Ionic Liquids Catalyzed Friedel–Crafts Alkylation of Substituted Benzenes with CCl4 Toward Trichloromethylarenes

Article abstract of DOI:10.1007/s10562-018-2633-8

Abstract: An ionic liquid catalyzed Friedel–Crafts alkylation reaction of substituted benzenes with CCl₄ was developed. The reaction proceeded efficiently under mild conditions, gave corresponding trichloromethylarenes with diversity functional groups in moderate to good yields. The influence of Lewis acidity of ionic liquids on the conversion of the alkylation reaction has been investigated. Notably, the probable mechanism of this reaction has been proposed with the assistance of ²⁷Al NMR spectroscopy. It was noteworthy that the predominance of [Al₂Cl₇]^? species in EmimCl–AlCl₃, N = 0.67 could be detected by ²⁷Al NMR spectral analysis, and [AlCl₄]^? was generated at the beginning of reaction. Additionally, it was found that [AlCl₄]^? could be transformed into [Al₂Cl₇]^? when the reaction finished. Some control experiments confirmed that the interaction between Lewis acidic species [Al₂Cl₇]^? of the ionic liquid and CCl₄ led to the change in speciation of aluminum during the alkylation reactions. Graphical Abstract: [Figure not available: see fulltext.].

Full text of DOI:10.1007/s10562-018-2633-8

Catalysis Letters
https://doi.org/10.1007/s10562-018-2633-8
Ionic Liquids Catalyzed Friedel–Crafts Alkylation of Substituted
Benzenes with CCl4 Toward Trichloromethylarenes
Xinyu Lyu1 · Wencheng Wang1 · Yiqun Sun1 · Qian Zhao1 · Tao Qiu1
Received: 27 October 2017 / Accepted: 12 February 2018
© Springer Science+Business Media, LLC, part of Springer Nature 2018
Abstract
An ionic liquid catalyzed Friedel–Crafts alkylation reaction of substituted benzenes with CCl4 was developed. The reaction
proceeded efficiently under mild conditions, gave corresponding trichloromethylarenes with diversity functional groups in
moderate to good yields. The influence of Lewis acidity of ionic liquids on the conversion of the alkylation reaction has
been investigated. Notably, the probable mechanism of this reaction has been proposed with the assistance of 27Al NMR
spectroscopy. It was noteworthy that the predominance of [Al2Cl7]− species in EmimCl–AlCl3, N=0.67 could be detected
by 27Al NMR spectral analysis, and [AlCl4]− was generated at the beginning of reaction. Additionally, it was found that
[AlCl4]− could be transformed into [Al2Cl7]− when the reaction finished. Some control experiments confirmed that the
interaction between Lewis acidic species [Al2Cl7]− of the ionic liquid and CCl4 led to the change in speciation of aluminum
during the alkylation reactions.
Graphical Abstract
Keywords Trichloromethylarenes · Friedel–Crafts alkylation · Ionic liquids · Catalysts · Mechanism
1 Introduction
Electronic supplementary material The online version of this
article (https://doi.org/10.1007/s10562-018-2633-8) contains
Trichloromethylarenes and their derivatives are important
supplementary material, which is available to authorized users.
compounds with a wide range of applications in organic
synthesis [1]. Traditionally, they could be prepared through
the direct chlorination of methyl aromatic hydrocarbons [2].
Moreover, Friedel–Crafts alkylation reaction of substituted
* Tao Qiu
qiutao@cczu.edu.cn
Extended author information available on the last page of the article
Vol.:(0123456789)
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X. Lyu et al.
benzenes with anhydrous CCl4 catalyzed by homogeneous
Lewis acids (such as AlCl3, TiCl4, SnCl4) represents another
important method toward trichloromethylarenes [3]. How-
ever, these procedures often suffer from the generation of
large amount of acidic effluents, difficulties in separation
and recovery of the catalysts, corrosion and environmental
hazard. Thus, the development of more green procedures to
generate trichloromethylarenes and their derivatives remains
an area of synthetic interest.
(HmimCl), 1-ethyl-3-methylimidazolium bromide (EmimBr),
1-butyl-3-methylimidazolium bromide (BmimBr), 1-hexyl-
3-methylimidazolium bromide (HmimBr) and 1-ethyl-3-meth-
ylimidazolium iodide were synthesized according to the above
method. EmimCl–AlCl3, EmimBr–AlCl3, BmimCl–AlCl3,
BmimBr–AlCl3, HmimCl–AlCl3, HmimBr–AlCl3, EmimI–AlCl3
and EmimCl–FeCl3 ILs were synthesized according to the pre-
vious reports [20, 21].
