Ni@Pd on yolk–shell Fe3O4@PANI as catalyst for nitrobenzene reduction
99
99
97
97
97
97
96
96
100
80
60
40
20
0
References
[1] K. Kamata, Y. Lu, Y. Xia, J. Am. Chem. Soc. 2003, 125, 2384.
[2] J. Liu, S. Z. Qiao, S. Budi Hartono, G. Q. M. Lu, Angew. Chem. Int. Ed.
2010, 49, 4981.
[3] L. Zhang, T. Wang, L. Yang, C. Liu, C. Wang, H. Liu, Y. A. Wang, Z. Su,
Chem. Eur. J. 2012, 18, 12512.
[4] J. C. Park, H. Song, Nano Res. 2011, 4, 33.
[5] J. Liu, S. Z. Qiao, J. S. Chen, X. W. D. Lou, X. Xing, G. Q. M. Lu, Chem.
Commun. 2011, 47, 12578.
[6] Y. Yin, R. M. Rioux, C. K. Erdonmez, S. Hughes, G. A. Somorjai,
A. P. Alivisatos, Science 2004, 304, 711.
[7] S. Wang, M. Zhang, W. Zhang, ACS Catal. 2011, 1, 207.
[8] N. Liu, H. Wu, M. T. McDowell, Y. Yao, C. Wang, Y. Cui, Nano Lett.
2012, 12, 3315.
[9] T. Yao, T. Cui, J. Wu, Q. Chen, X. Yin, F. Cui, K. Sun, Carbon 2012, 50, 2287.
[10] K. Zhang, X. Zhang, H. Chen, X. Chen, L. Zheng, J. Zhang, B. Yang,
Langmuir 2004, 20, 11312.
1
2
3
4
5
6
7
8
No. of recycling steps
Figure 10. Effect of recycling on the catalytic efficiency of yolk–shell
Fe3O4@PANI/Ni@Pd NPs.
reduced rapidly and that the position of substituent did not affect
the results substantially (Table 2, entries 2–4). When the catalyst
was employed to catalyze the reduction of nitrotoluene (Table 2,
entry 8), it displayed a lower activity than with nitroaniline and
nitrophenol, because, in the presence of NaBH4 and Ni@Pd NPs
catalyst, the reduction of nitrotoluene can produce amino and
nitroso forms, whereas nitroaniline and nitrophenol can only be
converted into the corresponding anilines.[43] This could be a result
of poor adsorption of nitrotoluene on the catalyst surface
compared to other nitro derivatives bearing a polar substituent
on the benzene ring. We also examined the reduction of
3-nitrophenyl acetate, which needed 13 min to complete (Table 2,
entry 8). Moreover, the results showed that nitro compounds
containing electron-donating or sterically crowded groups needed
more time to complete (Table 2, entries 5 and 7).
[11] N. Tian, Z.-Y. Zhou, S.-G. Sun, Y. Ding, Z. L. Wang, Science 2007,
316, 732.
[12] D. Astruc, Nanoparticles and Catalysis, Wiley-VCH, Weinheim, 2008.
[13] B. Zhou, S. Hermans, G. A. Somorjai, Nanotechnology in Catalysis, Vol.
1, Springer, Berlin, 2003.
[14] L. Zhang, M. Wan, J. Phys. Chem. B 2003, 107, 6748.
[15] L. Liang, J. Liu, C. F. Windisch Jr., G. J. Exarhos, Y. Lin, Angew. Chem.
Int. Ed. 2002, 41, 3665.
[16] Y. Wang, Y. Shen, A. Xie, S. Li, X. Wang, Y. Cai, J. Phys. Chem. C 2010,
114, 4297.
[17] M. Ma, Q. Zhang, D. Yin, J. Dou, H. Zhang, H. Xu, Catal. Commun.
2012, 17, 168.
[18] F. F. Tao, S. Zhang, L. Nguyen, X. Zhang, Chem. Soc. Rev. 2012, 41,
7980.
[19] Ö. Metin, S. F. Ho, C. Alp, H. Can, M. N. Mankin, M. S. Gültekin, M. Chi,
S. Sun, Nano Res. 2013, 6, 10.
[20] Y. Zhao, X. Yang, J. Tian, F. Wang, L. Zhan, Int. J. Hydrogen Energy
2010, 35, 3249.
[21] L. D. Pachón, M. B. Thathagar, F. Hartl, G. Rothenberg, PCCP 2006, 8,
151.
[22] M. R. Nabid, S. J. Tabatabaei Rezaei, Appl. Catal. A: Gen. 2009, 366,
108.
[23] M. R. Nabid, Y. Bide, S. J. Tabatabaei Rezaei, Appl. Catal. A: Gen. 2011,
406, 124.
