title: Electrochemically responsive heterogeneous catalysis for controlling reaction kinetics.
abstract: We report a method to control reaction kinetics using electrochemically responsive heterogeneous catalysis (ERHC). An ERHC system should possess a hybrid structure composed of an electron-conducting porous framework coated with redox-switchable catalysts. In contrast to other types of responsive catalysis, ERHC combines all the following desired characteristics for a catalysis control strategy: continuous variation of reaction rates as a function of the magnitude of external stimulus, easy integration into fixed-bed flow reactors, and precise spatial and temporal control of the catalyst activity. Herein we first demonstrate a facile approach to fabricating a model ERHC system that consists of carbon microfibers with conformal redox polymer coating. Second, using a Michael reaction whose kinetics depends on the redox state of the redox polymer catalyst, we show that use of different electrochemical potentials permits continuous adjustment of the reaction rates. The dependence of the reaction rate on the electrochemical potential generally agrees with the Nernstian prediction, with minor discrepancies due to the multilayer nature of the polymer film. Additionally, we show that the ERHC system can be employed to manipulate the shape of the reactant concentration-time profile in a batch reactor through applying customized potential-time programs. Furthermore, we perform COMSOL simulation for an ERHC-integrated flow reactor, demonstrating highly flexible manipulation of reactant concentrations as a function of both location and time.
authors.affiliation: Department of Chemical Engineering and ‡Department of Chemistry, Massachusetts Institute of Technology , 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.
authors.forename: Xianwen
authors.initials: X
authors.lastname: Mao
authors.forename: Wenda
authors.initials: W
authors.lastname: Tian
authors.forename: Jie
authors.initials: J
authors.lastname: Wu
authors.forename: Gregory C
authors.initials: GC
authors.lastname: Rutledge
authors.forename: T Alan
authors.initials: TA
authors.lastname: Hatton