Electrochimica Acta 330 (2020) 135234

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Electrochimica Acta
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Preparation of a Pt thin-film modified electrode for alkaline

electrocatalytic oxidation of methanol by Cu(OH)2 electrodeposition
and galvanic replacement reaction
Chunxiu Zhang, Long Chao, Linping Wang, Yan Cheng, Qingji Xie*
Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research (Ministry of Education of China), College of Chemistry and Chemical
Engineering, Hunan Normal University, Changsha, 410081, China

a r t i c l e i n f o a b s t r a c t

Article history: Improving the utilization and anti-poisoning ability of Pt for electrocatalysis applications is widely
Received 30 August 2019 concerned for years. Herein, a Pt thin-film modified electrode is prepared via a galvanic replacement
Received in revised form reaction (GRR) of the copper thin film originated from directly electrodeposited Cu(OH)2 for high-
22 October 2019
performance electrocatalytic oxidation of methanol in alkaline medium. In an unbuffered electrolyte
Accepted 5 November 2019
Available online 7 November 2019
solution of CuSO4 and p-benzoquinone (BQ), a uniformly distributed Cu(OH)2 thin-film is deposited on a
gold-plated glassy carbon electrode (Au/GCE) by electroreducing BQ to consume Hþ near the electrode
surface. The electroreduction of Cu(OH)2 to atomic copper and then its GRR with K2PtCl4 yields a Pt thin-
Keywords:
Uniform Cu(OH)2 electrodeposition
film modified Au/GCE (PtCu(OH)2/Au/GCE) with excellent performance for electrocatalytic oxidation of
p-benzoquinone reduction methanol in alkaline medium. The processes and mechanisms of electrode modification are investigated
Galvanic replacement reaction by electrochemistry, quartz crystal microbalance, scanning electron microscopy and energy-dispersive
Pt electrocatalyst spectroscopy. Under the optimal conditions, the electrocatalytic oxidation peak current obtained by
Alkaline methanol oxidation cyclic voltammetry (0.8 V～0.8 V, 50 mV s1) on PtCu(OH)2/Au/GCE is 21.8 mA cm2 Pt in 0.5 M aqueous
KOH containing 1 M methanol. The method is expected to be a good candidate for electrodepositing
other uniform films for wider applications.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction of the effective methods to improve the utilization of Pt. It has been
reported that, by using the strong mutual affinity between Cu and
Noble metal Pt catalyst has high activity for the catalytic Au atoms, monolayer Cu can be deposited on Au substrate by the
oxidation of many small organic molecules and can be used in underpotential deposition (UPD) method, and then a Pt-monolayer
direct methanol fuel cells (DMFCs) [1,2]. However, Pt is easily electrocatalyst with high Pt utilization can be prepared by the
poisoned by the adsorbed carbon monoxide (COads) intermediate galvanic replacement reaction (GRR) between atomic Cu and a Pt
generated in the process of methanol oxidation [3,4], which re- compound [11]. However, due to the desorption loss and surface
duces the catalytic performance. It is well known that the intro- reconstruction of atomic monolayer Pt on the electrode surface, the
duction of a second metal M to Pt can yield a PtM bimetallic catalyst long-term stability of such a Pt electrocatalyst is not good. There-
with improved catalysis performance, such as PtNi [5], PtRu [6], fore, the efficient preparation of Pt thin-film electrocatalysts with
PtAu [7], PtAg [8], PtCu [9], and PtCo [10]. On the other hand, Pt is good dispersion and stability is worthy of in-depth study.
expensive and has a rather limited abundance on the earth, thus Compared with the bulk electrodeposition of a metal, the more
hampering its large-scale industrial applications to some extent. uniform film can be obtained by depositing electron-insulating
Therefore, the issue how to improve the utilization of Pt has molecules or atoms on an electron-conducting substrate. Obvi-
aroused worldwide concern. It is obvious that the nano scalization ously, after the electrodeposition of electron-insulating molecules
of Pt materials, including the use of ultrathin Pt film catalyst, is one or atoms on some substrate surface sites, the electron-conductivity
of these sites will be decreased, and thus the subsequent electro-
deposition of electron-insulating molecules or atoms will occur
* Corresponding author.
preferentially on the more electron-conducting surface sites at
E-mail address: xieqj@[Link] (Q. Xie). which the fewer insulating molecules or atoms are deposited,

[Link]
0013-4686/© 2019 Elsevier Ltd. All rights reserved.
2 C. Zhang et al. / Electrochimica Acta 330 (2020) 135234

