The chemisorption of aromatic compounds, derivatized with different functional groups, on well-defined Pd(111) surfaces was studied by a combination of Auger electron spectroscopy (AES), low energy electron diffraction (LEED), high resolution electron energy loss spectroscopy (HREELS), and electrochemistry (EC). The results of this work led to the following trends and conclusions: (a) At low concentrations, 2,5-dihydroxythiophenol (DHT) chemisorbs on a Pd surface through both diphenolic ring and thiol group. At high concentrations, it chemisorbs only through the thiol group. (b) There is extensive intermolecular attraction between the co-adsorbed thiolated quinone and thiolated hydroquinone molecules. The interaction occurs through the Pd substrate and not through space. (c) The chemisorption properties of Nheteroaromatic compounds are pH-dependent. When the nitrogen heteroatom is protonated, it becomes very weakly surface-active. When the nitrogen heteroatom is deprotonated, surface activity stronger than the diphenolic ring is exhibited. (d) On a palladium surface, the binding strengths of ligands increase in the order: phenyl ring < quinonoid ring, < N-heteroatom < I < -SH.

Well-defined ultrathin films of palladium, with coverages ranging from submonolayer, &#920;Pd = 0.5 monolayer (ML), to multilayer, &#920;P d = 8 ML, were electrochemically deposited on Pt(111) using potentiostatic and potentiodynamic methods. In both methods, between the coverage regimes studied, the growth of the Pd films follows the Stranski-Krastanov mechanism. The interfacial electrochemical properties associated with the film-to-bulk transition were characterized by conventional voltammetric techniques in combination with low-energy electron diffraction (LEED) and Auger electron spectroscopy (AES). The voltammetric peaks associated with H-atom adsorption and desorption on terrace sites indicate that the Pd electrodeposit starts to exhibit bulk-like properties at a coverage of 3 ML. Voltammetric cycling, in sulfuric acid solution, between the hydrogen evolution and the double-layer regions, was found to exert minimal influence on the annealing (smoothening) of the electrodeposited Pd films. However, cycling within the same potential region in the presence of bromide anions (at which Br- adsorption/Br desorption takes place) smoothens the initially rough Pd films essentially as well as high-temperature annealing. The influence of chemisorbed bromine on the anodic dissolution of Pd was also studied; this was for comparison with previous work on the anodic dissolution of Pd, in inert electrolyte, catalyzed by chemisorbed iodine. The present studies indicated that a small but measurable amount of bromine was desorbed along with dissolution of the Pd step atoms; bromine at the Pd terrace behaved identically to iodine in that the coverage of iodine is maintained regardless of the amount or origin of the of anodically stripped Pd. Atomically smooth, well-defined ultrathin Pd films were prepared by a constant potential deposition (CPD) method followed by multiple potential cycles, in dilute Brsolution, within the double-layer region and reductive removal of Brads, by simple emersion at a potential just before the hydrogen evolution reaction potential (EHER). A previously adapted method for the same purpose involved the chemisorption of iodine onto ultrathin PdCPD films, from dilute I- solution, followed by reductive desorption of Iads in iodide-free solution at pH 10 and at a potential just before EHER.

Over the past few years, the need for a clean and renewable fuel has sharply risen. This is due to increasing fossil fuel costs and the desire to limit or eliminate harmful by-products which are created during the burning of these fuels. Hydrogen is the most abundant element in the universe and can be used in either fuel cells or traditional internal combustion engines to produce energy with no harmful emissions. One of the main obstacles facing the implementation of a hydrogen economy is its storage. Classical methods of storage involve either high and unsafe pressures or liquid storage involving a large amount of energy. Two alternative hydrogen storage methods are investigated - physisorption, which is the weak chemical bonding to a material, as well as chemisorption, which is a strong chemical bond of hydrogen to a host material. Polyaniline, a conducting polymer, is investigated in both its bulk form as well as in nanostructured forms, more precisely nanofibers and nanospheres, to store hydrogen via physisorption. It is found the bulk form of polyaniline can store only approximately 0.5wt.% hydrogen, which is far short of the 6wt.% required for practical applications. Nanofibers and nanospheres, however, have been developed, which can store between 4wt.% and 10wt.% of hydrogen at room temperature with varying kinetics. A new complex metal hydride comprised of LiBH4, LiNH2 and MgH2 has been developed to store hydrogen via chemisorption. While the parent compounds require high temperatures and suffer of slow kinetics for hydrogen sorption, the work performed as part of this dissertation shows that optimized processing conditions reduce the hydrogen release temperature from 250°C to approximately 150°C, while the addition of nano sized materials has been found to increase the kinetics of hydrogen sorption as well as further decrease the hydrogen release temperature, making this one of the first viable hydrogen storage materials available. This is the first time that nanostructured polyaniline has been investigated for its hydrogen performance. Additionally, the thorough investigation of the effects of nano sized additives and processing parameter optimization of the multinary hydride are first reported in this dissertation.

