University of SaskatchewanHARVEST
  • Login
  • Submit Your Research
  • About
    • About HARVEST
    • Guidelines
    • Browse
      • All of HARVEST
      • Communities & Collections
      • By Issue Date
      • Authors
      • Titles
      • Subjects
      • This Collection
      • By Issue Date
      • Authors
      • Titles
      • Subjects
    • My Account
      • Login
      JavaScript is disabled for your browser. Some features of this site may not work without it.
      View Item 
      • HARVEST
      • Electronic Theses and Dissertations
      • Graduate Theses and Dissertations
      • View Item
      • HARVEST
      • Electronic Theses and Dissertations
      • Graduate Theses and Dissertations
      • View Item

      Electrochemical and infrared studies of the electrosorption of 4-methoxypyridine on crystallographic surfaces of gold.

      Thumbnail
      View/Open
      UNNI-THESIS.pdf (1.358Mb)
      Date
      2016-03-01
      Author
      Unni, Bipinlal
      Type
      Thesis
      Degree Level
      Masters
      Metadata
      Show full item record
      Abstract
      A firm knowledge about the interaction between the metal surface and adsorbed molecules is imperative for formulating procedures to synthesize nanoparticles (NPs) with predetermined shape and size. The ligand‐metal interaction during NP formation can be mimicked on an electrode surface by electrosorbing ligand molecules on a charged metal surface. Electrochemical methods can provide an ideal platform to study the adsorption behaviour of molecules at the solid‐liquid interface. In addition to classical electrochemical techniques, the combination of spectroscopy with electrochemical methods amplifies mechanistic insights about the surface adsorption processes. The adsorption behaviour of pyridine and one of its derivatives, 4‐dimethylamino pyridine (DMAP) have been well studied due to their potential application in nanoparticle synthesis. However, prior to this work, there has been very limited and conflicting literature available about the adsorption of of pyridine derivatives analogous to DMAP. Among the pyridine derivatives that were studied, some reports indicate that, other than DMAP, only 4‐methoxy pyridine (MOP) can stabilize gold nanoparticles. However, very little is known about the possible differences in the adsorption energy and general behaviour of MOP compared to DMAP. Resolving this knowledge gap is imperative to resolving the conflicting information about pyridine‐based stabilizers for metal nanoparticle applications. The adsorption behaviour of MOP on different crystallographic Au surfaces as a function of pH and surface potential has been investigated in this project. These studied were carried out using classical electrochemical methods including chronocoulometry and differential capacity, as well as modern spectroscopic techniques like Surface Enhanced Infrared Absorption Spectroscopy (SEIRAS). The thermodynamic parameters obtained from electrochemical data shows that adsorption features of MOP is similar to that of DMAP. However, there is a significant difference in the adsorption strength of MOP and DMAP at positive potentials. The SEIRAS data provides much more detailed information about the potential depended orientation of MOP on polycrystalline Au. Cumulative analysis of electrochemical and spectroscopic data provides strong evidence that MOP can stabilize Au(111) facets over wide pH ranges. Moreover, this work provides convincing evidence that the basic nature of substituted pyridine alters the metal to ligand adsorption strength.
      Degree
      Master of Science (M.Sc.)
      Department
      Chemistry
      Program
      Chemistry
      Supervisor
      Burgess, Ian J.
      Committee
      Scott, Robert W.; Oguocha, Ikechukwuka N.
      Copyright Date
      February 2016
      URI
      http://hdl.handle.net/10388/ETD-2016-02-2417
      Subject
      Adsorption
      surface-enhanced IR
      differential capacitance
      surface excess
      nanoparticles
      Collections
      • Graduate Theses and Dissertations
      University of Saskatchewan

      University Library

      © University of Saskatchewan
      Contact Us | Disclaimer | Privacy