finally leading to the formation of a rather uniform thin-film of electrochemically treated and then inspected by cyclic voltamme-
electron-insulating molecules or atoms on the electrode. It is try (CV) of the Fe(CN)3-/4-
6 probe as follows [14e16]. The electrodes
generally believed that the nanometer-scale thickness of the were polished successively with sandpapers (fine sandpapers for
atomically/molecularly compact electron-insulating film deposited GCE, and metallographic sandpapers for the Au disk electrode and
on the electrode surface leads to a notably decreased and even Pt disk electrode), and 0.3 mm and 0.05 mm alumina slurries. After
near-zero electroactivity of the electrode [12]. After the GRR of such rinse with ultrapure water, they were ultrasonically cleaned (the
an appropriate electron-insulating film (or its derivatives) with a Pt disk GCE and the disk Au electrode were treated with water,
compound, a Pt thin-film electrocatalyst with high surface- ethanol and ultrapure water for 5 min, respectively; the Pt disk
dispersity can be obtained. Recently, we have electrodeposited a electrode were treated with the mixture HNO3/absolute ethanol (1/
CuCl film on a gold-plated electrode and then performed its GRR 1) for 5 min). For the GCE, it was treated with concentrated sulfuric
with a Pt compound to obtain a multilayer ultrathin Pt film catalyst acid for 15 s, then it was placed in 0.1 M aqueous H2SO4 for CV
after one round of experiments [13]. We believe that the further treatment (potential range: 1.0～1.0 V, scan rate: 0.05 V s1) until
research and development of such multilayer thin-film electro- the CV curves became reproducible. For the Au disk electrode, it
catalyst systems (versus the special CuCl system) are interesting was treated with Piranha solution (H2SO4: H2O2, 3:1 in v/v) for 15 s
and important. As far as we know, the strategy of the uniform and then electrochemically cleaned (2 V high potential treatment
electrodeposition of Cu(OH)2 thin film by electroreducing BQ to for 5 s, 0.35 V low potential treatment for 10 s) in 0.1 M aqueous
consume Hþ near the electrode surface in combination with an H2SO4, followed by CV treatment (potential range: 0.35 V～1.55 V,
appropriate GRR has not been reported to date for preparing noble scan rate: 2 V s1) until the CV curves became reproducible. For the
metal thin-film electrocatalysts. Pt disk electrode, it was electrochemically cleaned by CV in 0.1 M
Herein, a new and effective method for preparing a Pt thin-film aqueous H2SO4 (potential range: 0.35 V～1.55 V, scan rate:
electrocatalyst is suggested. First, in an unbuffered electrolyte so- 0.1 V s1) until the characteristic redox peaks became reproducible.
lution of copper sulfate and p-benzoquinone (BQ), electroreduction Finally, all the treated electrodes were characterized by CV (0.1 V
of BQ can consume Hþ near the electrode surface and thus lead to ～0.5 V, 0.05 V s1) in 0.1 M aqueous Na2SO4 containing
the uniform deposition of Cu(OH)2 on a gold-plated glassy carbon 2 mM K4Fe(CN)6, and the peak-to-peak separation of its redox peak
electrode (Au/GCE). Then, Cu(OH)2 is electroreduced to atomic in each case was within 75 mV, indicating that the treated elec-
copper, followed by the GRR between Cu and a Pt compound trodes had been well cleaned and had good electrochemical
(K2PtCl4) to yield a Pt thin-film modified Au/GCE (PtCu(OH)2/Au/ activity.
GCE). The Pt thin-film electrocatalyst exhibits excellent perfor- The preparation of the target electrode is described below, as
mance for alkaline electrocatalytic oxidation of methanol. shown in Scheme 1. (1) Au was potentiostatically deposited on the
cleaned GCE at 0.2 V for 200 s in stirred (1000 rpm) 0.5 M aqueous
2. Experimental section H2SO4 containing 2 mM HAuCl4 (Au/GCE). (2) Cu(OH)2 was poten-
tiostatically deposited on Au/GCE at 0 V for 50 s in 0.1 M pH 3.19
2.1. Instrumentation and reagents aqueous Na2SO4 containing 5 mM CuSO4 and 10 mM BQ (Cu(OH)2/
Au/GCE). (3) Atomic Cu was potentiostatically obtained on
All electrochemical experiments were performed on a CHI660A Cu(OH)2/Au/GCE at 1 V for 200 s in neutral 0.1 M aqueous Na2SO4
electrochemical workstation (CH Instrument Co., USA), using a (CuCu(OH)2/Au/GCE). (4) The CuCu(OH)2/Au/GCE was immediately
conventional three-electrode system. Glassy carbon electrode placed in N2 saturated 0.02 M aqueous H2SO4 containing
(GCE), Au disk electrode, and Pt disk electrode (all 3.0 mm diam- 1 mM K2PtCl4 for 300 s to yield PtCu(OH)2/Au/GCE.
eter) as well as their modified electrodes were used as the working In order to validate the successful preparation of the Cu(OH)2/
electrode, a KCl-saturated calomel electrode (SCE) was the refer- Au/GCE, an Au/GCE was modified with chemically synthesized
ence electrode, and a graphite rod was the counter electrode. All Cu(OH)2 (c-Cu(OH)2/Au/GCE) for CV comparison. Aqueous CuSO4
potentials reported here are cited versus SCE. The experiments of was thoroughly mixed with aqueous NaOH under stirring for 100 s
quartz crystal microbalance (QCM) and electrochemical quartz (CuSO4: NaOH, 1:2 in molar concentration), followed by centrifu-
crystal microbalance (EQCM) were carried out on an HP4395A gation (5000 rpm) isolation, water-rinse, and 40  C desiccation of
impedance analyzer, using gold-coated AT cut 9 MHz piezoelectric the product. A 0.1 g L1 Cu(OH)2 aqueous suspension was prepared,
quartz crystals (PQCs, JA5B, Beijing Chenjing). The PQC wafer was and the suspension with an appropriate volume was cast-coated
fixed at one end of a plastic tube using a silicon rubber adhesive and air-dried on Au/GCE to yield the c-Cu(OH)2/Au/GCE. The
(704, Wuxi, China), and only one side of the PQC touched the liquid following three control electrodes were prepared for electro-
solution. The geometric area of the exposed PQC Au electrode is catalytic performance comparison with the target electrode. (i)
0.14 cm2. Scanning electron microscopy (SEM) pictures were ob- PtCu-UPD/Au/GCE: UPD Cu was potentiostatically deposited on an
tained from a JEM-6700 field emission scanning electron micro- Au/GCE at 0.1 V for 300 s in 0.1 M pH 3.19 aqueous Na2SO4 con-
scope, and its X-ray energy-dispersive spectroscopy (EDS) taining 5 mM CuSO4 (Cu-UPD/Au/GCE), then the electrode was
accessory was used for elemental analysis. immediately placed in N2 saturated 0.02 M aqueous H2SO4 con-
HAuCl4, K2PtCl4 and CuSO4,5H2O were purchased from Tianjin taining 1 mM K2PtCl4 for 300 s, as reported previously [17]. (ii) Ptp/
Chemicals Factory (Tianjin, China). CH3OH, KOH, NaOH, H2SO4, Au/GCE: a Ptp/Au/GCE was prepared by pulse electroplating (pulse
H3BO3, H3PO4, CH3COOH, Na2SO4 and K4Fe(CN)6$3H2O were pur- potential: 0.75 to 0.2 V, pulse width: 0.25 s, total deposition time:
chased from Sinopharm Chemicals Co., Ltd. (Shanghai, China). 4 s) in 0.02 M aqueous H2SO4 containing 1 mM K2PtCl4. (iii) Nafion-
Other chemicals were of analytical grade or higher purity. All Pt/C/Au/GCE: 0.5 mg commercial Pt/C (20%) catalyst was added to
commercially obtained chemicals were used as received, without 1 mL ultrapure water, followed by ultrasonic dispersion for 1 h, and
further purification. All the solutions were prepared using Milli-Q 5.2 mL suspension was cast-coated on an Au/GCE, dried at room
ultrapure water (Millipore, >18 MU cm). temperature. Next, 4 mL of 0.5 wt% Nafion ethanol solution was
dropped on the electrode surface and then dried at room temper-
2.2. Preparation and characterization of modified electrodes ature. The Pt mass of Ptp/Au/GCE and Nafion-Pt/C/Au/GCE are
roughly the same as Pt(CuOH)2/Au/GCE, which is ca. 0.5 mg. All the
The bare disk electrodes were mechanically/chemically/ prepared electrodes were washed with ultrapure water and placed
 C. Zhang et al. / Electrochimica Acta 330 (2020) 135234 3

