Available online at www.sciencedirect.
com Current Opinion in
ScienceDirect
Review Article
On the electrode charge at the metal/solution interface
with specific adsorption
Meng-Ke Zhang, Jun Cai and Yan-Xia Chen
Abstract
The electrode charge is one of the most fundamental concepts
in electrochemistry. However, ambiguousness often comes to
its definition as specific adsorption occurs. In this review, three
types of electrode charges, the metallic excess charge, the
free charge, and the total charge, are discriminated via a
modelistic description at the metal/solution interface, and the
relationships between them are formulated. The total charge is
proved to be the thermodynamic charge in a general Lippmann
equation. Based on this equation, thermodynamic analysis can
be performed to estimate the adsorbate coverage, then the
free charge can be derived. As an example, manipulation has
been made on a previous work in the (bi)sulfate adsorption
system, the surface charging relations are obtained, displaying
nonmonotonic relationships. In addition, a modeling study for
specific adsorption is introduced and exemplarily performed in
the (bi)sulfate adsorption system.
Addresses
Hefei National Research Center for Physical Science at Microscale and
Department of Chemical Physics, University of Science and Technol-
ogy of China, Hefei, 230026, China
Corresponding author: Chen, Yan-Xia. (yachen@ustc.edu.cn)
Current Opinion in Electrochemistry 2022, 36:101161
This review comes from a themed issue on Fundamental and Theo-
retical Electrochemistry (2023)
Edited by Michael E.G. Lyons and Christopher Batchelor-McAuley
For complete overview about the section, refer Fundamental and
Theoretical Electrochemistry (2023)
Available online 9 October 2022
https://doi.org/10.1016/j.coelec.2022.101161
2451-9103/© 2022 Elsevier B.V. All rights reserved.
Keywords
Metallic excess charge, Free charge, Total charge, Thermodynamics of
the electrochemical interface, Nonmonotonic charge-
potential dependence.
Introduction
Ionic adsorptions constitute the underlying phenome-
nology of the solution side in the electric double layer
(EDL) of the electrochemical devices. The adsorption
behaviors, especially those of specific adsorptions, have
great impacts on the performance of such devices [1,2],
e.g., they may affect the reactivity of electrocatalytic
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Electrochemistry
reactions occurring at the electrode/electrolyte in-
terfaces [3,4], the capacitance of electrochemical
supercapacitors and their charging/discharging behavior
[5], and so on. As a compensation for the accumulated
charge of adsorbed species, the electrode charge serves
as a key parameter for regulating the adsorption behavior
of ions and influencing the local reaction conditions,
such as the electrostatic field, types of the ions, their
concentration as well as the special distribution, the
dielectric constant and consequently the electrode ki-
netics. However, when speaking of the definition of the
electrode charge, the specific adsorption generally
involving the generation of partially charged chem-
isorbates, often complicates the case. Understanding its
meaning within different cases is the basis for extracting
correct information from experiments.
In this brief review, three types of electrode charge, i.e.,
the metallic excess charge, the free charge, and the total
charge, are discriminated via a modelistic description for
the metal/solution interface. Then a general Lippman
Equation for systems involving specific adsorptions will
be deduced, to further prove that the charge in such a
thermodynamic relation is the total charge (stot ), not
the metallic excess charge (sM ). The relationship be-
tween stot sM and the free charge (sfree ) is clarified.
The potential dependence of the free charge is exem-
plified by taking sulfate adsorption on Pt (111), which
indicates that for the cases involving specific adsorption
at Pt (111), its free charge displays a nonmonotonic
potential dependence, as in contrast to what is expected
for the ideally polarizable electrode. At last, a modeling
study for specific adsorption at the metal/solution
interface is introduced and performed in the (bi)sulfate
adsorption system.
Ionic adsorption at the metal/solution
interface
As the metal and the solution come into contact, the
electric field across the metal/solution interface will be
established spontaneously (in the galvanic cell) or
exerted artificially by the outer circuit (in the electro-
lytic cell). The electrons (usually valency electrons
delocalized in the metal region) will respond quickly to
the interfacial field via flowing into or out of the metal
electrode, resulting in the electronic excess charge in a
surface region with a thickness of about 1e2  A.
Current Opinion in Electrochemistry 2022, 36:101161
2 Fundamental and Theoretical Electrochemistry (2023)
Meanwhile, the interaction between the charged metal
and ions in solution causes the excess of ions in a larger
region at the solution side with a typical thickness of
5e20  A, named ionic adsorption [6]. When the interface
reaches equilibrium, the electronic excess charge has to
be neutralized by the charge carried by the excess ions
to keep the whole interface electroneutral. The inter-
facial region distributed by the electronic excess charge
and the ionic excess charge is known as the electric
double layer (EDL), which plays a central role
in electrochemistry.
Since the 1930s, the widely applied model used in
studies of the EDL based on the concept introduced by
Koenig [7], is the ideally polarizable interface. In the
case of the ideally polarizable interface, no charge is
transferred across the metal and the solution interface.
Figure 1a depicts the interface in this situation. The
solvated ions are non-specifically adsorbed, which means
the ions are adsorbed due to the long-range coulombic
interaction between the electronic excess charge on the
metal and the ionic charge. Since the metal surface is
almost hydrated, non-specifically adsorbed ions are not
able to contact the metal surface and have to remain in
the second layer or stay even further away from the
electrode. In a modelistic consideration, the plane
drawn through the locus of centers of these non-
specifically ions closest to the metal surface is refer-
ring to the outer Helmholtz plane (OHP) [6]. The
region where there is an excess distribution of non-
specifically adsorbed ions is the diffuse layer of
the EDL.
Nevertheless, in most cases, the interface is not as simple
as described in Figure 1a. If it is thermodynamically
Figure 1
A modelistic description for the metal/solution interface in the case of a) non-specific adsorption of ions and b) specific adsorption of the ion Az with the
valency of z.
Current Opinion in Electrochemistry 2022, 36:101161
permissible, ions at the OHP may partially dehydrate and
replace several adsorbed water molecules to stay in direct
contact with the electrode surface, as shown in Figure 1b.
This process is referring to specific adsorption, also
known as contact adsorption in a modelistic consider-
ation [8]. Here ‘specific’ means the adsorption is specific
with a special characteristic of the concrete ion, not just
depending on the charge of the ion, because of the
involvement of short-range interactions between the
metal and the ion, whose form and strength depend on
the structure of both the ion and the metal surface. The
locus of centers of these specifically adsorbed species is
referring to the inner Helmholtz plane (IHP) [6]. The
specifically adsorbed ion may conserve all its charge and
form a pure physical bond with the metal, such adsorp-
tion belongs to physisorption. Usually, this is an extreme
case. In most cases, there is a certain degree of charge
transfer tantamount to covalent bonding between the
electrode and the ion, such adsorption is named chemi-
sorption. The adsorbate can share electrons with the
electrode to carry out the so-called partial charge transfer
(pct), resulting in the partially charged chemisorbate [9].
In any case, the specific adsorption of an ion can be
uniformly represented. For the specific adsorption of the
ion A z as shown in Figure 1b, it can be described as:

A z #A zþl
ad þ le (1)
ad is the adsorbate with the partial charge of z þ l.
where A zþl
z is the valency of the ion, and the positive value and the
negative value of z represent cases of cationic adsorption
and anionic adsorption, respectively. l is the pct coeffi-
cient, which is first introduced by Lorenz and Salie in the
1960s [10]. The cases of l ¼ 0 and l ¼ z correspond to
physisorption without charge transfer and chemisorption
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with complete charge transfer, respectively. For the
chemisorption with partial charge transfer, the value of l is
between 0 and  z. To determine the partial charge of
adsorbate or pct coefficient at the microscopic level, it is
necessary to distinguish between the electrons in the
valence energy levels of the metal and that of the adsor-
bate. For the commonly used density functional theory
(DFT) at the metal interface, even if we can integrate the
electronic density in a pre-divided region belonging to
adsorbate, the charge of electrons spilling over from the
metal skeleton is hard to eliminate. Recently, different
computational methods, such as Bader and Mulliken anal-
ysis, and the integration of the density of states projected
onto the adsorption layer, are used to estimate the partial
charge on the adsorbed chloride and give different values,
which indicates that the partial charge is not uniquely
determined, even in a metal/vacuum interface that far from
a real electrochemical interface [11].
Definitions of the metallic charge, the free
charge, and the total charge
With the understanding of the above adsorption pic-
tures, now we return to the definition of the electrode
charge. Hereafter, the quantities of the charge are
normalized to the unit surface area of the electrode. At
the metal/solution interface, we often equate the
‘electrode’ with the metal, so the electrode charge we
shall first introduce is the metallic excess charge (noted
as sM ). The metallic excess charge is the electronic
excess charge at the metal side, which is the sum charge
of electrons and nuclei of the metal. For a planar metal
electrode in the absence of specific adsorption (as
described in Figure 1a), one may integrate the electronic
excess density relative to that of the neutral metal along
the direction perpendicular to the metal surface to
obtain sM . In this case, since the interface is electro-
neutral, the charge of excess non-specifically adsorbed
ions at the solution side (noted as sS ) is equal in abso-
lute value and opposite in sign to the metallic excess
charge, that is sM ¼  sS . However, in the presence of
specific adsorption (Figure 1b), the excess charge of the
charged adsorbate layer and the metal can’t be separated
clearly, as discussed in the partial charge above. There-
fore, the value of sM is in the same situation as the
partial charge on adsorbates, which is hardly calculable.
Nevertheless, the total excess charge of the metal and
the adsorbate layer can be derived with the condition of
interfacial electroneutrality. For example, for the case
described in Figure 1b, we have:
sM ¼ sS  ðz þ lÞFGad (2)
where F is the Faraday constant, Gad is the mole number of
unit metal area for the specifically adsorbed A zþl
ad . Accord-
ing to the definition of the electrode charge sM , the
‘electrode’ refers to the metal phase, which is strongly
bonded to the adsorbate and its charge should be separated
from that of the adsorbate.
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On the Electrode Charge Zhang et al. 3
If we consider the metal and the adsorbate together as
the ‘electrode’, we could define the second electrode
charge, which is the sum of the excess charge of the
metal and adsorbates. Quantitatively, due to the elec-
troneutrality of the interface, the free charge is the
negative value of the excess charge of non-specifically
adsorbed ions sS , which can be estimated using an
appropriate model for the EDL [12]. Such an electrode
charge is referring to the free charge, designated as sfree .
According to its definition and Eq. (2), we have:
sfree ¼ sS ¼ sM þ ðz þ lÞFGad (3)
The meaning of the ‘free’ in sfree can be understood in the
following way. As the charged adsorbate attaches to the
metal surface, the metallic electrons around the adsorbate
will be repelled or attracted depending on whether the net
charge on the adsorbate is negative or positive. An image
charge, which has an equal absolute value but an opposite
sign to the net charge of the adsorbate, will be formed
beneath the adsorbate [9,13,14]. The excess electronic
charge contributed by the image charge is localized around
the adsorbate, and its amount depends on the coverage
and the partial charge of the adsorbate. In this sense, we
call it the bound charge (noted as sb ), which is the part of
the metallic excess charge that compensates for the excess
charge of specifically adsorbed species. For example,
considering the adsorbate A zþl ads (Figure 1b) with the
coverage of Gad , the bound charge induced by the adsor-
bate will be  ðz þlÞFGad . As an opposite meaning to the
bound charge, the free charge is the part of the metallic
excess charge remaining in addition to the bound charge,
which compensates for the excess charge of those non-
specifically adsorbed ions. With this interpretation, Eq.
(3) can be derived by subtracting the bound charge of
ðz þlÞFGad from the sM .
The free charge serves as a key descriptor for the
charging state of the EDL and is of great importance for
the kinetics of electrocatalytic reactions. On the one
hand, the free charge dictates the electrostatic in-
teractions between the charged electrode and ions in
the diffuse layer, and thus governs reaction conditions at
the reaction plane (often referred to as OHP), such as
ion concentrations, electrostatic potential, and so
on [15]. On the other hand, the free charge may influ-
ence the local environments of adsorption sites, such as
electric fields, orientations of adjacent adsorbed water
molecules, etc., which will modify the adsorption energy
of reaction intermediates and even lead to changes in
adsorption configuration or reaction pathway [16,17].
The variation of free charge with the electrode poten-
tial, named surface charging behavior, displays the
charging behavior of the capacitor part of the EDL [12].
The concept of the potential of the zero free charge
(pzfc) is a bridge connecting the charging state of the
EDL and the electrode potential which is experimental
controllable. It is firstly emphasized by Frumkin and
Current Opinion in Electrochemistry 2022, 36:101161
4 Fundamental and Theoretical Electrochemistry (2023)
Gorodetzkaya in 1928 [18], and defined as the electrode
potential when the free charge on the electrode is zero,
that is, the potential at which non-specific adsorptions
of all ions vanish. The value of the pzfc is influenced by
the spillover of metallic electrons and surface dipoles,
the latter is mainly induced by contact-adsorbed water
molecules and adsorbates [19,20].
However, the free charge, as well as the metallic excess
charge, are not directly measurable, since they are both
only parts of the coulombic charge flowing into the
electrode due to the involvement of partial electron
transfer. For establishing the relationship between the
free charge and the metallic excess charge with the
measured coulombic charge through the external circuit,
it comes to the definition of the third electrode charge,
which is quantitatively equal to the total coulombic
charge flowing into the metal through the external circuit
since the metal and the solution come into contact. This
kind of electrode charge is referring to the total charge
(denoted as stot ) following the proposal by Frumkin et al.
[21] With this consideration, sM comes from two parts,
the charge from the external circuit which is exactly the
stot , and the charge transferred from adsorbates to the
metal side. For the case in Figure 1b, the transferred
charge is  lFGad . Then we have:
sM ¼ stot  lFGad (4)
The above equation displays the relation between the
total charge and the metallic charge, from which we can
see that sM can’t be separated from stot when the
parameter l is not determined. The total charge is also
referring to the thermodynamic charge, which figures in
the thermodynamic relation [21]. In a thermodynamic
consideration of the specific adsorption of A z (Eq. (1)),
the transferred electrons from the metal to the ion
forming the covalent bond are thermodynamically
undistinguishable from those excess electrons existing in
the metal. Therefore, the excess charge of thermody-
namically undistinguishable electrons on the electrode is
exactly those excess charges existing in the metal (sM )
and those charges transferred away from the electrode
(lFGad ), which meets the stot in Eq. (4). For a more
detailed proof, the thermodynamic relation will be briefly
deduced in the next section. In this sense, the total
charge is the excess charge of those thermodynamically
undistinguishable electrons conserved at the interface
compared to the bare metal before the establishment of
the EDL, whose variation is the coulombic charge flowing
into the metal.
Combined with Eq. (3) and Eq. (4), we have the rela-
tionship between the free charge and the total charge:
Current Opinion in Electrochemistry 2022, 36:101161
stot ¼ sfree  zFGad (5)
Eq. (5) separates stot clearly into two parts corresponding
to the extent of non-specific adsorption and specific
adsorption, respectively. The variations of these two parts
with the electrode potential display the characteristics of
the EDL as a capacitor and a reactor, respectively. The
latter (  zFGad ) is the commonly encountered pseudo-
capacitive charge, which is not explicitly dependent on pct
coefficient [22]. In the commonly used cyclic voltammetry
in experiments, differentiating Eq. (5) concerning the time
t on both sides, we have:
d stot
jtot ¼ vscan ¼ jEDL  zFvad ¼ jEDL þ jF (6)
dE
where jtot is the measured current density in the experi-
ment, whose positive direction of the current is along the
outer circuit to the metal. jEDL ¼ d sfree =dE is the current
density coming from charging the EDL (capacitive current
density or non-Faradaic current density), vad ¼ d Gad =dt is
the net generation rate for the adsorbate, vscan is the scan
rate of the cyclic voltammetry, and the term jF ¼ zFvad is
the Faradaic current density. Therefore, the absolute value
of the total charge of the interface at any potential can be
obtained by integrating the measured current density jtot
from a known lower limit of integral, which is in most cases
referring to the potential of the zero total charge (pztc). The
pztc is the potential when the total charge is zero, which is
firstly introduced by Frumkin in 1970 [21]. The value of the
pztc can be determined by a number of strategies such as
N2O reduction [23], peroxodisulfate (PDS) reduction [24],
and the laser-induced temperature jump (LITJ)
method [25e27]. For Pt group metals, CO-charge
displacement experiments have been commonly taken to
evaluate the pztc [17,28,29]. According to Eq. (5), if the
coverage of the adsorbate can be detected or estimated by
other methods, such as vibrational spectroscopic methods or
radiotracer method [8,30], and so on, the potential-
dependent free charge can be derived by adding the
charge of zFGad into the total charge. In addition, the CO-
charge displacement and the LITJ experiments have also
been used to gain information about the free charge at
Pt electrodes [16].
In this section, three types of the electrode charge, sM ;
sfree ; stot , as well as relationships between them, are
discussed. sM and sfree are the electronic excess charge of
the pre-divided metallic region and the whole electrode
including the adsorption layer, respectively. sM ¼ sfree
works only in the condition of the ideally polarizable
interface or specific adsorption with complete charge
transfer (see Eq. (3)). stot is the charge of thermody-
namically undistinguishable electrons at the interface,
including the excess electrons existing in the metal and
those transferred from the metal to the ion during the
adsorption process. The variation of stot is the coulombic
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 On the Electrode Charge Zhang et al. 5

