Sn@Pt and Rh@Pt core–shell nanoparticles synthesis for glycerol oxidation

The development and optimization of electrocatalysts for application in fuel cell systems have been the focus of a variety of studies where core–shell structures have been considered as a promising alternative among the materials studied. We synthesized core–shell nanoparticles of Sn x @Pt y and Rh x @Pt y (Sn@Pt, Sn@Pt2, Sn@Pt3, Rh@Pt, Rh@Pt2, and Rh@Pt3) through a reduction methodology using sodium borohydride. These nanoparticles were electrochemically characterized by cyclic voltammetry and further analyzed by cyclic voltammetry studying their catalytic activity toward glycerol electro-oxidation; chronoamperometry and potentiostatic polarization experiments were also carried out. The physical characterization was carried out by X-ray diffraction, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy. The onset potential for glycerol oxidation was shifted in 130 and 120 mV on the Sn@Pt3/C and Rh@Pt3/C catalysts, respectively, compared to commercial Pt/C, while the stationary pseudo-current density, taken at 600 mV, increased 2-fold and 5-fold for these catalysts related to Pt/C, respectively. Thus, the catalysts synthesized by the developed methodology have enhanced catalytic activity toward the electro-oxidation of glycerol, representing an interesting alternative for fuel cell systems.

Reduction of Au3+ ions by activated surface atoms of platinum

In this work it is demonstrated that Pt electrodes can be activated by cathodic polarisation in the hydrogen evolution region which makes it prone to oxidation at potentials below that of bulk oxide formation. When an activated Pt electrode is placed in an aqueous HAuCl4 solution the electroless deposition of Au onto the surface of the electrode is observed and confirmed by cyclic voltammetry and XPS measurements. It is demonstrated that the oxidation of active Pt surface atoms provides the driving force for the spontaneous reduction of Au3+ ions into metallic Au to generate a Pt/Au surface which is highly active for the electro-oxidation of ethanol.

EQCM Investigation of the Electrodeposition of MnO2 and Its Capacitance Behavior

Electro-oxidation of Mn2+ to MnO2 by cyclic voltammetry on gold in acidic (0.1 M H2SO4) and neutral (0.1 M Na2SO4) media was studied using electrochemical quartz-crystal microbalance (EQCM). The cyclic voltammetric behavior of Au is different in these electrolytes. From EQCM data of mass variation during cycling, the rate of electrodeposition of MnO2 is higher in the neutral medium than in the acidic medium. Specific capacitance of MnO2 deposited from the neutral medium is higher than that deposited from the acidic medium owing to different crystallographic structures.

Electrooxidation of methanol in sulfuric-acid electrolyte on platized-carbon electrodes with several functional-group characteristics

The effect of acid/base functional-groups associated with platinized-carbon electrodes on their catalytic activity toward electro-oxidation of methanol in sulfuric acid electrolyte at 60-degrees-C is studied. Platinized-carbon electrodes with sm amounts of functional groups exhibit higher catalytic activity compared to those with large concentrations of acidic/basic surface functionalities. The overpotential for methanol oxidation is minimum on electrodes of platinized carbons with pHzpc values between 6 and 7. An x-ray photoelectron spectroscopic study of various platinized carbons suggests that the acid/base surface functional-groups produce ample amounts of surface Pt-oxides and a consequent decrease in activity toward methanol oxidation.

Direct evidence of redox interaction between metal ion and support oxide in Ce(0.98)Pd(0.02)O(2-delta) by a combined electrochemical and XPS study

A combined electrochemical method and X-ray photo electron spectroscopy (XPS) has been utilized to understand the Pd(2+)/CeO(2) interaction in Ce(1-x)Pd(x)O(2-delta) (x = 0.02). A constant positive potential (chronoamperometry) is applied to Ce(0.98)Pd(0.02)O(2-delta) working electrode which causes Ce(4+) to reduce to Ce(3+) to the extent of similar to 35%, while Pd remains in the +2 oxidation state. Electrochemically cycling this electrode between 0.0-1.2 V reverts back to the original state of the catalyst. This reversibility is attributed to the reversible reduction of Ce(4+) to Ce(3+) state. CeO(2) electrode with no metal component reduces to CeO(2-y) (y similar to 0.4) after applying 1.2 V which is not reversible and the original composition of CeO(2) cannot be brought back in any electrochemical condition. During the electro-catalytic oxygen evolution reaction at a constant 1.2 V for 1000 s, Ce(0.98)Pd(0.02)O(2-delta) reaches a steady state composition with Pd in the +2 states and Ce(4+) : Ce(3+) in the ratio of 0.65 : 0.35. This composition can be denoted as Ce(0.63)(4+)Ce(0.35)(4+)Pd(0.02)O(2-delta-y) (y similar to 0.17). When pure CeO(2) is put under similar electrochemical condition, it never reaches the steady state composition and reduces almost to 85%. Thus, Ce(0.98)Pd(0.02)O(2-delta) forms a stable electrode for the electro-oxidation of H(2)O to O(2) unlike CeO(2) due to the metal support interaction.

