Meixian Li

Selective detection of dopamine in the presence of ascorbic acid and uric acid by a carbon nanotubes-ionic liquid gel modified electrode

The electrochemistry of dopamine (DA) was studied by cyclic voltammetry at a glassy carbon electrode modified by a gel containing multi-walled carbon nanotubes (MWNTs) and room-temperature ionic liquid of 1-octyl-3-methylimidazolium hexafluorophosphate (OMIMPF(6)). The thickness of gel on the surface of the electrode has to be controlled carefully because the charging currents increase with the modified layer being thicker. The anodic peaks of DA, ascorbic acid (AA) and uric acid (UA) in their mixture can be well separated since the peak potential of AA is shifted to more negative values, while that of UA is shifted to more positive values due to the modified electrode. At pH 7.08 the three peaks are separated ca. 0.20 and 0.15V, respectively; hence DA can be determined in the presence of UA and more than 100 times excess of AA. Under optimum conditions linear calibration graphs were obtained over the DA concentration range 1.0x10(-6) to 1.0x10(-4)M. The detection limit of the current technique was found to be 1.0x10(-7)M based on the signal-to-noise ratio of 3. The modified electrode has been successfully applied for the assay of DA in human blood serum. This work provides a simple and easy approach to selectively detect dopamine in the presence of ascorbic acid and uric acid.

Enhanced electrocatalytic activity for hydrogen evolution reaction from self-assembled monodispersed molybdenum sulfide nanoparticles on an Au electrode

Ultrasmall molybdenum sulfide nanoparticles with diameters of 1.47 ± 0.16 nm were fabricated from bulk MoS2 by a combination of ultrasonication and centrifugation. The nanoparticles were then assembled on an Au surface to form a film with high electrocatalytic activity for hydrogen evolution reaction (HER). A Tafel slope of 69 mV per decade was measured for this film and the onset potential was estimated to be −0.09 V. The small loading (1.03 μg cm−2) and the high current density (0.92 mA cm−2 at η = 0.15 V) demonstrated extremely high catalytic efficiency. X-ray photoelectron spectroscopic results revealed that the assembled nanoparticle film was sulfur enriched with abundant S edges and a structural rearrangement of the S rich particles might occur during the self-assembly process, resulting in significantly enhanced electrocatalytic activity for HER. Electrochemical impedance measurements suggested that the assembling process optimized the conductivity of the nanoparticle film, which contributed to the enhanced HER catalytic activity. Our research has provided a new way to synthesize active molybdenum sulfide nanoparticles for HER and a new approach to achieve enrichment of S edges on molybdenum sulfide, which might have potential use not only for electrocatalytic HER, but also for photoelectrocatalytic HER and plasmon-enhanced water splitting.

Electrocatalytic Oxidation of Norepinephrine at a Glassy Carbon Electrode Modified with Single Wall Carbon Nanotubes

The voltammetric behavior of norepinephrine (NE) was studied at a glassy carbon (GC) electrode modified with single wall carbon nanotubes (SWNTs). In pH 5.72 B-R buffer solution, the SWNT-modified electrode shows high electrocatalytic activity toward NE oxidation. One well-defined reversible redox couple is obtained at scan rates lower than 0.15 V s−1. The peak current increases linearly with the concentration of NE in the range of 1.0×10−5 - 1.1×10−3 mol dm−3. The detection limit is 6.0×10−6 mol dm−3 and the diffusion coefficient (D) of NE is 8.53×10−6 cm2 s−1. The SWNT was characterized with scanning electron microscope (SEM). Furthermore, the SWNT-modified electrode has favorable electrocatalytic activity with dopamine, epinephrine, and ascorbic acid.

Biosensor Based on Ultrasmall MoS2 Nanoparticles for Electrochemical Detection of H2O2 Released by Cells at the Nanomolar Level

Monodispersed surfactant-free MoS2 nanoparticles with sizes of less than 2 nm were prepared from bulk MoS2 by simple ultrasonication and gradient centrifugation. The ultrasmall MoS2 nanoparticles expose a large fraction of edge sites, along with their high surface area, which lead to attractive electrocatalytic activity for reduction of H2O2. An extremely sensitive H2O2 biosensor based on MoS2 nanoparticles with a real determination limit as low as 2.5 nM and wide linear range of 5 orders of magnitude was constructed. On the basis of this biosensor, the trace amount of H2O2 released from Raw 264.7 cells was successfully recorded, and an efficient glucose biosensor was also fabricated. Since H2O2 is a byproduct of many oxidative biological reactions, this work serves as a pathway for the application of MoS2 in the fields of electrochemical sensing and bioanalysis.

