An experiment has been completed which demonstrated quantum mechanical tunneling of electrons between two gold electrodes separated in vacuum. The tunneling current between the gold electrodes has been measured, for fixed voltages of 0.1 and 0.01 volts, as the electrode spacing was varied from a distance of approximately 2.0 nm down to a point where the electrodes touched. Current-voltage characteristics for fixed electrode spacing in the direct tunneling region have also been measured. Numerical calculations of the tunneling current based on the free-electron model of the electrodes and the barrier, an image-potential reduced barrier, and a WKB approximation for the tunneling probability have been performed and compared with Simmons' theory and with the experimental results. Within experimental error the results indicate that an image potential reduced barrier with the modifications suggested by Lang and Kohn gives a close approximation to the true barrier for metal-vacuum-metal tunneling. For the first time, the work function of the electrodes in a tunneling experiment has been deduced from experimental parameters independent of the tunneling device.

Choline oxidase catalyzes the two-step oxidation of choline to glycine betaine, one of limited osmoprotectants, with the formation of betaine aldehyde as an enzyme bound intermediate. Glycine betaine accumulates in the cytoplasm of plants and bacteria as a defensive mechanism to withstand hyperosmolarity and elevated temperatures. This makes the genetic engineering of relevant plants which lack the property of salt accumulation of economic interest, and the biosynthetic pathway of the osmolyte a potential drug target in microbial infections. The reaction of alcohol oxidation occurs via a hydride ion tunneling transfer from the substrate donor to a flavin acceptor within a highly preorganized active site environment in which choline and FAD are in a rigidly close proximity. In this dissertation, factors contributing to the enzyme-substrate preorganization which is required for the hydride ion tunneling reaction mechanism in choline oxidase have been investigated. Crystallographic studies of wild-type choline oxidase revealed a covalent linkage between C8M atom of the FAD isoalloxazine ring and the N(3) atom of the side chain of a histidine at position 99, and a solvent excluded cavity in the substrate binding domain containing glutamic acid at position 312 as the only negatively charged amino acid residue in the active site of the enzyme. The role of the histidine residue and the contribution of the 8á-N(3)-histidyl covalent linkage of the flavin cofactor to the reaction of alcohol oxidation was investigated in a variant form of choline oxidase in which the histidine residue was replaced with an asparagine. The role of the glutamate residue and the importance of the spatial location of the negative charge at position 312 was investigated in variant forms of choline oxidase in which the negatively charged residue was replaced with glutamine and aspartate. Mechanistic data obtained for the variant enzymes and their comparison to previous data obtained for wild-type choline oxidase are consistent with the residues at positions 99 and 312 being important for relative positioning of the hydride ion donor and acceptor. The residues are important for the enzyme-substrate preorganization that is required for the hydride tunneling reaction in choline oxidase.

Στην παρούσα διατριβή αναπτύχθηκε ένα μοντέλο βασιζόμενο σε πρώτες αρχές με σκοπό την περιγραφή και την πρόβλεψη της πρωτονιακής αγωγιμότητας των πλήρως ενυδατωμένων μεμβρανών Nafion (το κυριότερο υλικό που χρησιμοποιείται ως ηλεκτρολύτης στις κυψέλες καυσίμου τύπου PEM) και των ιδιαίτερων χαρακτηριστικών αυτής, όπως τη γραμμική εξάρτηση από το πάχος της μεμβράνης, το δυναμικό του κελιού και τη μερική πίεση του υδρογόνου. Το μοντέλο εστιάζει στη μετανάστευση των πρωτονίων που είναι συνδεδεμένα στις σουλφονομάδες και χρησιμοποιεί την κατανομή φορτίου Poisson-Boltzmann γύρω από κάθε πρωτόνιο, σε συνδυασμό με την εξίσωση Gamow, που δίνει την πιθανότητα να συμβεί το φαινόμενο σήραγγος σε παραβολικό φράγμα δυναμικού. Προτείνεται ότι