No description available.

Die Elektrochemie und die Spektroelektrochemie von selbst-organisiererten Monoschichten (selfassembled monolayers, SAMs) gebildet aus 2-Mercaptopyridin (2MP) und 4-Mercaptopyridin (4MP) wurden an polykristallinen Goldelektroden in wässrigen Elektrolytlösungen untersucht. Folgende Untersuchungsmethoden wurden angewandt: zyklische Voltammetrie, elektrochemische Impedanzmessungen (EIM) und oberflächenverstärkte Raman Streuung (surface-enhanced Raman scattering, SERS). Die elektrochemischen Untersuchungen von 2MP und 4MP in wässriger saurer Lösung (0.5 M H2SO4) zeigten, dass 2MP stärker adsorbiert wird als 4MP aufgrund der Bildung eines S-Au-N Chelates, wobei die S-Au-Interaktionen bei 4MP stärker sind. Die Bildung eines Chelates im Falle von 2MP verringert die Wahrscheinlichkeit der Bildung eines Dimers. In sauren Lösungen wird das N-Atom von 2MP protoniert, was zu einer schwächeren Bindung von 2MP-Molekülen zur Substratoberfläche führt. Die Ergebnisse der SERS-Untersuchungen stimmen mit den Resultaten aus der zyklischen Voltammetrie überein. Man erhält eine Au-S-Streckschwingungsbande für 2MP zwischen 225 bis 250 cm-1 bei Abscheidung aus wässriger oder saurer Lösung und für 4MP bei ca. 263 cm-1 in beiden Lösungen. Die SERS-Experimente ergaben eine senkrechte Orientierung zur Goldoberfläche sowohl für 2MP als auch für 4MP. Die Thion-Thiol-Tautomerie von 2- Mercaptopyridinen wurde ebenfalls in Betracht gezogen. Die Unter- und Überpotentialabscheidung von Kupfer auf einer polykristallinen Goldelektrode in wässriger 0.1 M Schwefelsäure in An- und Abwesenheit von SAMs von 2- und 4- Mercaptopyridin wurde mit zyklischer Voltammetrie untersucht. Es zeigte sich, daß bei Vorhandensein der SAMs die Elektrodeposition von Kupfer verhindert wird, was auf starke Wechselwirkungskräfte zwischen dem Adsorbat (MP) und der Goldoberfläche zurückzuführen ist. 2MP zeigt eine grössere Inhibierung, was höchstwahrscheinlich auf die Bildung der Chelatstruktur zurückzuführen ist. Es wurden ebenso Untersuchungen zum Einfluss von 2MP und 4MP auf die abgeschiedene Kupfermonolage auf der Goldelektrode durchgeführt. Es zeigte sich, daß die Kupfermonolage teilweise durch 2MP oder 4MP ersetzt wird. Die Elektronenaustauschgeschwindigkeit für das Fe2+/Fe3+-Redoxsystem in An- und Abwesenheit von 2MP- oder 4MP-Monolagen wurde mit zyklischer Voltammetrie und elektrochemischen Impedanzmessungen (EIM) untersucht. Es stellte sich heraus, dass der Elektronenaustausch höchstwahrscheinlich über Defektstellen in der Monolage (Pinholes) erfolgt. In einer wässrigen Lösung verringert 4MP den Elektronenaustausch stärker als 2MP. Da die Packungsdichte bei 4MP größer ist als bei 2MP ist wahrscheinlich auch die Zahl der Pinholes geringer in der 4MP-Monolage. In saurer Lösung liegen die N-Atome protoniert vor. Man kann davon ausgehen, dass in saurer Lösung zwei Prozesse gleichzeitig ablaufen, die für den Elektronenaustausch entscheidend sind. Erstens kommt es zu einer Abstoßung zwischen der positiv geladenen Monolage und den positiv geladenen Redoxionen. Und zweitens erfolgt eine Abstoßung zwischen den positiv geladenen Molekülen der SAMs, was zu einer geringeren Packungsdichte führt. Der Ladungsaustausch wird dominiert durch den zweiten Effekt. Mit Hilfe von EIM wurden die Elektronenaustauschgeschwindigkeit und der Bedeckungsgrad bestimmt. Die korrosionshemmende Wirkung von 2MP und 4MP auf Stahl in 3.5 % wässriger NaCl-Lösung wurde mit Hilfe der EIM untersucht. 