Phase separation and surface segregation in ceria-zirconia solid solutions

Using a combination of density functional theory calculations and statistical mechanics, we show that a wide range of intermediate compositions of ceria – zirconia solid solutions are thermodynamically metastable with respect to phase separation into Ce-rich and Zr-rich oxides. We estimate that the maximum equilibrium concentration of Zr in CeO2 at 1373 K is ~2%, and therefore equilibrated samples with higher Zr content are expected to exhibit heterogeneity at the atomic scale. We also demonstrate that in the vicinity of the (111) surface, cation redistribution at high temperatures will occur with significant Ce enrichment of the surface, which we attribute to the more covalent character of Zr-O bonds compared to Ce-O bonds. Although the kinetic barriers for cation diffusion normally prevent the decomposition/segregation of ceria-zirconia solid solutions in typical catalytic applications, the separation behaviour described here can be expected to occur in modern three-way catalytic converters, where very high temperatures are reached.

Deposition of selenium thin layers on gold surfaces from sulphuric acid media: Studies using electrochemical quartz crystal microbalance, cyclic voltammetry and AFM

In this paper we report here new considerations about the relationship between the mass and charge variations (m/z relationship) in underpotential deposition (UPD), bulk deposition and also in the H(2)Se formation reaction. Nanogravimetric experiments were able to show the adsorption of H(2)SeO(3) on the AuO surface prior to the voltammetric sweep and that, after the AuO reduction, 0.40 monolayer of H(2)SeO(3) remains adsorbed on the newly reduced Au surface, which was enough to gives rise to the UPD layer. The UPD results indicate that the maximum coverage with Se(ads) on polycrystalline gold surface corresponds to approximately 0.40 monolayer, in good agreement with charge density results. The cyclic voltammetry experiments demonstrated that the amount of bulk Se obtained during the potential scan to approximately 2 Se monolayers, which was further confirmed by electrochemical quartz crystal microbalance (EQCM) measurements that pointed out a mass variation corresponding of 3 monolayers of Se. In addition, the Se thin films were obtained by chronoamperometric experiments, where the Au electrode was polarized at +0.10V during different times in 1.0 M H(2)SO(4) + 1.0 mM SeO(2). The topologic aspects of the electrodeposits were observed in Atomic Force Microscope (AFM) measurements. Finally, in highly negative potential polarizations, the H(2)Se formation was analyzed by voltammetric and nanogravimetric measurements. These finding brings a new light on the selenium electrodeposition and point up to a proposed electrochemical model for molecule controlled surface engineering. (c) 2009 Elsevier Ltd. All rights reserved.

Configurações magnéticas colineares e não-colineares em currais de Fe, Cr e Mn sobre a Pt (111)

Neste trabalho investigamos as propriedades magnéticas de currais de Fe, Cr e Mn adsorvidos sobre a superfície de Pt(111) utilizando o método RS-LMTO-ASA (Real Space Linear Muffin Tin Orbital - Atomic Sphere Approximation), o qual é um método de primeiros princípios baseado na Teoria do Funcional da Densidade (DFT-Density Functional Theory), que permite o cálculo de estruturas magnéticas não-colineares. Obtivemos que os átomos de Fe apresentam momentos magnéticos elevados, da ordem de 3.5µB /átomo, e têm uma interação de troca entre primeiros vizinhos forte e ferro-magnética. Isto leva a um arranjo magnético colinear no curral. Para os currais de Mn e Cr encontramos que estes possuem elevado momento magnético, da ordem de 4.51µB /átomo e 4.15µB /átomo, respectivamente, e interações de troca entre primeiros vizinhos antiferro-magnéticas. Isto conduz a arranjos magnéticos colineares em currais simples, assim como interessantes ordenamentos não-colineares, tais como estruturas tipo vértice (skyrmions), para os currais com uma geometria particular onde o antiferromagnetismo se apresenta frustado.