Table 1 such as the internal energy (U ), the entropy (S), the

Symbols used to denote the three electrode charges in this work
and in other papers.
Name This work Other works
Metallic excess sM qm [32], qM [9], qM [21], qe [42]
charge
Free charge sfree sM [33,34,43], s [29,31,32]
Total charge stot sM [9,36,37], Q [21,32–34,38,43],
q [29,31], s [42]
charge flowing into the metal through the external cir-
cuit, therefore, stot is experimentally measurable. stot ¼
sM works in the condition of the ideally polarizable
interface or pure physisorption, while stot ¼ sfree only
works in the condition of an ideally polarizable interface.
The three types of electrode charges have been denoted
by various symbols for theoretical discussions
[9,21,31,32] and experimental measurements in systems
with specific adsorption, such as (bi)sulfate
adsorption [33e35], halide adsorption [36e39],
hydrogen and hydroxyl adsorption [40,41], etc. To avoid
confusion in the understanding of related literature due
to notation, the symbols used for the electrode charges in
this work and other related papers are summarized in
Table 1. A point to note in Table 1 is that qm in ref. [9] and
qM in ref. [21] are called “free charge”, indeed corre-
sponding to the metallic excess charge as we discussed,
since they represent the electronic excess charge at the
metal side (qm ¼ FGe in ref. [9], where Ge is the
electronic excess charge of the metal) and “the charge of
the metal surface” [21], respectively.
mole numbers of species (ni ) deviate from those in the
bulk. Starting from the Gibbs adsorption isotherm,
we have:
X
metal X
ad X
sol
d g ¼ Gi d mi þ Gj;ad d mj;ad þ Gk d mk (7)
i j i
where g is the surface tension of the electrode/electrolyte
interface, Gi ; Gj;ad ; Gk are the interfacial mole numbers per
unit surface area of species in the metal, adsorbate layer,
and the solution, respectively. mi ; mj;ad ; mk are the electro-
chemical potentials of the respective species. The three
terms on the right-hand side of Eq. (7) are the sum for the
species at the metal side, in the adsorbate layer, and at the
solution side. On the metal side, the metal atom can be
treated as fully dissociated cationic cores and freely
movable valence electrons. Then we have:
Xmetal
Gi d mi ¼ GMzþ d mMzþ þ Ge d me
i
(8)
¼ ðzM FGMzþ  FGe Þd 4M ¼ sM d 4M
In thermodynamic equilibrium, the electrochemical po-
tential of species i at the interface is equal to that in the
bulk phase and thus can be separated into the chemical
part and the electrostatic part in the bulk phase according
to mi ¼ mi þ zi F4M . mi is the chemical potential of species
i, and viewed as a constant for the cationic core and the free
electron, which means d me ;d mMzþ ¼ 0. zi is the valency of
the species i, zM is the valency of the metal cationic core.
4M is the bulk potential of the metal. We notice that the
term in the parentheses of Eq. (8) is exactly the metallic
excess charge sM .

