Development of Metalloenzyme Dioxygen Reduction Cathodes

The prime thrust of this dissertation is to advance the development of fuel cell dioxygen reduction cathodes that employ some variant of multicopper oxidase enzymes as the catalyst. The low earth-abundance of platinum metal and its correspondingly high market cost has prompted a general search amongst chemists and materials scientists for reasonable alternatives to this metal for facilitating catalytic dioxygen reduction chemistry. The multicopper oxidases (MCOs), which constitute a class of enzyme that naturally catalyze the reaction O₂ + 4H⁺ + 4e^- → 2H₂O, provide a promising set of biochemical contenders for fuel cell cathode catalysts. In MCOs, a substrate reduces a copper atom at the type 1 site, where charge is then transferred to a trinuclear copper cluster consisting of a mononuclear type 2 or “normal copper” site and a binuclear type 3 copper site. Following the reduction of all four copper atoms in the enzyme, dioxygen is then reduced to water in two two-electron steps, upon binding to the trinuclear copper cluster. We identified an MCO, a laccase from the hyperthermophilic bacterium Thermus thermophilus strain HB27, as a promising candidate for cathodic fuel cell catalysis. This protein demonstrates resilience at high temperatures, exhibiting no denaturing transition at temperatures high as 95°C, conditions relevant to typical polymer electrolyte fuel cell operation.

In Chapter I of this thesis, we discuss initial efforts to physically characterize the enzyme when operating as a heterogeneous cathode catalyst. Following this, in Chapter II we then outline the development of a model capable of describing the observed electrochemical behavior of this enzyme when operating on porous carbon electrodes. Developing a rigorous mathematical framework with which to describe this system had the potential to improve our understanding of MCO electrokinetics, while also providing a level of predictive power that might guide any future efforts to fabricate MCO cathodes with optimized electrochemical performance. In Chapter III we detail efforts to reduce electrode overpotentials through site-directed mutagenesis of the inner and outer-sphere ligands of the Cu sites in laccase, using electrochemical methods and electronic spectroscopy to try and understand the resultant behavior of our mutant constructs. Finally, in Chapter IV, we examine future work concerning the fabrication of enhanced MCO cathodes, exploring the possibility of new cathode materials and advanced enzyme deposition techniques.

Green synthesis of highly stable platinum nanoparticles stabilized by amino-terminated ionic liquid and its electrocatalysts for dioxygen reduction and methanol oxidation

Preparation of monodispersed platinum nanoparticles with average size 2.0 nm stabilized by amino-terminated ionic liquid was demonstrated. The resulting platinum nanoparticles (Pt-IL) retained long-term stability without special protection. The Pt-IL nanoparticles exhibited high electrocatalytic activity toward reduction of oxygen and oxidation of methanol. Rotating disk electrode voltammetry and rotating ring-disk electrode voltammetry confirmed that the Pt-IL films could catalyze an almost four-electron reduction of dioxygen to water.

Alternate assemblies of polyelectrolyte functionalized carbon nanotubes and platinum nanoparticles as tunable electrocatalysts for dioxygen reduction

A novel method based on electrostatic layer-by-layer self-assembly (LBL) technique for alternate assemblies of polyelectrolyte functionalized multi-walled carbon nanotubes (MWNTs) and platinum nanoparticles (PtNPs) is proposed. The shortened MWNTs can be functionalized with positively charged poly(diallyldimethylammonium chloride) (PDDA) based on electrostatic interaction. Through electrostatic layer-by-layer assembly, the positively charged PDDA functionalized MWNTs (PDWNTs) and negatively charged citrate-stabilized PtNPs were alternately assembled on a 3-mercaptopropanesulfonic sodium (NIPS) modified gold electrode and also on other negatively charged surface, e.g. quartz slide and indium-tin-oxide (ITO) plate, directly forming the three-dimensional (3D) nanostructured materials. This is a very general and powerful technique for the assembling three-dimensional nanostructured materials containing carbon nanotubes (CNTs) and nanoparticles. Thus prepared multilayer films were characterized by ultraviolet-visiblenear-infrared spectroscopy (UV-vis-NIR), scanning electron microscopy (SEM) and cyclic voltammetry (CV). Regular growth of the mutilayer films is monitored by UV-vis-NIR.

