Influence of Additives on the Reversible Oxygen Reduction Reaction/Oxygen Evolution Reaction in the Mg2+ -Containing Ionic Liquid N-Butyl-N-Methylpyrrolidinium Bis(Trifluoromethanesulfonyl)imide.

The influence of different additives on the oxygen reduction reaction/oxygen evolution reaction (ORR/OER) in magnesium-containing N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide ([BMP][TFSI]) on a glassy carbon electrode was investigated to gain a better understanding of the electrochemical processes in Mg-air batteries. 18-Crown-6 was used as a complexing agent for Mg ions to hinder the passivation caused by their reaction with ORR products such as superoxide and peroxide anions. Furthermore, borane dimethylamine complex (NBH) was used as a potential water-removing agent to inhibit electrode passivation by reacting with trace impurities of water. The electrochemical processes were characterized by differential electrochemical mass spectrometry to monitor the consumed and evolved O2 in the ORR/OER and determine the number of transferred electrons. Crown ether and NBH efficiently masked Mg2+ . A stochiometric excess of crown ether resulted in reduced formation of a passivation layer, whereas at too high concentrations the reversibility of the ORR/OER was diminished.

A combined UHV-STM-flow cell set-up for electrochemical/electrocatalytic studies of structurally well-defined UHV prepared model electrodes.

We describe the construction and discuss the performance of a novel combined ultrahigh vacuum (UHV)-electrochemistry set-up, allowing the controlled preparation and structural characterization of complex nanostructured electrode surfaces by high resolution scanning tunnelling microscopy (STM) under UHV conditions on the one hand and, after electrode transfer under clean conditions, electrochemical measurements under continuous, controlled electrolyte mass transport conditions on the other. Electrochemical measurements can be coupled with online product detection, either using an additional collector electrode or by differential electrochemical mass spectrometry (DEMS). The potential of the set-up will be illustrated in two electrocatalytic reactions on complex, but structurally well-defined bimetallic electrode surfaces, O2 reduction on PtxAg1-x/Pt(111) monolayer surface alloys and bulk CO oxidation on Pt monolayer island modified Ru(0001) electrodes. We will particularly demonstrate the importance of structural characterization after the electrochemical measurements for identifying structural modifications induced by the electrochemical environment and thus avoiding misleading conclusions about the structure-activity relationships.

Infrared spectroscopy via substrate-integrated hollow waveguides: a powerful tool in catalysis research.

Substrate-integrated hollow waveguides (iHWG) represent an innovative generation of photon conduits, which can simultaneously serve as highly miniaturized gas cells with low sample volume. In this communication, we introduce a novel concept for analyzing the performance of catalysts via infrared gas phase analysis based on iHWGs. Due to rapid gas exchange and sample transient times within the iHWG, compositional changes of a continuous gas stream after interaction with a catalyst assembly can be monitored with high time resolution.

Inhibitor-assisted synthesis of silica-core microbeads with pepsin-imprinted nanoshells.

A novel approach for molecularly imprinting proteins, i.e. inhibitor-assisted imprinting, onto silica microspheres is discussed, which provides advanced functional materials addressing prevalent challenges in the field of protein purification and isolation from biotechnologically relevant media. Pepstatin-assisted surface-imprinted core-shell microbeads for the acidic protease pepsin were synthesized serving as selective sorbent materials for solid phase extraction (SPE) applications. The inorganic core, i.e. amino-functionalized silica spheres (AFSS), is prepared by the co-condensation of tetraethylorthosilicate (TEOS) and (3-aminopropyl) trimethoxysilane (APTMS) in water-in-oil (W/O) emulsion, which is then reacted with pepstatin, a selective inhibitor of pepsin, onto the surface of the AFSS via an amide bond. 3-Aminophenylboronic acid (APBA) serves as the functional monomer for establishing nanothin imprinted polymer films, i.e. poly(3-aminophenylboronic acid) (pAPBA) at the surface of the pepstatin-immobilized AFSS via oxidation by ammonium persulfate in aqueous solution in the presence (molecularly imprinted polymer, MIP) and absence (non-imprinted polymer; NIP) of pepsin. Thus obtained core-shell microbeads are packaged into SPE cartridges for evaluating the selectivity for pepsin. Each individual synthesis step is thoroughly characterized using x-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and BET methods. Finally, the imprinted core-shell microbeads indeed provide specific binding.

