Xing-Hua Xia

A Green Approach to the Synthesis of Graphene Nanosheets

Graphene can be viewed as an individual atomic plane extracted from graphite, as unrolled single-walled carbon nanotube or as an extended flat fullerene molecule. In this paper, a facile approach to the synthesis of high quality graphene nanosheets in large scale through electrochemical reduction of exfoliated graphite oxide precursor at cathodic potentials (completely reduced potential: -1.5 V) is reported. This method is green and fast, and will not result in contamination of the reduced material. The electrochemically reduced graphene nanosheets have been carefully characterized by spectroscopic and electrochemical techniques in comparison to the chemically reduced graphene-based product. Particularly, FTIR spectra indicate that a variety of the oxygen-containing functional groups have been thoroughly removed from the graphite oxide plane via electrochemical reduction. The chemically converted materials are not expected to exhibit graphenes electronic properties because of residual defects. Indeed, the high quality graphene accelerates the electron transfer rate in dopamine electrochemistry (DeltaE(p) is as small as 44 mV which is much smaller than that on a glassy carbon electrode). This approach opens up the possibility for assembling graphene biocomposites for electrocatalysis and the construction of biosensors.

Catalyst-Free Synthesis of Nitrogen-Doped Graphene via Thermal Annealing Graphite Oxide with Melamine and Its Excellent Electrocatalysis

The electronic and chemical properties of graphene can be modulated by chemical doping foreign atoms and functional moieties. The general approach to the synthesis of nitrogen-doped graphene (NG), such as chemical vapor deposition (CVD) performed in gas phases, requires transitional metal catalysts which could contaminate the resultant products and thus affect their properties. In this paper, we propose a facile, catalyst-free thermal annealing approach for large-scale synthesis of NG using low-cost industrial material melamine as the nitrogen source. This approach can completely avoid the contamination of transition metal catalysts, and thus the intrinsic catalytic performance of pure NGs can be investigated. Detailed X-ray photoelectron spectrum analysis of the resultant products shows that the atomic percentage of nitrogen in doped graphene samples can be adjusted up to 10.1%. Such a high doping level has not been reported previously. High-resolution N1s spectra reveal that the as-made NG mainly contains pyridine-like nitrogen atoms. Electrochemical characterizations clearly demonstrate excellent electrocatalytic activity of NG toward the oxygen reduction reaction (ORR) in alkaline electrolytes, which is independent of nitrogen doping level. The present catalyst-free approach opens up the possibility for the synthesis of NG in gram-scale for electronic devices and cathodic materials for fuel cells and biosensors.

Synthesis of boron doped graphene for oxygen reduction reaction in fuel cells

Boron atoms, with strong electron-withdrawing capability, are doped into graphene frameworks forming boron doped graphene (BG) via a catalyst-free thermal annealing approach in the presence of boron oxide. Atomic force microscopic (AFM) and transmission electron microscopic (TEM) characterizations reveal that the as-prepared BG has a flake-like structure with an average thickness of ca. 2 nm. X-ray photoelectron spectroscopy (XPS) analysis demonstrates that boron atoms can be successfully doped into graphene structures with the atomic percentage of 3.2%. Due to its particular structure and unique electronic properties, the resultant BG exhibits excellent electrocatalytic activity towards oxygen reduction reaction (ORR) in alkaline electrolytes, similar to the performance of Pt catalysts. In addition, the non-metallic BG catalyst shows long-term stability and good CO tolerance superior to that of Pt-based catalysts. These results demonstrate that the BG, as a promising candidate in advanced electrode materials, may substitute Pt-based nanomaterials as a cathode catalyst for ORR in fuel cells as well as other electrochemical applications similar to the reported nitrogen doped graphene.

Electrochemical sensor based on nitrogen doped graphene: simultaneous determination of ascorbic acid, dopamine and uric acid.

Nitrogen doped graphene (NG) was prepared by thermally annealing graphite oxide and melamine mixture. After characterization by atomic force microscopy and X-ray photoelectron spectroscopy etc., the electrochemical sensor based on NG was constructed to simultaneously determine small biomolecules such as ascorbic acid (AA), dopamine (DA) and uric acid (UA). Due to its unique structure and properties originating from nitrogen doping, NG shows highly electrocatalytic activity towards the oxidation of AA, DA and UA. The electrochemical sensor shows a wide linear response for AA, DA and UA in the concentration range of 5.0×10(-6) to 1.3×10(-3)M, 5.0×10(-7) to 1.7×10(-4)M and 1.0×10(-7) to 2.0×10(-5)M with detection limit of 2.2×10(-6)M, 2.5×10(-7)M and 4.5×10(-8)M at S/N=3, respectively. These results demonstrate that NG is a promising candidate of advanced electrode material in electrochemical sensing and other electrocatalytic applications.