Durable Transition-Metal-Carbide-Supported Pt-Ru Anodes for Direct Methanol Fuel Cells

Molybdenum carbide (MoC) and tungsten carbide (WC) are synthesized by direct carbonization method. PtRu catalysts supported on MoC, WC, and Vulcan XC-72R are prepared, and characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy in conjunction with electrochemistry. Electrochemical activities for the catalysts towards methanol electro-oxidation are studied by cyclic voltammetry. All the electro-catalysts are subjected to accelerated durability test (ADT). The electrochemical activity of carbide-supported electro-catalysts towards methanol electro-oxidation is found to be higher than carbon-supported catalysts before and after ADT. The study suggests that PtRu/MoC and PtRu/WC catalysts are more durable than PtRu/C. Direct methanol fuel cells (DMFCs) with PtRu/MoC and PtRu/WC anodes also exhibit higher performance than the DMFC with PtRu/C anode.

Reduced graphene oxide-supported nickel oxide catalyst with improved CO tolerance for formic acid electrooxidation

The superior catalytic activity along with improved CO tolerance for formic acid electro-oxidation has been demonstrated on a NiO-decorated reduced graphene oxide (rGO) catalyst. The cyclic voltammetry response of rGO-NiO/Pt catalyst elucidates improved CO tolerance and follows direct oxidation pathway. It is probably due to the beneficial effect of residual oxygen groups on rGO support which is supported by FT-IR spectrum. A strong interaction of rGO support with NiO nanoparticles facilitates the removal of CO from the catalyst surface. The chronoamperometric response indicates a higher catalytic activity and stability of rGO-NiO/Pt catalyst than the NiO/Pt and unmodified Pt electrode catalyst for a prolonged time of continuous oxidation of formic acid. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Performance comparison of low-temperature direct alcohol fuel cells with different anode catalysts

Low-temperature polymer electrolyte membrane fuel cells directly fed by methanol and ethanol were investigated employing carbon supported Pt, PtSn and PtRu as anode catalysts, respectively. Employing Pt/C as anode catalyst, both direct methanol fuel cell (DMFC) and direct ethanol fuel cell (DEFC) showed poor performances even in presence of high Pt loading on anode. It was found that the addition of Ru or Sn to the Pt dramatically enhances the electro-oxidation of both methanol and ethanol. It was also found that the single cell adopting PtRu/C as anode shows better DMFC performance, while PtSn/C catalyst shows better DEFC performance. The single fuel cell using PtSn/C as anode catalyst at 90degreesC shows similar power densities whenever fueled by methanol or ethanol. The cyclic voltammetry (CV) and single fuel cell tests indicated that PtRu is more suitable for DMFC while PtSn is more suitable for DEFC. (C) 2003 Elsevier B.V. All rights reserved.

Pt-based anode catalysts for direct ethanol fuel cells

In the present work, several carbon supported PtSn and PtSnRu catalysts were prepared with different atomic ratios and tested in direct ethanol fuel cells (DEFC) operated at lower temperature (T=90 degreesC). XRD and TEM results indicate that all of these catalysts consist of uniform nano-sized particles of narrow distribution and the average particle sizes are always less than 3.0 nm. As the content of Sn increases, the Pt lattice parameter becomes longer. Single direct ethanol fuel cell tests were used to evaluate the performance of carbon supported PtSn catalysts for ethanol electro-oxidation. It was found that the addition of Sn can enhance the activity towards ethanol electro-oxidation. It is also found that a single DEFC of Pt/Sn atomic ratioless than or equal to2, "Pt1Sn1/C, Pt3Sn2/C, and Pt2Sn1/C" shows better performance than those with Pt3Sn1/C and Pt4Sn1/C. But even adopting the least active PtSn catalyst, Pt4Sn1/C, the DEFC also exhibits higher performance than that with the commercial Pt1Ru1/C, which is dominatingly used in PEMFC at present as anode catalyst for both methanol electro-oxidation and CO-tolerance. At 90 degreesC, the DEFC exhibits the best performance when Pt2Sn1/C is adopted as anode catalysts. This distinct difference in DEFC performance between the catalysts examined here is attributed to the so-called bifunctional mechanism and to the electronic interaction between Pt and Sn. It is thought that -OHads, Surface Pt active sites and the ohmic effect of PtSn/C catalyst determines the electro-oxidation activity of PtSn catalysts with different Pt/Sn ratios. (C) 2004 Elsevier B.V. All rights reserved.

An improved palladium-based DMFCs cathode catalyst

A novel carbon-supported palladium-rich Pd3Pt1/C catalyst prepared by a modified polyol process showed a better cell performance than Pt/C in direct methanol fuel cells, which may be attributed to palladium's inactivity to methanol electro-oxidation while exhibiting good performance to oxygen reduction reaction.

