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Kinetics of Metal Deposition via Surface-Limited Redox Replacement Reaction

Conference Paper  in  ECS Transactions · January 2011

DOI: 10.1149/1.3641460

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 ECS Transactions, 35 (21) 11-22 (2011)
10.1149/1.3641460 © The Electrochemical Society

Kinetics of Metal Deposition via Surface-limited Redox Replacement Reaction

Dincer Gokcen a, Sang-Eun Bae a, Stanko R. Brankovic a,b,c*

a
Electrical and Computer Engineering Department
b
Chemical and Biomolecular Engineering Department
c
Chemistry Department
University of Houston, Houston, TX 77204-4005

Abstract
In this work, we examined the kinetics of metal deposition via
surface-limited redox replacement reaction (SLRR). The model
system was Pt submonolayer deposition on Au(111) via redox
replacement of Pb and Cu underpotentially deposited (UPD)
monolayers (MLs) on Au(111). The deposition kinetics were
studied through the formalism of the comprehensive analytical
model developed to fit open circuit potential (OCP) transients from
our deposition experiments. Reaction half time, reaction order, and
reaction rate constant were extracted and discussed within the
frame of their application to the design and control of deposition
experiments. Through the scope of the analytical model, different
aspects of SLRR (i.e., the nature of the UPD metal monolayer
participating in the redox reaction, the transport limitation, and the
role of the anions/electrolyte) were investigated in terms of their
effects on the reaction kinetics.

Introduction

The electrochemical deposition method based on surface-limited redox replacement

(SLRR) of underpotentially deposited (UPD) sacrificial metal monolayers (MLs) has
gained considerable attention in the scientific community due to its broad applications in
epitaxial ultra-thin film growth of highly active catalysts (1,2,3,4,5,6), nanoparticles
(7,8,9), and single crystal metal overlayers (10,11) and in spectroscopic studies of
modified surfaces ( 12 , 13 ). UPD unveils a unique method for potential controlled
adsorption of noble metals at the monolayer level at room temperature and pressure.
However, this capability is limited with some materials due to the kinetic aspects. Au, Pt,
and Pt group metals exhibit some of the exceptions where the monolayer design is not
directly conceivable by a UPD process. Owing to high catalytic properties, Pt and Pt
group metals represent a point of interest in many fuel cell applications. The UPD-
assisted SLRR technique offers the prospect to grow and to study these noble metals
down to a fraction of a monolayer while preserving the integrity of their interface.

Throughout the stoichiometric studies, we recently addressed the reaction

mechanism and the relation between the amount of the sacrificial UPD metal monolayer
and resulting deposits (14). The electrochemical and scanning tunneling microscopy
(STM) analyses emphasized the influence of the anions in determining the stoichiometry.
In our previous studies, a comprehensive analytical model was also developed to

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 ECS Transactions, 35 (21) 11-22 (2011)

illustrate the open circuit potential (OCP) transients during the redox replacement of the
sacrificial UPD metal layer by a more noble metal (15). The analytical model is endowed
with the appropriate framework to study and to quantify the kinetics of metal deposition
via SLRR reaction. Despite the fact that the concept behind this deposition method has
the potential for use in a wide range of applications, the governing parameters controlling
the reaction kinetics still need to be investigated in more detail for the design of optimum
deposition experiments.

In this work, our primary purpose is to elaborate on the factors influencing the
deposition flux and reaction kinetics of metal deposition via SLRR of UPD ML. For the
model system, we employed Pt submonolayer deposition on Au(111) via redox
replacement of Pb and Cu UPD MLs on Au(111) (in future text, denoted as
PbUPD/Au(111) and CuUPD/Au(111)) in HClO4 and H2SO4 supporting electrolytes, owing
to the motivation from extensive research studies conducted with these materials and
electrolytes. Reaction half time, reaction order, and reaction rate constant were the
primary parameters determining the reaction kinetics. Experimental findings are
correlated with the model reported previously to calculate these parameters, while we
also considered the effects of transport limitation and the role of anions/electrolyte on
deposition kinetics.

Experimental Procedure

The Au(111) single-crystal (Monocrystals Co.) rotating disk electrode (RDE)

with a diameter of 10 mm was used as the working electrode (WE). The single-crystal
surface preparation was carried out via several steps including mechanical polishing,
electropolishing, and hydrogen flame annealing. Following the mechanical polishing with
9, 3, 1, and 0.25 μm diamond suspensions, the crystal was electropolished by anodization
in a 2.5:1.5:1 solution of ethylene glycol, hydrochloric acid, and ethanol. The annealing
period was determined with special care to avoid surface reconstruction. As a result of the
entire treatment process, the typical Au(111) surface characteristics exhibited 100-1000
nm wide terraces separated with monoatomic high steps and step bunches. A Pt wire was
used as the counter electrode (CE) in the experiments, and all potentials are referred to
saturated calomel electrode (SCE) for convenience.