The influence of reactive side products on the electrooxidation of methanol--a combined in situ infrared spectroscopy and online mass spectrometry study.

Aiming at a better understanding of the impact of reaction intermediates and reactive side products on electrocatalytic reactions under conditions characteristic for technical applications, i.e., at high reactant conversions, we have investigated the electrooxidation of methanol on a Pt film electrode in mixtures containing defined concentrations of the reaction intermediates formaldehyde or formic acid. Employing simultaneous in situ infrared spectroscopy and online mass spectrometry in parallel to voltammetric measurements, we examined the effects of the latter molecules on the adlayer build-up and composition and on the formation of volatile reaction products CO2 and methylformate, as well as on the overall reaction rate. To assess the individual contributions of each component, we used isotope labeling techniques, where one of the two C1 components in the mixtures of methanol with either formaldehyde or formic acid was (13)C-labeled. The data reveal pronounced effects of the additional components formaldehyde and formic acid on the reaction, although their concentration was much lower (10%) than that of the main reactant methanol. Most important, the overall Faradaic current responses and the amounts of CO2 formed upon oxidation of the mixtures are always lower than the sums of the contributions from the individual components, indicative of a non-additive behavior of both Faradaic current and CO2 formation in the mixtures. Mechanistic reasons and consequences for reactions in a technical reactor, with high reactant conversion, are discussed.

Activation of molecular oxygen and the nature of the active oxygen species for CO oxidation on oxide supported Au catalysts.

Although highly dispersed Au catalysts with Au nanoparticles (NPs) of a few nanometers in diameter are well-known for their high catalytic activity for several oxidation and reduction reactions already at rather low temperatures for almost 30 years, central aspects of the reaction mechanism are still unresolved. While most studies focused on the active site, the active Au species, and the effect of the support material, the most crucial step during oxidation reactions, the activation of molecular oxygen and the nature of the resulting active oxygen species (Oact), received more attention just recently. This is topic of this Account, which focuses on the formation, location, and nature of the Oact species present on metal oxide supported Au catalysts under typical reaction conditions, at room temperature and above. It is mainly based on quantitative temporal analysis of products (TAP) reactor measurements, which different from most spectroscopic techniques are able to detect and quantify these species even at the extremely low concentrations present under realistic reaction conditions. Different types of pulse experiments were performed, during which the highly dispersed, realistic powder catalysts are exposed to very low amounts of reactants, CO and/or O2, in order to form and reactively remove Oact species and gain information on their formation, nature, and the active site for Oact formation. Our investigations have shown that the active oxygen species for CO oxidation on Au/TiO2 for reaction at 80 °C and higher is a highly stable atomic species, which at 80 °C is formed only at the perimeter of the Au-oxide interface and whose reactive removal by CO is activated, but not its formation. From these findings, it is concluded that surface lattice oxygen represents the Oact species for the CO oxidation. Accordingly, the CO oxidation proceeds via a Au-assisted Mars-van Krevelen mechanism, during which surface lattice oxygen close to the Au NPs is removed by reaction with CO, resulting in a partially reduced TiO2 surface, which is subsequently reoxidized by O2. We demonstrate that this is the dominant reaction pathway for Au catalysts based on reducible metal oxides in general, at typical reaction temperatures, while for less active Au catalysts based on nonreducible metal oxides, this reaction pathway is not possible and the remaining activity must arise from another pathway, most probably a Au-only mechanism. At lower reaction temperature, reactive removal of Oact becomes increasingly inhibited, leading to a change in the dominant reaction pathway.

High surface area crystalline titanium dioxide: potential and limits in electrochemical energy storage and catalysis.

