Developed rechargeable batteries are urgently required to make more efficient use of renewable energy sources to support our modern way of life. Among all battery types, lithium batteries have attracted the most attention because of the high energy density (both gravimetric and volumetric), long cycle life, reasonable production cost and the ease of manufacturing flexible designs. Indeed, electrode material characteristics need to be improved urgently to fulfil the requirements for high performance lithium ion batteries. TiO2-based anodes are highly promising materials for LIBs to replace carbon due to fast lithium insertion/extraction kinetics, environmentally-friendly behavior, low cost and low volume change (less than 4%) therewith, high structural stability as well as improved safety issues are obtained. Nevertheless, the low ionic and electric conductivity (≈ 10−12 S m−1) of TiO2 represent the main challenge. In short, the present work aims at developing, optimization and construction of novel anode materials for lithium ion batteries using materials that are stable, abundant and environmentally friendly. Herein, both of two-phase Ti80Co20 and single phase Ti-Sn alloys (with different Sn contents of 1 to 10 at.%) were used to fabricate highly ordered, vertically oriented and dimension-controlled 1D nanotubes of mixed transition metal oxides (TiO2-CoO and TiO2-SnO2) via a straight-forward anodic oxidation step in organic electrolytes containing NH4F. Surface morphology and current density for the initial nanotube formation are found to be dependent on the crystal structure of the alloy phases. Various characterization tools such as SEM, EDXS, TEM, XPS and Raman spectroscopy were used to characterize the grown nanotube films. The results reveal the successful formation of mixed TiO2-CoO and TiO2-SnO2 nanotubes under the selected voltage ranges. The as-formed nanotubes are amorphous and their dimensions are precisely controlled by tuning the formation voltage. The electrochemical performance of the grown nanotubes was evaluated against a Li/Li+ electrode at different current densities. The results revealed that TiO2-CoO nanotubes prepared at 60 V exhibited the highest areal capacity of ~ 600 µAh cm–2 (i.e. 315 mAh g–1) at a current density of 10 µA cm–2. At higher current densities TiO2-CoO nanotubes showed nearly doubled lithium ion intercalation and a coulombic efficiency of 96 % after 100 cycles compared to lower effective TiO2 nanotubes prepared under identical conditions. To further improve the electrochemical performance of the TiO2-CoO nanotubes, a novel ternary carbon nanotubes (CNTs)@TiO2-CoO nanotubes composite was fabricated by a two-step synthesis method. The preparation includes an initial anodic fabrication of well-ordered TiO2-CoO NTs from a Ti-Co alloy, followed by growing of CNTs horizontally on the top of the oxide films using a simple spray pyrolysis technique. The unique 1D structure of such a hybrid nanostructure with the inclusion of CNTs demonstrates significantly enhanced areal capacity and rate performances compared to pure TiO2 and TiO2-CoO NTs without CNTs tested under identical conditions. The findings reveal that CNTs provide a highly conductive network that improves Li+ ion diffusivity promoting a strongly favored lithium insertion into the TiO2-CoO NT framework, and hence results in high capacity and extremely reproducible high rate capability. On the other hand, the results demonstrate that TiO2-SnO2 nanotubes prepared at 40 V on a Ti-Sn alloy with 1 at.% Sn display an average 1.4 fold increase in areal capacity with excellent cycling stability over more than 400 cycles compared to the pure TiO2 nanotubes fabricated and tested under identical conditions. The thesis is organized as follows: Chapter 1: General introduction, in which the common situation of energy demand, along with the importance of lithium ion batteries in renewable energy systems and portable devices are discussed. A brief introduction to TiO2-based anode in lithium ion batteries and the genera strategies for developing TiO2 anodes are also presented. The scope of this thesis as well as the main tasks are summarized. Chapter 2: The basic concepts of lithium ion batteries with an overview about their main components are discussed, including a brief information about the anode materials and the crystal structure of TiO2 anode. A detailed review for TiO2 nanomaterials for LIBs including the fabrication methods and the electrochemical performance of various TiO2 nanostructures (nanoparticles, nanorods, nanoneedles, nanowires and nanotubes) as well as porousTiO2 nanostructures is presented. The fabrication of TiO2 nanotubes by anodic oxidation, along with the growth mechanism are highlighted. The factors affecting the electrochemical performance of anodically fabricated pure TiO2, TiO2/carbon composites and TiO2-mixed with another metal oxide are reviewed. Chapter 3: In this chapter, the synthesis of TiO2-CoO, (CNTs)@TiO2-CoO and TiO2-SnO2 nanotubes, along with the characterization techniques and the electrochemical basics and concepts are discussed. Chapter 4: Detailed results and discussion of synthesis, characterizations and the electrochemical performance of TiO2-CoO nanotubes and ternary (CNTs)@TiO2/CoO nanotube composites are presented. Chapter 5: Detailed results and discussion of synthesis, characterizations and the electrochemical performance of ternary (CNTs)@TiO2-CoO nanotube composites are explained. Chapter 6: Detailed results and discussion of synthesis, characterizations and the electrochemical performance of TiO2-SnO2 nanotubes are presented. Chapter 7: Summarizes the results presented in this work finishing with realistic conclusions, and highlights interesting work for the future.:1. Introduction and scope of the thesis 15 1.1 Batteries for renewable energy systems and portable devices 15 1.2 TiO2-based anodes in lithium ion batteries 17 1.3 Strategies for developing TiO2 anodes 17 1.4 Scope of work 19 1.5 Tasks 20 2. Basics and literature review 23 2.1 Lithium ion battery system 