Thin coatings of photoresponsive, pyrimidine-terminated molecules, attached to gold or quartz substrates in contact with water, undego photodimerisation and wettability changes when irradiated with UV light at 280 and 240mm. Spin-casting and chemisorption techniques were used to prepare the thin films. / Thesis (PhDApSc)--University of South Australia, 2000.

Thin coatings of photoresponsive, pyrimidine-terminated molecules, attached to gold or quartz substrates in contact with water, undego photodimerisation and wettability changes when irradiated with UV light at 280 and 240mm. Spin-casting and chemisorption techniques were used to prepare the thin films. / Thesis (PhDApSc)--University of South Australia, 2000.

Agricultural wastes; Albizia coriaria, Coffea canephora, Cyperus papyrus, Erythrina abyssinica and Musa spp were evaluated for uptake of aqueous Cd2+ and Pb2+ ions in single- and binary-component solutions. Untreated, base-treated and peroxide-treated biomasses were employed in batch studies. The optimal conditions for Cd2+ and Pb2+ ions biosorption were  pH 3.5 – 5 for contact time 3.0 – 3.5 hours and biosorbent dosage 10 – 12.5 g/L. Base-treated biosorbents showed a 10 – 17 %  sorption enhancement for Cd2+ ions and a 1.6 – 2.3 % uptake reduction for Pb2+ ions. The sorption capacities for Cd2+ and Pb2+ ions for base-treated biosorbents were between 1.738 and 1.760 mg g-1 compared to 1.415 – 1.539 mg g-1 for untreated materials. The maximum biosorption of peroxide treated materials in single component media was between 0.819 and 1.595 mg/g for Pb2+ ions and between 0.044 and 1.343 mg/g for Cd2+ ions while in binary component media it was between 0.472 and 1.303 mg/g for Pb2+ ions and between 0.008 and 0.195 mg/g for Cd2+ ions. The pseudo-second order kinetic model suitably fitted the Cd2+ and Pb2+ ions biosorption data with regression coefficients (R2); 0.892 – 1.000 for peroxide-treated materials and 0.9784 – 0.9999 for base-treated biosorbents which implied that the biosorption was mainly a chemisorption process. The base treated biosorbents had better sorption performance for Cd2+ ions than peroxide treated materials and untreated biomass whereas the order for Pb2+ ions biosorption was untreated &gt; base treated &gt; peroxide treated materials. All materials showed superior selectivity for Pb2+ ions biosorption in comparison to that of Cd2+ ions in single- and binary-component media. A. coriaria performed best of the base treated biosorbents while C. canephora performed best amongst peroxide treated materials for Cd2+ and Pb2+ ions biosorption in single-and binary-component media. In the competitive biosorption, Cd2+ ions showed higher synergistic effects than Pb2+ ions although Pb2+ ions were preferentially sequestered even when the Cd2+:Pb2+ ions ratio was increased through 3:2, 2:1, 3:1 and 5:1. Of the three isotherm models evaluated against the experimental data, the Langmuir model generally fitted the sorption data for both metals. Regression coefficients for the Langmuir model were; 0.983 ≤ R2 ≥ 1.000 for single-component and 0.939 ≤ R2 ≥ 1.000 for binary-component solutions which revealed that the biosorption was potentially monolayer. The biosorption equilibrium coefficient                          values and change in Gibbs’ free energy  values showed that Pb2+ ions biosorption was more thermodynamically favoured than that of Cd2+ ions in single-component and binary-component media. The materials studied displayed potential for use as biosorbents for remediation of aqueous Cd2+ and Pb2+ ions. / <p>QC 20140508</p>