Pt based anode catalysts for direct ethanol fuel cells

In the present work several Pt-based anode catalysts supported on carbon XC-72R were prepared with a novel method and characterized by means of XRD, TEM and XPS analysis. It was found that all these catalysts are consisted of uniform nanosized particles with sharp distribution and Pt lattice parameter decreases with the addition of Ru or Pd and increases with the addition of Sn or W. Cyclic voltammetry (CV) measurements and single direct ethanol fuel cell (DEFC) tests jointly showed that the presence of Sn, Ru and W enhances the activity of Pt towards ethanol electro-oxidation in the following order: Pt1Sn1/C > Pt1Ru1/C > Pt1W1/C > Pt1Pd1/C > Pt/C. Moreover, Pt1Ru1/C further modified by W and Mo showed improved ethanol electro-oxidation activity, but its DEFC performance was found to be inferior to that measured for Pt1Sn1/C. Under this respect, several PtSn/C catalysts with different Pt/Sn atomic ratio were also identically prepared and characterized and their direct ethanol fuel cell performances were evaluated. It was found that the single direct ethanol fuel cell having Pt1Sn1/C or Pt3Sn2/C or Pt2Sn1/C as anode catalyst showed better performances than those with Pt3Sn1/C or Pt4Sn1/C. It was also found that the latter two cells exhibited higher performances than the single cell using Pt1Ru1/C, which is exclusively used in PEMFC as anode catalyst for both methanol electro-oxidation and CO-tolerance. This distinct difference in DEFC performance between the catalysts examined here would be attributed to the so-called bifunctional mechanism and to the electronic interaction between Pt and additives. It is thought that an amount of -OHads, an amount of surface Pt active sites and the conductivity effect of PtSn/C catalysts would determine the activity of PtSn/C with different Pt/Sn ratios. At lower temperature values or at low current density regions where the electro-oxidation of ethanol is considered not so fast and its chemisorption is not the rate-determining step, the Pt3Sn2/C seems to be more suitable for the direct ethanol fuel cell. At 75 degreesC, the single ethanol fuel cell with Pt3Sn2/C as anode catalyst showed a comparable performance to that with Pt2Sn1/C, but at higher temperature of 90 degreesC, the latter presented much better performance. It is thought from a practical point of view that Pt2Sn1/C, supplying sufficient -OHads and having adequate active Pt sites and acceptable ohmic effect, could be the appropriate anode catalyst for DEFC. (C) 2003 Elsevier B.V. All rights reserved.

Controllable synthesis of pd nanocatalysts for direct formic acid fuel cell (DFAFC) application: From pd hollow nanospheres to pd nanoparticles

The controllable synthesis of nanosized carbon-supported Pd catalysts through a surface replacement reaction (SRR) method is reported in this paper. Depending on the synthesis conditions the Pd can be formed on Co nanoparticles surface in hollow nanospheres or nanoparticles structures. Citrate anion acts as a stabilizer for the nanostructures, and protonation of the third carboxyl anion and hence the nanostructure and size of the resulting catalysts are controlled via the pH of the synthesis solution. Pd hollow nanospheres, containing smaller Pd nanoparticles, supported on carbon are formed under the condition of pH 9 reaction solution. Meanwhile, highly dispersed carbon-supported Pd nanoparticles can be formed with higher pH (pH >= 10). All catalysts prepared through the SRR method show enhanced activities for the HCOOH electro-oxidation reaction compared to catalysts reduced by NaBH4.

In situ scanning tunneling microscopy studies of nanometer size palladium particles on highly oriented pyrolytic graphite

A special electrodeposition process of palladium was studied by cyclic voltammetry, X-ray photoelectron spectroscopy (XPS) and in situ scanning tunneling microscopy (STM). A kind of palladium(IV) complex was attached to the highly oriented pyrolytic graphite (HOPG) electrode surface by electro-oxidation of palladium(II) complex first, and was then reduced to palladium particles. The surface complexes and particles of palladium were both characterized by in situ STM and XPS. The Pd particles are in the nanometer range of size and exhibit electrocatalytic activity towards the oxidation of hydrazine and hydroxylamine.

ELECTROOXIDATION OF A CHLORIDE COMPLEX OF PLATINUM(II) AT A GLASSY-CARBON ELECTRODE

The electro-oxidation of PtCl42- was studied on a glassy carbon (GC) electrode. A Pt(IV) complex was formed on the electrode surface through coordination to the oxygen atom of an oxide functional group on the electrode, which results in its deactivation. The ferri/ferrocyanide redox couple was used as a probe to examine the activity of the GC electrode. X-ray photoelectron spectroscopy was employed to characterize the platinum on the electrode surface, and showed that the oxidation state of the Pt element changes depending on the electrochemical treatment of GC electrode. The platinum complex on the surface of the GC electrode can be transformed to Pt-0 by cycling the electrode between -0.25 and +1.65 V/SCE in 0.1 M H2SO4 solution. The above procedure can be used to disperse platinum ultramicroparticles on the surface of a GC electrode.

IN-SITU UV-VISIBLE SPECTROELECTROCHEMICAL AND CIRCULAR DICHROIC ELECTROCHEMICAL STUDY OF BILIRUBIN AND BILIRUBIN PLUS HUMAN SERUM-ALBUMIN COMPLEX

The electro-oxidation of bilirubin (BR) in aqueous solution was investigated by cyclic voltammetry and in-situ thin-layer spectroelectrochemical techniques, It was found that both oxidation processes of BR are two electron transfer reactions. A mechanism