Electrochimica Acta 139 (2014) 137–144

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Efficient electrochemical CO2 reduction on a unique

chrysanthemum-like Cu nanoflower electrode and direct observation
of carbon deposite
Jia-Fang Xie 1 , Yu-Xi Huang 1 , Wen-Wei Li, Xiang-Ning Song, Lu Xiong, Han-Qing Yu ∗
Department of Chemistry and Materials Science, University of Science & Technology of China, Hefei, 230026, China

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

Article history: The existing Cu-based electrocatalysts for electrochemical reduction of CO2 to chemical commodities
Received 24 February 2014 suffer instability and large reaction overpotentials. Here we report a novel Cu nanoflower (NF) catalyst
Received in revised form 2 June 2014 with a unique 3D chrysanthemum-like structure. Derived from CuO NFs, the Cu NFs were found to effi-
Accepted 5 June 2014
ciently catalyze the CO2 reduction with 400 mV lower overpotential than polycrystalline Cu. Besides,
Available online 11 July 2014
H2 production was suppressed to be below 25% in terms of Faradaic efficiency in a wide potential win-
dow, implying an excellent catalytic selectivity. Prolonged electrolysis showed that the Cu NFs kept a
Keywords:
high catalytic activity towards CO2 reduction for over 9 h. In addition, for the first time, the deposition
electrochemical catalysis
CO2 reduction
of amorphous carbon on the electrodes after catalysis was directly observed in this study. The reaction
CuO nanoflower pathways of electrocatalytic CO2 reduction and the involvement of the surface carbon in this process
stability were elucidated.
surface carbon © 2014 Elsevier Ltd. All rights reserved.

1. Introduction such as electrochemical deposition [18,19], alloying [20], ligand-

Conversion of CO2 to valuable chemicals and fuels has attracted
worldwide interests due to the significant environmental and
economic benefits [1–4]. Electrochemical reduction of CO2 is con-
sidered as a simple, environmentally friendly and well controllable
approach [5–7]. To achieve efficient and stable electrocatalysts, a
series of metal catalysts have been exploited in the past decades
[8–10]. Among them polycrystalline Cu has been demonstrated to
catalyze the reduction of CO2 to hydrocarbons at high Faradaic
efficiencies (FEs) (50%) under reasonable (∼5 mA cm−2 ) current
densities [9,11]. However, despite of the high catalytic activity of
such Cu catalysts, they suffer from poor stability and large reac-
tion overpotentials. Moreover, the catalytic mechanisms of Cu in
this conversion process are still controversial [12,13]. Therefore,
a better design of Cu catalysts and improved understanding of its
catalytic mechanisms are highly desired.
Several studies have shown that the selectivity of Cu catalyst
towards CO2 reduction was dependent highly on its surface struc-
ture, more specifically the crystal facets [14–17]. This finding has
inspired intensive interests in surface modification techniques,
∗ Corresponding author. Fax: +86 551 63607592.
E-mail address: hqyu@ustc.edu.cn (H.-Q. Yu).
1
These authors contributed equally to this work.
stabilization [21] and other approaches [22–24]. Although the
product selectivity was altered in these approaches, they also led
to an increased hydrogen production.
Moreover, how to maintain a long-term stability, i.e., robust
surface structure, of Cu-based catalyst remains a severe challenge
[25,26]. It has been reported that polycrystalline Cu rapidly lost its
catalytic activity towards CO2 reduction [23,25–27]. Formation of
graphitic carbon on the Cu surface was suspected to be a major
reason for the Cu catalyst deactivation [28,29], while some other
researches showed that it was able to be converted into hydrocar-
bons [30,31]. A recent theoretical study suggested that the surface
carbon was an important intermediate for the formation of CH4 and
C2 H4 [31]. These results imply a possibly significant role of surface
carbon in the Cu-catalyzed CO2 reaction process. However, no solid
evidence regarding the formation of graphitic carbon on Cu surface
has been provided so far.
In this study, we report the use of 3D Cu nanoflowers (NFs) as
a highly efficient and stable catalyst for electrochemical reduction
of CO2 in aqueous solution. The Cu NFs were derived from elec-
trochemical reduction of CuO NFs, which were obtained via in situ
pulsed anodic oxidation of Cu foil. Electrochemical preparation has
been demonstrated as an effective and convenient approach to
obtain metal-based nanostructures under mild conditions [32–34].
In particular, to create tunable surface morphology, surfactant
addition is usually applied [35,36]. Here, with a pulse controlled

