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www.elsevier.com/locate/ijhydene

adsorption isotherms of over-potentially deposited hydrogen for the

cathodic H2 evolution reaction at the poly-Pt/H2 SO4 aqueous

electrolyte interface

Jang H. Chuna, , Sang K. Jeona , Nam Y. Kima , Jin Y. Chunb

a Department of Electronic Engineering, Kwangwoon University, Seoul 139-701, South Korea

b School of Chemical Engineering, Seoul National University, Seoul 151-744, South Korea

Available online 22 January 2005

Abstract

A linear relationship between the behavior ( vs. E) of the phase shift (0 90 ) for the optimum intermediate

frequency and that ( vs. E) of the fractional surface coverage (1 0) of over-potentially deposited hydrogen (OPD H) for

the cathodic H2 evolution reaction (HER), i.e., the phase-shift method, at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface

has been veried using cyclic voltammetric, differential pulse voltammetric, and ac impedance techniques. The phase-shift

method for determining the suitable adsorption isotherm (Langmuir, Frumkin, Temkin) of OPD H for the cathodic HER at the

interface also has been proposed. At the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface, the Langmuir adsorption isotherm

( vs. E) of OPD H, the equilibrium constant (K =1.3104 ) for OPD H and the standard free energy (G0ads =22.2 kJ/mol)

of OPD H are determined using the phase-shift method. At the same interface, the Temkin adsorption isotherm ( vs. E) of

OPD H, the equilibrium constant (1.3 103 K 1.3 105 with , i.e., 0 1) for OPD H, and the standard free

energy (16.5 G0 27.9 kJ/mol with , i.e., 0 1) of OPD H are also determined using the phase-shift method. At the

intermediate values of , i.e., 0.2 < < 0.8, the Langmuir and Temkin adsorption isotherms of OPD H for the cathodic HER

at the interface are converted to each other. The equilibrium constant (K0 ) for the Temkin adsorption isotherm ( vs. E) is

ca. 10 times greater than that (K) for the corresponding Langmuir adsorption isotherm ( vs. E). The interaction parameter

(g) for the Temkin adsorption isotherm ( vs. E) is ca. 4.6 greater than that (g) for the corresponding Langmuir adsorption

isotherm ( vs. E). These numbers (10 times and 4.6) can be taken as constant conversion factors between the corresponding

adsorption isotherms (Temkin, Langmuir, Frumkin). The Temkin adsorption isotherm corresponding to the Langmuir or the

Frumkin adsorption isotherm, and vice versa, can be effectively converted using the constant conversion factors. Both the

phase-shift method and constant conversion factors can be effectively used as a new electrochemical method to determine the

suitable adsorption isotherms (Langmuir, Frumkin, Temkin) of H for the cathodic HER in electrochemical systems.

2005 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Keywords: Phase-shift method; Langmuir, Frumkin, and Temkin adsorption isotherms; Constant conversion factors; Hydrogen adsorption;

Pt electrode

1. Introduction

Corresponding author. Tel.: +82 2 940 5116;

E-mail address: jhchun@daisy.kwangwoon.ac.kr (J.H. Chun).

For clean environment and energy, the cathodic H2 evolution reaction (HER) at noble and transition-metal/aqueous

0360-3199/$30.00 2005 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

doi:10.1016/j.ijhydene.2004.12.005

1424

J.H. Chun et al. / International Journal of Hydrogen Energy 30 (2005) 1423 1436

electrolyte interfaces has been extensively studied in electrochemistry and electrochemical hydrogen technologies.

Many experimental methods have been used to study the adsorption sites and processes of under-potentially deposited

hydrogen (UPD H) and over-potentially deposited hydrogen

(OPD H) for the cathodic HER at these interfaces [120].

It is well known that UPD H and OPD H occupy different

surface adsorption sites and act as two distinguishable electroadsorbed H species, while only OPD H can contribute to

the cathodic HER [4,68,1420]. However, the kinetics and

mechanism of the cathodic HER have been studied mainly

using steady-state polarization experiments. Thus, there is

not much reliable kinetic and thermodynamic data, i.e., the

equilibrium constant and standard free energy relating to

the adsorption sites and process of the OPD H, at these

interfaces.

At interfaces, it is preferable to consider the adsorption

isotherm (Langmuir, Frumkin, Temkin) for H (UPD H,

OPD H) rather than an equation of the electrode kinetics

and thermodynamics for H (UPD H, OPD H), because

the adsorption isotherm (Langmuir, Frumkin, Temkin) can

be associated more directly with the atomic mechanism

of H (UPD H, OPD H) adsorption. A link between the

microscopic system of adsorption sites and processes on

atoms and the macroscopic system of electrode kinetics and

thermodynamics at interfaces has been extensively studied

in chemistry, physical electrochemistry, surface science,

etc. [21]. The adsorption isotherms (Langmuir, Frumkin,

Temkin) are effective for characterizing the relation, transition, and criterion between UPD H and OPD H for the

cathodic HER at interfaces. Thus, there is a technological

need for a fast, simple, and reliable technique to determine the suitable adsorption isotherm (Langmuir, Frumkin,

Temkin) of H (UPD H, OPD H) for the cathodic HER

at interfaces.

For the cathodic HER in electrochemical systems, the

currentpotential relationship is determined completely by

the electrode potential (E) dependence of the fractional surface coverage () of H. Thus, one can interpret that the

electrode kinetic parameters for H will depend on the corresponding adsorption isotherm ( vs. E) of H, which relates

the surface concentration of H to the bulk concentration of

H and to the electrode potential (E). At limited values of ,

i.e., 0 and 1, the distinction between the adsorption isotherms (Langmuir, Frumkin, Temkin) of H is almost

impossible. At low and high values of , e.g., < 0.2 and

0.8 < , the distinction between the adsorption isotherms

(Langmuir, Frumkin, Temkin) of H is difcult. At intermediate values of , e.g., 0.2 < < 0.8, the distinction between

the adsorption isotherms (Langmuir, Frumkin, Temkin) of

H is easy. It is related to the rate of change of vs. E, i.e.,

/E or d/dE, which is maximized at 0.5 and minimized at 0 and 1. However, a linear relationship between

the behavior ( vs. E) of the phase shift (0 90 )

for the optimum intermediate frequency and that ( vs. E)

of the fractional surface coverage (1 0) of intermedi-

between the adsorption sites and processes of H (UPD H,

OPD H) and the adsorption isotherms (Langmuir, Frumkin,

Temkin) of H (UPD H, OPD H) for the cathodic HER at

interfaces.

Recently, we have experimentally found that the

phase-shift method1 can be effectively used to determine the Langmuir or the Frumkin adsorption isotherms

of UPD H and OPD H for the cathodic HER at noble and transition-metal (Pt, Ir, Pd, Au, Re, Rh, PtRh

alloy, Ni)/aqueous electrolyte interfaces [2234]. This

method is an effective way to study the H adsorption

sites and processes for the cathodic HER, the relation, transition, and criterion between UPD H and OPD

H, the electrode kinetics and thermodynamics at these

interfaces.

