Chapter 14 – Chemically Modified Electrodes
Electrodes prepared by surface modification to produce an
electrode suited for a particular function – different properties from
those of the unmodified substrate.
Interest in surface modification:
Unmodified
• Protection from corrosion. Reaction
• Electrocatalysis.
admolecule
• Electrochromic devices (change
color with redox state).
Modified
• Sensing.
Relevant pages = 580-589.
Chapter 14 – Chemically Modified Electrodes
• Substrate or platform (electrode to be modified)
• Monolayer (one molecular layer thick)
a. Irreversible adsorption = many species spontaneously
adsorb on a substrate surface from solution because the
substrate environment is energetically more favorable than
the solution environment.
1. R-SH + Au → R-S-Au
2. aromatics, olefins and long chain aliphatics
adsorb on carbon and metal electrodes.
Chapter 14 – Chemically Modified Electrodes
b. Covalent attachment = attachment of the
admolecule via a strong covalent bond.
Chapter 14 – Chemically Modified Electrodes
Chapter 14 – Chemically Modified Electrodes
c. Organized layers = sometimes spontaneous
processes lead to an adlayer structure with some degree
of order imposed by lateral interactions between the
component molecules – self-assembly.
R R R R R R Hydrophobic interactions
S S S S S S
between component
molecules. Strong covalent
Au
bond with Au. Tilted adlayer.
Alkanethiols on Au
Chapter 14 – Chemically Modified Electrodes
• Multilayers (thick films)
a. Polymers
1. Electroactive polymers with redox groups
covalently attached (poly(vinylferrocene)).
2. Ion exchange polymers (Nafion, poly(styrene
sulfonate)).
3. Electrically conducting polymers – accompanied
by ion incorporation (polyaniline, polypyrrole).
Polymer (insulator) ↔ Polymer+(conductor) + A-
Chapter 14 – Chemically Modified Electrodes
• Inorganic Films
a. metal oxides (e.g., Al2O3) – adsorption and
electrocatalysis.
b. clays and zeolites (e.g., aluminosilicates) –
high surface area with ion exchange capabilities.
• Biologically Important Materials (usually for
chemical sensing)
a. Enzymes
b. Antibodies All interact with some target.
c. DNA
Chapter 14 – Chemically Modified Electrodes
O + ne - ↔ R O and or R adsorbed can significantly affect the
electrode reaction kinetics and mechanism.
1. Adsorption isotherm must be selected.
2. Degree to which adsorption equilibrium is attained before
the start of the electrochemical experiment.
3. Rate of ET to adsorbed species relative to that of the
dissolved species.
Adsorption can be both friend and foe!
1. Electrode fouling and deactivation.
2. Pre-requisite to rapid ET
Chapter 14 – Chemically Modified Electrodes
i/nFA = Do(∂Co(x,t)/∂x)x=0 - ∂Γo(t)/∂t = -DR(∂CR(x,t)/∂x)x=0 - ∂ΓR(t)/∂t
Γ = surface excess, mol/cm2
Γo(t) = βoΓ0,sCo(x,t)/[1+ βoCo(0,t) + βRCR(0,t)]
ΓR(t) = βRΓR,sCR(x,t)/[1+ βoCo(0,t) + βRCR(0,t)]
β = exp (- ∆Goi/RT) ∆Goi = standard free energy
of adsorption
Chapter 14 – Chemically Modified Electrodes
pp. 589-601 and 603-605
When one chemically modifies and electrode surface, there
are several important questions to answer.
• What is the surface coverage?
• What is the admolecule or molecular layer orientation on
the surface?
• What is the spatial uniformity of the admolecule or
molecular layer over the surface?
• What kind of “electrical connection” exists between the
admolecule or molecular layer and the electrode
surface? Through-molecule charge transport?
Chapter 14 – Chemically Modified Electrodes
Case 1 : Only Adsorbed O and R Electroactive - Nernstian
-∂Γo(t)/∂t = ∂ΓR(t)/∂t = i/nFA {no adsorption of desorption during scan}
Γo + ΓR = Γo*
ip = (n2F2/4RT)υAΓo*
Ep = Eo′ - (RT/nF)ln(bo/bR) = Eo′a
∆Ep,1/2 = 3.53 RT/nF = 90.6/n mV (25 oC)
Sweep rate fast enough that O does
not have time to diffuse to or from the
electrode. Electrolysis done without
mass-transfer limitations.
Chapter 14 – Chemically Modified Electrodes
• ip proportional to υ
• Area under the peak (the charge),
after correcting for the residual
current, is equal to nFAΓ*.
• Epa = Epc or ∆Ep = 0
The location of Ep with respect to
Eo′ depends on the relative
strength of adsorption of O and R.
b is a measure of the adsorption strength.
• If bo = bR then Ep = Eo’
• If bo > bR then Ep < Eo’ bo = βoΓo,s = exp(-∆Gio/RT)Γo,s
• If bo< bR then Ep > Eo’
bR = βRΓR,s = exp(-∆Gio/RT)ΓR,s
Chapter 14 – Chemically Modified Electrodes
Case 2: Only Adsorbed O Electroactive – Irreversible Rxn
• Deviations from the bell shape occur with
factors such as the inhomogeneity of the
adlayer, charge transport through the film,
structural and resistive changes in the adlayer
during changes in redox state.
ip = αnF2AυΓo*/2.7RT
Ep = Eo′ + RT/αnF ln(RTko/αFυ)
∆Ep,1/2 = 2.44(RT/αnF) = 62.5/αn mV (25 oC)
Chapter 14 – Chemically Modified Electrodes
Case 3: Both Dissolved and
Adsorbed Species Electroactive
Product R Strongly Adsorbed
• βo→ 0 and βR → large number.
•
• Pre- and post-waves observed.
• ip (ads) proportional to υ and Γ.
• ip (dissolved) proportional to υ1/2 and C*.
• Ep shifts with Γ.
Chapter 14 – Chemically Modified Electrodes
Chronoamperometry Chronocoulometry
E2 E2
E E
E1 E1
Time Time
Least distorted by
potential rise
i(t) = nFAD1/2C*/(πt)1/2
Q
i Q = nFN
Cumulative
charge Q(t) = 2nFAD1/2C*t1/2/π1/2
passed
Time Time
Chapter 14 – Chemically Modified Electrodes
∫i ∂t = nFAD1/2C*/π1/2∫t-1/2 ∂t
(integrate from t = 0 to t)
Q(t) = 2nFAD1/2C*t1/2/π1/2
Measurement Advantages
¾ Signal grows with time, better S/N
Qf
¾ Integration smooths random noise
¾ Contribution from Qdl and Qads meas.
Q
}
Excellent technique for examining •
electroactive adlayers! nFAΓ = Qads
Qdl
•
Qtotal = Qf + Qdl + Qads
Time1/2
Q = 2nFAD1/2C*t1/2/π1/2 + Qdl + nfAΓ Be aware that adlayer can affect Qdl
Chapter 14 – Chemically Modified Electrodes
Coulometry O + e- ↔ R (with O both ads and dissolved)
Qtotal
Qf = 2nFACo* (Dot/π)1/2 +
Q Qdl + nFAΓo
nFAΓo Qdl
t1/2
Once Qdl is determined, then nFAΓo can be obtained.