2MP zeigte eine grössere Hemmung als 4MP. / The electrochemistry and spectroelectrochemistry of the self-assembled monolayers (SAMs) prepared of 2-mercaptopyridine (2MP) and 4-mercaptopyridine (4MP) dissolved either in water or 0.1 M H2SO4 have been investigated at polycrystalline gold electrodes in aqueous electrolyte solutions using cyclic voltammetry, electrochemical impedance measurements (EIM) and surface enhanced Raman spectroscopy (SERS). Electrochemical studies of 2MP and 4MP monolayers in aqueous acidic solution (0.5 M H2SO4) suggest that 2MP is adsorbed more strongly than 4MP due to the formation of S-Au-N chelate. However, the S-Au bond was found to be stronger in 4MP as compared with 2MP. The formation of the chelate in case of 2MP diminishes the probability of dimer formation. In the acidic solvent, the N-atom of 2MP molecule will be protonated leading to a weaker interaction of 2MP molecules with the substrate surface. The SERS results are in good agreement with the cyclic voltammetry results. The Au-S stretching band was obtained in the region from 215 to 245 cm-1 for 2MP deposited from water and acidic solvent and around 263 cm-1 for 4MP in both solvents. The SERS measurements showed also a perpendicular orientation of both 2MP and 4MP on the gold surface. In explaining the SERS results, the thione-thiol tautomerisations of the mercaptopyridines were also taken into consideration. The under- and overpotential deposition of copper on a polycrystalline gold electrode in aqueous 0.1 M sulfuric acid in the presence and in the absence of SAMs of 2- and 4-mercaptopyridine has been studied using cyclic voltammetry. In general, the presence of these SAMs has been found to inhibit the electrodeposition process of copper, suggesting very strong interactions between these adsorbates and the Au surface. 2MP shows a higher degree of inhibition, which is due to a stronger interaction probably due to the formation of the chelate structure. Studies have also been made of the influence of mercaptopyridines SAMs on the copper monolayer electrodeposited on the gold surface. The copper adlayer was found to be partially displaced by 2MP and 4MP monolayers. The rate of electron transfer for the Fe3+/2+ redox system on the gold electrode has been probed in the absence and presence of 2MP and 4MP monolayers by cyclic voltammetry and electrochemical impedance measurements (EIM). The charge transfer process was suggested to occur through the defects (pinholes) in the monolayer. In case of aqueous solvent 4MP decreases the electron transfer reaction stronger than 2MP. Since the packing density for 4MP is higher than that of 2MP the number of pinholes might be lower in 4MP monolayer. In acidic solvent the N-atoms of the mercaptopyridines will be protonated. It is proposed that two effects, which exist at the same time, are responsible for the electron transfer process in acidic solution. First, there will be a repulsive interaction between the positively charged monolayer and the positively charged redox probe. Second, there is a repulsion among the positively charged monolayer molecules that results in a less compact monolayer. The charge transfer is dominated due to the latter effect. With the EIM the rate of electron transfer and the surface coverage were determined. 2MP and 4MP were examined as steel corrosion inhibitors in 3.5% aqueous NaCl solution using EIM. 2MP shows higher inhibition efficiency than 4MP.

