Chee Kok Poh

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.

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.

A Green Approach to the Synthesis of High-Quality Graphene Oxide Flakes via Electrochemical Exfoliation of Pencil Core

A simple, green and cost-effective approach has been reported to synthesize high-quality graphene oxide (GO) flakes via electrochemical exfoliation of pencil cores in aqueous electrolytes. The exfoliated GO flakes exhibit excellent electrocatalytic activity and toxicity tolerance for oxygen reduction reactions in alkaline solution. Our present results are promising for scaled-up preparation and further commercialization of graphene oxide in a low-cost and environmentally friendly way.

Nanostructured trimetallic Pt/FeRuC, Pt/NiRuC, and Pt/CoRuC catalysts for methanol electrooxidation

We report the preparation and characterization of metal–carbon nanocomposites (NiRuC, FeRuC, and CoRuC) with bimetallic Ni–Ru, Fe–Ru, and Co–Ru nanoparticles incorporated into the pore walls of ordered mesoporous carbon, which were synthesized via a template strategy. Pt nanoparticles were deposited on the nanocomposites separately, which is different from the traditional alloying method. Nitrogen adsorption, X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, and thermogravimetric analysis techniques were used to characterize the materials. It was found that bimetallic nanoparticles (Ni–Ru, Fe–Ru, and Ru–Co) are homogenously dispersed in the carbon matrix and Pt nanoparticles with a size of less than 5 nm are widely distributed within the nanocomposites. The Pt/CoRuC catalyst shows better catalytic activity for the methanol oxidation reaction (MOR) than Pt on FeRuC or NiRuC, and its performance is also closer to that of the commercial PtRu catalyst with a slightly higher metal loading. A kinetic-based impedance model was used to simulate the electrochemical properties of the catalysts and matches well with the MOR performances of the catalysts. The promotional effect of the bimetallic/carbon nanocomposites on the catalytic activity of Pt was evidenced, and more importantly, the ligand effect was demonstrated by our results to be the major factor in the enhancement. Our investigation not only provides further insight into the roles of Fe, Ni and Co in MOR, but also assists in the design and synthesis of the new types of nanostructured electrocatalyst supports.

Binary metal sulfides and polypyrrole on vertically aligned carbon nanotube arrays/carbon fiber paper as high-performance electrodes

Pseudocapacitive materials, such as binary metal sulfides, show great promise as electrode candidates for energy storage devices due to their higher specific capacitance than that of mono-metal sulfides and binary metal oxides, but generally suffer from low energy densities when assembled in supercapacitor devices. To push the energy density limit of pseudocapacitive materials in devices, a new class of electrode materials with favorable architectures is strongly needed. Here, rationally designed and coaxially grown Ni–Co–S and polypyrrole on vertically aligned carbon nanotube (VA-CNT) arrays/3D carbon fiber paper (CFP) is presented as a novel freestanding electrode for energy storage devices. Our study has revealed that the catalyst preparation is the key step and the presence of an Al2O3 buffer layer is essential for the growth of VA-CNTs. The 3D hierarchical VA-CNTs/CFP allows high areal loading and high utilization efficiency of the active materials. The binder-free asymmetric energy storage devices with Ni–Co–S/VA-CNTs/CFP as the positive electrode and polypyrrole/VA-CNTs/CFP as the negative electrode, respectively, demonstrate a high energy density of 82 W h kg−1 at 200 W kg−1.

A molecular quantum wire of linear carbon chains encapsulated within single-walled carbon nanotube (Cn@SWNT)

Pure sp-hybridized linear carbon chains possess unique physical properties of one-dimensional (1D) system. However, linear carbon chains are highly unstable and require to be stabilized within a matrix for direct experimental studies. Here we report a plasma-enhanced chemical vapor deposition method to encapsulate and stabilize linear carbon chains (Cn) within vertically aligned SWNTs to form a sp-sp2 hybrid system (Cn@SWNT). Intense Raman signals at ∼1760–1860 cm−1 (L bands) indicate the presence of linear carbon chains within SWNTs. Electron transport of Cn@SWNT bundle exhibits Luttinger-liquid behavior.