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1.
Biosensors (Basel) ; 11(9)2021 Sep 13.
Article in English | MEDLINE | ID: mdl-34562925

ABSTRACT

A series of gold (Au) nanostructures, having different morphologies, were fabricated for amperometric selective detection of carbon monoxide (CO), a biologically important signaling molecule. Au layers were electrodeposited from a precursor solution of 7 mM HAuCl4 with a constant deposition charge (0.04 C) at various deposition potentials. The obtained Au nanostructures became rougher and spikier as the deposition potential lowered from 0.45 V to 0.05 V (vs. Ag/AgCl). As prepared Au layers showed different hydrophobicity: The sharper morphology, the greater hydrophobicity. The Au deposit formed at 0.05 V had the sharpest shape and the greatest surface hydrophobicity. The sensitivity of an Au deposit for amperometric CO sensing was enhanced as the Au surface exhibits higher hydrophobicity. In fact, CO selectivity over common electroactive biological interferents (L-ascorbic acid, 4-acetamidophenol, 4-aminobutyric acid and nitrite) was improved eminently once the Au deposit became more hydrophobic. The most hydrophobic Au was also confirmed to sense CO exclusively without responding to nitric oxide, another similar gas signaling molecule, in contrast to a hydrophobic platinum (Pt) counterpart. This study presents a feasible strategy to enhance the sensitivity and selectivity for amperometric CO sensing via the fine control of Au electrode nanostructures.


Subject(s)
Electrochemical Techniques , Electroplating , Nanostructures , Biosensing Techniques , Carbon Monoxide , Electrodes , Glucose , Gold/chemistry , Limit of Detection , Platinum
2.
Nanoscale ; 13(32): 13776-13785, 2021 Aug 28.
Article in English | MEDLINE | ID: mdl-34477652

ABSTRACT

A variety of binary Ru-Co mixed oxide nanotubes (RuxCo1-xOy with x = 0.19, 0.33, 0.47, 0.64 and 0.77) were readily synthesized via electrospinning and subsequent calcination. RuxCo1-xOy nanotubes (0 < x < 0.77) were composed of both rutile (Ru in RuO2 is replaced with Co) and spinel (Co in Co3O4 is replaced with Ru) structures. This elemental substitution created oxygen vacancies in the rutile structure and also resulted in the incorporation of Ru3+ in the octahedral sites of the spinel structure. The as-prepared RuxCo1-xOy nanotubes were investigated for oxygen evolution reaction (OER) electrocatalytic activity in 1.0 M HClO4 aqueous solution. RuxCo1-xOy nanotubes with x≥ 0.47 presented an excellent OER activity comparable to pure RuO2, known to be the best OER catalyst. Even after more than half of the noble/active Ru content was replaced with cheap/less-active Co, Ru0.47Co0.53Oy showed a good OER activity and a greatly improved stability compared to RuO2 under the continuous OER. These attractive catalytic properties of RuxCo1-xOy can be attributed to the relatively large surface area of the tubular morphology and the substituted structures, presenting feasibility as a practical and economical OER catalyst.

3.
Nanomaterials (Basel) ; 10(6)2020 Jun 10.
Article in English | MEDLINE | ID: mdl-32531899

ABSTRACT

The nanotubular structures of IrO2 and Ir metal were successfully synthesized without any template. First, IrO2 nanotubes were prepared by electrospinning and post-calcination, where a fine control of synthetic conditions (e.g., precursor concentration and solvent composition in electrospinning solution, temperature increasing rate for calcination) was required. Then, a further thermal treatment of IrO2 nanotubes under hydrogen gas atmosphere produced Ir metal nanotubes. The electroactivity of the resultant Ir metal nanotubes was investigated toward carbon monoxide (CO) oxidation using linear sweep voltammetry (LSV) and amperometry. The anodic current response of Ir metal nanotubes was linearly proportional to CO concentration change, with a high sensitivity and a short response time. The amperometric sensitivity of Ir metal nanotubes for CO sensing was greater than a nanofibrous counterpart (i.e., Ir metal nanofibers) and commercial Pt (20 wt% Pt loading on carbon). Density functional theory calculations support stronger CO adsorption on Ir(111) than Pt(111). This study demonstrates that metallic Ir in a nanotubular structure is a good electrode material for the amperometric sensing of CO.