23 2.2 Anode materials 26 2.3 Crystal structure of TiO2 28 2.4 TiO2 nanomaterials for LIBs 30 2.4.1 TiO2 nanoparticles 30 2.4.2 TiO2 nanoneedles 36 2.4.3 Porous TiO2 nanostructures 39 2.5 TiO2 nanotubes prepared by electrochemical anodization 44 2.6 The mechanism of nanotube formation by anodic oxidation 47 2.7 Anodically fabricated TiO2 nanotubes as anodes in LIBs 49 2.7.1 Anodization electrolyte 50 2.7.2 Amorphous and crystalline TiO2 anodes 50 2.7.3 Influence of the nnealing atmospheres of TiO2 52 2.7.4 Free-standing TiO2 nanotube membranes 54 2.7.5 TiO2 nanotubes/carbon composites 55 2.7.6 Mixed oxide nanotubes 55 3. Materials and methods 61 3.1 Methodology 61 3.1.1 Synthesis of TiO2-CoO and TiO2 nanotubes 61 3.1.2 Synthesis of CNTs@TiO2-CoO NT composite 62 3.1.3 Synthesis of TiO2-SnO2 and TiO2 nanotubes 63 3.2 Characterization techniques 64 3.2.1 X-ray diffraction (XRD 64 3.2.2 Scanning electron microscopy (SEM 65 3.2.3 Energy-dispersive X-ray spectroscopy (EDXS 65 3.2.4 Transmission electron spectroscopy (TEM 66 3.2.5 X-ray photoelectron spectroscopy (XPS 66 3.2.6 Raman spectroscopy 67 3.2.7 Nitrogen sorption isotherms 67 3.2.8 Inductively coupled plasma optical emission spectroscopy (ICP–OES 68 3.3 Basic definitions and electrochemical concepts 68 3.3.1 Faraday’s law 68 3.3.2 Capacity 69 3.3.3 Discharging 69 3.3.4 Charging 69 3.4 Electrochemical techniques 70 3.4.1 Cyclic voltammetry 70 3.4.2 Galvanostatic discharging/charging cycling 70 3.4.3 Electrochemical impedance spectroscopy (EIS 71 3.5 Electrode preparation and measurement conditions 71 3.5.1 TiO2-CoO nanotube electrodes 71 3.5.2 CNTs@TiO2 and CNTs@TiO2/CoO NTs electrodes 72 3.5.3 TiO2-SnO2 nanotube electrodes 73 4. TiO2-CoO as anodes in lithium ion batteries 75 4.1 Introduction 76 4.2 Characterization 76 4.2.1 Phase identification of as cast Ti-Co alloy 76 4.2.2 Time-current density relationship 79 4.2.3 Morphology of the fabricated TiO2-CoO nanotubes 81 4.2.4 Phase identification of the fabricated TiO2-CoO nanotubes 85 4.2.5 Specific surface area of the fabricated TiO2-CoO nanotubes 87 4.2.6 Chemical state in the grown TiO2-CoO nanotubes 89 4.2.7 Raman spectroscopy of TiO2-CoO nanotubes 91 4.3 Electrochemical testing of TiO2-CoO electrodes 92 4.3.1 Cyclic voltammetry 92 4.3.2 Galvanostatic cycling with potential limitation 93 4.3.3 Electrochemical impedance spectroscopy (EIS) 97 4.3.4 Structural stability TiO2-CoO anodes over cycling 98 4.4 Summary of chapter 4 99 5. Ternary CNTs@TiO2-CoO nanotube composites: improved anode materials for LIBs 101 5.1 Introduction 102 5.2 Characterization 103 5.2.1 Morphology and Raman analysis of the fabricated CNTs@TiO2-CoO NTs 103 5.2.2 XRD analysis of the fabricated TiO2-CoO NTs before and after CNTs coating 106 5.3 Electrochemical properties 107 5.3.1 Cyclic voltammetry 107 5.3.2 Galvanostatic cycling with potential limitation 109 5.3.2 Electrochemical impedance spectroscopy (EIS 112 5.4 Summary of chapter 5 114 6. TiO2-SnO2 nanotubes as anodes in lithium ion batteries 115 6.1 Introduction 116 6.2 Characterization 117 6.2.1 ICP-OES analysis of the as-cast Ti-Sn alloys 117 6.2.2 SEM analysis of the as-cast Ti-Sn alloys 117 6.2.3 Phase analysis of the as-cast Ti-Sn alloys 118 6.2.4 Morphology of the fabricated TiO2-SnO2 nanotubes 121 6.2.5 XPS investigation of the grown TiO2-SnO2 nanotubes 127 6.2.6 Raman spectroscopy of TiO2-SnO2 nanotubes 129 6.3 Electrochemical Testing 130 6.3.1 Cyclic voltammetry 130 6.3.2 Galvanostatic cycling with potential limitation132 6.3.3 Specific surface area of the fabricated TiO2-SnO2 nanotubes135 6.3.4 Electrochemical impedance spectroscopy (EIS) and rate performance tests of the fabricated TiO2-SnO2 nanotubes 137 6.4 Summary of chapter 6140 7. Summary and outlook 141 7.1 Summary 141 7.2 Outlook 143 Appendix 145 Bibliography 157 List of figures 183 Glossary 191 Publications 193 Curriculum vitae 195 Acknowledgment 199 Declaration 201 / Um die zur Aufrechterhaltung unserer modernen Lebensweise unabdingbaren erneuerbaren Energiequellen effizient nutzen zu können, werden hochentwickelte wiederaufladbare Batterien dringend benötigt. Lithium-Ionenbatterien gelten aufgrund ihrer hohen Energiedichte (sowohl gravimetrisch als auch volumetrisch), ihrer langen Lebensdauer, moderater Produktionskosten und aufgrund der Möglichkeit, vielfältige Konzepte einfach herstellen zu können, als vielversprechend. Dennoch müssen die Elektrodenmaterialien dringend verbessert werden, um den Ansprüchen an zukünftige hochentwickelte Lithium-Ionenbatterien gerecht zu werden. TiO2-basierte Anoden gelten aufgrund ihrer schnellen Lade- und Entladekinetik, ihres umweltfreundlichen Verhaltens und niedriger Kosten als aussichtsreiche Alternativen zu Kohlenstoffen. Durch die geringe Volumenänderung beim Lithiumeinbau (unter 4%) werden außerdem eine hohe strukturelle Stabilität und erhöhte Sicherheit gewährleistet. Die hauptsächlichen Herausforderungen stellen die niedrige ionische und elektrische Leitfähigkeit (≈ 10−12 S m−1) von TiO2 dar. Zusammengefasst liegt das Ziel der vorliegenden Arbeit in der Entwicklung, Optimierung und Herstellung neuartiger Anodenmaterialien für Lithium-Ionenbatterien unter Verwendung stabiler, verfügbarer und umweltfreundlicher Materialien. In dieser Arbeit wurden sowohl zweiphasiges Ti80Co20 und einphasige Ti-Sn-Legierungen (mit verschiedenen Sn-Gehalten zwischen 1 und 10 at-%) zur Herstellung hochgeordneter, vertikal orientierter eindimensionaler Nanoröhren aus gemischten Übergangsmetalloxiden (TiO2–CoO und TiO2–SnO2) mittels anodischer Oxidation in NH4F-haltigen organischen Elektrolyten genutzt. Dabei wurden Abhängigkeiten der Oberflächenmorphologie und der Stromdichte für die Bildung der Nanoröhren von der Kristallstruktur der zugrundeliegenden Legierung beobachtet. Vielfältige Methoden wie REM, EDXS, TEM, XPS und Ramanspektroskopie wurden genutzt, um die Nanoröhren zu charakterisieren. Die Ergebnisse zeigen, dass gemischte TiO2-CoO und TiO2-SnO2 Nanoröhren in den gewählten Spannungsfenstern erfolgreich gebildet werden konnten. Die so hergestellten Nanoröhren