Scheme 1. Schematic illustration of the preparation of the modified electrode.

in 0.1 M H2SO4 for CV characterization (0.3 Ve1.45 V, 50 mV s1). 3. Results and discussion
Linear sweep anodic stripping voltammetry (LSASV) was used to
estimate the mass of deposited Cu. The real surface area of Au 3.1. Preparation and characterization of the modified electrodes
(SreAu) is calculated according to the electrical charge under the
reduction peak of gold oxides (AuOx) in 0.1 M aqueous H2SO4 [18], First of all, the electrochemical behavior of BQ was investigated
and the conversion factor is 390 mC cm2. The real surface area of Pt on GCE by CV. As shown in Fig. 1A, no large current peaks were
(SrePt) is calculated according to the underpotential adsorption/ observed on GCE in BQ-free 0.1 M Na2SO4 blank solution
desorption electrical charge of atomic H on Pt [19,20], and the (pH ¼ 3.19), and only a small reduction peak of dissolved oxygen
conversion factor is 210 mC cm2. The specific electrocatalytic ac- appeared at ca. 0.5 V. In unbuffered 0.1 M aqueous Na2SO4 con-
tivity (SECA) is defined as the catalytic current per unit SrePt on the taining 10 mM BQ (pH 1.21), only a pair of redox peaks a1/c1 with a
Pt-modified electrodes. formal potential at ca. 0.25 V was observed. In unbuffered 0.1 M
aqueous Na2SO4 containing 10 mM BQ at different solution pH
(from 1.21 to 5.11), the a1/c1 peaks were gradually decreased with
the pH increase; concurrently, a new pair of peaks a2/c2 with a
2.3. Electrocatalytic experiments relatively negative formal potential (ca. 0.2 V) was gradually
increased with the pH increase. In addition, similar experiments
Electrocatalytic oxidation of methanol: the prepared modified were carried out in 0.1 M Britton-Robinson (B-R) buffer
electrode was placed in 0.5 M aqueous KOH containing 1 M meth- (0.1 M H3BO3 þ 0.1 M H3PO4 þ 0.1 M CH3COOH, adjusting to desired
anol for CV (0.8 V～0.8 V, 50 mV s1) test. Chronoamperometry pH by adding an appropriate NaOH solution). As shown in Fig. 1B, in
tests were investigated at 0.2 V by recording the current-time (i-t) 0.1 M B-R buffer containing 0.1 M aqueous Na2SO4 and 10 mM BQ
curves. (pH 1.78, 3.19 or 9.03), only one pair of redox peaks was observed at
Stripping experiments of COads [19,21,22]: the modified elec- each pH value, and the formal potential negatively shifted with the
trode was placed in 0.5 M aqueous KOH containing 1 M CH3OH, pH increase. The formal potential is ca. 0.3 V in pH 1.78 B-R buffer,
followed by CH3OH-oxidation and CO-adsorption at 0.2 V for which is basically the same as that of the right a1/c1 peaks in
10 min. After washing the electrode with ultrapure water, it was Fig. 1A; and the formal potential is ca. 0.1 V in pH 9.03 B-R buffer,
placed in 0.1 M aqueous H2SO4 for oxidation stripping by CV (po- which is also basically the same as that of the left a2/c2 peaks in
tential range: 0.3 V～0.85 V, initial potential: 0.2 V, scan rate: Fig. 1A. Similar experimental phenomena were observed at the Au
0.05 V s1).