Titanium dioxide is one of the most intensely studied oxides due to its interesting electrochemical and photocatalytic properties and it is widely applied, for example in photocatalysis, electrochemical energy storage, in white pigments, as support in catalysis, etc. Common synthesis methods of titanium dioxide typically require a high temperature step to crystallize the amorphous material into one of the polymorphs of titania, e.g. anatase, brookite and rutile, thus resulting in larger particles and mostly non-porous materials. Only recently, low temperature solution-based protocols gave access to crystalline titania with higher degree of control over the formed polymorph and its intra- or interparticle porosity. The present work critically reviews the formation of crystalline nanoscale titania particles via solution-based approaches without thermal treatment, with special focus on the resulting polymorphs, crystal morphology, surface area, and particle dimensions. Special emphasis is given to sol-gel processes via glycolated precursor molecules as well as the miniemulsion technique. The functional properties of these materials and the differences to chemically identical, non-porous materials are illustrated using heterogeneous catalysis and electrochemical energy storage (battery materials) as example.

Interaction of CO and deuterium with bimetallic, monolayer Pt-island/film covered Ru(0001) surfaces.

The adsorption properties of structurally well defined bimetallic Pt/Ru(0001) surfaces, consisting of a Ru(0001) substrate partly or fully covered by monolayer Pt islands or a monolayer Pt film, were studied by temperature programmed desorption (TPD) using CO and deuterium as probe molecules. Additionally, the adsorption of CO was investigated by infrared reflection absorption spectroscopy (IRAS). The presence of the pseudomorphic platinum islands or monolayer film leads to considerable modifications of the adsorption properties for both adsorbates, both on the Pt covered and, to a smaller extent, on the bare Ru part of the surfaces. In addition to distinct weakly bound adspecies, which are adsorbed on the monolayer Pt islands, we find unique contributions from island edge desorption, from spill-over processes during the desorption run, and a general down-shift of the peak related to desorption from Pt-free Ru(0001) areas with increasing Pt coverage. These effects, which we consider as characteristic for adsorption on bimetallic surfaces with large contiguous areas of the respective types, are discussed in detail.

Formation, atomic distribution and mixing energy in two-dimensional Pd(x)Ag(1-x) surface alloys on Pd(111).

The formation and atom distribution in two-dimensional Pd(x)Ag(1-x)/Pd(111) monolayer surface alloys were studied by high resolution scanning tunnelling microscopy (STM) with chemical contrast. From short-range order (SRO) parameters, we calculate preferences for like or unlike nearest neighbours to elucidate the mixing behaviour of the two components for various sub monolayer Ag surface contents. In the regime of low Ag surface contents (<40% Ag), the system shows a weak tendency towards phase separation, high Ag coverages (>60% Ag) result in a disperse distribution of the atoms in the surface. Effective pair interactions (EPIs) were derived by comparing the measured distribution with distributions obtained using Monte Carlo (MC) simulations. From the EPIs, we derived a function for the mixing energy, which can describe the change from clustering to a disperse distribution. The effects of the resulting surface atom distributions and of the Ag coverage dependent surface mixing/demixing on catalytic reactions are discussed.

The interaction of CO with PdAg/Pd(111) surface alloys--a case study of ensemble effects on a bimetallic surface.

The interaction of CO with structurally well-defined PdAg/Pd(111) surface alloys was investigated by temperature-programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS) to unravel and understand contributions from electronic strain, electronic ligand and geometric ensemble effects. TPD measurements indicate that CO adsorption is not possible on the Ag sites of the surface alloys (at 120 K) and that the CO binding strength on Pd sites decreases significantly with increasing Ag concentration. Comparison with previous scanning tunneling microscopy (STM) data on the distribution of Pd and Ag atoms in the surface alloy shows that this modification is mainly due to geometric ensemble effects, since Pd(3) ensembles, which are the preferred ensembles for CO adsorption on non-modified Pd(111), are no longer available on Ag-rich surfaces. Consequently, the preferred CO adsorption site changes with increasing Ag content from a Pd(3) trimer via a Pd(2) dimer to a Pd monomer, going along with a successive weakening of CO adsorption. Additionally, the CO adsorption properties of the surface alloys are also influenced by electronic ligand and strain effects, but on a lower scale. The results are discussed in comparison with previous findings on PdAg bulk alloys, supported PdAg catalysts and PdAu/Pd(111) model systems.