We consider the determination of the suitable adsorption isotherm (Langmuir, Frumkin, Temkin) of H (UPD

H, OPD H) for the cathodic HER at these interfaces

as follows. First, we determine the Langmuir adsorption isotherm and then nd the interaction parameter (g)

for the Frumkin adsorption isotherm based on the relevant experimental results, e.g., the fractional surface

coverage for the electrode potential, the phase-shift prole for the optimum intermediate frequency, etc. Finally,

the applicability of the Temkin adsorption isotherm at

these interfaces can be considered. It appears that the

phase-shift method is effective for determining the suitable adsorption isotherm (Langmuir, Frumkin, Temkin)

of H (UPD H, OPD H) for the cathodic HER at these

interfaces.

In this paper, we represent the phase-shift method

for determining the Langmuir and Temkin adsorption

isotherms of OPD H for the cathodic HER at a polycrystalline platinum (poly-Pt)/0.5 M H2 SO4 aqueous

electrolyte interface. This method is useful for estimating the electrode kinetic and thermodynamic parameters of OPD H for the cathodic HER at the interface.

This method is also useful to facilitate selection of the

optimal cathodic HER materials for yielding electrochemical systems of maximum performance. This paper is intended to supplement the previously published

papers [24,25].

the phase shift (0 90 ) for the optimum intermediate

frequency and that ( vs. E) of the fractional surface coverage (1 0) of H (UPD H, OPD H) at noble and transitionmetal/aqueous electrolyte interfaces has been veried using cyclic

voltammetric, linear sweep voltammetric or differential pulse

voltammetric, and electrochemical impedance spectroscopic techniques. The behavior ( vs. E) of the fractional surface coverage

(1 0) of intermediates is well known as the electrochemical

adsorption isotherm (Langmuir, Frumkin, Temkin).

J.H. Chun et al. / International Journal of Hydrogen Energy 30 (2005) 1423 1436

2. Experimental

of the diffuse double layer and pH [35], an acidic aqueous electrolyte was prepared from H2 SO4 (Sigma Aldrich,

reagent grade) with puried water (resistivity: > 18 M cm)

obtained from a Millipore system. The 0.5 M H2 SO4 aqueous electrolyte was deaerated with 99.999% puried nitrogen gas for 20 min before the experiments.

A standard three-electrode conguration was employed

using a saturated calomel electrode (SCE) reference

electrode and a poly-Pt wire (Johnson Matthey, purity:

99.9985%, 1 mm diameter, estimated surface area: ca.

1.01 cm2 ) working electrode. It appears that Pt is suitable

for verifying the adsorption isotherm (Langmuir, Frumkin,

Temkin) of H (UPD H, OPD H) for the cathodic HER using

the phase-shift method. The poly-Pt working electrode was

prepared by ame cleaning and then quenched and cooled

in Millipore Milli-Q water and in air, sequentially. A Pt wire

(Johnson Matthey, purity: 99.95%, 1.5 mm diameter) was

used as counter electrode. Taking into account the OPD H

and its large current distribution, the working and counter

electrodes were separated by ca. 4 cm in the same compartment of a Pyrex cell using Teon holders [36]. At the steady

state, by comparing the 15th cyclic voltammogram with the

20th cyclic voltammogram shown in Fig. 1, one can interpret that the contamination from anodic produced species

for the cathodic HER is negligible. For ac impedance experiments, negative dc potentials are sequentially applied to

the interface. Note that this conguration is effective for the

cathodic HER rather than general electrochemical reactions.

2.2. Measurements

A cyclic voltammetric (CV) method was used to observe

the UPD H peak, which is useful for verifying the adsorption isotherm (Langmuir, Frumkin, Temkin) of UPD H or

OPD H at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface. The CV experiments were conducted at a scan rate

of 200 mV/s and a scan potential of 0.241 to 1.0 V vs. SCE

for the poly-Pt electrode. This high scan rate (> 100 mV/s)

was used to conrm the state of the poly-Pt working electrode at the commencement of the cyclic scan.

After the CV experiments, a differential pulse voltammetric (DPV) method was used to study the Tafel slopes at

the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface. The

DPV experiments were conducted at a scan rate of 1 mV/s,

pulse height of 25 mV, pulse width of 50 ms, step/drop time

of 2 s, reversible potential of ca. 0.694 V vs. SCE, and scan

potential of 0 to 0.65 V vs. SCE. This slow scan rate

(< 10 mV/s) was used to obtain the steady-state Tafel plots.

An ac impedance method was used to study the relation

between the phase-shift prole for the optimum intermediate frequency and the corresponding adsorption isotherm

0.4

Current Density (i ) / mA cm-2

2.1. Preparations

1425

0.2

0.0

-0.2

A

-0.4

0.0

0.4

0.8

Potential (E ) / V vs. RHE

15th scan

20th scan

1.2

aqueous electrolyte interface. Scan potential: 01.241 V vs. RHE.

Scan rate: 200 mV/s. Number of scans: 20. Region: (A) Hydrogen

adsorption process, i.e., hydrogen reduction reaction, (B) hydrogen

desorption process, i.e., hydrogen oxidation reaction, (C) oxygen

adsorption process, i.e., oxygen oxidation reaction, and (D) oxygen

desorption process, i.e., oxygen reduction reaction.

the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface. The

ac impedance experiments were conducted at a single sine

wave, scan frequency of 104 5 Hz, ac amplitude of 5 mV,

and dc potential of 0 to 0.42 V vs. SCE for the poly-Pt

electrode.

The CV and DPV experiments were performed using an

EG&G PAR Model 273A potentiostat controlled with the

PAR Model 270 software package. The ac impedance experiments were performed using the same apparatus in conjunction with a Schlumberger SI 1255 HF Frequency Response

Analyzer controlled with the PAR Model 398 software package. To obtain comparable and reproducible results, all measurements were carried out using the same preparations,

procedures, and conditions at room temperature. The international sign convention is used, i.e., cathodic currents and

lagged phase shifts or angles are taken as negative. To clarify the hydrogen adsorption in the different aqueous electrolytes, all potentials are given in the reversible hydrogen

electrode (RHE) scale.

3.1. UPD H peak

Fig. 1 shows a typical cyclic voltammogram of the steady

state at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface. The UPD H peaks, i.e., the hydrogen adsorption

peaks, due to the reduction of hydrogen occur at ca. 0.06

and 0.20 V vs. RHE. The hydrogen desorption peaks due to

the oxidation of hydrogen occur at ca. 0.08 and 0.22 V vs.

1426

J.H. Chun et al. / International Journal of Hydrogen Energy 30 (2005) 1423 1436

-0.85

-0.80

(b)

-0.75

(a)

-0.70

-0.5

0.0

0.5

1.0

1.5

2.0

cm-2

interface. (a) Slope: 31 mV/decade and (b) slope: 122 mV/decade.