Ethanol and Water Adsorption on Close-Packed 3d, 4d, and 5d Transition-Metal Surfaces: A Density Functional Theory Investigation with van der Waals Correction

Nowadays, there is a great interest in the economic success of direct ethanol fuel cells; however, our atomistic understanding of the designing of stable and low-cost catalysts for the steam reforming of ethanol is still far from satisfactory, in particular due to the large number of undesirable intermediates. In this study, we will report a first-principles investigation of the adsorption properties of ethanol and water at low coverage on close-packed transition-metal (TM) surfaces, namely, Fe(110), Co(0001), Ni(111), Cu(111), Ru(0001), Rh(111), Pd(111), Ag(111), Os(0001), Ir(111), Pt(111), and Au(111), employing density functional theory (DFT) calculations. We employed the generalized gradient approximation with the formulation proposed by Perdew, Burke, and Erzenholf (PBE) to the exchange correlation functional and the empirical correction proposed by S. Grimme (DFT+D3) for the van der Waals correction. We found that both adsorbates binds preferentially near or on the on top sites of the TM surfaces through the 0 atoms. The PBE adsorption energies of ethanol and water decreases almost linearly with the increased occupation of the 4d and 5d d-band, while there is a deviation for the 3d systems. The van der Waals correction affects the linear behavior and increases the adsorption energy for both adsorbates, which is expected as the van der Waals energy due to the correlation effects is strongly underestimated by DFT-PBE for weak interacting systems. The geometric parameters for water/TM are not affected by the van der Waals correction, i.e., both DFT and DFT+D3 yield an almost parallel orientation for water on the TM surfaces; however, DFT+D3 changes drastically the ethanol orientation. For example, DFT yields an almost perpendicular orientation of the C-C bond to the TM surface, while the C-C bond is almost parallel to the surface using DFT +D3 for all systems, except for ethanol/Fe(110). Thus, the van der Waals correction decreases the distance of the C atoms to the TM surfaces, which might contribute to break the C-C bond. The work function decreases upon the adsorption of ethanol and water, and both follow the same trends, however, with different magnitude (larger for ethanol/TM) due to the weak binding of water to the surface. The electron density increases mainly in the region between the topmost layer and the adsorbates, which explains the reduction of the substrate work function.

The influence of the Pt crystalline surface orientation on the glycerol electro-oxidation in acidic media

We investigated the electrochemical oxidation of glycerol on low-index Pt single crystals in acidic media (H2SO4 and HClO4) by cyclic voltammetry and Fourier Transform Infrared (FTIR) spectroscopy and we verified that this is a surface sensitive reaction. Pt(100) and Pt(110) surface structures favor the breaking of the C-C-C bond at low potentials (say 0.05 V), as seen by the formation of CO, one of the adsorbed residues of the glycerol dissociation, which poisons these surfaces even at high potentials. Pt(111) surface structure does not favor the C-C-C bond breaking at potentials as low as 0.05 V. However, Pt(111) is less poisoned by residues of glycerol dissociation and, for this reason, it is more active for glycerol oxidation than Pt(100) and Pt(110) at low potentials. Carbonyl containing compounds and CO2 were detected as reaction products of the glycerol oxidation on all investigated single-crystal Pt surfaces. The ratio between CO2 and carbonyl containing compounds is clearly much higher for Pt(100) and Pt(110) than for Pt(111). (C) 2012 Elsevier Ltd. All rights reserved.

Rastertunnelmikroskopie kombiniert mit optischen Methoden und ihre Anwendung für opto-elektronische Experimente an nanoskopischen Strukturen

Die vorliegende Arbeit untersucht mittels lichtunterstützter Tunnelmikroskopie (STM) den Elektronentransport in farbstoffbedeckten, nanoporösen TiO2-Schichten, die in photoelektrochemischen Solarzellen eingesetzt werden. Transportrelevante Eigenschaften wie die elektronische Zustandsdichte sowie lichtinduzierte Vorgänge wie der Aufbau einer lichtinduzierten Oberflächenladung und lokale Photoströme werden ortsaufgelöst gemessen. Für einen möglichen Einsatz in lichtunterstützter Tunnelmikroskopie werden desweiteren Gold-Nanopartikel auf einer Amino-Hexanthiol-Monolage auf Coulomb-Blockaden untersucht. Den zweite Schwerpunkt stellen methodische Arbeiten zur Messung optischer Nahfelder in STM-Experimenten dar. Erstens sollen die Vorteile von Apertur- und aperturloser optischer Rasternahfeld-Mikroskopie mit komplett metallisierten Faserspitzen verbunden werden, die durch die Faser beleuchtet werden. Es gelingt nicht, theoretisch vorhergesagte hohe optische Auflösungen zu bestätigen. Zweitens werden transparente Spitzen aus Sb-dotiertem Zinnoxid erfolgreich als Tunnelspitzen getestet. Die Spitzen ermöglichen STM-Elektrolumineszenz-Experimente zur Charakterisierung optischer Nahfelder, ohne diese durch eine metallische Spitze zu beeinträchtigen. In einer STM-Studie wird das Selbstorganisations-Verhalten von Oktanthiol und Oktandithiol auf Au(111) aus Ethanol untersucht. Bei geringer relativer Konzentration der Dithiole (1:2000), bildet sich eine Phase liegender Dithiole, deren Ordnung durch die Präsenz der Oktanthiole katalysiert wird. Schließlich wird ein als 'dynamische Tunnelmikroskopie' bezeichneter Modus für die Tunnelmikroskopie in elektrisch leitfähiger Umgebung erfolgreich getestet, der zur Unterdrückung des elektrochemischen Leckstromanteils die Ableitung des Stroms nach dem Abstand als STM-Abstandssignal verwendet.

