Adsorption and electrochemical activity: an in situ electrochemical scanning tunneling microscopy study of electrode reactions and potential-induced adsorption of porphyrins.

The effect of adsorption on molecular properties and reactivity is a central topic in interfacial physical chemistry. At electrochemical interfaces, adsorbed molecules may lose their electrochemical activity. The absence of in situ probes has hindered our understanding of this phenomenon and electrode reactions in general. In this work, classical electrochemistry and electrochemical scanning tunneling microscopy (EC-STM) were combined to provide molecular level insight into electrochemical reactions and the molecular adsorption state at the electrolyte-electrode interface. The metal-free porphyrin 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine (TPyP) adsorbed on Au(111) in 0.1 M H(2)SO(4) solution was chosen as a model system. TPyP is found to irreversibly adsorb on Au(111) over a wide range of potentials, from -0.25 to 0.6 V(SCE). The adsorption state of TPyP has a dramatic effect on its electrochemistry. Preadsorbed, oxidized TPyP displays no well-defined cathodic peaks in cyclic voltammograms in sharp contrast to solution-phase TPyP. Our present work provides direct, molecular level evidence of the electrochemically "invisible" species. Electrochemical activity of absorbed species is recovered by allowing the oxidized molecule sufficient time (tens of minutes) to reduce. The redox state of adsorbed TPyP also affects the nature of the adsorption. Oxidized species can apparently only form monolayers. However, multilayers, stable enough to be imaged by STM, can form when the adsorbed TPyP is in the reduced state. This suggests that by controlling the electrochemistry one can either promote or suppress the formation of multilayers.