sind amorph und in ihren Dimensionen präzise durch die Wahl der Spannung einstellbar. Eine elektrochemische Beurteilung der Nanoröhren erfolgte durch Tests gegen eine Li/Li+-Elektrode bei veschiedenen Stromdichten. Die Resultate zeigen, dass TiO2-CoO-Nanoröhren, welche bei 60 V hergestellt wurden, die höchsten Flächenkapazitäten von ~ 600 µAh cm–2 (d.h. 315 mAh g–1) bei einer Stromdichte von 10 µA cm–2 aufweisen. Bei höheren Stromdichten zeigen TiO2-CoO-Nanoröhren nahezu verdoppelte Lithiuminterkalation und eine Coulomb-Effizienz von 96 % nach 100 Zyklen, verglichen mit weniger effektiven TiO2–Nanoröhren, welche unter identischen Bedingungen hergestellt wurden. Um die elektrochemischen Eigenschaften der TiO2-CoO-Nanoröhren weiter zu verbessern, wurde ein neuer Komposit aus Kohlenstoff-Nanoröhren und TiO2-CoO-Nanoröhren ((CNT)s@TiO2/CoO) durch eine zweistufige Synthese hergestellt. Die Herstellung beinhaltet zunächst die anodische Bildung geordneter TiO2/CoO-Nanoröhren, ausgehend von einer Ti-Co-Legierung, gefolgt von einem horizontalen Kohlenstoff-Nanoröhren-Wachstum auf dem Oxid mittels einer simplen Sprühpyrolyse. Die einzigartige 1D-Struktur einer solchen hybriden Nanostruktur mit eingebundenen CNTs zeigt deutlich erhöhte Flächenkapazitäten und Belastbarkeiten im Vergleich zu Nanoröhren aus TiO2 und TiO2/CoO-Nanoröhren ohne CNTs, die unter identischen Bedingungen getestet wurden. Die Ergebnisse zeigen, dass die CNTs ein hochleitfähiges Netzwerk bilden, welches die Diffusion von Lithium-Ionen und deren Einbau in die TiO2/CoO-Nanoröhren begünstigt und somit hohe Kapazitäten und reproduzierbare hohe Belastbarkeiten bewirkt. Außerdem zeigen die Resultate, dass TiO2-SnO2 Nanoröhren, welche bei 40 V auf einer Ti-Sn-Legierung mit 1 at.% Sn hergestellt wurden, im Mittel eine 1,4-fache Erhöhung der Flächenkapazität und eine exzellente Zyklenstabilität über mehr als 400 Zyklen, verglichen mit unter identischen Konditionen hergestellten und getesteten TiO2-Nanoröhren, zeigen. Die Arbeit ist wie folgt organisiert: Kapitel 1: Allgemeine Einführung, in der die Energienachfrage und die Bedeutung von Lithium-Ionenbatterien in erneuerbaren Energiesystemen und tragbaren Geräten diskutiert wird. Eine kurze Einleitung zu TiO2-basierten Anoden in Lithium-Ionenbatterien und allgemeine Strategien zur Entwicklung von TiO2-Anoden werden ebenfalls gezeigt. Das Ziel der Arbeit und hauptsächliche Aufgaben werden zusammengefasst. Kapitel 2: Das grundlegende Konzept der Lithium-Ionenbatterie mit einem Überblick über ihre Hauptkomponenten wird diskutiert. Dies beinhaltet auch eine kurze Darstellung der Anodenmaterialien und der Kristallstruktur von TiO2-Anoden. Eine detaillierte Übersicht über TiO2-Nanomaterialien für LIB, welche Herstellungsmethoden und die elektrochemische Performance verschiedener TiO2-Nanostrukturen (Nanopartikel, Nanostäbe, Nanonadeln, Nanodrähte und Nanoröhren) und poröser TiO2-Nanostrukturen beinhaltet, wird gezeigt. Die Bildung von TiO2-Nanoröhren durch anodische Oxidation und der Wachstumsmechanismus werden hervorgehoben. Faktoren, welche die elektrochemische Performance anodisch hergestellter TiO2-Materialien, TiO2/Kohlenstoff-Komposite und TiO2 als Gemisch mit anderen Metalloxiden beeinflussen, werden diskutiert. Kapitel 3: In diesem Kapitel werden die Synthese von TiO2-CoO, (CNTs)@TiO2/CoO und TiO2-SnO2-Nanoröhren, die Charakterisierungsmethoden, elektrochemische Grundlagen und Konzepte diskutiert. Kapitel 4: Detaillierte Resultate und die Diskussion der Synthese, Charakterisierung und der elektrochemischen Performance der TiO2-CoO- Nanoröhren und der ternären (CNTs)@TiO2/CoO-Nanoröhrenkomposite werden gezeigt. Kapitel 5: Detaillierte Resultate und die Diskussion der Synthese, Charakterisierung und der elektrochemischen Performance der der ternären (CNTs)@TiO2/CoO-Nanoröhrenkomposite werden diskutiert. Kapitel 6: Detaillierte Resultate und die Diskussion der Synthese, Charakterisierung und der elektrochemischen Performance von TiO2-SnO2-Nanoröhren werden gezeigt. Kapitel 7: Eine Zusammenfassung der Resultate, die in dieser Arbeit gezeigt wurden und Schlussfolgerungen, sowie interessante Ansatzpunkte für zukünftige Arbeiten werden präsentiert.:1. Introduction and scope of the thesis 15 1.1 Batteries for renewable energy systems and portable devices 15 1.2 TiO2-based anodes in lithium ion batteries 17 1.3 Strategies for developing TiO2 anodes 17 1.4 Scope of work 19 1.5 Tasks 20 2. Basics and literature review 23 2.1 Lithium ion battery system 23 2.2 Anode materials 26 2.3 Crystal structure of TiO2 28 2.4 TiO2 nanomaterials for LIBs 30 2.4.1 TiO2 nanoparticles 30 2.4.2 TiO2 nanoneedles 36 2.4.3 Porous TiO2 nanostructures 39 2.5 TiO2 nanotubes prepared by electrochemical anodization 44 2.6 The mechanism of nanotube formation by anodic oxidation 47 2.7 Anodically fabricated TiO2 nanotubes as anodes in LIBs 49 2.7.1 Anodization electrolyte 50 2.7.2 Amorphous and crystalline TiO2 anodes 50 2.7.3 Influence of the nnealing atmospheres of TiO2 52 2.7.4 Free-standing TiO2 nanotube membranes 54 2.7.5 TiO2 nanotubes/carbon composites 55 2.7.6 Mixed oxide nanotubes 55 3. Materials and methods 61 3.1 Methodology 61 3.1.1 Synthesis of TiO2-CoO and TiO2 nanotubes 61 3.1.2 Synthesis of CNTs@TiO2-CoO NT composite 62 3.1.3 Synthesis of TiO2-SnO2 and TiO2 nanotubes 63 3.2 Characterization techniques 64 3.2.1 X-ray diffraction (XRD 64 3.2.2 Scanning electron microscopy (SEM 65 3.2.3 Energy-dispersive X-ray spectroscopy (EDXS 65 3.2.4 Transmission electron spectroscopy (TEM 66 3.2.5 X-ray photoelectron spectroscopy (XPS 66 3.2.6 Raman spectroscopy 67 3.2.7 Nitrogen sorption isotherms 67 3.2.8 Inductively coupled plasma optical emission spectroscopy (ICP–OES 68 3.3 Basic definitions and electrochemical concepts 68 3.3.1 Faraday’s law 68 3.3.2 Capacity 69 3.3.3 Discharging 69 3.3.4 Charging 69 3.4 Electrochemical techniques 70 3.4.1 Cyclic voltammetry 70 3.4.2 Galvanostatic discharging/charging cycling 70 3.4.3 Electrochemical impedance spectroscopy (EIS 71 3.5 Electrode preparation and measurement conditions 