Thermodynamic relation for electrode/
electrolyte interface involving specific
adsorption
Thermodynamically analyzing the adsorption processes
based on the thermodynamic relation is a classical sub-
ject in electrochemistry. In this section, the thermody-
namic relation including specific adsorptions will be
briefly deduced below, which can be also found similarly
in ref. [9,21].
For the second term in Eq. (7), we consider simply the
specific adsorption in Eq. (1). As the adsorption is in
equilibrium (mad þ lme ¼ mAz ), we have:
where 4S is the bulk potential in the solution. For the
solution side, expanding the electrochemical potential,
we have:

Gad d mad ¼ Gad ðd mAz  ld me Þ ¼ Gad d mAz þ zFGad d 4S þ lGad Fd 4M (9)

As the interface depicted in Figure 1b is in equilibrium, X

sol X
sol X
sol
the intensive quantities, such as the temperature (T ), Gk d mk ¼ Gk d mk þ zk Gk Fd 4S (10)
pressure (P), and the electrochemical potential of spe- k k k
cies i (mi ) remain constant across the interfacial region,
while the extensive quantities in the interfacial region,

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6 Fundamental and Theoretical Electrochemistry (2023)

By adding Eqs. (8)e(10), Eq. (7) can be rearranged into:

!
X
sol X
sol
d g ¼ ðsM þ lFGad Þd 4M þ zk FGk þ zFGad d 4S þ Gad d mAz þ Gk d mk (11)
k k

As the whole interface is electroneutral, we have: For an interface where there are multiple specific
adsorbed ions, a general Lippmann equation can be
X
sol derived in the same way and is given below without
sM þ ðz þ lÞFGad þ zk FGk ¼ 0 (12) detailed proof:
k
X
ad
stot d D4M
S þ Gj;ad d mj;ion
d g ¼ j
Then we have:
!
X
sol X
X
sol þ Gk d mk stot ¼ sfree  zj FGj;ad
d g ¼ ðsM þ lFGad Þd 4M
S þ Gad d mA þ
z Gk d mk k i
k
(17)
(13)
where mj;ad is the chemical potential of the ion form in so-
D4MS ¼ 4M  4S is the difference in the inner potential lution corresponding to the adsorbate j. For example, for the
between the bulk metal and the bulk solution. As can be specifically adsorbed hydrogen, its ion form is the hydrogen
seen clearly, the charge in the thermodynamic relation (the ion. The hydrogen adsorption with water molecule as the
term in the parentheses of Eq. (13)) is exactly the total precursor in the alkaline condition doesn’t need to be
charge defined by Eq. (4), i.e., considered, since they are the same processes in thermo-
dynamics, and can be represented as Hþ þ le #H1l ad .
X
sol
d g ¼ stot d 4M
S þ Gad d mA þ
z Gk d mk (14)
Eq. (17) can be rearranged into a form similar to the
k
Lippmann equation at the ideally polarizable interface
As a thermodynamic quantity in thermodynamic relation, (Eq. (16)):
stot is a state function of the interface, more specifically,
the ionic adsorption. By differentiating the surface tension X
sol
concerning D4M d g ¼ stot d D4M
S þ GP k d mk (18)
S at the fixed composition of the solution,
we have: k

!   where GP k is the total mole number of non-specifically

vg vg
¼ ¼ stot (15) adsorbed species k and specifically adsorbed species k.
vD4MS
vE mk
mk Since the adsorption processes are fast in most cases, the
interface including these adsorptions may be approximated
where E is the electrode potential which differs from D4M S to be in quasi-equilibrium, and thus the principles of
by a constant as the metal and the reference electrode are thermodynamic equilibrium are applicable. With the help
identified. From Eq. (15), it is clear that for the case with of the thermodynamic analysis, one may obtain conven-
specific adsorption the potential at the maximum of the tional concepts, such as the Esin-Markov coefficient,
electrocapillary curve, g  E plot, is the pztc. Only when formal partial charge, electrosorption valency, as well as
there is no specific adsorption, that’s the case of the ideally some important properties in the EDL, such as the ca-
polarized interface, the potential at the maximum of the pacity, the entropy, etc. [33,41,46] Furthermore, the
electrocapillary curve coincides with the pzfc. In this spe- coverage of adsorbates can also be estimated [33,38,43]. As
cial case, Eq. (14) will reduce to the classic Lippmann the coverage of adsorbates and the total charge are ob-
equation encountered mostly in the text- tained, the free charge can be calculated basing Eq. (5). In
books [6,44,45], i.e., this regard, estimation of the coverage basing the thermo-
dynamic relation will be addressed in the next section.
X
sol  
d g ¼ sM d D4M
S þ Gk d mk where sM ¼ stot ¼ sfree Estimation of adsorbate coverage in
k
thermodynamics
(16) Consider an electrochemical interface formed by the
contact of metal and solution consisting of HA and HB,

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 On the Electrode Charge Zhang et al. 7

where HA and HB are the acid corresponding to the the mole fraction of species k in bulk solution. As for the
anion A and the supporting electrolyte, respectively. dissociation equilibriums of H2O, HA, and HB, we have:
Supposing that only specific adsorption of A occurs in
the experimental potential range of interests, that is: d mH2 O ¼ d mHþ þ d mOH z0 (23)