The Tafel plot is based on the technique of current impulse vs.

potential step.

-0.85

(b)

-0.80

(a)

-0.75

-0.70

-0.5

0.0

0.5

1.0

1.5

2.0

cm-2

interface. (a) Slope: 31 mV/decade and (b) slope: 122 mV/decade.

The Tafel plot is based on the technique of current step vs. potential

step.

hydrogen at the interface are reversible. The UPD H peaks

and the corresponding potentials (E) are useful for verifying the adsorption isotherm (Langmuir, Frumkin, Temkin)

of UPD H or OPD H for the cathodic HER at the interface.

However, it is well known that only OPD H can contribute

to the cathodic HER.

sured against the standard reference electrode.2 The negative overpotential, < 0, implies the cathodic HER at the

interface. It is well known that Tafel plots depend on the

technique of pretreatment.

The Tafel slopes shown in Figs. 2(a) or 3(a) and 2(b) or

3(b) are 31 and 122 mV/decade, respectively. These results

are similar to the typical Tafel slopes at noble metal (Pt, Ir,

Rh) electrode interfaces [1,38,27,31,37]. It is well known

that the Tafel slopes due to the rate-determining steps of the

proton discharge reaction and the electrochemical desorption are 30 and 120 mV/decade, respectively. Considering

the sequential reaction for the cathodic HER, one can interpret that the proton discharge reaction corresponding to

the Tafel slopes of 31 mV/decade shown in Figs. 2(a) and

3(a) is the rate-determining step for the cathodic HER at the

poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface. At high

current densities, as shown in Figs. 2(b) and 3(b), the Tafel

slopes are usually ca. 120 mV/decade. Also, considering the

high values of the fractional surface coverage () of OPD H

for the cathodic HER, i.e., 1 (refer to Fig. 9), one can

interpret that the electrochemical desorption corresponding

to the Tafel slopes of 122 mV/decade shown in Figs. 2(b)

and 3(b) is the rate-determining step for the cathodic HER

at the interface.

Comparing Figs. 2 and 3 with Fig. 1 shows that the Tafel

slopes of Figs. 2 and 3 are plotted beyond the UPD H regions. This implies that the Tafel slopes shown in Figs. 2(a)

and 3(a) are attributed to the OPD H for the cathodic HER

at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface.

From Figs. 2(a) and 3(a), one can understand that the range

of for the rate-determining step of the proton discharge reaction is ca. 0.694 to 0.780 V vs. RHE. The range of ,

ca. 0.694 to 0.780 V vs. RHE, corresponding to the Tafel

slopes shown in Figs. 2(a) and 3(a) is necessary for verifying the proton discharge reaction of the adsorption isotherm

(Langmuir, Frumkin, Temkin) of OPD H for the cathodic

HER at the interface. This is discussed in more detail later.

3.3. Phase-shift prole for the optimum intermediate

frequency

The equivalent circuit for the cathodic HER is usually expressed as shown in Fig. 4(a) [38,39]. Taking into account

the various factors, e.g., the relaxation time effect, the surface diffusion process, the specic adsorption effect, etc.,

which are inevitable under the ac impedance experiment

[40,41], we dene the equivalent circuit elements shown in

Fig. 4(a). RS is the electrolyte resistance, RF is the equivalent resistance due to the adsorption process of OPD H and

Figs. 2 and 3 show Tafel plots at the poly-Pt/0.5 M H2 SO4

aqueous electrolyte interface. In Figs. 2 and 3, the overpotential () is dened as = E Er , where E is the electrode

potential and Er is the reversible potential at the equilibrium. Note that E is the actual electrode potential as mea-

in most experimental data, e.g., cyclic voltammograms, electrochemical impedance spectroscopies, electrochemical adsorption

isotherms, etc. Note that in the RHE scale is frequently used in

Tafel plots.

J.H. Chun et al. / International Journal of Hydrogen Energy 30 (2005) 1423 1436

RP

RF

CP

RS

CD

(a)

(b)

RS

RF

CP

poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface and (b) simplied equivalent circuit for the intermediate frequencies at the

interface.

its relaxation time effect at the interface, RP is the equivalent resistance due to the recombination reaction, CP is the

equivalent capacitance due to the adsorption process of OPD

H and its relaxation time effect at the interface, and CD is

the double-layer capacitance.

The two equivalent circuit elements, RF and CP , are the

equivalent resistance and capacitance associated with the

faradaic resistance (R ) and the adsorption pseudocapacitance (C ) of OPD H, respectively. Under the ac impedance

experiment, RF is smaller than R due to the surface diffusion process and the relaxation times of the previously

adsorbed hydrogen (OPD H), i.e., the increase of H+ on

the electrode surface. However, CP is greater than C due

to the surface diffusion process and the relaxation times

of the previously adsorbed hydrogen (OPD H), i.e., the increase of H+ on the electrode surface. Because a resistance

is inversely proportional to the concentration of charged

species, but a capacitance is proportional to the concentration charged species, the surface diffusion process and the

relaxation time effects of RF and CP can be compensated

together at the interface (refer to Eq. (2) and Table 1).

Note that both RF and CP cannot exist unless charge is

transferred across the interface. This implies that the behavior of RF and CP depends strongly on that of R and C

or , i.e., the proton discharge reaction of OPD H for the

cathodic HER. Therefore, the adsorption process of OPD H

corresponding to the combination of RF and CP can be correctly expressed in terms of the phase delay, i.e., the lagged

phase shift (). This aspect was not well interpreted in

our previously published papers [22,23]. The experimental results and discussions presented there are unchanged.

1427

However, it is well known that the fractional surface coverage () of H and the phase shift () depend on the applied

electrode potential (E) at the interface.

The frequency responses of the equivalent circuit shown

in Fig. 4(a) are essential for studying the relationship between the behavior ( vs. E) of the phase shift (0

90 ) for the optimum intermediate frequency and that

( vs. E) of the fractional surface coverage (1 0) of

OPD H for the cathodic HER at the interface. At low frequencies, the equivalent circuit for all frequencies shown in

Fig. 4(a) can be expressed as a series circuit of RS , RF , and

RP . At high frequencies, the equivalent circuit for all frequencies shown in Fig. 4(a) can be expressed as a series circuit of RS and CD . At intermediate frequencies, the equivalent circuit for all frequencies shown in Fig. 4(a) can be

simplied as the series circuit of RS , RF , and CP shown in

Fig. 4(b). For a wide range of , i.e., except for low values,

CP is much greater than CD . In practice, CP includes CD .

In addition, RP is much greater than both RF and |1/CP |

for intermediate frequencies. Therefore, RP and CD can be

eliminated from the equivalent circuit for the cathodic HER

shown in Fig. 4(a). This implies that the simplied equivalent circuit for the intermediate frequencies shown in Fig.

