458 J. Phys. Chem.

C 2008, 112, 458-471

Molecular Theory of Chemically Modified Electrodes by Redox Polyelectrolytes under

Equilibrium Conditions: Comparison with Experiment

Mario Tagliazucchi,† Ernesto J. Calvo,*,† and Igal Szleifer*,‡

Molecular Electrochemistry Group. INQUIMAE, DQIAyQF, Facultad de Ciencias Exactas y Naturales.
UniVersidad de Buenos Aires, 1428 Buenos Aires, Argentina, and Department of Chemistry, Purdue UniVersity,
West Lafayette, Indiana 47907
ReceiVed: April 23, 2007; In Final Form: June 6, 2007

A molecular theory is presented to describe chemically modified electrodes by redox polymers. The theory
is based on writing the free energy functional of the system which includes the size, shape, charge distribution,
and conformations of all of the molecular species as well as all of the inter and intramolecular interactions,
the acid-base equilibrium for the ionizable groups of the weak polyelectrolyte, and the redox equilibrium of
the electrochemical active sites with the metal. The minimization of the free energy leads to the molecular
organization of the film as a function of bulk pH, salt concentration, and applied electrode potential. The
approach is applied to the experimental system composed by osmium pyridine-bipyridine complex covalently
bound to poly(allylamine) backbone, which is adsorbed onto a mercapto-propane sulfonate thiolated gold
electrode. The redox and nonredox capacity of the electrode and its dependence on the electrode potential
calculated with the molecular theory shows very good agreement with linear scan voltammetric experiments
under reversible conditions (equilibrium scans) without the use of any free adjustable parameter. The predicted
film thickness is in line with ellipsometric measurements. Further, the theory predicts the swelling of the film
as a function of the electrode potential. The molecular theory provides the link between the molecular
organization within the film and the electrochemical behavior. It is shown that the electrostatic, excluded
volume, and van der Waals interaction fields are strongly coupled in a nontrivial way. Furthermore, the
degree of charge regulation and distribution of oxidized states couples to the molecular distributions and the
interaction fields. The application of the theory to different model systems demonstrates the importance of
incorporating molecular information into the theoretical approach and the very strong coupling that exists
between molecular structure, film organization, interactions fields, and electrochemical behavior.

1. Introduction microscopic model of Chidsey and Murray18 based on a cubic

lattice with site interactions and the chemical and mechanical
Since the first demonstration of a chemically grafted group
to a platinum electrode surface,1 chemically modified electrodes description of polymer-modified electrodes of Bowden et.
by single and multiple molecular layers have been extensively al.19-21 Even though the usefulness of these simple approaches
studied.2-4 These integrated chemical systems5 have found is not under discussion, they provide only a partial description
applications in chemical sensors, electrocatalysis, molecular of the electrochemical process and do not include specific
electronics, electrosynthesis, energy conversion, and as molec- molecular characteristics of the film. For example, the confor-
ular wires in amperometric enzyme electrodes.6 mational degrees of freedom of polymer chains, the shape and
Polymer-modified electrodes, built up by deposition of size of the molecules, the local activity coefficients of the
electroactive polymeric films on conductive substrates, have electroactive species, the properties of the underlying substrate,
been a major area of research for the last three decades.7,8 and the existence of coupled acid base equilibria have been
Despite the intense experimental activity in the area, much of neglected in those simplified treatments. For instance, despite
the theoretical work relies on phenomenological ideas, due to the extensive literature in polymer modified electrodes, only
the molecular complexity of the problem.7 Examples are the recent models from Posadas et al.22 and Lizarraga et al.23 have
Donnan partition model9 originally introduced by Anson and included some statistical description of polymer chains, based
Redepending10,11 to study the formal redox potential dependence on the Flory theories for polymer free energy of mixing and
on ionic strength; the Laviron12 model that takes account of elastic deformation.24
lateral interactions which determine the peak position, shape, There are extensive theoretical studies on the structure and
and width in cyclic voltamperograms; and the insights on charge properties of adsorbed polyelectrolytes. The methods that have
and mass transport within polymer film electrodes developed been applied include mean-field, scaling, self-consistent field
by Seveant and Andriuax13-16 and Laviron.17 There is also the and molecular theories. For an extensive review, see ref 25 and
references therein. However, to the best of our knowledge, there
* Corresponding authors: (E.J.C.) e-mail: calvo@qi.fcen.uba.ar; (I.S.) are no theoretical studies treating the link between the electro-
permanent address: Department of Biomedical Engineering, Northwestern chemical properties of redox-polymer modified electrodes with
University, 2145 Sheridan Rd., Evanston, IL. E-mail: igalsz@northwestern.edu.
† Universidad de Buenos Aires. the layer’s molecular organization. The aim of the work
‡ Purdue University. presented here is to provide such an approach.
10.1021/jp073123f CCC: $40.75 © 2008 American Chemical Society
Published on Web 08/30/2007
Molecular Theory of Chemically Modified Electrodes J. Phys. Chem. C, Vol. 112, No. 2, 2008 459

CHART 1: PAH-Os Chemical Structure explicitly considering the acid-base and redox equilibria. We
will provide a detailed derivation below of the theory with
special emphasis on the novel application to include redox
groups as well as the equilibrium with an electrode. For a
detailed derivation of the theory with a long discussion of
its advantages and limitations, the reader is referred to refs
34-36.
The PAH-Os modified electrode is schematically drawn in
Figure 1. The cartoon includes all of the chemical reactions
considered by the theory. The polyelectrolyte film is deposited
In the present work, we present for the first time a molecular on a thiolated gold surface, which acts both as an electrode and
theory for the complete description of reversible electrochemical as a support to anchor the redox polymer. The z axis is
processes in polymer film-coated electrodes. Namely, we study considered to be perpendicular to the electrode, and its origin
the equilibrium behavior of the polymer modified electrodes. (z ) 0) is located at the surface of the metal. For simplicity,
The general theory will be applied to the particular case of a we shall consider only inhomogeneities in the direction per-
single layer of poly(allylamine) derivatized with the osmium pendicular to the surface. The generalization to treating inho-
complex Os(bpy)2ClPy+/2+ covalently attached to the polymer mogeneous systems in all three dimensions has been demon-
backbone (PAH-Os, see Chart 1), adsorbed on a mercapto- strated elsewhere.36 It is important to emphasize that considering
propane sulfonate (MPS) modified Au electrode. This redox inhomogeneities only in the z direction does not imply that we
polyelectrolyte has been extensively studied as a molecular wire are not treating the lateral interactions. Rather, it implies that
in layer by layer self-assembled systems26,27 such as enzymatic for each distance z from the electrode, the x-y plane is
biosensors,28-32 and it is a model system of polymer modified homogeneous; that is, the lateral interactions at each z are treated
electrodes. within a mean-field approximation. This approximation is very
In this first report, a comparison of the molecular theory good, as it has been shown by comparisons of the predictions
predictions with experimental results of cyclic voltammetry (CV) of the theory with experimental observations for the structure
and ellipsometry under reversible conditions for the redox of poly(acrylic acid) layers as a function of pH and solution
polyelectrolyte modified electrode Au/MPS/(PAH-Os) will be ionic strength37 and in the adsorption of proteins on surfaces
presented.33 The theory predicts the molecular organization of modified with uncharged polymers.38,39 Therefore, we are
the film as a function of the electrode potential and solution confident that this approximation is well suited to the polymer
composition. By the molecular organization, we refer to the modified electrodes treated in this work. This assumption will
concentration profiles of all molecular species, including acid- be confirmed by the very good agreement that we find between
base equilibrium of the weak polyelectrolyte, the electrostatic the experimental observations and the predictions of the theory
potential profile, the conformations of the polymers, and the (see, e.g., Figures 2 and 3 below).
distribution of redox sites and oxidation states. In our treatment, the polymer is described in terms of its two
parts: the polymeric backbone and the tethered redox
The paper is organized in the following way: We present
sites. The polymer backbone is composed of segments repre-
the derivation of the theory followed by the molecular model
senting the allyl-amine units; each one bears a protonable amino
for PAH-Os. Section 4 describes the experimental studies.
group, and the volume of the segment is represented by Vp. The
Section 5 presents the comparison of the theoretical predictions
redox sites represent the pyridine-bipyridine osmium complex,
and experimental observations together with the molecular
which could be in the oxidized Os(III) or in the reduced Os(II)
structure of the film and its changes upon variation of the
state. The redox sites are attached to the polymer backbone and
experimental variables. The last section discusses some conclud-
modeled as spherical units of radius rOs and volume VOs. The
ing remarks and directions for future work.
modified electrode is immersed in an aqueous electrolyte
2. Theoretical Approach solution containing salt ions at concentration Csalt and protons
and hydroxyls ions at concentration given by the bulk solution
We have based our theoretical approach on the molecular pH.
theory (MT)34-37 which has been widely used to investigate The derivation of the theory is based on writing the total free
the properties of non-redox-grafted polymer and polyelectrolyte energy of the system. We will next describe each contribution
layers. The MT explicitly incorporates the size, shape, confor- to the free energy in detail, followed by the expressions used
mations, charge, and charge distribution of all molecular species. to determine the equilibrium electrochemistry that is compared
The theory is a density functional approach in which the with the experimental observations. We consider NP chains of
interaction fields are determined in a self-consistent fashion by PAH-Os and NMPS chains of MPS adsorbed over an electrode
considering very detailed models for each of the molecular of area A (see Figure 1). The total Helmholtz free energy for
components of the system. We obtain detailed structural this system can be written as
information of the film as well as the thermodynamic properties.
In particular, as it will be shown in the results section, we F ) -TSw,mix - TSA,mix - TSC,mix - TSH+,mix - TSOH-,mix -
demonstrate the strong coupling that exists between the ther- TSpol - TSMPS - TSNH2/NH3+ - TSSO3-/HSO3 - TSOs(III)/Os(II) +
modynamic state and the structure of the system. In this way
we study how variations in solution conditions, e.g., ionic Fe- + FvdW + FElec + FP-S + F0 (1)
strength and pH among others, and the electrode potential
changes the structure of the film as well as the thermodynamic For practical purposes it is convenient to use the free energy
properties. density, free energy per unit area βF/A, with β ) (kB.T)-1. We
The theory is derived by writing the free energy of the system now express each of the terms in the free energy density, eq 1,
as a functional of the densities of the species in solution, the as functionals of the corresponding densities and distribution
conformations of the polymer and the electrostatic potential, probabilities.
460 J. Phys. Chem. C, Vol. 112, No. 2, 2008 Tagliazucchi et al.