Study of the nonenzymatic glucose sensor based on highly dispersed Pt nanoparticles supported on carbon nanotubes

An amperometric biosensor for sensitive and selective detection of glucose has been constructed by using highly dispersed Pt nanoparticles supported on carbon nanotubes (Pt-MWCNTs) as sensing interface. The Pt-MWCNTs were synthesized by using the two-step pyrolysis method. This composite shows good electrocatalytic activity towards the oxidation of glucose in alkaline and thus can be used to selectively detect glucose. We found that detection potential and Nafion amount covered on the Pt-MWCNTs modified glassy carbon electrode had considerable influence on the selectivity for amperometric detection of glucose. Under optimal detection conditions (detection potential of 0.0V versus SCE and 10muL 1.5% Nafion), selective detection of glucose in the glucose concentration range of 1.0-26.5mM (correlation coefficient, >0.999) can be performed. The results demonstrate that the Pt-MWCNTs composite is promising for the fabrication of nonenzymatic glucose sensors.

Early stages in the oxidation of ethanol at low index single crystal platinum electrodes

Abstract Conventional electrochemical methods and in situ FTIR spectroscopy have been applied to study the early stages for adsorption oxidation of ethanol at Pt(111), Pt(110), and Pt(100). Spectroscopic results show that the electrooxidation of ethanol on all three surf is characterised by the formation of acetaldehyde, acetic acid and carbon dioxide as soluble products. Linearly and bridge bonded CC identified as adsorbed species. At Pt(110) other surface species containing CH and COH bonds are observed. In the hydrogen region the Pt(100) surface, the interconversion between bridge and linearly bonded CO, turns out to be a common feature during electrooxidation of small organic molecules. The important role played by adsorbed water is discussed. Adsorption of ethanol is the determining step.

Peroxidase-like activity of water-soluble cupric oxide nanoparticles and its analytical application for detection of hydrogen peroxide and glucose

Water-soluble cupric oxide nanoparticles are fabricated via a quick-precipitation method and used as peroxidase mimetics for ultrasensitive detection of hydrogen peroxide and glucose. The water-soluble CuO nanoparticles show much higher catalytic activity than that of commercial CuO nanoparticles due to their higher affinity to hydrogen peroxide. In addition, the as-prepared CuO nanoparticles are stable over a wide range of pH and temperature. This excellent stability in the form of aqueous colloidal suspensions makes the application of the water-soluble CuO nanoparticles easier in aqueous systems. A colorimetric assay for hydrogen peroxide and glucose has been established based on the catalytic oxidation of phenol coupled with 4-amino-atipyrine by the action of hydrogen peroxide. This analytical platform not only confirms the intrinsic peroxidase-like activity of the water-soluble cupric oxide nanoparticles, but also shows its great potential applications in environmental chemistry, biotechnology and medicine.

Hot Electron of Au Nanorods Activates the Electrocatalysis of Hydrogen Evolution on MoS2 Nanosheets

Efficient water splitting through electrocatalysis holds great promise for producing hydrogen fuel in modern energy devices. Its real application however suffers from sluggish reaction kinetics due to the lack of high-performance catalysts except noble metals such as platinum. Herein, we report an active system of plasmonic-metal Au nanorods/molybdenum disulfide (MoS2) nanosheets hybrids for the hydrogen evolution reaction (HER). The plasmonic Au-MoS2 hybrids dramatically improve the HER, leading to a ∼3-fold increase of current under excitation of Au localized surface plasmon resonance (LSPR). A turnover of 8.76 s(-1) at 300 mV overpotential is measured under LSPR excitation, which by far exceeds the activity of MoS2 catalysts reported recently. The HER enhancement can be largely attributed to the increase of carrier density in MoS2 induced by the injection of hot electrons of Au nanorods. We demonstrate that the synergistic effect of the hole scavengers can further facilitate electron-hole separation, resulting in a decrease of the overpotential of HER at MoS2 to ∼120 mV. This study highlights how metal LSPR activates the HER and promises novel opportunities for enhancing intrinsic activities of semiconducting materials.

Adsorption of water at Pt(111) electrode in HClO4 solutions. The potential of zero charge

FTIR reflection-absorption spectra at Pt(111) show potential dependent bands near 3100 and 1620 cm−1, corresponding respectively to the O-H stretching and H-O-H in-plane deformation of adsorbed water molecules. At around 0.35 V vs. RHE, water orientation changes from hydrogen down to oxygen down indicating that the zero charge potential of Pt(111) is close to this value. In the potential region corresponding to the anomalous wave of Pt(111) the bending frequency decreases, consistent with a strengthening of the H2O-Pt interaction. A band at 3270 cm−1 is assigned to adsorbed hydroxyl ions formed by partial dissociation of water. The vibrational behavior is correlated with the features in the voltammogram.

In Situ Growth of Porous Platinum Nanoparticles on Graphene Oxide for Colorimetric Detection of Cancer Cells

A green approach is proposed for in situ growth of porous platinum nanoparticles on graphene oxide (PtNPs/GO). The resulting nanocomposite has been proven to function as peroxidase mimetics that can catalyze the reaction of peroxidase substrate in the presence of hydrogen peroxide. On the basis of the peroxidase-like activity, we used the PtNPs/GO as a signal transducer to develop a colorimetric assay for the direct detection of cancer cells. By using folic acid as a recognition element, a total of 125 cancer cells (MCF-7) can be distinguished by naked-eye observation. We envision that this nanomaterial could be used as a power tool for a wide range of potential applications in biotechnology and medicine.