Hydrogenation of cinnamaldehyde over Pt/RHCs in supercritical carbon dioxide - Influence of support pretreatment and phase behavior

The selective hydrogenation of cinnamaldehyde (CAL) was investigated using rice husk-based porous carbon (RHCs) supported platinum catalysts in supercritical carbon dioxide (SCCO2). The effects of surface chemistry treatment of the support and the reaction phase behavior have been examined. The Pt/H-RHCs (HNO3-pretreated) was more active for CAL hydrogenation compared with Pt/NH3 - RHCs (NH3 center dot H2O-pretreated). The Pt/RHCs catalyst exhibited a higher selectivity to cinnamyl alcohol (COL) compared with commercial catalyst of Pt/C, which is relative to the micro - mesoporosity structure of the RHCs.

Green synthesis of nanowire-like Pt nanostructures and their catalytic properties

We reported a simple and effective green chemistry route for facile synthesis of nanowire-like Pt nanostructures atone step. In the reaction, dextran acted as a reductive agent as well as a protective agent for the synthesis of Pt nanostructures. Simple mixing of precursor aqueous solutions of dextran and K2PtCl4 at 80 degrees C could result in spontaneous formation of the Pt nanostructures. Optimization of the experiment condition could yield nanowire-like Pt nanostructures at 23:1 molar ratio of the dextran repeat unit to K2PtCl4.

In situ PEI and formic acid directed formation of Pt NPs/MWNTs hybrid material with excellent electrocatalytic activity

A hybrid material based on Pt nanoparticles (Pt NPs) and multi-walled carbon nanotubes (MWNTs) was fabricated with the assistance of PEI and formic acid. The cationic polyelectrolyte PEI not only favored the homogenous dispersion of carbon nanotubes (CNTs) in water, but also provided sites for the adsorption of anionic ions PtCl42- on the MWNTs' sidewalls. Deposition of Pt NPs on the MWNTs' sidewalls was realized by in situ chemical reduction of anionic ions PtCl42- with formic acid. The hybrid material was characterized with TEM, XRD and XPS. Its excellent electrocatalytic activity towards both oxygen reduction in acid media and dopamine redox was also discussed.

Theoretical studies on electronic structures, spectra and charge transporting properties of a series of Pt((CN)-N-Lambda)(2) complexes

We report a quantum-chemical study of electronic, optical and charge transporting properties of four platinum (II) complexes, pt((CN)-N-Lambda)(2) ((CN)-N-Lambda=phenylpyridine or thiophenepyridine). The lowest-lying absorptions at 442, 440, 447 and 429 nm are all attributed to the mixed transition characters of metal-to-ligand charge transfer (MLCT) and ligand-centered (LC) pi - pi(*) transition. While, unexpectedly, the lowest-lying phosphorescent emissions at 663, 660, 675 and 742 nm are mainly from metal-to-ligand charge transfer ((MLCT)-M-3) ligand-centered (LC) pi ->pi* transition. Ionization potential (IP), electron affinities (EA) and reorganization energy P (lambda(hole/electron)) were obtained to evaluate the charge transfer and balance properties between hole and electron.

A novel tris(2,2 '-bipyridine)ruthenium(II)/tripropylamine cathodic electrochemiluminescence in acetonitrile for the indirect determination of hydrogen peroxide

A novel tris(2,2'-bipyridine)ruthenium(II) (Ru(bpy)3(2+)) cathodic electrochemiluminescence (ECL) was generated at -0.78V at the Pt electrode in acetonitrile (ACN), which suggested that the cathodic ECL differed from conventional cathodic ECL It was found that tripropylamine (TPrA) could enhance this cathodic ECL and the linear range (log-log plot) was 0.2 mu M-0.2 mM. In addition, hydrogen peroxide (H2O2) could inhibit the cathodic ECL and was indirectly detected with the linear range of 27-540 mu M. The RSD (n = 12) of the ECL intensity in the presence of 135 mu M H2O2 was 0.87%. This method was also demonstrated for the fast determination of H2O2 in disinfectant sample and satisfactory results were obtained.