Fig. 1. (A) CV curves on GCE in 0.1 M aqueous Na2SO4 containing 0 or 10 mM BQ at different initial bulk-solution pH values (1.21, 2.13, 3.19, 4.05 and 5.11). (B) CV curves on GCE in
0.1 M B-R buffer containing 0.1 M aqueous Na2SO4 and 10 mM BQ at different pH values (1.78, 3.19, and 9.03). Scan rate: 0.05 V s1.
4 C. Zhang et al. / Electrochimica Acta 330 (2020) 135234

disk electrode and Au/GCE (not shown). Based on our previous Ksp ¼ 2.2  1020, thus the lowest pH for Cu2þ hydrolysis is pH
report [23], the occurrence of two pairs of CV redox peaks in Fig. 1A 5.32 at a Cu2þ concentration of 5 mM. Considering the hydrolysis of
(versus only one pair of CV redox peaks in each case of Fig. 1B) is Cu2þ, the solution pH should not exceed pH 5.32. On the other
briefly explained as follows. The electroreduction of BQ will hand, when the solution-pH is too low, the pH of the solution near
consume Hþ ions, the pH of the local solution near the electrode the electrode surface is not easy to be elevated by the electro-
surface can notably rise in the unbuffered solution, and thus the generated OH during reduction of BQ, making the electrodeposi-
two pairs of CV peaks result from the BQ electrochemistry in acidic tion of copper hydroxide difficult or impossible. Considering the
and then alkaline solutions both of some buffer capacities. In relatively large a1/c1 peaks favorable for controlling the Cu(OH)2-
contrast, 0.1 M B-R buffer has a strong buffer capacity to well sta- electrodeposition amount and the insignificant chemical dissolu-
bilize the local-solution pH near the electrode surface, thus only tion of electrodeposited Cu(OH)2 when taking out the electrode
one pair of CV redox peaks can be observed in 0.1 M B-R buffer that was located near the solution-air interface for further pro-
containing 0.1 M aqueous Na2SO4 and 10 mM BQ (pH 1.78, 3.19 or cessing, it is reasonable to choose pH 3.19 for this system (unbuf-
9.03). fered solution).
The electrochemical behavior of Cu2þ was also investigated at In order to investigate the concentration of Cu2þ required for
the Au disk electrode. As shown in Fig. 2, in 0.1 M aqueous Na2SO4 Cu(OH)2 deposition, the behavior of Cu(OH)2 electrodeposition at
containing 5 mM CuSO4 (pH ¼ 3.19), a pair of small redox peaks a’/a different Cu2þ concentrations was studied by EQCM technique, as
(Cu UPD and its stripping) appears at ca. 0.25 V, and a pair of shown in Fig. S1. The frequency is basically unchanged in Cu2þ-free
notably larger redox peaks b’/b (bulk deposition and stripping of 0.1 M pH 3.19 aqueous Na2SO4 containing 10 mM BQ. In 0.1 M pH
Cu) appears at ca. 0 V [24,25]. In 0.1 M aqueous Na2SO4 containing 3.19 aqueous Na2SO4 containing 10 mM BQ and 2 mM CuSO4, a
5 mM CuSO4 and 10 mM BQ (pH ¼ 3.19), a pair of redox peaks a1/c1 frequency response of ca. 300 Hz decrease (initial frequency versus
appears at ca. 0.25 V, which corresponds to the redox reaction of BQ the frequency at the negative potential limit) is seen. In 0.1 M pH
under acidic condition; and a pair of redox peaks a2/c2 appears at 3.19 aqueous Na2SO4 containing 10 mM BQ and 5 mM CuSO4, a
ca. 0.15 V, which mainly corresponds to the redox electrode re- frequency response of ca. 1000 Hz decrease is seen. In order to more
action of BQ under alkaline condition. The third pair of relatively efficiently prepare a Cu(OH)2 film, 5 mM CuSO4 was chosen as the
small redox peaks a3/c3 appears at ca. 0 V, as explained below. For optimum concentration. In order to confirm the absence of bulk
the redox peaks a3/c3, though the formal potential is basically the electrodeposition of copper potentiostatically at 0 V in the involved
same as the b’/b peaks for bulk deposition of Cu and its stripping. solution, CV and linear sweep anodic stripping voltammetry
However, the oxidation peak b’ is obviously higher than the (LSASV) experiments were performed on Au/GCE, as shown in
reduction peak b, while the oxidation peak a3 is lower than the Fig. S2. In 0.1 M aqueous Na2SO4 (pH ¼ 3.19) containing 5 mM
reduction peak c3, so the a3/c3 peaks here are unlikely the elec- CuSO4, when the negative potential limit is 0.01 V and 0 V, only
trodeposition and oxidation stripping of bulk copper. Cu2þ in the the Cu UPD and its stripping peaks are seen at ca. 0.25 V. However,
solution will consume the OH ions produced by the reduction of when the negative potential limit is shifted to 0.1 V, the current
BQ during negative sweep and thus Cu(OH)2 is formed, thereby ramp of bulk Cu deposition (negative to ca. 0.04 V) and the
changing the pH of local solution near the electrode. We term this stripping peak of bulk Cu (at 0.01 V for both CV and LSASV) newly
new phenomenon the possible “precipitation-buffering” phenom- emerge. These observations indicate the absence of bulk copper
enon of pH. Here, the oxidation peak a1 is notably higher than the electrodeposition potentiostatically at 0 V.
corresponding reduction peak c1, possibly because the electrode The electrochemical behavior of the main systems involved in
activity becomes better after the dissolution of electron-insulating this research is discussed as above, and we will deal with the step-
copper hydroxide, so the rapid oxidation of phenol on the electrode by-step preparation of the target electrode below. Briefly, the
surface leads to a significantly higher oxidation peak a1. Experi- preparation of PtCu(OH)2/Au/GCE involves the following four steps.
mental phenomena similar to those in Figs. 1 and 2 were also (1) Electrodeposition of Au on GCE; (2) Electrodeposition of
observed on Au/GCE, and thus the same conclusion can be drawn Cu(OH)2; (3) Electroreduction of Cu(OH)2 to Cu; (4) CueK2PtCl4
(not shown). GRR.
The above experiments show that the OH ions produced by BQ In the first step, Au/GCE was prepared by potentiostatic depo-
reduction on the electrode surface can adjust the acidity and sition on GCE for 200 s (optimized) at 0.2 V in 0.5 M aqueous
alkalinity of the electrode surface. When the solution pH is 3.19, the H2SO4 containing 2 mM HAuCl4. The corresponding chro-
concentration of BQ on the mM level can achieve a good local-pH- noamperometry curve is shown in Fig. S3A. Notable reduction
adjustment effect. The solubility product constant of Cu(OH)2 is currents are seen at 0 s, indicating the continuous electrodeposition