Fabrication of a metalloporphyrin - Polyoxometalate hybrid film by a layer-by-layer method and its catalysis for hydrogen evolution and dioxygen reduction

Tetrakis (N-methylpyridyl) porphyrinato] cobalt (CoTMPyP) and 1:12 silicotungstic acid (SiW12) were alternately deposited on a 4-aminobenzoic acid (4-ABA)-modified glassy carbon electrode through a layer-by-layer method. The resulting organic-inorganic hybrid films were characterized by cyclic voltammetry (CV) and UV/vis absorption spectroscopy. We proved that the prepared multilayer films are uniform and stable. SiW12-containing multilayer films (SiW12 as the outermost layer) exhibit remarkable electrocatalytic activity for the hydrogen evolution reaction (HER). The kinetic constants for HER were comparatively investigated at different layers Of SiW12/CoTMPyP multilayer film-modified electrodes by hydrogen evolution voltammetry. In addition, rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) voltammetric methods confirm that SiW12/CoTMPyP (CoTMPyP as the outermost layer) multilayer films catalyze almost a two-electron reduction of O-2 to H2O2 in pH 1-6 buffer solutions. Furthermore, P2W18/CoTMPyP films were also assembled, and their catalytic activity for HER is very different from that Of SiW12/CoTMPyP multilayer films.

Preparation of multilayer films containing pt nanoparticles on a glassy carbon electrode and application as an electrocatalyst for dioxygen reduction

In this paper, a simple route for the preparation of Pt nanoparticles is described. PtCl62- and [tetrakis-(N-methylpyridyl)porphyrinato] cobalt (CoTMPyP) were assembled on a 4-aminobenzoic acid modified glassy carbon electrode through the layer-by-layer method. The three-dimensional Pt nanoparticle films are directly formed on an electrode surface by electrochemical reduction of PtCl62- sandwiched between CoTMPyP layers. Regular growth of the multilayer films is monitored by UV-vis spectroscopy. X-ray photoelectron spectroscopy verifies the constant composition of the multilayer films containing Pt nanoparticles. Atomic force microscopy proves that the as-prepared Pt nanoparticles are uniformily distributed with average particle diameters of 6-10 nm. The resulting multilayer films containing Pt nanoparticles on the modified electrode possess catalytic activity for the reduction of dissolved oxygen. Rotating disk electrode voltammetry and rotating ring-disk electrode voltammetry confirm that Pt nanoparticle containing films can catalyze an almost four-electron reduction of O-2 to water in 0.5 M H2SO4 solution.

Simple preparation method of Pd nanoparticles on an Au electrode and its catalysis for dioxygen reduction

A simple method for the fabrication of Pd nanoparticles is described. The three-dimensional Pd nanoparticle films are directly formed on a gold electrode surface by simple electrodeposition at -200 mV from a solution of 1 M H2SO4+0.01 mM K2PdCl4. X-Ray photoelectron spectroscopy verifies the constant composition of the Pd nanoparticle films. Atomic force microscopy proves that the as-prepared Pd nanoparticles are uniformly distributed with an average particle diameter of 45-60 nm. It is confirmed that the morphology of the Pd nanoparticle films are correlated with the electrodeposition time and the state of the Au substrate. The resulting Pd-nanoparticle-film-modified electrode possesses high catalytic activity for the reduction of dissolved oxygen in 0.1 M KCl solution. Freshly prepared Pd nanoparticles can catalyze the reduction of O-2 by a 4-electron process at -200 mV in 0.1 M KCl, but this system is not very stable. The cathodic peaks corresponding to the reduction of O-2 gradually decrease with potential cycling and at last reach a steady state. Then two well-defined reduction peaks are observed at -390 and -600 mV vs. Ag/AgCl/KCl (sat.). Those two peaks correspond to a 2-step process for the 4-electron reduction pathway of O-2 in this neutral medium.

Fabrication of metalloporphyrin-polyoxometalyte hybrid film by layer-by-layer method and its catalysis for dioxygen reduction

Through layer-by-layer method [tetrakis(N-methylpyridyl)porphyrinato] cobalt (CoTMPyP) and polyoxometalyte were alternately deposited on 4-aminobenzoic acid (4-ABA) modified glassy carbon electrode. The resulting organic-inorganic hybrid films were characterized by cyclic voltammetry (CV), UV/visible absorption spectroscopy, and atomic force microscopy (AFM). It was proved that the multilayer films are uniform and stable. CoTMPyP-containing multilayer films exhibit remarkable electrocatalytic activity for the reduction of O-2. Rotating disk electrode (RDE) voltammetry and rotating ring-disk electrode (RRDE) voltammetry confirm that P2W18/CoTMPyP multilayer films can catalyze the four-electron almost reduction of O-2 to water in pH > 4.0 buffer solution, while SiW12/CoTMPyP multilayer films catalyze about two-electron reduction of O-2 to H2O2 in pH 1 - 6 buffer solutions. The kinetic constants for O-2 reduction were comparatively investigated at P2W18/CoTMPyP and SiW12/CoTMPyP multilayer films electrodes.