Electrochemistry at Ru(0001) in a flowing CO-saturated electrolyte--reactive and inert adlayer phases.

We investigated the electrochemical oxidation and reduction processes on ultrahigh vacuum prepared, smooth and structurally well-characterized Ru(0001) electrodes in a CO-saturated and, for comparison, in a CO-free flowing perchloric acid electrolyte by electrochemical methods and by comparison with previous structural data. Structure and reactivity of the adsorbed layers are largely governed by a critical potential of E = 0.57 V, which determines the onset of O(ad) formation on the CO(ad) saturated surface in the positive-going scan and of O(ad) reduction in the negative-going scan. O(ad) formation proceeds via nucleation and 2D growth of high-coverage O(ad) islands in a surrounding CO(ad) phase, and it is connected with CO(ad) oxidation at the interface between the two phases. In the negative-going scan, mixed (CO(ad) + O(ad)) phases, most likely a (2 × 2)-(CO + 2O) and a (2×2)-(2CO + O), are proposed to form at E < 0.57 V by reduction of the O(ad)-rich islands and CO adsorption into the resulting lower-density O(ad) structures. CO bulk oxidation rates in the potential range E > 0.57 V are low, but significantly higher than those observed during oxidation of pre-adsorbed CO in the CO-free electrolyte. We relate this to high local CO(ad) coverages due to CO adsorption in the CO-saturated electrolyte, which lowers the CO adsorption energy and thus the barrier for CO(ad) oxidation during CO bulk oxidation.

Product gas evolution above planar microstructured model catalysts--a combined scanning mass spectrometry, Monte Carlo, and Computational Fluid Dynamics study.

The transport and distribution of reaction products above catalytically active Pt microstructures was studied by spatially resolved scanning mass spectrometry (SMS) in combination with Monte Carlo simulation and fluid dynamics calculations, using the oxidation of CO as test reaction. The spatial gas distribution above the Pt fields was measured via a thin quartz capillary connected to a mass spectrometer. Measurements were performed in two different pressure regimes, being characteristic for ballistic mass transfer and diffusion involving multiple collisions for the motion of CO(2) product molecules between the sample and the capillary tip, and using differently sized and shaped Pt microstructures. The tip height dependent lateral resolution of the SMS measurements as well as contributions from shadowing effects, due to the mass transport limitations between capillary tip and sample surface at close separations, were evaluated and analyzed. The data allow to define measurement and reaction conditions where effects induced by the capillary tip can be neglected ("minimal invasive measurements") and provide a basis for the evaluation of catalyst activities on microstructured model systems, e.g., for catalyst screening or studies of transport effects.

Quantitative online analysis of liquid-phase products of methanol oxidation in aqueous sulfuric acid solutions using electrospray ionization mass spectrometry.

We describe a novel method and setup for quantitative online analysis of the liquid-phase methanol oxidation products in acidic aqueous solutions by electrospray ionization mass spectrometry (ESI-MS). This includes a specially designed flow system, which allows continuous online mixing, derivatization, extraction, separation, and quantitative detection within ca. 3 min. For electrospray ionization of formaldehyde, it is first online-derivatized by 2,4-dinitrophenyl hydrazine to form the easily ionizable 2,4-dinitrophenyl hydrazone. Then, both formic acid and derivatized formaldehyde are online extracted into an immiscible organic phase, which, after separation from the aqueous phase, is piped to the ESI-MS for analysis. This strategy ensures complete removal of the highly corrosive sulfuric acid from the analyte and allows the liquid-phase methanol oxidation reaction (MOR) products (formaldehyde and formic acid) to be quantitatively detected by ESI-MS. Finally, the potential of this method for online analysis in electroanalysis and electrocatalysis is discussed.

Transport effects in the electrooxidation of methanol studied on nanostructured Pt/glassy carbon electrodes.