Figure 1. Schematic representation of the Au/MPS/PAH-Os/solution interface. The red arrows indicate the chemical equilibria considered by the
theory. The redox polymer, PAH-Os (see Chart 1), is divided into the poly(allyl-amine) backbone (depicted as blue and light blue solid lines) and
the pyridine-bipyridine osmium complexes. Each osmium complex is in redox equilibrium with the gold substrate and, depending on its potential,
can be in an oxidized Os(III) (red spheres) or in a reduced Os(II) (blue sphere) state. The allyl-amine units can be in a positively charged protonated
state (plus signs on the polymer backbone lines) or in a neutral deprotonated state, which are related by an acid-base equilibrium. The self-
assembled layer of a mercapto-propane sulfonate, MPS, is covalently adsorbed on top of the gold substrate (depicted as a yellow layer covering the
electrode). The sulfonate groups in MPS are in acid-base equilibrium with protons in solution and thus could be in a protonated or in a deprotonated
state. The polymer-modified electrode is immersed in an aqueous electrolyte solution containing salt ions, protons, and hydroxyls in thermodynamic
equilibrium which a bulk solution. The normal direction from the electrode is denoted by z and has its origin on the metal surface.

The first five terms in eq 1 are the z-dependent translational and

(mixing) entropies for the mobile species
SSO3-/HSO3
Si,mix ∫
) - 〈nMPS(z)〉[fc,MPS(z) ln(fc,MPS(z)) +
AkB
)- ∫ Fi(z)[ln(Fi(z)Vw) - 1] dz (2) AkB
(1 - fc,MPS(z)) ln(1 - fc,MPS(z)) dz (6)
where Vw is the volume of the solvent (water), used as the In these equations fc(z) (fc,MPS(z)) is the fraction of the amino
volume unit throughout. Fi (z), i ) w, H+, OH-, C, A, is the (sulfonate) groups at z that are charged. The average densities
number density of water molecules, proton, hydroxyls, cations, of polymer (thiol) segments at a distance z from the surface are
and anions, respectively. The sixth term in eq 1 is the denoted as 〈nP(z)〉 (〈nMPS(z)〉). In the case of the polymer,
conformational entropy of the polymer chains given by 〈nP(z)〉 is calculated as
Spol NP
∑R PP(R) ln PP(R)]
NP
AkB
)-
A
[ (3) 〈nP(z)〉 )
A
∑R PP(R) nP(z, R) (7)

where PP(R) is the probability of having a chain in the where nP(z, R) is the number of polymer allyl-amine segments
conformation R. The conformation refers to the positions of each that a chain in conformation R has at z. A similar expression
of the segments and the redox sites; that is, each conformation holds for the thiol.
represents a particular volume distribution of the allyl-amine The redox sites could also exist in two different oxidation
segments and osmium complexes in space. states related by the redox equilibrium. The corresponding
The entropy of the thiol is described with a similar expression entropy of mixing for the two chemical states is
SMPS NMPS SOs(III)/Os(II)
AkB
)-
A
[ ∑γ PMPS(γ) ln PMPS(γ)] (4)
AkB
∫
) - 〈nOs(z)〉[fOs(z) ln(fOs(z)) +

(1 - fOs(z)) ln(1 - fOs(z)) dz (8)

with PMPS(γ) representing the probability of having the thiol
chain in conformation γ. where fOs(z) is the fraction of oxidized sites at z and 〈nOs(z)〉 is
The amino groups in the polymer and the sulfonate groups the average density of redox sites at z (see eq 7).
in the thiol may exist in two different states (protonated or The term Fe- in eq 1 is the electrical work necessary to bring
deprotonated), related by an acid-base chemical equilibrium. the redox sites in the system from a fully oxidized reference
The existence of more than one possible chemical state for a state to their final redox state. This process requires the flux of
given chemical moiety introduces a z-dependent entropic mixing Ne- electrons from the vacuum to the system. Since we are
contribution to the free energy of the two species. More dealing with a system in equilibrium
specifically
βFe- Ne-
SNH2/NH3+ ) β|e|Eabs
eq (9)
AkB
∫
) - 〈nP(z)〉[fc(z) ln(fc(z)) +
A A

where Eabs
eq is the electrode potential of the metal in the
(1 - fc(z)) ln(1 - fc(z)) dz (5) absolute scale.40 The required number of electrons in eq 9, Ne-,
Molecular Theory of Chemically Modified Electrodes J. Phys. Chem. C, Vol. 112, No. 2, 2008 461

is calculated from the final number of reduced redox sites in where the interactions between the polymer and the thiol are
the system modeled by a square well potential and thus

Ne-
) ∫〈nOs(z)〉[1 - fOs(z)] dz (10) Ups ) ∫0δ P
P-S〈nP(z)〉 dz + ∫0δ Os
Os-S〈nOs(z)〉 dz (17)
A
where P-S (Os-S) is the strength of the segment-surface (redox
Note that this term couples the potential of the electrode with
site-surface) interactions and δP (δOs) is the interaction range.
the oxidation fraction at each distance z from the surface.
The last term in the free energy, eq 1, includes the standard
FvdW in the free energy expression represents the van der
chemical potentials for the species in the system, µ0i
Waals (vdW) interactions. As it is well-known from the polymer
literature,41 this term represents the quality of the solvent and βF0
it measures the likeness of the polymer segments for the solvent.
A
) ∫〈nP(z)〉(fc(z)βµNH
0
3
+ + (1 - fc(z))βµNH
0
2
) dz +
In polymer solutions, the quality of the solvent is given by the
so-called Flory-Huggins interaction parameter, which is a ∫〈nMPS(z)〉(fc,MPS(z)βµSO
0
+ (1 - fc,MPS(z))βµHSO
3
-
0
) dz + 3
measure of the relative attractions between the polymer segments
as compared to the polymer-solvent interactions.41,42 This ∫〈nOs(z)〉(fOs(z)βµ0Os(III) + (1 - fOs(z))βµ0Os(II)) dz +
concept was generalized for inhomogeneous environments with
the molecular theory, originally to study polymer brushes in ∫µH0 FH (z) dz + ∫µOH
+
0
+ FOH (z) dz (18) - -