Fig. 2. CV curves on Au disk electrode in 0.1 M pH 3.19 aqueous Na2SO4 containing 5 mM CuSO4 (red), 10 mM BQ (blue) or 5 mM CuSO4 þ 10 mM BQ (black). Scan rate: 0.05 V s1.
(For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)
 C. Zhang et al. / Electrochimica Acta 330 (2020) 135234 5

of Au on GCE. The CV characterization of the prepared Au/GCE is previous report [13], a uniform film can be obtained by electro-
shown in Fig. 3. In 0.5 M aqueous H2SO4, no obvious CV peaks are depositing electron-insulating molecules or atoms on an electrode
seen on the bare GCE, but on Au/GCE, an anodic peak due to for- surface, so it is reasonable that the electrodeposited Cu(OH)2 film
mation of gold oxides (AuOx) appears at ca. 1.2 V and a cathodic on the electrode surface is rather uniform.
peak due to reduction of AuOx appears at ca. 0.86 V In the third step, CuCu(OH)2/Au/GCE was potentiostatically
(SreAu ¼ 0.91 cm2). treated at 1.0 V for 200 s in neutral 0.1 M aqueous Na2SO4. The
In the second step, Cu(OH)2/Au/GCE was prepared by poten- corresponding chronoamperometry curve is shown in Fig. S3C.
tiostatic deposition on Au/GCE for 50 s (optimized) at 0 V in 0.1 M Notable reduction currents indicate that Cu(OH)2 was reduced to
aqueous Na2SO4 (pH 3.19) containing 5 mM CuSO4 and 10 mM BQ. Cu on the electrode surface. In order to optimize the electro-
The corresponding chronoamperometry curve is shown in Fig. S3B. reduction time of Cu(OH)2 to Cu, LSASV experiments were per-
Notable reduction currents are seen, indicating the continuous formed on CuCu(OH)2/Au/GCE at different electroreduction time, as
reduction of BQ and thus the continuous electrodeposition of shown in Fig. 4B. In neutral 0.1 M aqueous Na2SO4, the oxidation
Cu(OH)2 on GCE. To validate the successful preparation of Cu(OH)2/ peak at 0.3 V first increases and then decreases with the increase
Au/GCE, its CV behavior was compared with that of c-Cu(OH)2/Au/ of the electroreduction time, with the highest peak at 20 s and
GCE in neutral 0.1 M aqueous Na2SO4, as shown in Fig. 4A. On Au/ almost zero changes after 150 s. This observation may be due to the
GCE, only the relatively small redox peaks due to the Au/AuOx redox fact that the OH produced after part Cu(OH)2 electroreduction
reactions and the reduction of dissolved oxygen are seen. On requires some time to diffuse into the bulk solution, and thus a
Cu(OH)2/Au/GCE, the reduction peaks (c1 and c2) are seen at small amount of CuOH and Cu(OH)2 can be formed on the electrode
ca. 0.25 V and 0.6 V. Here, c1 is attributed to the reduction of surface when Cu is dissolved by anodic stripping at relatively small
Cu(II) to Cu(I), while c2 is attributed to the reduction of Cu(I) to electroreduction time (e.g. 20 s), and at longer electroreduction
Cu(0) and the direct reduction of Cu(II) to Cu(0). Corresponding time (e.g. 150 s), no sufficient OH can exist near the electrode
oxidation peaks (a2, a1) are seen at ca. 0.3 V and 0.19 V. Here, a2 is surface after sufficient-time diffusion, so the anodic stripping of Cu
attributed to the oxidation of Cu(0) to Cu(I), while a1 is attributed to solely to soluble Cu2þ is observed. The peak height and peak elec-
the oxidation of Cu(I) to Cu(II) and the direct oxidation of Cu(0) to trical charge for anodic stripping of Cu to Cu2þ increase gradually
Cu (II) [26]. Similar features are seen on c-Cu(OH)2/Au/GCE. The with the increase of electroreduction time, and the almost un-
above experiments prove that a Cu(OH)2 thin film has been suc- changed charge values after 150 s electroreduction indicate the
cessfully prepared by BQ-based electrodeposition. Based on our complete electroreduction of Cu(OH)2 to atomic copper after 150 s.
In order to ensure the complete electroreduction of Cu(OH)2 to
atomic Cu, the optimum Cu(OH)2-electroreduction time is chosen
to be 200 s.
By using the Faraday law of electricity, m ¼ (Q/nF)  MCu (n is the
number of electrons transferred, here 2; F is the Faraday constant of
96485.3 C mol1; MCu is the molar mass of Cu) and the stripping
peak charge of Cu (the maximum stripping peak charge of Cu here
is Q ¼ 1.31  103 C), the molar number of atomic Cu is calculated to
be 6.81 nmol and its mass is 433 ng (MCu ¼ 63.55 g/mol). A simple
assumption of the dense packing of Cu atoms on the electrode
surface is considered, as shown in Scheme S1 (panel 1), and thus
the deposit thickness can be simply expressed. The radius of Cu
atom is rCu ¼ 0.157 nm, so the total number (N) and total mass (m)
of densely stacked monolayer Cu atoms per unit area can be
calculated as follows,