71 3.5.1 TiO2-CoO nanotube electrodes 71 3.5.2 CNTs@TiO2 and CNTs@TiO2/CoO NTs electrodes 72 3.5.3 TiO2-SnO2 nanotube electrodes 73 4. TiO2-CoO as anodes in lithium ion batteries 75 4.1 Introduction 76 4.2 Characterization 76 4.2.1 Phase identification of as cast Ti-Co alloy 76 4.2.2 Time-current density relationship 79 4.2.3 Morphology of the fabricated TiO2-CoO nanotubes 81 4.2.4 Phase identification of the fabricated TiO2-CoO nanotubes 85 4.2.5 Specific surface area of the fabricated TiO2-CoO nanotubes 87 4.2.6 Chemical state in the grown TiO2-CoO nanotubes 89 4.2.7 Raman spectroscopy of TiO2-CoO nanotubes 91 4.3 Electrochemical testing of TiO2-CoO electrodes 92 4.3.1 Cyclic voltammetry 92 4.3.2 Galvanostatic cycling with potential limitation 93 4.3.3 Electrochemical impedance spectroscopy (EIS) 97 4.3.4 Structural stability TiO2-CoO anodes over cycling 98 4.4 Summary of chapter 4 99 5. Ternary CNTs@TiO2-CoO nanotube composites: improved anode materials for LIBs 101 5.1 Introduction 102 5.2 Characterization 103 5.2.1 Morphology and Raman analysis of the fabricated CNTs@TiO2-CoO NTs 103 5.2.2 XRD analysis of the fabricated TiO2-CoO NTs before and after CNTs coating 106 5.3 Electrochemical properties 107 5.3.1 Cyclic voltammetry 107 5.3.2 Galvanostatic cycling with potential limitation 109 5.3.2 Electrochemical impedance spectroscopy (EIS 112 5.4 Summary of chapter 5 114 6. TiO2-SnO2 nanotubes as anodes in lithium ion batteries 115 6.1 Introduction 116 6.2 Characterization 117 6.2.1 ICP-OES analysis of the as-cast Ti-Sn alloys 117 6.2.2 SEM analysis of the as-cast Ti-Sn alloys 117 6.2.3 Phase analysis of the as-cast Ti-Sn alloys 118 6.2.4 Morphology of the fabricated TiO2-SnO2 nanotubes 121 6.2.5 XPS investigation of the grown TiO2-SnO2 nanotubes 127 6.2.6 Raman spectroscopy of TiO2-SnO2 nanotubes 129 6.3 Electrochemical Testing 130 6.3.1 Cyclic voltammetry 130 6.3.2 Galvanostatic cycling with potential limitation132 6.3.3 Specific surface area of the fabricated TiO2-SnO2 nanotubes135 6.3.4 Electrochemical impedance spectroscopy (EIS) and rate performance tests of the fabricated TiO2-SnO2 nanotubes 137 6.4 Summary of chapter 6140 7. Summary and outlook 141 7.1 Summary 141 7.2 Outlook 143 Appendix 145 Bibliography 157 List of figures 183 Glossary 191 Publications 193 Curriculum vitae 195 Acknowledgment 199 Declaration 201

Gegenstand dieser Arbeit war: - die Optimierung und Modellierung des CVD-Wachstums von Fe-gefüllten CNTs aus Ferrocen, - die Auswahl geeigneter Schichtsysteme für das orientierte Wachstum Fe-gefüllter CNTs, - eine umfassende Charakterisierung der Nanostrukturen und deren Bezug zu den Wachstumsparametern, - die Formulierung eines allgemeingültigen Wachstumsmodels. Es wurde eine Anlage zur thermisch induzierten chemischen Gasphasenabscheidung bei Atmosphärendruck verwendet. Im Mittelpunkt der Syntheseexperimente standen Fe-gefüllte MWCNTs. Als Precursoren dienten Ferrocen und Cyclopentadienyl-eisen-dicarbonyl-dimer. Für die Darstellung von CNT-Ensembles mit idealerweise paralleler Ausrichtung der Einzelindividuen kamen thermisch oxidierte Si-Substrate (Schichtdicke des Oxid: 1 µm) zum Einsatz. Das Wachstum der CNTs wurde überwiegend als cokatalysierter Prozess durchgeführt, d.h. neben dem Fe aus dem Precursor dienten dünne Metallschichten (Fe, Co, oder Ni, Schichtdicke ≤ 10 nm), die auf den Substraten deponiert waren, als Katalysatorreservoir. Zunächst ging es darum den CVD-Prozess hinsichtlich tubularer CNTs mit senkrechter Vorzugsorientierung zur Substratoberfläche, einer guten Kristallinität der Hülle, sowie einem hohen Füllungsanteil der ferromagnetischen α-Fe-Phase zu überprüfen. Generell ließ sich die Abscheidung gefüllter CNTs für mittlere Substrattemperaturen im Bereich von 1013 – 1200 K durchführen. Die optimale Wachstumstemperatur lag bei ≈ 1103 K. Mit den beiden Precursoren - Ferrocen und Cyclopentadienyl-eisen-dicarbonyl-dimer ließen sich Fe-gefüllte CNTs in guter Qualität darstellen. Letztere Verbindung verringerte die Abscheidung von amorphem Kohlenstoff auf der CNT-Oberfläche, barg allerdings die Nachteile einer Sauerstoffkontamination und höherer Verdampfungs-temperaturen in sich. Aus der Vielzahl von Experimenten konnte abgeleitet werden, dass die Haupteinflussgrößen für den Innen- und Außendurchmesser der CNTs die Katalysatorschicht auf dem Substrat, die Synthesetemperatur und der Precursormassenstrom sind. Höhere Temperaturen und/oder ein Mehrangebot an Precursor äußerten sich stets in größeren Durchmessern. Zusätzliche Metallschichten auf den oxidierten Si-Substraten erlaubten eine gezielte Durchmesservariation. Beispielsweise zeigte sich an Substraten mit 2 nm Fe bzw. 2 nm Ni, dass sich die mittleren CNT-Außendurchmesser gegenüber dem auf unbeschichteten Substraten (34 nm) zu 44 nm bzw. 30 nm verändern lässt. Mit Al-Zwischenschichten konnten sogar Durchschnittswerte für den CNT-Außendurchmesser von 18 nm erzielt werden. Durch Röntgenstrukturuntersuchungen und Mössbaueranalysen an CNT-Ensembles wurde α-Fe als Hauptbestandteil der Füllung identifiziert. Auf den hohen Anteilen der α-Fe-Phase beruhte auch das magnetische Verhalten der Nanodrähte. Ein Beleg für die Schlüsselrolle des Systems Fe-C während des Wachstumsprozesses war die Phase Fe3C, mit orthorhombischer Struktur. Weniger häufig ließ sich γ-Fe nachweisen. Darüber hinaus konnten sämtliche CNT-Füllungen mittels SAED und HRTEM als Einkristalle charakterisiert werden. Die innerhalb der CNTs eingeschlossenen Fe- oder Fe-C-Nanodrähte wiesen außerdem keine kristallographische(n) Vorzugsrichtung(en) gegenüber den CNT-Wänden auf. Anhand der experimentellen Befunde war es möglich ein phänomenologisches Wachstumsmodell vorzuschlagen, welche eine Erweiterung des VLS-Mechanismus darstellt. Das in der vorliegenden Arbeit vorgestellte Modell greift das base-growth-Konzept auf und favorisiert die Akkumulation von Katalysatormaterial über die geöffneten Enden der CNTs. Eine genauere kinetische und thermodynamische Beschreibung war aufgrund der im Nanometerbereich nur schwer zugänglichen Stoffdaten nicht möglich.