Two-dimensional assembly and local redox-activity of molecular hybrid structures in an electrochemical environment

The self-assembly and redox-properties of two viologen derivatives, N-hexyl-N-(6-thiohexyl)-4,4-bipyridinium bromide (HS-6V6-H) and N,N-bis(6-thiohexyl)-4,4-bipyridinium bromide (HS-6V6-SH), immobilized on Au(111)-(1x1) macro-electrodes were investigated by cyclic voltammetry, surface enhanced infrared spectroscopy (SEIRAS) and in situ scanning tunneling microscopy (STM). Depending on the assembly conditions one could distinguish three different types of adlayers for both viologens: a low coverage disordered and an ordered striped phase of flat oriented molecules as well as a high coverage monolayer composed of tilted viologen moieties. Both molecules, HS-6V6-H and HS-6V6-SH, were successfully immobilized on Au(poly) nano-electrodes, which gave a well-defined redox-response in the lower pA–current range. An in situ STM configuration was employed to explore electron transport properties of single molecule junctions Au(T)|HS-6V6-SH(HS-6V6-H)|Au(S). The observed sigmoidal potential dependence, measured at variable substrate potential ES and at constant bias voltage (ET–ES), was attributed to electronic structure changes of the viologen moiety during the one-electron reduction/re-oxidation process V2+ V+. Tunneling experiments in asymmetric, STM-based junctions Au(T)-S-6V6-H|Au(S) revealed current (iT)–voltage (ET) curves with a maximum located at the equilibrium potential of the redox-process V2+ V+. The experimental iT–ET characteristics of the HS-6V6-H–modified tunneling junction were tentatively attributed to a sequential two-step electron transfer mechanism.

On-Surface Synthesis of BN-Substituted Heteroaromatic Networks

We report on the bottom-up fabrication of BN-substituted heteroaromatic networks achieved by surface-assisted polymerization and subsequent cyclodehydrogenation of specifically designed BN-substituted precursor monomers based on a borazine core structural element. To get insight into the cyclodehydrogenation pathway and the influence of molecular flexibility on network quality, two closely related precursor monomers with different degrees of internal cyclodehydrogenation have been employed. Scanning tunneling microscopy shows that, for both monomers, surface-assisted cyclodehydrogenation allows for complete monomer cyclization and the formation of covalently interlinked BN-substituted polyaromatic hydrocarbon networks on the Ag(111) surface. In agreement with experimental observations, density functional theory calculations reveal a significantly lower energy barrier for the cyclodehydrogenation of the conformationally more rigid precursor monomer, which is also reflected in a higher degree of long-range order of the obtained heteroaromatic network. Our proof-of-concept study will allow for the fabrication of atomically precise substitution patterns within BNC heterostructures.