4(b) can be applied to the poly-Pt/0.5 M H2 SO4 aqueous

electrolyte interface regardless of H2 evolution. However,

the simplied equivalent circuit shown in Fig. 4(b) is not for

the change of the cathodic HER itself, but only the intermediate frequency response. The behavior of RF and CP depends strongly on that of R and C or . In other words, it

is valid for studying the adsorption sites and process of OPD

H at the interface. The frequency responses of the equivalent

circuit shown in Fig. 4(a) are described elsewhere [38,39].

The impedance (Z) of the equivalent circuit for the intermediate frequencies shown in Fig. 4(b) and the corresponding phase shift () are given by

Z = (RS + RF ) j/CP ,

(1)

(2)

(for a wide range of ),

(3)

i.e., j2 = 1, (=2f ) is the angular frequency, R is the

faradaic resistance for the proton discharge reaction of OPD

H and depends on of OPD H, and C is the adsorption

pseudocapacitance for the adsorption process of OPD H and

also depends on of OPD H.

The minus sign in Eq. (2) implies a lagged phase. In practice, for a wide range of , RS and CD can be neglected

compared to RF and CP at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface. From Eq. (2), the lagged phase

shift () depends strongly on RF and CP , i.e., R and

C or . This implies that also depends markedly on

the adsorption process of OPD H, i.e., , at the interface.

However, CP should not be confused with C , which has a

1428

J.H. Chun et al. / International Journal of Hydrogen Energy 30 (2005) 1423 1436

Table 1

Measured values of the equivalent circuit elements for the optimum intermediate frequency (ca. 5 Hz) and the estimated fractional surface

coverage () at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface

E (V vs. RHE)

RS + RF ( cm2 )

CP a (F cm2 )

b (deg)

(deg)

c

0.061

0.041

0.021

0.001

0.019

0.039

0.059

0.079

0.099

0.119

0.139

0.159

2.241

2.700

11.484

16.887

7.299

2.756

1.673

1.444

1.422

1.414

1.418

1.479

433

431

511

1147

4925

23,050

90,050

249,703

478,811

681,387

899,505

1,123,762

88.25

87.91

79.56

58.69

41.54

26.63

11.94

5.05

2.68

1.89

1.43

1.10

88.3

87.9

79.6

58.7

41.5

26.6

11.9

5.0

2.7

1.9

1.4

1.1

0

0.005

0.100

0.339

0.537

0.708

0.876

0.955

0.982

0.991

0.997

1

800

20

600

15

10

400

(b)

(a)

200

-0.2

0 and 1 [3841]. Also, it should be understood that the

simplied equivalent circuit shown in Fig. 4(b) is not for the

change of the cathodic HER itself but only the intermediate

frequency response. Consequently, the simplied equivalent

circuit for the intermediate frequencies shown in Fig. 4(b)

is valid for determining the suitable adsorption isotherm

(Langmuir, Frumkin, Temkin) of OPD H for the cathodic

HER at the interface.

Figs. 5(a) and (b) show the proles of the measured RF

and CP vs. E for the optimum intermediate frequency (ca.

5 Hz) at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface, respectively. As previously described, Fig. 5(a) shows

that RF is smaller than R , because the left side of the prole (RF vs. E) is lower than the right side of the prole. This

is attributed to the superposition of the adsorption process,

the surface diffusion process, the relaxation time effect of

RF , and the nature of a resistance, which is inversely proportional to the concentration of charged species. However,

as described, Fig. 5(b) shows that CP is greater than C ,

because the prole (CP vs. E) increases from the right side

to the left side, i.e., towards more negative potentials. Similarly, this is attributed to the superposition of the adsorption

process, the surface diffusion process, the relaxation time

effect of CP , and the nature of a capacitance, which is proportional to the concentration of charged species.

Note that the equivalent resistance prole (RF vs. E)

shown in Fig. 5(a) has a peak. But, the equivalent capacitance prole (CP vs. E) shown in Fig. 5(b) has no peak. As

described, this is attributed to the reciprocal nature between

the resistance and the capacitance at the interface. This also

implies that the H+ at the interface increases consistently

with increase of the electrode potential (E) or the fractional

surface coverage (). However, Fig. 5(b) shows that CP

).

b Calculated using R , R , C , and Eq. (2).

S

F

P

c Estimated using the measured phase shift ().

aC

-0.1

0.0

0.1

Potential (E ) / V vs. RHE

CP ) vs. E for the optimum intermediate frequency (ca. 5 Hz) at

the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface. Single sine

wave; scan frequency: 104 5 Hz; ac amplitude: 5 mV; dc potential;

0.081 to 0.179 V vs. RHE. (a) Equivalent resistance prole (RF

vs. E) and (b) equivalent capacitance prole (CP vs. E).

vs. RHE) of the equivalent resistance prole (RF vs. E). It

is understood that C has a maximum value at the peak potential, i.e., =0.5, due to the adsorption process of OPD H.

The determination of the optimum intermediate frequency

J.H. Chun et al. / International Journal of Hydrogen Energy 30 (2005) 1423 1436

100

(a)

(b)

80

60

1429

(c)

40

(d)

20

(e)

(f)

(g)

0

20

40

60

80

2

3

Frequency ( log f ) / Hz

poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface. Vertical solid

line: ca. 5 Hz; single sine wave; scan frequency: 104 5 Hz; ac

amplitude: 5 mV; dc potential: (a) 0.061 V, (b) 0.021 V, (c) 0.001 V,

(d) 0.019 V, (e) 0.039 V, (f) 0.059 V, and (g) 0.139 V vs.

RHE.

is discussed in more detail later. Consequently, one can interpret that the surface diffusion process and the relaxation

time effects of RF and CP are unique features for analyzing the adsorption sites and process of OPD H at the polyPt/0.5 M H2 SO4 aqueous electrolyte interface. The surface

diffusion process and the relaxation time effects of RF and

CP are compensated together at the interface (refer to Eq.

(2) and Table 1). The various effects on the adsorption process of OPD H are negligible at the interface.

Fig. 5 and Eq. (2) show that the real surface area problem

of the poly-Pt electrode is not important for studying the

phase-shift prole for the optimum intermediate frequency.

The real surface area effects of RF and CP are completely

compensated together. Also, the adsorption sites and process

of OPD H at the interface can be expressed in terms of the

lagged phase shift (). In practice, RF is greater than RS

for a wide range of (refer to Fig. 5 and Table 1), and

so described in Eq. (2) can be substantially determined

by the series circuit of RF and CP . In other words,

is substantially characterized by the adsorption sites and

process of OPD H, i.e., . This implies that the behavior (

vs. E) of the phase shift (0 90 ) for the optimum

intermediate frequency can be linearly related to that ( vs.