http://dx.doi.org/10.1016/j.electacta.2014.06.034
0013-4686/© 2014 Elsevier Ltd. All rights reserved.
138 J.-F. Xie et al. / Electrochimica Acta 139 (2014) 137–144
electrochemical anodic oxidation of Cu foil, the CuO growth was
directed towards the formation of 3D chrysanthemum-like nano-
structure without need for dosing any surfactant. The as-prepared
3D Cu NFs not only exhibited much lower overpotentials and higher
FEs for the CO2 reduction compared to polycrystalline Cu foil, but
also showed excellent stability in prolonged electrolysis. Moreover,
formation of amorphous carbon on Cu after catalysis was directly
observed in our study, providing new clues in explaining the role
of the amorphous carbon and revealing the detailed CO2 reduction
reaction pathways.
2. Materials and Methods
2.1. Preparation of the CuO NFs electrode
Cu foils (Alfa Aesar, 0.127-mm thick, annealed, 99.9%) were
ultrasonically-treated in 2 M HCl, followed by electropolishing
using a modified procedure [37]. Briefly, the electropolishing was
conducted at +2 V applied potential, with a Cu foil used as the
counter electrode. The electrolyte was prepared by mixing 85%
phosphoric acid, 95% sulfuric acid, and water in a volume ratio of
13: 4: 2. The electropolished Cu foil was then rinsed with deionized
water, and transferred into a solution containing 200 g L−1 of NaCl
and 4 g L−1 of NaOH to prepare CuO NFs.
In a typical process of electrochemical pulsed anodic oxidation,
chronoamperometry was applied to a piece of Cu foil for 2160 s. The
chronoamperometry parameters were as follows: anodic current
(ia ) = 0.2 mA cm−2 ; cathodic current (ic ) = 0 mA cm−2 ; reaction time
in each cycle for the anodic process (ta ) and cathodic process (tc )
were 10 s and 2 s, respectively. A piece of 2 × 2 cm2 Pt foil was used
as the counter electrode, and a KCl saturated Ag/AgCl electrode as
reference electrode. The prepared CuO NFs electrode was carefully
rinsed with deionized water for three times and dried under N2
atmosphere).
2.2. Characterization of the electrodes
Transmission electron microscopy (TEM) images of the work-
ing electrodes were obtained with a JEOL-2010 high-resolution
TEM (JEOL Co., Japan). Scanning transmission electron microscopy
(STEM) and energy filtered transmission electron microscopy
(EFTEM) images of the electrodes were obtained using a JEM-
ARM200F STEM (JEOL Co., Japan). Scanning electron microscopy
(SEM) imaging was performed on a Sirion 200 SEM (FEI Inc., USA).
X-ray photoelectron spectroscopy (XPS) analysis was performed
using an ESCALAB 250 instrument (Thermo-VG Scientific Inc., USA)
with a monochromatic Mg K␣ X-ray source. X-ray diffraction (XRD)
analysis was conducted using an X’Pert PRO instrument (Philips Co.,
USA). Raman spectra were obtained using a LABRAM-HR Raman
spectrometer (JY Co., France) with an excitation wavelength of
514.5 nm generated by an Ar+ laser.
2.3. Electrochemical reduction of CO2 and product analysis
The CO2 electrochemical reduction tests were conducted in a
customized two-compartment cell separated by a proton exchange
membrane (Nafion 212, Dupont Inc., USA). The catholyte contained
85 mL of 0.1 M KHCO3 (Sinopharm Co., China, 99.99%) saturated
with CO2 at pH 6.8. The headspace volume of the cathodic compart-
ment was 26 mL. A Cu foil or a Cu NFs electrode with a geometric
surface area of 10 × 10 mm2 was used as the working electrode. A
KCl-saturated Ag/AgCl electrode with a Luggin capillary was used
as the reference electrode, and a Pt foil was used as the counter
electrode. All the potential values were converted to reversible
hydrogen electrode (RHE) scale according to the equation E (vs
RHE) = E (vs Ag/AgCl) + 0.210 V + 0.0591 V × pH [26]. The CO2 elec-
trochemical reduction test was conducted with a potentiostat (CHI
760D, CH Instrument Co., China) at 10 ◦ C and 1 atm. The temper-
ature was chosen at 10 ◦ C rather than 25 ◦ C, as the polycrystalline
Cu foil lost its catalytic activity towards hydrocarbons formation
quickly at 25 ◦ C, which made it hard to complete the potential-
dependent test. Therefore, the tests were conducted at a lower