The excellent electrical and mechanical properties of carbon nanotubes (CNTs) provide interesting opportunities to realize new types of strain gauges. However, there are still challenges for the further development of CNT film strain gauges, for instance the lack of design rules, the homogeneity, stability and reproducibility of CNT films. This thesis aims to address these issues from two sides: simulation and experiment. Monte Carlo simulations show that both the sheet resistance and gauge factor of CNT films are determined essentially by the two-dimensional exclude area of CNTs. It was shown, for the first time, that the variation of the CNT film gauge factor follows the percolation scaling law. The sheet resistance and gauge factor both have a power-law divergence when approaching the percolation threshold. The standard deviation of film resistances, however, also increases correspondingly. These findings of simulations provide a general guide to the tailoring of material property of CNT films in strain sensing applications: a compromise should be made between the reproducibility, conductivity and sensitivity of CNT films depending on application purposes. From the experimental side, the processing parameters for the preparation of CNT dispersions were first investigated and optimized. The reproducibility of the film resistance is significantly improved by selecting a suitable sonication time. In strain measurements it was found that for most CNT films the film resistance responses nonlinearly to the applied strain. The dependence of the film resistance on the strain can be roughly divided into two regions with nearly linear behavior respectively. The gauge factor varies with the quality of CNTs and the depositing method. A gauge factor up to 8 was achieved in the high strain region. The nonlinear response behavior was found in simulations when the CNT waviness is properly taken into account. To achieve a high gauge factor and simultaneously retain the high conductivity and reproducibility, good-quality MWCNTs were integrated in polyethylene oxide (PEO). A high gauge factor up to 10 was achieved for the composite film with CNT weight fraction of 2.5%. The resistance and gauge factor can be tuned by changing the MWCNT weight fraction with respect to PEO. A careful comparison of simulation and experiment results show that a good qualitative agreement can be achieved between them in many respects.

Background: In addition to conventional chemotherapeutics, nucleic acid-based therapeutics like antisense oligodeoxynucleotides (AS-ODN) represent a novel approach for the treatment of bladder cancer (BCa). An efcient delivery of AS-ODN to the urothelium and then into cancer cells might be achieved by the local application of multiwalled carbon nanotubes (MWCNT). In the present study, pristine MWCNT and MWCNT functionalized with hydrophilic moieties were synthesized and then investigated regarding their physicochemical characteristics, dispersibility, biocompatibility, cellular uptake and mucoadhesive properties. Finally, their binding capacity for AS-ODN via hybridization to carrier strand oligodeoxynucleotides (CS-ODN), which were either non-covalently adsorbed or covalently bound to the diferent MWCNT types, was evaluated. Results: Pristine MWCNT were successfully functionalized with hydrophilic moieties (MWCNT-OH, -COOH, -NH2, -SH), which led to an improved dispersibility and an enhanced dispersion stability. A viability assay revealed that MWCNTOH, MWCNT-NH2 and MWCNT-SH were most biocompatible. All MWCNT were internalized by BCa cells, whereupon the highest uptake was observed for MWCNT-OH with 40% of the cells showing an engulfment. Furthermore, all types of MWCNT could adhere to the urothelium of explanted mouse bladders, but the amount of the covered urothelial area was with 2–7% rather low. As indicated by fuorescence measurements, it was possible to attach CS-ODN by adsorption and covalent binding to functionalized MWCNT. Adsorption of CS-ODN to pristine MWCNT, MWCNT-COOH and MWCNT-NH2 as well as covalent coupling to MWCNT-NH2 and MWCNT-SH resulted in the best binding capacity and stability. Subsequently, therapeutic AS-ODN could be hybridized to and reversibly released from the CS-ODN coupled via both strategies to the functionalized MWCNT. The release of AS-ODN at experimental conditions (80 °C, bufer) was most efective from CS-ODN adsorbed to MWCNT-OH and MWCNT-NH2 as well as from CS-ODN covalently attached to MWCNT-COOH, MWCNT-NH2 and MWCNT-SH. Furthermore, we could exemplarily demonstrate that AS-ODN could be released following hybridization to CS-ODN adsorbed to MWCNT-OH at physiological settings (37 °C, urine). Conclusions: In conclusion, functionalized MWCNT might be used as nanotransporters in antisense therapy for the local treatment of BCa.

Downscaling of the contact length Lc of a side-contacted carbon nanotube field-effect transistor (CNTFET) is challenging because of the rapidly increasing contact resistance as Lc falls below 20–50 nm. If in agreement with existing experimental results, theoretical work might answer the question, which metals yield the lowest CNT–metal contact resistance and what physical mechanisms govern the geometry dependence of the contact resistance. However, at the scale of 10 nm, parameter-free models of electron transport become computationally prohibitively expensive. In our work we used a dedicated combination of the Green function formalism and density functional theory to perform an overall ab initio simulation of extended CNT–metal contacts of an arbitrary length (including infinite), a previously not achievable level of simulations. We provide a systematic and comprehensive discussion of metal–CNT contact properties as a function of the metal type and the contact length. We have found and been able to explain very uncommon relations between chemical, physical and electrical properties observed in CNT–metal contacts. The calculated electrical characteristics are in reasonable quantitative agreement and exhibit similar trends as the latest experimental data in terms of: (i) contact resistance for Lc = ∞, (ii) scaling of contact resistance Rc(Lc); (iii) metal-defined polarity of a CNTFET. Our results can guide technology development and contact material selection for downscaling the length of side-contacts below 10 nm.