E) of the fractional surface coverage (1 0) of OPD H,

i.e., the suitable adsorption isotherm ( vs. E) of OPD H,

at the interface. This is discussed in more detail later.

Fig. 6 compares the phase-shift curves ( vs. log f ) for

the different electrode potentials (E) at the poly-Pt/0.5 M

H2 SO4 aqueous electrolyte interface. In this gure, and

vs. log f are markedly different at intermediate frequencies due to the combination of RF and CP , i.e., the adsorption process of OPD H, at the interface. The intermediate

-0.4

-0.2

0.0

0.2

Potential ( E ) / V vs. RHE

0.4

Fig. 7. Phase-shift prole ( vs. E) for the optimum intermediate frequency (ca. 5 Hz) at the poly-Pt/0.5 M H2 SO4 aqueous

electrolyte interface.

frequency, i.e., a vertical solid line (ca. 5 Hz) on the phaseshift curves ( vs. log f ) shown in Fig. 6, can be set as the

optimum intermediate frequency for the phase-shift prole

( vs. E). Note that the optimum intermediate frequency

(ca. 5 Hz) indicates a maximum lagged phase shift on the

phase-shift curve ( vs. log f ) shown in Fig. 6(a).

At a maximum lagged phase shift for the optimum intermediate frequency, it appears that the adsorption process

of OPD H and the various effects at the interface are minimized. In other words, of the OPD H can be set to zero,

as shown in Table 1. Therefore, from Eq. (2) and Fig. 6,

has a maximum value of 90 , as shown in Fig. 6(a). At a

minimum lagged phase shift for the optimum intermediate

frequency, it appears that the adsorption process of OPD H

and the various effects at the interface are maximized or almost saturated. In other words, of the OPD H can be set to

unity, as shown in Table 1. Therefore, from Eq. (2) and Fig.

6, has a minimum value of 0 , as shown in Fig. 6(g).

Also, by comparing the calculated phase shift () with the

measured phase shift () shown in Table 1, one can interpret that the discussions on the simplied equivalent circuit

for the optimum intermediate frequency shown in Fig. 4(b)

and derived Eqs. (1)(3) are valid. The determination of the

optimum intermediate frequency for the phase-shift prole

( vs. E) is described elsewhere [2234].

Finally, the electrode potential (E) and the corresponding

phase shift (0 90 ) for the optimum intermediate frequency (ca. 5 Hz) at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface can be plotted as the phase-shift

prole ( vs. E) for the optimum intermediate frequency

(ca. 5 Hz) shown in Fig. 7. The same shape of vs. E

can also be obtained around the optimum intermediate frequency (ca. 5 Hz), e.g., 10 and 20 Hz, as shown in Fig. 8.

Fig. 8 also shows that the determination of the optimum intermediate frequency for the phase-shift prole ( vs. E)

1430

J.H. Chun et al. / International Journal of Hydrogen Energy 30 (2005) 1423 1436

1.0

5 Hz

10 Hz

20 Hz

20

40

60

80

experimental data

fitted data

0.8

0.6

0.4

0.2

0.0

-0.4

-0.2

0.0

0.2

Potential ( E ) / V vs. RHE

0.4

different intermediate frequencies (ca. 5, 10, and 20 Hz) at the

poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface.

of OPD H at the interface is reasonable.

Table 1 shows that both ()/E or d()/dE and

/E or d/dE are maximized at 0.5 and minimized

at 0 and 1. It is a unique feature of the adsorption

isotherms (Langmuir, Frumkin, Temkin) of intermediates

for sequential reactions in electrochemical systems. As discussed, it implies that the relaxation time effects of RF and

CP , and the surface diffusion process do not conict with

analysis of the adsorption sites and process of OPD H at the

interface. In other words, described in Eq. (2) depends

strongly on R and C , i.e., . Consequently, it appears

that the shape of the phase-shift prole ( vs. E) for the

optimum intermediate frequency can be linearly related to

the form of the suitable adsorption isotherm ( vs. E) of

OPD H at the interface. The various effects on the adsorption isotherm (Langmuir, Frumkin, Temkin) of OPD H for

the cathodic HER are negligible at the interface.

3.4. Langmuir adsorption isotherm of OPD H

The Langmuir adsorption isotherm assumes that the electrode surface is homogeneous and that the lateral interaction effect is negligible. However, oxide layer formations,

different single-crystal face substrates, and different phase

substrates are serious considerations for the Langmuir adsorption process of OPD H, and these should be considered

inhomogeneous. In this case, the Frumkin or the Temkin

adsorption process of OPD H should be applied to the interface. This is discussed in more detail later.

The derivation of the practical form of the electrochemical adsorption isotherms (Langmuir, Frumkin, Temkin)

is described elsewhere [4245]. The Langmuir adsorption

isotherm ( vs. E) of OPD H for the cathodic HER at the

poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface can be

-0.4

-0.2

0.0

0.2

Potential ( E ) / V vs. RHE

0.4

Langmuir adsorption isotherm ( vs. E) of OPD H for the cathodic

HER at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface;

K = 1.3 104 .

expressed as

[/(1 )] = KC +

H [exp(EF /RT )],

(4)

+

the equilibrium constant for OPD H, CH

is the H+ concentration in the bulk electrolyte, E is the electrode potential, F

is the Faraday constant, R is the gas constant, and T is the

absolute temperature. In Eq. (4), as previously described,

E is not the overpotential () but the actual electrode potential as measured against the standard reference electrode.

Therefore, Eq. (4) can be expressed in terms of as follows

[43,44]:

[/(1 )] = KC +

H [exp(F /RT )],

(5)

where (=E Er ) is the overpotential and Er is the reversible potential at the equilibrium.

For the poly-Pt/0.5 M H2 SO4 aqueous electrolyte (pH

0.46) interface, the tted data, i.e., the numerically calculated Langmuir adsorption isotherm ( vs. E) for K = 1.3

104 using Eq. (4), are shown in Fig. 9. As expected, the

Langmuir adsorption isotherm ( vs. E) shown in Fig. 9

can be linearly related to the phase-shift prole ( vs. E)

for the optimum intermediate frequency (ca. 5 Hz) shown

in Fig. 7. From Figs. 7 and 9, one infers that the Langmuir

adsorption isotherm for K = 1.3 104 is applicable to the

formation of OPD H at the interface. This also implies that

the applicability of the Frumkin adsorption isotherm ( vs.

E) of OPD H for the cathodic HER at the interface is trivial

(refer to Fig. 12). Figs. 10(a)(c) show the three numerically

calculated Langmuir adsorption isotherms corresponding to

K = 1.3 102 , 1.3 104 , and 1.3 106 , respectively.