Nanoelectronics is an essential technology for down-scaling beyond the limit of silicon-based electronics. Single-Wall Carbon Nanotubes (SWNT) are semiconducting components that exhibit a large variety of properties that make them usable for sensing, telecommunication, or computational tasks. Due to their high surface to volume ratio, carbon nanotubes are strongly affected by molecular adsorptions, and almost all properties depend on surface adsorption. SWNT with smaller diameters (0.7-0.9nm) show a stronger sensitivity to surface effects. An optimized synthesis route was developed to produce these nanotubes directly. They were produced with a clean surface, high quality, and large lengths of 2 μ m. The results complement previous studies on larger diameters (0.9-1.4nm). They allow performing statistically significant assumptions for a perfect nanotube, which is selected from a subset of nanotubes with good emission intensity, and high mechanical durability. The adsorption of molecules on the surface of carbon nanotubes influences the motion and binding strength of chargeseparated states in this system. To gain insight into the adsorption processes on the surface with a minimum of concurrent overlapping effects, a microscopic setup, and a measurement technique were developed. The system was estimated to exhibit excellent properties like long exciton diffusion lengths (>350nm), and big exciton sizes (8.5(5)nm), which was substantiated by a simulation. We studied the adsorption processes at the surface of Single-Wall Carbon Nanotubes for molecules in the gas phase, solvent molecules, and surfactant molecules. The experiments were all carried out on suspended individualized carbon nanotubes on a silicon wafer substrate. The experiments in the gas-phase showed that the excitonic emission energy and intensity experiences a rapid blue shift during observation. This shift was associated with the spontaneous desorption of large clusters of gaseous molecules caused by laser heat up. The measurement of this desorption was essential for creating a reference to an initially clean surface and allows us to perform a comparison with previous measurements on this topic. Furthermore, the adsorption of hydrogen on the nanotube surface at high temperatures was investigated. It was found that a new emission mode arises slightly red-shifted to the excitonic emission in these systems. The new signal is almost equally strong as the main excitonic peak and was associated with the brightening of dark excitons at sp3-defects through a K-phonon assisted pathway. The finding is useful for the direct synthesis of spintronic devices as these systems are known to act as single-photon emitters. The suspended nanotubes were further studied to estimate the effect of solvent adsorption on the excitonic states during nanotube dispersion for each nanotube individually. A significant quantum yield loss is observable for hexane and acetonitrile, while the emission intensity was found to be the strongest in toluene. The reference to a clean surface allowed us to estimate the exact influence of the dielectric environment of adsorbing solvents on the excitonic emission energy. Solvent adsorption was found to lead to an energy shift that is almost twice as high as suggested in previous studies. The amount of this energy shift, however, was comparably similar for all solvents, which suggests that the influence of the distinct dielectric constant in the outer environment less significantly influences the energy shift than previously thought. An interesting phenomenon was found when using acetonitrile as a solvent, which leads to greatly enhanced emission properties. The emission is more than twice as high as in the same air-suspended nanotubes, which suggests a process that depends on the laser intensity. In this study, it was reasonably explained how an energy down-conversion is possible through the coupling of the excitonic states with solvent vibrations. The strength of this coupling, however, also suggests adsorptions to the inside of the tubular nanotube structure leading to a coupled vibration of linear acetonitrile molecules that are adsorbed to the inner surface. The findings are important for the field of nanofluidics and provide an excellent system for efficient energy down-conversion in the transmission window of biological tissue. Having separated the pure effect of solvent