catalysts

Article
Highly Efficient Electrocatalytic Carboxylation
of 1-Phenylethyl Chloride at Cu Foam Cathode
La-Xia Wu 1,† ID , Qi-Long Sun 2,† , Man-Ping Yang 2 , Ying-Guo Zhao 1 , Ye-Bin Guan 1, *,
Huan Wang 2, * and Jia-Xing Lu 2, *
1 Anhui Province Key Laboratory of Optoelectronic and Magnetism Functional Materials,
School of Chemistry and Chemical Engineering, Anqing Normal University, Anqing 246011, China;
wulaxia.1230@163.com (L.-X.W.); zhaoyg@aqnu.edu.cn (Y.-G.Z.)
2 Shanghai Key Laboratory of Green Chemistry and Chemical Processes,
School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China;
sunqilong376@163.com (Q.-L.S.); YMP2018@126.com (M.-P.Y.)
* Correspondence: guanyb@aqnu.edu.cn (Y.-B.G.); hwang@chem.ecnu.edu.cn (H.W.);
jxlu@chem.ecnu.edu.cn (J.-X.L.);
Tel.: +86-556-5708022 (Y.-B.G.); +86-21-52134935 (H.W.); +86-21-62233491 (J.-X.L.)
† These authors contributed equally to this work.




Received: 11 June 2018; Accepted: 2 July 2018; Published: 6 July 2018


Abstract: A simple and efficient electrocatalytic carboxylation of benzyl chloride with CO2 is
described. The reaction operates under 1 atm CO2 and room temperature in an undivided cell
with Cu foam cathode and Mg sacrificial anode without any additional catalyst. For the model
compound 1-phenylethyl chloride, the influence of cathode material, solvent, charge, current density
and temperature were investigated. Under optimized conditions, 99% yield of 2-phenylpropionic
acid could be obtained. Moreover, reasonable yields were also achieved with other benzyl chlorides.

Keywords: electrocatalytic; carboxylation; carbon dioxide; benzyl chlorides; Cu foam

1. Introduction
CO2 reutilization is regarded as a plausible strategy to recycle the waste CO2 emissions from
energy-intensive industrial activities [1,2]. Therefore, a number of strategies for CO2 fixation are being
developed, despite its thermodynamic stability and kinetic inertness [3–7]. CO2 can be used as a
simple renewable feedstock for various high-value-added chemicals such as methanol, formic acid,
methane, urea, organic carbonates, and carboxylic acid derivatives [3]. Among them, carboxylic acids
have widespread applications, which are widely used in the synthesis of bioactive compounds and
value-added chemicals [8].
Conventionally, organometallic nucleophiles such as Grignard reagents were used to synthesize
carboxylic acids from CO2 . However, such reaction processes generate a large amount of waste
regents [6,7]. Electrocarboxylation may use clean electricity for the synthesis of carboxylic acids,
providing a worthy alternative [9–22]. The electrocatalytic reduction of organic halides on different
cathodes (Pt, Zn, Hg, Sn, Bi, Pb, Au, Cu, Ag) had been studied by Bellomunno and coworkers [23],
who showed that the group 11 metals have good catalytic properties towards this reduction process.
Many researchers also demonstrated that a silver electrode has extraordinary electrocatalytic effect
for carboxylation of halogenated compounds [14–20], which was also confirmed by our previous
work [14,15]. In the subsequent research, it was found that silver nanoparticles (Ag NPs) exhibit better
electrocatalytic activity than silver flakes [16]. On the other hand, Cu, being low cost compared to
noble metals, is one of the most effective electrodes for CO2 reduction reaction [24,25]. The potential
use of Cu electrode for the electrocarboxylation of organic chlorides has not been demonstrated before.

Catalysts 2018, 8, 273; doi:10.3390/catal8070273 www.mdpi.com/journal/catalysts

Catalysts 2018, 8, 273 2 of 9
Catalysts 2018, 8, x FOR PEER REVIEW 2 of 9

Catalysts 2018, 8, x FOR PEER REVIEW

In this work, 2 of 9
In this work, wewe reportthe
report theelectrochemical
electrochemicalcarboxylation
carboxylation of of 1-phenylethyl
1-phenylethylchloride chloride(1a) (1a)with
withCuCu
foam electrode,
foam electrode, avoiding the use of noble metals and catalysts (Figure 1). We showed that CO 2 can
In avoiding thereport
this work, we use the
of noble metals and
electrochemical catalysts
carboxylation of (Figure 1). We
1-phenylethyl showed
chloride thatCu
(1a) with CO2 can be
be converted
foam into carboxylic
electrode, avoiding acids
the onofthe
use nobleCumetals
foamand electrode
catalystsunder mild
(Figure 1). Weconditions.
showed thatInCOaddition,
can Ag–
converted into carboxylic acids on the Cu foam electrode under mild conditions. In addition, Ag–Cu 2

Cu dendrite electrode
be converted intowas used for
carboxylic the
acids onfirst
the Cutime inelectrode
foam the electrocarboxylation
under mild conditions. of 1-phenylethyl
In addition, Ag–chloride
dendrite electrode was used for the first time in the electrocarboxylation of 1-phenylethyl chloride to
to studyCu dendrite
the effect electrode
of cathode wasmaterial.
used for the first time in the electrocarboxylation of 1-phenylethyl chloride
study the effect
to studyofthe
cathode
effect of material.
cathode material.