 .
2
N ¼ 1=2rCu  1=2rCu ¼ 1 2  0:157  107

¼ 1:01  1015 cm2

Fig. 3. CV curves on bare GCE, Au/GCE and PtCu(OH)2/Au/GCE in 0.1 M aqueous H2SO4.
Scan rate: 0.05 V s1.

Fig. 4. (A) CV curves on Au/GCE, Cu(OH)2/Au/GCE and c-Cu(OH)2/Au/GCE in neutral 0.1 M aqueous Na2SO4. Scan rate: 0.05 V s1. (B) LSASV curves of CuCu(OH)2/Au/GCE in 0.1 M
aqueous Na2SO4 after electroreduction of the Cu(OH)2/Au/GCE at 1 V for different time (0, 5, 10, 20, 50, 100, 150, 200, 250, 300 and 350 s). Scan rate: 0.1 V s1. Inset: The cor-
responding LSASV peak charge of CuCu(OH)2/Au/GCE. The preparation of Cu(OH)2/Au/GCE is shown in Fig. S3B.
6 C. Zhang et al. / Electrochimica Acta 330 (2020) 135234

to 0.25 V is due to hydrogen evolution.

. EQCM technology was used to estimate the mass load of Pt. A
m ¼ M  n ¼ M  N NA ¼ 63:55  1:01  1015 =6:02  1023 gold-plated QCM Au electrode (real surface area of 0.91 cm2) was
¼ 107 ng cm2 employed. The molar number (nPt-exp) of the GRR-deposited Pt
atoms is calculated from the Sauerbrey equation Df0-Pt-
6
The real surface area of Au/GCE is 0.91 cm2, and thus the total exp ¼ 2.264  10  f20g  Dm/A, and Df0-Pt-exp is the dry-
mass of densely stacked monolayer Cu atoms on Au/GCE is theo- frequency shift before (bare PQC) and after the loading of Pt. The
retically equal to 107  0.91 ¼ 97.4 ng. Then, the experimentally experimental Df0-Pt-exp is 690 Hz, so Dm ¼ 524 ng, nPt-
obtained 433 ng atomic Cu is equivalent to 433/97.4 ¼ 4.45 layers of exp ¼ 2.67 nmol. The densely stacked Pt atoms on the QCM Au
densely stacked Cu atoms. surface is assumed, as shown in Scheme S1 (panel 2). The radius of
QCM technology can dynamically monitor the nanogram-scale Pt atoms is rPt ¼ 0.183 nm, so the total number (N) and total mass
mass change of the electrode during the reaction process [27,28]. (m) of densely stacked monolayer Pt atoms per unit area are
EQCM technology was used to study the LSASV process of copper, as calculated as follows,
shown in Fig. S4A. According to the experimental frequency



