Rapid room temperature synthesis of electrocatalytically active Au nanostructures

We describe a facile route for the one-pot room temperature synthesis of anisotropic Au nanostructures in aqueous solution in the absence of seeds or surfactants and their electrocatalytic activity. The Au nanostructures were synthesized using piperazine derivatives 1-(2-hydroxyethyl)piperazine and 1,4-Bis(2-hydroxyethyl)piperazine as reducing agents. The Au nanostructures were characterized by spectral, transmission electron microscopic (TEM), X-ray diffraction and electrochemical measurements. The absorption spectrum of colloidal nanoparticles displays two bands ~580 and ~930 nm, corresponding to the dipole and quadrupole plasmon resonance, respectively. TEM measurements show that the Au nanostructures have penta-twined polyhedral shape with an average size of 52 nm. X-ray and selected area electron diffraction patterns reveal the existence of face centered cubic nanocrystalline Au. The concentration of Au(III) controls the stability of the nanoparticles. The nanoparticles were immobilized on 3-D silicate network pre-assembled on a conducting support to examine their electrocatalytic activity. The nanoparticle-based electrochemical interface was characterized by spectral, voltammetric and impedance measurements. The nanoparticle shows high catalytic activity in the oxidation of NADH and reduction of oxygen. Unique inverted 'V' shape voltammogram was obtained for the oxidation of NADH at less positive potential. The nanoparticle-based interface favors two-step four-electron reduction of oxygen to water in neutral pH. Significant decrease in the overpotential for the oxidation of NADH and reduction of oxygen with respect to the polycrystalline Au electrode was observed. The electrocatalytic performance of the polyhedral nanoparticle is compared with the conventional citrate stabilized spherical nanoparticles.     

Morphology dependent electrocatalytic activity of Au nanoparticles

The electrocatalytic activity of spherical shape Au particles chemically grown on a sol–gel derived 3D silicate network modified conducting surface has been studied using ascorbate as a model. The nanostructured Au particles show morphology dependent electrocatalytic activity towards ascorbate. Unusual voltammetric behavior for ascorbate has been observed. Unlike the polycrystalline Au electrode, the nanostructured electrode shows two well defined voltammetric peaks for ascorbate at 0 and 0.3 V in neutral and alkaline pHs. These voltammetric peaks are assigned for the oxidation of ascorbate to dehydroascorbate (DHA) and the further oxidation of 2,3-diketogluonic acid (DKG), the hydrolyzed product of DHA. The voltammetric peak corresponding to the oxidation of DKG is very sensitive to the supporting electrolyte anions and solution pH. Voltammetric behavior of DHA has been investigated to support the oxidation pathway of ascorbate on the nanostructured electrode. Surface morphology of the particle controls the electrocatalytic activity.     

钛基纳米多孔金电极对甲醛氧化的电催化活性

采用水热法制备了钛基纳米金微粒修饰电极(Au/Ti)。扫描电镜图表明纳米金颗粒粒径大约为300 nm,在钛基体表面构成三维多孔网状结构。运用循环伏安,电位阶跃和交流阻抗等电化学技术研究了碱性介质中甲醛在Au/Ti电极上的电氧化行为。循环伏安图显示,甲醛在Au/Ti上的起始氧化电位在-0.90 V左右,相对于多晶金电极提前大约0.2 V,交流阻抗测试表明,甲醛在Au/Ti电极上电氧化表现出低的电荷传递电阻。研究结果表明钛基纳米金微粒修饰电极对甲醛氧化具有良好的电催化活性。     

Ternary Ag/Polyaniline/Au nanocomposites: Preparation,characterization and electrochemical properties

Ternary Ag/Polyaniline/Au nanocomposites were synthesized successfully by immobilizing of Au nanoparticles (NPs) on the surface of Ag/Polyaniline (PANI) nanocomposites. Ag/PANI nanocomposites were prepared via in situ chemical polymerization of aniline in the presence of 4-aminothiophenol (4-ATP) capped silver colloidal NPs. Then, uniform gold (Au) NPs were assembled on the surface of resulted Ag/PANI nanocomposites through electrostatic interaction to get Ag/Polyaniline/Au nanocomposites. The nanocomposites were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX), ultraviolet visible spectroscopy (UV-Vis), thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FTIR). Moreover, Ag/PANI/Au nanocomposites were immobilized on the surface of a glassy carbon electrode and showed enhanced electrocatalytic activity for the reduction of H₂O₂ compared with Ag/PANI.     

