Dingshan Yu

Scalable synthesis of hierarchically structured carbon nanotube-graphene fibres for capacitive energy storage

Micro-supercapacitors are promising energy storage devices that can complement or even replace batteries in miniaturized portable electronics and microelectromechanical systems. Their main limitation, however, is the low volumetric energy density when compared with batteries. Here, we describe a hierarchically structured carbon microfibre made of an interconnected network of aligned single-walled carbon nanotubes with interposed nitrogen-doped reduced graphene oxide sheets. The nanomaterials form mesoporous structures of large specific surface area (396 m2 g−1) and high electrical conductivity (102 S cm−1). We develop a scalable method to continuously produce the fibres using a silica capillary column functioning as a hydrothermal microreactor. The resultant fibres show a specific volumetric capacity as high as 305 F cm−3 in sulphuric acid (measured at 73.5 mA cm−3 in a three-electrode cell) or 300 F cm−3 in polyvinyl alcohol (PVA)/H3PO4 electrolyte (measured at 26.7 mA cm−3 in a two-electrode cell). A full micro-supercapacitor with PVA/H3PO4 gel electrolyte, free from binder, current collector and separator, has a volumetric energy density of ∼6.3 mWh cm−3 (a value comparable to that of 4 V–500 µAh thin-film lithium batteries) while maintaining a power density more than two orders of magnitude higher than that of batteries, as well as a long cycle life. To demonstrate that our fibre-based, all-solid-state micro-supercapacitors can be easily integrated into miniaturized flexible devices, we use them to power an ultraviolet photodetector and a light-emitting diode. Hierarchical hybrid carbon fibres consisting of a network of nitrogen-doped reduced graphene oxide and single-walled carbon nanotubes are synthesized and subsequently used to make a supercapacitor with high volumetric energy density.

Polyelectrolyte Functionalized Carbon Nanotubes as Efficient Metal-free Electrocatalysts for Oxygen Reduction

Having a strong electron-withdrawing ability, poly(diallyldimethylammonium chloride) (PDDA) was used to create net positive charge for carbon atoms in the nanotube carbon plane via intermolecular charge transfer. The resultant PDDA functionalized/adsorbed carbon nanotubes (CNTs), either in an aligned or nonaligned form, were demonstrated to act as metal-free catalysts for oxygen reduction reaction (ORR) in fuel cells with similar performance as Pt catalysts. The adsorption-induced intermolecular charge-transfer should provide a general approach to various carbon-based efficient metal-free ORR catalysts for oxygen reduction in fuel cells, and even new catalytic materials for applications beyond fuel cells.

Vertically Aligned BCN Nanotubes as Efficient Metal-Free Electrocatalysts for the Oxygen Reduction Reaction: A Synergetic Effect by Co-Doping with Boron and Nitrogen

Abstract : The oxygen reduction reaction (ORR) is an important process in many fields, including energy conversion (fuel cells, metal air batteries), corrosion, and biosensing. For fuel cells, the cathodic oxygen reduction is a major factor limiting their performance. The ORR can proceed either through a four-electron process to directly combine oxygen with electrons and protons into water as the end product, or a less efficient two-step, two-electron pathway involving the formation of hydroperoxide ions as intermediate. Oxygen reduction also occurs, albeit too slowly to be of any practical significance, in the absence of an ORR catalyst on the cathode. Platinum nanoparticles have long been regarded as the best catalyst for the ORR and are still commonly used in fuel cells due to their relatively low overpotential and high current density with respect to other commercial catalysts. However, the ORR kinetics on the Pt-based electrode is sluggish, and the Pt electrocatalyst still suffers from multiple drawbacks, such as susceptibility to fuel crossover from the anode, deactivation by CO, and poor stability under electrochemical conditions. In addition, the high cost of Pt and its limited natural reserves are the major barriers to mass-market fuel cells for commercial applications.

Highly Efficient Metal-Free Growth of Nitrogen-Doped Single-Walled Carbon Nanotubes on Plasma-Etched Substrates for Oxygen Reduction

We have for the first time developed a simple plasma-etching technology to effectively generate metal-free particle catalysts for efficient metal-free growth of undoped and/or nitrogen-doped single-walled carbon nanotubes (CNTs). Compared with undoped CNTs, the newly produced metal-free nitrogen-containing CNTs were demonstrated to show relatively good electrocatalytic activity and long-term stability toward oxygen reduction reaction (ORR) in an acidic medium. Owing to the highly generic nature of the plasma etching technique, the methodology developed in this study can be applied to many other substrates for efficient growth of metal-free CNTs for various applications, ranging from energy related to electronic and to biomedical systems.