Efficient substrates for surface-enhanced Raman spectroscopy (SERS) are under constant development, since time-consuming and costly fabrication routines are often an issue for high-throughput spectroscopy applications. In this research, we use a two-step fabrication method to produce self-organized parallel-oriented plasmonic gold nanostructures. The fabrication routine is ready for wafer-scale production involving only low-energy ion beam irradiation and metal deposition. The optical spectroscopy features of the resulting structures show a successful bidirectional plasmonic response. The localized surface plasmon resonances (LSPRs) of each direction are independent from each other and can be tuned by the fabrication parameters. This ability to tune the LSPR characteristics allows the development of optimized plasmonic nanostructures to match different laser excitations and optical transitions for any arbitrary analyte. Moreover, in this study, we probe the polarization and wavelength dependence of such bidirectional plasmonic nanostructures by a complementary spectroscopic ellipsometry and Raman spectroscopy analysis. We observe a significant signal amplification by the SERS substrates and determine enhancement factors of over a thousand times. We also perform finite element method-based calculations of the electromagnetic enhancement for the SERS signal provided by the plasmonic nanostructures. The calculations are based on realistic models constructed using the same particle sizes and shapes experimentally determined by scanning electron microscopy. The spatial distribution of electric field enhancement shows some dispersion in the LSPR, which is a direct consequence of the semi-random distribution of hotspots. The signal enhancement is highly efficient, making our SERS substrates attractive candidates for high-throughput chemical sensing applications in which directionality, chemical stability, and large-scale fabrication are essential requirements.

Surface- and tip-enhanced resonant Raman scattering (resonant SERS and TERS) by optical phonons in a monolayer of CdSe quantum dots (QDs) is demonstrated. The SERS enhancement was achieved by employing plasmonically active substrates consisting of gold arrays with varying nanocluster diameters prepared by electron-beam lithography. The magnitude of the SERS enhancement depends on the localized surface plasmon resonance (LSPR) energy, which is determined by the structural parameters. The LSPR positions as a function of nanocluster diameter were experimentally determined from spectroscopic micro-ellipsometry, and compared to numerical simulations showing good qualitative agreement. The monolayer of CdSe QDs was deposited by the Langmuir–Blodgett-based technique on the SERS substrates. By tuning the excitation energy close to the band gap of the CdSe QDs and to the LSPR energy, resonant SERS by longitudinal optical (LO) phonons of CdSe QDs was realized. A SERS enhancement factor of 2 × 10³ was achieved. This allowed the detection of higher order LO modes of CdSe QDs, evidencing the high crystalline quality of QDs. The dependence of LO phonon mode intensity on the size of Au nanoclusters reveals a resonant character, suggesting that the electromagnetic mechanism of the SERS enhancement is dominant. Finally, the resonant TERS spectrum from CdSe QDs was obtained using electrochemically etched gold tips providing an enhancement on the order of 10⁴. This is an important step towards the detection of the phonon spectrum from a single QD. / Dieser Beitrag ist aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

The adsorbate formed by adsorption of thiophenol on a polycrystalline gold electrode and brought into contact with aqueous solutions of 1 M HClO4 and 0.1 M KClO4 has been studied using cyclic voltammetry and surface-enhanced Raman spectroscopy. A strong adsorption is deduced from observations made using cyclic voltammetry. From the SER spectra, interactions of thiophenol with the gold surface via a gold–sulfur bond with the aromatic ring pointing away from the surface is concluded for both electrolyte solutions. / Dieser Beitrag ist aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