Figure 1. Electrocatalytic carboxylation of 1-phenylethyl chloride with CO2 at Cu foam.

Figure 1. Electrocatalytic carboxylation of 1-phenylethyl chloride with CO2 at Cu foam.
Figureand
2. Results 1. Electrocatalytic
Discussion carboxylation of 1-phenylethyl chloride with CO2 at Cu foam.
2. Results and Discussion
2.1.and
2. Results Characterization
Discussion of Electrode Materials

2.1. Characterization
The Cuof Electrode
foam Materials
and bimetallic Ag–Cu electrode were characterized by many methods. Figure 2b
2.1. Characterization
displays the XRDof Electrode
patterns of Materials
Cu foam, the (111), (200) and (220) crystal faces were observed. It is
The notable
Cu foam that noand
trace bimetallic Ag–Cusuch
of any other substance electrode wereor characterized
as copper oxide cuprous oxide wasby manyin methods.
contained
Thethis
Cumaterial.
foam and The bimetallic
FE–SEM Ag–Cu
patterns electrode
(Figure 2a) of were
the Cucharacterized
foam revealed by
thatmany
this methods.
electrode has Figure 2b
a observed.
Figure 2b displays the XRD patterns of Cu foam, the (111), (200) and (220) crystal faces were
displaysporous
the XRD patterns
network of Cu
structure, foam,large
indicating the active
(111),area.
(200)The
and (220)
SEM crystal
pattern faces were
of bimetallic observed.
material Ag– It is
It is notable that no trace of any other substance such as copper oxide or cuprous oxide was contained
notable Cuthatobtained
no traceat 10
of mM
any AgNO for 10 min was
other3 substance suchshown in Figure
as copper 2c; the
oxide or dendrites
cuprous uniformly
oxide was formed
contained in
in this material. The FE–SEM
and almost patterns (Figure 2a) of the Cu foam revealed thatdispersive
this electrode has a
this material. Thecovered
FE–SEM the whole electrode
patterns surface,
(Figure 2a) which
of thehadCubeen confirmed
foam revealedby energy
that this X- has
electrode a
porous network structure,
Ray fluoresence indicating
spectrometer (EDX,large active
Figure 2d). area. The SEM pattern of bimetallic material Ag–Cu
porous network structure, indicating large active area. The SEM pattern of bimetallic material Ag–
obtained at 10 mM AgNO3 for 10 min was shown in Figure 2c; the dendrites uniformly formed and
Cu obtained at 10 mM AgNO3 for 10 min was shown in Figure 2c; the dendrites uniformly formed
almost covered
and almost the whole
covered electrode
the whole surface,
electrode which
surface, had had
which beenbeen
confirmed
confirmed by energy
by energy dispersive X-Ray
dispersive X-
fluoresence spectrometer (EDX, Figure
Ray fluoresence spectrometer (EDX, Figure 2d). 2d).

Figure 2. Characterization of Cu foam and Ag–Cu: SEM of Cu foam (a) and Ag–Cu (c); XRD of Cu
foam (b); EDX of Ag–Cu (d).

Figure 2. Characterization of Cu foam and Ag–Cu: SEM of Cu foam (a) and Ag–Cu (c); XRD of Cu
Figure 2. Characterization of Cu foam and Ag–Cu: SEM of Cu foam (a) and Ag–Cu (c); XRD of Cu
foam (b); EDX of Ag–Cu (d).
foam (b); EDX of Ag–Cu (d).
Catalysts 2018, 8, 273 3 of 9

2.2. Electrocarboxylation of 1-Phenylethyl Chloride

The typical electrocatalytic carboxylation was carried out in 0.05 M 1-phenylethyl chloride (1a,
as model substrate) in 10 mL CO2 -saturated tetraethylammonium iodide–acetonitrile (TEAI–MeCN)
solution, with Cu foam as the cathode and sacrificial magnesium (Mg) as the anode (Figure 1).
After electrolysis, the products were detected quantitatively by HPLC. The results showed that
2-phenylpropionic acid (2a) was the main product. The effects of various parameters on the process
such as cathode material, the solvent, the current density (J), the charge passed (Q) and the temperature
(T) were investigated. The results of the electrolysis are summarized in Table 1.
To study the effect of the electrode material, the reaction was firstly carried out at Cu foam electrode.
73% yield of 2a can be obtained (Table 1, entry 1). Since it is reported that Ag-based nanocatalysts [26–31]
were efficient in the one-electron reductive cleavage of C–X bonds [31], the Ag–Cu dendrite electrode
was synthesized and applied to the reaction. The yield of 2a obtained with Ag–Cu dendrite electrode
was higher than that with Ag flake electrode (Table 1, entries 2, 3), which is consistent with our previous
study [16]. However, it is lower than that with Cu foam electrode (Table 1, entries 1, 2). In order to
explain this phenomenon, cyclic voltammetry (CV) was used to study the reaction.
The cyclic voltammograms were recorded in 0.1 M TEABF4 –MeCN solution at a sweep rate
of 0.1 V s−1 (Figure 3). Firstly, the CV of the background was scanned on the Ag electrode,
and oxidation–reduction peaks have not been found (curve a). Then, 1-phenylethyl chloride (1a, 4 mM)
was added into the electrolyte solution, an irreversible reduction peak appeared which corresponds
to 2e− reduction of 1a [17]. Compared to the reduction of 1a on Ag disk electrode (curve b), a more
positive onset potential was observed on Cu disk (curve c), which indicates that the reduction occurs
more easily at Cu electrode. To some extent, this result can explain the above phenomena. However,
the specific reasons are still in further study.