Biocompatible graphene oxide-based glucose biosensors

This letter demonstrates that a novel, highly efficient enzyme electrode can be directly obtained using covalent attachment between carboxyl acid groups of graphene oxide sheets and amines of glucose oxidase. The resulting biosensor exhibits a broad linear range up to 28 mM x mm(-2) glucose with a sensitivity of 8.045 mA x cm(-2) x M(-1). The glucose oxidase-immobilized graphene oxide electrode also shows a reproducibility and a good storage stability, suggesting potentials for a wide range of practical applications. The biocompatibility of as-synthesized graphene oxide nanosheets with human cells, especially retinal pigment epithelium (RPE) cells, was investigated for the first time in the present work. Microporous graphene oxide exhibits good biocompatibility and has potential advantages with respect to cell attachment and proliferation, leading to opportunities for using graphene-based biosensors for the clinical diagnosis.

Polyelectrolyte-Functionalized Graphene as Metal-Free Electrocatalysts for Oxygen Reduction

Poly(diallyldimethylammonium chloride), PDDA, was used as an electron acceptor for functionalizing graphene to impart electrocatalytic activity for the oxygen reduction reaction (ORR) in fuel cells. Raman and X-ray photoelectron spectroscopic measurements indicate the charge transfer from graphene to PDDA. The resultant graphene positively charged via intermolecular charge-transfer with PDDA was demonstrated to show remarkable electrocatalytic activity toward ORR with better fuel selectivity, tolerance to CO posing, and long-term stability than that of the commercially available Pt/C electrode. The observed ORR electrocatalytic activity induced by the intermolecular charge-transfer provides a general approach to various carbon-based metal-free ORR catalysts for oxygen reduction.

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.

Soluble P3HT-grafted graphene for efficient bilayer-heterojunction photovoltaic devices.

CH(2)OH-terminated regioregular poly(3-hexylthiophene) (P3HT) was chemically grafted onto carboxylic groups of graphene oxide (GO) via esterification reaction. The resultant P3HT-grafted GO sheets (G-P3HT) are soluble in common organic solvents, facilitating the structure/property characterization and the device fabrication by solution processing. The covalent linkage and the strong electronic interaction between the P3HT and graphene moieties in G-P3HT were confirmed by spectroscopic analyses and electrochemical measurements. A bilayer photovoltaic device based on the solution-cast G-P3HT/C(60) heterostructures showed a 200% increase of the power conversion efficiency (η = 0.61%) with respect to the P3HT/C(60) counterpart under AM 1.5 illumination (100 mW/cm(2)).

Vertically Aligned Carbon Nanotube Arrays Co-doped with Phosphorus and Nitrogen as Efficient Metal-Free Electrocatalysts for Oxygen Reduction

Using a mixture of ferrocene, pyridine, and triphenylphosphine as precursors for injection-assisted chemical vapor deposition (CVD), we prepared the first vertically aligned multiwalled carbon nanotube array co-doped with phosphorus (P) and nitrogen (N) with a relatively high P-doping level (designated as PN-ACNT). We have also demonstrated the potential applications of the resultant PN-ACNTs as high-performance electrocatalysts for the oxygen reduction reaction (ORR). PN-ACNT arrays were shown to exhibit a high ORR electrocatalytic activity, superb long-term durability, and good tolerance to methanol and carbon monoxide, significantly outperforming their counterparts doped with P (P-ACNT) or N (N-ACNT) only and even comparable to the commercially available Pt-C catalyst (45 wt % Pt on Vulcan XC-72R; E-TEK) due to a demonstrated synergetic effect arising from the co-doping of CNTs with both P and N.

Hole and Electron Extraction Layers Based on Graphene Oxide Derivatives for High-Performance Bulk Heterojunction Solar Cells

By charge neutralization of carboxylic acid groups in graphene oxide (GO) with Cs(2)CO(3) to afford Cesium-neutralized GO (GO-Cs), GO derivatives with appropriate modification are used as both hole- and electron-extraction layers for bulk heterojunction (BHJ) solar cells. The normal and inverted devices based on GO hole- and GO-Cs electron-extraction layers both outperform the corresponding standard BHJ solar cells.