A  #A l1
ad þ le
 (19)
d mHB ¼ d mHþ þ d mB ¼ 0 (24)
where A could be OH, F, Cl, Br, HCOO, CH3COO, etc.
Under this condition, Eq. (17) can be written as: d mHA ¼ d mHþ þ d mA (25)
X
sol
Herein, mH2 O is assumed to be a constant due to its large
d g ¼ stot dE þ Gad d mA þ Gk d mk
k (20) amount. Combined with Eq. (23)e(25) and Eq. (22),
þ   
d mB ; d mA ; d mOH can be canceled, then we have:
ðk ¼ H ; A ; OH ; B ; HA; H2 OÞ

!
  X
d g ¼ stot dE þ Gad þ GA ðH2 OÞ þ GHAðH2 OÞ d mHA þ  Gad þ zk GkðH2 OÞ d mHþ (26)
k

where k ¼ Hþ ;A  ;OH ;B . According to the definitions

where stot ¼ sfree þ FGad , Gad is the coverage of A ad
l1
.E
of stot and sfree , we have:
is the electrode potential referenced to the standard

! !
X X
stot ¼ sfree þ FGad ¼ FGad  F zk Gk ¼ FGad  F zk GkðH2 OÞ (27)
k k

hydrogen electrode (SHE), which differs from D4M S by a The second equal sign in Eq. (27) states that the free
constant. Here the supporting electrolyte HB is considered charge is the negative value of the excess charge of non-
completely dissociated (d mHB ¼ 0). Eq. (20) contains specific adsorbed ions. The third equal sign uses the
dependent variables (the chemical potential of k species in electroneutrality of bulk solution, which gives that
P
solution) which can be reduced by the Gibbs-Duhem zk xk ¼ 0. Eq. (26) is thus simplified to:
equation and dissociation equilibriums in bulk solution. k
The Gibbs-Duhem equation gives:  m þ  
stot d E  H þ Gad þ GA ðH2 OÞ þ GHAðH2 OÞ
X
sol d g ¼ F
xk d mk ¼ 0ðk ¼ Hþ ; A  ; OH ; B ; HA; H2 OÞ (21)
k
d mHA
(28)

By substituting Eq. (21) into Eq. (20) to eliminate the  m 

term d mH2 O , we have: The term E  FHþ differs from the electrode potential
referenced to the reversible hydrogen electrode (ERHE )
X
sol by a constant. As indicated by Eq. (28), the coverage of
d g ¼ stot dE þ Gad d mA þ GkðH2 OÞ d mk adsorbates can’t be separated from the relative surface
k (22) excess of A and HA. This is reasonable since HA, A
þ    and adsorbates are in equilibrium, and can’t be distin-
ðk ¼ H ; A ; OH ; B ; HAÞ
guished in thermodynamics. However, some assump-
 
tions can be made. As a neutral species, the non-specific
where GkðH2 OÞ ¼ Gk  GH2 O xk
is the relative surface
xH2 O adsorption of HA can be neglected, that is GHAðH2 OÞ z0.
excess of species k [44], that is the excess amount of spe- For rational neglection of GA ðH2 OÞ relative to Gad ,
cies k in the interfacial region relative to the bulk solution enough supporting electrolyte HB should be added to
with the same amount of interfacial water molecules. xk is

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8 Fundamental and Theoretical Electrochemistry (2023)
inhibit the non-specific adsorption of A. With the
above assumptions, we have:
d g ¼ stot d ERHE þ Gad d mHA
Then the coverage of adsorbates can be given by
differentiating g concerning mHA at constant electrode
potential, that is:
   
vg 1 vg
Gad ¼  ¼ 
vmHA ERHE RT vln aHA ERHE
where mHA ¼ m0HA þ RT ln aHA , m0HA and aHA are the
standard chemical potential and activity of HA, respec-
tively. Consider a series of solutions with different con-
centrations of HA (cHA ) and fixed concentration of HB
(cHB ), where cHA is small enough and much smaller than
cHB . In this condition, aHA zcHA , and the solution pH is
almost uniquely determined by cHB so that this series of
solutions can be applied to studying the adsorption be-
haviors of A at a constant pH. For each specific solution
composition (cHA ), stot  ERHE curve can be obtained by
integrating the CV from a known pztc, as introduced in
section 2. Then the surface tension at a certain value of
electrode potential can be integrated by Eq. (29) (where
d mHA ¼ 0):
Z the electrode potential measured in the pure supporting
ERHE
gðERHE Þ ¼ g  stot d ERHE
ERHE
where g is the integration constant and ERHE is the
electrode potential at which the surface tension is g .
ERHE is commonly chosen at which specific adsorption has
not occurred for all concentrations of HA. For the case of
anion adsorption, it should be negative enough. The
interface at such an electrode potential is negligibly
perturbed by trace amounts of HA, and thus g can be
approximated as a common constant for all cHA . Then the
coverage can be estimated by Eq. (30) (d g will be zero for
all cHA ). Indeed, the absolute value of stot is not necessary,
we can use an integration charge from any specific elec-
trode potential of CV, denoted as q, which differs from stot
by a constant in a specific solution. The surface pressure of
adsorbed anion can be defined as [35, 38, 39]:
Z ERHE 

pg ¼ g0  g ¼ stot  s0tot d ERHE
ERHE
Z (32)
ERHE
¼ ðq  q0 Þd ERHE
ERHE
where g0 ; q0 and g; q are the surface tension and the inte-
gration charge measured in the pure supporting electrolyte
solution and HA-containing solution, respectively. Since g0
is not related to cHA , the differential d g in Eq. (30) can be
replaced by  d pg.
Current Opinion in Electrochemistry 2022, 36:101161
However, for specific adsorption occurring in a narrow
potential range, the total charge usually varies steeply
with the electrode potential, and integration of the total
(29) charge along the electrode potential (Eq. (31)) may
cause mathematical artifacts in data analysis. An alter-
native scheme can be performed by changing the inde-
pendent variable from electrode potential to total charge
through the so-called Legendre transformation for Eq.
(29) [39,43]. By introducing the Parsons function x ¼
g þ stot ERHE [47], Eq. (29) can be reformulated as:
d x ¼ ERHE d stot þ Gad d mHA (33)
(30)
The coverage is estimated similarly to Eq. (30), where x
can be integrated by Eq. (33) (d mHA ¼ 0):
Z stot

xðstot Þ ¼ x þ ERHE d stot (34)
stot
where x and stot are the Parsons function and the total
charge at ERHE . The surface pressure in this condition can
also be defined similarly [33,39]:
Z q
 