temperature, which would help to promote the longevity of poly-
crystalline Cu. To remove dissolved O2 in the catholyte, continuous
CO2 (purity 99.999%) purging (30 mL min−1 ) of the catholyte was
applied under stirring for 1 h prior the electrolysis.
The gaseous products were analyzed by gas chromatography
(GC) every 10 min during the potential-dependence electrolysis
and every 30 min during the stability tests. The H2 and CO concen-
trations were detected using an SP-6890 GC (Rainbow Instrument
Co., China) equipped with a Molecular Sieve 5A column and ther-
mal conductivity detector. An Agilent 6890 N GC (Agilent Co., USA)
equipped with a Plot Q-19095P-Q04 column and flame ionization
detector was used for hydrocarbon detection. The liquid phase
products were sampled and analyzed using a high performance
liquid chromatography (HPLC, 1260 Infinity, HPX-87H, Agilent Co.,
USA) with a UV detector. The FEs of the main products were calcu-
lated from the total charge obtained by the potentiostat.
3. Results and Discussion
3.1. Characterization of the CuO NF
Uniform 3D chrysanthemum-like NFs with a diameter of around
1 ␮m were clearly observed by SEM in Fig. 1a and 1b. The TEM
image of a single CuO NF revealed that the petals were over 600 nm
in length and about 40 nm in width (Fig. 1c). Fig. 1d shows a typical
HRTEM image of a single petal peeled off from the NFs. The petal
exhibited irregular spacing and structure dislocation, implying a
polycrystallinity of the CuO NFs. Moreover, a lattice fringe spacing
of 2.5 Å was measured in several orientation regions (Fig. 1d), corre-
sponding to the (111̄) lattice plane of CuO. The XPS spectra (Fig. 1e
and 1f) are referenced to C 1s peak at 285 eV [38]. The full spec-
trum shows only Cu, C and O elements exist on the sample surface
(Fig. 1e). Detailed XPS spectrum of Cu 2p showed two strongest
peaks at 934.1 eV and 954.0 eV (Fig. 1f), which belonged to CuO
Cu 2p3/2 and Cu 2p1/2 respectively. Two satellite peaks located at
941.9 eV and 962.2 eV were also observed, further confirming the
existence of CuO on the sample surface. On the other hand, the
poor symmetry of the two strongest peaks suggested that Cu in
other valences also existed. According to the fitting result in Fig. 1f,
the two small peaks with binding energy of 952.5 eV and 932.7 eV
should be attributed to the Cu 2p of Cu(I) or Cu.
The formation of CuO was further confirmed by the XRD anal-
ysis. As shown in Fig. 1g, three most remarkable peaks with 2
theta values of 43.3◦ , 50.4◦ , 74.2◦ (marked with hollow triangles)
were ascribed to metallic Cu (JCPDS card No. 04-0836), while two
small peaks at 35.5◦ , 38.7◦ (marked with stars) corresponded to
CuO (JCPDS No. 48-1548). However, since the CuO layer was very
thin, the intensity of the CuO peaks was much weaker than that of
the polycrystalline Cu substrate. Notably, no characteristic peaks
of Cu2 O were detected in the XRD spectra, indicating that the NFs
surface layer was solely constituted by CuO.
Based on the results of this work and previous studies [39,40] on
Cu oxides synthesis via anodic oxidation of Cu foil in concentrated
NaCl alkaline solution, we propose the following CuO NFs formation
pathway in our system:
Cu + nCl− = CuCl1−n
n + e− (n = 2, 3) (1)
2CuCl1−n
n + 2OH− = Cu2 O + 2nCl− + H2 O (2)
 J.-F. Xie et al. / Electrochimica Acta 139 (2014) 137–144
Fig. 1. SEM images (a, b), TEM images (c, d), XPS spectra (e, f) and XRD pattern (g) of the as-prepared CuO NF.
Cu2 O + 2OH− 2CuO + H2 O + 2e−
2H2 O + 2e− H2 + 2OH−
4Cu + O2 = 2Cu2 O
Here, Reactions 1, 3 and 4 are the principal electrochemical reac-
tions, while Reactions 2 and 5 are the main chemical reactions. In
the Cu2 O synthesis, Cu2 O was formed spontaneously on the surface
of the Cu foil according to Reaction 5, while the cathodic reaction
proceeded following Reaction 4. In a typical pulse cycle, CuCl1−n n trode was started at -0.6 V with the FE of 6%, and its FE increased
was firstly formed (Reaction 1) at 0.2 mA cm−2 of applied anodic
current for 10 s. The CuCl1−n
n ion subsequently underwent chemi-
cal precipitation (Reactions 2 and 3) to form CuO. In this process,