poor solvents,34,43 to lead for the free energy the expression

In eq 18, we have included only the standard chemical potentials
βFvdW βχ(|z - z′|) of the species that participate in chemical equilibria, since the
A
) ∫∫ 2
[〈φOs(z)〉 + 〈φP(z)〉][〈φOs(z′)〉 + others have no thermodynamic consequences. We should
mention that all of the chemical potentials and standard chemical
〈φP(z′)〉] dz dz′ (11) potentials in the theory include the electrostatic contribution and
therefore correspond to the electrochemical potentials used in
Here χ(|z - z′|) is a distance dependent vdW interaction
the electrochemical literature.8
parameter (generalized Flory-Huggins interaction parameter)
The repulsive interactions between all molecular species are
that accounts for the non-homogeneous distribution of the
not explicitly included in the free energy expression, eq 1. We
polymer segments. 〈φP(z)〉 and 〈φOs(z)〉 are the polymer backbone
model them as excluded volume interactions. They are included
and redox site volume fractions respectively, given by
in the theory in the generation of the chains, which are all self-
NP avoiding (see the Supporting Information) and as packing
〈φP(z)〉 )
A
∑R PP(R) VP(z, R) (12) constraints for the intermolecular repulsions. Namely, the sum
of the volume that each of the species occupies at z should be
equal to the total available volume at z. This leads to
NP
〈φOs(z)〉 )
A
∑R PP(R) VOs(z, R) (13) ∑i φi(z) ) 1 (19)

where VP(z, R) and VOs(z, R) are the volume occupied at distance for all z, where φi(z) is the volume fraction for the species i at
z from the surface by the polymer segments and the redox sites, z. For solvent (water), protons, hydroxyls ions, cations, and
respectively, when the chain is in conformation R. anions (i ) w, H+, OH-, C, and A), φi(z) is equal to Fi(z)Vi,
The electrostatic contribution to the free energy is given where Vi is the molecular volume of the species i. For polymer
by36,44,45 segments, redox sites, and MPS molecules, it is equal to the
average volume fractions 〈φi(z)〉 (i ) P, Os, and MPS) as defined
βFElec
A
)β ∫[〈FQ(z)〉ψ(z) - 21(z)(∇zψ(z))2] dz (14) by eqs 12 and 13.
We require the global electroneutrality of the system.
Therefore, we impose the following constraint to the free energy
where ψ(z) and (z) are the z-dependent outer electrostatic
potential and dielectric coefficient respectively, and 〈FQ(z)〉 is
the average density of charges at z given by ∫〈FQ(z)〉 dz + σM ) 0 (20)

where σM is the charge on the metal and the integral includes

〈FQ(z)〉 ) 〈nP(z)〉fc(z)qNH3+ + 〈nOs(z)〉 [qOs(III)fOs(z) +
all of the charges in the system up to, and including, the bulk
qOs(II) (1 - fOs(z))] + 〈nMPS(z)〉fc,MPS(z)qMPS + FA(z)qA + solution. The distribution of the charged species as a function
FC(z)qC + FH+(z)qH+ + FOH-(z)qOH- (15) of the distance from the surface is an important output of the
theory, and as it will be shown, it depends on the experimental
which includes contributions from the poly(ally amine) back- conditions.
bone, the redox sites, the thiol molecules, salt anions and cations, The polymer-modified electrode is in equilibrium with a bulk
protons and hydroxyl ions respectively. In this equation, qi is solution. Therefore, at thermodynamic equilibrium, the chemical
the charge of the specie i in units of the elemental charge. potential of all of the free species in the solution should be the
FP-S in eq 1 represents the vdW interaction between the same at all z. Note that this condition does not apply to the
polymer and the thiolated layer; that is, it can be thought as the polymer and the thiol since they are attached to the surface.
polymer adsorption energy, and it is given by Namely, we are treating the polymer layer under the assumption
that the total number of adsorbed polymers is known and fixed.
βFP-S NP Thus, we need to consider a semi-grand-canonical potential, W,

A
)
A
[ ∑R PP(R)βUPS(R)] (16) which is canonical for polymer and thiol and grand canonical
for the other species. Writing explicitly the packing and
462 J. Phys. Chem. C, Vol. 112, No. 2, 2008 Tagliazucchi et al.

electroneutrality constraints to the free energy and including FH+(z)Vw ) exp[-VH+βπ(z) - βµH0 + - qH+β(ψ(z) + λ)]
the chemical equilibrium with the bulk solution through the
(25)
chemical potentials leads to
FOH-(z)Vw ) exp[-VOH-βπ(z) - βµOH
0
- - qOH-β(ψ(z) + λ)]
βW βF
A
)
A
+ ∫βπ(z)[∑φi(z) - 1] dz + λ∫〈FQ(z)〉 dz - (26)
i
Fw(z)Vw ) exp(-Vwβπ(z)) (27)
∫ ∫
βµC FC(z) dz - βµA FA(z) dz (21)
It is convenient to express these relationships in terms of the
with λ and π(z) being the Lagrange multipliers associated with
the electroneutrality and packing constraints respectively. As experimentally accessible bulk number densities, Fbulk
i , i.e.
was explained in ref 36, the chemical potentials of protons,
hydroxyls ions, and solvent molecules do not appear explicitly Fi(z)Vw ) Fbulk
i Vw exp(-Viβ[π(z) - πbulk] -
in this equation because the presence of constraints (charge
qiβ[ψ(z) - ψbulk]) (28)
neutrality and packing constraint) reduces the number of
independent thermodynamic variables by three.
The extremum of the semi-grand-potential functional with Fw(z)Vw ) Fbulk
w Vw exp(-Vwβ[π(z) - π
bulk
]) (29)
respect to Fi(z), fc(z), fOs(z), fc,MPS(z), ψ(z), and P(R) provides
for explicit expressions for the volume fraction of the free where eq 28 holds for the anions, cations, protons and hydroxyls
species, the probability distribution functions of the polymer, ions and eq 29 for the solvent (water).
and the z-dependent chemical equilibria. The variation of eq 21 with respect to fc(z) and fc,MPS(z) yields
The variation with respect to P(R) leads to the probability

( )
distribution function (PDF) for the polymer chains
fc(z)

{∫
ln ) -βµOH
0
- - βµNH + + βµNH -
0 0

1 1 - fc(z) 3 2
PP(R) ) exp - nP(z, R)[ln(fc(z)) + qNH3+(βψ(z) + λ) +
ξ VOH-β[π(z) - πbulk] - ln(FOH-(z)) (30)
∫nOs(z, R)[qOs(II)(βψ(z) + λ) +
( )
+] dz -
0
βµNH 3 fc,MPS(z)
) -βµH0 + - βµSO
0
- + βµHSO -
0
ln(1 - fOs(z)) + βµ0Os(II)] dz - βUPS(R) - ∫[VP(z, R) +
ln
1 - fc,MPS(z) 3 3

[
VOs(z, R)] βπ(z) + ∫βχ(|z - z′|)(〈φP(z′)〉 + 〈φOs(z′)〉) dz′ -
VH+β[π(z) - πbulk] - ln(FH+(z)) (31)

1 d(z)
2 d(〈φP(z)〉 + 〈φOs(z)〉) z ]}
(∇ ψ(z))2 dz (22)
The fractions of charged species has two contributions, one is
the standard reaction free energy ∆G0c ) µOH 0
- + µNH + - µNH
0
3
for the allyl-amine backbone segments, eq 30, and ∆Gc,MPS )
0
0
2

