Network films of conducting polymer-linked polyoxometalate-modified gold nanoparticles: Preparation and electrochemical characterization

The ability of Keggin-type phosphododecamolybdate (PMo₁₂O₄₀³⁻, PMo₁₂) to undergo chemisorption on solid surfaces (including gold) is explored here to convert (by ligand place-exchange and phase transfer to aqueous solution) the alkanothiolate-modified Au nanoparticles of controlled size (prepared in toluene) into a stable colloidal solution of PMo₁₂-protected gold nanoparticles, PMo₁₂-AuNPs, the sizes of which are ca. 4-5 nm as determined by transmission electron microscopy. By dip-coating, PMo₁₂-AuNPs were assembled on carbon electrode substrates. The step-by-step assembly, by which alternate exposures to the solutions of PMo₁₂-AuNPs and either anilinium cations or pyrrole monomers, was utilized to grow in controlled manner hybrid network films in which the negatively charged PMo₁₂-AuNP deposits were linked, or electrostatically attracted, by ultra-thin, positively charged conducting polymer (polyaniline or polypyrrole) structures. The three-dimensionally distributed PMo₁₂-AuNPs immobilized within the polypyrrole-based composite film exhibited some electrocatalytic reactivity towards reduction of hydrogen peroxide.     

Modification of Pt nanoparticles with polyoxometallate monolayers: Competition between activation and blocking of reactive sites for the electrocatalytic oxygen reduction

Surfaces of bulk platinum and unsupported (Vulcan-free) Pt nanoparticles, that are modified and stabilized with such Keggin type heteropolyacids of molybdenum and tungsten as H₃PMo₁₂O₄₀ and H₃PW₁₂O₄₀, have been characterized using cyclic voltammetry, FTIR (by reflectance), as well as transmission and scanning electron microscopies. The presence of the polyoxometallate monolayer on platinum results in the partial suppression of the interfacial formation of PtOH/PtO oxides. Both molybdates and tungstates seem to interact with Pt surface via their corner oxygen atoms. The existence of spacious, largely hydrated, polyoxometallate monolayers on platinum does not block access of reactant (oxygen) to the catalytic Pt sites. The electrocatalytic properties of H₃PMo₁₂O₄₀ and H₃PW₁₂O₄₀ modified Pt nanoparticles towards reduction of oxygen in acid medium have been examined and compared using rotating ring-disk voltammetry. Reactivity of Pt-free H₃PMo₁₂O₄₀ and H₃PW₁₂O₄₀ with respect to reduction of hydrogen peroxide has also been considered. Our results clearly show that modification of Pt nanoparticles with PW₁₂ (but not with PMo₁₂) results in the enhancement of the electrocatalytic reduction of oxygen.     

Preparation and Electrocatalytic Application of Composites Containing Gold Nanoparticles Protected with Rhodium-Substituted Polyoxometalates

Substitution of a metal center of phosphomolybdate, PMo₁₂O₄₀³⁻ (PMo₁₂), or its tungsten analogue with dirhodium(II) and subsequent stabilization of gold nanoparticles, AuNPs, with Rh₂PMo₁₁ are demonstrated. The AuNP-Rh₂PMo₁₁ mediates oxidations but adsorbs too weakly for direct modification of electrode materials. Stability in quiescent solution was achieved by modifying glassy carbon (GC) with 3-aminopropyltriethoxysilane (APTES) and then electrostatically assembling AuNP-Rh₂PMo₁₁. At GC|APTES|AuNP-Rh₂PMo₁₁, cyclic voltammetry showed the expected set of three reversible peak-pairs for PMo₁₁ in the range −0.2 to 0.6 vs. (Ag/AgCl)/V and the reversible Rh^II,III couple at 1.0 vs. (Ag/AgCl)/V. The presence of AuNPs increased the current for the reduction of bromate by a factor of 2.5 relative to that at GC|Rh₂PMo₁₁, and the electrocatalytic oxidation of methionine displayed characteristics of synergism between the AuNP and Rh^II. To stabilize AuNP-Rh₂PMo₁₁ on a surface in a flow system, GC was modified by electrochemically assisted deposition of a sol–gel with templated 10-nm pores prior to immobilizing the catalyst in the pores. The resulting electrode permitted determination of bromate by flow-injection amperometry with a detection limit of 4.0 × 10⁻⁸ mol dm⁻³.     