Recently, many organic reactions [4, 5], especially Frie-
del–Crafts reaction [6], have used Al-containing zeolites [7],
sulfated ZrO2 [8], heteropolyacid salts [9], ion-exchanged
clays [10], or modified mesoporous silicas [11] as alterna-
tives in the acidcatalyzed synthesis. On the other hand, ionic
liquids (ILs) [12, 13] have been widely used in chemical
reactions, material synthesis, separation and fractionation
due to their unique properties, such as negligible vapor
pressure, high thermal stability [14], excellent solubility
[15–17]. Most importantly, they could be separated [18] and
recycled easily [19].
2.3 Reaction Procedure and Analysis
Substituted benzenes and CCl4 were added into a 100 mL
three-neck flask equipped with a stirrer, a reflux condenser
with a drying pipe and a thermometer. Then an appropriate
amount of ILs was added dropwise to the flask in 10 min with
stirring. The alkylation reaction was carried out for 2 h at
ambient atmosphere. Then the reaction mixture was placed
to form two phases. The ionic liquid phase could be purified
by washing with hexane and directly recycled in subsequent
runs. Meanwhile, the lower clear phase was pipetted off for
gas chromatography analysis. A GC–MS (QP2010-SE) was
used to evaluate the concentration of reactants and products.
Herein, we would like to report our study in this regard.
Firstly, the ILs are synthesized via the reaction of AlCl3 with
organic halide. Subsequently, Trichloromethylarenes and its
derivatives were synthesized via Friedel–Crafts alkylation of
aromatics with CCl4 in ILs of 1-ethyl-3-methylimidazolium
chloride–AlCl3 (EmimCl–AlCl3). In addition, the key inter-
mediates were investigated by 27Al NMR spectroscopy. All
these researches show that the products have easy separation
and quick reaction rate. Meanwhile, all these ILs could be
recycled for four times without losing much of their catalytic
activity obviously.
2.4 Determination of the Acidity of ILs
The acidity of ILs was determined by using acetonitrile as a
base probe molecule and this detailed procedure was the same
as that described in the previous literature [22].
2.5 The Ion Morphology [23] of EmimCl–AlCl3,
N = 0.67
Ethanol was used as solvent to prepare different concentrations
of ILs. In addition, the structures of ILs were investigated by
UV–Vis3600.
2 Experiment
2.1 Materials
2.6 27Al NMR Studies [24]
2,4-Dichlorofluorobenzene, xylene, trimethylbenzene,
dichlorobenzene, CCl4, FeCl3 and AlCl3 were purchased
from Sinopharm Chemical Reagent Co., Ltd. 1-methylimi-
dazole and bromoethane, 1-bromobutane, 1-bromohexane,
chloroethane, 1-chlorobutane, 1-chlorohexane, iodoethane,
CD2Cl2 (>99.9%) were acquired from Aladdin Co., Ltd.
The 400 MHz spectrometer was used to evaluate all spectra.
The detection of aluminum-27 resonance was optimized at
130 MHz by tuning the receiver coil of the spectrometer.
The anhydrous AlCl3 was chosen as an external standard (δ
0.0 ppm) for all spectra. These samples were prepared by
quickly dissolving approximately 5 mg of reaction liquids in
600 µL of CD2Cl2.
2.2 Preparation of ILs
Bromoethane (0.13 mol, 14 g) was added into 1-methylimida-
zole (0.1 mol, 8.2 g) in a 100 mL three necked flask. The mix-
ture was stirred at 70 °C for 24 h. When the reaction was over,
the white solid was collected by filtration, washed with ethyl
acetate (3×10 mL) and oven-dried under vacuum at 50 °C for
6 h. The precursors EmimCl, 1-butyl-3-methylimidazolium
chloride (BmimCl), 1-hexyl-3-methylimidazolium chloride
1 3

Ionic Liquids Catalyzed Friedel–Crafts Alkylation of Substituted Benzenes with CCl4 Toward…
related to intermediate carbenium ions. When the molar
3 Results and Discussions
ratio of AlCl3 to EmimCl–AlCl3 is 2, the actual catalytic
species are mainly accepted to be Al2Cl7−. High acid
strength will favor side reactions (dialkylation) [25]. And
the Lewis acidity of Al2Cl7− is slightly weaker than that of
AlCl3. The electrostatic field of ILs and the high polarity
can make the carbenium ion intermediates more stable and
favor main reactions. In addition, using EmimCl–AlCl3 as
catalyst can simplify product isolation, and the process is
environmentally friendly.