The Langmuir adsorption isotherm shown in Fig. 9 is

attributed to OPD H for the cathodic HER. As discussed,

the Langmuir adsorption isotherm due to UPD H has not

J.H. Chun et al. / International Journal of Hydrogen Energy 30 (2005) 1423 1436

1.0

Fractional Surface Coverage ()

1.0

0.8

0.6

(c)

(b)

(a)

0.4

0.2

0.0

1431

-0.4

-0.2

0.0

0.2

0.4

Fig. 10. Comparison of three numerically calculated Langmuir adsorption isotherms ( vs. E) of OPD H for the cathodic HER

at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface: (a)

K = 1.3 102 , (b) K = 1.3 104 , and (c) K = 1.3 106 .

been observed at the cathodic potential range. It is understood that the adsorption sites of UPD H on the poly-Pt

electrode surface are almost masked due to the high H+

concentration in 0.5 M H2 SO4 aqueous electrolyte and/or

anionic adsorption effects under the steady-state conditions

[19,20,2325,30,31,46]. Note that the Langmuir adsorption

isotherm of OPD H shown in Fig. 9 or 10(b) is located

beyond the UPD H peaks (ca. 0.06 and 0.20 V vs. RHE)

on the cyclic voltammogram shown in Fig. 1. This implies

that the Langmuir adsorption isotherm of OPD H is located

beyond that of UPD H, which cannot be obtained at the

poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface. The

Langmuir adsorption isotherms ( vs. E) of UPD H and

transitions between UPD H and OPD H regions at noble

metal (Pt, Ir)/alkaline aqueous electrolyte interfaces are

described elsewhere [2325,30,31].

As discussed, the shape of the phase-shift prole (

vs. E) for the optimum intermediate frequency (ca. 5 Hz)

shown in Fig. 7 is the exact form of the Langmuir adsorption

isotherm ( vs. E) of OPD H shown in Fig. 9. Therefore,

one can interpret that the various assumptions and effects,

e.g., the simplied equivalent circuit for the optimum intermediate frequency, the relaxation time effect, the surface

diffusion process, the compensation effects, the lateral interaction effect, the homogeneous surface, etc., are well supplemented for the Langmuir adsorption isotherm of OPD H

at the interface. It especially appears that the assumption of

a linear relationship between the phase-shift prole ( vs.

E) for the optimum intermediate frequency and the Langmuir adsorption isotherm ( vs. E) of OPD H is valid.

Fig. 11 compares three different ranges of , which are estimated using the measured phase shift () shown in Table

1 and through the previously described procedures, for the

Langmuir adsorption isotherm of OPD H, K = 1.3 104 ,

0.8

( 0.2 < < 0.8 )

0.6

0.4

0.2

0.0

-0.4

-0.2

0.0

0.2

0.4

Fig. 11. Comparison of three different ranges of for the Langmuir

adsorption isotherm ( vs. E) of OPD H for the cathodic HER at the

poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface; K=1.3104 .

In contrast to the different values of K shown in Fig. 10,

different ranges of are not of serious concern for determining the Langmuir adsorption isotherm of OPD H corresponding to K (=1.3 104 ), as shown in Fig. 11. For

a wide range of , except for low values, CP and RF are

much greater than CD and RS , respectively. Therefore, the

phase-shift prole ( vs. E) for the optimum intermediate frequency (ca. 5 Hz) can be linearly related to the

Langmuir adsorption isotherm ( vs. E) of OPD H at the interface. In addition, both C and R have maximum values

at = 0.5 and minimum values at 0 and 1. This implies

that the rates of change, i.e., ()/E or d()/dE and

/E or d/dE, are maximized at 0.5 and minimized

at 0 and 1, as described in Table 1. This also implies

that the linear portion of the phase-shift prole ( vs. E)

for the optimum intermediate frequency (ca. 5 Hz) shown

in Fig. 7 can be related to that of the Langmuir adsorption

isotherm ( vs. E) of OPD H shown in Fig. 9 through the

previously described procedures, as shown in Figs. 10 and

11. In other words, the Langmuir adsorption isotherm ( vs.

E) of OPD H shown in Fig. 9 can be denitively determined

by the superposition of the linear portion of the phase-shift

prole ( vs. E) for the optimum intermediate frequency

shown in Fig. 7. However, there are unique features of the

Langmuir adsorption isotherm and process at the interface.

Consequently, it appears that the behavior ( vs. E) of

the phase shift (0 90 ) for the optimum intermediate frequency can be linearly related to that ( vs. E) of

the fractional surface coverage (1 0) of OPD H at the

poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface.

As shown in Figs. 10 and 11, the Langmuir adsorption

isotherm of OPD H described in Eq. (4) is denitively determined by the value of K, which is dened by the ratio (kf /kr ) between the rate constant (kf ) of the forward

J.H. Chun et al. / International Journal of Hydrogen Energy 30 (2005) 1423 1436

constant (kr ) of the reverse reaction, i.e., the hydrogen desorption reaction, in the proton discharge reaction [4245].

Thus, by comparing Fig. 9 with Figs. 2 and 3, one can conrm the validity of the Langmuir adsorption isotherm of the

OPD H for the cathodic HER at the interface. In other words,

the range of , ca. 0.694 to 0.780 V vs. RHE, shown in

Figs. 2 and 3 corresponds to the range of , ca. 0.3490.927,

shown in Fig. 9. Note that 0.0 V vs. RHE on the potential

(E) scale shown in Fig. 9 is equivalent to 0.694 V vs.

RHE on the overpotential () scale shown in Figs. 2 and 3.

The range of , ca. 0.3490.927, which corresponds to the

portion of the rate-determining step of the proton discharge

reaction on the Langmuir adsorption isotherm plot, is sufciently large to verify the mechanism of OPD H for the cathodic HER at the interface. Thus, the Langmuir adsorption

isotherm of OPD H for the cathodic HER shown in Fig. 9 is

valid. At limited values of , i.e., 1, it is well known that

the rate-determining step of the cathodic HER is determined

by the electrochemical desorption or the recombination reaction. However, it should be understood that the proton discharge reaction corresponding to the Langmuir adsorption

isotherm of OPD H proceeds continuously at the interface

regardless of H2 evolution. The nature of the Langmuir adsorption isotherm of OPD H is not the rate-determining step,

but the proton discharge reaction itself. Finally, considering the high negative values of and the rate-determining

step of the proton discharge reaction corresponding to the

range of , one can conclude that the Langmuir adsorption

isotherm of OPD H for the cathodic HER shown in Fig. 9 is

acceptable at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte

interface.

3.5. Frumkin and Temkin adsorption isotherms of OPD H

Considering an inhomogeneous Pt/0.5 M H2 SO4 aqueous

electrolyte interface, the Frumkin or the Temkin adsorption

isotherm should be applied to the interface. The practical

form of the electrochemical Frumkin adsorption isotherm (

vs. E) of OPD H can be expressed as follows [4245]:

+

[/(1 )] exp(g) = K0 CH

[exp(EF /RT )],

(6)

g r/RT ,

(7)

K = K0 exp(g),

(8)

adsorption isotherm, K0 is the equilibrium constant for

OPD H at g = 0, K is the equilibrium constant for OPD H,

and r is the rate of change of the standard free energy of

OPD H with , i.e., 0 1.

