Overview of Processes at Modified Electrodes

Multidimensional. Complex surface structure is designed to (i) facilitate an

electrode process (electrocatalysis), (ii) inhibit a reaction (corrosion), or (iii)
produce selectivity toward a process (enzyme-mediated processes). 1
 Characteristic Currents and Limiting Behavior

= CA (film)/CA (solution)
Partitioning to
give higher film
concentration i = (nFADfilmCA*)/
i/nFA = rate

1. Events in film are fast then rate of conversion of reactant is controlled by

mass transport to outer boundary of film.
2. Outside diffusion is fast as is heterogeneous ET rateat electrode surface,
then rate controlled by transport through the film. 2
 Enzyme-Mediated Process

Turn-over the catalyst (return to oxidized form)

Mediator shuttles electrons to and from enzyme 3

 Cross Reaction in a Film

ik = nFAkCA*CP*

partitioning

Cp* = concentration of electrons in the film = concentration of redox-

active sites in film
4
Interplay of Dynamical Elements

5
 Electron Transfer by Tunneling Through
Blocking Films
Formation of a blocking film
lowers the capacitance compared
to the bare electrode since the
distance of closest approach of the
counter ions, d, will be increased
by the thickness of the layer

ko(x) = ko(x=o)exp(-x)
Electron tunneling important in blocking films thinner than about
1.5 nm. For example, tunneling through a lipid bilayer (3-4 nm thick)
is negligibly small. 6
 Electron Transfer by Tunneling Through
Blocking Films
1. Blocking film + dissolved redox mediator
2. Tethered redox molecule

Effects of distance, orientation and

potential on the rate are important to
study.

i(t) = kQexp(-kt)
Rate constants for tethered redox molecules can be determined by voltammetry
or chronoamperometry. k(s-1) = rate constant. Q=nFA. Correct an i-t curve for
double layer charging and plot ln[i(t)] vs. t. Plot should be linear with a slope
proportional to k. 7