4.
ACS Appl Mater Interfaces ; 11(50): 46886-46893, 2019 Dec 18.
Article in English | MEDLINE | ID: mdl-31815407

ABSTRACT

RhCo alloy nanotubes were synthesized via the reduction of single-phase Co2RhO4 nanotubes. The reduction was conducted by thermal annealing of the Co2RhO4 nanotubes under hydrogen gas flow. The crystallinity of the prepared RhCo alloy nanotubes depended on the reduction temperature: amorphous phase (200 °C reduction) and the crystalline phase (300 °C reduction). The hydrogen evolution reaction (HER) on RhCo alloys was investigated with voltammetry in 1.0 M HClO4 solution. Amorphous RhCo alloys provided lower overpotential than the crystalline counterpart despite their similar morphology and composition. Of great interest, amorphous RhCo alloy nanotubes exhibited an outstanding HER electroactivity verified with a low overpotential at -10 mA cm-2 (-22 mV) and a small Tafel slope (-24.1 mV dec-1), outperforming commercial Pt, pure Rh metal, and the other previously reported Rh-based catalysts. This excellent HER activity of amorphous RhCo nanotubes was attributed to the amorphous structure having a large electrochemical surface area and maximized Rh-Co interfaces in the alloy facilitating HER. Active but expensive Rh alloyed with less active but cheap Co was successfully demonstrated as a potential cost-effective HER catalyst.

5.
Sensors (Basel) ; 19(15)2019 Jul 26.
Article in English | MEDLINE | ID: mdl-31357512

ABSTRACT

By means of electrospinning with the thermal annealing process, we investigate a highly efficient sensing platform driven by a hierarchical hetero-nanostructure for the sensitive detection of biologically relevant molecules, consisting of single crystalline ruthenium dioxide nanorods (RuO2 NRs) directly grown on the surface of electrospun tungsten trioxide nanofibers (WO3 NFs). Electrochemical measurements reveal the enhanced electron transfer kinetics at the prepared RuO2 NRs-WO3 NFs hetero-nanostructures due to the incorporation of conductive RuO2 NRs nanostructures with a high surface area, resulting in improved relevant electrochemical sensing performances for detecting H2O2 and L-ascorbic acid with high sensitivity.


Subject(s)
Ascorbic Acid/isolation & purification , Biosensing Techniques , Electrochemical Techniques , Hydrogen Peroxide/isolation & purification , Ascorbic Acid/chemistry , Hydrogen Peroxide/chemistry , Nanofibers/chemistry , Nanostructures/chemistry , Nanotubes/chemistry , Oxides/chemistry , Ruthenium Compounds/chemistry , Tungsten/chemistry
6.
Nanoscale ; 11(23): 11379, 2019 Jun 21.
Article in English | MEDLINE | ID: mdl-31162520

ABSTRACT

Correction for 'Single phase of spinel Co2RhO4 nanotubes with remarkably enhanced catalytic performance for the oxygen evolution reaction' by So Yeon Kim et al., Nanoscale, 2019, 11, 9287-9295.

7.
Nanoscale ; 11(19): 9287-9295, 2019 May 16.
Article in English | MEDLINE | ID: mdl-31049518

ABSTRACT

We report the effective crystal growth for a unique single phase of spinel cobalt rhodium oxide (Co2RhO4) nanotubes via the electrospinning process combined with the thermal annealing process. In the spinel structure of the electrospun Co2RhO4 nanotubes, Co3+ cations and Rh3+ cations randomly occupy the octahedral sites, while the remaining half of the Co2+ cations occupy the centres of the tetrahedral sites as proved by microscopic and spectroscopic observations. Furthermore, electrospun spinel Co2RhO4 nanotubes exhibit excellent catalytic performances with the least positive onset potential, greatest current density, and low Tafel slope which are even better than those of the commercial Ir/C electrocatalyst for the oxygen evolution reaction (OER) in alkaline solution. Our demonstration of significantly enhanced OER activity with a single phase of electrospun spinel Co2RhO4 nanotubes thus opens up the broad applicability of our synthetic methodology for accessing new OER catalysis.