το μήκος που διανύεται κατά την πραγματοποίηση του φαινομένου σήραγγος ισούται με το μήκος κύματος του πρωτονίου και ότι κάθε πρωτόνιο περιβάλλεται από το νέφος Debye-Hückel. Το μοντέλο, που δεν εμπεριέχει προσαρμόσιμες παραμέτρους, λύνεται αναλυτικά και οι προβλέψεις του είναι σε ημιποσοτική συμφωνία με το πείραμα. Στις προβλέψεις αυτές συμπεριλαμβάνεται η τάξη μεγέθους της αγωγιμότητας, η γραμμική εξάρτηση της αγωγιμότητας με το πάχος της μεμβράνης, η εκθετική εξάρτηση από το δυναμικό και η ισχυρή εξάρτηση με τη μερική πίεση του υδρογόνου. Μελετήθηκε η κινητική, οι ταλαντώσεις και η ηλεκτροχημική ενίσχυση της οξείδωσης του CO σε καταλυτικό υμένιο Pt εναποτεθειμένο σε YSZ, χρησιμοποιώντας ως βάση την απόλυτη κλίμακα του ηλεκτροδίου του οξυγόνου. Βρέθηκε ότι η ηλεκτροχημική ενίσχυση είναι μικρή (ρ<3, Λ~300) όταν οι τιμές του δυναμικού του καταλύτη, UWR, είναι ανάμεσα σε 0.2 και 0.4 V και πολύ σημαντική (ρ~9, Λ~1500) όταν το UWR υπερβαίνει την τιμή 0.4 V. Η απότομη αλλαγή που παρατηρείται κατά την μετάβαση στην έντονη ηλεκτροχημική ενίσχυση συνοδεύεται και από απότομη αλλαγή στην κινητική της αντίδρασης και στο δυναμικό του καταλύτη. Μέσω της σύγκρισης των πειραματικών αποτελεσμάτων του κεφαλαίου και ανεξάρτητων μετρήσεων του έργου εξόδου μεταβάλλοντας το δυναμικό του καταλύτη για το ίδιο σύστημα, βρέθηκε ότι η μετάβαση οφείλεται στην έντονη μετανάστευση προωθητικών ειδών, Ο2-, από τη YSZ στην επιφάνεια του καταλύτη και την συνεπαγόμενη δημιουργία μιας πυκνής αποτελεσματικής διπλοστιβάδας στη διεπιφάνεια του καταλύτη με τα αέρια αντιδρώντα. Τέλος εξετάστηκε μια τροποποιημένη κυψέλη καυσίμου τύπου PEM η οποία λειτουργεί σε συνθήκες δηλητηρίασης από CO κατά την τριοδική λειτουργία. Στο τριοδικό κελί καυσίμου τύπου PEM εκτός της ανόδου και της καθόδου εισάγεται ένα τρίτο ηλεκτρόδιο το οποίο δημιουργεί ένα επιπλέον βοηθητικό κύκλωμα το οποίο λειτουργεί με ηλεκτρολυτικά ρεύματα και επιτρέπει τη λειτουργία της κυψέλης σε δυναμικά μεταξύ της ανόδου και της καθόδου ανέφικτα κατά τη συμβατική λειτουργία. Βρέθηκε ότι είναι δυνατό να ενισχυθεί η συνολική θερμοδυναμική ενεργειακή απόδοση όταν χρησιμοποιείται ως καύσιμο μίγμα αναμόρφωσης μεθανόλης που αντιστοιχεί σε συνθήκες έντονης δηλητηρίασης από CO. / In the present work a first principles model was developed to describe and predict the protonic conductivity of fully hydrated Nafion membranes and its peculiar non-linear dependence on membrane thickness, potential and PH2. The model focuses on the surface migration of protons between adjacent sulfonate groups and utilizes the Poisson-Boltzmann charge distribution around each proton combined with the basic Gamow equation of quantum mechanics for proton tunneling, for parabolic potential barrier. It was shown that the proton tunneling distance equals the proton wavelength and that each proton surrounded by its Debye-Hückel cloud behaves as a leaking nanobattery. The model, which contains no adjustable parameters, is solved analytically and its predictions are in semiquantitative agreement with experiment, including the magnitude of the conductivity, its linear increase with membrane thickness, its exponential increase with potential and its strong dependence on partial pressure of hydrogen. Moreover it was investigated the kinetics, rate oscillations and electrochemical promotion of CO oxidation on Pt deposited on YSZ using a standard oxygen reference electrode. It was found that electropromotion is small (ρ<3) when the catalyst potential UWR, is between 0.2 and 0.4V and very pronounced (ρ~9, Λ~1500) when UWR exceeds 0.4V. This sharp transition in the electropromotion behavior is accompanied by an abrupt change in reaction kinetics and in catalyst potential. It was shown via comparison with independent catalyst potential–catalyst work function measurements that the transition corresponds to the onset of extensive O2- spillover from YSZ onto the catalyst surface, and concomitant establishment of an effective double layer at the catalyst-gas interface, which is the cause of the highly active electropromoted state Furthermore it was studied a modified PEM fuel cell running in CO poisoning conditions by the triode operation. In addition to the anode and cathode, the triode PEM fuel cell introduces a third electrode together with an auxiliary circuit which is run in the electrolytic mode and permits fuel cell operation under previously inaccessible anode-cathode potential differences. It was found that it is possible to enhance the overall thermodynamic efficiency when it is used a methanol reformate mixture as a fuel, which corresponds to intense CO poisoning conditions.