[24] M. R. Nabid, Y. Bide, M. Niknezhad, Chem. Cat. Chem. 2014, 6, 538.
doi:10.1002/cctc.201300984.
[25] M. R. Nabid, Y. Bide, Appl. Catal. A: Gen. 2014, 469, 183.
[26] M. R. Nabid, Y. Bide, E. Aghaghafari, S. J. T. Rezaei, Catal. Lett. 2014,
144, 355. DOI:10.1007/s10562-013-1107-2.
[27] H. Ahmar, A. R. Fakhari, M. R. Nabid, S. J. T. Rezaei, Y. Bide, Sens. Ac-
tuators B 2012, 171, 611.
[28] N. C. Smythe, J. C. Gordon, Eur. J. Inorg. Chem. 2010, 2010, 509.
[29] A.-J. Wang, H.-Y. Cheng, B. Liang, N.-Q. Ren, D. Cui, N. Lin, B. H. Kim,
K. Rabaey, Environ. Sci. Technol. 2011, 45, 10186.
[30] A. Latifoglu, M. D. Gurol, Water Res. 2003, 37, 1879.
[31] J. Liu, Z. Sun, Y. Deng, Y. Zou, C. Li, X. Guo, L. Xiong, Y. Gao, F. Li,
D. Zhao, Angew. Chem. Int. Ed. 2009, 48, 5875.
[32] H. Deng, X. Li, Q. Peng, X. Wang, J. Chen, Y. Li, Angew. Chem. Int. Ed.
2005, 44, 2782.
[33] T. Yamamoto, D. K. Moon, Makromol. Chem. Rapid Commun. 1993, 14, 495.
[34] Z.-B. Wang, P.-J. Zuo, G.-J. Wang, C.-Y. Du, G.-P. Yin, J. Phys. Chem. C
2008, 112, 6582.
[35] S. Xuan, Y.-X. J. Wang, K. C.-F. Leung, K. Shu, J. Phys. Chem. C 2008,
112, 18804.
[36] X. Feng, C. Mao, G. Yang, W. Hou, J.-J. Zhu, Langmuir 2006, 22, 4384.
[37] M. Trchová, E. N. Konyushenko, J. Stejskal, J. Kovářová, G. Ćirić-
Marjanović, Polym. Degrad. Stab. 2009, 94, 929.
[38] Z. Sun, Z. Liu, B. Han, S. Miao, Z. Miao, G. An, J. Colloid Interface Sci.
2006, 304, 323.
[39] B. Fıçıcılar, A. Bayrakçeken, İ. Eroğlu, J. Power. Sources 2009, 193, 17.
[40] S. K. Ghosh, M. Mandal, S. Kundu, S. Nath, T. Pal, Appl. Catal. A: Gen.
2004, 268, 61.
Recycling Yolk–Shell Fe3O4@PANI/Ni@Pd NPs
The recyclability and reusability of the yolk–shell Fe3O4@PANI/
Ni@Pd NPs catalyst were tested for the reduction reaction of o-NA
as a model reaction for up to eight cycles. The results shown in
Fig. 10 demonstrate that after every run the product yield did not
change significantly, demonstrating the fair stability of catalyst
under experimental conditions.
It should be noted that magnetic extraction precludes the
need for filtration or centrifugation steps and workup of the final
reaction mixture to recover the catalyst.
Conclusion
In this report we have achieved several important objectives: (i) a het-
erogeneous catalyst having the advantage of being magnetically
separable and therefore removing the need for catalyst filtration af-
ter completion of the reaction; (ii) employment of a hollow structure
with a larger vacant space, lower density and higher surface area
compared to the corresponding core–shell; (iii) use of PANI-
conducting polymers as anchor sites for metal ions with unique elec-
trical properties, easy preparation and high environmental stability;
(iv) providing an atom-economical catalyst containing core–shell
Ni@Pd NPs with a cheap metal core and a noble metal shell; and
(v) development of an efficient and green synthetic process for the
facile and selective catalytic reduction of nitrobenzenes.
[41] I. Pogorelić, M. Filipan-Litvić, S. Merkaš, G. Ljubić, I. Cepanec, M. Litvić,
J. Mol. Catal. A: Chem. 2007, 274, 202.
Acknowledgment
[42] R. R. Tykwinski, Angew. Chem. Int. Ed. 2003, 42, 1566.
[43] D. M. Dotzauer, S. Bhattacharjee, Y. Wen, M. L. Bruening, Langmuir
2009, 25, 1865.
We are grateful to Shahid Beheshti University Research Council
for partial financial support of this work.
Appl. Organometal. Chem. (2014)
Copyright © 2014 John Wiley & Sons, Ltd.
wileyonlinelibrary.com/journal/aoc