This article describes the synthesis of branched flower-like gold (Au) nanocrystals and their electrocatalytic activity toward the oxidation of methanol and the reduction of oxygen. Gold nanoflowers (GNFs) were obtained by a one-pot synthesis using N-2-hydroxyethylpiperazine-N-2-ethanesulphonic acid (HEPES) as a reducing/stabilizing agent. The GNFs have been characterized by UV-visible spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), and electrochemical measurements. The UV-visible spectra show two bands corresponding to the transverse and longitudinal surface plasmon (SP) absorption at 532 and 720 nm, respectively, for the colloidal GNFs. The GNFs were self-assembled on a sol-gel-derived silicate network, which was preassembled on a polycrystalline Au electrode and used for electrocatalytic applications. The GNFs retain their morphology on the silicate network; the UV-visible diffuse reflectance spectra (DRS) of GNFs on the silicate network show longitudinal and transverse bands as in the case of colloidal GNFs. The GNFs show excellent electrocatalytic activity toward the oxidation of methanol and the reduction of oxygen. Oxidation of methanol in alkaline solution was observed at approximately 0.245 V, which is much less positive than that on an unmodified polycrystalline gold electrode. Reduction of oxygen to H2O2 and the further reduction of H2O2 to water in neutral pH were observed at less negative potentials on the GNFs electrode. The electrocatalytic activity of GNFs is significantly higher than that of the spherically shaped citrate-stabilized Au nanoparticles (SGNs).

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A nonenzymatic electrochemical method is described for the detection of glucose by using gold (Au) nanoparticles self-assembled on a three-dimensional (3D) silicate network obtained by using sol-gel processes. The nanosized Au particles have been self-assembled on the thiol tail groups of the silicate network and enlarged by hydroxylamine. The Au nanoparticles efficiently catalyze the oxidation of glucose at less-positive potential (0.16 V) in phosphate buffer solution (pH 9.2) in the absence of any enzymes or redox mediators. The Au nanoparticle-modified transducer (MPTS-nAuE) was successfully used for the amperometric sensing of glucose and it showed excellent sensitivity with a detection limit of 50 nM. The common interfering agent ascorbate (AA) does not interfere with the detection of glucose. The MPTS-nAuE transducer showed individual voltammetric responses for glucose and AA. This transducer responded linearly to glucose in the range of 0-8 mM and the sensitivity of the transducer was found to be 0.179 nA cm(-2) nM(-1). Excellent reproducibility, and long-term storage and operational stability was observed for this transducer.

The development of an active, earth-abundant, and inexpensive catalyst for the oxygen evolution reaction (OER) is highly desirable but remains a great challenge. Here, by combining experiments and first-principles calculations, we demonstrate that MoS2 quantum dots (MSQDs) are efficient materials for the OER. We use a simple route for the synthesis of MSQDs from a single precursor in aqueous medium, avoiding the formation of unwanted carbon quantum dots (CQDs). The as-synthesized MSQDs exhibit higher OER activity with a lower Tafel slope in comparison to that for the state of the art catalyst IrO2/C. The potential cycling of the MSQDs activates the surface and improves the OER catalytic properties. Density functional theory calculations reveal that MSQD vertices are reactive and the vacancies at the edges also promote the reaction, which indicates that the small flakes with defects at the edges are efficient for the OER. The presence of CQDs affects the adsorption of reaction intermediates and dramatically suppresses the OER performance of the MSQDs. Our theoretical and experimental findings provide important insights into the synthesis process of MSQDs and their catalytic properties and suggest promising routes to tailoring the performance of the catalysts for OER applications.

Development of a highly sensitive nanostructured electrochemical biosensor based on the integrated assembly of dehydrogenase enzymes and gold (Au) nanoparticle is described. The Au nanoparticles (AuNPs) have been self-assembled on a thiol-terminated, sol-gel-derived, 3-D, silicate network and enlarged by hydroxylamine seeding. The AuNPs on the silicate network efficiently catalyze the oxidation of NADH with a decrease in overpotential of approximately 915 mV in the absence of any redox mediator. The surface oxides of AuNP function as an excellent mediator, and a special inverted "V" shape voltammogram at less positive potential was observed for the oxidation of NADH. The AuNP self-assembled sol-gel network behaves like a nanoelectrode ensemble. The nanostructured electrode shows high sensitivity (0.056 +/- 0.001 nA/nM) toward NADH with an amperometric detection limit of 5 nM. The electrode displays excellent operational and storage stability. A novel methodology for the fabrication of a NADH-dependent dehydrogenase biosensor based on the integration of dehydrogenase enzyme and AuNPs with the silicate network is developed. The enzymatically generated NADH is, in turn, electrocatalytically detected by the AuNPs on the silicate network. The integrated assembly has been successfully used for the amperometric biosensing of lactate and ethanol at a potential of -5 mV. The biosensor is very stable and highly sensitive, and it has a fast response time. The excellent performance validates the integrated assembly as an attractive sensing element for the development of new dehydrogenase biosensors.