Transport effects in the methanol oxidation reaction (MOR) were investigated using nanostructured Pt/glassy carbon (GC) electrodes and, for comparison, a polycrystalline Pt electrode. The nanostructured Pt/GC electrodes, consisting of a regular array of catalytically active cylindrical Pt nanostructures with 55 +/- 10 nm in diameter and different densities supported on a planar GC substrate, were fabricated employing hole-mask colloidal lithography (HCL). The MOR measurements were performed under controlled transport conditions in a thin-layer flow cell interfaced to a differential electrochemical mass spectrometry (DEMS) setup. The measurements reveal a distinct variation in the MOR activity and selectivity (product distribution) with Pt nanostructure density and with electrolyte flow rate, showing an increasing overall activity, reflected by a higher Faradaic reaction current, as well as a pronounced increase of the turnover frequency for CO(2) formation and of the CO(2) current efficiency with decreasing flow rate and increasing Pt coverage. These findings are discussed in terms of the "desorption-readsorption-reaction" model introduced recently (Seidel et al. Faraday Discuss. 2008, 140, 67). Finally, consequences for applications in direct methanol fuel cells are outlined.

X-ray photoelectron spectrum in surface interfacing of gold nanoparticles with polymer molecules in a hybrid nanocomposite structure.

In situ Au3+--> reaction and dispersion of the resulting gold in the form of nanoparticles (NPs) in a reactive polymer medium, such as poly(vinyl alcohol) (PVA) molecules in hot water, are explored to devise a composite Au-PVA structure of self-standing films. The Au-NPs (0-2 wt%) tailor a violet to purple to a yellowish color of films from a colorless base polymer. A distinct surface interface (of thickness 2-5 nm) from the core (20-30 nm diameter) is resolved in transmission electron microscope images. The x-ray photoelectron spectrum (XPS) in the 81-91 eV range accounts for the effect which causes asymmetric shapes of the 4f(7/2) and 4f(5/2) Au bands. In a model structure, the asymmetry arises in the contribution of the surface Au atoms, which extend a chemical bridging with surface O atoms from the PVA molecules in a surface layer. A similar asymmetry also arises in C 1s and O 1s bands in the counterpart PVA molecules at 287.79 and 532.35 eV, respectively. At Au content as large as 2 wt%, no separate XPS band arises on a negligibly small fraction of surface Au atoms when Au-NPs have been grown in thin laminates (or cuboids and prisms).

Pt(x)Ru(1-x)/Ru(0001) surface alloys-formation and atom distribution.

The formation of PtRu surface alloys by deposition of submonolayer Pt films on a Ru(0001) substrate and subsequent annealing to about 1350 K and the distribution of the Pt atoms in the surface layer were investigated by scanning tunneling microscopy. Quantitative statistical analysis reveals (i) negligible losses of Pt into subsurface regions up to coverages close below 1 monolayer, (ii) a homogeneous distribution of the Pt atoms over the surface, and (iii) the absence of a distinct long-range or short-range order in the surface layer. In addition, the density of specific adsorption ensembles is analyzed as a function of Pt surface content. Possible conclusions on the process for surface alloy formation are discussed. The results are compared with the properties of PtRu bulk alloys and the findings in previous adsorption studies on similar surface alloys (H. Rauscher, T. Hager, T. Diemant, H. Hoster, F. Bautier de Mongeot and R. J. Behm, Surf. Sci., 2007, 601, 4608; T. Diemant, H Rauscher and R. J. Behm, J. Phys. Chem. C, in press).

Transport effects in the oxygen reduction reaction on nanostructured, planar glassy carbon supported Pt/GC model electrodes.

The role of transport and re-adsorption processes on the oxygen reduction reaction (ORR), and in particular on its selectivity was studied using nanostructured model electrodes consisting of arrays of Pt nanostructures of well-defined size and separation on a planar glassy carbon (GC) substrate. The electrochemical measurements were performed under controlled transport conditions in a double-disk electrode thin-layer flow-cell configuration; the model electrodes were fabricated by colloidal lithography techniques, yielding Pt nanostructures of well defined and controlled size and density (diameter: 140 or 85 nm, height: 20 or 10 nm, separation: from 1-2 to more than 10 diameters). The nanostructured model electrodes were characterized by scanning electron microscopy and electrochemical probing of the active surface area (via the hydrogen adsorption charge). The electrocatalytic measurements revealed a pronounced variation of the hydrogen peroxide yield, which increases by up to two orders of magnitude with increasing separation and decreasing size of the Pt nanostructures. Similar, though less pronounced effects were observed upon varying the electrolyte flow and thus the mass transport characteristics. These effects are discussed in a reaction model which includes (i) direct reduction to H(2)O on the Pt surface and (ii) additional H(2)O(2) formation and desorption on both Pt and carbon surfaces and subsequent partial re-adsorption and further reduction of the H(2)O(2) molecules on the Pt surface.