3.1 Friedel–Crafts Alkylation
of 2,4‑Dichlorofluorobenzene with CCl4
in Different ILs
We initiated our investigation on the model reaction of
2,4-dichlorofluorobenzene with CCl4 to optimize the
critical reaction parameters. We investigated alkyla-
tion of 2,4-dichlorofluorobenzene with CCl4 in ILs,
EmimCl–AlCl3 etc., 0.67 ≥ N > 0.5. The corresponding
results of reactions in various ILs are shown in Table 1.
As shown in Table 1, alkylation of 2,4-dichlorofluor-
obenzene and CCl4 with EmimCl–AlCl3 (N = 0.67) as
catalyst gave a higher yield of 1,5-dichloro-2-fluoro-4-
(trichloromethyl)benzene than that of AlCl3 as catalyst
(70%). The mechanistic details of alkylation reactions are
3.2 Result of Acidity Determination
The Lewis acidic strength of EmimCl–AlCl3 is regulated
by changing the mole fraction of AlCl3. Acetonitrile
here was used as an IR probe to determine the acidity
of ILs [22]. It is shown from Fig. 1 that pure acetoni-
trile displays two characteristic νCN stretching vibrations
Table 1 Selected results for screening the optimized reaction conditions
Entry
Ionic liquid
na
Conversion (%)
Selectivityb (%)
GC yield (%)
1
2
3
4
5
6
7
8
EmimBr–AlCl3
EmimBr–AlCl3
EmimBr–AlCl3
BmimBr–AlCl3
BmimBr–AlCl3
BmimBr–AlCl3
HmimBr–AlCl3
HmimBr–AlCl3
HmimBr–AlCl3
EmimCl–AlCl3
EmimCl–AlCl3
EmimCl–AlCl3
BmimCl–AlCl3
BmimCl–AlCl3
BmimCl–AlCl3
HmimCl–AlCl3
HmimCl–AlCl3
HmimCl–AlCl3
EmimI–AlCl3
1
1.5
2
1
1.5
2
1
1.5
2
1
1.5
2
1
1.5
2
1
1.5
2
0
0
0
81.4
100
0
91.2
100
20.1
30.4
91.7
0
84.5
100
2.4
93.5
100
26.3
40.5
98.2
96.6
55.4
58.1
73.3
0
28.3
48.6
0
0
0
0
55.0
83.5
0
24.6
47.8
0
0
0
66.4
30.3
47.3
73.3
0
25.8
48.6
0
0
0
0
46.5
83.5
0
23
47.8
0
0
0
64.2
16.8
9
10
11
12
13
14
15
16
17
18
19
20
2
2
EmimBr–FeCl3
Entries 1–20 are the reaction of 2,4-dichlorofluorobenzene (0.01 mol) with CCl4 (0.04 mol) at the 60 °C in 0.01 mol of ILs
aThe molar ratio of AlCl3 or FeCl3 to EmimX, BmimX, HmimX
1
bThe main product is 1,5-dichloro-2-fluoro-4-(trichloromethyl)benzene (the H NMR data is shown in Table S1-Entry 1), the side product is
bis(2,4-dichloro-5-fluorophenyl)dichloromethane
1 3

X. Lyu et al.
Fig. 2 Ultraviolet–vis absorption spectrum of EmimCl (a) and
EmimCl–AlCl3 (b, c)
Fig. 1 IR spectra of mixtures of acetonitrile and EmimCl–AlCl3
ILs: (a) pure acetonitrile (b) molar ratio of AlCl3 to EmimCl=0.5;
(c) molar ratio of AlCl3 to EmimCl=1.0; (d) molar ratio of AlCl3 to
EmimCl=1.5; (e) molar ratio of AlCl3 to EmimCl=2.0
-
-
l-
Al
l
2Al l
C 4
2C 7
C
at 2250 and 2291 cm−1. When acetonitrile is combined
with EmimCl–AlCl3 with n = 0.5, there is almost noth-
ing changed in νCN stretching frequencies. This should be
attributed to acetonitrile does not interact with ILs. By
contrast, when n > 1, a third band appears at 2334 cm−1
and all these bands had a monotonic blue shift. The band
at around 2334 cm−1 is indicative of Lewis acid–base
interaction between acetonitrile and ILs. With the increase
of n, the intensity of the peak near 2334 cm−1 becomes
stronger. These results indicate that varying the fraction of
AlCl3 in ILs can modify the Lewis acidic strength of ILs.