A simple one-step preparation of high utilization AuPt nanoparticles supported on MWCNTs for methanol oxidation in alkaline medium

A simple one-step preparation of gold–platinum electrocatalysts supported on multi-walled carbon nanotubes (MWCNTs) with high utilization is reported. A low Pt loading series of bimetallic AuPt/MWCNTs catalysts were prepared by the improved ethylene glycol reduction method, and then they were compared in terms of the electrocatalytic activity for methanol oxidation using cyclic voltammetry (CV) and chronoamperometry in alkaline solutions. The structure of AuPt/MWCNTs was characterized by the transmission electron microscopy (TEM), X-ray diffraction (XRD) and energy-dispersive X-ray spectroscopy (EDS). The results showed high Pt utilization, uniform AuPt nanoparticles size and good electrocatalytic activity for methanol electro-oxidation. The effect of Au/Pt mass ratio on electrocatalytic activity was also investigated by CV and chronoamperometry. The highest peak current density, lowest onset potential and best anti-poisoning effect for methanol electro-oxidation appeared at the Au/Pt/MWCNTs mass ratio of 2:4:32.     

A novel hydrogen peroxide sensor based on Ag nanoparticles electrodeposited on chitosan-graphene oxide/cysteamine-modified gold electrode

A novel strategy to fabricate a hydrogen peroxide sensor based on Ag nanoparticles electrodeposited on chitosan-graphene oxide nanocomposites/cysteamine-modified gold (Au) electrode was reported. The chitosan-graphene oxide nanocomposites were first assembled on a cysteamine-modified Au electrode to produce chitosan-graphene oxide/cysteamine/Au electrode. Then Ag nanoparticles were electrodeposited on the modified Au electrode and formed Ag nanoparticles/chitosan-graphene oxide/cysteamine/Au electrode. The chitosan-graphene oxide nanocomposites and the electrodeposited Ag nanoparticles were characterized by atomic force microscopy and scanning electron microscopy. The results showed the Ag nanoparticles were uniformly dispersed on the chitosan-graphene oxide/cysteamine/Au electrode. The cyclic voltammagrams and amperometric method were used to evaluate electrocatalytic properties of the Ag nanoparticles/chitosan-graphene oxide/cysteamine/Au electrode. The results showed that the modified electrode displayed good electrocatalytic activity to the reduction of hydrogen peroxide with a detection limit of 0.7 μM hydrogen peroxide based on a signal-to-noise ratio of 3. The sensor has good reproducibility, wide linear range, and long-term stability.     

Gold particles supported on self-organized nanotubular TiO2 matrix as highly active catalysts for electrochemical oxidation of glucose

Au/TiO₂/Ti electrode was prepared by a two-step process of anodic oxidation of titanium followed by cathodic electrodeposition of gold on resulted TiO₂. The morphology and surface analysis of Au/TiO₂/Ti electrodes was investigated using scanning electron microscopy and EDAX, respectively. The results indicated that gold particles were homogeneously deposited on the surface of TiO₂ nanotubes. The nanotubular TiO₂ layers consist of individual tubes of about 60–90 nm in diameter, and the electrode surface was covered by gold particles with a diameter of about 100–200 nm which are distributed evenly on the titanium dioxide nanotubes. This nanotubular TiO₂ support provides a high surface area and therefore enhances the electrocatalytic activity of Au/TiO₂/Ti electrode. The electrocatalytic behavior of Au/TiO₂/Ti electrodes in the glucose electro-oxidation was studied by cyclic voltammetry. The results showed that Au/TiO₂/Ti electrodes exhibit a considerably higher electrocatalytic activity toward the glucose oxidation than that of gold electrode.     