Table 1. Electrocarboxylation of 1-phenylethyl chlorides under different conditions. a

Entry Cathode J (mA/cm2 ) Q (F/mol) T (◦ C) Yield b (%)

1 Cu foam 5 2.0 18 73
2 Ag–Cu 5 2.0 18 64
3 Ag flake 5 2.0 18 57
4c Cu foam 5 2.0 18 6
5 Cu foam 7 2.0 18 77
6 Cu foam 8 2.0 18 84
7 Cu foam 9 2.0 18 87
8 Cu foam 11 2.0 18 78
9 Cu foam 13 2.0 18 75
10 Cu foam 9 1.0 18 45
11 Cu foam 9 1.5 18 68
12 Cu foam 9 2.5 18 92
13 Cu foam 9 3.0 18 93
14 Cu foam 9 2.5 35 83
15 Cu foam 9 2.5 0 94
16 Cu foam 9 2.5 -10 99
a Electrolyses were carried out in undivided cell, Mg anode, electrolyte solution: MeCN (10 mL)–TEAI
(0.1 M)–substrate (0.05 M). b Determined by HPLC. c Dimethylforamide DMF as solvent.

The CVs also showed that Ag electrode has a greater current density, indicating a greater
electroreduction rate at Ag electrode. To increase the reaction rate at Cu electrode, Cu foam instead
of Cu flake was used. Greater reaction rate on Cu foam than that on Cu flake has been confirmed by
constant potential electrolysis. Constant potential electrolysis was carried out under peak potential
of 1-phenylethyl chloride reduced on Cu electrode (ca. −1.18 V) with Cu foam and Cu flake cathode,
respectively. After the consumption of 70 C charges, the current was switched off. The resulting Q–t
curves (Figure 4) show that the time required on the Cu foam is shorter, about 4/5 of that on the Cu
Catalysts 2018, 8, x FOR PEER REVIEW 4 of 9
Catalysts 2018,8,8,273
Catalysts2018, x FOR PEER REVIEW 4 4ofof9 9

curves (Figure 4) show that the time required on the Cu foam is shorter, about 4/5 of that on the Cu
curves (Figure 4) show that the time required on the Cu foam is shorter, about 4/5 of that on the Cu
flake electrode. In
flake electrode. In addition,
addition, aa slightly higher yield
slightly higher yield of
of the
the target
target product was obtained
product was obtained on
on the
the Cu
Cu foam
foam
flake electrode. In addition, a slightly higher yield of the target product was obtained on the Cu foam
electrode (Table
electrode (Table S1).
S1). Hence,
Hence, Cu
Cu foam
foam was
was used
used as
as cathode
cathode inin the
the next
next study.
study.
electrode (Table S1). Hence, Cu foam was used as cathode in the next study.

b
b
0.10
0.10 c
c
0.08
0.08

0.06
I (mA)

0.06
I (mA)

0.04
0.04

0.02
0.02
a
a
0.00
0.00
-0.4
-0.4 -0.6
-0.6 -0.8
-0.8 -1.0
-1.0 -1.2
-1.2 -1.4
-1.4 -1.6
-1.6 -1.8
-1.8
-
E (V
E (V vs
vs Ag/AgI/I
Ag/AgI/I)) -

Figure3.3.Cyclic
Figure Cyclicvoltammograms
voltammogramsof
voltammograms ofof444mM
mM1-phenylethyl
mM 1-phenylethyl
1-phenylethyl chloride recorded
chloride
chloride atdifferent
recorded
recorded at different cathodes
at different inin0.1
cathodes
cathodes 0.1
in
M
0.1 TEABF –MeCN solution at a sweep rate of 0.1 V s −
−1 at 1
18 °C ◦
saturated with N (a) background; (b)
MM TEABF
TEABF 4
4 –MeCN
4–MeCN solution
solution at aatsweep
a sweep raterate of 0.1
of 0.1 V sV at
−1 s 18at°C
18saturated
C saturated
withwith2
N2 (a)N2background;
(a) background;
(b)
Ag
(b)
AgAgdisk; (c)
(c)Cu
disk;
disk; (c) disk.
CuCu disk.
disk.

80
80
aa bb

60
60

40
40
(C)
Q (C)
Q

20
20

00

00 4000 8000
8000 12000
12000 16000
16000
t (s)
(s)

Figure4.
Figure
Figure 44 Q–t
Q–t curve
curve on
curve on different
different cathode
on different cathode(a)
cathode (a) Cu
Cu foam,
foam,(b)
(b)Cu
Cuflake.
flake.