adsorption allowed us to study the undisturbed molecular adsorption of polymers in these systems. The addition of polyfluorene polymer leads to a slow but stepwise intensity increase. The intensity increase is overlapping with a concurrent process that leads to an intensity decrease. Unfortunately, observing the stepwise process has a low spacial resolution of only 100-250nm, which is in the range of the exciton diffusion length in these systems and hinders detailed analysis. The two competing and overlapping processes processes are considered to originate from slow π-stacking and fast side-chain binding. Insights into this process are essential for selecting suitably formed polymers. However, the findings also emphasize the importance of solvent selection during nanotube dispersion since solvent effects were proven to be far more critical on the quantum yield in these systems. These measurements can shed light on the ongoing debate on polymers adsorption during nanotube individualization and allow us to direct the discussion more towards the selection of suitable solvents. This work provides fundamental insights into the adsorption of various molecules on the surface of individually observed suspended Single-Wall Carbon Nanotubes. It allows observing the adsorption of individual molecules below the optical limit in the solid, liquid, and gas phases. Nanotubes are able to act as sensing material for detecting changes in their direct surrounding. These fundamental findings are also crucial for increasing the quantum yield of solvent-dispersed nanotubes. They can provide better light-harvesting systems for microscopy in biological tissue and set the base for a more efficient telecommunication infrastructure with nano-scale spintronics devices and lasing components. The newly discovered solvent alignment in the nanotube surrounding can potentially also be used for supercapacitors that are needed for caching the calculation results in computational devices that use polymer wrapped nanotubes as transistors. Although fundamental, these studies develop a strategy to enlighten this room that is barely only visible at the bottom of the nano-scale. / Nanoelektronik ist eine wichtige Technologie um das Größen-Limit gegenwärtiger Silizium-basierter Technologie zu überwinden. Einwandige Kohlenstoffnanoröhren sind halbleitende Moleküle, die eine Reihe von Eigenschaften dafür zur Verfügung stellen. Sie sind einsetzbar als Sensoren, in der Fernmeldetechnik und für elektronische Rechenoperationen. Aufgrund ihres hohen Verhältnisses von Oberfläche zu Volumen werden nahezu alle Eigenschaften von Kohlenstoffnanoröhren stark von Adsorption beeinflusst. Einwandige Kohlenstoffnanoröhren mit kleineren Durchmessern (0.7-0.9nm) zeigen einen stärkeren Einfluss auf Phänomene, die an der Oberfläche auftreten. Um speziell diese Nanoröhren genauer zu untersuchen wurde eine Synthese Strategie entwickelt, die Nanoröhren mit hoher Qualität und Länge herstellen kann und dabei eine saubere Oberfläche gewährleisten ohne ihre Emissions-Stärke durch Bündelung zu verlieren. Die erhaltenen Ergebnisse unterstützen Studien aus der Literatur, die zumeist an Röhren mit größeren Durchmessern durchgeführt wurden. Die Größe des Datensatzes erlaubt es, Nanoröhren mit perfekten Emissions-Eigenschaften und großer mechanischer Stabilität auszuwählen. Adsorptionen beeinflussen die Bewegung und Bindungs-Stärke der Excitonen, da sie ein Coulomb Potential an der Außenseite der Röhre ausbilden. Um die Adsorptionsprozess an der Oberfläche mit minimalen konkurrierenden Effekten zu untersuchen, wurde ein spezielles mikroskopisches Setup gewählt und eine Messmethode entwickelt um dieses System zu untersuchen. Das System wurde mit Hilfe von Bildern und Spektren charakterisiert. Über eine Simulation wurde außerdem gezeigt dass die untersuchten Nanoröhren große Diffusionslängen (>350nm) und Exciton Größen (<8.5nm) besitzen müssen. Der Adsorptions Prozess an Kohlenstoffnanoröhren wurde sowohl mit Molekülen