Microelectrode Voltammetry of Dioxygen Reduction in a Phosphonium Cation-Based Room-Temperature Ionic Liquid: Quantitative Studies

Microelectrode voltammetry is used to study the electrochemical reduction of dioxygen, O-2, in the room-temperature ionic liquid trihexyl(tetradecyl)phosphonium trifluorotris(pentafluoroethyl)phosphate [P6,6,6,14][FAP]. The nature of the unusual voltammetric waves is quantitatively modeled via digital simulation with the aim of clarifying apparent inconsistencies in the literature. The reduction is shown to proceed via a two-electron reaction and involve the likely capture of a proton from the solvent system. The oxidative voltammetric signals seen at fast scan rates are interpreted as resulting from the reoxidation of HO2 center dot. In the presence of large amounts of dissolved carbon dioxide the reductive currents decrease by a factor of ca. two, consistent with the trapping of the superoxide radical, O-2(center dot), intermediate in the two-electron reduction process.

Preparation of DNA - Silver nanohybrids in multilayer nanoreactors by in situ electrochemical reduction, characterization, and application

Novel nanocomposite films containing DNA-silver nanohybrids have been successfully fabricated by combined use of the layer-by-layer self-assembly technique and an in situ electrochemical reduction method with the DNA-Ag+ complex as one of the building blocks. UV-vis absorption spectroscopy was employed to monitor the buildup of the multilayer films, which suggested a progressive deposition with almost an equal amount of the DNA-Ag+ complex in each cycle. The following electrochemical reduction of silver resulted in the formation of metal nanoparticles in the film, which was evidenced by the evolution of the intense plasmon absorption band originating from silver. Scanning electron microscopy indicated that the particles formed in the multilayer films possessed good monodispersity and stability, thanks to the surrounding polymers. X-ray photoelectron spectroscopy further confirmed the presence of the main components (such as DNA and metallic silver) of the nanocomposite films. In addition, we show that the size of the metal nanoparticles and the optical property of the film could be readily tuned by manipulating the assembly conditions.

KINETIC-STUDY OF ELECTROCATALYTIC REDUCTION OF HYDROGEN-PEROXIDE AT IRON(III) PORPHYRIN MODIFIED GLASSY-CARBON ELECTRODE IN ALKALINE-MEDIUM USING THE ROTATION-SCAN METHOD

Reduction of hydrogen peroxide at a glassy carbon (GC) electrode modified with sigma-bonded pyrrole iron(III) octaethylporphyrin complex, (OEP)Fe(Pyr), was studied by cyclic voltammetry and a rotating disk electrode. In 0.1N NaOH solution, it is shown that such an (OEP)Fe(Pyr)/GC electrode has a significant catalytic activity towards hydrogen peroxide reduction (E(D) = -0.80 V, k = 0.066 cm s(-1)); however, the electrode stability is low. The deactivation is observed when the reaction charge (Q) is passing through the (OEP)Fe(Pyr)/GC disk electrode. A linear rotation scan method is applied to study the kinetic process by determining the disk electrochemical response (i(D)) to rotation rate (omega) at a definite disk potential (E(D)). Considering that the number of adsorbed electroreduced catalyst molecules (Red) varies according to the disk potential, a factor theta(= Gamma(Red)/(Gamma(Red) + Gamma(Ox))) is introduced to describe the electrode surface area fraction for electroreduced species. The obtained Koutecky-Levich equation is applicable whatever the potential is.