8.
ACS Appl Mater Interfaces ; 11(2): 1979-1987, 2019 Jan 16.
Article in English | MEDLINE | ID: mdl-30582793

ABSTRACT

Nanocomposites of gold (Au) and iridium (Ir) oxide with various compositions (denoted as Au xIr1- xO y, x = 0.05, 0.10, or 0.33, Au precursor molar ratio to Ir precursor) were synthesized via electrospinning and subsequent calcination method with two different solvent composition ratios of ethanol to N, N-dimethylformamide (DMF) in the electrospinning solution (ethanol/DMF = 70:30 or 50:50% v/v). Simple single-step electrospinning successfully fabricated a hierarchical nanostructure having Au nanoparticles formed on fibrous main frames of Ir/IrO2. Different solvent composition in the electrospinning solution induced the formation of main frames with distinct nanostructures; nanoribbons (Au xIr1- xO y-70) with ethanol/DMF = 70:30; and nanofibers (Au xIr1- xO y-50) with ethanol/DMF = 50:50. The pure Ir or Au counterparts (IrO y and Au) were also prepared by the same synthetic procedure as Au xIr1- xO y. Oxygen evolution reaction (OER) activities of as-synthesized Au xIr1- xO y were investigated in 0.5 M H2SO4 and compared to those of IrO y, Au, and commercial iridium (Ir/C, 20% Ir loading on Vulcan carbon). Among them, Au0.10Ir0.90O y-50 exhibited the best OER activity, even better than previously reported catalysts containing both Ir and Au. The high OER activity of Au0.10Ir0.90O y-50 was mainly attributed to the fiber frame structure and the optimal interfacial areas between Au and Ir/IrO2, which are electrophilic OER active sites. The stability of Au0.10Ir0.90O y-50 was also evaluated to be much higher than that of Ir/C during OER. The current study suggests that the presence of Au on the Ir/IrO2 surface improves the OER activity of Ir/IrO2.

9.
Analyst ; 144(1): 258-264, 2018 Dec 17.
Article in English | MEDLINE | ID: mdl-30393795

ABSTRACT

Nitric oxide (NO) is a biologically multifunctional gaseous signaling molecule. For electrochemical NO detections, complex membranes are commonly adopted to acquire the selectivity for NO over other oxidizable biological species. In this study, we demonstrate the improved selectivity in amperometric NO measurements at nanostructured Pt. The Pt layers were electrodeposited on Au substrate electrodes at a constant potential (-0.2 V vs. Ag/AgCl) with a constant deposition charge (0.08 C). The various distinctive nanostructures of Pt deposits were obtained via either changing the precursor concentrations (from 5 to 75 mM K2PtCl4) or using a different precursor (75 mM H2PtCl6). With a higher K2PtCl4 concentration, the Pt deposition became less sharp and the smoothest Pt was deposited with 75 mM H2PtCl6. The most greatly sharp-pointed nanostructures were generated with the lowest precursor concentration (5 mM K2PtCl4) and exhibited the highest sensitivity, which was attributed to the hydrophobic property of sharply nanostructured Pt. A hydrophobic neutral gas molecule, NO, possibly has a more favorable access to the inner surface of more hydrophobic Pt deposition and eventually increases the oxidation current. NO current sensitivity was enhanced at the more hydrophobic Pt surface, whereas the oxidation currents of acetaminophen, l-ascorbic acid, nitrite and hydrogen peroxide, four oxidizable biological interfering species, were independent of the Pt nanostructure. Conclusively, the enhanced amperometric selectivity to NO was achieved by the simple electrodeposition method without any additional membranes.

10.
Nanotechnology ; 29(17): 175702, 2018 Apr 27.
Article in English | MEDLINE | ID: mdl-29438103

ABSTRACT

NiO/NiCo2O4 nanotubes with a diameter of approximately 100 nm are synthesized using Ni and Co precursors via electro-spinning and subsequent calcination processes. The tubular structure is confirmed via transmission electron microscopy imaging, whereas the structures and elemental compositions of the nanotubes are determined using x-ray diffraction, energy dispersive x-ray spectroscopy, and x-ray photoelectron spectroscopy. N2 adsorption isotherm data reveal that the surface of the nanotubes consists of micropores, thereby resulting in a significantly higher surface area (∼20 m2 g-1) than expected for a flat-surface structure (<15 m2 g-1). Herein, we present a study of the catalytic activity of our novel NiO/NiCo2O4 nanotubes for CO and acetaldehyde oxidation. The catalytic activity of NiO/NiCo2O4 is superior to Pt below 100 °C for CO oxidation. For acetaldehyde oxidation, the total oxidation activity of NiO/NiCo2O4 for acetaldehyde is comparable with that of Pt. Coexistence of many under-coordinated Co and Ni active sites in our structure is suggested be related to the high catalytic activity. It is suggested that our novel NiO/NiCo2O4 tubular structures with surface microporosity can be of interest for a variety of applications, including the catalytic oxidation of harmful gases.