Preparation, characterization and electrocatalytic properties of poly(luminol) and polyoxometalate hybrid film modified electrodes

Hybrid films composed of poly(luminol) and nanometer-sized clusters of polyoxometalate, SiMo₁₂O₄₀⁴⁻ and PMo₁₂O₄₀³⁻ have been prepared in acidic aqueous solutions. These films are stable and electrochemically active, and produced on glassy carbon, platinum, gold and transparent semiconductor tin oxide electrodes. The electrochemical quartz crystal microbalance and cyclic voltammetry were used to study in situ growth of the hybrid poly(luminol)/SiMo₁₂O₄₀⁴⁻ and poly(luminol)/PMo₁₂O₄₀³⁻. Both the poly(luminol)/SiMo₁₂O₄₀⁴⁻ and poly(luminol)/PMo₁₂O₄₀³⁻ hybrid films showed four redox couples and the electrochemical properties were compared to SiMo₁₂O₄₀⁴⁻ and PMo₁₂O₄₀³⁻. When transferred to various acidity aqueous solutions, the four redox couples and the formal potentials of two hybride film were observed to be pH-dependent. The electrocatalytic reduction of ClO₃⁻, BrO₃⁻, IO₃⁻, S₂O₈²⁻ and NO₂⁻ by a poly(luminol)/PMo₁₂O₄₀³⁻ hybrid film in an acidic aqueous solution showed an electrocatalytic reduction activity of IO₃⁻ > BrO₃⁻ and ClO₃⁻. The electrocatalytic oxidation of dopamine and epinephrine by a poly(luminol)/PMo₁₂O₄₀³⁻ hybrid film was also investigated.     

Initial stages of Pt deposition on Au(111) and Au(100)

The deposition of Pt onto unreconstructed Au(111) and Au(100) was studied with cyclic voltammetry and in-situ STM. The latter revealed that in [PtCl₄]²⁻ containing electrolytes, both surfaces are covered by an ordered adlayer of the complex. For the adsorbed [PtCl₄]²⁻ a slightly compressed (√7×√7) R19.1°-structure was assumed for Au(111) and a (3×√10) for Au(100). In both cases, a rather high overpotential for Pt deposition was observed, most probably due to the high stability of the [PtCl₄]²⁻ complex. Nucleation of Pt starts mainly at defects like step edges for low deposition rates and three-dimensional clusters are formed. Due to the high overpotential, some nuclei appear also on terraces at random sites. Higher coverages of Pt lead to a cauliflower like appearance. It is not possible to dissolve the platinum clusters at positive potentials without severely roughening the gold surface. The [PtCl₄]²⁻ complex is oxidized to the [PtCl₆]²⁻ complex at about 0.7 V, when metallic Pt is on the surface.     

Polyoxometallate-stabilized platinum catalysts on multi-walled carbon nanotubes for fuel cell applications

A novel catalyst, Pt-PMo₁₂-CNT, with well-dispersed Pt nanoparticles and monolayer PMo₁₂ on multi-walled carbon nanotubes (CNTs) is reported. A polyoxometallate (PMo₁₂) was chemically adsorbed on the surface of Pt nanoparticles and on outer walls of CNTs. These effectively prevented the agglomeration of Pt nanoparticles and CNTs due to the electrostatic repulsive interactions between negatively charged PMo₁₂ monolayers. The as-prepared Pt-PMo₁₂-CNT materials show higher electrocatalytic activity, higher cycle stability, and better tolerance to poisoning species in methanol oxidation than do Pt-CNT catalysts prepared by the same method. The reasons for the improved catalytic performance of the Pt-PMo₁₂-CNT catalysts are discussed.     