Propriedades magnéticas de trímeros de FexCo1-x depositados em Pt(111)

Quais propriedades magnéticas são modificadas quando se agrupam átomos de Fe/Co para formar estruturas quasi-2D, se comparadas aos nanofios (quasi-1D) de FexCo1-x? E como estas propriedades reagem com a variação da proporção de Fe/Co nos aglomerados? A fim de responder a estas questões, trímeros de FexCo1-x depositados em Pt(111) são investigados utilizando o método de primeiros princípios Real Space-Linear Muffin-Tin Orbital-Atomic Sphere Approximation (RS-LMTO-ASA) no âmbito da Teoria do Funcional da Densidade (DFT). Diferentes configurações de trímeros triangulares são consideradas, variando-se as posições e a concentração dos átomos de Fe/Co. Neste trabalho, demonstra-se a ocorrência de uma tendência não-linear estritamente decrescente dos momentos orbitais médios como função da concentração de Fe, distinta do encontrado tanto para os nanofios de FexCo1-x (dependência linear) quanto para a monocamada correspondente (dependência não-linear). Os resultados obtidos mostram ainda que os momentos orbitais variam com o ambiente local e com a direção de magnetização, especialmente quando associados aos átomos de Co, em concordância com publicações anteriores. A mudança de dimensionalidade quasi-1D (nanofios) para quasi-2D (trímeros compactos) não afeta o comportamento dos momentos de spin, que permanecem descritos por uma função linear com respeito à proporção de Fe/Co. Ambos o formato e a concentração de Fe nos sistemas apresentam um papel importante nos valores de energia de anisotropia magnética. Em adição, observou-se que o subtrato de Pt opera ativamente na definição das propriedades magnéticas dos aglomerados. Embora todas as configurações lineares e compactas dos aglomerados de FexCo1-x sejam estáveis e exibam interações fortemente ferromagnéticas entre os primeiros vizinhos, nem todas revelaram o ordenamento colinear como estado fundamental, apresentando uma interação de Dzyaloshinskii-Moriya não-desprezível induzida pelo acoplamento spin-órbita. Estes casos específicos são: o trímero triangular de Co puro e o trímero linear (nanofio) de Fe puro, para o qual foi verificado o acoplamento do tipo Ruderman-Kittel-Kasuya-Yosida entre os átomos de Fe constituintes. Os resultados obtidos contribuem para o entendimento de quais mecanismos definem o magnetismo nos trímeros de FexCo1-x/Pt(111), e discutem as questões presentes atualmente na literatura no contexto destes sistemas.

NO adsorption on Pt (111)/Bi surfaces

The adsorption of nitric oxide (NO) on a Pt (111) surface modified with irreversible adsorbed bismuth adatoms is reported. While the voltammetric results reveal a close interaction between the two co-adsorbed compounds. In-situ infrared spectroscopy and scanning tunnelling microscopy indicate the formation of segregated adlayers. Formation of compressed Bi adlayers with modified redox properties is proposed to reconcile both results. This agrees with the observation of Bi islands in the STM images when NO is coadsorbed, not observed in the absence of NO.

A fast XPS investigation of NO-promoted acetylene cyclotrimerisation on Pd{111}

The strong promotion by NO of acetylene cyclotrimerisation to benzene on Pd{1 1 1} has been investigated by fast XPS, supported by LEED and Δφ data. Islands of NO act to compress co-existing islands of acetylene. The resulting increase in acetylene density dramatically lowers the nominal threshold acetylene coverage required for reaction. In addition, the threshold reaction temperature is reduced from 150 to <100 K, and increased lateral interactions within the organic domains promote formation of tilted benzene. Co-adsorption of NO with benzene itself accelerates the desorption of both tilted and flat-lying benzene at low temperatures. These factors act to increase the yield of reactively formed benzene to 100%, completely suppressing carbon deposition that would otherwise result from decomposition of reactant and product.

A fast XPS study of sulphate promoted propene decomposition over Pt{111}

SO2 oxidation has been followed by Fast XPS over Pt{111}. Preadsorbed oxygen reduces the low temperature saturation coverage of SO2 with respect to the clean surface. Heating a mixed O2/SO2 adlayer results in efficient oxidation of both upright and flat-lying SO2 molecules to surface-bound SO4. Sulphate decomposes above room temperature liberating gas-phase SO2 and SO3. Propene adsorbs molecularly at 100 K over clean Pt{111} and dehydrogenates above 250 K to form a stable propylidyne adlayer, which in turn decomposes above 400 K to form graphitic carbon. Preadsorbed surface sulphate enhances the sticking probability of propene via formation of an alkyl-sulphate complex. Thermal decomposition of this complex accounts for low temperature propene combustion and is accompanied by atomic sulpur deposition. Propylidyne forms as on clean Pt but is less reactive undergoing partial oxidation above 450 K with residual surface oxygen.

