Technische Universität Ilmenau Fakultät für Mathematik und Naturwissenschaften Institut für Chemie und Biotechnik Fachgebiet Chemie Synthese und elektrochemische Anwendungen von modifizierten Kohlenstoffnanoröhren HABILITATIONSSCHRIFT Zur Erlangung der Lehrbefähigung fur das Fach Anorganische Chemie an der Fakultät fur Mathematik und Naturwissenschaften der Technische Universität Ilmenau eingereicht von Dr. rer. nat. Nikos Tsierkezos Ilmenau, Mai 2016
TABLE OF CONTENTS 1 ABSTRACT 1 2 INTRODUCTION 2 2.1 Synthesis of pristine and doped multi-walled carbon nanotubes 2 2.2 Modification of multi-walled carbon nanotubes 5 2.2.1 Modification with chemical oxidation 5 2.2.2 Modification with metal nanoparticles 7 2.3 Structural and morphological studies of multi-walled carbon nanotubes 9 2.3.1 Pristine multi-walled carbon nanotubes 9 2.3.2 Nitrogen-doped multi-walled carbon nanotubes 10 2.3.3 Phosphorus-doped multi-walled carbon nanotubes 11 2.3.4 Boron-doped multi-walled carbon nanotubes 12 2.4 Raman spectroscopy studies of multi-walled carbon nanotubes 14 2.5 Electrochemical characterization of multi-walled carbon nanotubes 16 2.5.1 Cyclic voltammetry and differential pulse voltammetry 16 2.5.2 Electrochemical impedance spectroscopy 19 2.6 Electrochemical characterization of nitrogen-doped multi-walled carbon 22 nanotubes modified with metal nanoparticles 2.6.1 Cyclic voltammetry 22 2.6.2 Electrochemical impedance spectroscopy 26 2.7 Application of multi-walled carbon nanotubes for analysis of inorganic 27 compounds 2.7.1 cw-[dichloride-bis(triphenyl phosphine)-(2-(2'-pyridyl)quinoxaline)- 27 ruthenium(ii)] 2.7.2 Tris(bipyridine)ruthenium(II) 28 2.7.3 Oxygen reduction in alkaline and acidic media 29 2.8 Application of multi-walled carbon nanotubes for analysis of 29 biomolecules 2.8.1 Pristine and nitrogen-doped multi-walled carbon nanotubes 29 2.8.2 Phosphorus-doped multi-walled carbon nanotubes 31 2.8.3 Boron-doped multi-walled carbon nanotubes 31 2.9 Application of nitrogen-doped multi-walled carbon nanotubes modified 33 with metal nanoparticles for analysis of biomolecules
2.9.1 Simultaneous analysis of ascorbic acid, dopamine, and uric acid 33 2.9.2 Simultaneous analysis of 7V-acetylcysteine and acetaminophen 39 2.9.3 Simultaneous analysis of glucose and uric acid 41 3 COMPARISON OF RESULTS WITH LITERATURE DATA 42 4 REFERENCES 45 5 SUMMARY 51 6 ZUSAMMENFASSUNG 54 7 ORIGINAL PUBLICATIONS AND MANUSCRIPTS 57 7.01 Electrocatalytic properties of carbon nanotube carpets grown on Si-wafers 57 7.02 Synthesis and electrochemistry of multi-walled carbon nanotube films 61 directly attached on silica substrate 7.03 Electrochemical studies of the bis(triphenyl phosphine) ruthenium(ii) 11 complex, cis-[rucl2(l)(pph 3 ) 2 J, with L=2-(2 '-pyridyl)quinoxaline 7.04 Electrochemical impedance spectroscopy and cyclic voltammetry of 93 ferrocene in acetonitrile/acetone system 7.05 Determination of impedance spectroscopic behavior of triphenylphosphine 105 on various electrodes 7.06 Application of films consisting of carbon nanoparticles for electrochemical 123 detection of redox systems in organic solvent media 7.07 Electrochemistry on multi-walled carbon nanotubes in organic solutions 137 7.08 Multi-walled carbon nanotubes as electrode materials for electrochemical 151 studies of organometallic compounds in organic solvent media 7.09 Oxidation of dopamine on multi-walled carbon nanotubes 163 7.10 Electrochemical and thermodynamic properties of hexacyanoferrate(ii) 175 /(HI) redox system on multi-walled carbon nanotubes 7.11 Simultaneous detection of ascorbic acid and uric acid at multi-walled 183 carbon nanotubes modified electrodes 7.12 Electrochemical responses and sensitivities of films based on multi-walled 199 carbon nanotubes in aqueous solutions 7.13 Non-enzymatic analysis of glucose on printed films based on multi-walled 213 carbon nanotubes 7.14 Influence of concentration of supporting electrolyte on electrochemistry of 221 redox systems on multi-walled carbon nanotubes 7.15 Nitrogen-doped carbon nanotubes as metal-free catalysts for the oxygen 231 ii
reduction in alkaline and acidic media 7.16 Nitrogen-doped multi-walled carbon nanotubes for paracetamol sensing 239 7.17 Electrochemistry of tris(2,2'-bipyridine)ruthenium(ii) on nitrogen-doped 251 multi-walled carbon nanotubes 7.18 Electrochemical sensor consisting of nitrogen-doped multi-walled carbon 257 nanotubes decorated with platinum nanoparticles 7.19 Thermodynamic investigation of ferrocyanide/ferricyanide redox system on 267 nitrogen-doped multi-walled carbon nanotubes decorated with gold nanoparticles 7.20 Multi-walled carbon nanotubes modified with gold nanoparticles with 277 various diameters for the simultaneous analysis of dopamine and uric acid in a single experiment 7.21 Voltammetric study on pristine and nitrogen-doped multi-walled carbon 287 nanotubes decorated with gold nanoparticles 7.22 Influence of ozone on N-doped multi-walled carbon nanotubes 299 7.23 Nitrogen-doped carbon nanotubes modified with gold nanoparticles for 313 simultaneous analysis of N-acetylcysteine and acetaminophen 7.24 Nitrogen-doped multi-walled carbon nanotubes modified with platinum, 325 palladium, rhodium and silver nanoparticles in electrochemical sensing 7.25 Electrocatalytic activity of nitrogen-doped carbon nanotubes decorated with 341 gold nanoparticles 7.26 Sensors based on multi-walled carbon nanotubes for bioanalysis 353 7.27 Synthesis, characterization, and electrochemical application of phosphorus- 359 doped multi-walled carbon nanotubes 7.28 Electrochemical studies on novel films consisting of phosphorus-doped 311 multi-walled carbon nanotubes 7.29 Application of multi-walled carbon nanotubes modified with boron oxide 387 nanoparticles in electrochemistry 7.30 Properties and electrochemical characteristics of boron-doped multi-walled 399 carbon nanotubes 7.31 Multi-walled carbon nanotubes doped with boron as an electrode material 409 for electrochemical studies on dopamine, uric acid, and ascorbic acid 7.32 Electrochemical analysis of ascorbic acid, dopamine, and uric acid on nobel 425 metal modified nitrogen-doped carbon nanotubes iii
7.33 Electrochemical response of nitrogen-doped multi-walled carbon nanotubes 439 decorated with gold and iridium nanoparticles towards ferrocyanide / ferricyanide redox system 8 APPENDIX 451 8.1 Lebenslauf 451 8.2 Lehrerfahrung 453 8.3 Vollständige Publikationsliste 455 8.4 Teilnahme an Konferenzen und Ausbildungsseminaren 470 IV