Solvents have
Solvents have theirtheir own
own physical
physical chemical
chemical and and electrochemical
electrochemical properties,
properties, and and manymany
Solvents have their own physical chemical and electrochemical properties, and many
electrochemicalreactions
electrochemical reactions are
are affected
affected by by the
the nature
nature of
of the
the solvents.
solvents. Thus,
Thus, the
the influence
influence ofofsolvent
solvent has
has
electrochemical reactions are affected by the nature of the solvents. Thus, the influence of solvent has
been studied.
been studied.
studied.TheThe electrolysis
Theelectrolysis
electrolysiswaswas
was conducted
conducted in both
in both MeCN
MeCN and DMF (Table 1, entries 3, 4). The
been conducted in both MeCN and and
DMFDMF (Table(Table 1, entries
1, entries 3, 4). The 3, 4). The
results
results show
results show that
that higher
higher 2a2a yield
yield waswas obtained
obtained in in MeCN
MeCN which
which may
may be
be attributed
attributed totothe
the larger
larger
show that higher 2a yield was obtained in MeCN which may be attributed to the larger solubility of
solubilityof
solubility ofCO
CO22in in MeCN
MeCN compared
compared with with DMF
DMF [32].
[32].
CO 2 in MeCN compared with DMF [32].
The
The current
current density
density and
and charge
charge passed
passed during electrolyses
during electrolyses alsoalsoinfluenced
influencedthe theyield
yieldofof of2a.
2a. In fact,
The current density and charge passed during electrolyses also influenced the yield 2a. InIn fact,
fact,
both
both low
low and
and high
high current
current densities
densities led
led to
to lower
lower yields
yields (Table
(Table 1,
1, entries
entries 3,
3,5–9).
5–9). The
The results
results obtained
obtained
both low and high current densities led to lower yields (Table 1, entries 3, 5–9). The results obtained at
atatlow
low
lowcurrent
currentdensities
current
densities can
densities
can probably
probably be
can probably
be ascribed
be at
ascribed to
ascribed to side
to sideside reactions
reactions
reactions such
such
such as
asthe
as the the reduction
reduction
reduction CO
COCO2 2totoC1C1oror
C2 compounds [33,34]. The results high current densities can be ascribed to a 2 to C1
lower
or C2
current
C2 compounds
compounds [33,34].
[33,34]. The results
The results at current
high current densities can be ascribed tocurrent
a lower current
efficiency with
efficiency with increased
increased ohmicatcomponent.
ohmic
high
component. densities
The
The highest
highest
can be ascribed
yield
yield of
of 2a
2a wastoachieved
was
a lower
achieved with
with 99efficiency
mA/cm
mA/cm
2
with increased ohmic component. The highest yield of 2a was achieved with 9 mA/cm 2 current density2
current density and 2.5 F mol−1 charge of 1a (92%, Table 1, entry 12). With further increase of
−1
current
and 2.5 Fdensity
mol −1 and
charge2.5 of
F 1a
mol charge
Tableof1,1a (92%,12).Table
With1,further
entry increase
12). Withoffurther increase of
consumed charge, the yield of (92%,
2a increased entry
insignificantly. consumed charge,
consumed charge, the yield of 2a
the yield of 2a increased insignificantly. increased insignificantly.
Catalysts 2018, 8, 273 5 of 9

The temperature can be a key factor for this reaction, which mainly affect the thermodynamics
and kinetics of the reaction as well as the solubility of CO2 [32]. Therefore, the effects of the reaction
temperature were examined (Table 1, entries 12, 14–16). Increasing the temperature from −10 ◦ C to
35 ◦ C, the yield of 2a decreased. The highest yield of 2a was obtained at −10 ◦ C (99%, Table 1, entry 16),
a relatively low temperature. That is mainly because carbon dioxide is one of the raw materials of
the reaction, and its solubility increases with decreasing temperature. It is worth emphasizing that
the Cu foam cathode generated very good results for electrocatalytic carboxylation of 1-phenethyl
chloride. Even at room temperature 18 ◦ C, normal pressure, 92% yield of 2a could be achieved (Table 1,
entry 12).
The results of this work may be comparable with literature data on the electrocarboxylation of
ArCH(CH3 )Cl. We have previously reported on the electrocarboxylation of 1-phenethyl bromide
with CO2 at a Ag NP electrode [16]. Best yield (98%) of 2a was obtained at 273 K using 5 mA cm−2
current density and 2.5 F mol−1 charge. Under the optimized conditions, with 1-phenethyl chloride
as substrate, the yield of 2a was 86%. Isse and coworkers studied the electrocatalytic reduction of
arylethyl chlorides at silver cathodes in the presence of carbon dioxide, the acid yields were 70–81% at
273.15 K [18]. They also reported electrochemical carboxylation of arylethyl chlorides catalysed either
by nickel(I) Schiff base complexes or by radical anions derived from aromatic esters, and yielded acids
in the range of 26–88% [22]. Tateno and coworkers developed a novel electrochemical carboxylation
system for CO2 fixation to benzyl halides using a microreactor. In this system, 52–98% yield of acids
was obtained with Pt anode [12]. The acid yields reported in this work are well comparable with these
data. On the other hand, the use of noble metals and catalysts were avoided.