Reaction 1 would occur at non-uniform rates throughout the sur-
face due to the polycrystallinity of Cu foil, leading to the uneven
distribution CuCl1−n
n ions on the Cu foil surface. As a result, those
areas with a higher CuCl1−nn concentration would nucleate faster,
thus offering more opportunities for the growth of CuO petals com-
pared to those with a lower CuCl1−n n concentration. During this
period, the surface concentration of Cl− did not change, while OH−
was considerably consumed (Reactions 2 and 3). Then, the electro-
chemical reactions were paused for 2 s, with a cathodic current of
0 mA cm−2 applied. This period provided a lag time for the diffu-
sion of OH− ion from bulk solution to electrode surface and for the
outward diffusion of CuCl1−n
n ion, resulting in a vertically growth of
the CuO NF petals. Thus, as the pulse cycle repeated, the separated
3D chrysanthemum-like structure was eventually obtained.
3.2. Potential-dependent tests on the Cu NFs
To evaluate the catalytic performance of the as-prepared Cu NFs
towards CO2 reduction, the reduction products at different applied
potentials (ranging from -0.6 V to -1.6 V vs reversible hydrogen
electrode, RHE) were analyzed. In addition, the catalytic perfor-
mance of a polycrystalline Cu foil was also tested under identical
conditions for comparison. Fig. 2 shows the total current densities
(jtot ), i.e., the overall current densities contributed by H2 , HCOOH,
CH4 and C2 H4 formation, and the FEs of the products at different
potentials. When the applied potential became more negative, the
139
(3) jtot of Cu NFs was rapidly increased to up to 21 mA cm−2 at -1.0 V,
and then decreased slightly to 18.7 mA cm−2 at -1.6 V. In contrast,
(4)
the jtot of the Cu foil was increased continuously and slowly from
(5) 0.2 mA cm−2 at -0.6 V to 15 mA cm−2 at -1.6 V (Fig. 2a). Thus, a
higher jtot was achieved by the Cu NFs at a much lower overpo-
tential, indicating that the Cu NFs was more efficient in catalyzing
CO2 reduction compared to the Cu foil.
Fig. 2b shows the FEs of H2 and HCOOH production at different
applied potentials. The production of HCOOH at the Cu NFs elec-
significantly from -1.0 V. In contrast, the production of HCOOH on
Cu foil electrode was started at -1.0 V, and the FE was increased
rapidly to a maximum value of 40% at -1.2 V, followed by a sharp
decrease to 12% at -1.3 V. For the hydrogen evolution reaction
(HER), a constant H2 FE of about 47% was achieved at the poly-
crystalline Cu foil electrode, while a much lower FE of 23% was
obtained at the Cu NFs electrode. In addition, Cu NFs started to
produce CH4 and C2 H4 when the applied voltages became nega-
tive than -0.7 V. The FE of C2 H4 quickly increased to about 10% at
-0.9 V and maintained stable thereafter. A similar phenomenon was
observed for CH4 , which kept a constant FE of about 4%. Therefore,
the ratio of CH4 :C2 H4 was about 0.4 at -1.3 V. In comparison, at the
Cu foil, CH4 was initially detected with a FE of 18% at -1.2 V and
increased quickly to 37.6% at -1.6 V, and C2 H4 initially appeared at
-1.3 V with FE of 1.6% and increased slowly to 2.7% at -1.6 V. The cor-
responding FE ratio of CH4 :C2 H4 was more than 9 at -1.3 V. Neither
the Cu NFs nor the Cu foil produced detectable CO in our exper-
iments even after concentrating the gaseous product with NaOH.
This result is in agreement with previous reports that the forma-
tion of CO during the electrochemical reduction of CO2 at Cu or
Cu oxide electrodes occurred at a very low FE [15,41]. It should
be noted that the total Faradaic efficiencies of the two electrodes
were apparently lower than 100% from -0.6 to -1.0 V, which could
be ascribed to the following two reasons. One possible reason was
the reduction of Cu oxides spontaneously during the transfer and
operation processes in air. Another possible reason was the for-
mation of amorphous carbon (as discussed in Sub-sections 3.3 and
3.4), which actually contributed to the total Faradaic efficiency. This
phenomenon warrants further investigations.
140 J.-F. Xie et al. / Electrochimica Acta 139 (2014) 137–144