Enhancement of oxygen reduction by incorporation of heteropolytungstate into the electrocatalytic ink of carbon supported platinum nanoparticles

Nafion stabilized inks of Vulcan XC-72 supported platinum (20 wt.%) nanoparticles (Pt/XC-72) were utilized to produce electrocatalytic films on glassy carbon. The catalysts were modified (activated) with phosphododecatungstic acid H₃PW₁₂O₄₀ (PW₁₂). Comparison was made to bare (PW₁₂-free) electrocatalytic films. Electroreduction of dioxygen was studied at 25 °C in 0.5 mol dm⁻³ H₂SO₄ electrolyte using rotating disk voltammetry. For the same loading of platinum (≈95 μg cm⁻²) and for the approximately identical distribution of the catalyst, the reduction of oxygen at a glassy carbon electrode modified with the ink containing PW₁₂ proceeded at ca. 30-60 mV more positive potential (depending on the PW₁₂ content), and the system was characterized by a higher kinetic parameter (rate of heterogeneous electron transfer), when compared to the PW₁₂-free electrocatalyst. Gas diffusion electrodes with Pt/XC-72 supported on carbon paper (Pt loading 1 mg cm⁻²) were also tested. Under the same experimental conditions, while the exchange current density and the total resistance contribution to polarization components, computed from the galvanostatic polarization curves were found to be clearly higher and lower, respectively, for the ink modified with PW₁₂ relative to the unmodified system. The results demonstrate that addition of heteropolytungstatic acid (together with Nafion) enhances the electrocatalytic activity of platinum towards reduction of oxygen.     

Investigations of multilayer polyoxometalates-modified carbon nanotubes for electrochemical capacitors

A simple and effective method to improve over previous approaches to add pseudocapacitance to carbon substrates through deposition of polyoxometalates (POMs) was demonstrated on multi-walled carbon nanotubes (MWCNTs). By superimposing layers of different pseudocapacitive polyoxometalates, SiMo₁₂O₄₀⁻⁴ (SiMo₁₂) and PMo₁₂O₄₀⁻³ (PMo₁₂), the POMs exhibited continuous overlapped oxidation/reduction reactions and achieved an up to fourfold increase in area specific capacitance when compared with the double layer capacitance of bare MWCNTs. The superimposed SiMo₁₂ and PMo₁₂ layers were studied by Scanning Electron Microscopy (SEM) and X-ray Photoelectron Spectroscopy (XPS). Analyses of the potential/pH relationship provided important insights into the deposition mechanism and suggested that the layer closest to the electrode substrate was dominating in terms of chemistry and kinetics of the coated MWCNT.     

Well-dispersed surfactant-stabilized Pt/C nanocatalysts for fuel cell application: Dispersion control and surfactant removal

A simple surfactant-stabilized method was investigated for the preparation of well-dispersed platinum nanoparticles supported on carbon black (Pt/C), using 3-(N, N-dimethyldodecylammonio) propanesulfonate (SB12) as the stabilizer. First, TEM analysis demonstrated that Pt dispersion can be improved by the increase of molar ratio of SB12 to Pt precursor. Moreover, pH environment plays a crucial role in Pt dispersion, and the optimal dispersion with an average Pt particle size of 2.2 nm was obtained under neutral or slightly alkaline environment. Pt dispersion mechanism was shown to involve the electrosteric stabilization of Pt nanoparticles by the zwitterionic surfactant SB12, which is highly pH-dependent. At pH ≥ 7, a stable electrosteric repulsion exists between the Pt particles covered by SB12, where the positively charged part is adsorbed on the particle surface and the negatively charged part (SO₃⁻) and the bulky alkyl chain (C₁₂H₂₅) are pointed away from particles. At pH < 7, protons H⁺ directly interact with Pt particles or SO₃⁻ groups of SB12, resulting in the destruction of the electrosteric stabilization and the following agglomeration of Pt nanoparticles. Furthermore, XPS and cyclic voltammetry showed that the surfactant on Pt particles can be efficiently removed by ethanol wash without any destruction on the dispersion and particle size of Pt, when compared to heat treatment and centrifugation. Electrochemical measurements showed that the ethanol-washed pH-controlled Pt/C catalyst has higher electrochemical surface area and catalytic performance than the commercial one.     