Les travaux de la thèse portent sur l’impact de la structure des électrolytes hautement concentrés (ÉHC) à base de Lithium Bis[trifluorométhane(sulfonyl)]imide (LITFSI) et d’acétonitrile (ACN) dans les réactions de transfert d’électron et les interactions présentes avec les différentes espèces en jeu. Ces électrolytes sont étudiés comme électrolyte dans les dispositifs de stockage d’énergie (batteries, supercapaciteurs), mais la recherche sur les transferts d’électron dans ces ÉHC est presque inexistante. Les travaux sont présentés en deux volets; dans le premier, nous nous sommes concentrés à assurer de la qualité des ÉHC. Nous avons identifié les principales sources d’eau dans ces électrolytes : la présence d’eau varie selon le fournisseur de sel et le taux d’adsorption d’eau de l’électrolyte. Nous avons aussi analysé les impacts de la quantité d’eau sur les propriétés physicochimiques et la fenêtre de stabilité électrochimique. Une teneur d’eau dans les ÉHC sous 1000 ppm n’affecte pas les propriétés physicochimiques. Cependant, la fenêtre de stabilité électrochimique est affectée par une faible présence d’eau (>200 ppm), particulièrement la stabilité en réduction. Le second volet porte sur l’étude du transfert d’électron du couple Fc+/Fc dissout et adsorbé à l’électrode dans les ÉHC LiTFSI : ACN. Nous avons montré que la cinétique du transfert d’électron varie avec la concentration (dilué vs. hautement concentré) et avec l’état d’oxydation du couple rédox (Fc+ vs Fc). La constante de transfert d’électron est plus élevée avec le Fc+ que le Fc dans les milieux dilués, mais la situation est inversée dans les ÉHC. En complément à l’électrochimie, les études Raman couplées à l’électrochimie ont révélé que cette différence provient de l’environnement chimique qui diffère entre les deux espèces, dues à la charge des deux espèces (Fc+ vs. Fc) aux différentes concentrations de sel. Les travaux de cette thèse sont les premiers à montrer l’électrochimie d’une molécule électroactive couplée avec l’utilisation de méthode spectroscopique pour le couple Fc+/Fc dans les ÉHC. Cette recherche ouvre la porte à l’utilisation de ces méthodes d’analyse pour les ÉHC et montre un grand potentiel pour des applications autre que le stockage d’énergie. Les résultats obtenus sont un premier pas vers la formulation d’ÉHC adaptés aux applications d’électrocatalyse : l’utilisation des interactions électrostatiques présentes à haute concentration pourraient ralentir les réaction secondaires formant des cations ou ralentir la diffusion de cations impliqués dans les réactions de transfert d’électron couplées. / The work of this thesis focuses on the impact of the structure of highly concentrated electrolytes (HCE) based on Lithium Bis[trifluoromethane(sulfonyl)]imide (LITFSI) and acetonitrile (ACN) on the electron transfer reactions and the interactions present with the different species involved. These electrolytes are studied as electrolytes in energy storage devices (batteries, supercapacitors), but research on electron transfers in these HCE is almost non-existent. The work is presented in two parts; in the first part, we focused on ensuring the quality of HCE. We identified the main sources of water in these electrolytes: the presence of water varies depending on the salt supplier and the water adsorption rate of the electrolyte. We also analyzed the impacts of the amount of water on the physicochemical properties and the electrochemical stability window. A water content in HCE below 1000 ppm does not affect the physicochemical properties. However, the electrochemical stability window is affected by low water content (>200 ppm), especially the reduction stability. The second part deals with the study of the electron transfer of the dissolved and adsorbed Fc+/Fc couple at the electrode in LiTFSI: ACN HCE. We have shown that the electron transfer kinetics varies with concentration (dilute vs. highly concentrated) and with the oxidation state of the redox couple (Fc+ vs. Fc). The electron transfer constant is higher with Fc+ than Fc in dilute media, but the situation is reversed in HCE. In addition to electrochemistry, Raman studies coupled with electrochemistry revealed that this difference in electron transfer comes from the chemical environment which differs between the two species, due to the charge of the two species (Fc+ vs. Fc) at different salt concentrations. The work of this thesis is the first to show the electrochemistry of an electroactive molecule coupled with the use of spectroscopic methods for the Fc+/Fc couple in HCE. This research opens the door to the use of these analytical methods for HCE and shows a great potential for applications other than energy storage. The results obtained are a first step towards the formulation of HCE adapted to electrocatalysis applications: the use of electrostatic interactions present at high concentration could slow down the secondary reactions forming cations or slow down the diffusion of cations involved in coupled electron transfer reactions.