Scheme 1 The reaction of complex ion
Scheme 2 The detailed mechanism of the alkylation reaction
3.4 27Al NMR Spectrum of ILs and the Mechanistic
Details of the Reaction
3.3 UV Spectroscopy of EmimCl–AlCl3
The mechanism of alkylation has been well documented
using AlCl3 as a Lewis acid by studying the kinetics of the
reaction [29]. In order to get a deeper insight into the mecha-
nistic details of the reactions in these non-normal ILs, com-
prehensive 27Al NMR studies seemed to be worthwhile to
carry out [30]. We can figure out details of the mechanism
with 27Al NMR giving the survey on the speciation of alu-
minum. This acid/base behavior of ILs is under the control
of by Scheme 2, which is considered to sufficiently describe
the speciation of aluminum in chloroaluminate liquids over a
wide range of compositions. The equilibrium constant of this
reaction is of the order of 1017–1018 near ambient tempera-
ture [31, 32]. Therefore, the predominant anionic species
In ILs, the addition of Lewis bases, such as EmimCl, is
conducive to accelerating the dissolution of AlCl3. In chlo-
raluminate ILs, when the molar ratio of AlCl3 to EmimCl
−
is 2, there is mainly Al2Cl7−, with AlCl4 rarely existing
[26, 27]. So we use ethanol as solvent to diluting ILs and
its precursor to a dispersion of 0.05 and 0.1 mol/L. From
Fig. 2 (curves a), the precursor shows an absorption peak
at 292 nm. And the second absorption peak at 360 nm
indicates the formation of complex ion according to crystal
field theory [28].
From Beer–Lambert Law, we figured out the absorbance
of ILs. With the concentration reducing, the absorbance of
line b at 360 nm is 0.243, the absorbance of curves (c) at
360 nm is 0.552, Ac/Ab =2.3; and at the 292 nm, the absorb-
ance of curves (b) is 0.497, the absorbance of line c is 1.02,
Ac/Ab = 2.0. That means the equilibrium constant of the
reaction in Scheme 1 moves forward.
−
is Al2Cl7 in acidic ILs. Our survey herein was primarily
restricted to the researches in EmimCl–AlCl3, N=0.67.
The changes of 27Al NMR spectrum are displayed in
−
−
Fig. 3. The chemical shifts of AlCl4 and Al2Cl7 in the
27Al NMR spectrum appeared at δ 79.6 and 74.5 ppm, in
1 3

Ionic Liquids Catalyzed Friedel–Crafts Alkylation of Substituted Benzenes with CCl4 Toward…
Fig. 3 (a) 27Al NMR spectrum of EmimCl–AlCl3, N=0.67; (b) 27Al
NMR spectrum of EmimCl–AlCl3, N=0.67, CCl4 and 2,4-dichloro-
fluorobenzene in the molar proportion 1.0∶4.0∶1.0, after 0.5 h; (c)
27Al NMR spectrum of reaction mixtures after 1 h; (d) 27Al NMR
spectrum of reaction mixtures after 1.5 h; (e) 27Al NMR spectrum of
the lower ILs after the reaction
Fig. 4 Results of repeated use of EmimCl–AlCl3, N=0.67 catalyst.
Run 1–5 are the reaction of 2,4-dichlorofluorobenzene (0.01 mol)
with CCl4 (0.04 mol) at the 60 °C in 0.01 mol of the same ILs
agreement with literature values: 79.3 and 73.9 ppm. From
curves (a), EmimCl–AlCl3, N=0.67 displayed a broad sig-
hexane. And the weight of ILs would be reduced by about
2% between each cycle. The 27Al NMR spectrum shows the
structure of EmimCl–AlCl3, N=0.67 remain unchanged when
the reaction completed. According to the results mentioned, it
is reasonable to draw a conclusion that the ionic liquid cata-
lysts could be reused and the results of recycling are shown in
Fig. 4. The ILs of EmimCl–AlCl3, N=0.67 were recycled for
four times with only a moderate loss of activity. These results
also imply that EmimCl–AlCl3 still keeps its structure of the
Al2Cl7− ion after the alkylation reaction.