Background: In addition to conventional chemotherapeutics, nucleic acid-based therapeutics like antisense oligodeoxynucleotides (AS-ODN) represent a novel approach for the treatment of bladder cancer (BCa). An efcient delivery of AS-ODN to the urothelium and then into cancer cells might be achieved by the local application of multiwalled carbon nanotubes (MWCNT). In the present study, pristine MWCNT and MWCNT functionalized with hydrophilic moieties were synthesized and then investigated regarding their physicochemical characteristics, dispersibility, biocompatibility, cellular uptake and mucoadhesive properties. Finally, their binding capacity for AS-ODN via hybridization to carrier strand oligodeoxynucleotides (CS-ODN), which were either non-covalently adsorbed or covalently bound to the diferent MWCNT types, was evaluated. Results: Pristine MWCNT were successfully functionalized with hydrophilic moieties (MWCNT-OH, -COOH, -NH2, -SH), which led to an improved dispersibility and an enhanced dispersion stability. A viability assay revealed that MWCNTOH, MWCNT-NH2 and MWCNT-SH were most biocompatible. All MWCNT were internalized by BCa cells, whereupon the highest uptake was observed for MWCNT-OH with 40% of the cells showing an engulfment. Furthermore, all types of MWCNT could adhere to the urothelium of explanted mouse bladders, but the amount of the covered urothelial area was with 2–7% rather low. As indicated by fuorescence measurements, it was possible to attach CS-ODN by adsorption and covalent binding to functionalized MWCNT. Adsorption of CS-ODN to pristine MWCNT, MWCNT-COOH and MWCNT-NH2 as well as covalent coupling to MWCNT-NH2 and MWCNT-SH resulted in the best binding capacity and stability. Subsequently, therapeutic AS-ODN could be hybridized to and reversibly released from the CS-ODN coupled via both strategies to the functionalized MWCNT. The release of AS-ODN at experimental conditions (80 °C, bufer) was most efective from CS-ODN adsorbed to MWCNT-OH and MWCNT-NH2 as well as from CS-ODN covalently attached to MWCNT-COOH, MWCNT-NH2 and MWCNT-SH. Furthermore, we could exemplarily demonstrate that AS-ODN could be released following hybridization to CS-ODN adsorbed to MWCNT-OH at physiological settings (37 °C, urine). Conclusions: In conclusion, functionalized MWCNT might be used as nanotransporters in antisense therapy for the local treatment of BCa.

Der elektrochemische Nachweis von polycyclischen aromatischen Kohlenwasserstoffen (PAK), zu denen Anthracen und Pyren gehören, bietet eine kostengünstigere, einfachere und schnellere alternative Analysemethode als herkömmliche Methoden wie GC und HPLC. Im Vergleich zu diesen Methoden weist er jedoch nach wie vor eine geringere Empfindlichkeit auf. Einige neuere Bemühungen haben an einem Mangel an Selektivität gelitten, entweder aufgrund der elektrodenmodifizierende Schicht mit hohem Hintergrundstrom oder der Wahl eines Leitelektrolyten, der die Detektion stört. Bei dem vorliegenden Versuch wurden Pt-Pd-Nanopartikel (NPs) und MWCNTs verwendet, um eine Glaskohlenstoffelektrode (GCE) zum empfindlichen Nachweis von Anthracen und Pyren zu modifizieren. Die verwendeten NPs wurden unter Verwendung eines wässrigen Extrakts aus Blättern von E. grandis synthetisiert, einem nachhaltigen und umweltfreundlichen Syntheseweg. Durch einer Optimierung der Mengen an Pt- und Pd-Ionen im Vorläufer wurden NPs mit einer durchschnittlichen Größe von 10 nm erhalten, wobei ein Verhältnis von 1 Pt-Ion zu 3 Pd-Ionen die kleinste Größe ergab. Durch XPS wurde festgestellt, dass die Zusammensetzung der NPs von Pt2+ und Pd0 dominiert wird. Die XRD-Analyse ergab eine kristalline Natur mit einer flächenzentriert-kubischen Struktur. Die Pt-Pd-NPs bewirkten eine Erhöhung des Spitzenstroms um 94 % für Pyren, führten jedoch zu niedrigeren Spitzenströmen für Anthracen. Wenn die NPs weiter mit MWCNTs zum Nachweis von Pyren verwendet wurden, wurde eine Spitzenstromsteigerung von etwa 200 % mit einem Dynamikbereich von 66–130 μM und einer LOD von 23 μM beobachtet. Es wurde auch festgestellt, dass der elektrochemische Prozess gemischt diffusions- und adsorptionskontrolliert ist. Aufgrund des Einflusses der Adsorption musste die Akkumulationszeit im Analyseverfahren berücksichtigt werden. MWCNTs wurden beim Nachweis von Anthracen angewendet, wobei eine Erhöhung des Spitzenstroms um 74 % und eine Verringerung des Überpotentials um 53 mV beobachtet wurde. Ein dynamischer Bereich von 50–146 µM und eine LOD von 42 µM wurden bestimmt. Niedrigere Konzentrationen wurden mit einer Leitungswasserprobe gemessen, die mit Anthracen versetzt war, hauptsächlich wegen der geringen Löslichkeit von PAK in Wasser. Der Einfluss der Säurebehandlung von MWCNTs auf den Nachweis von Anthracen und Pyren wurde ebenfalls untersucht. Die Säurebehandlung ermöglichte das Laden von mehr Material ohne Ablösen der modifizierten Schicht, was zu höheren Spitzenstromverbesserungen für Anthracen (533 %) und Pyren (448 %) führte. Für Anthracen und Pyren wurden LODs von 40 µM bzw. 14 µM bestimmt, die nur geringfügig niedriger sind als die bei MWCNTs/GCE und Pt-PdNPs/MWCNTs/GCE beobachteten Werte. Der Nachweis von Anthracen wurde durch die Anwesenheit von Pyren und gewöhnlichen Ionen gestört, während die LOD für Pyren in Gegenwart von Anthracen 18 µM betrug. Es wurde festgestellt, dass die auf MWCNTs basierende elektrochemische Nachweisplattform eine bessere Reaktion auf Pyren aufweist.:Bibliographische Beschreibung i Referat i Abstract iii Zeitraum, Ort der Durchführung v Acknowledgements vi Dedication vii Table of Contents viii List of Abbreviations and Symbols xii Chapter 1 1 Introduction 1 1.1 Overview 1 1.2 Polycyclic Aromatic Hydrocarbons 2 1.3 Electrochemical Sensors 7 1.3.1 General Response Curve for Chemical Sensors 10 1.4 Carbon Nanotubes 13 1.5 Use of Nanoparticles in Electrochemical Detection 18 1.6 Green Synthesis of Nanoparticles and The Rationale Behind It 21 1.7 Previous Efforts in the Electrochemical Detection of Polycyclic Aromatic Hydrocarbons 24 1.8 Objectives of the Study 26 Chapter 2 28 Experimental 28 2.1 Chemicals 28 2.1.1 Preparation of Anthracene and Pyrene Solutions 28 2.2 Collection and Preparation of Plant Material 29 2.3 Synthesis and Preparation of Materials 29 2.3.1 Synthesis of Metallic Nanoparticles 29 2.3.2 Acid Treatment of Multi-walled Carbon Nanotubes 30 2.4 Characterization of the Nanomaterials 30 2.4.1 UV-Vis Spectrophotometry 30 2.4.2 SEM/EDX and TEM Analysis 30 2.4.3 Powder X-ray Diffractometry 31 2.4.4 XPS Analysis 31 2.5 Electrochemical Measurements 31 2.5.1 Preparation of the Bare and Modified Glassy Carbon Electrode 32 2.5.2 Characterization of the Bare and the Modified Glassy Carbon Electrode 33 2.5.3 Electrocatalytic Oxidation of Anthracene on the Bare and Modified GCEs 33 2.5.4 Electrocatalytic Oxidation of Pyrene on the Bare and Modified GCEs 34 Chapter 3 35 Synthesis, Characterization, and