(a) (b) (c)

20 Cu foil 40 Cu foil
90

Faradaic efficiency (%)

Faradaic efficiency (%)

H2 CH4
75 HCOOH C2H4
30
jtot (mA cm )
-2

15 Cu NFs Cu NFs
60 H2
CH4
10 45
HCOOH
20 C2H4

30
5 10
Cu foil 15
Cu NFs
0 0 0
-0.6 -0.8 -1.0 -1.2 -1.4 -1.6 -0.6 -0.8 -1.0 -1.2 -1.4 -1.6 -0.6 -0.8 -1.0 -1.2 -1.4 -1.6
Potential (V vs RHE) Potential V vs RHE Potential (V vs RHE)

Fig. 2. CO2 reduction with Cu NFs and Cu foil as working electrodes at different voltages in 0.1 M KHCO3 . Total current densities (a), FEs for H2 and HCOOH (b), and FEs for
CH4 and C2 H4 (c)

The above results showed that the Cu NFs improved the cat- such different behaviors of CH4 and C2 H4 production at the Cu NFs,
alytic performance of CO2 electrochemical reduction compared to a further exploration into the dynamic relationship between the
the Cu foil. The much larger jtot of Cu NFs should be associated with reaction pathway and the surface morphology of the catalyst would
its unique 3D chrysanthemum-like structure, which increased the be essential.
surface areas without blocking the mass transport [42]. The onset Therefore, the surface morphology of the Cu NFs after 5-h and
potential of HCOOH production was -0.6 V for the Cu NFs, which 9-h prolonged electrolysis was examined (Fig. 4 and Figure S2),
was 0.4 V more positive than that for the Cu foil. Meanwhile, the and the Cu foil after 9-h electrolysis was also characterized (Fig-
Cu NFs exhibited much lower onset potentials for the production ure S3). As shown in Fig. 4a and 4b, the flower-like structure of
of CH4 and C2 H4 than the Cu foil. In terms of catalytic selectiv- the Cu NFs remained intact after 5 h of electrolysis, indicating that
ity, the Cu foil favored the production of CH4 , while the Cu NFs the structure of NFs was robust in the CO2 reduction reaction. In
favored C2 H4 formation. All these results indicate that the Cu NFs addition, the XPS spectrum (Fig. 4c) showed that only Cu, C and O
could lower the overpotential of CO2 reduction greatly and alter were present, while the Cu 2p spectrum (Fig. 4d) exhibited a dis-
the reaction pathways due to a changed structure [24,43]. In com- appearance of Cu(II). Thus, it could be concluded that a complete
parison with the polycrystalline Cu foil which consisted mainly of reduction of CuO was achieved in this process.
low index crystal facets, the flower-like structure of Cu NFs signif- Interestingly, some small particles were also observed on the
icantly increased the number of low-coordination sites, which are petals of the NFs after 5 h electrolysis (Fig. 4), which should be
more active towards CO2 reduction due to the lower free adsorption attributed to the dissolution and redeposition of the surface Cu.
energy of the adsorbates. This result implies that a slow structure transformation occurred
It is noteworthy that, within the potential window from -1.2 V during the electrochemical reaction. After 9-h electrolysis, the NFs
to -1.6 V, the product distribution of the Cu NFs was not obviously were fully reconstructed to small particles (Figure S1). This pro-
affected by the potential, which seems to conflict with previous cess coincided with the observation that the FE of C2 H4 fluctuated
reports [12,13,43]. Usually, due to the competition among the dif- in the initial 5 h and declined in the subsequent 4 h. Therefore, it
ferent reaction pathways, the FEs for CO2 reduction would drop at seems that the variation trend of C2 H4 was associated with the sur-