−
nal at δ 74.5 ppm corresponding to Al2Cl7 species. We
made a plan to investigate on the participation of either
completely polarized ion pair [CCl3][AlCl4] in alkylation
−
reactions or the coordination complex of CCl4 with Al2Cl7 .
From curves (b), the ILs, CCl4 and 2,4-dichlorofluoroben-
zene were mixed in a molar ratio of 1.0∶4.0∶1.0, it is clearly
seen that the peak at δ 79.6 ppm was far higher than before
after 0.5 h, corresponding to Al2Cl7− species. From curves
(c) to (d), the peak at δ 79.6 ppm had an upward trend. This
indicated that the Al2Cl7− ion were converted to AlCl4− ion
with the reaction time increasing. After 2 h, we extracted the
samples from ILs when cooling separation of the system.
From curves (e), we surprisedly found the main ion still
was Al2Cl7− and the AlCl4− ion was less than before. The
phenomenon was different from the one which described in
the recent literature [24].
After the recycling, the loss of ILs are unavoidable. We
think that the loss of ILs resulted in a decrease of yield. We
also had added AlCl3 to recycled ILs, then the results indicated
that the GC yield returned to 82.4%. This finding shown that
the activity of ILs could be recover by supplement of AlCl3.
3.6 Substrate Expansion
In accordance with the conclusions mentioned from the
above experiments, the reasonable mechanisms of alkyla-
tion in EmimCl–AlCl3, N=0.67 ionic liquid are as follows
(Scheme 2).
After considerable experimentation, we found that the com-
bination of 1 equiv of substituted benzenes, 4 equiv of CCl4
and 1 equiv of ILs served as the optimal conditions for this
transformation. With the optimized reaction condition in
hand, we then explored the scope and limitation of the sub-
stituted benzenes. As shown in Table 2, di- or tri-substituted
benzenes proceeded smoothly with CCl4 and generated the
desired trichloromethylarenes in moderate to good yields.
3.5 Recycling of the ILs
Easy separation of the products which had high purity is one
of the strengths of ILs. The substrates used here and their
products are practically insoluble in the ILs but have good
solubility in CCl4. After the completion of the reaction, the
products would dissolve easily in CCl4 and form a separate
phase at the bottom of ILs, so we can get high-purity products
in CCl4 by decantation. After each run, ILs were separated
from the organic phase and purified by washing with fresh
4 Conclusion
In conclusion, we have developed an ILs catalyzed Frie-
del–Crafts alkylation reaction of substituted benzenes
with CCl4 toward a series of trichloromethylarenes.
1 3

X. Lyu et al.
Table 2 Friedel–Crafts alkylation of substituted benzenes with CCl4 in EmimCl–AlCl3, N=0.67
GC
Yield
(%)
Temperature Conversion Selectivityb
Entry
1
Substrate
Producta
(oC)
/%
/%
40
93.4
71.8
67.1
69.2
61.9
81.6
2
3
4
40
40
60
90.5
88.7
100
76.5
69.8
81.6
5
60
60
98.6
98.4
54.2
63.7
53.4
62.7
6-1
6-2
60
98.4
14.5
14.3
7
8
60
60
95.7
93.4
77.3
65.7
73.9
61.4
aThe 1H NMR data of substituted benzenes are shown in Table S1-entry 2–9
bThe side product is bis(substituted phenyl)dichloromethane
EmimCl–AlCl3 was considered as a reaction solvent and
Lewis acid catalysts in this reaction. These ILs had a good
performance in both high selectivity for mono-alkylated
products and quick reaction rate. Furthermore, the mecha-
nistic details of the reaction were investigated by 27Al NMR
spectra. Then, we investigated the scope and limitation of
this transformation on the presence of a variety of substituted
benzenes. Finally, these ILs could serve as potential alterna-
tives of AlCl3 in organic solvent and had more applications
in similar organic synthesis.
Acknowledgements We are thankful for assistance from the staff at
Jiangsu Key Laboratory of Advanced Catalytic Materials and Technol-
ogy (Changzhou University). This research did not receive any specific
1 3

Ionic Liquids Catalyzed Friedel–Crafts Alkylation of Substituted Benzenes with CCl4 Toward…
grant from funding agencies in the public, commercial, or not-for-profit
sectors.