px ¼ x0  x ¼ ERHE;0  ERHE dq (35)
q
where x0 ; ERHE;0 and x; ERHE are the Parsons function and
electrolyte solution and HA-containing solution, respec-
(31)
tively. Thus, the differential d x in Eq. (33) can be replaced
by  d px. For the practical applications of the above
thermodynamical estimation method in specific systems,
the readers are recommended to refer to these excellent
works [33e35,38e40]. In the next section, the system with
(bi)sulfate adsorption will be analyzed as a typical example.
Nonmonotonic surface charging relation for
the Pt (111) interface with specific
adsorption of the sulfate
The (bi)sulfate adsorption (adsorption of sulfate ion or
bisulfate ion) on the surface of Pt group metals is an
important model process in interfacial electrochemistry.
The relevant knowledge has important implications for
Nafion-based fuel cell systems containing sulfonic acid
groups. Combining the thermodynamic analysis and
FTIRRAS (Fourier transform infrared reflection ab-
sorption spectrometry) on Pt (111), Feliu et al. found
that the predominant adsorbed species on Pt (111) is
sulfate [34], which is also suggested by a combination of
theoretical calculations and vibrational frequency anal-
ysis [48]. The same conclusions are drawn on Au (111)
and Pd (111) [49,50]. Therefore, possible adsorption
processes are:
HSO þ
4 #SO4;ad þ H þ le
l1 
(36)
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 On the Electrode Charge Zhang et al. 9

Figure 2

Potential dependence of a) cyclic voltammetry and b) the total charge c) the coverage of adsorbates and d) the estimated free surface charge at Pt (111)
with the assumption that SOl24;ad is the dominating adsorbate in solution with composition of (0.5-x) M HClO4 and x M H2SO4, where x equals 0.0001,
0.001, 0.01, 0.1, pH = 0.43. vscan is the scan rate ranging from 50 to 1 mV/s. The cyclic voltammetry, the total charge, and the coverage of adsorbates are
adapted from the reference, [33] and the free charge is calculated by Eq. (38).

A complete thermodynamic study of the (bi)sulfate


4 #SO4;ad þ le
SO2 l2
Eqs. (36) and (37) are specific adsorptions of the sulfate
SOl
4;ad with the bisulfate ion and the sulfate ion as the
precursor, respectively. l is the pct coefficient. As
mentioned above, the adsorption processes of Eq. (36)
and Eq. (37) are indeed the same in thermodynamics,
then the relationship between the free charge and the
total charge is (z ¼ 2 in Eq. (5)):
sfree ¼ stot  2FGad
Herein, Gad is specifically referred to the coverage of spe-
cies SOl
4;ad . In the following, we will analyze the surface
charging behaviors of (bi)sulfate adsorption system based
on Eq. (38) and the work of Feliu and co-workers.
adsorption on Pt (111) in solutions with different con-
(37)
centrations of sulfuric acid has been carried out by Feliu
et al. [33] The characteristic voltammetric curves of the
(bi)sulfate adsorption on Pt (111) in different solution
compositions are shown in Figure 2a. All curves display a
broad peak followed by a sharp current spike, which is
referred to as ‘butterfly’ in electrochemistry, the spike
corresponds to a disorder-order phase transition in the
adlayer [51]. By the methods of integrating the current
density in Figure 2a from the pztc and thermodynamic
analysis, the total charge and the coverage of adsorbates
(38) are obtained and shown in Figures 2b and 2c, respec-
tively [33]. As is seen from Figure 2c, the coverage of
adsorbates firstly increases slowly and then increases
steeply as the potential exceeds the phase transition
potential, e.g., ca. 0.48 V in solution with 0.01 M sul-
furic acid.

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10 Fundamental and Theoretical Electrochemistry (2023)
The free charge is estimated according to Eq. (38), and
shown in Figure 2d. As depicted in Figure 2d, it can be
found that the surface charging relations in solutions
with different concentrations of added sulfuric acid
display nonmonotonic sfree  E relations. For example,
for the case in the solution with 0.01 M sulfuric acid, the
free charge firstly increases with the increase of the
electrode potential up to ca. 0.45 V, then decreases in
the potential range from ca. 0.45 V to ca. 0.51 V, and
increases again when the potential is above 0.51 V. The
charging behavior in the higher potential range (0.45
Ve0.51 V) doesn’t meet the conventional charging
behavior for an ideally polarizable electrode. The reason
for this unconventional charging behavior originates
from the generation of the adsorbate. Since the total
charge increase monotonically with the electrode po-
tential (Figure 2b), according to Eq. (38), the decrease
of the free charge in the potential range from ca. 0.45 V
to ca. 0.51 V is caused by the increasing coverage of the
adsorbed sulfate. We can also find that the potential
range that the free charge steeply decreases is exactly
the potential range at which the coverage of the adsor-
bate steeply increases, e.g., from ca. 0.48 Ve0.51 V in
solution with 0.01 M sulfuric acid. As for the micro-
scopical explanation for this charging behavior, Huang
ascribes it to the surface dipoles induced by the partially
charged chemisorbate [12,52].
In this method of estimating the free charge, the total
charge and the pseudocapacitive charge are quantities
much larger than the free charge, and the small error of
the coverage or the total charge may cause a large
fluctuation in the value of the free charge. Therefore,
the reliability of the free charge estimated by Eq. (38)
will mainly depend on the measured coverage and the
pztc. For example, the coverage in Figure 2c theoreti-
cally includes that of specifically adsorbed sulfate and
that of surface relative excess of non-specifically
adsorbed sulfate ion since they are indistinguishable
in thermodynamic relation and this may lead to over-
estimation of the coverage for specifically adsorbed
sulfate and thus underestimate the free charge. Hence,
in this work, we only choose the set of data measured
from the experiment, where enough supporting elec-
trolyte, (0.5-x) M HClO4, is added into the solution to
inhibit the non-specific adsorption of the sul-
fate ion [33].
Modeling study for specific adsorption at
the metal/solution interface
As discussed in sections 2 and 3, the concept of pct co-
efficient is now in such a situation that cannot be
uniquely determined in a theoretical way or experi-
mental way but have potential significance in behaviors
of specific adsorption [9,52,53]. To reveal the role of pct
coefficient played in adsorption phenomenon, an
appropriate model can be proposed to describe EDL and
Current Opinion in Electrochemistry 2022, 36:101161
the specific adsorption process occurring at the electrode
surface. The model with quantitative relationships be-
tween the free charge, coverage, electrode potential,
etc., can be used to simulate the experimental results,
such as total charge, and current density, as well as their
dependence on experimental conditions, such as elec-
trode potential, solution pH, ion concentration, and so
on. The parameterized values of the parameters involved
in the model, such as pct coefficient, lateral interaction
factor, etc., will certainly help us with a quantitative
understanding of their effects on the experimental
phenomenon. For this reason, a modeling study of spe-
cific adsorption will be introduced and exemplarily
performed in the above (bi)sulfate adsorption system.
For performing the fitting to the total charge or the
current density, quantitative relationships between the
electrode potential, the coverage, and the free charge
have to be established. One of the relationships can be
formulated in the equilibrium approximation of the
adsorption process. Taking the model reaction (Eq. (1))
as an example, when adsorptions (including the specific
adsorption and non-specific adsorption) are in equilib-
rium, which means the specific adsorption itself and the
transportation of ions are fast enough, we have
mAz ¼ mad þ lme (39)
where mAz is the electrochemical potential of A z in the bulk
solution. The electrochemical potential of species can be
expanded as the followings:
mAz ¼ m0Az þ RT ln cAz þ zF4S (40)
mad ¼ m0ad þ gðqad Þ þ ðz þ lÞF4IHP (41)
me ¼ me  F4M (42)
where 4IHP is the potential at the IHP, qad ¼ Gad =Gmax is
the normalized coverage to the maximum coverage of ad-
sorbates (Gmax ). m0Az ; m0ad are the standard chemical poten-
tials of A z and adsorbates. gðqad Þ is a function of coverage,
whose form depends on the structure and lateral interac-
tion among the adsorbate. e.g., if the adsorbate conforms to
the Frumkin type isotherm [6], it can be formulated as:
 