Raman spectroscopy is a powerful analytical method that allows deposited and/or immobilized cells to be evaluated without complex sample preparation or labeling. However, a main limitation of Raman spectroscopy in cell analysis is the extremely weak Raman intensity that results in low signal to noise ratios. Therefore, it is important to seize any opportunity that increases the intensity of the Raman signal and to understand whether and how the signal enhancement changes with respect to the substrate used. Our experimental results show clear differences in the spectroscopic response from cells on different surfaces. This result is partly due to the difference in spatial distribution of electric field at the substrate/cell interface as shown by numerical simulations. We found that the substrate also changes the spatial location of maximum field enhancement around the cells. Moreover, beyond conventional flat surfaces, we introduce an efficient nanostructured silver substrate that largely enhances the Raman signal intensity from a single yeast cell. This work contributes to the field of vibrational spectroscopy analysis by providing a fresh look at the significance of the substrate for Raman investigations in cell research.

Les polymères à empreintes moléculaires (MIP), également appelés "anticorps en plastique", sont des récepteurs biomimétiques synthétiques qui sont capables de reconnaître et lier une molécule cible avec une affinité et une spécificité comparables à celles des récepteurs naturels tels que des enzymes ou des anticorps. En effet, les MIP sont utilisés comme éléments de reconnaissance synthétiques dans les biocapteurs et biopuces pour la détection de petits analytes et les protéines. La technique d'impression moléculaire est basée sur la formation de cavités de reconnaissance spécifiques dans des matrices polymères par un procédé de moulage à l'échelle moléculaire. Pour la conception de capteurs et biopuces, une cinétique d'adsorption et une réponse du capteur rapide, l'intégration des polymères avec des transducteurs, et une haute sensibilité de détection sont parmi les principaux défis. Dans cette thèse, ces problèmes ont été abordés par le développement de nanocomposites MIP / d'or via le greffage du MIP sur les surfaces en utilisant des techniques de polymérisation dédiées comme l'ATRP qui est une technique de polymérisation radicalaire contrôlée (CRP). Ces techniques CRP sophistiquées sont en mesure d'améliorer considérablement les matériaux polymères. L'utilisation de l'ATRP dans le domaine de MIP a été limitée jusqu'à présent en raison de son incompatibilité inhérente avec des monomères acides comme l'acide méthacrylique (MAA), qui est de loin le monomère fonctionnel le plus largement utilisé dans les MIP. Ici, un nouveau procédé est décrit pour la synthèse de MIP par ATRP photo-initiée utilisant fac-[Ir(Ppy)3] comme catalyseur. La synthèse est possible à température ambiante et est compatible avec des monomères acides. Cette étude élargit considérablement la gamme de monomères fonctionnels et de molécules empreintes qui peuvent être utilisés lors de la synthèse de MIP par ATRP. La méthode proposée a été utilisée pour la fabrication de nanocomposites hiérarchiquement organisés sur des surfaces métalliques nanostructurés avec des nano-trous et nano-ilots, présentant des effets plasmoniques pour l'amplification du signal. La synthèse de films de MIP à l'échelle du nanomètre localisés sur la surface d'or a été démontrée. Des méthodes de transduction optiques, à savoir la résonance de plasmons de surface localisée (LSPR) et la spectroscopie Raman exaltée par effet de surface (SERS) ont été exploitées. Ces techniques se sont montrées prometteuses pour l'amélioration de la limite de détection dans la détection d'analytes biologiquement pertinents, y compris les protéines et le médicament propranolol. / Molecularly imprinted polymers (MIPs), also referred to as plastic antibodies, are synthetic biomimetic receptors that are able to bind target molecules with similar affinity and specificity as natural receptors such as enzymes or antibodies. Indeed, MIPs are used as synthetic recognition elements in