11.
ACS Appl Mater Interfaces ; 10(1): 541-549, 2018 Jan 10.
Article in English | MEDLINE | ID: mdl-29250950

ABSTRACT

Electrochemical hydrogen evolution reaction (HER) has been an interesting research topic in terms of the increasing need of renewable and alternative energy conversion devices. In this article, IrxRu1-xOy (y = 0 or 2) nanofibers with diverse compositions of Ir/IrO2 and RuO2 are synthesized by electrospinning and calcination procedures. Their HER activities are measured in 1.0 M NaOH. Interestingly, the HER activities of IrxRu1-xOy nanofibers improve gradually during repetitive cathodic potential scans for HER, and then eventually reach the steady-state consistencies. This cathodic activation is attributed to the transformation of the nanofiber surface oxides to the metallic alloy. Among a series of IrxRu1-xOy nanofibers, the cathodically activated Ir0.80Ru0.20Oy shows the best HER activity and stability even compared with IrOy and RuOy, commercial Pt and commercial Ir (20 wt % each metal loading on Vulcan carbon), where a superior stability is possibly ascribed to the instant generation of active Ir and Ru metals on the catalyst surface upon HER. Density functional theory calculation results for hydrogen adsorption show that the energy and adsorbate-catalyst distance at metallic Ir0.80Ru0.20 are close to those at Pt. This suggests that mixed metallic Ir and Ru are significant contributors to the improved HER activity of Ir0.80Ru0.20Oy after the cathodic activation. The present findings clearly demonstrate that the mixed oxide of Ir and Ru is a very effective electrocatalytic system for HER.

12.
ACS Appl Mater Interfaces ; 9(40): 35057-35066, 2017 Oct 11.
Article in English | MEDLINE | ID: mdl-28920424

ABSTRACT

Here, we report the unique transformation of one-dimensional tubular mixed oxide nanocomposites of iridium (Ir) and cobalt (Co) denoted as IrxCo1-xOy, where x is the relative Ir atomic content to the overall metal content. The formation of a variety of IrxCo1-xOy (0 ≤ x ≤ 1) crystalline tubular nanocomposites was readily achieved by electrospinning and subsequent calcination process. Structural characterization clearly confirmed that IrxCo1-xOy polycrystalline nanocomposites had a tubular morphology consisting of Ir/IrO2 and Co3O4, where Ir, Co, and O were homogeneously distributed throughout the entire nanostructures. The facile formation of IrxCo1-xOy nanotubes was mainly ascribed to the inclination of Co3O4 to form the nanotubes during the calcination process, which could play a critical role in providing a template of tubular structure and facilitating the formation of IrO2 by being incorporated with Ir precursors. Furthermore, the electroactivity of obtained IrxCo1-xOy nanotubes was characterized for oxygen evolution reaction (OER) with rotating disk electrode voltammetry in 1 M NaOH aqueous solution. Among diverse IrxCo1-xOy, Ir0.46Co0.54Oy nanotubes showed the best OER activity (the least-positive onset potential, greatest current density, and low Tafel slope), which was even better than that of commercial Ir/C. The Ir0.46Co0.54Oy nanotubes also exhibited a high stability in alkaline electrolyte. Expensive Ir mixed with cheap Co at an optimum ratio showed a greater OER catalytic activity than pure Ir oxide, one of the most efficient OER catalysts.