Here ξ is the normalization constant which guarantees ΣR P(R) µH0 + + µSO

0
3
- - µHSO for the acid-base equilibrium of the
0
3

) 1. Inspection of eq 22 provides further insight about the sulfonate end-groups of the thiol, eq 31. The second contribution
Lagrange multipliers: λ, enforcing the electroneutrality condi- is related to the different packing of the reactants as compared
tion, is a constant term added to the electrostatic potential and to the products. This is one more manifestation of the close
π(z), which assures the packing constrain at each z, is a lateral coupling between chemical equilibrium and the other interac-
osmotic pressure.34-36 Note that the standard chemical potentials tions.
and λ are constant contributions to the PDF and therefore could Equations 30 and 31 can be rearranged to obtain the
be included in ξ. generalized acid-base equilibria equations
The probability for a given chain conformation in eq 22 has
contributions from several of the chemical equilibria and K0b ) exp[-β∆G0c ] )
interactions considered by the theory. Namely, the pdf includes
the acid-base equilibrium of the amino groups, the redox FOH-(z)fc(z)
exp(VOH-β[π(z) - πbulk]) (32)
equilibrium of the osmium complexes, the vdW interactions, 1 - fc(z)
and the electrostatic and packing forces. The later two interac-
tions are determined by the interaction fields ψ(z) and π(z). K0a ) exp[-β∆Gc,MPS
0
])
These fields are self-consistently determined from the concen-
FH+(z)fc,MPS(z)
tration profiles of all the molecular species in the system. As a exp(VH+β[π(z) - πbulk]) (33)
consequence, a main characteristic of the present theory is that 1 - fc,MPS(z)
it considers the coupling between the interactions fields and
the fact that they are highly nonlocal.
The variation of eq 21 with respect to Fi(z) yields the Here K0b and K0a are the thermodynamic equilibrium con-
following general relationships for the density profiles of the stants, which can be multiplied by the constant factor NA/Fbulk
w
anion, cation, proton, hydroxyl and solvent: (with NA equal to Avogadro’s number) to obtain the commonly
used equilibrium constants based on molar bulk concentrations.36
FA(z)Vw ) exp[-VAβπ(z) + βµA - qAβ(ψ(z) + λ)] (23) Note that K0b and K0a are determined by the ratio of the
activities at each z and not of the concentrations.
FC(z)Vw ) exp[-VCβπ(z) + βµC - qCβ(ψ(z) + λ)] (24) We will now discuss the expressions obtained upon the free
energy minimization for the fraction of oxidized sites, fOs(z)
Molecular Theory of Chemically Modified Electrodes J. Phys. Chem. C, Vol. 112, No. 2, 2008 463

ln ( fOs(z)
1 - fOs(z) ) ) β|e|Eabs
eq - βµOs(III) + βµOs(II) -
0 0
i. The charge at the metal electrode due to thiol, polyions,
mobile ions, and solvent dipoles, characterized by a non-redox
capacity, Cnon-redox which is equivalent to the double layer
β(qox - qred)(ψ(z) + λ) (34) capacity of an ideally polarizable mercury electrode immersed
in an electrolyte solution.
In analogy with the relationships found between local acid base The non-redox capacity is given by
equilibria and the thermodynamic equilibrium constants, eq 34
is a generalized Nerst equation for the Os(II)/Os(III) couple ∂σM
Cnon-redox ) (39)

( )
fOs(z) ∂Eabs
eq
1
eq ) EOs(III)/Os(II) +
Eabs +
0,abs
ln
β|e| 1 - fOs(z)
where σM is the charge on the metal, determined from
(qox - qred)
(ψ(z) + λ) (35) ∂ψ
|e| σM ) -(0) (0) (40)
∂z
where Eabs
and
eq
0,abs
EOs(II)/Os(III)
are the electrode potential in
equilibrium and the standard redox potential for the osmium ii. The charge stored in the electroactive material or redox
complex in the absolute potential scale40,46 capacity, Credox. The redox capacity is calculated from the
potential dependence of total fraction of oxidized redox sites
0,abs
EOs(III)/Os(II) ) [
µ0Os(III) - µ0Os(II)
|e| ] (36)
as

∂ΓOs(III) ∫
∂ 〈nOs(z)〉fOs(z) dz
The third term in eq 35 accounts for the local electrostatic Credox ) F )F (41)
activity of the redox sites. Although simple in appearance, the
∂Eabs
eq ∂Eabs
eq
strong coupling between the interaction fields and their nonlocal
character make this term dependent on all of the interactions where F is the Faraday constant and ΓOs(III) is the total number
and molecular features considered in the theory. Note that in of oxidized redox sites per unit area.
eq 35 the Lagrange multiplier λ appears as an additive constant The molecular theory allows the straightforward calculation
to the electrostatic potential. for the electrode capacity from the excess charge in the metal
Finally, the extremum of the semi-grand-potential with respect and the excess redox concentration in the polymer film. In
to ψ(z) provides the Maxwell equation for electrostatics previous theoretical models for polymer modified electrodes,
these contributions are calculated independently with different
∇((z)∇ψ(z)) ) -〈FQ(z)〉 (37) models.4 The non-redox contribution is usually calculated with
a constant double layer capacitance directly determined from
The boundary conditions for eq 37 are the outer electrostatic the experiment. On the other hand, in the molecular theory, both
potential of the metal, (ψM + λ) and the outer potential of the contributions are coupled and are obtained from the same
bulk solution (ψbulk + λ). Since only the difference between theoretical framework.
these potentials is relevant, we have used ψbulk ) 0 and λ ) 0
and therefore ψM could be determined from the absolute 3. PAH-Os Molecular Model
electrode potential as40 In this section, we define the molecular details of the species
that are used in the calculations, namely the molecular size and
ΦeM- ΦeM- shape, the strength of the molecular interactions, the equilibrium
eq ) (ψ + λ) - (ψ
Eabs + λ) + ) ψM +
M bulk
(38)
|e| |e| constants, and the surface coverage of the thiol molecules and
the polymer chains. These input parameters constitute the
M
where Φe- is the work function of the metal. Note that Eabs eq
molecular model of the system. The conformation of the chains
M
and ψ in eq 38 differ only by a constant. and how they are generated is explained in the Supporting
Equation 37 is a generalized Poisson-Boltzmann (P-B) Information. We will refer to the model described in this section
equation since the charge densities depend on the total potential as the PAH-Os molecular model since it incorporates specific
of mean-force. Namely, although the P-B approach considers molecular details for this redox polymer and it will be compared
the local charge to be only a function of the local electrostatic with the experimental observations. In the results section, we
potential,47 our molecular theory shows how the local charge present two other models to demonstrate the importance of the
depends upon the coupling between all of the interactions and molecular details in the predicted behavior of the polymer
the different chemical equilibria involved, see, e.g., eq 22. The modified electrode.
strong influence of all of the interactions, as well as the highly We have considered the thiol molecules within the same
nonlocal character of the coupling between the different fields, theoretical framework as the polymer chains. In practice, the
is seen by realizing that the right-hand side of eq 37 is obtained thiol molecules are restricted to the first 0.5 nm from the metal,
by replacing the PDF, eq 22, and the density profiles eqs which is equal to the discretization length (see the Supporting
23-26 into the total charge expression, eq 15. Information). Therefore, in this model, all conformations of the
In order to apply the theory, we need to solve the coupled thiol molecule are equivalent, and we can write

{
packing constrain equation, eq 19, and the generalized P-B
equation, eq 37. The procedure to carry out the calculations is σMPS
0 nm < z < 0.5 nm
found in the Supporting Information and in refs 34-36. 〈nMPS(z)〉 ) 0.5 nm (42)
The ability to store charge at the electrode-redox polyelec- 0 z > 0.5 nm
trolyte interface has two contributions that result in the electrode
capacity (capacitance per unit area, e.g., F cm-2).18 〈φMPS(z)〉 ) 〈nMPS(z)〉VMPS (43)
464 J. Phys. Chem. C, Vol. 112, No. 2, 2008 Tagliazucchi et al.