biosensors and biochips for the detection of small analytes and proteins. The molecular imprinting technique is based on the formation of specific recognition cavities in polymer matrices by a templating process at the molecular level. For sensor and biochip development, fast binding kinetics of the MIP for a rapid sensor response, the integration of the polymers with transducers, and a high sensitivity of detection are among the main challenges. In this thesis, the above issues are addressed by developing MIP/gold nanocomposites by grafting MIPs on surfaces, using dedicated techniques like atom transfer radical polymerization (ATRP) which is a versatile controlled radical polymerization (CRP) technique. Theses ophisticated CRP techniques, are able to greatly improve the polymeric materials. The use of ATRP in the MIP field has been limited so far due to its inherent incompatibility with acidic monomers like methacrylic acid (MAA), which is by far the most widely used functional monomer. Herein, a new method is described for the MIP synthesis through photo-initiated ATRP using fac-[Ir(ppy)3] as ATRP catalyst. The synthesis is possible at room temperature and is compatible with acidic monomers. This study considerably widens the range of functional monomers and thus molecular templates that can be used when MIPs are synthesized by ATRP. The proposed method was used for fabrication of hierarchically organised nanocomposites based on MIPs and nanostructured metal surfaces containing nanoholes or nanoislands, exhibiting plasmonic effects for signal amplification. The fabrication of nanometer scale MIP coatings localized on gold surface was demonstrated. Optical transduction methods, namely Localized Surface Plasmon Resonance (LSPR) and Surface Enhanced Raman Spectroscopy (SERS) were exploited and shown that they hold great promise for enhancing the limit of detection in sensing of biologically relevant analytes including proteins and the drug propranolol.

To increase the survival rate from infectious- and noncommunicable diseases, reliable diagnostic during the preliminary stages of a disease onset is of vital importance. This is not trivial to achieve, a highly sensitive and selective detection system is needed for measuring the low concentrations of biomarkers available. One possible route to achieve this is through biosensing based on plasmonic nanostructures, which during the last decade have demonstrated impressive diagnostic capabilities. These nanoplasmonic surfaces have the ability to significantly enhance fluorescence- and Raman signals through localized hotspots, where a stronger then normal electric field is present. By further utilizing a periodic sub-wavelength nanohole array the extraordinary optical transmission phenomena is supported, which open up new ways for miniaturization. In this study a nanoplasmonic chip (NPC) composed of a nanohole array —with lateral size on the order of hundreds of nanometer— covered in a thin layer of gold is created. The nanohole array is fabricated using soft nanoimprint lithography on two resists, hydroxypropyl cellulose (HPC) and polymethyl methacrylate (PMMA). An in depth analysis of the effect of thickness is done, where the transmittance and Raman scattering (using rhodamine 6G) are measured for varying gold layers from 5 to 21 nm. The thickness was proved to be of great importance for optimizing the Raman enhancement, where a maximum was found at 13 nm. The nanohole array were also in general found beneficial for additionally enhancing the Raman signal. A transmittance minima and maxima were found in the region 200-1000 nm for the NPCs, where the minima redshifted as the thickness increased. The extraordinary transmission phenomena was however not observed at these thin gold layers. Oxygen plasma treatment further proved an effective treatment method to reduce the hydrophobic properties of the NPCs. Care needs be taken when using thin layers of gold with a PMMA base, as the PMMA structure could get severely damaged by the plasma. HPC also proved inadequate for this projects purpose, as water-based fluids easily damaged the surface despite a deposited gold layer on top.