a more negative potential, while the HER would become the dom- face reconstruction process of the Cu NFs. As mentioned earlier, the
inant reaction due to its fast reaction kinetics. Thus, our results flower-like structure of the Cu NFs contained myriad low coordi-
imply that the Cu NFs could suppress the HER effectively in a wide nation sites such as steps and edges, which could be related to high
potential window, leading to a high conversion efficiency of CO2 index crystal facets like Cu(211), Cu(311), Cu(511) and Cu(711). It
reduction. has been reported that on high index facets the C2 H4 formation was
more favorable over the CH4 production [14,15]. A consistent result
3.3. Stability tests on the Cu NF was also obtained in this study. As the surface structure of the Cu
NFs slowly changed during the electrolysis, the surface Cu atoms
The stabilities of the Cu NFs and the Cu foil were tested at - were reconstructed to form nanoparticles. Thus, the high index
1.3 V in 0.1 M KHCO3 for 9 h. The FEs for the reduction products facets might have increased in the initial 2 h and gradually disap-
are shown in Fig. 3. For the Cu foil, the FE of H2 was drastically peared afterwards, leading to the short-term increase followed by a
increased from 40% to over 100% within 1 h, accompanied with a continuous decrease in the C2 H4 production (Fig. 3b). Interestingly,
sharp decrease in HCOOH, CH4 and C2 H4 production within 2 h. the CH4 production was less affected by the surface morphology
Such a rapid decline in catalytic activity of the polycrystalline Cu changes, indicating a different reaction pathway of CH4 production.
has been also reported previously [25–27]. For the Cu NFs, the FE of For the Cu foil, some dark regions were clearly observed on the
HCOOH production increased slightly in the initial 5 h from 26% to surface after 9 h electrolysis (Figure S2), indicating some solid was
32%, and then further to 70% at the end of the test. However, its FEs deposited during the CO2 reduction. The SEM image of the Cu NFs
for H2 and CH4 production kept stable throughout the experiment after the stability test was also taken. However, no distinct dark
(around 40% for H2 and 3% for CH4 ), while that of C2 H4 production region was observed on the Cu NFs electrode, possibly because the
increased in the initial 2 h and gradually declined subsequently till rough surface of the Cu NFs made it difficult to identify such depo-
the end of the test. sitions. Therefore, these two electrodes were further characterized
The stability test results showed that the Cu NFs could maintain by Raman spectroscopy. The Raman spectrum of the Cu foil shows
a high catalytic activity for CO2 reduction for at least 9 h, which two perceptible peaks at 1382 cm−1 and 1608 cm−1 , corresponding
is a remarkable improvement compared to the polycrystalline Cu. to amorphous carbon (Figure S3) [44,45], while no signal of carbon
On the other hand, the different behaviors of CH4 and C2 H4 dur- was detected on the Cu NFs.
ing the prolonged electrolysis imply that the reaction pathways Furthermore, energy filtered TEM (EFTEM) was applied to get
of C2 H4 and CH4 production were different. To better understand a better insight into this deposition layer. Fig. 5a and 5c clearly
 J.-F. Xie et al. / Electrochimica Acta 139 (2014) 137–144 141

(a) 140 (b)

