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ChemComm
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DOI: 10.1039/C8CC00969D
COMMUNICATION
Journal Name
charge (Q), current density and the solvent were investigated size of 25×28 cm at one time. Pt-NPs@NCNFs@CC could be
to optimize the yield of 2a. The results were summarized in directly used as cathode for electrochemical reduction as well
2
Table S2. Under optimized reaction conditions, 2a with 99% as carboxylation of CO , for which formate with 91% Faradaic
yield and more than 99% selectivity was obtained (Table 1, efficiency and 2-phenylpropionic acid with 99% yield could be
entry 1) at the Pt-NPs@NCNFs@CC cathode. Pt- obtained, respectively. Pt-NPs@NCNFs@CC also has
NPs@NCNFs@CC could be easily-recovered and all the remarkable stability and reusability, which might have
reactions were conducted under room temperature and practical applications in the future.
pressure. The yield and selectivity obtained at Pt-
NPs@NCNFs@CC are even comparable to those achieved
8
using homogeneous metal complex catalysts.
, 9
Notes and references
The financial support of the National Natural Science
Foundation (NNSF) of China (21574084 and 21571131), the
Natural Science Foundation of Guangdong Province
(
2015A030313554 and 2017A040405066), and Shenzhen
Government’s Plan of Science and Technology
JCYJ20160308104704791) are gratefully acknowledged.
2
Scheme 1 Electro-carboxylation of CO with 1a.
(
a
Table 1 Electrochemical carboxylation of 1a with CO
2
at different cathodes .
1
2
J. Albo, M. Alvarez-Guerra, P. Castañoa, A. Irabienb, Green
Chem., 2015, 17, 2304−2324.
J. Kim, T. A. Johnson, J. E. Miller, E. B. Stechel, C. T.
Maravelias, Energy Environ. Sci., 2014, 5, 8417−8429.
L. Zhang, Z. Hou, Chem. Sci., 2013, 4, 3395−3403.
b
b
Yield
Selectivity
Entry
Cathode
(%)
(%)
>99
-
1
2
3
4
5
Pt-NPs@NCNFs@CC
NCNFs@CC
CC
99
<1
<1
97
32
3
4
5
Y. Tsuji, T. Fujihara, Chem. Commun., 2012, 48, 9956−9964.
C. Costentin, M. Robert, J. M. Saveant, Chem. Soc. Rev., 2013,
-
Pt-NPs@NCNFs
Pt-NPs/CC
>99
84
4
2
, 2423−2436.
K. P. Kuhl, E. R. Cave, D. N. Abram, T. F. Jaramillo, Energy
Environ. Sci., 2012, , 7050−7059.
K. J. P. Schouten, Y. Kwon, C. J. M. van der Ham, Z. Qin,
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221−1224
M. Börjesson, T. Moragas, D. Gallego, R. Martin, ACS Catal.,
016, , 6739−6749.
6
7
8
9
a
5
2
Anode: Mg, 20 mL CO -saturated MeCN, 0.1 M 1a, supporting electrolyte: 0.1 M
-2
-1
b
TEAI, current density: 3 mA cm , charge: 2.5 F mol , CO
2
pressure: 1 atm, 25 °C.
2
Determined by HPLC.
,
1
Similar results could also be achieved using Pt-NPs@NCNFs.
In contrast, 2a with less than 1% yield was detected under the
2
6
same conditions using NCNFs@CC or CC as cathode, and 2a 10 H. P. Yang, Y. N. Yue, Q. L. Sun, Q. Feng, H. Wang, J. X. Lu,
with 32% yield and 84% selectivity was obtained at Pt-NPs/CC
Fig. S8). These phenomena indicated that Pt NPs are
indispensable for the formation of 2a. NCNFs alone could not
produce 2a, but they could adsorb CO molecule and increase
the CO
Chem. Commun., 2015, 51, 12216−12219.
1 L. J. Goossen, N. Rodríguez, K. Gooßen, Angew. Chem., Int.
Ed., 2008, 47, 3100−3120.
1
(
1
2 H. Maag, Prodrugs of Carboxylic Acids; Springer: New York,
2
2
007.
2
concentration around Pt NPs, which might account for 13 G. Seshadri, C. Lin, A. B. Bocarsly, J. Electroanal. Chem., 1994,
the much higher yield obtained at Pt-NPs@NCNFs@CC than
that of pure Pt NPs. Using reaction conditions of Table 1, entry
372, 145−150.
4 E. B. Cole, P. S. Lakkaraju, D. M. Rampulla, A. J. Morris, E.
Abelev, A. B. Bocarsly, J. Am. Chem. Soc., 2010, 132, 11539−
1
1
1
, other benzyl halides were also tested for electro-
carboxylation with CO . According to Fig. S7 and Table S3, Pt-
NPs@NCNFs@CC could be applicable to the carboxylation of
CO with wide range of substrates. In addition, we also test the
reusability of Pt-NPs@NCNFs@CC in CO carboxylation under
1
1551.
2
5 S. Lin, C. S. Diercks, Y. B. Zhang, N. Kornienko, E. M. Nichols,
Y. Zhao, A. R. Paris, D. Kim, P. Yang, O. M. Yaghi, C. J. Chang,
Science, 2015, 349, 1208−1213.
2
1
1
6 I. Hod, M. D. Sampson, P. Deria, C. P. Kubiak, O. K. Farha, J. T.
2
Hupp, ACS Catal., 2015,
7 Y. Liu, S. Chen, X. Quan, H. Yu, J. Am. Chem. Soc., 2015, 137
1631−11636.
5, 6302−6309.
the same conditions as Table 1 entry 1, the yield of 2-
phenylpropionic acid could maintain around 98% (Fig. S9).
,
1
After CO
NPs@NCNFs@CC cathode was characterized by multiple
methods. N adsorption-desorption measurement showed
that Pt-NPs@NCNFs@CC still had a specific surface area of
2
reduction and carboxylation reactions, the Pt- 18 H. P. Yang, S. Qin, H. Wang, J. X. Lu, Green Chem., 2015, 17
5144−5148.
9 H. P. Yang, Y. N. Yue, S. Qin, H. Wang, J. X. Lu, Green Chem.,
016, 18, 3216−3220.
0 H. P. Yang, S. Qin, Y. N. Yue, L. Liu, H. Wang, J. X. Lu, Catal. Sci.
Technol., 2016, , 6490−6494.
patterns, the chemical composition of Pt-NPs@NCNFs@CC 21 H. Wang, J. Jia, P. Song, Q. Wang, D. Li, S. Min, C. Qian, L.
,
1
2
2
2
2
-1
around 230 m g . According to the XRD, XPS and TEM
6
also didn’t change (Fig. S10). In
a
word, our Pt-
Wang, Y. F. Li, C. Ma, T. Wu, J. Yuan, M. Antonietti, G. A. Ozin,
Angew. Chem. Int. Ed., 2017, 56, 7847−7852.
NPs@NCNFs@CC composite own remarkable stability and
reusability, which are significant for practical applications.
In conclusion, Pt-NPs@NCNFs@CC, a highly efficient and
binder-free catalyst was preparaed by electrospinning with the
2
2
2 D. Xiang, D. Magana, R. B. Dyer, J. Am. Chem. Soc., 2014, 136
4007−14010.
3 D. Guo, R. Shibuya, C. Akiba, S. Saji, T. Kondo, J. Nakamura,
,
1
Science, 2016, 351, 361−365.
4
| J. Name., 2012, 00, 1-3
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