2.3.Electrocarboxylation of Other Benzyl Chlorides

Encouraged by excellent results obtained with 1-phenethyl chloride (1a), the reaction was
further studied under the conditions of Table 1 entry 12, with the following organic halides:
chlorodiphenylmethane (1b), benzyl chloride (1c), 2-methylbenzyl chloride (1d), 3-methylbenzyl
chloride (1e), 4-methylbenzyl chloride (1f), 4-methoxybenzylchloride (1g), 4-trifluoromethylbenzyl
chloride (1h), chlorobenzene (1i) and 2-chloronaphthalene (1j). The results are reported in Table 2.
In the case of 1b, 80% yield of 2b was obtained (Table 2, entry 2), lower than that of 2a (Table 2,
entry 1). That is mainly due to the larger steric hindrance of the phenyl group as compared to a
methyl group. When the methyl group of 1a was substituted by a H atom, namely 1c, 83% yield
of 2c was achieved (Table 2, entry 3). The lower yield of 2c might be attributed to a side reaction
(e.g., dimerization) of 1c.
To study the effect of different substituted positions on the reaction, three isomers of o-, m- and
p-methylbenzyl chloride (1d–1f) were used as substrate, and the corresponding carboxylic acid yields
were 85%, 88% and 72%, respectively (Table 2, entries 4–6). The yields of 2d (entry 4) and 2e (entry 5) are
comparable to that of 2c (entry 3), whereas the yield 2f (entry 6) is lower than that of 2c. This indicates
that the electron-donating group located at the ortho and meta positions of the halo group has little
effect on the reactivity of the C–X bond, while it has a passivation effect on the reactivity of the C–X
bond at the para-position. In order to confirm this conclusion, benzyl chlorides substituted by an
electron-donating group (–OCH3 ) and an electron-withdrawing group (–CF3 ) at the para positions
have been studied (entries 7, 8). Low yield was obtained with the electron-donating group (–OCH3 ),
while high yield was achieved with the electron-withdrawing group (–CF3 ). The results are consistent
with the above conclusion.
As for chlorobenzene (1i) and 2-chloronaphthalene (1j), no supposed carboxylic acid (2i, 2j) could
be detected (entries 9, 10). That is mainly because the C–X bonds of 1i and 1j were not easily broken
(p, π-conjugate effect), and because of the unfavourable reaction to form carboxylic acid.
 Catalysts 2018, 8, 273 6 of 9
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Table 2. Electrocatalytic
TableTable
Table Table
2. Electrocatalytic
2. Electrocatalytic
2. carboxylation
2. Electrocatalytic
Electrocatalytic
carboxylation
Electrocatalytic
carboxylation of different
carboxylation
of different
of different
carboxylation substrates
substrates
of different
substrates on
of different
different
on
on Cu foam
substrates
Cu foam
substrates
Cu foam cathode.
on
cathode.
on Cu foam
cathode. aaaacathode.
Cu foam
foam a aaaa
cathode. a
Table
Table 2. Electrocatalytic
Table 2. carboxylation of different
carboxylation substrates
of on Cu foam
substrates cathode.
on Cu cathode.
cathode.aaaa
Table 2.
2. Electrocatalytic carboxylation of
of different
different substrates
differenton Cu
Cu foam cathode.
Table 2.
2. Electrocatalytic
Electrocatalytic carboxylation of different substrates on a
Cu foam
foam
Table
Electrocatalytic
Table 2. carboxylation
Electrocatalytic carboxylation
carboxylation of
substrates
of on
different substrates
foam on
substrates Cu
cathode.
on Cu a
a
foam cathode.
cathode.
Entry
Entry
Entry Substrate
Entry
Substrate
Substrate Substrate Product
Product
Product ProductYield
Yield
Yield bb b (%)
b
Yield
(%)Yield b (%)
b
b
Entry Substrate ProductYield bbbb (%) Yield Yield
(%)b (%)
b
Entry
Entry Substrate
Entry
Substrate
Entry Substrate
Substrate Product
Product Product
ProductYield (%)
(%) b (%)
b
Entry
Entry Substrate
Substrate Product Yield
Product (%)Yield b (%)
b

111 1a 2a 92
COOH
11 1 1a
1a
1a 1a COOH
COOH
COOH
COOH
COOH
2a
COOH
2aCOOH
COOH
2a 2a
92
92
92 92
1 1 11 1a
1a 1a
1a
1a COOH
COOH
COOH
COOH
2a
COOH
COOH
2a
COOH
2a
92
2a
922a
92
92 92