Cu foil Cu NFs 20 Cu foil Cu NFs
120

Faradaic efficiency (%)

Faradaic efficiency (%)

H2 H2 CH4 CH4
HCOOH HCOOH C2H4 C2H4
100 15
80
10
60
40
5
20
0 0
0 1 2 3 4 5 6 7 8 9 0 1 2 3 4 5 6 7 8 9
Time (h) Time (h)

Fig. 3. The FEs of the CO2 reduction products on Cu NFs and Cu foil at -1.3 V vs electrolyzing time, H2 and HCOOH (a), CH4 and C2 H4 (b).

show that a layer of substance with poor crystallinity on the sur-
faces of both Cu NFs and Cu foil. The thickness of this layer was
about 2 nm and 15 nm for the Cu NFs and Cu foil, respectively.
There are two possibilities regarding the composition of this amor-
phous thin layer: one is amorphous carbon; another is amorphous
layer of Cu2 O. Since Cu2 O can be formed spontaneously in air
and is instable, it could be destroyed when exposed under high
energy electron beam to form an amorphous thin layer. Fig. 5b and
5d shows the elemental mappings of C and Cu for the two elec-
trodes. Strong response and clear boundary of carbon element can
be observed on both samples, indicating that carbon did emerge
after the CO2 reduction. More importantly, the elemental mappings
show that the amorphous region only contains carbon. Therefore,
the possibility for the existence of Cu2 O could be ruled out, and
it could be concluded that amorphous carbon was formed on the
electrode surface during the CO2 reduction. In addition, the much
thinner thickness of the carbon layer on the Cu NFs than that of
the Cu foil could explain why the amorphous carbon on the Cu NFs
could not be detected by Raman. Notably, although several previ-
ous studies have reported the formation of surface carbon on the
polycrystalline Cu surface after electrolysis by using XPS or Raman
scattering and auger electron spectroscopy [28–30], to the best our
knowledge, this might be the first report about a direct imaging and
analysis of amorphous carbon deposited on Cu surface during CO2
reduction.
3.4. Roles of the amorphous carbon on the Cu NF surface
CO has been demonstrated to be a key intermediate for the for-
mation of hydrocarbon from CO2 [12,16,46]. However, there are
great controversies regarding how CO is converted to CH4 and C2 H4 .
It is proposed that adsorbates such as CHO and/or COH played a

Fig. 4. SEM images (a), TEM images (b) and XPS spectra (c, d) of the Cu NFs after 5 h of catalysis
142 J.-F. Xie et al. / Electrochimica Acta 139 (2014) 137–144

Fig. 5. EFTEM images and the corresponding elemental mappings of C and Cu for the Cu NFs (a, b) and Cu foil (c, d) after catalysis

significant role [16,31], while it is recognized the formation of CO
dimer as an intermediate [12,17], which led to a different path-
way for CH4 production. Here, we focus on the possible roles of
the amorphous carbon in this process. As mentioned above, amor-
phous carbon layers with different thicknesses were found on the
Cu NFs and the Cu foil electrodes after the prolonged electrolysis.
This phenomenon might provide important clues for elucidating
the reaction pathways from CO to CH4 and C2 H4 during CO2 reduc-
tion.
Previous studies have reported about the formation of carbon
on Cu surface [28–30], but so far the origins and roles of such a
surface carbon layer remained unclear. DeWulf et al. [28] and Lee
et al. [29] suggested that the carbon might be originated from a side
reaction and was likely a major poisoning species to Cu. However,
Smith et al. [30] reported the carbon as an intermediate towards
hydrocarbon formation. In our study, the Cu foil lost its activity in a
short time period, and a relatively thick carbon layer (∼15 nm) was
formed after 9-h electrolysis. Such a thick carbon layer might be an
important reason for the deactivation of the Cu foil, which blocked
the active sites of Cu. On the other hand, a much thinner carbon
layer was formed on the Cu NFs surface, and hydrocarbons were
still produced at the end of 9-h electrolysis. This result indicates
that the surface carbon of thin layer might have been consumed
for hydrocarbon formation, leading to less carbon accumulation.
Thus, our results prove that the surface carbon formed during CO2
reduction is in essential a key intermediate towards hydrocarbon
formation. However, when the carbon layer become too thick, the
surface blocking would become severe and it would turn into a
poisoning species, as in the case of the Cu foil.
In addition, it is also possible that the alleviated carbon depo-
sition on the Cu NFs might be attributed to a morphologic
effect. Under such a circumstance, the carbon formation would be