All solutions were prepared using ultrapure chemicals (99.999%, Alfa Aesar,
Merck) and 18.2 MΩ ultrapure water (Millipore Direct Q-UV with Barnstead A1007 pre-
distillation unit). Triple-distilled HClO4 was used to ensure the residual content of Cl- in
the solutions was lower than 10-7 M. UPD experiments were performed from 10-3M X +
0.1M HClO4 (X=Cu2+ and Pb2+). The redox replacement reaction experiments were
performed from 10-3 M and 10-5 M {PtCl6}2- solutions with either 0.1 M H2SO4 or HClO4
supporting electrolytes. The solutions were deaerated with ultra-high-purity Argon gas
for 2 hours to reduce to dissolved oxygen content in the solutions. Including STM
measurements, all experiments were carried out in a Nitrogen-purged glove box.
Following a 2-hour deaeration, the typical oxygen reduction current density on the Pt
electrode at 0 V versus SCE was measured ~ 25 nA.cm−2, indicating the residual oxygen
level in the solutions was negligible (< 10−6 M) (16,17).

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 ECS Transactions, 35 (21) 11-22 (2011)

Sequential steps of the experimental procedure have been described in detail

elsewhere (14). Briefly, the procedure begins with the Cu and Pb UPD ML formation
from 10-3 M X + 0.1 M HClO4 (X=Cu2+ and Pb2+). The UPD process is followed by
redox replacement of CuUPD/Au(111) or PbUPD/Au(111) from 10-3 and 10-5 M {PtCl6}2-
solutions with either 0.1 M H2SO4 or HClO4 supporting electrolytes. Between these steps,
the crystal is cleaned with 1:1 HNO3 and 18.2 MΩ ultrapure water. For characterization
of surface structures, STM measurements are carried out using a Nanoscope MultiMode
V scanning probe microscope inside the glove box. Electrochemically etched 85/15 Pt/Ir
wires, coated with Apiezon wax, are used as STM tips.

Results

1. SLRR Rate Equations

SLRR reaction rate (rSLRR) can be described by the decrease in UPD ML coverage
(concentration; CM,UPD) in a certain time (t), viz (15):
dCM ,UPD
− = rSLRR [1]
dt
Deposition via SLRR might be limited by the transport of noble metal ions from
the bulk solution towards the electrode surface. The transport-limiting conditions exist
when the concentration of ions in the displacement solution (in future text, denoted as
Pp+) is very low. In the previous work, we defined this phenomenon as transport-limited
redox replacement (TLRR) of UPD ML (15). Throughout this sort of exchange process,
the rate of the metal deposition via SLRR reaction is controlled by the concentration of
Pp+ ions in the bulk solution rather than by the concentration of the UPD adatoms or Pp+
ions in the electrode surface. Thus, the TLRR reaction simply has zero order in terms of
UPD ML coverage. In this set of materials, the rate equation for transport-limiting
conditions was derived as (18):
θ UPD = 1 − k 0 ⋅ t [2]
p+
In some other conditions, the diffusion limiting flux of P might be much
larger than the rate of SLRR reaction. This simply implies that the solution phase does
not limit reaction kinetics. The concentration of P ions in the solution apparently reaches
a steady state throughout the SLRR reaction in this sort of reaction. Relying on our
previous study, for Nth-order reaction kinetics, the rate equation can be simply expressed
by (15)
θ UPD = (1 + K ⋅ t )1 (1− N ) [3]
st
and the rate equation for 1 -order reaction kinetics is found by the integration of Eq. [3],
viz (15):
θ UPD = exp( − k ' t ) [4]

2. Formation of UPD ML and Adsorption Isotherms for UPD Systems

Fig. 1 shows the representative cyclic voltammograms for Pb and Cu UPD

systems from 10-3 M X + 0.1 M HClO4 (X=Cu2+ and Pb2+). General features of cyclic
voltammograms for Cu and Pb UPD systems are in agreement with the literature (19,20).
Prior to each redox replacement reaction, it is crucial to obtain the characteristic features

