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A.K.M.L. Rahman et al. / Catalysis Communications 12 (2011) 1198–1200
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12
8
80
60
40
20
0
Yield (%)
Scheme 1. Proposed pathway for synthesis of formic acid from partial oxidation of
methane.
Selectivity (%)
Appendix A. Supplementary data
4
Supplementary data to this article can be found online at
doi:10.1016/j.catcom.2011.04.001.
0
100
200
300
Amount of H2O2 (mmol)
References
Fig. 3. Yield and selectivity of HCOOH as a function of the amount of H2O2.
[1] R.A. Periana, D.J. Taube, E.R. Evitt, D.G. Loffler, P.R. Wentrcek, G. Voss, T. Masuda,
Science 259 (1993) 340–343.
[2] R.A. Periana, D.J. Taube, S. Gamble, H. Taube, T. Satoh, H. Fujii, Science 280 (1998)
560–564.
[3] N. Basickes, T.E. Hogan, A. Sen, J. Am. Chem. Soc. 118 (1996) 13111–13112.
[4] K. Nakata, Y. Yamaoka, T. Miyata, Y. Taniguchi, K. Takaki, Y. Fujiwara, J. Organomet.
Chem. 473 (1994) 329–334.
[5] D.G. Piao, K. Inoue, H. Shibasaki, Y. Taniguchi, T. Kitamura, Y. Fujiwara, J. Organomet.
Chem. 574 (1999) 116–120.
[6] M. Asadullah, T. Kitamura, Y. Fujiwara, Angrew. Chem. Int. Ed. 39 (2000)
2475–2478.
[7] T. Osako, E.J. Watson, A. Dehestani, B.C. Bales, J.M. Mayer, Angew Chem, Int. Ed. 45
(2006) 7433–7436.
[8] G. Suss-Fink, S. Stanislas, G.B. Shul'pin, G.V. Nizova, Appl. Organometal. Chem. 14
(2000) 623–628.
[9] G.V. Nizova, B. Krebs, G. Suss-Fink, S. Schindler, L. Westerheide, L.G. Cuervo, G.B.
Shul'pin, Tetrahedron 58 (2002) 9231–9237.
[10] G.B. Shul'pin, G.V. Nizova, Y.N. Kozlov, L.G. Cuervo, G. Suss-Fink, Adv. Synth. Catal.
346 (2004) 317–332.
[11] Q. Yuan, W. Deng, Q. Zhang, Y. Wang, Adv. Synth. Catal. 349 (2007) 1199–1209.
[12] A.B. Sorokin, E.V. Kudrik, D. Bouchu, Chem. Commun. (Camb). 22 (2008)
2562–2564.
[13] G.V. Nizova, G. Suss-Fink, G.B. Shul'pin, Tetrahedron 53 (1997) 3603–3614.
[14] A.O. Kuzmin, G.L. Elizarova, L.G. Matvienko, E.R. Savinova, V.N. Parmon,
Mendeleev Communications Electronic Version 6 (1998) 207–208.
[15] J.S. Min, H. Ishige, M. Misono, N. Mizuno, Journal of Catalysis 198 (2001) 116–121.
[16] Y. Seki, J.S. Min, M. Misono, N. Mizuno, J. Phys. Chem. B 104 (2000) 5940–5944.
[17] S. Han, D.J. Martenak, R.E. Palermo, J.A. Pearson, D.E. Walsh, Journal of Catalysis
136 (1992) 578–583.
[18] D.E. Walsh, S. Han, R.E. Palermo, J. Chem. Soc., Chem. Commun. (1991) 1259–1260.
[19] K.X. Wang, H.F. Xu, W.S. Li, C.T. Au, X.P. Zhou, Applied Catalysis A: General 304
(2006) 168–177.
Yield increases with increasing amounts of H2O2, reaches a maximum
of 13.0% with a selectivity of 66.8% at 121.88 mmol of H2O2, and
decreases slightly at higher amounts of H2O2 because of oxidation of
HCOOH with H2O2 or gaseous O2. Under the reaction conditions used,
the decomposition of H2O2 is 98% with the efficiency to produce
HCOOH of 14.0%, estimated by mole of HCOOH per mole of H2O2 with
subtraction of the O2 produced from initial amount of H2O2. On the
other hand, selectivity decreases gradually with increasing H2O2
amounts.
Acetaldehyde (CH3CHO) and CH3OH were observed by GC–MS in
the reaction product. Larger amounts of CH3CHO were associated with
larger amounts of HCOOH product obtained. HCOOH has been
speculated to form by the oxidation of CH3CHO [22]. Bar-Nahun et
al. [23] reported that CH4 can be transformed to CH3CHO via CH3OH.
Therefore, the CH3COOH obtained in our experiments might be from
further oxidation of CH3CHO. CH3OH is considered to be the
intermediate product in direct methane oxidation [16, 17]. Although
reaction mechanism on H-ZSM-5 is not clear in details, however,
CH3OH might be a possible intermediate in synthesis of HCOOH.
Considering the fairly large amount of CO2 formed, we tentatively
propose Scheme 1 for reaction pathways on H-ZSM-5 catalyst.
Anyway it could be proposed that the strong solid acid of H-ZSM-5
is highly active in synthesis of HCOOH by direct partial oxidation of
CH4 using H2O2 as oxidant.
[20] Y. Fan, M. Ding, X. Bao, Catal. Lett. 130 (2009) 286–290.
[21] H.K. Farizul, N.A.S. Amin, D. Suhardy, A.S. Saiful, S.M. Nazry, Jurnal Teknologi,
Keluaran Khas. Dis 47 (2007) 55–67.
[22] J.B. Conant, C.O. Tongberg, Converse Memorial Laboratory of Harvard University,
Acknowledgements
[23] I. Bar-Nahum, A.M. Khenkin, R. Neumann, J. Am. Chem. Soc. 126 (2004)
10236–10237.
We gratefully acknowledge the financial support of the Nano
Environmental Catalyst Project from the Ministry of Education,
Culture, Sports, Science and Technology, (MEXT) Japan.