Field emission is the emission of electrons from a solid under an intense electric field, of the order of 109 V/m. Emission occurs by the quantum mechanical tunneling of electrons through a potential barrier to vacuum. Field emission sources offer several attractive features such as instantaneous response to field variation, resistance to temperature fluctuation and radiation, a high degree of focusing ability in electron optics, good on/off ratio, ballistic transport, and a nonlinear current-voltage relationship. Carbon nanotubes (CNTs) are potential candidates as field emitters since they possess high aspect ratio and are chemically inert to poisoning, and physically inert to sputtering during field emission. They can carry a very high current density and do not suffer field-induced tip sharpening like metallic tips. In addition, the CNT field emitters have the advantage of charge transport through 1D channels and electron emission at the sharp tips due to large enhancement. But the injection of electrons from the back contact remains a technical challenge which requires binding of CNT emitters to metallic substrate. Also, detachment of the CNT from the substrate tends to occur with time. The electrically conducting mixtures of CNTs and polymer can provide an alternative route to address these issues in the field emission of CNTs. The composites can be casted on any substrate in desired shape and the polymer matrix provides necessary support. The research work reported in this thesis includes the preparation of high quality multiwall carbon nanotubes (MWCNTs), MWCNT-polystyrene (PS) composites, and experimental investigation on field emission properties of MWCNT¬PS composites in two different configurations. Electrical conductivity and percolation threshold of the MWCNT-PS composites are also investigated to ensure their high quality prior to the field emission studies. The study has been further extended to reduced graphene oxide (rGO) coated on polymer substrate. The main results obtained in present work are briefly summarized below. This thesis contains eight chapters. Chapter 1 provides an overview of basics of field emission, and the potential of CNT and CNT-polymer composites as field emitters. Chapter 2 deals with the concise introduction of various structural characterization tools and experimental techniques employed in this study. Chapter 3 describes the synthesis of MWCNTs and characterization by using electron microscopy and Raman spectroscopy. MWCNTs are synthesized by chemical vapor deposition (CVD) of toluene [(C6H5) CH3] and ferrocene [(C5H5)2 Fe] mixture at 980 °C. Here toluene acts as carbon source material and ferrocene provides catalytic iron (Fe) particles. The MWCNT formation is based on the thermal decomposition of the precursor mixture. Scanning electron microscopy (SEM) characterization shows that the MWCNTs are closely packed and quite aligned in one direction. The average length of MWCNTs is about 200 μm and outer diameter lies in the range of 50-80 nm. The high quality of as-prepared MWCNT sample is confirmed by Raman spectroscopy. The as-grown MWCNTs are encapsulated with catalytic Fe nanoparticles, revealed by transmission electron microscopy. The Fe nanoparticles trapped within the MWCNT serve as fantastic system for studying the magnetic properties. Three types of MWCNT samples filled with Fe nanoparticles of different aspect ratio (~10, 5 and 2) are synthesized by varying the amount of ferrocene in the precursor material, and their magnetic properties are investigated. Enhanced values of coercivity (Hc) are observed for all samples, Hc being maximum (~2.6 kOe) at 10 K. The enhancement in Hc values is attributed to the strong shape anisotropy of Fe nanoparticles