Simple and rapid voltammetric determination of morphine at electrochemically pretreated glassy carbon electrodes

A simple and rapid method for morphine detection has been described based on electrochemical pretreatment of glassy carbon electrode (GCE) which was treated by anodic oxidation at 1.75 V, following potential cycling in the potential range from 0 V to 1.0 V vs. Ag vertical bar AgCl reference electrode. The sensitivity for morphine detection was improved greatly and the detection limit was 0.2 mu M. The reproducibility of the voltammetric measurements was usually less than 3% RSD for six replicate measurements. Moreover, this method could readily discriminate morphine from codeine. And an electrochemical detection of morphine in spiked urine sample was succeeded with satisfactory results.

Synthesis, photophysical and electrophosphorescent properties of mononuclear Pt(II) complexes with arylamine functionalized cyclometalating ligands

Four cyclometalated Pt(II) complexes, i.e., [(L-2)PtCl] (1b), [(L-3)PtCl] (1c), [(L-2)PtC CC6H5] (2b) and [(L-3)PtC CC6H5] (2c) (HL2 = 4-[p-(N-butyl-N-phenyl)anilino]-6-phenyl-2,2'-bipyridine and HL3 = 4-[p(-N,N'-dibutyl-N'-phenyl)phenylene-diamino]-phenyl-6-phenyl-2,2'-bipyridine), have been synthesized and verified by H-1 NMR, C-13 NMR and X-ray crystallography. Unlike previously reported complexes [(L-1)PtCl] (1a) and [(L-1)PtC CC6H5] (2a) (HL1 = 4,6-diphenyl-2,2'-bipyridine), intense and continuous absorption bands in the region of 300-500 nm with strong metal-to-ligand charge transfer ((MLCT)-M-1) (d pi(Pt) -> pi*(L)) transitions (epsilon similar to 2 x 10(4) dm(3) mol (1) cm (1)) at 449-467 nm were observed in the UV-Vis absorption spectra of complexes 1b, 1c, 2b and 2c.

Ethanol electrooxidation on Pt/C catalysts promoted with praseodymium oxide nanorods

The Pt/C electrocatalysts containing Pr6O11 nanorods were successfully prepared. By various electrochemical characterization methods, it was demonstrated that the Pr6O11 nanorods have an obviously promotive role for ethanol electrooxidation catalyzed by Pt/C. However, according to the stripping experiment, the promotive effect of Pr6O11 does not result from the easier electrooxidation of the intermediate adsorbate on Pt-Pr6O11/C than on Pt/C. It was supposed that Pr6O11 could promote a certain step in ethanol oxidation, and that the special morphology of the nanorods could further enhance the activity compared with nanoparticles.

Pt Nanoparticles Supported on TiO2 Colloidal Spheres with Nanoporous Surface: Preparation and Use as an Enhancing Material for Biosensing Applications

An easy surface-modified method has been developed to link -NH2 groups to the TiO2 colloidal spheres with nanoporous surface (f-TiO2). It was found that the as-prepared f-TiO2 is positively charged in neutral conditions and could act as an electrostatic anchor for nanosructures with opposite charge, Furthermore, platinum nanoparticles (Pt NPs) are successfully assembled on the f-TiO2 mainly via electrostatic interaction to fabricate a new kind of Pt NPs/TiO2 hybrid nanomaterial (f-TiO2-Pt NPs). The morphology, structure, and composition of the hybrids were characterized by the means of diverse techniques such as transmission electron microscopy, scanning electron microscopy, X-ray powder diffraction, and Raman spectra. Electrochemical experiments indicate the electrode modified with f-TiO2-Pt NPs shows prominent electrocatalytic activity toward the oxidation of hydrogen peroxide.

In Situ Scanning Tunneling Microscopy on the Dynamic Process of the Replacement of Coronene on Au (111) by 6-Mercapto-1-Hexanol

The replacement of coronene monolayer on Au (111) by 6-mercapto-1-hexanol (MHO) was studied by in situ scanning tunneling microscopy (STM) in solutions. It was found that the rate of replacement depends strongly on the concentration of MHO. The replacement finished within a second at a higher concentration of MHO. At a lower concentration, the slow replacement could be followed by in situ STM. The replacement occurred initially near the elbow position of reconstructed Au (111) with the formation of pits in a single or several missing molecules. With the proceeding of replacement, these small pits expanded, and the surrounding coronene molecules were gradually substituted by MHO, which developed into ordered domains within a spatial confined environment. Meanwhile, the reconstruction of Au (111) was lifted. The replacement expanded fast along the reconstruction lines in the domain. For the fast replacement, a (root 3 x root 3) R30 degrees adlattice was observed, while a c(4 x 2) superlattice was observed for the slow replacement.