Mesoscopic mass transport effects in electrocatalytic processes.

The role of mesoscopic mass transport and re-adsorption effects in electrocatalytic reactions was investigated using the oxygen reduction reaction (ORR) as an example. The electrochemical measurements were performed on structurally well-defined nanostructured model electrodes under controlled transport conditions in a thin-layer flow cell. The electrodes consist of arrays of Pt ultra-microelectrodes (nanodisks) of defined size (diameter approximately 100 nm) separated on a planar glassy carbon (GC) substrate, which were fabricated employing hole-mask colloidal lithography (HCL). The measurements reveal a distinct variation in the ORR selectivity with Pt nanodisk density and with increasing electrolyte flow, showing a pronounced increase of the H2O2 yield, by up to 65%, when increasing the flow rate from 1 to 30 microL s(-1). These results are compared with previous findings and discussed in terms of a reaction model proposed recently (A. Schneider et al., Phys. Chem. Chem. Phys., 2008, 10, 1931), which includes (i) direct reduction to H2O on the Pt surface and (ii) additional H2O2 formation and desorption on both Pt and carbon surfaces and subsequent partial re-adsorption and further reduction of the H2O2 molecules on the Pt surface. The potential of model studies on structurally defined catalyst surfaces and under well-defined mass transport conditions in combination with simulations for the description of electrocatalytic reactions is discussed.

Design and characterization of a temporal analysis of products reactor.

We describe an improved temporal analysis of products (TAP) reactor design whose main new features in comparison to the recent TAP-2 design of Gleaves et al. [Appl. Catal. A 160, 55 (1997)] are the use of a turbomolecular pump, piezoelectrically driven pulse valves, and a newly designed, differentially pumped gate valve. The gate valve allows fast and simple changes between high pressure operation, in which in situ catalyst treatment can be performed, and the analytic mode with a direct line-of-sight connection to the analysis chamber and the mass spectrometer. The heating system and pulse valves are located outside the vacuum chamber, resulting in a system that is easy to operate and modify. The high stability and reproducibility of the pulse intensity allows for direct, quantitative evaluation of single-pulse and multipulse experiments. The performance of the system is demonstrated using the CO oxidation over a Au/TiO(2) catalyst as test reaction.

Scanning mass spectrometer for quantitative reaction studies on catalytically active microstructures.

We describe an apparatus for spatially resolving scanning mass spectrometry which is able to measure the gas composition above catalytically active microstructures or arrays of these microstructures with a lateral resolution of better than 100 mum under reaction conditions and which allows us to quantitatively determine reaction rates on individual microstructures. Measurements of the three-dimensional gas composition at different vertical distances and separations between active structures allow the evaluation of gas phase mass transport effects. The system is based on a piezoelectrically driven positioning substage for controlled lateral and vertical positioning of the sample under a rigidly mounted capillary probe connecting to a mass spectrometer. Measurements can be performed at pressures in the range of <10(-2)-10 mbars and temperatures between room temperature and 450 degrees C. The performance of the setup is demonstrated using the CO oxidation reaction on Pt microstructures on Si with sizes between 100 and 300 mum and distances in the same order of magnitude, evaluating CO(2) formation and CO consumption above the microstructures. The rapidly decaying lateral resolution with increasing distance between sample and probe underlines the effects of (lateral) gas transport in the room between sample and probe. The reaction rates and apparent activation energy obtained from such measurements agree with previous data on extended surfaces, demonstrating the feasibility of determining absolute reaction rates on individual microstructures.