Porous, conductive metallic nanostructures are required in several fields, such as energy conversion, low-cost sensors etc. This thesis reports on the development of an electrocatalytically active and conductive membrane for use in Polymer Electrolyte Membrane Fuel Cells (PEMFCs) and fabrication of low-cost substrates for Surface Enhanced Raman Spectroscopy (SERS). One of the main challenges facing large-scale deployment of PEMFCs currently is to fabricate a catalyst layer that minimizes platinum loading, maximizes eletrocatalytically active area, and maximizes tolerance to CO in the feed stream. Modeling the kinetics of platinum catalyzed half cell reactions occurring in a PEMFC using the kinetic theory of gases and incorporating appropriate sticking coefficients provides a revealing insight that there is scope for an order of magnitude increase in maximum current density achievable from PEMFCs. To accomplish this, losses due to concentration polarization in gas diffusion layers, which occur at high current densities, need to be eliminated. A novel catalyst design, based on a porous metallic nanostructure, which aims to overcome the limitations of concentration polarization as well as minimize the amount of platinum loading in PEMFCs is proposed. Fabrication steps involving controlled in-plane fusion of self-assembled arrays of core-shell gold-platinum nanoparticles (Au@Pt) is envisioned. The key steps involved being the development of a facile synthesis route to form Au@Pt nanoparticles with tunable platinum shell thicknesses in the 5 nm size range, the formation of large-scale 2D arrays of Au@Pt nanoparticles using guided self-assembly, and optimization of an RF plasma process to promote in-plane fusion of the nanoparticles to form porous, electrocatalytically active and electrically conductive membranes. This thesis consists of seven chapters. The first chapter provides an introduction into the topic of PEMFCs, some perspective on the current status of research and development of PEMFCs, and an outline of the thesis. The second chapter provides an overview on the methods used, characterization techniques employed and protocols followed for sample preparation. The third chapter describes the modelling of a PEMFC using the Kinetic theory of gases to arrive at an estimate of the maximum feasible current density, based on the kinetics of the electrocatalytic reactions. The fourth chapter presents the development of a simple protocol for synthesizing Au@Pt nanoparticles with control over platinum shell thicknesses from the sub monolayer coverage onwards. The results of spectroscopic and microscopic characterization establish the uniformity of coating and the absence of secondary nucleation. Chapter five describes the formation of a nanoporous, electrocatalytically active membrane by self-assembly to form bilayers of 2D arrays of Au@Pt nanoparticles and subsequent fusion using an RF plasma based process. The evolution of the electrocatalytic activity and electrical conductivity as a function of the duration of RF plasma treatment is monitored for Au@Pt nanoparticles with various extent of platinum coating. Spectroscopic, microscopic, electrical and cyclic voltammetry characterization of the samples at various stages were used to understand the structural evolution with RF plasma treatment duration and discussed. Next durability studies were carried out on the nanoporous, Au@Pt bilayer nanoparticle array with an optimum composition of Pt/Au atomic ratio of 0.88 treated to 16 minutes of argon plasma exposure. After this the novel catalyst membrane design of PEM fuel cell is revisited. Two different techniques are proposed so that the thin, nanoporous, metallic catalyst membrane achieves horizontal electronic resistance equivalent to that of the conventional gas diffusion layer with catalyst layer. The first technique proposes the introduction of gold coated polymeric mesh in between the thin, nanoporous, metallic catalyst membrane and bipolar plate and discusses the advantages. Later the gold coated polymeric mesh is introduced in a conventional membrane electrode assembly and efficiency of the polarization curves probed with and without the introduction of gold coated polymeric mesh. The second technique describes the results of fabrication of a nanoporous metallic membrane using multiple layers of 2D Au@Pt nanoparticle arrays at an optimum composition of Pt/Au atomic ratio of 0.88 to reduce the horizontal electronic resistance. Preliminary studies on the permeability of water through such membranes supported on a porous polycarbonate filter membrane are also presented. In chapter six, a simple reactive inkjet printing process for fabricating SERS active silver nanostructures on paper is presented. The process adapts a simple room temperature protocol, using tannic acid as the reducing agent, developed earlier in our group to fabricate porous silver nanostructures on paper using a commercial office inkjet printer. The results of SERS characterization, spectroscopic and microscopic characterizations of the samples and the comparison of the substrate’s long-term performance with respect to a substrate fabricated using sodium borohydride as the reducing agent is discussed. Preliminary findings on attempts to fabricate a conductive silver network using RF plasma induced fusion area also presented. Chapter seven provides a summary of the results, draws conclusions and a perspective on work required to accomplish the goals of incorporating the porous metallic nanostructures into PEMFCs.