Scheme 1. Proposed reaction pathways for the formation CH4 and C2 H4 from CO2 .
 J.-F. Xie et al. / Electrochimica Acta 139 (2014) 137–144
structure sensitive, thus a slow reconstruction of the flower-like
structure into particles would lead to a further carbon accumulation
on the Cu NFs. However, as shown in Fig. 4b and 5a, such a pro-
cess did not occur, and the thickness of the carbon layer remained
almost the same during the electrolysis. Hence, it is reasonable to
conclude that the carbon deposition on the Cu NFs was a result of
carbon consumption duly by the subsequent hydrocarbon forma-
tion reaction, rather than a morphologic effect.
Based on the above analysis, the reaction pathways for CO2
reduction in our system are presented (Scheme 1), with an empha-
sis on the two key intermediates, the adsorbed CO and carbon.
During the prolonged electrolysis when CO is formed on the Cu NFs,
there are two parallel pathways for its further reduction. In Path I,
CO dimer is formed, which is eventually converted into C2 H4 . In
Path II, the adsorbed CO is converted to the adsorbed carbon via
CHO and/or COH intermediate, followed by the formation of C-H
bond successively, leading to production of both CH4 and C2 H4 .
Afterwards, the active sites for CO dimer formation are gradually
diminished along with the surface reconstruction process until the
Cu NFs are totally turned into particles. Hence, the production of
C2 H4 from Path I is continuously decreased till the end of the pro-
longed electrolysis. However, such a structure change causes little
distinct impacts on Path II, where the adsorbed carbon is used as
an intermediate. Once the adsorbed carbon is formed, it is reduced
to CH4 and C2 H4 rapidly. Therefore, in our study, the production
of CH4 remained stable throughout the 9-h electrolysis and a cer-
tain amount of C2 H4 could be detected at the end of the test. As
a result of timely consumption of the surface carbon, only a small
amount of carbon deposited on the Cu NFs surface after 9 h (Fig. 5a).
In comparison, the consumption rate of the adsorbed carbon on the
polycrystalline Cu foil was apparently much slower than its forma-
tion rate, leading to the rapid accumulation of surface carbon and
subsequently a suppressed or even terminated CO2 reduction. This
explains the observation that the Cu foil rapidly lost its catalytic
activity towards hydrocarbon production within 2 h.
4. Conclusions
In summary, our results show that unique 3D chrysanthemum-
like CuO NFs, which are prepared by in situ electrochemical pulsed
anodic oxidation of Cu foil without addition of surfactants, could
maintain their structure when being electrochemically reduced.
The resulting Cu NFs are able to catalyze the reduction of CO2 to
HCOOH, CH4 and C2 H4 at onset potentials much more positive than
the polycrystalline Cu foil, and significantly suppress the HER in a
relatively wide potential window. Furthermore, the Cu NFs keep a
high activity towards CO2 reduction for at least 9 h, a remarkable
improvement compared to the polycrystalline Cu foil. In addition, a
deposition of amorphous carbon on the electrode surface is directly
imaged for the first time. Such a surface carbon layer is proven to
play important roles in the reduction CO2 to CH4 and C2 H4 in our
system. First, it serves as a key intermediate towards hydrocar-
bon formation. However, when the carbon layer becomes too thick,
the surface blocking would become severe and it would turn into
a poisoning species. Therefore, this study provides new evidence
to uncover the reaction pathways of CO2 reduction with Cu-based
catalysts. In addition, the electrochemical synthetic approach pro-
posed in this study may offer an effective and facile way for the
preparation of nanomaterials with tunable structures and catalytic
properties.
Acknowledgements
The authors wish to thank the National Basic Research Program
of China (2011CB933700) and the Program for Changjiang Scholars
143
and Innovative Research Team in University, China for the partial
support of this work.
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