Application of Pt-Pd Nanoparticles in the Electrochemical Detection of Anthracene and Pyrene 35 3.1 Test for Flavonoids and Polyphenols in the E. grandis Leaves’ Extract 35 3.2 Synthesis of Nanoparticles 35 3.3 Characterization of Nanoparticles 37 3.3.1 TEM Analysis 37 3.3.2 SEM Analysis 40 3.3.3 EDX Analysis 41 3.3.4 Powder X-Ray Diffraction Analysis 45 3.3.5 XPS Analysis of Pt-Pd Particles 46 3.4 Impedance Measurements of the Bare and Nanoparticle-modified Glassy Carbon Electrode 49 3.5 Electrochemical Oxidation of Anthracene and Pyrene at the Bare and Nanoparticles-modified Glassy Carbon Electrode 51 3.6 Conclusions 53 Chapter 4 55 Pt-PdNPs/MWCNTs-Modified GCE for the Detection of Pyrene 55 4.1 Impedance Measurement with Pt-PdNPs/MWCNTs/GCE 55 4.2 Electrochemical Oxidation of Pyrene on Pt-PdNPs/MWCNTs/GCE 56 4.3 Analysis of Varying Concentrations of Pyrene on Pt-PdNPs/MWCNTs/GCE 59 4.4 Selectivity 61 4.5 Conclusions 62 Chapter 5 64 Exploring Multi-walled Carbon Nanotubes for the Detection of Anthracene 64 5.1 Impedance Measurement of MWCNT-Modified Glassy Carbon Electrode 64 5.2 Electrochemical Oxidation of Anthracene on MWCNT/GCE 65 5.3 Analysis of Varying Concentrations of Anthracene Using MWCNTs/GCE 68 5.4 Detection of Anthracene in Tap Water 71 5.5 Conclusions 72 Chapter 6 73 Effect of Acid Treatment of Multi-walled Carbon Nanotubes on the Detection of Anthracene and Pyrene 73 6.1 Characterization of fMWCNTs 74 6.2 Electrochemical Oxidation of Anthracene on fMWCNTs/GCE 75 6.2.1 Effect of Change in Scan Rate 76 6.2.2 Effect of Accumulation Time 77 6.2.3 Application of fMWCNTs/GCE in the Analysis of Varying Concentrations of Anthracene 77 6.3 Electrochemical Oxidation of Pyrene on fMWCNTs/GCE 79 6.4 Selectivity 82 6.4.1 Co-detection of Anthracene and Pyrene at fMWCNTs/GCE 83 6.4.2 Interference of Some Common Ions 85 6.5 Detection of Pyrene in Tapwater using fMWCNTs/GCE 86 6.6 Conclusions 87 Chapter 7 88 Summary and Outlook 88 7.1 Summary 88 7.2 Outlook 90 References 92 Selbständigkeitserklärung 101 Curriculum Vitae 102 / Electrochemical detection of polycyclic aromatic hydrocarbons (PAHs), which include anthracene and pyrene, offers a cheaper, simpler, and faster alternative method of analysis than conventional methods like GC and HPLC. However, it still is not as sensitive as these methods. Some recent efforts have suffered from lack of selectivity, either from the electrode modifying layer having high background current or from the choice of supporting electrolyte interfering with the detection. In this work, Pt-Pd nanoparticles (NPs) and MWCNTs were used to modify a glassy carbon electrode (GCE) for sensitive detection of anthracene and pyrene. The NPs used were synthesized using an aqueous extract from E. grandis leaves, a sustainable and environmentally friendly synthetic route. NPs with an average size of 10 nm were obtained by optimizing the amounts of Pt- and Pd-ions in the precursor, with a ratio of 1:3 Pt to Pd-ions producing the smallest size. Through XPS, the composition of the NPs was established to be dominated by Pt2+ and Pd0. XRD analysis revealed a crystalline nature with a face-centered cubic structure. The Pt-Pd NPs produced 94 % enhancement in the peak current for pyrene but resulted in lower peak currents for anthracene. When the NPs were further used with MWCNTs for the detection of pyrene, about 200% peak current enhancement was observed with a dynamic range of 66–130 µM and LOD of 23 µM. The electrochemical process was also established to be mixed diffusion- and adsorption-controlled. The influence of adsorption necessitated the employment of accumulation time in the analysis procedure. MWCNTs were applied in the detection of anthracene and a 74 % peak current enhancement and a reduction in the overpotential by 53 mV were observed. A dynamic range of 50–146 µM and LOD of 42 µM were determined. Lower concentrations were recovered from a tap water sample that was spiked with anthracene, mainly because of the low solubility of PAHs in water. Effect of acid treatment of MWCNTs on the detection of anthracene and pyrene was also investigated. Acid treatment allowed for loading of more material without peeling off of the modified layer which resulted in higher peak current enhancements for anthracene (533%) and pyrene (448%). LODs of 40 µM and 14 µM were determined for anthracene and pyrene respectively, which are only slightly lower than what was observed at MWCNTs/GCE and Pt-PdNPs/MWCNTs/GCE. Detection of anthracene was interfered by the presence of pyrene and common ions, while the LOD for pyrene in the presence of anthracene was 18 µM. The MWCNTs based electrochemical detection platform was found to have a better response towards pyrene.:Bibliographische Beschreibung i Referat i Abstract iii Zeitraum, Ort der Durchführung v Acknowledgements vi Dedication vii Table of Contents viii List of Abbreviations and Symbols xii Chapter 1 1 Introduction 1 1.1 Overview 1 1.2 Polycyclic Aromatic Hydrocarbons 2 1.3 Electrochemical Sensors 7 1.3.1 General Response Curve for Chemical Sensors 10 1.4 Carbon Nanotubes 13 1.5 Use of Nanoparticles in Electrochemical Detection 18 1.6 Green Synthesis of Nanoparticles and The Rationale Behind It 21 1.7 Previous Efforts in the Electrochemical Detection of Polycyclic Aromatic Hydrocarbons 24 1.8 Objectives of the Study 26 Chapter 2 28 Experimental 28 2.1 Chemicals 28 2.1.1 Preparation of Anthracene and Pyrene Solutions 28 2.2 Collection and Preparation of Plant Material 29 2.3 Synthesis and Preparation of Materials 29 2.3.1 Synthesis of Metallic Nanoparticles 29 2.3.2 Acid Treatment of Multi-walled Carbon Nanotubes 30 2.4 Characterization of the Nanomaterials 30 2.4.1 UV-Vis Spectrophotometry 30 2.4.2 SEM/EDX and TEM Analysis 30 2.4.3 Powder X-ray Diffractometry 31 2.4.4 XPS Analysis 31 2.5 Electrochemical Measurements 31 2.5.1 Preparation of the Bare and Modified Glassy Carbon Electrode 32 2.5.2 Characterization of the Bare and the Modified Glassy Carbon Electrode 33 2.5.3 Electrocatalytic Oxidation of Anthracene on the Bare and Modified GCEs 33 2.5.4 Electrocatalytic Oxidation of Pyrene on the Bare and Modified GCEs 34 Chapter 3 35 Synthesis, Characterization, and Application of Pt-Pd Nanoparticles in the Electrochemical Detection of Anthracene and Pyrene 35 3.1 Test for Flavonoids and Polyphenols in the E. grandis Leaves’ Extract 35 3.2 Synthesis of Nanoparticles 35 3.3 Characterization of Nanoparticles 37 3.3.1 TEM Analysis 37 3.3.2 SEM Analysis 40 3.3.3 EDX Analysis 41 3.3.4 Powder X-Ray Diffraction Analysis 45 3.3.5 XPS Analysis of Pt-Pd Particles 46 3.4 Impedance Measurements of the Bare and Nanoparticle-modified Glassy Carbon Electrode 49 3.5 Electrochemical Oxidation of Anthracene and Pyrene at the Bare and Nanoparticles-modified Glassy Carbon Electrode 51 3.6 Conclusions 53 Chapter 4 55 Pt-PdNPs/MWCNTs-Modified GCE for the Detection of Pyrene 55 