122nd General Meeting of the KCS

Type Poster Presentation
Area Electrochemistry
Room No. Grand Ballroom
Time 10월 19일 (금요일) 11:00~12:30
Code ELEC.P-486
Subject Altering the catalytic activity by tuning the electronic property of a catalyst via applied external potential
Authors Loorthuraja Rasu, Mu-Hyun Baik1,*
Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science, KAIST, Sri Lanka
1Department of Chemistry, Korea Advanced Institute of Science and Technology, Korea
Abstract Catalytic activity depends on electronic nature and steric factors. The catalytic activity is often changed by altering its electronic property. An electron-withdrawing or donating functional group is employed for this purpose. Louis P. Hammett reported the relationship between the reactivity and functional group in 1937, which is then referred as a Hammett principle. Some of the classic examples are hydrolysis of benzoic acid and benzoic ester, which shows how the reactivity was affected by substituents on meta or para position. The substituents affect the reaction by stabilizing or destabilizing the transition states. In other words, substituents alter the electronic property of a reaction center and thus affect the reactivity. The Hammett principle is widely used in several reactions to understand the reaction mechanism. To study the Hammett relationship, functionalization of the reaction center or catalyst is a key part. However, functionalization of the catalysts are often problematic and requires tedious synthetic routes. So developing a new technique to tune the electronic nature of a reaction center would be a fruitful method in catalysis. For this purpose, we introduce a new phenomenon called electroinductive effect. In electroinductive effect, the electronic nature of a catalyst or a reaction center can be altered by an external applied potential within a window that does not involve oxidation or reduction. In theory, positive or negative applied potential would resemble both electron-withdrawing and electron-donating group respectively. To demonstrate the electroinductive effect, we immobilize catalysts on an electrode and illustrate a new way to study Hammett principle. References: Hammett, L. P. J. Am. Chem. Soc. 1937, 59, 96−103.
E-mail rasu@ualberta.ca