J. Zakzeski et al. / Applied Catalysis A: General 394 (2011) 79–85
85
veratryl alcohol conversion, are given in Fig. 10. Despite a discol-
oration of the catalyst possibly attributable to the formation of
coke-like species, the Co-ZIF-9 catalyst showed no apparent deac-
tivation even after the 3rd recycle.
After 12 h of reaction in the presence of Co-ZIF-9 (with added
NaOH), the colorless toluene turned slightly yellow. This coloration
can be attributed to toluene itself being slightly reactive towards
the catalytic system under reaction conditions, and two products
of its oxidation, benzyl alcohol and benzaldehyde, were found in
trace quantities (< 0.1%) after 4 h. The formation of the aldehyde
likely occurs from oxidation of the benzyl alcohol [37]. No benzoic
acid was detected.
[2] A.M. Romano, M. Ricci, J. Mol. Catal. A: Chem. 120 (1997) 71–74.
[3] P. Li, H. Alper, J. Mol. Catal. 72 (1992) 143–152.
[4] K. Kervinen, M. Allmendinger, M. Leskelä, T. Repo, B. Rieger, Phys. Chem. Chem.
Phys. 5 (2003) 4450–4454.
[5] K. Kervinen, H. Korpi, J.G. Mesu, F. Soulimani, T. Repo, B. Rieger, M. Leskelä, B.M.
Weckhuysen, Eur. J. Inorg. Chem. 13 (2005) 2591–2599.
[6] J. Zakzeski, A.L. Jongerius, B.M. Weckhuysen, Green Chem. 12 (2010)
1225–1236.
[7] J. Zakzeski, P.C.A. Bruijnincx, B.M. Weckhuysen, Green Chem. (2011),
doi:10.1039/C0GC00437E.
[8] A. Phan, C. Doonan, F.J. Uribe-Romo, C.B. Knobler, M. O’Keeffe, O.M. Yaghi, Acc.
Chem. Res. 43 (2009) 58–67.
[9] R. Banerjee, A. Phan, B. Wang, C. Knobler, H. Furukawa, M. O’Keeffe, O.M. Yaghi,
Science 319 (2008) 939–943.
[10] D. Farrusseng, S. Aguado, C. Pinel, Angew. Chem. Int. Ed. 48 (2009)
7502–7513.
[11] K.S. Park, Z. Ni, A.P. Cote, J.Y. Choi, R. Huang, F.J. Uribe-Romo, H.K. Chae, M.
O’Keeffe, O.M. Yaghi, Proc. Natl. Acad. Sci. U.S.A. 103 (2006) 10186–10191.
[12] Y. Li, F. Liang, H. Bux, W. Yang, J. Caro, J. Membr. Sci. 354 (2010) 48–54.
[13] B. Wang, A.P. Cote, H. Furukawa, M. O’Keeffe, O.M. Yaghi, Nature 453 (2008)
207–211.
[14] A. Phan, C.J. Doonan, F.J. Uribe-Romo, C.B. Knobler, M. O’Keeffe, O.M. Yaghi, Acc.
Chem. Res. 43 (2010) 58–67.
[15] W. Morris, C.J. Doonan, H. Furukawa, R. Banerjee, O.M. Yaghi, J. Am. Chem. Soc.
130 (2008) 12626–12627.
[16] H.-L. Jiang, B. Liu, T. Akita, M. Haruta, H. Sakurai, Q. Xu, J. Am. Chem. Soc. 131
(2009) 11302–11303.
[17] J.Y. Lee, O.K. Farha, J. Roberts, K.A. Scheidt, S.B.T. Nguyen, J.T. Hupp, Chem. Soc.
Rev. 38 (2009) 1450–1459.
[18] A. Corma, H. Garcia, F.X. Llabrés, I. Xamena, Chem. Rev. 110 (2010)
4606–4655.
[19] F.X. Llabrés i Xamena, A. Abad, A. Corma, H. Garcia, J. Catal. 250 (2007)
294–298.