and significant dipolar interactions between Fe nanoparticles. Chapter 4 deals with the field emission studies of MWCNT-PS composites in the parallel configuration. By incorporating as-prepared MWCNTs in PS matrix in a specific ratio, composites with varying loading from 0.01-0.45 weight (wt.) fraction are prepared using solution mixing and casting. High degree of dispersion of MWCNTs in PS matrix without employing any surfactant is achieved by ultrasonication. Low percolation threshold (~0.0025 wt. fraction) in the MWCNT-PS composites ensures the good connectivity of filler in the fabricated samples. Field emission of MWCNT¬PS composites is studied in two different configurations: along the top surface of the film (parallel configuration) and along the cross section of the sample (perpendicular configuration). In this chapter field emission results of the MWCNT-PS composites in parallel configuration are presented. The effect of charge transport in limiting the field emission of MWCNT-PS composite is discussed. Field emission results of MWCNT-PS composites in parallel configuration indicate that the emission performance can be maximized at moderate wt. fraction of MWCNT (0.15). The obtained current densities are ~10 µA/cm2 in the parallel configuration. Chapter 5 presents the study of field emission characteristics of MWCNT¬PS composites of various wt. fractions in the perpendicular configuration. Till date most studies using nanotube composites tend to have the nanotubes lying in two dimensional plane, perpendicular to the applied electric field. In the perpendicular configuration, the nanotubes are nearly aligned parallel to the direction of the applied electric field which results in high field enhancement, and electron emission at lower applied fields. SEM micrographs in cross-sectional view reveal that MWCNTs are homogeneously distributed across the thickness and the density of protruding tubes can be scaled with wt. fraction of the composite film. Field emission from composites has been observed to vary considerably with density of MWCNTs in the polymer matrix. High emission current density of 100 mA/cm2 is achieved at a field of 2.2 V/µm for 0.15 wt. fraction. The field emission is observed to follow the Fowler– Nordheim tunneling mechanism, however, electrostatic screening plays a role in limiting the current density at higher wt. fractions. Chapter 6 highlights the field emission response of rGO coated on a flexible PS film. Field emission of rGO coated PS film along the cross section of the sample is studied in addition to the top film surface of the film. The effect of geometry on the improved field emission efficiency of rGO coated polymer film is demonstrated. The emission characteristics are analyzed by Fowler–Nordheim tunneling for field emission. Low turn-on field (~0.6 V/µm) and high emission current (~200 mA/cm2) in the perpendicular configuration ensure that rGO can be a potential field emitter. Furthermore, stability and repeatability of the field emission characteristics are also presented. Chapter 7 deals with the synthesis, characterization, and field emission of two different kinds of hybrid materials: (1) MWCNT coated with zinc oxide (ZnO) nanoparticles (2) ZnO/graphitic carbon (g-C) core-shell nanowires. The field emission from the bucky paper is improved by anchoring ZnO nanoparticles on the surface of MWCNT. A shift in turn on field from 3.5 V/µm (bucky paper) to 1.0 V/µm is observed by increasing the ZnO nanoparticle loading on the surface of MWCNT with an increase in enhancement factor from 1921 to 4894. Field emission properties of a new type of field emitter ZnO/g-C core-shell nanowires are also presented in this chapter. ZnO/g-C core/shell nanowires are synthesized by CVD of zinc acetate at 1300 °C. Overcoming the problems of ZnO nanowire field emitters, which in general possess high turn on fields and low current densities, the core-shell nanowires exhibit excellent field emission performance with low turn on field of 2.75 V/µm and high current density of 1 mA/cm2. Chapter 8 presents a brief summary of the important results and future perspectives of the work reported in the thesis.