Development of calix[4]arene-functionalized microcantilever array sensing system for the rapid, sensitive and simultaneous detection of metal ions in aqueous solutions

The work described in this thesis was conducted with the aim of: 1) investigating the binding capabilities of calix[4]arene-functionalized microcantilevers towards specific metal ions and 2) developing a new16-microcantilever array sensing system for the rapid, and simultaneous detection of metal ions in fresh water. Part I of this thesis reports on the use of three new bimodal calix[4]arenes (methoxy, ethoxy and crown) as potential host/guest sensing layers for detecting selected ions in dilute aqueous solutions using single microcantilever experimental system. In this work it was shown that modifying the upper rim of the calix[4]arenes with a thioacetate end group allow calix[4]arenes to self-assemble on Au(111) forming complete highly ordered monolayers. It was also found that incubating the microcantilevers coated with 5 nm of Inconel and 40 nm of Au for 1 h in a 1.0 M solution of calix[4]arene produced the highest sensitivity. Methoxy-functionalized microcantilevers showed a definite preference for Ca²⁺ ions over other cationic guests and were able to detect trace concentration as low as 10⁻¹² M in aqueous solutions. Microcantilevers modified with ethoxy calix[4]arene displayed their highest sensitivity towards Sr²⁺ and to a lesser extent Ca²⁺ ions. Crown calix[4]arene-modified microcantilevers were however found to bind selectively towards Cs⁺ ions. In addition, the counter anion was also found to contribute to the deflection. For example methoxy calix[4]arene-modified microcantilever was found to be more sensitive to CaCl₂ over other water-soluble calcium salts such as Ca(NO₃)₂ , CaBr₂ and CaI₂. These findings suggest that the response of calix[4]arene-modified microcantilevers should be attributed to the target ionic species as a whole instead of only considering the specific cation and/or anion. Part II presents the development of a 16-microcantilever sensor setup. The implementation of this system involved the creation of data analysis software that incorporates data from the motorized actuator and a two-axis photosensitive detector to obtain the deflection signal originating from each individual microcantilever in the array. The system was shown to be capable of simultaneous measurements of multiple microcantilevers with different coatings. A functionalization unit was also developed that allows four microcantilevers in the array to be coated with an individual sensing layer one at the time. Because of the variability of the spring constants of different cantilevers within the array, results presented were quoted in units of surface stress unit in order to compare values between the microcantilevers in the array.

The nature of alkanethiol self-assembled monolayer adsorption on sputtered gold substrates

A detailed study of the self-assembly and coverage by 1-nonanethiol of sputtered Au surfaces using molecular resolution atomic force microscopy (AFM) and scanning tunneling microscopy (STM) is presented. The monolayer self-assembles on a smooth Au surface composed predominantly of {111} oriented grains. The domains of the alkanethiol monolayer are observed with sizes typically of 5-25 nm, and multiple molecular domains can exist within one Au grain. STM imaging shows that the (4 × 2) superlattice structure is observed as a (3 × 2√3) structure when imaged under noncontact AFM conditions. The 1-nonanethiol molecules reside in the threefold hollow sites of the Au{111} lattice and aligned along its lattice vectors. The self-assembled monolayer (SAM) contains many nonuniformities such as pinholes, domain boundaries, and monatomic depressions which are present in the Au surface prior to SAM adsorption. The detailed observations demonstrate limitations to the application of 1-nonanethiol as a resist in atomic nanolithography experiments to feature sizes of ∼20 nm.

Anisotropic Assembly of Colloidal Nanoparticles: Exploiting Substrate Crystallinity

We show that the crystal structure of a substrate can be exploited to drive the anisotropic assembly of colloidal nanoparticles. Pentanethiol-passivated Au particles of approximately 2 nm diameter deposited from toluene onto hydrogen-passivated Si(111) surfaces form linear assemblies (rods) with a narrow width distribution. The rod orientations mirror the substrate symmetry, with a high degree of alignment along principal crystallographic axes of the Si(111) surface. There is a strong preference for anisotropic growth with rod widths substantially more tightly distributed than lengths. Entropic trapping of nanoparticles provides a plausible explanation for the formation of the anisotropic assemblies we observe.