Ionic liquid–polymer electrolyte for amperometric solid-state NO2 sensor

A new ionic liquid–polymer electrolyte was successfully tested in the planar amperometric solid-state sensor sensitive towards nitrogen dioxide. The electrolyte consists of 1-butyl-3-methylimidazolium hexafluorophosphate (BMIPF₆) and poly(ethylene glycol) methyl ether methacrylate (PEGMEMA) in the ratio 57:43 mol.% and exhibits ionic conductivity 1.6 × 10⁻⁴ S cm⁻¹ at 20 °C, high electrochemical stability (over 4 V on gold or glassy carbon) and thermal stability (over 230 °C). The analyte, gaseous nitrogen dioxide in air, was determined using the electrochemical reduction at −900 mV vs. Pt/air on gold minigrid indicating electrode with Pt/air as a reference electrode. The sensor response is linear in the NO₂ concentration range 0.3–1.1 ppm and is reproducible and long-term stable.     

A sensitive amperometric bromate sensor based on multi-walled carbon nanotubes/phosphomolybdic acid composite film

An amperometric sensor for bromate was developed based on multi-walled carbon nanotubes (MWNTs)/phosphomolybdic acid (PMo₁₂) composite film coated on a pyrolytic graphite (PG) electrode. MWNTs are dispersed in PMo₁₂ aqueous solution through spontaneous and strong chemisorption between carbon and polyoxometalate, which results in a homogeneous MWNTs/PMo₁₂ composite. Due to the unique electronic and electrocatalytic properties of MWNTs and PMo₁₂, the combination of MWNTs and PMo₁₂ results in a remarkable synergistic augmentation on the response current. The bromate sensor based on the PG/MWNTs/PMo₁₂ electrode has excellent characteristics, such as a detection limit of 0.5 μM, a sensitivity of 760.9 μA mM⁻¹ cm⁻², a response time less than 2 s and a linear range from 5 μM to 15 mM.     

Particle size effects of gold on the kinetics of the oxygen reduction at chemically prepared Au/C catalysts

Gold nanoparticles with narrow and controlled size distributions have been synthesized chemically and deposited onto a carbon support. Using the resulting gold on carbon (Au/C) catalysts, Au particle size effects on the kinetics of the oxygen reduction reaction (ORR) were analyzed in acidic media (0.5 M H₂SO₄). From rotating ring-disk electrode (RRDE) voltammetric studies, it was found that, for bulk gold, the number of electrons, n, involved in the ORR was nearly constant at potentials above −0.2 V. On the contrary, for the catalysts with diameters less than 10-15 nm, the value of n increased as the potential became more negative, and the highest value of n was obtained when the size of Au particles was less than 3 nm. Those results showed that further reduction of H₂O₂ or direct 4-electron reduction of O₂ proceeded at relatively low overpotential on extremely small gold clusters.     

Nb–TiO2 supported platinum nanocatalyst for oxygen reduction reaction in alkaline solutions

Platinum based nanocatalyst at home made Nb–TiO₂ support was synthesized and characterized as the catalyst for oxygen reduction reaction in 0.1 mol dm⁻³ NaOH, at 25 °C. Nb doped TiO₂ catalyst support, containing 5% of Nb, has been synthesized by modified acid-catalyzed sol–gel procedure in non-aqueous medium. BET and X-ray diffraction (XRD) techniques were applied for characterization of synthesized supporting material. XRD analysis revealed only presence of anatase TiO₂ phase in synthesized support powder. Existence of any peaks belonging to Nb compounds has not been observed, indicating Nb incorporated into the lattice.Nb–TiO₂ supported Pt nanocatalyst synthesized, using borohydride reduction method, was characterized by TEM and HRTEM techniques. Platinum nanoparticles distribution, over Nb doped TiO₂ support, was quite homogenous. Mean particle size of about 4 nm was found with no pronounced particle agglomeration. Electrochemical techniques: cyclic voltammetry and linear sweep voltammetry at rotating disc electrode were applied in order to study kinetics and estimate catalytic activity of this new catalyst for the oxygen reduction reaction in alkaline solution. Two different Tafel slopes were found: one close to −90 mV dec⁻¹ in low current density region and other approximately −200 mV dec⁻¹ in high current density region, which is in good accordance with literature results for oxygen reduction at Pt single crystals, as well as Pt nanocatalysts in alkaline solutions. Similar specific catalytic activity (expressed in term of kinetic current density per real surface area) of Nb(5%)–TiO₂/Pt catalyst for oxygen reduction reaction in comparison with the carbon supported platinum (Vulcan/Pt) nanocatalyst, was found.     