TABLE 1: Charge and Volume Used in the PAH-Os In order to estimate the vdW interaction strengths, we will
Molecular Model take advantage of our previous knowledge about PAH-Os. Let
electrostatic molecular (segment) us consider the end-to-end distance for free polymer, in the
charge, qi volume, Vi (Å3) absence of interactions this is equal to n1/2l, where n is the chain
water 0 30 length and l is the length of a segment.24 We can use n ) 780
cation +1 33.5 and l ) 0.5 to obtain an end to end distance of 14.0 nm, which
anion -1 33.5 is very different from the experimental thickness observed for
proton +1 30 PAH-Os layers of 1-2 nm.26,53 Based on this observation,
hydroxyl ions -1 30
polymer segment + 1 (NH3+) 113
hydrophobic polymer-polymer and polymer-thiol interactions
(allyl-amine) 0 (NH2)a must exist in order to constrain the chains to the surface. The
thiol molecule -1 (SO3-) 580 existence of hydrophobic polymer-polymer interactions is also
0 (HSO3)b supported by the high solubility of totally deprotonated PAH
redox site +2 (OsIII) 1770 in nonpolar solvents. We model the poor solvent characteristics
(osmium complex) +1 (OsII) of the allyl-amine segments using the interaction parameters
a
pKb ) 5. b pKa ) -1. shown in the Supporting Information which are based on the
calculations presented in ref 43. These conditions correspond
where σMPS is the surface coverage of the thiol molecules equal to an effective temperature for the solvent that is 0.75θ, where
to NMPS/A and VMPS is the molecular volume of the thiol θ is the temperature at which the second virial coefficient of
molecule (see Table 1). We have employed the experimentally the polymer chains vanishes.42 The polymer-thiolated surface
reported MPS surface coverage of 4.6 × 10-10 mol cm-2.48 interaction, P-S, and the redox site-thiolated surface interaction,
Short chain thiols yield disordered films with submonolayers P-Os, have been taken as -1.0 and -2.0 kT respectively with
coverages on gold48 in contrast to the compact monolayers an interaction range of 1.0 nm. These values are similar to those
observed for longer thiols.49 In this model, 80% of the metal usually employed in Monte Carlo54 and molecular dynamics55
surface is covered by thiols, and thus, water and ions permeate simulations to describe the adsorption of polymers on flat
into the layer. On the basis of calculations results (not shown) surfaces.
that showed that polymer chains practically do not penetrate On the basis of previous work,36,44 we will assume that the
the thiol layer, we have not allowed polymer at z < 0.5 nm to dielectric function, (z) is constant in the polymer/solution
simplify the calculations. region. However, the permeable thiol layer has a different value
The high surface density of the thiol molecules motivated and therefore the model is that of a metal for z < 0, (z) ) tiol
the inclusion in the theory of the sulfonate acid-base equilib- ) 3.8 for 0 < z < 0.5 nm and (z) ) w ) 78 for z > 0.5 nm.
rium. Even though the sulfonic moieties are strong acids, the Using the molecular model described in this section, with
highly negative environment in the MPS layer favors the parameters found in Table 1, we have solved the nonlinear
protonation of the sulfonate groups, in a process known as coupled equations for each condition of interest as described in
charge regulation.50 Our calculations (using pKa ) -1) indicate the Supporting Information.
that it is necessary to include this effect since the effective charge
of the thiols, fc,MPS, is highly dependent on the bulk pH, salt 3. Experimental Section
concentration, and electrode potential. For example, we find a
decrease in the degree of dissociation from 0.96 in a solution 3.1. Reagents and Materials. All solutions were prepared
with a salt concentration of 0.1 M to 0.82 in a low salt (Csalt ) with 18 MΩ Milli-Q (Millipore) water. Sodium 3-mecapto-
10-3 M) solution, where ions are unable to screen MPS charges. propane-sulfonate, MPS (Aldrich) was used as received. The
The lower degree of charge at low salt concentrations is also chemicals employed in electrolyte solutions, NaNO3 and HNO3,
predicted to be potential dependent. We find that fc,MPS increases were of analytical grade and used without further purification.
about 7% when increasing the electrode potential in the range The osmium bipyridine derivatized redox polymer Os(bpy)2-
studied in sections 5.1 and 5.4. ClPyCH2NH-poly(allylamine) (PAH-Os) was synthesized as
The PAH-Os chains on top of the thiol are constrained to previously reported56. Thiol solutions of 20 mM 3-mercapto-
have at least one segment in 0.5 nm < z < 1.0 nm in order to 1-propane-sulfonic acid (MPS) (Aldrich) in 10 mM sulfuric acid
prevent chain desorption. In the present work, we have not (Merck) were prepared before each experiment in order to avoid
theoretically studied the adsorption of the redox polymer but oxidation in air. The PAH-Os solution was adjusted to pH 8.3
calculated the polymer surface coverage (2.1 segments/nm2) employing 0.1 M solutions of HCl or NaOH respectively.
from the oxidation charge obtained from CV experiments (2.6 3.2. Surface Modification. Silicon (100) substrates were
( 0.2 µC.cm-2) and the ratio of redox sites to polymer segments coated with a 200 nm gold layer on a 20 nm titanium and 20
(1:13) determined from XPS measurements.51 Although the nm palladium adhesion layer by thermal evaporation with an
theory requires as an input all of the possible conformations of Edwards Auto 306 vacuum coating system at P < 1.10-8 bar
the polymer, this is impossible for the chain lengths considered and employed as electrodes.
in this work, and therefore, we have used a large representative The gold film substrates were primed with sulfonate groups
set of 105 conformations (see the Supporting Information for by immersion in an MPS solution for 30 min and rinsed again
details on chain generation). The experimental polymer chain with deionized water. The polymer modified electrode was
length (n) of ∼780 allylamine segments is too long for proper constructed by immersion in PAH-Os solution for 30 min,
generation of independent conformations;52 thus, we have followed by thoroughly rinsing with Milli-Q water.
studied the effect of the chain length in the range of 26-156 3.3. Electrochemical Experiments. Redox polymer modified
segments. Since the electrochemical response was found to electrodes were probed by cyclic voltammetry at 25 mV/s in
became independent of the chain length for n > 78 (see the solutions containing 1 mM HNO3 (pH 3) and different NaNO3
Supporting Information), we decided to describe the experi- concentrations. The measurements were carried out at room
mental polymer chains of 780 segments as 6 independent chains temperature (25 °C) with an Autolab PGSTAT 30 potentiostat
of n ) 130. (Autolab, Ecochemie, Holland). All experiments were performed
Molecular Theory of Chemically Modified Electrodes J. Phys. Chem. C, Vol. 112, No. 2, 2008 465