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 ECS Transactions, 35 (21) 11-22 (2011)

on the cyclic voltammograms of UPD systems. The quality of the cyclic voltammetry
needs to be ensured for the consistency of the replacement reaction, because our
structural examinations revealed that Pt cluster distribution and surface eminence highly
depend on the sacrificial monolayer. CV of CuUPD/Au(111) shows an identical
asymmetric cathodic peak with a poorly defined maximum due to the slow reorganization
of Cu adatoms and coadsorbed anions. In the case of PbUPD/Au(111) from 0.1 M HClO4
containing solution, a sharp cathodic peak is followed by two identical anodic peaks.
Relying on cyclic voltammetry studies, full Cu and Pb UPD ML were consistently
deposited at 30mV underpotential. Compatible with literature data (19,20), STM
characterization confirmed the characteristic crystallography of PbUPD/Au(111) and
CuUPD/Au(111). Unlike CuUPD/Au(111), in situ STM observations exposed the
appearance of atomic-size vacancies on some regions after stripping the Pb(UPD)
monolayer. This means there might be Pb-Au alloying as reported in the literature (21).

Figure 1. CV of (A) CuUPD/Au(111) from a 10-3 M Cu2+ + 0.1 M HClO4 solution, (B)
PbUPD/Au(111), solution: 10-3 M Pb2+ + 0.1 M HClO4. The insets show the atomic
resolution images of full MLs.

The UPD is a potential dependent adsorption/desorption process, and UPD

coverage can be defined as a function of applied potential (ΔE). Over the years, the
potential dependent adsorption process of UPD has been modeled using Langmuir
(22,23), Temkin (24), and Frumkin (25) isotherms. Among all, the analytical model of
Swathirajan and Bruckenstein (S&B) can be applied to any UPD system to interpret the
adsorption isotherms (26). The S&B isotherm covers Langmuir, Temkin, and Frumkin

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 ECS Transactions, 35 (21) 11-22 (2011)

foundations all together. Langmuir implies the additivity basis of the various UPD
adatom-substrate and adatom-adatom interactions, while Temkin and Frumkin parameters,
respectively, describe UPD adatom-substrate interactions and lateral atom interactions. In
our analytical studies, we preferred to utilize the S&B model to interpret Pb and Cu
adsorption isotherms for in-depth interpretations of our experimental findings. Simpler
isotherms could yield less accurate representations of UPD systems. Considering the
electrosorption valence of UPD adatoms is equal to the oxidation state of the metal ions,
the S&B isotherm can be given by
RT ⎡ ⎛ θ ⎞ 3/ 2 ⎤
E = Eθ → 0 − ⋅ ⎢ln⎜ ⎟ + fθ + gθ ⎥ [5]
m⋅F ⎣ ⎝1 − θ ⎠ ⎦
Here, Eθ→0 refers to the equilibrium potential where UPD ML approaches zero. f and g
represent Temkin and Frumkin parameters, respectively. The RT/mF term is constant
with a numerical value of 0.026/m where m is the oxidation state of the UPD metal (Mm+)
in the SLRR reaction.

3. Open Circuit Potential Transients

OCP transients during SLRR of UPD metal ML are an indirect way to study θUPD
vs. t. The analytical model describing potential as a function of time (E vs. t) can be
derived by combining the expression for the rate equation with the S&B adsorption
isotherm (15). From Eqs. (2) and (5), zero-order reaction kinetics in terms of θUPD
(deposition via TLRR) can be expressed by (15)

RT ⎡ ⎛ 1 − k 0 t ⎞ ⎤
E = Eθ → 0 − ⋅ ⎢ln⎜⎜ ⎟⎟ + f ⋅ (1 − k 0 t ) + g ⋅ (1 − k 0 t ) 3 2 ⎥ [6]
mF ⎣⎢ ⎝ k 0 t ⎠ ⎦⎥
where the fitting parameters are Eθ→0, k, f, and g. In a similar vein, from Eqs. (3) and (5),
we obtain E vs. t dependence for the 1st-order reaction kinetics in terms of θUPD
(deposition via SLRR), and the general expression for E vs. t dependence for Nth-order
reaction kinetics can be given by (15)