2
response Df0 and the Sauerbrey equation, N ¼ 1=2rpt  1=2rpt ¼ 1= 2  0:183  107
Df0 ¼ 2.264  106  f20g  Dm/A (f0g is the gas-phase resonance
frequency of QCM, here 9 MHz, and A is the piezoelectric active ¼ 7:47  1014 cm2
area, here 0.14 cm2), the mass change Dm can be obtained. Exper-
imentally in the LSASV process of copper, the stripping peak charge .
m ¼ M  n ¼ M  N NA
of copper is 4.90  104 C, so the molar number and the mass of
.
atomic copper is n ¼ 2.54 nmol and m ¼ 161 ng; while the fre-
¼ 195:1  7:47  1014 6:02  1023
quency rises by ca. Df0 ¼ 220 Hz, so the molar number and the mass
of Cu is Dm ¼ 167 ng and n ¼ 2.63 nmol. The real surface area of ¼ 242 ng cm2
QCM Au electrode is 0.378 cm2, so the mass of one monolayer of
densely stacked Cu atoms on the QCM Au surface is Therefore, the mass of densely stacked monolayer Pt atoms on
107  0.378 ¼ 40.5 ng. Hence, it can be obtained that the number of the gold-plated QCM Au surface is 242  0.91 ¼ 220 ng, and the
closely stacked Cu-atom layers is equivalent to 161/40.45 ¼ 3.98 equivalent thickness of Pt deposit is equal to 524/220 ¼ 2.38 layers
layers (electrical charge method) and 167/40.45 ¼ 4.12 layers (QCM of densely stacked Pt atoms.
frequency method). These two results are basically consistent with SEM and corresponding EDS characterizations of the relevant
the results on Au/GCE (4.45 Cu atomics layers, electrical charge electrodes were also performed, as shown in Fig. 5 with listed
method). elemental analysis results from EDS. The bare GCE surface is
QCM monitoring of the electrodeposition and the open circuit smooth and the EDS picture shows a large number of C element
stability of a thin-film copper was performed, as shown in Fig. S4B. (Fig. 5A and F). Au nanostructures with ca. 60 nm size are seen on
In neutral 0.1 M aqueous Na2SO4 containing 5 mM CuSO4, QCM Au Au/GCE, and the EDS shows a large amount of Au element (Fig. 5B
was first electrodeposited at 0.1 V for 10 s (the resulting dissolu- and G). Some Cu(OH)2 nanosheets covering the periphery of Au are
tion charge of copper is similar to the final dissolution charge of seen on Cu(OH)2/Au/GCE, and the EDS shows the presence of Cu
copper in Fig. 4B), and then the frequency change was monitored in and O element (Fig. 5C and H). After Cu(OH)2 is reduced to Cu, the
situ at open-circuit potentials. It is seen that the frequency de- surface changes back to a similar Au/GCE morphology, with some
creases rapidly at the first 10 s due to the electrodeposition of inconspicuous fine nanoparticles covering the Au surface, and the
copper on QCM Au. It continues to slowly decrease after 10 s, and EDS shows the presence of Cu element (Fig. 5D and I). After
then remains essentially unchanged, which may be due to the replacing Cu with Pt, it seems that some small nanoparticles are
partial oxidation of thin layer nano-copper by oxygen dissolved in formed on the Au surface, and EDS shows the presence of a small
the solution. The above experiments show that the total amount of amount of Pt element (Fig. 5E and J).
thin-layer atomic copper is basically stable on the electrode in 0.1 M
Na2SO4, so the basic phenomena and conclusions of the LSASV 3.2. Electrocatalytic oxidation of methanol
experiments shown in Fig. 4B are reliable.
In the fourth step, a 300 s GRR experiment was performed in Oxidation of methanol is a proton-coupled electron transfer
0.02 M aqueous H2SO4 containing 1 mM K2PtCl4. Corresponding process, so its electrocatalytic oxidation reaction in an alkaline
open circuit potential (OCP)-time curves are shown in Fig. S5. The medium is more advantageous. The relationship between the
OCP of CuCu(OH)2/Au/GCE and Cu-UPD/Au/GCE in 0.02 M H2SO4 electrocatalytic methanol-oxidation performance and experi-
is 0.02 V and 0.16 V, respectively. A rapid OCP rise to ca. 0.6 V is mental parameters was investigated in 0.5 M aqueous KOH. Fig. S6
seen soon after the addition of 1 mM K2PtCl4, indicating that Cu on shows the peak currents of the modified electrode for catalytic
the electrode surface can be replaced by Pt. The CV characterization oxidation of methanol with different Au-electrodeposition time,
of PtCu(OH)2/Au/GCE is shown in Fig. 3. In 0.5 M aqueous H2SO4, the different Cu(OH)2-electrodeposition time and different GRR time,
redox peaks of PtCu(OH)2/Au/GCE between 0 V and 0.25 V are the respectively. Generally, the electrocatalysis peak current gradually
hydrogen adsorption/desorption peaks, which are different from increases with the time increase of Au-electrodeposition, Cu(OH)2-
the two separated redox pairs of peaks on the Pt disk electrode and electrodeposition, or GRR, and level off after some time. Hence, the
indicate that the Pt atoms on the modified electrode are epitaxially Au-electrodeposition time of 200 s, the Cu(OH)2-electrodeposition
grown [29]. Oxidation currents are seen after positive sweep to ca. time of 50 s, and the GRR time of 50 s are chosen for subsequent
0.6 V due to the oxidation of platinum (formation of PtOy), the ramp experiments.
currents at potentials positive of ca. 1.3 V are due to the oxidation of CV experiments on PtCu(OH)2/Au/GCE, PtCu-UPD/Au/GCE, bare Pt
H2O. The reduction peak of AuOx at ca. 0.86 V is notably smaller electrode, Ptp/Au/GCE, Nafion-Pt/C/Au/GCE and Au/GCE were con-
than that on Au/GCE, because of the Pt coverage on the Au sites. The ducted in 0.1 M aqueous H2SO4, as shown in Fig. 6A. The SrePt values
reduction peak at 0.3 V is due to the reduction of PtOy and dissolved follow the order PtCu(OH)2/Au/GCE (0.381 cm2) > PtCu-UPD/Au/GCE
oxygen, and the reduction current ramp at potentials negative (0.223 cm2) > Ptp/Au/GCE (0.167 cm2) > Nafion-Pt/C/Au/GCE
 C. Zhang et al. / Electrochimica Acta 330 (2020) 135234 7

Fig. 5. SEM images and EDS (with listed elemental analysis results) of bare GCE (A and F), Au/GCE (B and G), Cu(OH)2/Au/GCE (C and H), CuCu(OH)2/Au/GCE (D and I) and PtCu(OH)2/Au/
GCE (E and J).