[20] C.N. Kato, M. Hasegawa, T. Sato, A. Yoshizawa, T. Inoue, W. Mori, J. Catal. 230
(2005) 226–236.
[21] F.X. Llabrés i Xamena, O. Casanova, R. Galiasso Tailleur, H. Garcia, A. Corma, J.
Catal. 255 (2008) 220–227.
[22] P. Bovicelli, A. Sanetti, R. Bernini, Tetrahedron 530 (1997) 9755–9760.
[23] R. Bourbonnais, M.G. Paice, Biochem. J. 255 (1988) 445–450.
[24] K.B. Lee, M.B. Gu, S.-H. Moon, Eng. Life Sci. 6 (2001) 238–245.
[25] P.J. Harvey, H.E. Schoemaker, J.M. Palmer, FEBS 195 (1986) 243–246.
[26] K. Kervinen, P. Lathinen, T. Repo, M. Svahn, M. Leskelä, Catal. Today 75 (2002)
183–188.
[27] J.J. Bozell, B.R. Hames, D.R. Dimmel, J. Org. Chem. 60 (1995) 2398–2404.
[28] N. Dimitratos, A. Villa, D. Wang, F. Porta, D. Su, L. Prati, J. Catal. 244 (2006)
113–121.
4. Conclusions
Co-ZIF-9 can be effectively used as a heterogeneous catalyst for
the oxidation of several small aromatic molecules in the presence of
molecular oxygen. After 20 min under reaction conditions, nearly
complete phthalan conversion was obtained to yield three prod-
ucts, consisting of phthalide, phthalaldehyde, and small amounts
of phthalic acid. In addition to phthalan, the alcohol functional-
ity of vanillyl alcohol, veratryl alcohol, and cinnamyl alcohol was
also similarly oxidized to yield the corresponding aldehydes in high
yields and excellent selectivity. UV–vis absorption spectroscopy
and ICP analysis performed on the hot filtered reaction mixture
confirmed the heterogeneous nature of the Co-ZIF-9 material. The
catalyst was stable under the reaction conditions employed, as sup-
ported by TGA analysis; however, temperatures in excess of 560 K
lead to the decomposition of the catalyst framework. Although the
principle framework structure remained intact during reactions,
long-range reordering of the catalyst occurred as determined by
XRD analysis. The reaction rates were significantly enhanced in the
presence of NaOH, which was not ultimately consumed during the
course of the reaction. Co-ZIF-9 materials thus represent an attrac-
tive alternative to homogeneous catalysts for similar oxidations.
[29] M. Musawir, P.N. Davey, G. Kelly, I.V. Kozhevnikov, Chem. Commun. (2003)
1414–1415.
[30] T.L. Stuchinskaya, I.V. Kozhevnikov, Catal. Commun 4 (2003) 417–422.
[31] A. Abad, C. Amela, A. Corma, H. Garcia, Chem. Commun. (2006)
3178–3180.
[32] A. Abad, P. Concepcion, A. Corma, H. Garcia, Angew. Chem. Int. Ed. 44 (2005)
4066–4069.
[33] J.-D. Grunwaldt, C. Keresszegi, T. Mallat, A. Baiker, J. Catal. 213 (2003) 291–295.
[34] V.O. Sippola, A.O.I. Krause, J. Mol. Catal. A: Chem. 194 (2003) 89–97.
[35] K. Kervinen, M. Allmendiger, M. Leskelä, T. Repo, B. Rieger, Phys. Chem. Chem.
Phys. 5 (2003) 4450–4454.
Acknowledgements
JZ gratefully thanks the National Science Foundation Interna-
tional Research Fellowship Program for support of this research
under Award No. 0856754. AD thanks the Erasmus Programme for
financial support.
References
[36] J.P. Lourenco, M.F. Ribeiro, F.R. Ribeiro, Zeolites 18 (1997) 398–407.
[37] K.R. Sheddon, A. Stark, Green Chem. 4 (2002) 119–123.
[1] J. Zakzeski, P.C.A. Bruijnincx, A.L. Jongerius, B.M. Weckhuysen, Chem. Rev. 110
(2010) 3552–3599.