2
222 2 1b
1b
1b 1b 2b
2b
2b 80
2b
80
80 80
2 2 2 222 1b
1b
1b 1b
1b
1b
1b 2b
2b
2b
2b
80
2b
802b
2b
80
80
80
80 80
COOH
COOH COOH
3 1c COOH
COOH COOH
COOH
2c
COOH 83
333 3 1c
1c 1c COOH
COOH 2c
COOH
2c
COOH 2c
83
83 83
333 1c 1c 2c 2c
83 83
COOH COOH
3 33 1c
1c 1c 1c
1c COOH COOH
2c
2c 2c
832c
2c
83 83
83 83
COOH
COOH COOH
44 1d COOH
COOH
COOH COOH
COOH
2d
COOH 85
4 1d 1d COOH
2d 2d
85 85
4 44 1d 2d 85
COOH COOH
4 444 1d 1d 2d 2d
85 85
COOH COOH
4 1d
1d 1d 1d
1d COOH COOH
2d
2d 2d
852d
85
2d 85
85 85
COOH
COOH COOH
COOH
COOH
COOH COOH
COOH
COOH
55 1e COOH
COOH COOH
2e
COOH
COOH 87
5 55
5 1e
1e 1e COOH 2e
COOH
2e 2e
87
87 87
5
5 555 1e
1e
1e 1e 1e
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87
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66 6 1f
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6 66 1f 2f 72
6
6 666 1f
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1f 2f
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722f
2f
2f
72
72
72
72 72