RT ⎡ ⎛ (1 + Kt ) 1 (1− N ) ⎞ ⎤
E = Eθ → 0 − ⋅ ⎢ln⎜⎜ 1 (1− N )
⎟⎟ + f ⋅ (1 + Kt ) 1 (1− N ) + g ⋅ (1 + Kt ) 3 ( 2 − 2 N ) ⎥ [7]
mF ⎣ ⎝ 1 − (1 + Kt ) ⎠ ⎦
Representative surface morphologies and OCP transients of the Pt deposition via
SLRR of PbUPD/Au(111) and CuUPD/Au(111) in 10-3 M {PtCl6}2- + 0.1 M H2SO4
containing solution are shown in Fig. 2. The high concentration of the sulfate anions
confirms that Pb and Cu UPD adatoms are oxidized to the most stable oxidation state in
this electrolyte, 2+ ions (Pb2+, Cu2+). Since the oxidation state of Pt in the
hexachloroplatinate complex is 4+, the corresponding stoichiometries of both SLRR
reactions are described as follows (15,18):
0
2PbUPD 4+
/ Au(111) + Pt solv ⇒ 2Pbsolv
2+
+ Pt s0 / Au(111) [8]
0
2CuUPD 4+
/ Au(111) + Pt solv ⇒ 2Cu solv
2+
+ Pt s0 / Au(111) [9]

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 ECS Transactions, 35 (21) 11-22 (2011)

Figure 2. OCP transients for Pt deposition via SLRR of (A) CuUPD/Au(111) and (B)
PbUPD/Au(111), in 10-3 M {PtCl6}2- + 0.1 M H2SO4 with the model fit (Eq. [7]). Insets
show the representative morphology of deposited Pt.

In both cases, the stoichiometries suggest that two UPD adatoms are displaced by one Pt
ion. Since these stoichiometries represent basic reactions, these SLRR processes can be
elaborated in terms of 2nd-order reaction kinetics. As shown in Fig. 2, the analytical
model shown in Eq. [7] fits the experimental data very well. The fitting parameters (i.e.,
Eθ→0, K, f, and g) are calculated for each SLRR reaction, shown in Table 1. Relying on the
analytical model and experimental findings, the Pt deposition via SLRR of
PbUPD/Au(111) is approximately two times faster than that of CuUPD/Au(111). As
discussed in our previous study, the faster reaction kinetics result in a lower activation
energy for the activated complex (15,24). Therefore, the activated complex of {PtCl6}2- -
Pb UPD adatom has a lower activation energy as compared to the activated complex of
{PtCl6}2- -Cu UPD adatom. Carrying Pb and Cu UPD adatoms to the activated state,
where electron transfer to {PtCl6}2- exists, causes the difference in kinetics and activation
energies. Since Pb UPD adatoms have a lower work function, they are activated more
easily than Cu UPD adatoms. In the same supporting electrolyte, the UPD metal with the
lower work function stimulates the faster kinetics of the SLRR reaction. The trend of
reaction kinetics in Pt deposition via these SLRR reactions is a reasonable reflection of
physical phenomena. The qualitative thermodynamic difference between Pb and Cu UPD
systems causes the difference in Eθ → 0 values. Eθ → 0 of CuUPD/Au(111) shows a more

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 ECS Transactions, 35 (21) 11-22 (2011)

positive value as compared to PbUPD/Au(111), and this phenomenon is in agreement with

the literature data (19,20).

SLRR reaction experiments were also carried out in 10-3 M{PtCl6}2- + 0.1 M
HClO4 containing solution to examine the effect of supporting electrolytes on reaction
kinetics. Representative OCP transients of the SLRR reaction of PbUPD/Au(111) and
CuUPD/Au(111) systems are shown in Fig. 3. The SLRR of the Pb UPD system can be
stated with the same stoichiometry as the previous one, since there is no change in m, p,
or RT/mF. Therefore, the same model is used to fit OCP transients in Fig. 3. Table 2
demonstrates the values extracted from the model. The value of the rate constant is
smaller than the one for the experiment where the supporting electrolyte was H2SO4,
because the SLRR reaction is affected by the anions in the supporting electrolyte. This
means the rate of Pt deposition via SLRR of PbUPD/Au(111) can be altered by the proper
choice of the supporting electrolyte. {SO4}2- is a strong ligand for metal ions while
{ClO4}- is considered to have no complexing affinity towards metal ions (27,28). The
higher stability of {SO4}2- promotes the metal dissolution/oxidation process during the
SLRR reaction in the {SO4}2- containing electrolyte.