13.
ACS Appl Mater Interfaces ; 8(48): 32833-32841, 2016 Dec 07.
Article in English | MEDLINE | ID: mdl-27934168

ABSTRACT

This paper reports the synthesis and characterization of silver-cobalt (AgCo) bimetallic composite nanotubes. Cobalt oxide (Co3O4) nanotubes were fabricated by electrospinning and subsequent calcination in air and then reduced to cobalt (Co) metal nanotubes via further calcination under a H2/Ar atmosphere. As-prepared Co nanotubes were then employed as templates for the following galvanic replacement reaction (GRR) with silver (Ag) precursor (AgNO3), which produced AgCo composite nanotubes. Various AgCo nanotubes were readily synthesized with applying different reaction times for the reduction of Co3O4 nanotubes and GRR. One hour reduction was sufficiently long to convert Co3O4 to Co metal, and 3 h GRR was enough to deposit Ag layer on Co nanotubes. The tube morphology and copresence of Ag and Co in AgCo composite nanotubes were confirmed with SEM, HRTEM, XPS, and XRD analyses. Electroactivity of as-prepared AgCo composite nanotubes was characterized for ORR with rotating disk electrode (RDE) voltammetry. Among differently synthesized AgCo composite nanotubes, the one synthesized via 1 h reduction and 3 h GRR showed the best ORR activity (the most positive onset potential, greatest limiting current density, and highest number of electrons transferred). Furthermore, the ORR performance of the optimized AgCo composite nanotubes was superior compared to pure Co nanotubes, pure Ag nanowires, and bare platinum (Pt). High ethanol tolerance of AgCo composite nanotubes was also compared with the commercial Pt/C and then verified its excellent resistance to ethanol contamination.

14.
Anal Chim Acta ; 933: 59-65, 2016 Aug 24.
Article in English | MEDLINE | ID: mdl-27496997

ABSTRACT

In this work, we synthesized tantalum (Ta) nanoclusters on carbon black (Ta/CB) via simple electrodeposition in non-aqueous solvent, acetonitrile (ACN) at ambient temperature. Transmission electron microscopy (TEM) images showed that the electrodeposited Ta nanoclusters consisted of tiny Ta nanoparticles. X-ray photoelectron spectroscopy (XPS) result represented that the outermost Ta formed the native oxide on Ta/CB due to its ambient exposure to air. Electrochemical catalytic properties of prepared Ta/CB on glassy carbon electrode (Ta/CB/GC) were investigated toward reductions of oxygen and hydrogen peroxide, and oxidations of ascorbic acid and dopamine. For oxygen reduction reaction (ORR) in acid, Ta/CB/GC represented a decent electrocatalytic performance which was better or comparable to bare Pt. The operational stability in acidic condition was maintained up to 500 repetitive potential cycles presumably due to the protective native Ta oxide layer. Ta/CB/GC also showed high amperometric sensitivity (4.5 (±0.16) mA mM(-1) cm(-2), n = 5) for reduction of hydrogen peroxide in 0.1 M phosphate buffer solution (PBS, pH 7.4). In addition, Ta/CB/GC was demonstrated for the possibility of simultaneous detection of ascorbic acid and dopamine using differential pulse voltammetry (DPV).

15.
Biosens Bioelectron ; 77: 1144-52, 2016 Mar 15.
Article in English | MEDLINE | ID: mdl-26569445

ABSTRACT

This paper reports that the high electrocatalytic activity of RuO2 nanowires grown on electrospun TiO2 nanofibers for the oxidation of l-ascorbic acid (AA); and the application of these materials for direct selective sensing of AA in complex samples. Compared to bare glassy carbon (GC) electrode, RuO2 nanowires on TiO2 nanofibers-loaded GC electrode facilitates the oxidation of AA most drastically among the tested species: AA, 4-acetamidophenol (AP), dopamine (DA), uric acid (UA), and glucose. The amperometric response of RuO2 nanowires on TiO2 nanofibers at the applied potential of 0.018 V (vs. SCE) exhibits high sensitivity (268.2 ± 3.7 µAmM(-1)cm(-2), n=5), low detection limit (<1.8 µM), great linearity, reasonable stability, and exclusive selectivity over AP, DA, glucose and UA at their physiological levels. In differential pulse voltammetry, it is verified that the potential resolution of RuO2 nanowires on TiO2 nanofibers is able to differentiate AA, DA, UA, and AP one from the others. In addition, as prepared RuO2 nanowires on TiO2 nanofibers are successfully applied for direct and selective AA measurements in commercial vitamin samples and for the real-time direct analysis of AA generated from living rat liver tissue in vitro.