Fig. 6. CV curves on PtCu(OH)2/Au/GCE (a), PtCu-UPD/Au/GCE (b), bare Pt (c), Ptp/Au/GCE (d), Nafion-Pt/C/Au/GCE (e) and Au/GCE (f) in 0.1 M aqueous H2SO4 (A), 1 M CH3OH þ 0.5 M
KOH (B), the corresponding SECA (C). Scan rate: 0.05 V s1.

(0.108 cm2) > bare Pt (0.106 cm2). The CV curves in 0.5 M aqueous alkaline methanol oxidation, as listed in Table 1.
KOH containing 1 M methanol is shown in Fig. 6B. There are no In order to investigate the stability of the prepared electrode, the
obvious methanol oxidation peaks on Au/GCE, indicating that Au/ potentiostatic experiments of electrocatalyzed methanol oxidation
GCE has no obvious electrocatalytic effect on methanol oxidation, was studied. As shown in Fig. S7A, PtCu(OH)2/Au/GCE has the highest
while an oxidation peak is observed at ca. 0.24 V on bare Pt. current response within 1200 s. The resulting current decay is
Obvious oxidation peaks are observed on PtCu-UPD/Au/GCE, Ptp/Au/ quantified by a poisoning rate [30e32], d ¼ (dI/dt)t>500 s  (100/I0),
GCE, Nafion-Pt/C/Au/GCE and PtCu(OH)2/Au/GCE. Our PtCu(OH)2/Au/ where d is the current-decay rate in % s1, (dI/dt)t>500 s is the slope
GCE has the largest oxidation peak current of 8.3 mA and the largest of the linear current-decay portion and I0 is the current at the start
SECA of 21.8 mA cm2 Pt (Fig. 6C). The good performance can be of polarization back extrapolated from the linear current decay.
ascribed to the fact that the Pt deposits on our PtCu(OH)2/Au/GCE are At 0.2 V, Nafion-Pt/C/Au/GCE is easily poisoned at a poisoning rate
rather uniform in electrochemical principle and Au can enhance the of 0.038% s1; the d of bare Pt, Ptp/Au/GCE and PtCu-UPD/Au/GCE are
anti-poisoning ability of Pt. Compared with the literature results, 0.025% s1, 0.026% s1 and 0.016% s1, respectively; PtCu(OH)2/Au/
our electrode performs well among the Pt electrocatalysts for GCE has a low poisoning rate of 0.011% s1. As shown in Fig. S7B, the
8 C. Zhang et al. / Electrochimica Acta 330 (2020) 135234

Table 1
Electrochemical performance of some Pt-based catalysts toward methanol electrooxidation by CV in alkaline media.

Catalysta Potential range of CV (V) Scan rate (mV s1) Solution SECA (mA cm2
Pt ) Reference

Pt(CuCl)1/Au/GCE 0.7 to 0.2, vs SCE 50 1 M methanol þ 0.5 M KOH 24.1 [13]

PtAuNA/G 0.8 to 0.4, vs Ag/AgCl 50 0.5 M methanol þ 1 M NaOH 7.3 [33]
Pt-NPG 0.8 to 0.6, vs Ag/AgCl 20 5 M methanol þ 0.5 M KOH 0.81 [34]
Pt1$0Au/RGO 0.9 to 0.5, vs SCE 50 2 M methanol þ 0.5 M KOH 10.5 [35]
PteAg/C 0.8 to 0.8, vs RHE 50 0.5 M methanol þ 0.5 M KOH 1.6 [36]
PtePd@PANI-CSA/graphene 0.8 to 1.2, vs Ag/AgCl 50 1 M methanol þ 0.5 M KOH 79.2 [37]
Graphene-Pt NP hybrid 0.1 to 1.3, vs RHE 10 0.5 M methanol þ 0.1 M KOH 2.4 [38]
PteBi/GNs 1 to 0.3, vs SCE 50 1 M methanol þ 1 M KOH 4.4 [39]
PtCu(OH)2/Au/GCE 0.8 to 0.8, vs SCE 50 1 M methanol þ 0.5 M KOH 21.8 This work
PtCu-UPD/Au/GCE 0.8 to 0.8, vs SCE 50 1 M methanol þ 0.5 M KOH 13.5 This work
a
PtAuNA/G: homogeneously distributed PtAu nanoalloy anchored to graphene; Pt-NPG: Pt nanoparticles on three dimensional nanoporous gold; PtePd@PANI-CSA/gra-
phene: platinum-palladium supported on polyaniline-doped camphorsulfonic acid/graphene.

catalytic oxidation peak current of PtCu(OH)2/Au/GCE can maintain Scholars Program (2011), and Foundation of the Science & Tech-
93% of the initial value after 30 repeated CV experiments, indicating nology Department of Hunan Province (2016SK2020).
its good stability.
The anti-poisoning ability is one of the important factors to Appendix A. Supplementary data
evaluate the electrocatalysis performance of the modified elec-
trode. In the process of catalyzed methanol oxidation, Pt is easily Supplementary data to this article can be found online at
poisoned by the produced intermediate COads, since COads occupies [Link]
the active site of Pt to greatly reduce the catalytic performance. As
shown in Fig. S8, the anti-poisoning abilities of Nafion-Pt/C/Au/
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