in der Gas-Phase untersucht, also auch in Lösungsmitteln und mit Feststoffen. Alle Experimente wurde dabei an frei hängenden Röhren durchgeführt, die auf einem Silizium Wafer Substrat aufgebracht wurden. Die Experimente in der Gas Phase zeigten, dass die excitonische Emissions-Energie eine instantane und schnelle Blauverschiebung erfährt wenn die Nanoröhren mit einem Laser angeregt werden. Diese Verschiebung wurde auf die Desorption von Oberflächenverunreinigungen zurückgeführt, die an Luft inhärent die Messung beeinflussen. Durch die Annahme, nach der Untersuchung eine reine Oberfläche zu erhalten, konnte die Referenz der Vakkum-Emission erstellt werden, was es ermöglicht, den Einfluss der dielektrischen Umgebung genauer zu bestimmen. In einem weitern Experiment wurde die Adsorption von Wasserstoff getestet. In diesen Systemen bildet sich durch die Ausbildung von sp 3 -Defekten eine neue Emissionsbande aus. Solche Emissionen werden derzeit für die Anwendung als Einzelphotonenemitter diskutiert. Die hier vorgestellte Methode erlaubt die direkte Synthese solcher Systeme im CVD Ofen. Die frei hängenden Nanoröhren wurden weiter analysiert um den Effekt des Lösungsmittels auf die Emission detailiert zu untersuchen. Es wurde gezeigt, dass in Hexan und Acetonitril ein signifikant hoher Quantenausbeute-Verlust zu beobachten ist. Toluol hingegen zeigte sich hier am Besten. Die Energie-Verschiebungen waren insignifikant unterschiedlich zwischen den Lösungsmitteln. Ein Spezialfall war bei Acetonitril zu beobachten, in dem sich über den Zeitraum von 24h eine starke Emission herausbildet, die auf eine Kopplung mit Lösungsmittel-Schwingungen zurückgeführt wird. Die Stärke dieser Emission erlaubt die Vermutung, dass es sich um eine gekoppelte Schwingung von linear orientiertem Acetonitril in der Nanoröhre handelt. Eine solch starke Emission könnte zu Anwendungen in Zell-Gewebe führen, da weder Anregung noch Emission sich im Fenster der Blut- und Wasserabsorption befindet. Durch die eindeutige Identifizierung von Lösungsmitteleffekten auf die Dispergierung von Kohlenstoffnanoröhren war es möglich, den Prozess der Anlagerung von Polyfluorene Polymeren direkt zu beobachten. Das Hinzufügen von Polymer zur Lösung führt zu einem schrittweisen reversiblen Anstieg der Emissions Intensität. Dieser Anstieg wird von einem gleichzeitigen irreversiblen schrittweisen Abfall der Emissionsintensität begleitet. Leider ist das System nur geeignet, Adsorptionen bis maximal 100nm Länge aufzulösen. Eine detaillierte Analyse ist daher schwer. Trotzdem wird vermutet, dass es sich bei dem langsamen Prozess um das Ausbilden von π -Stapeln handelt, wobei der schnelle Prozess mit der nicht-kovalenten Bindung der Polymer-Seitenketten an die Oberfläche assoziiert wird. Obwohl über die eigentliche Bindung des Polymers nur Vermutungen angestellt werden können, so wirft die Untersuchung doch einen Fokus auf die Wahl des Lösungsmittels, da diese Entscheidung einen viel größeren Effekt verursacht, als die Bindung des Polymers selbst. Diese Arbeit stellt fundamentale Betrachtungen zur Adsorption von verschiedenen Molekülen an Kohlenstoffnanoröhren auf. Die Betrachtungen wurden mit festen, flüssigen und gasförmigen Molekülen durchgeführt. Die Ergebnisse zeigen, dass Nanoröhren geeignet sind, als Molekül-Sensoren verwendet zu werden, da sie stark auf Änderungen in ihrer Umgebung reagieren können. Weiterhin wurden Lösungsmittel und Eigenschaften aufgezeigt, die die Quanteneffizienz signifikant beeinflussen. Eine Anwendung in der biologischen Mikroskopie ist denkbar, genauso wie für eine effizientere und sicherere Fernmeldeinfrastruktur. Weiterhin wurden Wege aufgezeigt, Super-Kondensatoren auf Nanorohr-Basis zu bauen, die als Anwendung in einem Kohlenstoffnanorohr-basierenden Computer von Interesse sein könnten. Obwohl die Erkenntnisse fundamental sind, zeigen diese Studien, dass es mit bestimmten Tricks möglich ist, den Raum am unteren Ende der Nanometerskala zu erforschen und zu entdecken.

