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Dalton Transactions
Page 7 of 9
DOI: 10.1039/C8DT01243A
Journal Name
ARTICLE
1
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comparison of the IR spectra of the used and the fresh catalyst
(Fig S10 in the ESI†), indicaꢀng that the catalyst was not
relatively stable in this system.
In the studied oxidation processes, the mechanism may be
similar to the one already reported.36 Firstly, the generation of
active species occurred by the interaction of the oxidant H2O2
with the terminal bonds WVI O that generates POM peroxo
species that can oxidize the sulfur compounds into sulfones.
Subsequently, the peroxo species transfer an oxygen atom to
the sulfur substrate and the initial WVI O is regenerated and
utilizable again to restart the catalytic cycle.
2
3
(a) S.-T. Zheng and G.-Y. Yang, Chem. Soc. Rev., 2012, 41,
7623–7646; (b) H. N. Miras, J. Yan, D.-L. Long and L. Cronin,
Chem. Soc.Rev., 2012, 41, 7403–7430; (c) S.-S. Wang and G.-
Y. Yang, Chem. Rev., 2015, 115
, 4893–4962. (d) K.
Oxidation of the organosulfur compounds in model oil
Wassermann, M. H. Dickman and M. T. Pope, Angew.Chem.,
Int. Ed. Engl., 1997, 36, 1445–1448; (e) F. Hussain, B.
Spingler, F. Conrad, M. Speldrich, P. Kögerler, C. Boskovic
and G. R. Patzke, Dalton Trans., 2009, 23, 4423–4425.
(a) C.-D. Wu, C.-Z. Lu, H.-H. Zhuang and J.-S. Huang, J.
Am.Chem. Soc., 2002, 124, 3836–3837; (b) J.-Y. Niu, M.-L.
Wei, J.-P. Wang and D.-B. Dang, Eur. J. Inorg.Chem., 2004, 1,
160–170; (c) H.-Y. An, Y.-G. Li, D.-R. Xiao, E.-B. Wang and C.-
Y. Sun, Cryst. Growth Des., 2006, 6, 1107–1112.
Based on the promising results achieved for the recalcitrant
organosulfur compounds described above, the catalytic
performance of
1 was evaluated for the oxidation of model
4
5
fuel (MF), consisting of a mixture of DBT and BT, in octane. The
reactions occurred in a CH3CN/octane (1:3) medium at room
temperature.36 The solvent mixtures are very common in this
type of study, as can be profusely found in the literature.37 Fig
S11 in the ESI† illustrates the results of the GC-FID monitoring
(a) R. D. Peacock and T. J. R. Weakley, J. Chem. Soc. A., 1971,
1836–1839; (b) M. Sadakane, A. Ostuni and M. T. Pope, J.
Chem. Soc. Dalton Trans., 2002, 1, 63–67; (c) M. Sadakane,
profile of the oxidation of MF by H2O2 in the presence of 1,
M. H. Dickman and M. T. Pope, Inorg. Chem., 2001, 40
,
after 60, 120 and 180 min of reaction. Two substrates are fully
converted into the corresponding oxidized products and, in
2715–2719; (d) J. Cao, S. Liu, R. Cao, L. Xie, Y. Ren, C. Gao and
L. Xu, Dalton Trans, 2008, 115–120; (e) C. Boglio, G. Lenoble,
C. Duhayon, B. Hasenknopf, R. Thouvenot, C. Zhang, R. C.
Howell, B. P. Burton-Pye, L. C. Francesconi, E. Lacôte, S.
Thorimbert, M. Malacria, C. Afonso and J.-C. Tabet, Inorg.
Chem., 2006, 45, 1389–1398; (f) W.-D. Wang, X.-X. Li, W.-H.
Fang and G.-Y. Yang, J. Clust. Sci., 2011, 22, 87–95; (g)B. S.
Bassil, M. H. Dickman, B. von der Kammer and U. Kortz,
Inorg. Chem., 2007, 46, 2452–2458.
J. Zhao, Q. Han, D. Shi, L. Chen, P. Ma, J. Wang and J. Niu, J.
Solid State Chem., 2011, 184, 2756–2761.
K. Wassermann, M. H. Dickman and M. T. Pope*, Angew.
Chem. 1997, 109, 1513–1516.
accordance with the above-mentioned results. The catalyst
1
seems to be more efficient for DBT oxidation. In fact, after 50
min of reaction, DBT is hardly observed in the corresponding
chromatogram, whereas the BT is still present.
Conclusions
6
7
8
9
In conclusion, catalyst
1 was synthesized by a simple and
controllable one-pot reaction system, and applied to the
oxidation of recalcitrant sulfur compounds. An efficient and
environmental friendly oxidation experiment for BT and DBT in
CH3CN catalytic system at room temperature is demonstrated.
Excellent organosulfur compound conversion values were
obtained even in high ratio of substrate to catalyst (up to
1500), but the recyclability was found to be insufficient under
F. Hussain and G. R. Patzke, CrystEngComm, 2011, 13, 530–
536.
K. Wassermann and M. T. Pope, Inorg. Chem., 2001, 40
2763–2768.
,
10 F. Hussain, F. Conrad and G. Patzke, Angew. Chem. Int. Ed.,
2009, 48, 9088–9091.
11 F. Hussain, R. W. Gable, M. Speldrich, P. Kögerler and C.
Boskovic, Chem Commun, 2009, 3, 328–330.
12 W. L. Chen, Y. G. Li, Y. H. Wang, E. B. Wang and Z. M. Su,
Dalton Trans., 2007, 38, 4293–4301.
the mild reaction conditions. The high potential of
1 for
application in ODS processes was verified through the results
achieved in the oxidation of model fuels by H2O2. These results
13 C. Ritchie, M. Speldrich, R. W. Gable, L. Sorace, P. Kögerler
and C. Boskovic, Inorg. Chem., 2011, 50, 7004–7014.
14 C. Ritchie, E. G. Moore, M. Speldrich, P. Kögerler and C.
Boskovic, Angew. Chem. Int. Ed., 2010, 49, 7702–7705.
15 S. Li, Y. Wang, P. Ma, J. Wang and J. Niu, CrystEngComm,
2014, 16, 10746–10749.
indicate that
1 is a promising heterogeneous catalyst for ODS.
In the near future, we intend to develop our studies by using
stable POM-based heterogeneous catalysts in the oxidation of
this kind of recalcitrant compounds, and also in real fuel
samples.
16 Y. Wang, X. Sun, S. Li, P. Ma, J. Wang and J. Niu, Dalton
Trans., 2015, 44, 733–738.
17 Y. Wang, X. Sun, S. Li, P. Ma, J. Niu and J. Wang, Cryst.
Growth Des., 2015, 15, 2057−2063.
Acknowledgements
18 A. M. Kirillov and G. B. Shul’pin, Coord. Chem. Rev., 2013,
257, 732–754.
We gratefully acknowledge financial support from the National
Natural Science Foundation of China and Natural Science
Foundation of Henan Province.
19 (a) R.J. Butcher, J.W. Overman and E. Sinn, J. Am. Chem. Soc.,
1980, 102, 3276−3278; (b) C.J. O’Connor, C.L. Klein, R.J.
Majeste and L.M. Trefonas, Inorg. Chem., 1982, 21, 64−67.
20 T. Ueda, K. Yamashita and A. Onda, Appl. Catal. Gen., 2014,
485, 181–187.
Notes and references
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
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