SLRR of CuUPD/Au(111) by Pt represents a more complicated system for the

determination of oxidation states. In our previous study (14), experimental conditions
suggested that Cu UPD adatoms oxidize to Cu(I) ions rather than Cu(II) ions in the
HClO4 containing solution. The residual chlorides in the HClO4 containing solution form
a strong complexing ligand that promotes the stability of Cu(I) over Cu(II) ions. The Cl-
content in the solution was lower than 10-7 M, and no presence of other UPD adlayer
structures or phase transitions was observed. The oxidation and dissolution of Cu UPD
adatoms liberates Cl- ions, and this process supplies enough Cl- content to favor stability
of Cu(I) over Cu(II) ions. Considering the complexity due to the Cl- ions as a spectator
species, the final SLRR stoichiometry for this system is given by

solv + 2Cl ⇒ 4{CuCl2 }solv + Pts / Au(111) [10]

0 − −
4CuUPD / Au(111) + {PtCl6 }2− 0

Unlike previous stoichiometries, here, the value of m is 1. The model fits the
experimental data well, while Cl- content is also considered. The fitting parameter values
extracted from Eq. [7] are shown in Table 2. The slight decrease in the Eθ→0 value is
observed for solutions containing HClO4 as compared to the solutions containing H2SO4.
The accuracy of the model fit also reveals that Cu UPD adatom oxidation/dissolution
promotes Cu+ ({CuCl2}-) in the HClO4 electrolyte. The difference in values of Eθ→0 was
predicted, because the standard redox potential of the Cu/{CuCl2}- couple is more
negative than that of Cu/Cu2+ (34). The rate constant for the SLRR of CuUPD/Au(111)
appears to be slightly slower for the SLRR reactions carried out from solutions containing
HClO4. It is important to note that the Pt deposition rate and SLRR reaction kinetics are
not tremendously affected by the change of the electrolyte. Our results also suggest that
the SLRR of CuUPD/Au(111) in solution containing HClO4 has the same reaction order
(~2) as the SLRR of CuUPD/Au(111) in solution containing H2SO4. Our previous study
also indicated that, regardless of the stoichiometry of the SLRR reaction for a particular
metal deposition, the order of the reaction should be considered as 2 when more than one
UPD adatom is necessary for the reduction of the depositing metal ion (15).

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 ECS Transactions, 35 (21) 11-22 (2011)

The faster reaction kinetics of SLRR with the PbUPD/Au(111) system were
observed for the experiments carried out from the H2SO4 containing solution. Extracted
values of reaction kinetics imply the existence of a reverse trend. The formation of
insoluble PbCl2 as an intermediate for the formation of solvated Pb2+ in 0.1 M HClO4
causes delay as compared to the reaction kinetics of SLRR of CuUPD/Au(111). The
nature of both UPD metal and dominant anions has a significant effect on the SLRR
reaction kinetics. Electrolyte type does not have any impact on the thermodynamics of
SLRR of PbUPD/Au(111), because extracted values of Eθ → 0 during Pt deposition via
SLRR in 0.1 M HClO4 and 0.1 M H2SO4 are the same. Even though the complexity of the
mechanistic pathway for the formation of Pb2+ ions caused by the presence of Cl- in 0.1
M HClO4 affects the speed of Pt deposition, the driving force remains unaffected.

Figure 3. OCP transients for Pt deposition via SLRR of (A) CuUPD/Au(111) and (B)
PbUPD/Au(111), in 10-3 M {PtCl6}2- + 0.1 M HClO4 with the model fit (Eq.[7]). Insets
show the representative morphology of deposited Pt.

We also elaborated on the effect of the concentration of depositing metal ions and
ion transport across the diffusion layer. Considering that SLRR reaction kinetics are
directly proportional to the surface concentration of depositing metal ions, the
concentration of the {PtCl6}2- ions was switched to 10-5 M to examine TLRR. Our
previous study suggested that, in the SLRR process, the surface concentration of
depositing metal ions is proportional to their concentration in bulk (15). Our experimental
data indicates that faster kinetics are observed when the reaction volume of the solution

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 ECS Transactions, 35 (21) 11-22 (2011)

has a higher concentration of {PtCl6}2-. Fig. 4A shows the OCP transient for the Pt
deposition via SLRR of CuUPD/Au(111) where the concentration of {PtCl6}2- is a hundred
times smaller as compared to previous experiments. The model fit suggests that the
decrease in the concentration of {PtCl6}2- makes the rate constant forty times smaller,
indicating that the metal ion concentration in the reaction solution largely controls the
kinetics of deposition via SLRR of UPD ML. As a result, a higher concentration of
{PtCl6}2- ions stimulates faster kinetics of SLRR reactions and so a higher deposition rate.