qad
gðqad Þ ¼ RT ln þ rad qad (43)
1  qad
where rad is the lateral interaction factor. Substituting Eq.
(40)e(42) into Eq. (39), Eq. (39) can be rearranged into:
 
gðqad Þ ¼ RT ln cAz þ lF E  E0  ðz þ lÞFD4IHP
S
(44)
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where E ¼ D4M S  me =F  Eabs is the electrode poten-
SHE
tial on the standard hydrogen electrode (SHE) scale, E0 ¼
ðm0ad m0Az Þ=ðlFÞ  ESHE
abs is the standard equilibrium po-
tential for the adsorption reaction (Eq. (1)) on the SHE
scale. ESHE
abs is the absolute electrode potential of SHE.
D4IHP
S ¼ 4IHP  4S is the potential difference between
the IHP and the solution bulk. To express this term, the
EDL structure needs to be built up to express the potential
drop across the interface. As for the modelistic description
of the EDL in Figure 1b, the potential difference D4M S can
be given by a primitive form [9,52]:
 
sb dIHP NA Gmax qad mad NA Gw mw
D4M ¼ cM þ þ þ
S
εIHP εIHP εIHP
 
dIHP dOHP
þsfree þ þ D4d
εIHP εOHP
(45)
On the right-hand side of Eq. (45), the first term cM is the
surface potential due to the spillover of metallic electrons.
The terms in the first parentheses represent the potential
drop caused by surface dipoles in the region between the
metal surface and the IHP. The terms in the numerator are
surface dipoles that are formed by the partial charge on the
adsorbate and the corresponding image charge, the orien-
tation of permanent dipoles of adsorbates, and the orien-
tation of permanent dipoles of adsorbed water molecules,
respectively. sb ¼ ðz þlÞFGmax qad is the bound charge
defined in section 3, NA is the Avogadro constant. mad is the
average dipole moment per adsorbate, whose value de-
pends on the magnitude of the permanent dipole and the
adsorption configuration of the adsorbate. For spatially
symmetric adsorbate, this term can be neglected, e.g.,
adsorbed oxygen atom, adsorbed sulfate. Gw ; mw are the
coverage and the average dipole moment of adsorbed water
molecules, respectively. The third term represents the
potential drop in the region between the metal surface and
the OHP, which is caused by the free charge on the elec-
trode. εIHP ; dIHP are the average permittivity and the
thickness of the space between the metal surface and the
IHP, respectively. εOHP ; dOHP are the average permittivity
and the thickness of the space between the IHP and the
OHP, respectively. The last term D4d , is the potential drop
over the diffuse layer of the EDL.
Transforming the potential difference D4M S and c
M in
Eq. (45) into the electrode potential on the SHE scale,
we have:
 
sb dIHP NA Gmax qad mad NA Gw mw
E ¼ cM;SHE
þ þ þ where CEDL ¼
εIHP εIHP εIHP
 
dIHP dOHP
þsfree þ þ D4d
εIHP εOHP
(46)
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On the Electrode Charge Zhang et al. 11
where cM;SHE ¼ cM  me =F  ESHE
abs . The potential dif-
ference D4IHP
S is then:
 
dOHP
D4IHP ¼ sfree þ D4d (47)
S
εOHP
Substituting Eq. (47) into Eq. (44), we have
 
gðqad Þ ¼ RT ln cAz þ lF E  E0
  (48)
dOHP
ðz þ lÞF sfree þ D4d
εOHP
The terms on the right-hand side of Eq. (46) can be
further refined. For example, the surface dipole induced
by the oriented water molecules can be described by a
two-state model [6] or a detailed statistical
model [54,55]. For the diffuse layer, it can be described
by the Poisson-Boltzmann equation [45] or in more
complicated forms [56,57]. Anyway, the terms in Eq.
(46) can be described by suitable sub-models related to
the free charge and the coverage. Combining Eq. (46)
and Eq. (48), the free charge and the coverage can be
solved as functions of the electrode potential while other
parameters are chosen, then the total charge can be
calculated according to Eq. (5). Parameters that can’t be
obtained from experiment and theoretical calculation,
such as the partial charge, the lateral interaction factor,
etc., can be estimated by parametrizing the experimental
results. To be more specific, we simply treat the sulfate
adsorption (Eq. (37)) in the following.
For potential drops in Eq. (46), we ignore the term
generated by permanent dipoles of SOl2 4;ad due to its
configurational symmetry, and neglect of the potential
drop caused by adsorbed water molecules for simplicity.
If enough supporting electrolyte is added, e.g., nearly
0.5 M HClO4 in Figure 2, the potential drop in the
diffuse layer D4d can be approximated as a linear change
with the potential in the potential range not far from the
pzfc, which means D4d ¼ sfree =Cd , where Cd is the
capacitance of the diffuse layer. Eq. (46) then can be
simplified to (z ¼  2):
ð2  lÞFGmax qad sfree
E ¼ cM;SHE þ þ (49)
CIHP CEDL
 1
dIHP
εIHP þ dεOHP
OHP
þ C1d is the capacitance of
the EDL. CIHP ¼ εIHP =dIHP is the average capacitance in
the region between the metal surface and the IHP. As for
the adsorption process, we use the Frumkin type isotherm
(Eq. (43)), then Eq. (48) can be written as:
Current Opinion in Electrochemistry 2022, 36:101161
12 Fundamental and Theoretical Electrochemistry (2023)