Amino group position dependent orientation of self-assembled monomolecular films of tetraaminophthalocyanatocobalt(II) on Au surfaces

Self-assembled monomolecular films of 1,8,15,22-tetraaminophthalocyanatocobalt(II) (4α-CoIITAPc) and 2,9,16,23-tetraaminophthalocyanatocobalt(II) (4β-CoIITAPc) on Au surfaces were prepared by spontaneous adsorption from solution. These films were characterized by cyclic voltammetry and Raman spectroscopy. Both the surface coverage (Γ) and intensity of the in-plane stretching bands obtained from Raman studies vary for these monomolecular films, indicating different orientations adopted by them on Au surfaces. The 4α-CoIITAPc-modified electrode exhibits an E1/2 of 0.35 V, while the 4β-CoIITAPc-modified electrode exhibits an E1/2 of 0.19 V, corresponding to the CoII/CoIII redox couple in 0.1 M H2SO4. The Γ estimated from the charge associated with the oxidation of Co(II) gives (2.62 ± 0.10) × 10-11 mol cm-2 for 4α-CoIITAPc and (3.43 ± 0.14) × 10-10 mol cm-2 for 4β-CoIITAPc. In Raman spectral studies, the intensity ratio between in-plane phthalocyanine (Pc) stretching and the Au−N stretching was found to be 6.6 for 4β-CoIITAPc, while it was 1.6 for 4α-CoIITAPc. The obtained lower Γ and intensity ratio values suggest that 4α-CoIITAPc adopts nearly a parallel orientation on the Au surface, while the higher Γ and intensity ratio values suggest that 4β-CoIITAPc adopts a perpendicular orientation. The electrochemical reduction of dioxygen was carried out using these differently oriented Pc's in phosphate buffer solution (pH 7.2). Both the Pc's catalyze the reduction of dioxygen; however, the 4α-CoIITAPc-modified electrode greatly reduces the dioxygen reduction overpotential compared to 4β-CoIITAPc-modified and bare Au electrodes.

A novel urchinlike gold/platinum hybrid nanocatalyst with controlled size

In this paper, we have explored a simple and new strategy to obtain quasimonodisperse Au/Pt hybrid nanoparticles (NPS) with urchinlike morphology and controlled size and Pt shell thickness. Through changing the molar ratios of Au to Pt, the Pt shell thickness of urchinlike Au/Pt hybrid NPs could be easily controlled; through changing the size of Au NPs (the size was easily controlled from similar to 3 to similar to 70 nm via simple heating of HAuCl4-citrate aqueous solution), the size of urchinlike Au/Pt hybrid NPs could be facilely dominated. It should be noted that heating the solution (100 degrees C) was very necessary for obtaining three-dimensional (3D) urchinlike nanostructures while H2PtCl6 was added to gold NPs aqueous solution in the presence of reductant (ascorbic acid). The electrocatalytic oxygen reduction reaction (ORR, a reaction greatly pursued by scientists in view of its important application in fuel cells) and the electron-transfer reaction between hexacyanoferrate(III) ions and thiosulfate ions of urchinlike Au/Pt hybrid NPs were investigated. It is found that the as-prepared urchinlike Au/Pt hybrid NPs exhibited higher catalytic activities than that of similar to Pt NPs with similar size.

High-efficiency and low-cost hybrid nanomaterial as enhancing electrocatalyst: Spongelike AWN core/shell nanomaterial with hollow cavity

A high-efficiency and low-cost spongelike Au/Pt core/shell electrocatalyst with hollow cavity has been facilely obtained via a simple two-step wet chemical process. Hollow gold nanospheres were first synthesized via a modified galvanic replacement reaction between Co nanoparticles in situ produced and HAUCl(4). The as-prepared gold hollow spheres were employed as seeds to further grow spongelike Pt shell. It is found that the surface of this hybrid nanomaterial owns many Pt nanospikes, which form a spongelike nanostructure. All experimental data including scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and UV-vis-near-infrared spectroscopy have been employed to characterize the obtained Au/Pt hybrid nanomaterial. The rapid development of fuel cell has inspired us to investigate the electrocatalytic properties for dioxygen and methanol of this novel hybrid nanomaterial. Spongelike hybrid nanomaterial mentioned here exhibits much higher catalytic activity for dioxygen reduction and methanol oxidation than the common Pt electrode.

A method to construct polyelectrolyte multilayers film containing gold nanoparticles

Gold nanoparticles in polyelectrolyte multilayers film can be easily prepared by repeating immersion of a substrate in poly(diallyl dimethylammonium) chloride (PDDA)-AuCl4- complexes solution followed by reduction Au3+ through heating. UV-vis spectroscopy, cyclic voltammetry (CV) and tapping-mode atomic force microscopy (AFM) are used to confirm the successful construction of the polyelectrolyte multilayers film and the formation of gold nanoparticles. The multilayers film shows electrocatalytic activity to dioxygen reduction.