Iwona A. Rutkowska

Metal oxide photoanodes for solar hydrogen production

The development of sustainable hydrogen production is a key target in the further facilitation of a hydrogen economy. Solar hydrogen generation through the photolytic splitting of water sensitised by semiconductor materials is attractive as it is both renewable and does not lead to problematic by-products, unlike current hydrogen sources such as natural gas. Consequently, the development of these semiconductor materials has undergone considerable research since their discovery over 30 years ago and it would seem prescient to review the more practical results of this research. Among the critical factors influencing the choice of semiconductor material for photoelectrolysis of water are the band-gap energies, flat band potentials and stability towards photocorrosion; the latter of these points directs us to focus on metal oxides. Careful design of thin films of photocatalyst material can eliminate potential routes of losses in performance, i.e., recombination at grain boundaries. Methods to overcome these problems are discussed such as coupling a photoanode for photolysis of water to a photovoltaic cell in a “tandem cell” device.

Electrocatalytic oxidation of ethanol in acid medium: Enhancement of activity of vulcan-supported Platinum-based nanoparticles upon immobilization within nanostructured zirconia matrices

Composite electrocatalytic materials that utilize carbon (Vulcan) supported Pt or PtRu nanoparticles dispersed within thin films of zirconia (ZrO2) are considered here for oxidation of such a biofuel as ethanol in acid medium. The systems were characterized using electrochemical techniques as well as transmission electron microscopy. The enhancement of activity was clearly evident upon comparison of the respective voltammetric and chronoamperometric current densities recorded (at room temperature in 0.5 mol dm-3H2SO4 containing 0.5 mol dm-3 ethanol) using the Vulcan supported Pt and PtRu catalysts in the presence and absence of zirconia. In all cases, the noble metal loading was the same, 100 μg cm-2. Apparently, the existence of large population of hydroxyl groups (originating from zirconia) in the vicinity of Pt-based catalyst, in addition to possible specific interactions between zirconia and the ruthenium component of PtRu, facilitated the oxidative removal (from Pt) of the passivating (e.g., CO) reaction intermediates (adsorbates). By utilizing carbon supported, rather than bare or unsupported, Pt or PtRu nanoparticles (dispersed within the semiconducting zirconia), the overall charge distribution at the electrocatalytic interface was improved.

Nanocomposite Semi-Solid Redox Ionic Liquid Electrolytes with Enhanced Charge-Transport Capabilities for Dye-Sensitized Solar Cells

The ability of Pt nanostructures to induce the splitting of the II bond in iodine (triiodide) molecules is explored here to enhance electron transfer in the iodine/iodide redox couple. Following the dispersal of Pt nanoparticles at 2 % (weight) level, charge transport was accelerated in triiodide/iodide-containing 1,3-dialkylimidazolium room-temperature ionic liquid. If both Pt nanoparticles and multi-walled carbon nanotubes were introduced into the ionic-liquid-based system, a solid-type (nonfluid) electrolyte was obtained. By using solid-state voltammetric (both sandwich-type and microelectrode-based) methodology, the apparent diffusion coefficients for charge transport increased to approximately 1×10(-6)  cm(2)  s(-1) upon the incorporation of the carbon-nanotube-supported iodine-modified Pt nanostructures. A dye-sensitized solar cell comprising TiO2 covered with a heteroleptic Ru(II) -type sensitizer (dye) and the semisolid triiodide/iodide ionic liquid electrolyte admixed with carbon-nanotube-supported Pt nanostructures yielded somewhat higher power conversion efficiencies (up to 7.9 % under standard reporting conditions) than those of the analogous Pt-free system.

Enhancement of oxygen reduction at Co-porphyrin catalyst by supporting onto hybrid multi-layered film of polypyrrole and polyoxometalate-modified gold nanoparticles

Three-dimensional multi-layered films (on glassy carbon) composed of networks of polyoxometallate (PMo12O403−)-modified gold nanoparticles linked together through the alternately deposited ultra-thin layers of polypyrrole have served as active supports for Co-porphyrin catalytic centers. The hybrid organic-inorganic films (supports) have been prepared by using the layer-by-layer approach. The fact that polyanionic (phosphomolybdate) adsorbates on gold nanoparticles are attracted by positively charged sites of conducting polymer (polypyrrole) structures leads to the stabilizing effect and facilitates distribution of Au nanostructures. The systems have been characterized using scanning electron microscopy, as well as with chronoamperometric and voltammetric techniques. By supporting Co-porphyrin centers onto the hybrid film of the polymer-linked phosphomolybdate-stabilized gold nanoparticles, significant electrocatalytic enhancement effects (namely voltammetric current increases) have been observed during the electroreduction of oxygen in acid medium relative to a standard response of the simple porphyrin deposit on glassy carbon measured under analogous conditions. Among important issues is the high activity of the hybrid film (support) itself toward the reductive decomposition of hydrogen peroxide to water. When it comes to performance of the Co-porphyrin-containing system, it is reasonable to expect that the O2 reduction process is initiated at Co-porphyrin catalytic sites (two-electron reduction to H2O2) and continued (two-electron reduction to H2O) at the hybrid film containing gold nanoparticles dispersed within the highly porous cauliflower-like structures of polypyrrole multi-layers. While the gold networks facilitate charge distribution within the hybrid electrocatalytic film, non-covalent π-π interactions of porphyrin rings with polypyrrole interlayers and charge transfers between negatively charged (PMo12O403− modified) gold nanoparticles and positively charged nitrogen sites of polypyrrole could also cause synergism.