16. Howarth J, James P, Dai J (2000) Tetrahedron Lett
41(52):10319–10321
17. Xie X, Lu J, Chen B, Han J, She X, Pan X (2004) Tetrahedron Lett
45(4):809–811
18. Wasserscheid P, Keim W (2000) Angew Chem Int Ed
39(21):3772–3789
References
19. Shill K, Padmanabhan S, Xin Q, Prausnitz JM, Clark DS, Blanch
HW (2011) Biotechnol Bioeng 108(3):511–520
20. Gutowski KE, Broker GA, Willauer HD, Huddleston JG, Swat-
loski RP, Holbrey JD, Rogers RD (2003) J Am Chem Soc
125(22):6032–6033
1. Belen’kii LI, Brokhovetskii DB, Krayushkin MM (1991) Tetra-
hedron 47(3):447–456
2. Rondestvedt CS (1976) J Org Chem 41(22):3569–3574
3. Rosca SI, Stan R, Bratu C, Deleanu C (2010) Rev Chim
61(10):940–945
21. Abbott AP, Capper G, Davies DL, Munro HL, Rasheed RK,
Tambyrajah V (2001) Chem Commun 19(19):2010–2011
22. Piao LY, Fu X, Yang YL, Tao GH, Kou Y (2004) Catal Today
93–95:301–305
4. Zhao H, Holladay JE, Brown H, Zhang ZC (2007) Science
316(5831):1597–1600
5. Hu P, Wang Y, Meng X, Zhang R, Liu H, Xu C, Liu Z (2017) Fuel
189:203–209
23. Li WK, Zhou GD, Mak T (2008) Advanced structural inorganic
chemistry. Oxford University Press, New York
24. Nara SJ, Harjani JR, Salunkhe MM (2001) J Org Chem
66(25):8616–8620
6. Li C, Liu W, Zhao Z (2007) Catal Commun 8(11):1834–1837
7. Antunes MM, Lima S, Neves P, Magalhães AL, Fazio E, Fer-
nandes A, Neri F, Silva CM, Rocha SM, Ribeiro MF, Pilinger M,
Urakawa A, Valente AA (2015) J Catal 329(2):522–537
8. Liao Y, Huang X, Liao X, Shi S (2011) J Mol Catal A
347(1–2):46–51
25. Olah GA (1963) Friedel-Crafts and related reactions. Interscience
Publishers, New York
26. Abbott AP, Fulian Q, Abood HM, Ali MR, Ryder KS (2010) Phys
Chem Chem Phys 12(8):1862–1872
9. Leng Y, Wang J, Zhu D, Wu Y, Zhao P (2009) J Mol Catal A
313(1–2):1–6
27. Jiang T, Brym Chollier MJ, Dubé G, Lasia A, Brisard GM (2006)
Surf Coat Technol 201(1):10–18
10. Catrinescu C, Fernandes C, Castilho P, Breen C (2015) Appl Catal
A 489:171–179
28. Furukawa J, Kobayashi E, Arai Y (1971) J Polym Sci B
9(11):805–812
11. Wang G, Yu N, Peng L, Tan R, Zhao H, Yin D, Qiu H, Fu Z, Yin
D (2008) Catal Lett 123(3–4):252–258
29. Jensen FR, Brown HC (1958) J Am Chem Soc 80(15):4042–4045
30. Matsumoto T, Ichikawa K (1984) Chemischer Informationsdienst
15(44):4316–4320
12. Earle MJ, Seddon KR (2000) Pure Appl Chem 72(7):1391–1398
13. Shiflett MB, Yokozeki A (2016) J Chem Eng Data 54(1):108–114
14. Zhou D, Zhou R, Chen C, Yee WA, Kong J, Ding G, Lu X (2013)
J Phys Chem B 117(25):7783–7789
31. Karpinski ZJ, Osteryoung RA (1984) Chemischer Informations-
dienst 15(33):1491–1494
15. Park S, Kazlauskas RJ (2003) Curr Opin Biotechnol
14(4):432–437
32. Hussey CL, Scheffler TB, Wilkes JS, Fanin AA Jr (1986) J Elec-
trochem Soc 133(7):1389–1391
Affiliations
Xinyu Lyu1 · Wencheng Wang1 · Yiqun Sun1 · Qian Zhao1 · Tao Qiu1
1
Jiangsu Key Laboratory of Advanced Catalytic Materials
and Technology, Changzhou University, No. 1, Gehu Road,
Wujin District, Changzhou 213164, Jiangsu, China
1 3