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Journal Name
PleaseRd So Cn oA t da vd aj un s ct ems argins
DOI: 10.1039/C6RA21942J
ARTICLE
disappeared in the subsequent aliquots. Thus we can say then
conversion of phenyl hydroxylamine to aniline is a kinetically
favourable step and occurs relatively fast. Surprisingly the
Chem., 2014, 16, 4493–4505.
M. B. Gawande, P. S. Branco and R. S. Varma, Chem. Soc.
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7
8
9
1
T. Aditya and T. Pal, Chem. Commun., 2015, 51, 9410–
reaction aliquot showed no peak at reference R
matching the authentic sample.
t
of azobenzene
9
431.
H. Hu, J. H. Xin, H. Hu, X. Wang, D. Miao and Y. Liu, J.
Mater. Chem. A, 2015, 3, 11157–11182.
X. Le, Z. Dong, Y. Liu, Z. Jin, T. Huy, M. Le and J. Ma, J.
Mater. Chem. A Mater. energy Sustain., 2014, 2, 19696–
For further verification the same reaction was carried out on
both the intermediates, viz; nitrosobenzene and azobenzene
separately. It was realised that within half an hour
nitrosobenzene showed 100% conversion and gave aniline as
0
1
9706.
the sole product, while azobenzene remained at only 56% 11
conversion at the end of four hours also selectively giving only
aniline as the product. Thus we decisively say that the reaction 12
J. R. Chiou, B. H. Lai, K. C. Hsu and D. H. Chen, J. Hazard.
Mater., 2013, 248-249, 394–400.
H. Lu, H. Yin, Y. Liu, T. Jiang and L. Yu, Catal. Commun.,
2
008, 10, 313–316.
R. K. Sharma, Y. Monga and A. Puri, J. Mol. Catal. A Chem.,
014, 393, 84–95.
M. Rajabzadeha, H. Eshghia, R. Khalifehb and M. Bakavolia,
RSC Adv., 2016, 19331–19340.
M. B. Gawande, Y. Monga, R. Zboril and R. K. Sharma,
Coord. Chem. Rev., 2015, 288, 118–143.
K. Pradhan, S. Paul and A. R. Das, Catal. Sci. Technol., 2014,
of nitro reduction over our catalyst proceeded via direct route
1
1
1
1
1
3
4
5
6
7
only as proposed in Scheme 2.
2
4. Conclusions
2 2 4
As per our observations, Cu/SiO @NiFe O shows much better
activity for 4-NP reduction as compared to other samples
tested. This indicated that the activity is solely due to finely
dispersed Cu on the magnetic support. Considering the
percentage of Cu present in the total amount of catalyst used
4
, 822–831.
K. Faungnawakij, R. Kikuchi, N. Shimoda, T. Fukunaga and
K. Eguchi, Angew. Chem. Int. Ed. Engl., 2008, 47, 9314–
9
317.
per test it is quite remarkable that such low quantity of 18
catalyst could give such high activity. It also could be
successfully recycled for 5 consecutive run cycles within 1 h. As 19
per the kinetic studies we obtained a very high rate constant
K. Yu, X. Zhang, H. Tong, X. Yan and S. Liu, Mater. Lett.,
2013, 106, 151–154.
Z. Sun, H. Li, G. Cui, Y. Tian and S. Yan, Appl. Surf. Sci., 2016,
360, 252–262.
-1
2
0
S. M. D. Watson, N. G. Wright, B. R. Horrocks and A.
Houlton, Langmuir, 2010, 26, 2068–2075.
Z. Zheng, J. Yu, S. Cheng, Y. Lai, Q. Zheng and D. Pan, J.
Mater. Sci. Mater. Electron., 2016, 27, 5810–5817.
R. Singh Yadav, J. Havlica, J. Masilko, L. Kalina, J.
Wasserbauer, M. Hajdúchová, V. Enev, I. Kuřitka and Z.
Kožáková, J. Magn. Magn. Mater., 2015, 394, 439–447.
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Mathe and a. K. Das, J. Alloys Compd., 2011, 509, 4404–
4413.
of 0.325 min with just 10.58 μg Cu (3.48 ppm Cu) in the
catalyst which is noteworthy.
-
1
21
Even the obtained Eact for the system of 30.4 K J mol is
remarkably low. To the best of our knowledge the obtained
2
2
2
3
-
1
-1
activity factor of 0.511 sec mg is by far the lowest for any
non-noble metal catalyst for the said reaction. Given the fact
that nitroso-benzene could be traced as being formed as the
intermediate during the reduction of nitrobenzene, a well-
established mechanistic pathway could be assigned with
authorization for the course of the reduction process. Hence 24
A. A. Vernekar, S. Patil, C. Bhat and S. G. Tilve, RSC Adv.,
2
013, 3, 13243–13250.
we hereby report non-noble and comparatively inexpensive
2
2
2
2
2
3
5
6
7
8
9
0
S. Wunder, F. Polzer, Y. Lu, Y. Mei and M. Ballauff, J. Phys.
Chem. C, 2010, 114, 8814–8820.
J. Li, C. Liu and Y. Liu, J. Mater. Chem., 2012, 22, 8426–
2 2 4
Cu/SiO @NiFe O as a novel catalytic system for 4-NP
reduction with high k, low Eact and highest K reported till date,
as well as a methodology which could very well be classified as
green, highly efficient as well as an economical protocol for
nitroarene reduction in general.
8
430.
Y. Sun, L. Xu, Z. Yin and X. Song, J. Mater. Chem. A, 2013, 1,
2361–12370.
1
S. J. Hoseini, M. Rashidib and M. Bahramia, J. Mater.
Chem., 2011, 21, 16170–16176.
J. Zhang, G. Chen, M. Chaker, F. Rosei and D. Ma, Appl.
Catal. B Environ., 2013, 132-133, 107–115.
Acknowledgements
Authors thank UGC-BSR for financial assistance.
X. Wu, X. Wu, J. Shen and H. Zhang, RSC Adv., 2014, 4,
4
9287–49294.
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