Table 1. Parameters of the S&B isotherm describing θUPD vs. E dependence during SLRR
of UPD metal MLs.

UPD Red-ox Reaction Solution, E θ → 0 , [V] vs.

f g
Metal Reaction ω=1000 rpm SCE
10-3 M {PtCl6}2- +0.1 M -14 ±
0.53 ± 0.003 30 ± 0.8
PbUPD/Au(1 H2SO4 0.9
eq.(8)
11) 10-3 M {PtCl6}2- +0.1 M
0.54 ± 0.009 10 ± 0.8 -4 ± 0.4
HClO4
10-3 M {PtCl6}2- +0.1 M
eq.(9) 0.58 ± 0.00 4.2 ± 0.6 46 ± 0.5
H2SO4
10-3 M {PtCl6}2- +0.1 M 0.156 ± 18.6 ±
0.56 ± 0.002
HClO4 0.015 0.08
CuUPD/Au(
10-5 M {PtCl6}2- +0.1 M
111) 0.55 ± 0.00 -4.2 ± 0.19 69 ± 0.3
eq.(10) HClO4
10-5 M {PtCl6}2- +0.1 M
HClO4 -19.7 ±
0.54 ± 0.00 22 ± 0.002
0.3
NO MIXING, ω=0 rpm

Table 2. Parameters of the reaction kinetics.

Rate
Reaction Reaction
Red-ox Constant, Reaction
UPD Metal Solution, Half Time,
Reaction K or k0 Order,
ω=1000 rpm t½ [s]
[s-1]
10-3 M {PtCl6}2-
9.71±1.05 0.10
+0.1 M H2SO4
PbUPD/Au(111) eq.(8) 2*
10-3 M {PtCl6}2-
0.87±0.06 1.15
+0.1 M HClO4
10-3 M {PtCl6}2-
eq.(9) 4.08±0.07 0.24 2*
+0.1 M H2SO4
10-3 M {PtCl6}2-
3.61±0.03 0.27 2.07 1*
+0.1 M HClO4
10-5 M {PtCl6}2- 0.089±0.0
CuUPD/Au(111) 11.2 2*
+0.1 M HClO4 008
eq.(10)
10-5 M {PtCl6}2-
+0.1 M HClO4 0.0020±0.
250 0
NO MIXING, 0002
ω=0 rpm
* Reaction order determined from the reaction stoichiometry, see text for more details

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 ECS Transactions, 35 (21) 11-22 (2011)

To ensure the sufficiency of the transport rate of the {PtCl6}2- ions towards the
electrode surface, in previous experiments, the rotation rate was kept at 1000 rpm. Low
concentrations of {PtCl6}2- ions establish conditions where SLRR is controlled by the
transport (i.e., TLRR). Fig 4B shows the OCP transient acquired for the same solution,
but there was no rotation of the electrode. The model developed in our previous work fits
the data very well except for the initial interval of ~20 seconds (15). This is because
conditions for the TLRR reaction were not established immediately.

Figure 4. OCP transients for Pt deposition via (A) SLRR of CuUPD/Au(111) in 10-5 M
{PtCl6}2- + 0.1 M HClO4 (1000 rpm rotation rate), (B) TLRR of CuUPD/Au(111) in 10-5 M
{PtCl6}2- + 0.1 M HClO4 (no rotation).

Conclusion

The practical parameters of kinetics of SLRR reactions were extracted from the
formulism of comprehensive analytical models developed to fit OCP transients. Since
PbUPD/Au(111) has a lower work function than CuUPD/Au(111), faster deposition
kinetics were observed for the Pb UPD system in the H2SO4 containing solution. An

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 ECS Transactions, 35 (21) 11-22 (2011)

inverse phenomenon was observed in the HClO4 containing solution, indicating that the
presence of Cl- as complexing anions affects the reaction rate significantly. Our analysis
suggests that the supporting electrolytes do have a significant impact on the kinetics of
the Pt deposition via SLRR of PbUPD/Au(111); however, this effect is not valid for SLRR
of CuUPD/Au(111). Our results reveal that the optimum Pt deposition rate can be achieved
by altering the concentration of {PtCl6}2- ions. Higher concentrations result in higher
reaction rates, and low concentrations establish the TLRR process. We do believe that
this study will stimulate further understanding of the SLRR of UPD ML.

Acknowledgements

This research was supported in part by the National Science Foundation, Division of
Electrical, Communications, and Cyber Systems (NSF ECCS-0824215) and the
American Chemical Society Petroleum Research Fund (PRF-47849-G5).

References

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