Electrochemical DNAzyme sensor for lead based on amplification of DNA-Au bio-bar codes.

An electrochemical DNAzyme sensor for sensitive and selective detection of lead ion (Pb(2+)) has been developed, taking advantage of catalytic reactions of a DNAzyme upon its binding to Pb(2+) and the use of DNA-Au bio-bar codes to achieve signal enhancement. A specific DNAzyme for Pb(2+) is immobilized onto an Au electrode surface via a thiol-Au interaction. The DNAzyme hybridizes to a specially designed complementary substrate strand that has an overhang, which in turn hybridizes to the DNA-Au bio-bar code (short oligonucleotides attached to 13 nm gold nanoparticles). A redox mediator, Ru(NH3)6(3+), which can bind to the anionic phosphate of DNA through electrostatic interactions, serves as the electrochemical signal transducer. Upon binding of Pb(2+) to the DNAzyme, the DNAzyme catalyzes the hydrolytic cleavage of the substrate, resulting in the removal of the substrate strand along with the DNA bio-bar code and the bound Ru(NH3)6(3+) from the Au electrode surface. The release of Ru(NH3)6(3+) results in lower electrochemical signal of Ru(NH3)6(3+) confined on the electrode surface. Differential pulse voltammetry (DPV) signals of Ru(NH3)6(3+) provides quantitative measures of the concentrations of Pb(2+), with a linear calibration ranging from 5 nM to 0.1 microM. Because each nanoparticle carries a large number of DNA strands that bind to the signal transducer molecule Ru(NH3)6(3+), the use of DNA-Au bio-bar codes enhances the detection sensitivity by five times, enabling the detection of Pb(2+) at a very low level (1 nM). The DPV signal response of the DNAzyme sensor is negligible for other divalent metal ions, indicating that the sensor is highly selective for Pb(2+). Although this DNAzyme sensor is demonstrated for the detection of Pb(2+), it has the potential to serve as a general platform for design sensors for other small molecules and heavy metal ions.

Size‐Dependent Enhancement of Electrocatalytic Oxygen‐Reduction and Hydrogen‐Evolution Performance of MoS2 Particles

MoS2 particles with different size distributions were prepared by simple ultrasonication of bulk MoS2 followed by gradient centrifugation. Relative to the inert microscale MoS2, nanoscale MoS2 showed significantly improved catalytic activity toward the oxygen-reduction reaction (ORR) and hydrogen-evolution reaction (HER). The decrease in particle size was accompanied by an increase in catalytic activity. Particles with a size of around 2 nm exhibited the best dual ORR and HER performance with a four-electron ORR process and an HER onset potential of -0.16 V versus the standard hydrogen electrode (SHE). This is the first investigation on the size-dependent effect of the ORR activity of MoS2, and a four-electron transfer route was found. The exposed abundant Mo edges of the MoS2 nanoparticles were proven to be responsible for the high ORR catalytic activity, whereas the origin of the improved HER activity of the nanoparticles was attributed to the plentiful exposed S edges. This newly discovered process provides a simple protocol to produce inexpensive highly active MoS2 catalysts that could easily be scaled up. Hence, it opens up possibilities for wide applications of MoS2 nanoparticles in the fields of energy conversion and storage.

