Application of photothermal deflection spectroscopy to electrochemical interfaces

摘要

This dissertation discusses the theory and practice of Photothermal Deflection Spectroscopy (PDS, which is also known as probe beam deflection spectroscopy, PBDS, probe deflection technique, and mirage effect spectroscopy) with respect to electrochemical systems. Much of the discussion is also relevant to non-electrochemical systems. PDS can measure the optical absorption spectrum of interfaces and concentration gradients in the electrolyte adjacent to the electrode. These measurements can be made on a wide variety of electrode surfaces and can be performed under dynamic conditions. The first three chapters discuss the theory of the phenomena that can be detected by PDS, and the equipment used in a PDS system. A ''secondary gradient technique'' is proposed, which places the probe beam on the back of an electrode. The results of a numerical model yield a method for determining the offset of the probe beam from the electrode surface based on the frequency response of the PDS signal. The origin and control of noise in the PDS signal are discussed. A majority of the signal noise appears to be acoustic in origin. The electrochemical oxidation of platinum is used to demonstrate that PDS has sub-monolayer sensitivity necessary to study interfacial chemistry. The results allow us to propose a two-reaction oxidation mechanism: the platinum is electrochemically oxidized to form platinum dihydroxide and dehydrated by a non-electrochemical second-order reaction. The final chapter discusses the relation of PDS to similar and competing techniques, and considers possibilities for the future of the technique.