Electrochemical Biosensor Utilizing Supramolecular Association of Enzyme on Sol−gel Matrix Embedded Gold Nanoparticles Supported Reduced Graphene Oxide−cyclodextrin Nanocomposite

Herein we present β‐cyclodextrin (CD)‐functionalized reduced graphene oxide (RGO) nanosheets supported on silicate sol‐gel matrix‐embedded gold nanoparticles (Au NPs) modified electrode as a new affinity binding nanocomposite. The modified electrode is fabricated through layer‐by‐layer drop casting followed by immobilization of chemically modified enzyme conjugate (horse radish peroxidase (HRP)?adamantane carboxylic acid (ADA)). This affinity system is based on the supramolecular association between CDs and HRP?ADA and is mimicking the biological avidin?biotin interactions. CDs‐functionalized RGO (RGO?CD) functions as a macrocyclic host to form stable supramolecular inclusion complexes with enzyme conjugate. Besides Au NPs improve the interfacial interaction with RGO?CD nanosheets, and thus exhibit synergistic electrocatalytic effect toward H₂O₂ reduction in the presence of 1 mM hydroquinone.     

Selective electronalysis of peracetic acid in the presence of a large excess of H2O2 at Au(1 1 1)-like gold electrode

Peracetic acid (PAA) has been selectively electroanalyzed in the presence of a large excess of hydrogen peroxide (H₂O₂), about 500 fold that of PAA, using Au (1 1 1)-like gold electrode in acetate buffer solutions of pH 5.4. Au(1 1 1)-like gold electrode was prepared by a controlled reductive desorption of a previously assembled thiol, typically cysteine, monolayer onto the polycrystalline gold (poly-Au) electrode. Cysteine molecules were selectively removed from the Au(1 1 1) facets of the poly-Au electrode, keeping the other two facets (i.e., Au(1 1 0) and Au(1 0 0)) under the protection of the adsorbed cysteine. It has been found that Au(1 1 1)-like gold electrode positively shifts the reduction peak of PAA, while, fortunately, shifts the reduction peak of H₂O₂ negatively, achieving a large potential separation (around 750 mV) between the two reduction peaks as compared with that (around 450 mV) obtained at the poly-Au electrode. This large potential separation between the two reduction peaks enabled the analysis of PAA in the presence of a large excess of H₂O₂. In addition, the positive shift of the reduction peak of PAA gives the present method a high immunity against the interference of the dissolved oxygen.     

Synthesis of atomic gold clusters with strong electrocatalytic activities

Small atomic gold clusters in solution, Au n , stabilized by tetrabutyl ammonium bromide (TBABr), have been synthesized by a simple electrochemical technique, based on the anodic dissolution of a gold electrode in the presence of TBABr salt, and using acetronitrile as solvent. The presence of clusters in the range Au3-Au11 were detected by MALDI-TOF spectroscopy, and further characterized by UV-vis absorption spectroscopy, TEM, AFM, X-ray diffraction, and cyclic voltammetry. Clusters display a semiconductor behavior with a band edge of approximately 2.5 eV. We report here their extraordinarily high electrocatalytic activity toward the O2 reduction reaction in acid solutions, which can explain Zhang's results, showing that a four-electron mechanism seems to occur because of the facile reduction of H2O2 on gold clusters compared to bulk gold or larger gold nanoparticles.     

Electrocatalytic mechanism and kinetics of SOMs oxidation on ordered PtPb and PtBi intermetallic compounds: DEMS and FTIRS study

The electrocatalytic activities and mechanisms of PtPb and PtBi ordered intermetallic phases towards formic acid, formaldehyde and methanol oxidation have been studied by DEMS and FTIRS, and the results compared to those for a pure polycrystalline platinum electrode. While PtPb exhibits an enhanced electrocatalytic activity for the oxidation of all three organic molecules when compared to a Pt electrode, PtBi exhibits an enhanced catalytic activity towards formic acid and formaldehyde oxidation, but not methanol. FTIRS data indicate that adsorbed CO does not form on PtPb or PtBi intermetallic compounds during the oxidation of formic acid, formaldehyde and methanol, and therefore their oxidation on both PtPb and PtBi intermetallic compounds proceeds via a non-CO(ads) pathway. Quantitative DEMS measurements indicate that only CO(2) was detected as a final product during formic acid oxidation on Pt, PtPb and PtBi electrodes. At a smooth polycrystalline platinum electrode, the oxidation of formaldehyde and methanol produces mainly intermediates (formaldehyde and formic acid), while CO(2) is a minor product. In contrast, CO(2) is the major product for formaldehyde and methanol oxidation at a PtPb electrode. The high current efficiency of CO(2) formation for methanol and formaldehyde oxidation at a PtPb electrode can be ascribed to the complete dehydrogenation of formaldehyde and formic acid due to electronic effects. The low onset potential, high current density and high CO(2) yield make PtPb one of the most promising electrocatalysts for fuel cell applications using small organic molecules as fuels.     