in a purpose built three electrode Teflon cell, with an electrode The comparison of these parameters in the entire range of ionic
exposed area of approximately 0.25 cm2 delimited by an inert strengths is displayed in Figure 3. There is very good agreement
O-ring. between the predictions and the experimental observations for
An Ag/AgCl 3 M KCl (0.210 V vs NHE) electrode was the entire range of salt concentrations. The predictive power of
employed as reference electrode; a platinum gauze auxiliary the theory enables us to look in detail at the relationship between
electrode of large area was employed. Before thiol adsorption the structure of the polymer film and the electrochemical
the electrode potential was cycled in 2 M sulfuric acid between observed behavior. In particular, how molecular variables and
0.2 and 1.6 V at 0.1 V s-1 to check for surface contamination solution conditions affect the molecular structure of the film
and electrochemically active areas were calculated from the and its relationship to the electrochemical response.
reduction peak of gold oxide.57 The shift of the redox peak toward positive potentials with
The liquid junction potentials across the reference electrode the decrease in the ionic strength is attributed to the presence
frit were estimated using the Henderson equation8 and used to of the Donnan interfacial potential9 due to the positive electro-
correct the experimentally measured current potential curves. static charges of the polymer that exclude ions of same charge
from the solution. It is interesting to note that the usually called
4. Results and Discussion Donnan equilibrium is explicitly included in the molecular
4.1. Theory-Experiment Comparison. The current- theory. However, due to the strong coupling between molecular
potential curves in linear scan voltammetry experiments under organization and the (local) electrostatic potential, changes in
reversible conditions can be calculated from the theory using the Donnan equilibrium are associated with changes in the
distribution of molecular species, some of which we describe
j ) jnon-redox + jredox ) (Cnon-redox + Credox)V (44) in detail below. The Donnan equation, on the other hand, makes
use of an adjustable parameter (the molar concentration of
where V is the experimental scan rate parameter V ) dEabs polymer charged sites), whereas the theory provides the same
eq /dt.
We will use hereafter the convention, which assigns positive quantities from a first principle calculation and without adjust-
values for the oxidation (anodic) currents. able parameters.
In order to compare the predictions of the theory with the The prediction of the peak broadening at low ionic strengths
electrochemical experiments, it is necessary to relate the absolute beyond the ideal value of 90.6 mV for a one-electron reaction12
electrode potentials with the potentials measured during the is very remarkable. In previous models, peak broadening has
electrochemical experiments against Ag/AgCl reference elec- been related to repulsive interactions that result in a distribution
trode. On the basis of the work of Trasatti40 on the absolute of activity coefficients dependent on the degree of film
potential scale, we can write oxidation60 or a Gaussian distribution of formal redox potentials
due to heterogeneities in the layer,61 therefore introducing
Eabs ) EAg/AgCl
abs
+ EAg/AgCl (45) adjustable parameters obtained from the experiment. Changes
in the Donnan potential due to changes in the electrostatic charge
abs
where EAg/ACl is the potential of the Ag/AgCl electrode in the in the polymer could also lead to peak broadening in the
absolute scale (-4.65 V) and EAg/AgCl is a potential measured particular case of electrodes modified by permselective redox
against Ag/AgCl. This equation can be used to calculate polymers.62 Interestingly, the molecular theory is capable of
0,abs providing a microscopic picture for the distribution of lateral
EOs(II)/Os(III) (-4.385 V) in eq 36 from the experimental redox
interactions as a function of the distance form the surface. As
potential of the redox couple in solution (0.265 V vs Ag/AgCl).27
we will show below (see, e.g., Figures 5-8), the distribution
Equation 45 has also been employed to convert the theoretical
of redox sites and other charges, as well as the electrostatic
potentials back to the Ag/AgCl reference scale after solving
potential, is not trivial, and it is highly inhomogeneous.
the theory. To determine ψM from Eabs eq using eq 38, we have Moreover, a distribution of formal redox potentials results from
used Φe- M
) -4.7 eV (the work function of polycrystalline the thermodynamic requirement of constant chemical (electro-
gold58,59). The electrode potentials in the rest of this work are chemical) potential for all surface distances and for all of the
expressed in the Ag/AgCl reference potential scale. molecular species. Thus, our theoretical treatment does not
It is also important to recall that eq 44 is only valid when all impose one or the other mechanisms for the peak broadening.
of the redox sites in the film are in electrical equilibrium with Rather, we find that they are a result of a combination of the
the metal. In other words, the experimental characteristic time two effects coupled with changes in the molecular organization
must be much longer that the characteristic times for charge as a function of the solution ionic strength.
transfer at the film-metal interface and diffusional charge
A second piece of experimental information that can be
transport inside the film. We have found a constant charge for
checked against the predictions of the theory is the film
electrochemical measurements at V < 0.1 V/s, and thus, we
thickness. Ellipsometry provides a nonelectrochemical source
performed the experiments at a lower scan rate (0.025 V/s) in
to determine this quantity. The theoretically average film
order to eliminate charge transfer and transport effects.
thickness, 〈z〉, is defined as the first moment of the volume
Figure 2 shows the calculated and measured current-potential
fraction distribution of the polymers. Namely
curves for two different salt concentrations. Note the almost
zero peak separation in the experimental voltamperograms,
indicating that the redox equilibrium is fulfilled in the entire ∫(〈φP(z)〉 + 〈φOs(z)〉)(z - δMPS) dz
system at each electrode potential as it is required in order to 〈z〉 ) (46)
compare with the molecular theory of reversible redox process. ∫(〈φP(z)〉 + 〈φOs(z)〉) dz
The predicted current-potential curves reproduce most, if not
all, of the experimental measurements. We have chosen two The in situ ellipsometric thickness for a completely reduced
salient features of the cyclic voltammetric surface waves to layer on PAH-Os on Au/MPS immersed in a 0.2 M KNO3 pH
demonstrate the predictive power of the theory: the peak 7.3 buffer solution has been measured and reported elsewhere.26
position (Epeak) and the peak full width at half-height (fwhh). Under the same conditions and employing the parameters in
466 J. Phys. Chem. C, Vol. 112, No. 2, 2008 Tagliazucchi et al.

Figure 2. Comparison of experimental (A) and theoretical (B) current-

potential plots measured at V ) 0.025 V/s for a Au/MPS/PAH-Os
electrode in HNO3 1 mM (pH 3) and two different salt (NaNO3)
Figure 3. Plots of peak potential position (A) and peak width (B) vs
concentrations. The currents have been normalized with the scan rate
salt concentration in the bulk solution determined from the experimental
and a common scale has been used in both figures.
and theoretical redox waves in the same conditions of Figure 2. The
section 3, the theory predicts a thickness of 1.2 nm in good experimental data presented is an average from the oxidation and
reduction peaks obtained from three different sets of cyclic voltammetry
agreement with the experimental value of 1.5 nm. experiments. The error bars indicate three standards deviations from
The ability of the theory to predict the current-potential the average.
curves and independently the film thickness strongly suggests
that the structural information obtained from the theory (and thickness of 1.5 nm measured in ref 26. The peak position
the resulting electrochemical behavior) is correct. We will show predicted by this model, as shown in Figure 4A, differs also
next how changes in the molecular properties of the redox appreciably with that of the PAH-Os model and, thus, with the
polyions result in rather different predictions for both the experimental observations. Differences in the peak widths
structure and current-potential curves. Thus, a proper descrip- between the two qualities of solvent are not as evident.
tion of the film requires a detailed molecular treatment and
further, we can use the theory as a design tool for the type of The second example that we show to demonstrate the
molecular structure that can lead to a given electrochemical coupling between molecular structure, film organization, and
response. electrochemical behavior corresponds to a polymer in which
4.2. Effect of the Molecular Model. The strength of the the redox site is assumed to be smaller that in PAH-Os. The
theory is in its ability to rationally design integrated electro- small redox site molecular model is modeled with redox sites
chemical systems based on the understanding of the relationship whose radiuses are 4.6 Å (estimated for example for amino
between the properties of the system and its molecular details. ruthenium complexes63). This radius is to be compared with
This point is illustrated in Figure 4, where we show predictions 7.5 Å estimated for the pyridine-bipyridine osmium complex
for different molecular models for the polymer that differ from used in the PAH-Os model. Figure 4, panels A and B, shows
the PAH-Os molecular model defined in section 3. the remarkable influence of the redox sites size on the peak
We call good solvent molecular model a polymer that likes parameters. In particular note the slope of the peak potential
to be surrounded by the solvent. As explained in the Theory position vs salt concentration, for low Csalt, which is close to
section, the quality of the solvent is accounted for through the 22 mV per order of magnitude in salt concentration. This is
strength of the vdW interaction parameter, χ(|z - z′|). In the much less than the 60 mV predicted by the Donnan equation27
good solvent χ(|z - z′|) ) 0, and therefore, the only nonelec- for a one-electron anion-permselective process. The different
trostatic interactions included in the system are excluded volume molecular organization of the different molecular models is
repulsions. This implies that the polymer molecules would like described below. At this point, it is important to emphasize that
to swell as much as possible. In the PAH-Os molecular model the treatment of the polymer film of interest with the Donnan
however, solvent is considered poor and the polymer chains equation is inadequate due to the finite thickness of the film.64,65
tend to form compact (collapsed) structures. The good solvent On the other hand, our theoretical treatment can be thought as
molecular model systematically predicts thicker films than those a generalized Poisson-Boltzmann method, see section 2.
experimentally observed, i.e., 〈z〉 ) 5.8 nm vs an ellipsometric Therefore, the predictions from the theory provide the full
Molecular Theory of Chemically Modified Electrodes J. Phys. Chem. C, Vol. 112, No. 2, 2008 467

Figure 5. Theoretical volume fraction profiles for the polymer

backbone (full line), the redox sites (dashed line), and the whole redox
polymer (dot-dashed line) obtained for the PAH-Os molecular model
described in section 3 (A), and the small redox site molecular model
described in section 4.2 (B). The calculations were performed at E )
0
EOs(II)/Os(III) using Csalt ) 0.1 M and pH ) 3. The shaded region (z <
0.5 nm) is occupied by the thiol layer.