碱基腺嘌呤与胸腺嘧啶在Au(111)电极上的共吸附

用循环伏安法(CV)和电化学扫描隧道显微镜(ECSTM)在HClO4溶液中研究了配对碱基腺嘌呤(Adenine,A)与胸腺嘧啶(Thymine,T)在Au(111)电极上的共吸附行为。CV曲线表明,A和T的电化学共吸附行为更接近于A的电化学吸附行为。高分辨STM图像显示,在物理吸附区域碱基A和T分子之间通过氢键作用形成一种不同于单组分的网络结构。根据STM图像提出一个可能的模型,并给出了在Au(111)电极上共吸附时A和T分子之间可能的氢键作用方式。

High-efficiency and low-cost hybrid nanomaterial as enhancing electrocatalyst: Spongelike AWN core/shell nanomaterial with hollow cavity

A high-efficiency and low-cost spongelike Au/Pt core/shell electrocatalyst with hollow cavity has been facilely obtained via a simple two-step wet chemical process. Hollow gold nanospheres were first synthesized via a modified galvanic replacement reaction between Co nanoparticles in situ produced and HAUCl(4). The as-prepared gold hollow spheres were employed as seeds to further grow spongelike Pt shell. It is found that the surface of this hybrid nanomaterial owns many Pt nanospikes, which form a spongelike nanostructure. All experimental data including scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and UV-vis-near-infrared spectroscopy have been employed to characterize the obtained Au/Pt hybrid nanomaterial. The rapid development of fuel cell has inspired us to investigate the electrocatalytic properties for dioxygen and methanol of this novel hybrid nanomaterial. Spongelike hybrid nanomaterial mentioned here exhibits much higher catalytic activity for dioxygen reduction and methanol oxidation than the common Pt electrode.

Antioxidant Sensors Based on Iron Diethylenetriaminepentaacetic Acid, Hematin, and Hemoglobin Modified TiO2 Nanoparticle Printed Electrodes

Antioxidant amperometric sensors based on iron-containing complexes and protein modified electrodes were developed. Indium tin oxide glass was printed with TiO2 nanoparticles, onto which iron-containing compounds and protein were adsorbed. When applied with negative potentials, the dissolved oxygen is reduced to H2O2 at the electrode surface, and the H2O2 generated in situ oxidizes Fe-II to Fe-III, and then electrochemical reduction of Fe-III therefore gives rise to a catalytic current. In the presence of antioxidants, H2O2 was scavenged, the catalytic current was reduced, and the decreased current signal was proportional to the quantity of existing antioxidants. A kinetic model was proposed to quantify the H2O2 scavenging capacities of the antioxidants. With the use of the sensor developed here, antioxidant measurements can be done quite simply: put the sensor into the sample solutions (in aerobic atmosphere), perform a cathodic polarization scan, and then read the antioxidant activity values. The present work can be complementary to the previous studies of antioxidant sensor techniques based on OH radicals and superoxide ions scavenging methods, but the sensor developed here is much easier to fabricate and use.

Polyaniline/Pt Hybrid Nanofibers: High-Efficiency Nanoelectrocatalysts for Electrochemical Devices

A simple and facile procedure to synthesize a novel hybrid nanoelectrocatalyst based on polyaniline (PANI) nanofiber-supported supra-high density Pt nanoparticles (NPs) or Pt/Pd hybrid NPs without prior PANI nanofiber functionalization at room temperature is demonstrated. This represents a new type of ID hybrid nanoelectrocatalyst with several important benefits. First, the procedure is very simple and can be performed at room temperature using commercially available reagents without the need for templates and surfactants. Second, ultra-high density small "bare" Pt NPs or Pt/Pd hybrid NPs are grown directly onto the surface of the PANI nanofiber, without using any additional linker. Most importantly, the present PANI nanofiber-supported supra-high density Pt NPs or Pt/Pd hybrid NPs can be used as a signal enhancement element for constructing electrochemical devices with high performance.