Fabrication of Nanostructured Palladium Within Tridentate Schiff-Base-Ligand Coordination Architecture: Enhancement of Electrocatalytic Activity Toward CO2 Electroreduction

There has been growing interest in the electrochemical reduction of carbon dioxide (CO2), a potent greenhouse gas and a contributor to global climate change, and its conversion into useful carbon-based fuels or chemicals [1–5]. Numerous homogeneous and heterogeneous catalytic systems have been proposed to induce the CO2 reduction and, depending on the reaction conditions (applied potential, choice of buffer, its strength and pH, local CO2 concentration, or the catalyst used) various products that include carbon monoxide, oxalate, formate, carboxylic acids, formaldehyde, acetone, or methanol, as well as such hydrocarbons as methane, ethane, and ethylene, are typically observed at different ratios. These reaction products are of potential importance to energy technology, food research, medical applications, and fabrication of plastic materials. Given the fact that the CO2 molecule is very stable, its electroreduction processes are characterized by large overpotentials, and they are not energy efficient. To produce highly efficient and selective electrocatalysts, the transitionmetal-based molecular materials are often considered [6–8]. The latter systems are capable of driving multi-electron transfers and, in principle, produce highly reduced species. In reality, such multi-electron charge transfer catalysts tend to effectively induce the two-electron reduction of CO2 to CO rather than yield highly reduced products in large amounts. Metallic copper electrodes are unique in this respect because they can drive multi-electron transfers. Mechanisms of the successful electrochemical reductions of CO2 to methane and ethylene can be interpreted in terms of complex processes occurring at copper electrodes [9, 10]. It is believed that, during electroreduction, the rate limiting step is the protonation of the adsorbed CO product to form the CHO adsorbate [11]. Significant decrease of the reaction overpotentials can be achieved with the use of the metal complex modified electrodes capable of both mediating electron transfers and stabilizing the reduced products [12]. Because reduction of CO2 can effectively occur by hydrogenation [13], in the present work, we concentrate on such a model catalytic system as nanostructured metallic palladium capable of absorbing reactive hydrogen in addition to the ability to adsorb monoatomic hydrogen at the interface [14–16]. Under such conditions, the two-electron reduction of CO2 typically to CO [12] is favored. When the reaction proceeds on palladium in aqueous KHCO3 solutions, carbon monoxide together with hydrogen and small amounts of formate are produced [17–19]. Further, it has been postulated that CO and COOH adsorbates are expected to be formed at the surfaces of Pd electrodes at −1.0 V (vs. Ag/AgCl) and, subsequently, desorbed at even more negative potentials [20]. To produce highly dispersed and stabilized palladium nanoparticles (as for Fig. 1a), we have generated them by electrodeposition (through consecutive potential cycling) from the thin film of N-coordination complex of palladium(II), [Pd(C14H12N2O3)Cl2]2 MeOH. The ligand and its palladium complex (their detailed crystallographic, IR, and NMR features will be a subject of our next publication) were synthesized via typical condensation reaction as published earlier [21, 22]. The resulting metallic Pd nanoparticles (diameters, 5–10 nm), rather than Pd cationic species, are stabilized and activated by nitrogen coordination centers from the macromolecular matrix. Supramolecular architectures of active and well-defined Schiff-base-ligands containing nitrogen donor atoms are of primary importance because A. Wadas : I. A. Rutkowska : P. J. Kulesza (*) Faculty of Chemistry, University of Warsaw, Pasteura 1, 02093 Warsaw, Poland e-mail: pkulesza@chem.uw.edu.pl

Electrochemically assisted fabrication of size-exclusion films of organically modified silica and application to the voltammetry of phospholipids

Modification of electrodes with nanometer-scale organically modified silica films with pore diameters controlled at 10- and 50-nm is described. An oxidation catalyst, mixed-valence ruthenium oxide with cyano cross-links or gold nanoparticles protected by dirhodium-substituted phosphomolybdate (AuNP-Rh2PMo11), was immobilized in the pores. These systems comprise size-exclusion films at which the biological compounds, phosphatidylcholine and cardiolipin, were electrocatalytically oxidized without interference from surface-active concomitants such as bovine serum albumin. Ten-nanometer pores were obtained by adding generation-4 poly(amidoamine) dendrimer, G4-PAMAM, to a (CH3)3SiOCH3 sol. Fifty-nanometer pores were obtained by modifying a glassy carbon electrode (GC) with a sub-monolayer film of aminopropyltriethoxylsilane, attaching 50-nm diameter poly(styrene sulfonate), PSS, spheres to the protonated amine, transferring this electrode to a (CH3)3SiOCH3 sol, and electrochemically generating hydronium at uncoated GC sites, which catalyzed ormosil growth around the PSS. Voltammetry of Fe(CN)63− and Ru(NH3)63+ demonstrated the absence of residual charge after removal of the templating agents. With the 50-nm system, the pore structure was sufficiently defined to use layer-by-layer electrostatic assembly of AuNP-Rh2PMo11 therein. Flow injection amperometry of phosphatidylcholine and cardiolipin demonstrated analytical utility of these electrodes.