Figure 4. Plots of peak potential position (A) and peak width (B) vs Figure 4 has shown that the electrochemical response of the
salt concentration in the bulk solution calculated for different molecular polymer-modified electrodes depends dramatically on the mo-
models described in section 4.2 using pH ) 3. lecular nature of the polymers. To show the link between that
response and the molecular structure of the film, Figure 5B
variation of the electrostatic and redox potentials as a function displays the volume fraction distribution for the small redox
of the distance from the surface. site molecular model. In this case, the redox sites are not
4.3. Structure of the Electrode/Polymer/Solution Interface. excluded from the surface due to the much smaller size as
We shall discuss now the molecular insights of the electrode/ compared to the osmium pyridine-bipyridine complex (see
polymer/solution interface obtained from the theory. Figure 5 Figure 5A). The presence of the small redox groups in the
shows the volume fraction for the polymer backbone, the vicinity of the negatively charged thiols surface decreases the
osmium complex, and the whole redox polymer as a function local electrostatic potential sensed by these sites and gives rise
of the distance form the surface, z, at E ) EOs(II)/Os(III)
0
. Fig- to the low slope observed in Figure 4A. The effect of the redox
ure 5A corresponds to the experimentally studied system, i.e., site size underlines the strong coupling that exists between the
PAH-Os model. The distribution of the polymer segments is structure and the electrochemical response the polymer film.
found mostly close to the surface; however, the profiles do not This coupling emphasizes the need for a molecular approach
completely decay to zero until approximately 12 nm. This to describe the complexity of the polymer modified electrodes.
indicates a strong adsorption of most of the allyl-amine segments A more detailed manifestation of the complexity of the system
of the polymer on the thiol layer and a small population of can be seen by looking at the electrostatic potential as a function
extended dangling tails protruding into the solution. Another of the distance from the surface. This is displayed in Figure 6
interesting feature in the density profiles is the exclusion of the together with the total polymer volume fraction. The electrostatic
bulky and rigid redox sites from the surface by the smaller and potential starts positive on the surface as a result of the applied
more flexible polymeric chains. This result is relevant to the
potential on the metal. It has a sharp decrease to negative values
distance-dependent electron-transfer rate. For instance, the
heterogeneous electron-transfer rate constant at the polymer/ within the thiol layer due to the presence of the negatively
electrode interface measured by electrochemical impedance charged sulfonate end groups of the thiol. There is an increase
spectroscopy has been found to be much less than the rate of the potential to positive values in the region of the adsorbed
constant for a soluble osmium complex.26 The kinetics of polymer. The maximum of the potential coincides with the
electron transfer are beyond the scope of the present work. inflection point in the volume fraction of the polymer profile,
However, the predictions of the MT can be used to formulate which corresponds to the maximum in the distribution of the
a theory for the kinetics of electron transfer with the proper osmium groups. The maximum is followed by a long tail of
incorporation of the distribution of redox sites. positive potential that reflects the dangling polymer tails.
468 J. Phys. Chem. C, Vol. 112, No. 2, 2008 Tagliazucchi et al.

Γq(z) ) σM + ∫0z 〈Fq(z′)〉 dz′ (47)

where σM is the charge density on the metal surface. The

cumulative charge density represents the total (integrated)
charged from the metal surface up to the distance z. As can be
seen from the figure, the polymer layer exhibits the effect of
charge reversal. Namely, there is a distance from the surface
where the total charge becomes compensated, and at further
distances, the effective surface charge changes sign. This is
important because it shows the position where a second layer
of polymers or proteins is expected to adsorb in the formation
of layer by layer assembly.66 The magnitude of charge reversal
is not very large in the case shown. Moreover, we do not attempt
Figure 6. Electrostatic potential as a function of the distance from to quantify the optimal conditions for this effect.67 The important
the metal (full line, left axis) calculated for a Au/MPS/PAH-Os electrode result is how the charge reversal arises from the molecular
with the PAH-Os molecular model for the same conditions as Figure organization of the film and the distribution of the different
5. The total polymer volume fraction profile is shown by the dashed charged components. This is explicitly shown in Figure 7B.
line (left axis).
There is a large adsorption of cations inside the thiol layer
to compensate for the large charge arising from the negatively
charged sulfonate groups from the thiol. There is a further large
adsorption of positive charges arising from both the polymer
and the Os. Within this region, 0.5 nm < z < 2.5 nm, there is
also an adsorption of anions to reduce the possibility of very
large local positive charge that would result in strong electro-
static repulsion. The number of polyions, with their associated
Os groups, is large enough to compensate for all of the negative
charge at about z ) 2 nm resulting in the charge reversal. The
positive charge is maintained up to z ) 4 nm, where all of the
charge is compensated for again by the anions, and the
cumulative charge is zero from there to the bulk solution.
A very insightful result obtained from Figure 7 is that the
charges are not localized in well-defined surfaces but are
distributed in a way to optimize electrostatic interactions,
molecular packing effects, and entropic effects, e.g., counterion
release. It is well-known that in polymer layers where charge
regulation is possible, for example by acid-base equilibrium,
the degree of dissociation is highly inhomogeneous.25,36,68,69 In
the present case, and with particular relevance to the electro-
chemical behavior, the question that arises is what is the
distribution of oxidized (and reduced) groups along the adsorbed
polymer layer.
Figure 8 displays the total distribution of osmium groups
together with the fraction of the oxidized sites. According to
the applied potential in the case shown, one would expect in a
bulk solution of free osmium complexes to have half of the
Figure 7. A. Total charge density (dashed line, left axis), eq 15, and
cumulative charge density (full line, right axis), eq 47, as a function of
moieties oxidized and half of them reduced. However, the
the distance from the electrode. B. Charge density profile for each of predictions of the theory show that this is not at all the case in
the charged molecular species considered by the theory. The calculations the film, and there is a rather large variation of the fraction of
were performed using the PAH-Os Molecular Model for the conditions oxidized groups depending on the location relative to the
of Figure 5. For a better visualization of the densities of protons see electrode surface. This implies the existence of a z-dependent
the inset in Figure 8. distribution of redox sites with different formal redox poten-
tials due to local environment effects, which result in peak
Interestingly, the decay length of the potential is not related to broadening.
the Debye length, which in this case is of the order of 1 nm, The fraction of oxidized states is a nonmonotonic function
but rather it is the distribution of charges driven by the molecular of the distance from the electrode. The quantitative effect is
organization of the polymer that controls the electrostatic very large, with the minimum in the fraction of oxidized
group reaching 0.15. This value is a factor of 3 smaller that
potential.
what would be expected from the free osmium in solution at E
The complete distribution of charges, 〈Fq(z)〉, and the con- ) EOs(II)/Os(III)
0
in the absence of local environment effects, i.e.,
tribution from each molecular species are shown in Figure 7. fOs ) 0.5. The understanding of the source of the effect can
bulk

The total charge at each distance from the surface reflects the be traced to eq 34, where the fraction of oxidized groups is
same trends described with the electrostatic potential. The found to be related to the electrode and standard potentials and
interesting result shown in Figure 7A is the cumulative charge to the local electrostatic potential. However, as shown in the
density defined by derivation of the theory, the electrostatic potential is strongly
Molecular Theory of Chemically Modified Electrodes J. Phys. Chem. C, Vol. 112, No. 2, 2008 469