Subject(s)
Ascorbic Acid/metabolism , Conductometry/instrumentation , Liver/metabolism , Nanowires/chemistry , Ruthenium Compounds/chemistry , Titanium/chemistry , Adsorption , Animals , Computer Systems , Electroplating/methods , Equipment Design , Equipment Failure Analysis , Male , Nanofibers/chemistry , Nanofibers/ultrastructure , Nanowires/ultrastructure , Rats , Rats, Sprague-Dawley , Reproducibility of Results , Rotation , Sensitivity and Specificity , Tissue Distribution
16.
Phys Chem Chem Phys ; 17(36): 23496-502, 2015 Sep 28.
Article in English | MEDLINE | ID: mdl-26293115

ABSTRACT

A ZnO-MnO composite was synthesized using a simple solvothermal method combined with a high-temperature treatment. To observe the phase change during the heating process, in situ high-temperature XRD analysis was performed under vacuum conditions. The results indicated that ZnMn2O4 transformed into the ZnO-MnO composite phase starting from 500 °C and that this composite structure was retained until 700 °C. The electrochemical performances of the ZnO-MnO composite electrode were evaluated through galvanostatic discharge-charge tests and cyclic voltammetry analysis. Its initial coulombic efficiency was significantly improved to 68.3% compared to that of ZnMn2O4 at 54.7%. Furthermore, the ZnO-MnO composite exhibited improved cycling performance and enhanced rate capability compared with untreated ZnMn2O4. To clarify the discharge-charge mechanism of the ZnO-MnO composite electrode, the structural changes during the charge and discharge processes were also investigated using ex situ XRD and TEM.

17.
ACS Appl Mater Interfaces ; 7(28): 15321-30, 2015 Jul 22.
Article in English | MEDLINE | ID: mdl-26133193

ABSTRACT

Highly single-crystalline ruthenium dioxide (RuO2) nanoneedles were successfully grown on polycrystalline electrospun titanium dioxide (TiO2) nanofibers for the first time by a combination of thermal annealing and electrospinning from RuO2 and TiO2 precursors. Single-crystalline RuO2 nanoneedles with relatively small dimensions and a high density on electrospun TiO2 nanofibers are the key feature. The general electrochemical activities of RuO2 nanoneedles-TiO2 nanofibers and Ru(OH)3-TiO2 nanofibers toward the reduction of [Fe(CN)6](3-) were carefully examined by cyclic voltammetry carried out at various scan rates; the results indicated favorable charge-transfer kinetics of [Fe(CN)6](3-) reduction via a diffusion-controlled process. Additionally, a test of the analytical performance of the RuO2 nanoneedles-TiO2 nanofibers for the detection of a biologically important molecule, hydrogen peroxide (H2O2), indicated a high sensitivity (390.1 ± 14.9 µA mM(-1) cm(-2) for H2O2 oxidation and 53.8 ± 1.07 µA mM(-1) cm(-2) for the reduction), a low detection limit (1 µM), and a wide linear range (1-1000 µM), indicating H2O2 detection performance better than or comparable to that of other sensing systems.

18.
Phys Chem Chem Phys ; 17(11): 7435-42, 2015 Mar 21.
Article in English | MEDLINE | ID: mdl-25704092

ABSTRACT

We present a facile synthetic route to ruthenium dioxide (RuO2)-rhenium oxide (ReO3) electrospun composite nanofibers and their electrocatalytic responses for capacitance and H2O2 sensing. The contents of rhenium oxide of electrospun ruthenium dioxide (RuO2) were carefully controlled by an electrospinning process with the preparation of the precursor solutions followed by the thermal annealing process in air. The electrochemical applications of RuO2-ReO3 electrospun composite nanofibers were then investigated by modifying these materials on the surface of glassy carbon (GC) electrodes, RuO2-ReO3(n)/GC (n = 0.0, 0.07, 0.11, and 0.13), where n denotes the relative atomic ratio of Re to the sum of Ru and Re. Specific capacitance and H2O2 reduction sensitivity were remarkably enhanced depending on the amount of ReO3 increased. Among the four compositions of RuO2-ReO3(n), RuO2-ReO3(0.11)/GC showed the highest performances, i.e., a 20.9-fold higher specific capacitance (205 F g(-1) at a potential scan rate (v) of 10 mV s(-1); a capacity loss of 19% from v = 10 to 2000 mV s(-1)) and a 7.6-fold higher H2O2 reduction sensitivity (668 µA mM(-1) cm(-2), normalized by GC disk area), respectively, compared to only RuO2/GC.