A semiconductor–enzyme photoelectrode for oxygen reduction by direct transfer of photo-generated electrons to laccase

An electrochemically functionalized surface of p-type silicon was used as a nanostructured material for immobilization and activation of a redox metalloprotein. A protocol resulting in the stable enzyme adsorption and utilization was applied to Trametes versicolor laccase (TvL), the “blue” copper-containing oxidase enzyme, a model bio-electrocatalyst for oxygen reduction. The obtained system was tested as a photocatalytic electrode for oxygen sensing through its electroreduction at copper ionic active sites following illumination with visible light. Processes related to the photoexcitation and charge separation occur within the semiconductor (SC) material. Direct, rather than mediated by 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonate) (ABTS), electron transfers from the semiconductor to the enzyme were observed. The topography of the p-Si substrate was assessed by transmission electron microscopy (TEM) and tapping mode atomic force microscopy (TM AFM) methods. The electronic properties of the systems were tested using synchrotron radiation photoelectron spectroscopy (SRPES). The nature of the biomolecule immobilization was studied by TM AFM.

Polyaniline-Supported Bacterial Biofilms as Active Matrices for Platinum Nanoparticles: Enhancement of Electroreduction of Carbon Dioxide

A hybrid matrix composed of a porous polyaniline underlayer, a robust bacterial biofilm and a multiwalled carbon nanotube overlayer has been demonstrated to function as highly active support for dispersed Pt catalytic nanoparticles during the electroreduction of carbon dioxide in neutral medium (phosphate buffer at pH 6.1). In contrast with bare Pt nanoparticles (deposited at a glassy carbon substrate), application of the hybrid system produces sizeable CO2-reduction currents in comparison to those originating from hydrogen evolution. The result is consistent with an enhancement in the reduction of carbon dioxide. However, the biofilm-based matrix tends to inhibit the catalytic properties of platinum towards proton discharge (competitive reaction) or even oxygen reduction. The hydrated structure permits easy unimpeded flow of aqueous electrolyte at the electrocatalytic interface. Although application of the polyaniline underlayer can be interpreted in terms of stabilization and improvement of the biofilm adherence, the use of carbon nanotubes facilitates electron transfer to Pt catalytic sites. It is apparent from the voltammetric stripping-type analytical experiments that, although formation of some methanol and methanoic acid cannot be excluded, carbon monoxide seems to be the main CO2-reduction product.

Nanoporous platinum electrodes as substrates for metal oxide-supported noble metal electrocatalytic nanoparticles: Synergistic effects during electrooxidation of ethanol

Electrocatalytic oxidation of ethanol in acid medium (0.5 mol dm–3 H2SO4) was significantly enhanced by not only supporting bimetallic PtRu nanoparticles on nanostructured metal oxides (TiO2 or WO3), but also by depositing such catalytic systems on planar nanoporous platinized electrode substrates. Incorporation of TiO2 or WO3 into the electrocatalytic interface was likely to improve proton mobility and to provide –OH groups capable of inducing the removal of poisoning species, such as CO, from the Pt sites in the bimetallic PtRu catalyst. Synergistic interactions between ruthenium and titania were also possible. Regularly porous nanostructured platinum substrate also permitted development of submicro ‘reactors’ where reactant molecules, electrolyte ions, and all active components (TiO2 or WO3, Pt substrate, PtRu catalytic sites) could co-exist and become easily accessible. While WO3 was able to undergo fast reversible redox transitions to non-stoichiometric oxides, efficient utilization of inert (non-electroactive) TiO2 required admixing with carbon nanotubes to ensure easy charge distribution and good conductivity at the electrocatalytic interface.

Toward Pt-Free Anion-Exchange Membrane Fuel Cells: Fe–Sn Carbon Nitride–Graphene Core–Shell Electrocatalysts for the Oxygen Reduction Reaction

We report on the development of two new Pt-free electrocatalysts (ECs) for the oxygen reduction reaction (ORR) process based on graphene nanoplatelets (GNPs). We designed the ECs with a core–shell morphology, where a GNP core support is covered by a carbon nitride (CN) shell. The proposed ECs present ORR active sites that are not associated with nanoparticles of metal/alloy/oxide but are instead based on Fe and Sn subnanometric clusters bound in coordination nests formed by carbon and nitrogen ligands of the CN shell. The performance and reaction mechanism of the ECs in the ORR are evaluated in an alkaline medium by cyclic voltammetry with the thin-film rotating ring-disk approach and confirmed by measurements on gas-diffusion electrodes. The proposed GNP-supported ECs present an ORR overpotential of only ca. 70 mV higher with respect to a conventional Pt/C reference EC including a XC-72R carbon black support. These results make the reported ECs very promising for application in anion-exchange membrane fu...