Improved capacitance characteristics during electrochemical charging of carbon nanotubes modified with polyoxometallate monolayers

By modification of surfaces of multi-walled carbon nanotubes with ultra-thin monolayer-type films of phosphododecamolybdic acid, H₃PMo₁₂O₄₀, an electrode material with improved capacitance properties is produced. It is apparent from three distinct test experiments (based on cyclic voltammetry, galavanostatic charging-discharging and AC impedance) that capacitors utilizing H₃PMo₁₂O₄₀-modified carbon nanotubes are characterized by specific capacitances and energy densities on the levels of 40 F g⁻¹ and 1.3 Wh kg⁻¹, whereas the respective values for the systems built from bare carbon nanotubes are lower, 22 F g⁻¹ and 0.7 Wh kg⁻¹. It is reasonable to expect that fast and reversible multi-electron transfers of the Keggin-type H₃PMo₁₂O₄₀ account for the pseudocapacitance effect and significantly contribute to the observed overall capacitance.     

Strategy for the syntheses of isolated fine silver nanoparticles and polypyrrole/silver nanocomposites on gold substrates

In this work, isolated fine silver nanoparticles and polypyrrole/silver nanocomposites with diameters of about 10 nm on gold substrates were first prepared by electrochemical methods. First, an Ag substrate was cycled in a deoxygenated aqueous solution containing 0.1 M HCl from −0.30 to +0.30 V versus Ag/AgCl at 5 mV/s with 30 scans. Subsequently the Ag working electrode was immediately replaced by an Au electrode and a cathodic overpotential of 0.2 V was applied under controlled sonication to synthesize Ag nanoparticles on the Au electrode. Then pyrrole monomers were encouragingly found to be polymerized on the deposited Ag nanoparticles. This polymerization is distinguishable from the known chemical or electrochemical one, due to the electrochemical activity of unreduced species of Ag_n⁺ clusters inside the nanoparticles. Also, this polymerization may be ascribed to the oxidizing agent of AuCl₄⁻, which is present on the Au electrode.     

Fabrication of network films of conducting polymer-linked polyoxometallate-stabilized carbon nanostructures

The ability of a Keggin-type polyoxometallate, phosphododecamolybdate (PMo₁₂O₄₀³⁻), to form stable anionic monolayers on carbon nanoparticles and multi-wall nanotubes is explored here to produce stable colloidal solutions of polyoxometallate covered carbon nanostructures and to disperse them within conducting polymer, poly(3,4-ethylenedioxythiophene), i.e. PEDOT, or polyaniline multilayer films. By repeated alternate treatments in the colloidal suspension of PMo₁₂O₄₀³⁻-protected carbon nanoparticles or nanotubes, and in the acid solution of a monomer (3,4-ethylenedioxythiophene or aniline), the amount of the material can be increased systematically (layer-by-layer) to form stable three-dimensional organized arrangements (networks) of interconnected organic and inorganic layers on electrode (e.g. glassy carbon) surfaces. In hybrid films, the negatively charged polyoxometallate-covered carbon nanostructures interact electrostatically with positively charged conducting polymer ultra-thin layers. Consequently, the attractive electrochemical charging properties of conducting polymers, reversible redox behavior of polyoxometallate, as well as the mechanical and electrical properties of carbon nanoparticles or nanotubes can be combined. The films are characterized by fast dynamics of charge transport, and they are of potential importance to electrocatalysis and charge storage in redox capacitors.     