7 77
77 7 1g
1g
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762g
76 76 76
7
7
7 777 1g
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76
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76
76
76
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8 88
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88
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88 88
8
8
8 888 1h
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9 99
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10 10
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a Electrolyses
aaaa
Electrolyses were
a Electrolyses
Electrolyses a were carried
aaa Electrolyses
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were
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under
carried
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under the same
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the same as Table 1,
conditions
asconditions
Table
conditions
conditions as Table entry
1,Table
as1, entry
entry 12.
as Table
Table
12.
1,12.
bb Determined
entry
bbb1, entry
Determined
12.
Determined by HPLC.
12. bbbbbb Determined
b Determined Determined
by HPLC.
by HPLC. by HPLC.
by HPLC. HPLC.
Electrolyses
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aaaa Electrolyses
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were
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Table 1,
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12. Determined
b1, entry 12.
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12. bb Determined
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12. bb1,
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1, entry 12. HPLC. by
Determined by HPLC.
3.
3. Materials
3. Materials
Materials and
3.and
and Methods
Materials
Methods
Methods and Methods
Methods
3.
3. Materials 3. and Methods
Materials and
3. Materials
Materials 3. and
and Methods
Materials
Methods and Methods
3. Materials and Methods
3.1. Materials
3.1. Materials
3.1. Materials 3.1. and
and
and Instruments
Materials
Instruments
Instruments and Instruments
Instruments
3.1.
3.1. Materials 3.1. and Instruments
Materials and
3.1. Materials
Materials
3.1.
3.1.
Materials
and
and Instruments
Materials
Instruments
and
and
Instruments
Instruments
All
All
All benzyl
benzyl chlorides
All benzyl
chlorides and
and chlorides acids
acids were
and
were commercially
acids
commercially were available
commercially
available from J&K
available
from J&K Chemical
from
Chemical J&K Co. (Beijing,
Chemical
Co. (Beijing, Co. (Beijing,
All benzyl
All
All benzyl
benzylAll
benzyl
chlorides
All benzyland
chlorides
All benzyl
chlorides
benzyl
chlorides and
and
and
chlorides
chlorides
chlorides
acids
acids were
acids
acids
and acids
were
and
were
and
were
commercially
acids
commercially
acids
commercially
commercially were
were
available
available from
were commercially
commercially
available
commercially
available from J&K
J&K Chemical
available
J&K
available
from
available
from J&K
from J&K
Chemical
from
Chemical
from
Chemical
J&KCo.
J&K (Beijing,
Chemical
Co. (Beijing,
Chemical
Co. (Beijing,
Chemical
Co. (Beijing,
Co. (Beijing,
Co.
Co. (Beijing,
(Beijing,
China).
China).
China). MeCN
MeCN
All
MeCN China). and
and
benzyl
China). and DMF
MeCN
DMF
DMF
MeCN chlorideswere
and
were
were
and kept
DMFkept
DMF and
kept over
were
over
over
were acids 4-Å
kept
4-Å
4-Å
kept molecular
were over
molecular
molecular
over 4-Å sieves.
molecular
sieves.
commercially
4-Å sieves.
molecular All
All
All other
sieves.
other
available
other
sieves. reagents
All
reagents
reagents
All other
from
other were
wereJ&K used
reagents
were used
used
reagents as
were
as
Chemical
as
were used
used as
Co.as
as
China).
China). MeCNChina). and DMF
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and DMFkept over
were 4-Å
kept molecular
over 4-Å sieves.
molecular All other
sieves. reagents
All other were used
reagents as
were used
China). MeCN
received. MeCNChina). and
andMeCN
Galvanostatic
received.
DMF
DMF were
and
wereDMF
electrosynthesis
Galvanostatic
kept
kept over
were
overwas
electrosynthesis
4-Å
kept molecular
over 4-Å molecular
4-Åperformed
molecular
was
sieves.
sieves.aAll
using
performed All other
sieves. reagents
otherdirect
digital
using a
All other
reagents were
reagents
were used
used
current-regulated
digital direct
as
were
as used
current-regulated
as
received.
received.(Beijing,
received. Galvanostatic
Galvanostatic
China).
Galvanostatic
received.
received. Galvanostatic
Galvanostatic electrosynthesis
electrosynthesis
MeCN
electrosynthesis
Galvanostatic
electrosynthesisand DMF
electrosynthesis was
was
were
was performed
performed
kept
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was performed
performed over
was using
using
4-Å
using
performed aa
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digital
molecular
digital
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digital direct
direct
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direct
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direct
current-regulated reagents
current-regulatedwere
received.
power supplyreceived.
(HY3005MT, Galvanostatic
electrosynthesis
Hangzhou, electrosynthesis was
China). was performed
Voltammetric using
measurementsusing direct
a were
digital direct current-regulated
current-regulated
conducted using
power
power
power used supply
supply
supplypower
power
aspower
received. supply
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(HY3005MT,
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(HY3005MT,
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China). Voltammetric
China).
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electrosynthesis
China). China).
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China). Voltammetric
measurements
measurements
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was performed
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were
a were
measurements
digital
were directwere
conducted
conductedwere
conducted conducted
using
using
conducted
current-regulated
using using
using
power
power supply
supplypower supply
(HY3005MT,
supply
(HY3005MT, (HY3005MT,
Hangzhou,
(HY3005MT,
Hangzhou, Hangzhou,
China).
Hangzhou,
China). China).
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China).
Voltammetric Voltammetric
measurements
Voltammetric
measurements measurements
were
measurements
were were
conducted
were
conducted conducted
using
conducted
using using
using
the
thethe CHI650C
CHI650C
CHI650C the
the electrochemical
CHI650C
electrochemical
electrochemical
CHI650C electrochemical
electrochemicalstation
station
station (Chenhua,
(Chenhua,
(Chenhua, station
station Shanghai,
(Chenhua,
Shanghai,
Shanghai,
(Chenhua, China)
Shanghai,
China)
China)
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in
in a
a
a conventional
China) in
conventional
conventional
China) a three-electrode
conventional
three-electrode
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in aaa conventional
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Hangzhou, (Chenhua, station China). Shanghai,
Voltammetric
(Chenhua, China)
Shanghai, in aChina)
conventional
measurements in three-electrode
were conducted
conventional using the
three-electrode
the CHI650C
cell. CHI650C
The product
cell.
electrochemical
CHI650C
electrochemical
The yield electrochemical
product was
station
station
determined
yield
(Chenhua,
(Chenhua,
was
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determined
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Shanghai,
high-performance
by
China)
Shanghai,
China) in
in a
liquid
high-performance
conventional
aChina) in
conventional
chromatography
liquid
three-electrode
three-electrode three-electrode
(HPLC)
chromatography (HPLC)
cell.
cell.
cell.
cell. The
The
The
CHI650C
The product
product
cell.
product
cell.
product The yield
yield
product
yield
electrochemical
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yield was
was
was
was determined
determined
yield
determined
station
yield
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by
determined
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determined
by high-performance
high-performance
by
high-performance
Shanghai,
by
high-performance China) liquid
liquid
high-performance
liquid
high-performance in
liquid a chromatography
chromatography
liquid
chromatography
conventional
liquid
chromatography (HPLC)
(HPLC)
chromatography
(HPLC)
three-electrode
chromatography
(HPLC) (HPLC)
cell.
(HPLC)
cell. The product
instrument cell.
(DIONEXTheyield product was yield
Ultimate 3000 was determined
determined
pump) by pump)
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high-performance
Scientific, liquid Germering,
Germering, liquid chromatography
chromatography
Germany) equipped (HPLC)
with (HPLC)
instrument
instrument
instrument instrument
(DIONEX
(DIONEX
instrument
(DIONEX (DIONEX
Ultimate
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(DIONEX
Ultimate 3000Ultimate
3000 pump)
pump)
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3000 (Thermo
(Thermo pump)
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Scientific,
Germering, Germany)
Germany)
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Germany) Germany)
equipped
equipped
Germany)
equipped equipped
with
with
equipped
with with
with
The product
instrument
instrument instrument
(DIONEX
instrument
(DIONEX yieldUltimate
was determined
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(DIONEX
Ultimate Ultimate
3000 pump)
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3000 pump) by
3000
3000 high-performance
pump)
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pump)
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Scientific, liquid chromatography
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Scientific, Scientific,
Germering, Germering,
Germany)
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Germany)
equipped
Germany)
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detector.
Germany)
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SU8000/S4800
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3.2.
3.2. General
radiation
3.2. General
General Procedure
3.2. (k
Procedure
Procedure
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= 1.5406
General Electrode
Å). of
Procedure
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3.2.
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3.2. General of Electrode Treatment
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5 min.
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was
The Ag–Cu
The Ag–Cu The
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dentrite
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to [35].
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Cu foam
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immersed The
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electrode.
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33 solution
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water and
Cu
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foam
water was Agavoiding
and3immersed
ethanol 33
photoreduction.
photoreduction.
photoreduction. The
The
photoreduction.
The
photoreduction. resulting
resulting
resulting The
The dendritic
dendritic
resulting
dendritic
resulting Ag–Cu
Ag–Cu
dendritic
Ag–Cu
dendritic was
was
was Ag–Cuwashed
washed
Ag–Cu
washed was
waswith
with
withwashed
washeddeionized
deionizedwith
deionized
with water
water
deionized
water
deionized and
and
and ethanol
ethanol
water
ethanol
water and
and3
33 ethanol
photoreduction.
photoreduction. The resulting
photoreduction.
The resulting dendritic
Thedendritic
resulting Ag–Cu Ag–Cu
dendritic was
was Ag–Cuwashed
washed was with
withwasheddeionized water and
with deionized
deionized water and water
ethanol
ethanol and 33 ethanol 33
ethanol
in 10 mM AgNO3 solution without any surfactant for 10 min in the dark avoiding Ag photoreduction.
Catalysts 2018, 8, 273 7 of 9

