The use of scanning electrochemical microscopy for the detection and quantification of adsorbed intermediates at electrodes

dc.contributor.advisorBard, Allen J.en
dc.contributor.committeeMemberCrooks, Richard M.en
dc.contributor.committeeMemberStevenson, Keith J.en
dc.contributor.committeeMemberMullins, C. B.en
dc.contributor.committeeMemberHenkelman, Graemeen
dc.creatorRodriguez Lopez, Joaquin, 1983-en 2010en
dc.description.abstractScanning electrochemical microscopy (SECM) was used for the study and characterization of catalytic and electrocatalytic processes occurring at electrodes. The Surface Interrogation mode (SI-SECM) was introduced for the detection and quantification of adsorbed intermediates and products of catalyzed chemical and electrochemical reactions at noble metals (Pt, Au). In SI-SECM two micro electrodes (i.e. an SECM tip and a substrate of the desired material) are aligned concentrically at a micrometric distance where SECM feedback effects operate. A contrast mechanism based on feedback effects allows for the detection of reactive adsorbed intermediates at the substrate: the SECM tip generates a reactive homogeneous species that “micro-titrates” the substrate adsorbates to yield an electrochemical signal that contains information about the amount of intermediate and about its kinetics of reaction with the redox mediator. The technique was used for the study of the reactivity of three model small adsorbates: 1) the reactivity of adsorbed oxygen on Au and Pt with a reducing mediator was explored and suggested the detection of “incipient oxides” at these surfaces; kinetic parameters of the reactivity of Pt oxides with mediators were obtained, fit to theory and used to explain observations about the electrocatalytic behavior of Pt under anodizing conditions; 2) the reactivity of oxidizing mediators with adsorbed hydrogen on Pt was studied and showed the cation of N,N,N,N-tetramethyl-p-phenylenediamine (TMPD) to be a successful interrogation agent, the detection of hydrogen generated by the decomposition of formic acid on Pt at open circuit was investigated; 3) electrogenerated bromine was used to catalytically interrogate carbon monoxide at Pt, this reaction was previously unreported. The mentioned applications of SECM were validated through the use of digital simulations of diffusion in the complex SECM geometry through flexible commercial finite element method software.en
dc.description.departmentChemistry and Biochemistryen
dc.subjectReaction intermediatesen
dc.subjectElectrode surface analysisen
dc.subjectElectroanalytical techniquesen
dc.subjectSurface interrogationen
dc.titleThe use of scanning electrochemical microscopy for the detection and quantification of adsorbed intermediates at electrodesen