Finely dispersed Pt nanoparticles in conducting poly(o-anisidine) nanofibrillar matrix as electrocatalytic material

A new approach based on stepwise oxidation of o-anisidine is explored for generating nanoporous films of poly(o-anisidine), POA and loading of Pt nanoparticles that are subsequently used for electrocatalysis of methanol oxidation are presented and compared with bulk Pt. POA film can easily be prepared by stepwise electro-oxidation procedure with very high porosity consisting of nanofibrillar structure using without templates. Controlled sizes of Pt nanoparticles were entrapped into POA matrix by a two-step process in which first PtCl₆²⁻ ions are sorbed into the pores of polymer matrix followed by electroreduction at −0.55 V in a 0.5 M H₂SO₄ solution. Loading of Pt nanoparticles (10-200 μg/cm²) onto POA matrix were accomplished by varying the concentration (2-10 mM) of the sorbate, i.e., H₂PtCl₆. The sizes of the Pt nanoparticles were determined from TEM analysis and Pt particles were found to be in the range of 10-20 nm. The crystallite phase of Pt particles in POA was examined from XRD pattern. AFM image further supports Pt particles embedded in POA matrix.     

In situ radiotracer and voltammetric study of the formation of surface adlayers in the course of Cr(VI) reduction on polycrystalline and (1 1 1) oriented platinum

This paper is focused on the in situ radiotracer and voltammetric studies of the induced HSO₄⁻/SO₄²⁻ adsorption at Pt(poly) and Pt(1 1 1) surfaces in 0.1 mol dm⁻³ HClO₄ solution in the course of Cr(VI) electroreduction. Besides this, the sorption behavior of HSO₄⁻/SO₄²⁻ ions on bare Pt(poly) and Pt(1 1 1) electrodes is compared and discussed. From the experimental results it can be stated that: (i) although the extent of bisulfate/sulfate adsorption is strongly dependent upon the crystallographic orientation of Pt surfaces, the maximum coverage on the Pt(1 1 1) does not exceed 0.2 monolayer; (ii) the Cr(VI) electroreduction on both poly- and (1 1 1) oriented platinum proceeds via a ce (chemical-electron-transfer) mechanism to yield Pt surfaces covered with intermediate surface adlayers containing Cr(VI) particles (and reduced Cr-containing adspecies) and ‘strongly bonded’ HSO₄⁻/SO₄²⁻ ions; (iii) while the coverage of platinum surfaces by the intermediate complexes formed in the course of Cr(VI) electroreduction at E > 0.20 V is basically independent of the crystallographic orientation of the Pt electrode, the onset for rapid Cr(VI) reduction is highly affected by the nature and crystallographic orientation of the electrode.     

A voltammetric and nanogravimetric study of Te underpotential deposition on Pt in perchloric acid medium

This work describes the study of Te underpotential deposition on Pt in acid media using cyclic voltammetry, rotating ring-disc electrode and electrochemical quartz crystal microbalance techniques. The voltammetric results indicate the presence of two dissolution peaks in the positive scan with a total charge density of 420 μC cm⁻². These phenomena are attributed to the deposition of one Te monolayer with the occupancy of two active Pt sites by each ad-atom. This is confirmed by rotating ring-disc electrode results. The electrochemical quartz crystal microbalance (EQCM) experiments yielded the small mass variation of −32 ng cm⁻² (while the theoretical one is −140.4 ng cm⁻² for a complete Te monolayer). This low value can be attributed to the simultaneous adsorption of water, perchlorate anions and the formation of platinum oxide.     

Enhanced electrocatalytic activity of a polyoxometalates-based film decorated by gold nanoparticles

A K₆P₂MoW₁₇O₆₂-based film decorated by gold nanoparticles was prepared by layer-by-layer self-assembly method. It was fabricated on quartz, silicon and ITO substrates in a progressive and uniform manner monitored by UV–vis spectroscopy, and characterized by atomic force microscopy (AFM), cyclic voltammograms (CVs) and electrochemical impedance spectra (EIS). A set of experimental results revealed that the incorporation of Au nanoparticles into K₆P₂MoW₁₇O₆₂-based film enhanced the conductivity of the film, leading to several or more than tenfold increase in electrocatalytic efficiency of this film for reduction of H₂O₂, IO₃⁻, NO₂⁻ compared to the no use of Au nanoparticles. It also has been found that presence of Au nanoparticles endowed the film electrocatlytic activity towards oxidation of ascorbic acid and the photo-luminescence property arising from inter electron transitions between occupied 5d bands to 6sp conduction bands of AuNPs.