Figure 3

Some representative simulated results in solution with 0.49 M HClO4 + 0.01 M sulfuric acid: a) the simulated total charge and experimentally measured
total charge, b) normalized coverages of adsorbates obtained by the simulation and the thermodynamic analysis, and c) the simulated surface charging
relation. Parameters used are: cM;SHE ¼ 0:27 V, CEDL ¼ 0:46 F=m2 , CIHP ¼ 0:5 F=m2 , pKa ¼ 1:92; F ¼ 96500 C=mol, T ¼ 298:15 K; R ¼
8:314 J=ðmol ,KÞ, l ¼ 1:7; Gmax ¼ 5 × 106 mol=m2 , E 0 ¼ 0:34 V before the phase transition and 0:48 V in the phase transition region, rad ¼ 7:5 RT
before the phase transition and 4RT in the phase transition region, the phase transition potential is 0.48 V obtained from Figure 2b.

CIHP ; rad , are obtained by fitting the total charge shown

   
qad rad qad lF E  E0 in Figure 2b.
ln þ ¼ ln cSO2 þ
1  qad RT 4 RT
  (50) Some representative simulation results in solution with
ð2  lÞF 1 1 0.49 M HClO4 þ 0.01 M H2SO4 are shown in Figure 3.
þ  sfree
RT CEDL CIHP As can be seen from Figure 3a, the total charge in the
simulation agrees well with that measured by the
where cSO2 is the bulk concentration of sulfate ions, and experiment. Figure 3b shows the normalized coverage in
4
can be calculated based on the dissociation equilibrium of the simulation, which displays a similar adsorption
the sulfuric acid: behavior to the normalized coverage estimated by the
c0 thermodynamic analysis. The parameterized maximum
cSO2 ¼ pKapH (51) coverage of adsorbates Gmax is 5  106 mol=m2 , which
4
10 þ1
is a bit larger than the maximum coverage
where c0 is the total concentration of sulfate ions and 4:36  106 mol=m2 estimated by thermodynamic
bisulfate ions, pKa is the dissociation coefficient of the analysis. This small difference between the coverage
bisulfate ion. estimated by these two methods causes a large differ-
ence between the estimated free charge. However, the
As for the selection of parameters, cM;SHE is assumed to sfree  E profiles derived from both the simulation and
be potential-independent and found from reference. thermodynamic analysis based on Eq. (38) display a
[29] CEDL is obtained by linearly fitting the total charge nonmonotonic relationship. The parameterized value of
in the potential range where specific adsorbed sulfate the pct coefficient is given to be 1.7, indicating the
reaches saturation, e.g., ca. 0.5 Ve0.6 V in solution with specifically adsorbed sulfate is partially charged, which
0:01 M sulfuric acid as shown in Figure 2b. Two different induces the above nonmonotonic relationship of free
values of E0 and rad are applied in the potential regions of charge (Figure 3c) [12]. The positive value of the lateral
adsorption of disordered adsorbates and phase transition interaction factor before the phase transition indicates
region (broad peak region and sharp peak region) to the repulsive interactions between disordered adsor-
describe the effects of the disorder-order phase transi- bates. As the disorder-order phase transition occurs, the
tion to the adsorption isotherm. The standard equilib- lateral interaction factor becomes negative correspond-
rium potential E0 is approximated to be the onset ing to the attractive lateral interaction between ordered
potential of the adsorption, e.g., ca. 0.34 V and ca. 0.48 V adsorbates. The transition from disordered and repul-
in the broad peak region and sharp peak region in solution sive adsorbates to ordered and attractive adsorbates
with 0.01 M sulfuric acid. The remaining parameters sharps the current peak and induces the ‘butterfly’,
except for some experimental known, such as l; Gmax ; which is also indicated by the kinetic Monte Carlo

Current Opinion in Electrochemistry 2022, 36:101161 www.sciencedirect.com


simulation [51]. The interaction between the adsorbed
sulfate whose partial charge is indeed potential-
dependent, and co-adsorbed water molecules among
the sulfate chains probably act as glue leading to such a
transition of lateral interaction forms, which requires a
more refined model and will be further scrutinized.
Conclusions
In this brief review, three types of electrode charges, the
metallic excess charge, the free charge, and the total
charge, are introduced and discriminated via a model-
istic description at the metal/solution interface. The
metallic excess charge is the electronic excess charge at
the metal side, which is hardly separated from the par-
tial charge of adsorbates. The free charge is the sum of
the metallic excess charge and the net charge of adsor-
bates, which compensates for the excess charge of non-
specifically adsorbed ions. The total charge is the excess
charge of those electrons in the metal and transferred
from the metal to the ion, quantitively equal to the
coulombic charge flowing into the electrode from the
external circuit as the metal and the solution come into
contact, it’s experimentally measurable. The total
charge is then proved to be the thermodynamic charge
in a general Lippmann equation. Based on the Lipp-
mann equation, thermodynamic analysis can be
performed to estimate the coverage of the adsorbate,
and then the free charge can be derived. As an example,
a simple manipulation has been made on a previous work
in the (bi)sulfate adsorption system, the surface
charging relations are obtained, displaying a nonmono-
tonic relationship. The modeling study for specific
adsorption is introduced and exemplarily performed in
the (bi)sulfate adsorption system. Understanding the
meanings of the electrode charge in different cases, as
well as their relationships and potential dependence, is
of great importance for developing or performing quan-
titative analysis for electrochemical systems.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could
have appeared to influence the work reported in
this paper.
Data availability
Data will be made available on request.
Acknowledgment
We appreciate invaluable discussions with Prof. Jun Huang, R. Compton,
W. Schmickler, E. Santos, J. Feliu and V. Climent. This work was supported
by National Natural Science Foundation of China (NO.
22172151, 21972131).
Appendix A. Supplementary data
Supplementary data to this article can be found online
at https://doi.org/10.1016/j.coelec.2022.101161.
www.sciencedirect.com
On the Electrode Charge Zhang et al. 13
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