Controlled Synthesis of Gold Nanobelts and Nanocombs in Aqueous Mixed Surfactant Solutions

Well-defined gold nanobelts as well as unique gold nanocombs made of nanobelts were readily synthesized by the reduction of HAuCl4 with ascorbic acid in aqueous mixed solutions of the cationic surfactant cetyltrimethylammonium bromide (CTAB) and the anionic surfactant sodium dodecylsulfonate (SDSn). Single-crystalline gold nanobelts grown along the <110> and <211> directions were prepared in mixed CTAB-SDSn solutions at 4 and 27 degrees C, respectively. Furthermore, single-crystalline gold nanocombs consisting of a <110>-oriented stem nanobelt and numerous <211>-oriented nanobelts grown perpendicularly on one side of the stem were fabricated by a two-step process with temperature changing from 4 to 27 degrees C. It was proposed that the mixed cationic-anionic surfactants exerted a subtle control on the growth of gold nanocrystals in solution due to the cooperative effect of mixed surfactants. This synthetic strategy may open a new route for the mild fabrication and hierarchical assembly of metal nanobelts in solution. The obtained gold nanobelts showed good electrocatalytic activity toward the oxidation of methanol in alkaline solution; in particular, the electrode modified with the nanobelts obtained at 27 degrees C exhibited an electrocatalytic activity considerably higher than normal polycrystalline gold electrode. Moreover, the gold nanobelts were used as the surface-enhanced Raman scattering (SERS) substrate for detecting the enhanced Raman spectra of p-aminothiophenol (PATP) molecules, and the gold nanobelts obtained at 4 degrees C exhibited an unusual larger enhancement of the b2 modes relative to the a1 modes for the adsorbed PATP molecules.

Electrocatalytic oxidation of 3,4-dihydroxyphenylacetic acid at a glassy carbon electrode modified with single-wall carbon nanotubes

Abstract The voltammetric behavior of 3,4-dihydroxyphenylacetic acid (DOPAC) was studied at a glassy carbon (GC) electrode modified with single-wall carbon nanotubes (SWNTs). In 0.1 M HAc–NaAc buffer solution (pH 4.4), the SWNT-modified electrode shows high electrocatalytic activity toward oxidation of DOPAC. One well-defined redox couple is obtained. The peak current increases linearly with the concentration of DOPAC in the range of 1.0×10 −6 –1.2×10 −4 M. The detection limit is 4.0×10 −7 M. The results indicate that DOPAC undergoes a two-electron oxidation to o -quinone followed by a dimerization reaction. Rate constant for this dimerization reaction was calculated to be 2.10×10 3 dm 3 mol −1 s −1 . The SWNT was characterized with scanning electron microscope (SEM). This SWNT-modified electrode can also separate the electrochemical responses of DOPAC and 5-hydroxytryptamine (5HT).

Electrochemically Fabricated Polypyrrole and MoSx Copolymer Films as a Highly Active Hydrogen Evolution Electrocatalyst

DOI: 10.1002/adma.201400265 surface area, as well as good stability. [ 14 ] Moreover, It has been demonstrated that [MoS 4 ] 2− and some other molybdenum sulfi de anions can be doped into PPy during the polymerization process, [ 15 ] which makes it an ideal carrier for MoS x . Herein, we demonstrate a simple way to fabricate polypyrrole/MoS x hybrid (PPy/MoS x ) fi lms by a one-step electrochemical copolymerization. The PPy/MoS x fi lms exhibit an outstanding HER performance that is comparable to that of commercial Pt/C catalysts. The highly active PPy/MoS x fi lms for HER were prepared in 0.1 M NaClO 4 containing 0.5 M pyrrole (Py) and 2 m M

Electrocatalytic Hydrogen Evolution Reaction on Edges of a Few Layer Molybdenum Disulfide Nanodots

The design and development of inexpensive highly efficient electrocatalysts for hydrogen production underpins several emerging clean-energy technologies. In this work, for the first time, molybdenum disulfide (MoS2) nanodots have been synthesized by ionic liquid assisted grinding exfoliation of bulk platelets and isolated by sequential centrifugation. The nanodots have a thickness of up to 7 layers (∼4 nm) and an average lateral size smaller than 20 nm. Detailed structural characterization established that the nanodots retained the crystalline quality and low oxidation states of the bulk material. The small lateral size and reduced number of layers provided these nanodots with an easier path for the electron transport and plentiful active sites for the catalysis of hydrogen evolution reaction (HER) in acidic electrolyte. The MoS2 nanodots exhibited good durability and a Tafel slope of 61 mV dec(-1) with an estimated onset potential of -0.09 V vs RHE, which are considered among the best values achieved for 2H phase. It is envisaged that this work may provide a simplistic route to synthesize a wide range of 2D layered nanodots that have applications in water splitting and other energy related technologies.