept, we have deposited MnO2 and polypyrrole (Ppy) on the GF/CNT films and successfully fabricated lightweight and flexible asymmetric supercapacitors (ASCs). These ASCs assembled from GF/CNT/MnO2 and GF/CNT/Ppy hybrid films with high loading of electroactive materials in an aqueous electrolyte are able to function with an output voltage of 1.6 V, and deliver high energy/power density (22.8 W h kg−1 at 860 W kg−1 and 2.7 kW kg−1 at 6.2 W h kg−1). The rate performance can be further improved with less loading of electroactive materials (10.3 kW kg−1 at 10.9 W h kg−1). The ASCs demonstrate remarkable cycling stability (capacitance retention of 90.2–83.5% after 10 000 cycles), which is among the best reported for ASCs with both electrodes made of non-carbon electroactive materials. Also the ASCs are able to perfectly retain their electrochemical performance at different bending angles. These ASCs demonstrate great potential as power sources for flexible and lightweight electronic devices.

Raman spectroscopy of epitaxial graphene on a SiC substrate

may speed up the application of graphene for future electronic devices. The interaction of EG and the SiC substrate is critical to its electronic and physical properties. In this work, the Raman spectroscopy was used to study the structure of EG and its interaction with SiC substrate. All the Raman bands of EG blueshift from that of bulk graphite and graphene made by micromechanical cleavage, which was attributed to the compressive strain induced by the substrate. A model containing 13 13 honeycomb lattice cells of graphene on carbon nanomesh was constructed to explain the origin of strain. The lattice mismatch between graphene layer and substrate causes the compressive stress of 2.27 GPa on graphene. We also demonstrate that the electronic structures of EG grown on Si- and C-terminated SiC substrates are quite different. Our experimental results shed light on the interaction between graphene and SiC substrate, which are critical to the future applications of EG.

Probing Layer Number and Stacking Order of Few‐Layer Graphene by Raman Spectroscopy

Graphene is a two-dimensional material defined as a planar honeycomb lattice of close-packed carbon atoms, where the electrons exhibit a linear dispersion near Dirac K points and behave as massless Dirac fermions. However, the valence and conduction bands in an AB stacked graphene bilayer split into two parabolic branches near the K point originating from the interaction of p electrons, and the electrons are hence described by massive Dirac fermions. Moreover, a graphene bilayer is a tunable-gap semiconductor under electric-field biasing. With a further increase in the number of layers along with AB stacking, the electronic structure reveals stepwise variations that eventually approach that of the three-dimensional counterpart. Considering the close relation between the electronic properties and layer number of few-layer graphene (FLG), the ability to accurately determine the layer number and correlating this with the electronic structure is a prerequisite in understanding the evolution of the electronic properties from twoto threedimensional graphitic materials. In addition to graphene layers with AB stacking, FLG with arbitrary stacking (Figure 1) is considered to possess distinct properties arising from its different crystalline structure and p electron interactions. Experimentally, it has been observed that the electroand magnetotransport properties for folded graphene sheets are different to thoseofAB stackedbilayers. Furthermore,FLG grown on SiC, Ni, and Ru also have non-AB stacking order. Therefore, elucidating the detailed character-

Surface-Energy Engineering of Graphene

Contact angle goniometry is conducted for epitaxial graphene on SiC. Although only a single layer of epitaxial graphene exists on SiC, the contact angle drastically changes from 69 degrees on SiC substrates to 92 degrees on graphene. It is found that there is no thickness dependence of the contact angle from the measurements of single-, bi-, and multilayer graphene and highly ordered pyrolytic graphite (HOPG). After graphene is treated with oxygen plasma, the level of damage is investigated by Raman spectroscopy and the correlation between the level of disorder and wettability is reported. By using a low-power oxygen plasma treatment, the wettability of graphene is improved without additional damage, which can solve the adhesion issues involved in the fabrication of graphene devices.

A V2O5/Conductive‐Polymer Core/Shell Nanobelt Array on Three‐Dimensional Graphite Foam: A High‐Rate, Ultrastable, and Freestanding Cathode for Lithium‐Ion Batteries

A thin polymer shell helps V2O5 a lot. Short V2O5 nanobelts are grown directly on 3D graphite foam as a lithium-ion battery (LIB) cathode material. A further coating of a poly(3,4-ethylenedioxythiophene) (PEDOT) thin shell is the key to the high performance. An excellent high-rate capability and ultrastable cycling up to 1000 cycles are demonstrated.

Raman spectra of CuO nanocrystals

CuO nanoparticles were successfully prepared by a one-step solid-state reaction under ambient conditions. Three pellet samples with different grain sizes were obtained by annealing at high temperature. The room temperature Raman spectra of these samples show that as the grain size decreases, the Raman peaks shift to lower wavenumber and become broader owing to size effects. The dependences of the Raman spectra on the wavelength of the excitation laser and temperature were also investigated. Copyright