Reaction rates of catalytic cycles over supported metal catalysts are normalized by the exposed metal atoms on the catalyst surface, reported as site time yields which provide a rigorous standard to compare distinct metal surfaces. Defined as the fraction of exposed metal surface atoms to the total number of metal atoms, it is important to measure the dispersion of supported metal catalysts to report standardized rates for kinetic investigations. Multiple characterization techniques such as electron microscopy, spectroscopy and chemisorption are exploited for catalyst dispersion measurements. While effective, electron microscopy and spectroscopy are not readily accessible due to cost and maintenance requirements. Commercial instruments therefore typically rely on chemisorption measurements, but can be cost prohibitive nonetheless, hindering the ability of catalysis research to report rigorous measures of activity. Thus, a dispersion measurement technique based on gas chromatograph (GC) ubiquitous in catalysis research is proposed, based on the principle of dynamic carbon monoxide (CO) chemisorption, where number of exposed metal surface atoms are estimated based on the amount of adsorbed CO. In this technique, the supported metal catalyst is packed into a liner, and inserted in the temperature-controlled inlet of the GC. The catalyst is pre-treated, purged with inert gas, and pulses of known amount of CO are passed through it via an automated sequence. The CO chemically adsorbs on the supported metal catalyst and the unadsorbed CO is detected by the flame ionization detector/methanizer on the GC. The amount of CO adsorbed is estimated by the difference between the amount of CO pulsed and detected, translated to estimate the number of exposed metal surface atoms using a stoichiometry factor. Dispersion measurements for several group VIII metal catalysts were conducted using this technique to demonstrate its applicability across a range of weight loadings and support identities. An agreement between catalyst dispersion measured using this technique and commercially available instruments indicated the reliability of this technique. The amount of dispersed metal as low as 0.02 mg could be estimated by this technique.

We develop a theoretical framework for a priori estimation of catalytic activity of metal nanoparticles using geometry-based reactivity descriptors of surface atoms and kinetic analysis of reaction pathways at various types of active sites. We show that orbitalwise coordination numbers 𝐶𝑁^α (α = 𝑠 or 𝑑) can be used to predict chemical reactivity of a metal site (e.g., adsorption energies of critical reaction intermediates) by being aware of the neighboring chemical environment, outperforming their regular (𝐶𝑁) and generalized (𝐶̅𝑁̅) counterparts with little added computational cost. Here we include two examples to illustrate this method: CO oxidation on Au (5𝑑¹⁰6𝑠¹) and O₂ reduction on Pt (5𝑑⁹6𝑠¹). We also employ Bayesian learning and the Newns-Anderson model to advance the fundamental understanding of adsorbate-surface interactions on metal nanocatalysts, paving the path toward adsorbate-specific tuning of catalysis. / Doctor of Philosophy / The interactions between reaction intermediates and catalysts should be neither too strong nor too weak for catalytic optimization. This Sabatiers principle arising from the scaling relations among the energetics of reacting species at geometrically similar sites, provides the conceptual basis for designing improved catalysts, but imposes volcano-type limitations on the attainable catalytic activity and selectivity. One of the greatest challenges faced by the catalysis community today is how to develop design strategies and ultimately predictive models of catalytic systems that could circumvent energy scaling relations. This work brings the quantum-chemical modeling and machine learning technique together and develops a novel stochastic modeling approach to rationally design the catalysts with desired properties and bridges our knowledge gap between the empirical kinetics and atomistic mechanisms of catalytic reactions.

Aqueous-phase reforming (APR) is reported for the first time for the production of H2 from actual biomass. The experiments are carried out in batch using a 100mL Parr microreactor heated to 225C. In this one-pot, two-step process, acid hydrolysis is used to break down the polymeric constituents of biomass to smaller soluble molecules and these species are reformed using a Pt/Al2O3 catalyst. The experiments show that increasing the acid concentration from 1% to 5% causes more than a twelve-fold increase in H2 concentration, with hydrogen a minor product accounting for 18% of the non-condensable gas phase and CO2 as the major product. In the presence of the Pt/Al2O3 reforming catalyst, both the selectivity and yield of hydrogen in the gas phase increase. This is accompanied by a noticeable decrease in carbon monoxide production. Comparison with other feeds such as glucose, wastepaper and ethylene glycol showed that the amount of hydrogen produced from biomass is of a comparable magnitude per gram of feed, although biomass yields more hydrogen per gram of carbohydrate than either glucose or wastepaper. Baseline experiments with only the catalysts in the absence of any biomass show no increase in the reactor system pressure when only water and helium are present, indicating that the observed hydrogen produced is sourced form the biomass.