Figure 8. Fraction of oxidized redox sites (solid line, left axis) and Figure 9. Theoretical predicted thickness-potential curves calculated
osmium site volume fraction (dashed line, right axis) as a function of for two different salt concentrations at pH ) 3.
the distance from the electrode at E ) EOs(II)/Os(III)
0
. Inset: local pH vs
distance from the electrode. The PAH-Os molecular model and the swelling is the same in both cases, and it can be traced to the
conditions of Figure 5 were used in the calculations. fact that the increase in the electrostatic charge increases the
electrostatic repulsions. The system relaxes in different ways:
coupled to the interactions, and therefore, it is the result of local by swelling, by the uptake of counterions, and by charge
and nonlocal electrostatic and packing effects. Namely, the regulation (protonation effects). The results in Figure 9 show
highly nonmonotonic electrostatic potential presented in Figure contributions from all three effects.
6 is responsible for the variations of fOs(z), but as discussed During the electrochemical oxidation process, the flux of
above the shape of the electrostatic potential in these complex electrons into/from the polymeric film requires a simultaneous
systems depends on the packing and the distribution of all the exchange of mobile ions with the bulk solution in order to
charged (and uncharged) molecules. sustain the system electroneutrality. As an example, during
Another manifestation of the non-trivial distribution of Os(II) oxidation, anion uptake or cation release are expected to
molecular species in the film is seen in the local pH, defined occur. Although it is not possible to study the ion exchange
by pH(z) ) -log[H+(z)]. This is shown in the inset of Figure mechanism using only electrochemical techniques, there are
8. Note that the proton distribution is also shown in Figure 7B; several in situ methods, such as EQCM and probe beam
however, its distance dependence cannot be observed on the deflection (PBD), which can probe the ionic fluxes close to the
scale of that plot. The thin film is very acidic in the thiol region electrode surface. The molecular theory allows the straightfor-
due to the presence of the sulfonate groups there. In the region ward calculation of the individual ionic contributions to the non-
rich in osmium and amino groups, there is a large repulsion to redox and redox capacities18 and therefore to the ionic fluxes
the protons and, therefore, a higher pH value as compared to under electrochemical reversible conditions. Following the same
the bulk value. The shape of the local pH profile follows that ideas used in the derivation of eqs 39, 41, and 44, the individual
of the fraction of oxidized redox sites. The smaller the fraction normalized ionic current for each ion is determined from the
of oxidized osmium sites, the smaller the concentration of potential dependence of its surface excess. Namely
protons. Interestingly, the changes in local pH from the metal
to the maximal pH are very dramatic, reflecting changes in the ji ∫
∂ (Fi(z) - Fbulk
i ) dz
local concentration of protons larger than 2 orders of magnitudes ) -qiF (48)
within 1 nm. This large gradient in pH may have potential V abs
∂Eeq
applications in the design of sensors and they have to be taken
into account in understanding chemical reactivity in nanocon- In the particular case when i ) H+, eq 48 should be modified
fined environments. Local variations of pH have been observed to include the protons associated with the polymer and MPS to
experimentally in LbL films by v. Klitzing and Möwald.70 lead to

(∫
4.4. Theoretical Description of the Electrochemical Pro-
cess. The swelling of polymer films during redox switching and j H+ ∂ (FH+(z) - FHbulk
+ ) dz ∫
∂ fc(z)〈nP(z)〉 dz
the resulting changes in film volume upon changes in the ) -qH+F + +
V ∂Eabs ∂Eabs

)
oxidation state are well established in polymer electrochemistry.7 eq eq
The electrochemical driven swelling has been studied in layer
by layer53,71 polymer modified electrodes with PAH-Os by
∫
∂ [(1 - fc,MPS(z))〈nMPS(z)〉] dz
(49)
electrochemical quartz crystal microbalance (EQCM) and in situ ∂Eabs
eq
ellipsometry.
The molecular theory can predict the redox-driven swelling; Figure 10 exhibits the scan rate normalized ionic currents during
in order to show this, we have plotted the calculated average film oxidation under permselectivity conditions (low ionic
film thickness as a function of the applied electrode potential strength). The concentrations of protons and hydroxyls ions are
in Figure 9 for two different solution ionic strengths. The shape coupled by the water self-dissociation equilibrium, and therefore,
of the thickness-potential curves and the inflection point at E their ionic fluxes cannot be addressed individually but as a
) Epeak is in very good qualitative agreement with previous combined current. It is also worthwhile to note that the sum of
ellipsometric measurements in PAH-Os/poly(vinyl-sulfonate) all ionic currents is equal to the total electronic current obtained
multilayers.71 Although a direct comparison of these experi- by combination of its redox and non-redox components.
mental observations is not possible since the theory has been For either totally oxidized or totally reduced redox polymers,
applied to a single PAH-Os layer, the driving force for the i.e., E e 0.10 or E g 0.55 V in Figure 10, we find that cations
470 J. Phys. Chem. C, Vol. 112, No. 2, 2008 Tagliazucchi et al.

This prediction is consistent with previous experimental findings

and is the driving force for the formation of polyelectrolyte
multilayers.
The distribution of the allyl-amine segments forming the
polymer backbone is found to be mostly that of a tightly
adsorbed layer with most of the segments in the close vicinity
of the surface with a few long dangling tails protruding into
the solution. The osmium complex concentration fraction profile
exhibits a maximum at a distance from the electrode surface as
a result of the bulky size of the osmium pyridine-bipyridine
moiety. This result is relevant to understand the distance-
dependent electron-transfer process with the metal electrode.
The distribution of the formal redox potentials in the direction
normal to the electrode predicted by the theory is the result of
Figure 10. Scan rate normalized ionic currents vs electrode potential the complex interplay between the electrostatic potential, the
calculated with eqs 48 and 49 and the PAH-Os molecular model for molecular packing, and the distribution of charged species. The
Csalt ) 10 mM and pH ) 3. Inset: Scheme showing the directions of
existence of a nonuniform formal redox potential is consistent
ionic and electronic currents.
with the concepts of Anson et al.60 and Albery et al.61 to explain
the peak broadening.
are responsible for non-redox charging. The compensation of The comparisons with the experimental observations have
redox charge, on the other hand, is achieved mainly by the been carried out for a model polymer that is in a poor solvent
anions and to a lesser extent by the cations. Thus, the theory environment. This condition leads to the tendency of the polymer
predicts the exchange of both anions and cations, which is to collapse. On the other hand, the strong electrostatic repulsions
consistent with previous PBD experiments in PAH-Os capped tend to swell the polymer as much as possible. Overall, the
PAH-Os/PVS multilayers.72,73 compromise results in a polymer in a mildly poor solvent. The
thickness of the predicted film is in line with experimental
To the best of our knowledge, this is the first theoretical
observations based on ellipsometry. We have shown that the
prediction of volume change and ionic contribution to the charge
theory applied to the case of a good solvent predicts a much
compensation in chemically modified electrodes.
thicker layer than the experimental observations and the
electrochemical peak positions are poorly predicted.
5. Conclusions The size of the redox sites has a dramatic influence on the
structure and current potential curves of the polymer film. This
We have applied a molecular theory to study the structure
demonstrates the important coupling that exists between mo-
and thermodynamic properties of a monolayer of redox poly-
lecular organization and electrochemical response, and it furthers
electrolyte adsorbed on a mercapto propane sulfonate thiolated
points out to the need to describe the polymer layer at the
gold electrode in contact with an aqueous electrolyte. The theory
molecular level.
explicitly incorporates the size, shape, conformations, charge,
The predictive capacity of the molecular theory presented here
and charge distribution of all of the molecular species. Through
brings the possibility of a rational design of chemically modified
a free energy formulation, we include conformational dependent
electrodes tailored to precise properties. Furthermore, the theory
electrostatic, van der Waals, adsorption and excluded volume
allows the determination of the conditions where approximate
interactions, as well as the chemical equilibrium for the different
(analytical) models are valid. We are currently extending the
acid-base and redox groups. The approximations used in the
molecular approach to study LbL deposition in polyelectrolytes
derivation of the theory as well as its limitations have been
and proteins. Moreover, we are coupling the structural features
extensively discussed elsewhere.34-36
predicted by the theory to the kinetics of electron transfer.
The theory predicts the current-potential curves under
reversible conditions, the dependence of the peak potential Acknowledgment. E.J.C. and M.T. acknowledge financial
position and the peak width with the electrolyte concentration, support from CONICET (Argentina), the University of Buenos
and the film thickness and its dependence on the electrolyte Aires, and ANPCyT (BID 1728 OC-AR PICT 2003 No. 06-
concentration and the electrode potential. Excellent agreement 17170). M.T. has a cooperative CONICET-FUDETEC industrial
of these predictions with the experimental results for the Au/ research grant. E.J.C. is a permanent research staff of CONICET.
MPS/PAH-Os system has been found for different experimental I.S. acknowledges the financial support from the National
conditions without the use of any free adjustable parameter. It Science Foundation of the United States CTS-0338377 and
is important to emphasize that the theoretical approach presented NIRT-0403903 and the Raices-Milstein Program of the Argen-
here does not separate double layer charging and redox tine Secretary for Science and Technology (SETPCyT).
pseudocapacitive currents as independent quantities, as is usually Supporting Information Available: A detailed description
done in most electrochemical literature. The molecular theory of the numerical methods used to solve the molecular theory;
accounts for the total flow of charge, including any possible the chain model and generation method and the effect of the
cross interaction, and enables the understanding of the relation- chain length and complete ref 69. This material is available free
ship between the current-potential curves observed and the of charge via the Internet at http://pubs.acs.org.
molecular structure of the film.
The theory predicts the distribution profiles of all molecular References and Notes
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