19.
Langmuir ; 30(12): 3579-88, 2014 Apr 01.
Article in English | MEDLINE | ID: mdl-24617746

ABSTRACT

This paper reports the facile synthesis and characterization of spongelike nanoporous Pd (snPd) and Pd/Au (snPd/Au) prepared by a tailored galvanic replacement reaction (GRR). Initially, a large amount of Co particles as sacrificial templates was electrodeposited onto the glassy carbon surface using a cyclic voltammetric method. This is the key step to the subsequent fabrication of the snPd/Au (or snPd) architectures by a surface replacement reaction. Using Co films as sacrificial templates, snPd/Au catalysts were prepared through a two-step GRR technique. In the first step, the Pd metal precursor (at different concentrations), K2PdCl4, reacted spontaneously to the formed Co frames through the GRR, resulting in a snPd series. snPd/Au was then prepared via the second GRR between snPd (prepared with 27.5 mM Pd precursor) and Au precursor (10 mM HAuCl4). The morphology and surface area of the prepared snPd series and snPd/Au were characterized using spectroscopic and electrochemical methods. Rotating disk electrode (RDE) experiments for oxygen reduction in 0.1 M NaOH showed that the snPd/Au has higher catalytic activity than snPd and the commercial Pd-20/C and Pt-20/C catalysts. Rotating ring-disk electrode (RRDE) experiments reconfirmed that four electrons were involved in the electrocatalytic reduction of oxygen at the snPd/Au. Furthermore, RDE voltammetry for the H2O2 oxidation/reduction was used to monitor the catalytic activity of snPd/Au. The amperometric i-t curves of the snPd/Au catalyst for a H2O2 electrochemical reaction revealed the possibility of applications as a H2O2 oxidation/reduction sensor with high sensitivity (0.98 mA mM(-1) cm(-2) (r = 0.9997) for H2O2 oxidation and -0.95 mA mM(-1) cm(-2) (r = 0.9997) for H2O2 reduction), low detection limit (1.0 µM), and a rapid response (<∼1.5 s).


Subject(s)
Electrochemical Techniques , Gold/chemistry , Metal Nanoparticles/chemistry , Palladium/chemistry , Catalysis , Electrodes , Hydrogen Peroxide/chemical synthesis , Hydrogen Peroxide/chemistry , Molecular Structure , Particle Size , Porosity , Surface Properties
20.
Anal Chim Acta ; 819: 94-101, 2014 Mar 28.
Article in English | MEDLINE | ID: mdl-24636416

ABSTRACT

We report a new nonenzymatic amperometric detection of ascorbic acid (AA) using a glassy carbon (GC) disk electrode modified with hollow gold/ruthenium (hAu-Ru) nanoshells, which exhibited decent sensing characteristics. The hAu-Ru nanoshells were prepared by the incorporation of Ru on hollow gold (hAu) nanoshells from Co nanoparticle templates, which enabled AA selectivity against glucose without aid of enzyme or membrane. The structure and electrocatalytic activities of the hAu-Ru catalysts were characterized by spectroscopic and electrochemical techniques. The hAu-Ru loaded on GC electrode (hAu-Ru/GC) showed sensitivity of 426 µA mM(-1) cm(-2) (normalized to the GC disk area) for the linear dynamic range of <5 µM to 2 mM AA at physiological pH. The response time and detection limit were 1.6 s and 2.2 µM, respectively. Furthermore, the hAu-Ru/GC electrode displayed remarkable selectivity for ascorbic acid over all potential biological interferents, including glucose, uric acid (UA), dopamine (DA), 4-acetamidophenol (AP), and nicotinamide adenine dinucleotide (NADH), which could be especially good for biological sensing.


Subject(s)
Ascorbic Acid/analysis , Gold/chemistry , Nanoshells/chemistry , Ruthenium/chemistry , Carbon/chemistry , Electrochemical Techniques , Electrodes , Particle Size , Porosity , Surface Properties
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