The resulting dendritic Ag–Cu was washed with deionized water and ethanol 3 times, then dried for
24 h at 35 ◦ C under vacuum. After that, dendritic Ag–Cu was used as the cathode for electrolysis.

3.3. General Process of Cyclic Voltammetry

Cyclic voltammetric studies were undertaken with CHI650C electrochemical workstation
(Chenhua, Shanghai, China). A conventional three-electrode cell was employed with Cu (r = 1 mm)
and Ag (r = 1 mm) disk working electrode, a platinum sheet (1 cm × 2 cm) counter electrode
and a Ag/AgI/0.1 mol L−1 TBAI reference electrode, scanning for the electrochemical behavior
of 1-phenylethyl chloride (4 mM) at different cathodes with a sweep rate of 0.1 V s−1 in a
nitrogen atmosphere.

3.4. General Electrolysis Procedure

A typical galvanostatic electrolysis was carried out in a mixture of 1-phenylethyl chloride (50 mM),
supporting electrolyte TEAI (0.1 M) and 10 mL MeCN saturated with CO2 (1 atm) in an undivided
glass cell equipped with a sacrificial magnesium (Mg) rod anode and Cu foam cathode (r = 1 cm).
Continuous CO2 flow was maintained throughout the duration of the whole electrolysis process.
After consuming a charge of 2.0 F mol−1 , the current was switched off. MeCN was removed by rotary
evaporation, then the rest was hydrolyzed with HCl (0.2 M, 15 mL) and extracted with Et2 O (20 mL)
3 times, and the organic layers were washed with H2 O, dried over MgSO4 , and then evaporated.
The main features of the aimed products were identified by HP 6890/5973N GC/MS (Agilent, USA)
and the yields were determined by high-performance liquid chromatography (HPLC) instrument
(DIONEX Ultimate 3000 pump).

3.5. General Process of Constant-Potential Electrolysis

The potentiostatic electrolysis was carried out in a mixture of 1-phenylethyl chloride (50 mM),
supporting electrolyte TEAI (0.1 M) and 10 mL MeCN saturated with CO2 (1 atm) in an undivided glass
cell equipped with a sacrificial magnesium (Mg) rod counter electrode, Cu flake (1.5 cm × 2 cm) and
Cu foam working electrode (r = 1 cm), and Ag/AgI/0.1 mol L−1 TBAI reference electrode. Continuous
CO2 flow was maintained throughout the duration of the whole electrolysis process. Electrolytic
potential is the peak potential of 1-phenylethyl chloride reduction on Cu electrode (ca. −1.18 V);
after the consumption of 70 C charges, the current was switched off. Post-processing and detection are
the same as galvanostatic electrolysis.

4. Conclusions
In conclusion, a Cu foam electrode was effective for the electrocatalytic carboxylation of
1-phenylethyl chloride. 99% yield of 2-phenylpropionic acid was obtained under optimized conditions.
Moderate-to-good yields were also achieved with other benzyl chlorides. Considering the high
effectiveness, the economic benefits and the bigger availability of Cu foam cathode, we believe
that the synthesis method described in this study has good potential for practical applications.

Supplementary Materials: The following are available online at http://www.mdpi.com/2073-4344/8/7/273/s1,

Figure S1: Cyclic voltammograms of 4 mM 1-phenylethyl chloride recorded at different cathodes in 0.1 M
TEABF4-MeCN soultion at a sweep rate of 0.1 V s−1 at 18 ◦ C saturated with N2 (a) background; (b) Ag disk;
(c) Cu disk. Table S1: Constant potential electrolysis on different cathode a .
Author Contributions: Author Contributions: Conceptualization, J.-X.L.; Data curation and Investigation, L.-X.W.
and Q.-L.S.; Formal analysis, Y.-B.G. and H.W.; Methodology, M.-P.Y., Y.-G.Z. and H.W.; Resources, Y.-B.G., H.W.
and J.-X.L.; Supervision and Visualization, J.-Xi.L.; Validation, M.-P.Y. and Y.-G.Z.; Writing—original draft, L.-X.W.
Funding: This research received no external funding.
Acknowledgments: This work was financially supported by the funds from the National Natural Science
Foundation of China (21773071, 21473060, 41402037), Natural Science Program of Anhui Province University
Catalysts 2018, 8, 273 8 of 9

(AQKJ2014B003, KJ2018A378, KJ2017A348), and Research Fund for the Doctoral Program of Anqing Normal
University (K05000323).
Conflicts of Interest: The authors declare no conflict of interest.

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