4.1 Impedance Measurement with Pt-PdNPs/MWCNTs/GCE 55 4.2 Electrochemical Oxidation of Pyrene on Pt-PdNPs/MWCNTs/GCE 56 4.3 Analysis of Varying Concentrations of Pyrene on Pt-PdNPs/MWCNTs/GCE 59 4.4 Selectivity 61 4.5 Conclusions 62 Chapter 5 64 Exploring Multi-walled Carbon Nanotubes for the Detection of Anthracene 64 5.1 Impedance Measurement of MWCNT-Modified Glassy Carbon Electrode 64 5.2 Electrochemical Oxidation of Anthracene on MWCNT/GCE 65 5.3 Analysis of Varying Concentrations of Anthracene Using MWCNTs/GCE 68 5.4 Detection of Anthracene in Tap Water 71 5.5 Conclusions 72 Chapter 6 73 Effect of Acid Treatment of Multi-walled Carbon Nanotubes on the Detection of Anthracene and Pyrene 73 6.1 Characterization of fMWCNTs 74 6.2 Electrochemical Oxidation of Anthracene on fMWCNTs/GCE 75 6.2.1 Effect of Change in Scan Rate 76 6.2.2 Effect of Accumulation Time 77 6.2.3 Application of fMWCNTs/GCE in the Analysis of Varying Concentrations of Anthracene 77 6.3 Electrochemical Oxidation of Pyrene on fMWCNTs/GCE 79 6.4 Selectivity 82 6.4.1 Co-detection of Anthracene and Pyrene at fMWCNTs/GCE 83 6.4.2 Interference of Some Common Ions 85 6.5 Detection of Pyrene in Tapwater using fMWCNTs/GCE 86 6.6 Conclusions 87 Chapter 7 88 Summary and Outlook 88 7.1 Summary 88 7.2 Outlook 90 References 92 Selbständigkeitserklärung 101 Curriculum Vitae 102

The excellent electrical and mechanical properties of carbon nanotubes (CNTs) provide interesting opportunities to realize new types of strain gauges. However, there are still challenges for the further development of CNT film strain gauges, for instance the lack of design rules, the homogeneity, stability and reproducibility of CNT films. This thesis aims to address these issues from two sides: simulation and experiment. Monte Carlo simulations show that both the sheet resistance and gauge factor of CNT films are determined essentially by the two-dimensional exclude area of CNTs. It was shown, for the first time, that the variation of the CNT film gauge factor follows the percolation scaling law. The sheet resistance and gauge factor both have a power-law divergence when approaching the percolation threshold. The standard deviation of film resistances, however, also increases correspondingly. These findings of simulations provide a general guide to the tailoring of material property of CNT films in strain sensing applications: a compromise should be made between the reproducibility, conductivity and sensitivity of CNT films depending on application purposes. From the experimental side, the processing parameters for the preparation of CNT dispersions were first investigated and optimized. The reproducibility of the film resistance is significantly improved by selecting a suitable sonication time. In strain measurements it was found that for most CNT films the film resistance responses nonlinearly to the applied strain. The dependence of the film resistance on the strain can be roughly divided into two regions with nearly linear behavior respectively. The gauge factor varies with the quality of CNTs and the depositing method. A gauge factor up to 8 was achieved in the high strain region. The nonlinear response behavior was found in simulations when the CNT waviness is properly taken into account. To achieve a high gauge factor and simultaneously retain the high conductivity and reproducibility, good-quality MWCNTs were integrated in polyethylene oxide (PEO). A high gauge factor up to 10 was achieved for the composite film with CNT weight fraction of 2.5%. The resistance and gauge factor can be tuned by changing the MWCNT weight fraction with respect to PEO. A careful comparison of simulation and experiment results show that a good qualitative agreement can be achieved between them in many respects.

Carbon nanotubes (CNTs) have attracted great attentions in the field of electronics, sensors, healthcare, and energy conversion. Such emerging applications have driven the carbon nanotube research in a rapid fashion. Indeed, the structure control over CNTs has inspired an intensive research vortex due to the high promises in electronic and optical device applications. Here, this in-depth review is anticipated to provide insights into the controllable synthesis and applications of high-quality CNTs. First, the general synthesis and post-purification of CNTs are briefly discussed. Then, the state-of-the-art electronic device applications are discussed, including field-effect transistors, gas sensors, DNA biosensors, and pressure gauges. Besides, the optical sensors are delivered based on the photoluminescence. In addition, energy applications of CNTs are discussed such as thermoelectric energy generators. Eventually, future opportunities are proposed for the Internet of Things (IoT) oriented sensors, data processing, and artificial intelligence

Miniaturization has become a driving force in different areas of technology including microelectronics, sensoric- and bio-technologies and in fundamental science. Because of the well-known limitations of conventional lithographic methods, newly emerging bottom-up approach, utilizing self-assembly of various nanoobjects including single polymer molecules and carbon nanotubes constitutes a very promising alternative for fabrication of ultimately small devices. Carbon nanotubes are attractive materials for nanotechnology and hold much promise to revolutionize fundamental science in a investigation of phenomena, associated with the nanometer–sized objects.It was found in this work that grafted chains of poly(2-vinylpyridine) form a shell covering the carbon nanotubes that makes them dispersible in organic solvents and in acidic water (CNTs-g-P2VP).The positively charged poly(2-vinylpyridine) shell is responsible for the selective deposition of carbon nanotubes onto oppositely charged surfaces. It was established that the deposition CNTs-g-P2VP from aqueous dispersions at low pH is an effective method to prepare ultra-thin films with a tunable density of carbon nanotubes.It was shown that poly(2-vinylpyridine) grafted to carbon nanotubes is a universal support for the immobilization of various nanoclusters at the carbon nanotube's surface. Prussian Blue nanoparticles were selectively attached to the surface of CNTs-g-P2VP.Conducting polymer nanowires are another very promising kind of nanomaterials that could be also suitable for applications in nanodevices and nanosensors. In this work was developed a simple method to control the conformation and orientation of single adsorbed polyelectrolyte molecules by co-deposition with octylamine. A simple chemical route to conductive polypyrrole nanowires by the grafting of polypyrrole from molecules of polystyrensulfonic acid was developed. The dc conductivity of individual polypyrrole nanowires approaches the conductivity of polypyrole in bulk.The conductivity can be described using variable-range hopping model.