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 activity of a novel titanium-supported nanoporous gold catalyst for glucose oxidation

A novel Ti-supported gold catalyst (nanoAu/Ti) with a nanoporous 3D texture has been fabricated using a hydrothermal method. Au particles were stably deposited on the Ti surface from the mixture of aqueous tetrachlororoauric acid and polyethylene glycol at 180 °C. Voltammetry (CV) and chronoamperometry were used to characterize the nanoAu/Ti electrode and assess its electroactivity towards glucose oxidation. Compared to polycrystalline Au, the nanoAu/Ti electrode shows similar CV profiles in alkaline solution. However, in an alkaline solution containing 10 mM glucose, the nanoAu/Ti electrode presents much higher anodic current densities and a more negative onset potential (ca. ?0.75 V) for glucose oxidation than a bulk Au electrode. Analysis for Tafel plot of the nanoAu/Ti electrode shows that electro-oxidation of glucose takes place via a one-electron rate-determining step. Results indicate a high and (relatively) stable electrocatalytic activity of the nanoAu/Ti for glucose oxidation.     

分形等离激元黑金的热电子催化性能

借鉴电镀工业中过电流“烧焦”现象, 在过电流沉积条件下一步制备出等离激元黑金. 扫描电子显微镜、 透射电子显微镜、 X射线衍射和紫外-可见-近红外吸收光谱等表征结果显示, 该黑金是具有三维分形结构的多晶纳米金, 可以在 400~1800 nm宽波段范围内吸收光. 电催化甲醇结果显示, 黑金在宽波长光照下可以将甲醇的电催化效率提高 15.2%, 其主要贡献来源于等离激元生成的热电子, 而一小部分来自环境热. 在不同的单色光照条件下, 黑金的催化效率差别不大, 表明其对光能的利用没有明显的波长选择性.     

Direct electrochemistry of glucose oxidase on sulfonated graphene/gold nanoparticle hybrid and its application to glucose biosensing

Sulfonated graphene nanosheet/gold nanoparticle (SGN/Au) hybrid was synthesized by electrostatic self-assembly of anionic SGN and positively charged gold nanoparticles. Due to the well-dispersivity of SGN in aqueous solution and its adequate negative charge, Au nanoparticles were assembled uniformly on graphene surface with high distribution. With the advantages of both graphene and Au nanoparticles, SGN/Au hybrid showed enhanced electrocatalytic activity towards O₂ reduction. Furthermore, it provided a conductive and favorable microenvironment for the glucose oxidase (GOD) immobilization and thus promoted its direct electron transfer at the glassy carbon electrode. Based on the consumption of O₂ caused by glucose at the interface of GOD electrode modified with SGN/Au hybrid, the modified electrode displayed satisfactory analytical performance, including high sensitivity (14.55 μA mM^?1 cm^?2), low detection limit (0.2 mM), an acceptable linear range from 2 to 16 mM, and also the prevention from the interference of some species. These results indicated that the prepared SGN/Au hybrid is a promising candidate material for high-performance glucose biosensor.     

葡萄糖在纳米金修饰金电极上电化学行为研究

利用电还原氯金酸制备了纳米金(Nano-gold,NG)修饰Au电极。该电极对葡萄糖有催化作用,可能是由于纳米金降低了OH-表面吸附能,增加了OH-在电极表面的吸附量。通过循环伏安法研究了扫描速度、温度、本体浓度和溶液pH值对葡萄糖氧化的影响。     

Effect of the iridium oxide thin film on the electrochemical activity of platinum nanoparticles

The influence of the iridium oxide thin film on the electrocatalytic properties of platinum nanoparticles was investigated using the electro-oxidation of methanol and CO as a probe. The presence of the IrO(2) thin film leads to the homogeneous dispersion of Pt nanoparticles. For comparison, polycrystalline platinum and Pt nanoparticles dispersed on a Ti substrate in the absence of an IrO(2) layer (Ti/Pt) were also investigated in this study. Inverted and enhanced CO bipolar peaks were observed using an in situ electrochemical Fourier transform infrared technique during the methanol oxidation on the Pt nanoparticles dispersed on a Ti substrate. Electrochemical impedance studies showed that the charge transfer resistance was significantly lower for the Ti/IrO(2)/Pt electrode compared with that of the massive Pt and Ti/Pt nanoparticles. The presence of the IrO(2) thin film not only greatly increases the active surface area but also promotes CO oxidation at a much lower electrode potential, thus, significantly enhancing the electrocatalytic activity of Pt nanoparticles toward methanol electro-oxidation.     