Figs. 12(a)(c) show the three numerically calculated

Frumkin adsorption isotherms ( vs. E) of OPD H corresponding to g = 0, 5, and 10 for K0 = 1.3 104 at the

poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface, respectively. As g increases, changes more slowly with E. In

1.0

Fractional Surface Coverage ()

1432

( 0.1 < < 0.9 )

0.8

0.6

Langmuir

Frumkin

0.4

0.2

0.0

-0.4

-0.2

0.0

0.2

Potential (E ) / V vs. RHE

0.4

adsorption isotherm ( vs. E) for K = 1.3 104 and three numerically calculated Frumkin adsorption isotherms ( vs. E) for

K0 = 1.3 104 at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte

interface: (a) g = 0, i.e., Langmuir adsorption isotherm, (b) g = 5,

and (c) g = 10 for K0 = 1.3 104 (OPD H).

Langmuir adsorption isotherm for K = 1.3 104 . By comparing the Frumkin adsorption isotherms with the Langmuir

adsorption isotherm shown in Fig. 12, one can interpret that

the applicability of the Frumkin adsorption isotherms is unreasonable at the interface. The phase-shift method for determining the Frumkin adsorption isotherms of OPD H for

the cathodic HER at metal (Pd, Ni)/aqueous electrolyte interfaces is described elsewhere [22,26].

At intermediate values of , [/(1 )] changes little

with compared to the changing of exp(g) in Eq. (6).

Under the approximate conditions, the Temkin adsorption

isotherm can be simply derived from the Frumkin adsorption

isotherm described in Eq. (6). The practical form of the

electrochemical Temkin adsorption isotherm ( vs. E) of

OPD H can be expressed as follows:

+

exp(g) = K0 CH

[exp(EF /RT )].

(9)

Fig. 13 compares the experimentally determined Langmuir adsorption isotherm ( vs. E) for K = 1.3 104

and the three numerically calculated Temkin adsorption isotherms ( vs. E) for K0 = 8.1 102 at the

poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface. Figs.

13(a)(c) show the three numerically calculated Temkin

adsorption isotherms corresponding to g = 0, 12, and 15,

respectively, at the same potential range for the Langmuir

adsorption isotherm. Under the Temkin adsorption conditions, as shown in Figs. 13(b) and (c), changes linearly

and more slowly with E than it does under the Langmuir

adsorption conditions. By comparing the Temkin adsorption

isotherms with the Langmuir adsorption isotherm shown

in Fig. 13, one can interpret that the applicability of the

J.H. Chun et al. / International Journal of Hydrogen Energy 30 (2005) 1423 1436

1.0

( 0.0 < <1.0 )

0.8

( 0.2 < < 0.8 )

Langmuir

Temkin

0.6

(c)

(b) (a)

0.4

0.2

0.0

-0.4

-0.2

0.0

0.2

0.4

Fig. 13. Comparison of the experimentally determined Langmuir

adsorption isotherm ( vs. E) for K = 1.3 104 and three numerically calculated Temkin adsorption isotherms ( vs. E) for

K0 = 8.1 102 at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte

interface: (a) g = 0, (b) g = 12, and (c) g = 15 for K0 = 8.1 102

(OPD H).

1.0

( 0.0 < <1.0 )

( 0.1 < < 0.9 )

0.8

Langmuir

0.6

Temkin

0.4

0.2

0.0

-0.4

-0.2

0.0

0.2

0.4

Fig. 14. Comparison of the experimentally determined Langmuir

adsorption isotherm ( vs. E) for K = 1.3 104 and three numerically calculated Temkin adsorption isotherms ( vs. E) for

K0 = 1.3 103 at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte

interface: (a) g = 0, (b) g = 4.6, and (c) g = 10 for K0 = 1.3 103

(OPD H).

1433

with , i.e., 0 1. Taking into account the determination

of the suitable adsorption isotherm (Langmuir, Frumkin,

Temkin) of OPD H for the cathodic HER at the interface

and the behavior of the Temkin adsorption isotherms shown

in Figs. 13 and 14, the validity of the Temkin adsorption isotherm at the interface is unclear even though the

range of K is acceptable. However, it should be noted that

Fig. 14(b) shows an overlapped region between the Langmuir and Temkin adsorption isotherms ( vs. E) of OPD H

at the range of , ca. 0.2 < < 0.8. At 0.2 < < 0.8, using

Eq. (8), the range of K is 5.2 104 > K > 3.3 105

with . At = 0.5, it especially appears that the equilibrium constant (K = 1.3 104 ) for the Temkin adsorption

isotherm is the same as that (K = 1.3 104 ) for the corresponding Langmuir adsorption isotherm. It is attributed

to a maximum value of R and C vs. E at = 0.5, which

cannot be measured at the interface, and a maximum rate

of change of and vs. E for the optimum intermediate

frequency at 0.5 (refer to Table 1). The equilibrium

constants (K) for OPD H corresponding to the adsorption

isotherms (Langmuir, Temkin, Frumkin) of OPD H and

are summarized in Table 2. Consequently, one can interpret

that the Langmuir and Temkin adsorption isotherms ( vs.

E) of OPD H for the cathodic HER are converted to each

other even though the adsorption conditions are different

from each other. Correspondingly, one can interpret that

the Frumkin and Temkin adsorption isotherms ( vs. E) of

OPD H for the cathodic HER are converted to each other.

Note that the equilibrium constant (K0 ) for the Temkin

adsorption isotherms ( vs. E) is ca. 10 times greater

than that (K) for the corresponding Langmuir adsorption

isotherm ( vs. E). Similarly, note that the interaction parameter (g) for the Temkin adsorption isotherm ( vs. E)

is ca. 4.6 greater than that (g) for the corresponding Langmuir adsorption isotherm ( vs. E). These numbers (10

times and 4.6) can be taken as constant conversion factors

between the corresponding adsorption isotherms (Temkin,

Langmuir, Frumkin) [47]. This implies that the Temkin

adsorption isotherm corresponding to the Langmuir or the

Frumkin adsorption isotherms, and vice versa, can be effectively converted using the constant conversion factors. This

aspect was not well interpreted in our previously published

papers[2234].

3.6. Standard free energy of OPD H

interface.

Fig. 14 also compares the experimentally determined

Langmuir adsorption isotherm ( vs. E) for K = 1.3 104

and the three numerically calculated Temkin adsorption

isotherms ( vs. E) for K0 =1.3103 at the poly-Pt/0.5 M

H2 SO4 aqueous electrolyte interface. Figs. 14(a)(c) also

show the three numerically calculated Temkin adsorption

isotherms corresponding to g = 0, 4.6, and 10, respectively.

For g = 4.6 and K0 = 1.3 103 shown in Fig. 14(b), using

The standard free energy of OPD H is given by the difference between the standard molar Gibbs free energy of

OPD H and that of a number of water molecules on the

adsorption sites of the poly-Pt electrode surface. Under the

Langmuir adsorption conditions, the relation between the

equilibrium constant (K) for OPD H and the standard free

energy (G0ads ) of OPD H is given [42] as follows:

2.3RT log K = G0ads .

(10)

1434

J.H. Chun et al. / International Journal of Hydrogen Energy 30 (2005) 1423 1436

Table 2

Comparison of the equilibrium constants (K) for OPD H corresponding to the adsorption isotherms (Langmuir, Temkin, Frumkin) of OPD

H and fractional surface coverages () at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface

Adsorption isotherm

Langmuir (g = 0)

Temkin (g = 4.6)

Frumkin

K

01

= 0.5

1.3 104

1.3 103 K 1.3 105

1.3 104

5.2 104 > K > 3.3 105

1.3 104

1.3 104

the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface, using Eq. (10), G0ads is 22.2 kJ/mol for K = 1.3 104

(OPD H). As expected, in contrast to the exothermic reaction, G0ads < 0, in the UPD H region, an endothermic

reaction, G0ads > 0, occurs in the OPD H region of the

poly-Pt electrode interface. This implies that the OPD H

on the adsorption sites of the poly-Pt electrode surface requires 22.2 kJ/mol to remove the appropriate number of water molecules.

Under the Temkin adsorption conditions, the relation between the equilibrium constant (K) for OPD H and the standard free energy (G0 ) of OPD H is given as [42]

2.3RT log K = G0 .

(11)

isotherm, both K and G0 depend strongly on . At the

poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface, using Eqs. (8) and (11), G0 is 16.5 G0 27.9 kJ/mol

for 1.3 103 K 1.3 105 (OPD H) with , i.e.,

0 1. Similarly, using Eqs. (8) and (11), G0 is

18.7 < G0 < 25.6 kJ/mol for 5.2104 > K > 3.3105

(OPD H) with , i.e., 0.2 < < 0.8.

3.7. Complementary statement

A linear relationship between the phase-shift proles for

the optimum intermediate frequencies and the corresponding Langmuir and Temkin adsorption isotherms of OPD H

at the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface

was proposed based on purely empirical relationships. The

behavior ( vs. E) of the phase shift (0 90 )

for the optimum intermediate frequency can be linearly related to that ( vs. E) of the fractional surface coverage

(1 0) of the OPD H at the interface. This implies that

the phase-shift method experimentally provides the link between the microscopic system of the adsorption sites and

process of OPD H on the atoms and the macroscopic system of the electrode kinetics and thermodynamics for OPD

H at the interface.

The Langmuir and Temkin adsorption isotherms ( vs. E)

of OPD H at the poly-Pt electrode interface can be practically determined using the phase-shift curves ( vs. log f )

and the phase-shift prole ( vs. E) for the optimum intermediate frequency. It appears that the phase-shift method

is a simple and efcient tool for determining the electrode

kinetic and thermodynamic data (, K, K0 , g, G0ads , G0 )

relating to the adsorption sites and processes of H (UPD

H, OPD H) for the cathodic HER at the interface. Note

that the other tedious procedures described in this paper are

only used to verify the validity of the phase-shift method.

However, at rst glance, it seems that there is no linear relationship between the phase-shift proles ( vs. E) for

the optimum intermediate frequencies and the adsorption

isotherms ( vs. E) of H (UPD H, OPD H) for the cathodic

HER at the interfaces [5053]. At present, the various effects on the adsorption sites and processes of H (UPD H,

OPD H) for the cathodic HER have not been combined into

a single equation for the linear relationship. Therefore, it

seems difcult to obtain a relationship based on theoretical

derivations or numerical calculations.

4. Conclusions

The phase-shift method for determining the suitable adsorption isotherm (Langmuir, Frumkin, Temkin) of H (UPD

H, OPD H) for the cathodic HER in electrochemical systems

is proposed. The simplied equivalent circuit for the optimum intermediate frequency and the corresponding phaseshift equation are well tted to the poly-Pt/0.5 M H2 SO4

aqueous electrolyte interface. The phase-shift method experimentally veries that the behavior ( vs. E) of the

phase shift (0 90 ) for the optimum intermediate

frequency can be linearly related to that ( vs. E) of the fractional surface coverage (1 0) of OPD H, i.e., the Langmuir and Temkin adsorption isotherms ( vs. E) of OPD H,

at the interface. At the poly-Pt/0.5 M H2 SO4 aqueous electrolyte interface, the Langmuir adsorption isotherm ( vs.

E) of OPD H, the equilibrium constant (K =1.3104 ) for

OPD H and the standard free energy (G0ads = 22.2 kJ/mol)

of OPD H are determined using the phase-shift method. At

the same interface, the Temkin adsorption isotherm ( vs. E)

of OPD H, the equilibrium constant (1.3103 K 1.3

105 with , i.e., 0 1) for OPD H, and the standard free

energy (16.5 G0 27.9 kJ/mol with , i.e., 0 1) of

OPD H are also determined using the phase-shift method.

J.H. Chun et al. / International Journal of Hydrogen Energy 30 (2005) 1423 1436

At the intermediate values of , i.e., 0.2 < < 0.8, the Langmuir and Temkin adsorption isotherms of OPD H for the

cathodic HER at the interface are converted to each other.

The equilibrium constant (K0 ) for the Temkin adsorption

isotherm ( vs. E) is ca. 10 times greater than that (K)

for the corresponding Langmuir adsorption isotherm ( vs.

E). The interaction parameter (g) for the Temkin adsorption isotherm ( vs. E) is ca. 4.6 greater than that (g) for

the corresponding Langmuir adsorption isotherm ( vs. E).

These numbers (10 times and 4.6) can be taken as constant conversion factors between the corresponding adsorption isotherms (Temkin, Langmuir, Frumkin). The Temkin

adsorption isotherm corresponding to the Langmuir or the

Frumkin adsorption isotherm, and vice versa, can be effectively converted using the constant conversion factors.

The phase-shift method experimentally provides the link between the microscopic system of the adsorption sites and

process of OPD H on the atoms and the macroscopic system of the electrode kinetics and thermodynamics for OPD

H at the interface. Both the phase-shift method and constant conversion factors can be effectively used as a new

electrochemical method to determine adsorption isotherms

(Langmuir, Frumkin, Temkin) of intermediates for sequential reactions in electrochemical systems.

[8]

[9]

[10]

[11]

[12]

[13]

[14]

[15]

[16]

Acknowledgements

[17]

of Chemistry, Queens University, Canada) and Reviewers

for their valuable suggestions and encouragements on the

phase-shift method. This work has been performed through

the Support Project of University Information Technology

Research Center (ITRC) supported by the Ministry of Information & Communication of Korea.

[18]

[19]

[20]

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