Electroless synthesis of multibranched gold nanostructures encapsulated by poly(o-phenylenediamine) in Nafion

Multibranched gold (Au) nanocomposite materials encapsulated by poly(o-phenylenediamine) (PoPD) (Au@PoPD) were synthesized in a Nafion polymer film through the electroless synthetic route. The micro-heterogeneous structured Nafion film acted as a reaction vessel and as the template for the formation of Au@PoPD nanocomposite materials leading to the formation of highly uniform distribution of high density of the polymer-gold nanocomposite material. The formation of Au@PoPD nanomaterials at the GP/Nf surface was scrutinized by recording in situ absorption spectra and was characterized. The formation of the (111) plane of gold was dominant at the Au@PoPD nanocomposite. The ratio of the benzenoid and quinoid units of the PoPD (ca. 1.65) observed for the Au@PoPD confirmed that the micro-heterogeneous structure of Nf film acted as a reaction vessel and as template for the formation of Au@PoPD nanocomposite material. Both PoPD and Au at the Au@PoPD nanocomposite showed electrochemical activities at the GC/Nf-Au@PoPD modified electrode. The electrocatalytic activity of the GC/Nf-Au@PoPD modified electrode was studied for oxygen reduction reaction (ORR).     

Improvement of Selectivity and Stability of Amperometric Detection of Hydrogen Peroxide Using Prussian Blue‐PAMAM Supramolecular Complex Membrane as a Catalytic Layer

A novel hydrogen peroxide (H₂O₂) sensor was fabricated by using a submonolayer of 3‐mercaptopropionic acid (3‐MPA) adsorbed on a polycrystalline gold electrode further reacted with poly(amidoamine) (PAMAM) dendrimer (generation 4.0) to obtain a film on which Prussian Blue (PB) was later coordinated to afford a mixed and stable electrocatalytic layer for H₂O₂ reduction. On the basis of the electrochemical behaviors, atomic force microscopy (AFM) and X‐ray photoelectron spectra (XPS), it is suggested that the PB molecules are located within the dendritic structure of the surface attached PAMAM dendrimers. It was found that the PB/PAMAM/3‐MPA/Au modified electrode showed an excellent electrocatalytic activity for H₂O₂ reduction. The effects of applied potential and pH of solution upon the response of the modified electrode were investigated for an optimum analytical performance. Even in the presence of dissolved oxygen, the sensor exhibited highly sensitive and rapid response to H₂O₂. The steady‐state cathodic current responses of the modified electrode obtained at ?0.20 V (vs. SCE) in air‐saturated 0.1 mol L^?1 phosphate buffer solution (PBS, pH 6.50) showed a linear relationship to H₂O₂ concentration ranging from 1.2×10^?6 mol L^?1 to 6.5×10^?4 mol L^?1 with a detection limit of 3.1×10^?7 mol L^?1. Performance of the electrode was evaluated with respected to possible interferences such as ascorbic acid and uric acid etc. The selectivity, stability, and reproducibility of the modified electrode were satisfactory.     

基于SnO2为修饰层的Au-Pt / SnO2 / Au复合电极研究

用真空镀膜法在Au电极上沉积SnO₂薄膜，在HAuCl₄和H₂PtCl₄的混合溶液中利用直接还原法，将Au-Pt双金属纳米颗粒组装在SnO₂ / Au电极上，得到Au-Pt / SnO₂ / Au复合电极。采用SEM、TEM、XPS及CV曲线测定对Au-Pt / SnO₂ / Au复合电极进行了表征。结果表明:复合电极上双金属纳米颗粒分布均匀，粒子粒径约为25 nm左右。SnO₂作为修饰层以配位键与双金属纳米粒子结合。Au-Pt / SnO₂ / Au复合电极具有良好对甲醇氧化的电化学性能。