Abstract
Molybdenum blue (MB), is a polyoxometalate with a nanoring structure comprising Mo5+–O–Mo6+ bridges, which is active for the catalytic oxidation of cyclohexane to cyclohexanol and cyclohexanone. However, little is known about the mechanistic features responsible of this catalytic activity. In the present work, the Mo5+–O–Mo6+ moieties embedded in the MB nanoring structure were characterized using diffuse reflectance-UV–Visible spectroscopy and solid state EPR spectroscopy. The amount of Mo5+ centres was then varied by thermal treatment of the polyoxometalate in the absence of oxygen, and the resultant effect on the catalytic activity was investigated. It was observed that, an increased amount of Mo5+ centres preserved the conversion of cyclohexane (ca. 6 %) but led to a loss of selectivity to cyclohexanol giving cyclohexanone as the major product, and the simultaneous formation of adipic acid. To rationalise these results the catalysts were studied using EPR spin trapping to investigate the decomposition of cyclohexyl hydroperoxide (CHHP), a key intermediate in the oxidation process of cyclohexane. This analysis showed that CHHP has to be bound to the MB surface in order to explain its catalytic activity and product distribution.
Graphical Abstract
Similar content being viewed by others
References
He Z, Honeycutt C (2005) Commun Soil Sci Plan 36:1373
Deng SP, Tabatabai MA (1994) Soil Biol Biochem 26:473
Müller A, Meyer J, Krickemeyer E, Diemann E (1996) Angew Chem Int Ed 35:1206
Müller A, Serain C (2000) Acc Chem Res 33:2
Xuan W, Surman AJ, Miras HN, Long DL, Cronin L (2014) J Am Chem Soc 136:14114
Long DL, Tsunashima R, Cronin L (2010) Angew Chem Int Ed 49:1736
Miras HM, Richmond CJ, Long DL, Cronin L (2012) J Am Chem Soc 134:3816
Zhong D, Sousa FL, Müller A, Chi L, Fuchs H (2011) Angew Chem Int Ed 50:7018
Liu X, Conte M, Weng W, He Q, Jenkins RL, Watanabe M, Knight DW, Murphy DM, Whiston K, Kiely CJ, Hutchings GJ (2015) Catal Sci Technol 5:217
Vanoppen DL, De Vos DE, Genet MJ, Rouxhet PG, Jacobs PA (1995) Angew Chem Int Ed 34:560
Guo CC, Chu MF, Liu Q, Liu Y, Guo DC, Liu XQ (2003) Appl Catal A 246:303
Kumar R, Sithambaram S, Suib SL (2009) J Catal 262:304
Dapurkar SE, Sakthivel A, Selvam P (2004) J Mol Catal A 223:241
Hereijgers BPC, Weckhuysen BM (2010) J Catal 270:16
Ressler T, Walter A, Huang ZD, Bensch W (2008) J Catal 254:170
Conte M, Chechik V (2010) Chem Commun 46:3991
Langhals H (2000) Spectrochim Acta A 56:2207
Leandri R (2001) J. Chemometrics 15:559
Alper JS, Gelb RI (1990) J Phys Chem 94:4741
Simulations were carried out using WinSim software: http://www.niehs.nih.gov/research/resources/software/tox-pharm/tools/index.cfm
Conte M, Ma Y, Loyns C, Price P, Rippon D, Chechik V (2009) Org Biomol Chem 7:2685
Walling C, Buckler SA (1955) J Am Chem Soc 77:6032
Labanowska M (1999) Phys Chem Chem Phys 1:5385
Qiu H, Xu T, Wang Z, Ren W, Nan H, Ni Z, Chen Q, Yuan S, Miao F, Song F, Long G, Shi Y, Sun L, Wang J, Wang X (2013) Nat Commun 4:2642
Dyrek K, Che M (1997) Chem Rev 97:305
Bugayev AA, Nikitin SE (2000) Opt Commun 180:69
Glover SD, Kubiak CP (2011) J Am Chem Soc 133:8721
Brunschwig BS, Creutz C, Sutin N (2000) Chem Soc Rev 31:168
Canzi G, Goeltz JC, Henderson JS, Park RE, Maruggi C, Kubiak CP (2014) J Am Chem Soc 136:1710
Chithambararaj A, Sanjini NS, Velmathi S, Bose AC (2013) Phys Chem Chem Phys 15:14761
Hussain Z (2001) J Mater Res 16:2695
Uemura T, Ohba M, Kitagawa S (2004) Inorg Chem 43:7339
He T, Yao J (2003) J Photochem Photobiol C 4:125
Chudnovskii FA, Schaefer DM, Gavrilyuk AI, Reifenberger R (1992) Appl Surf Sci 62:145
Ganduglia-Pirovano MV, Hofmann A, Sauer J (2007) Surf Sci Rep 62:219
Torok B, Torok M, Rozsa-Tarjani M, Palinko I, Horvath LI, Kiricsi I, Molnar A (2000) Inorg Chim Acta 298:77
Catoire B (ed) (1992) Electron spin resonance (ESR) applications in organic and bioorganic materials. Springer, Berlin, p 190
Berliner L (ed) (2003) In Vivo EPR (ESR): Theory and Application in Biologic Magnetic resonance. Kluwr/Plenum publishers, New York, p 442
Chiesa M, Giamello E, Che M (2010) Chem Rev 110:1320
Liu X, Ryabenkova Y, Conte M (2015) Phys Chem Chem Phys 17:715
Partenheimer W (1995) Catal Today 23:69
Hermans I, Jacobs PA, Peeters J (2006) Chem Eur J 12:4229
Weinstein J, Bielski BHJ (1979) J Am Chem Soc 101:58
Tanase S, Bouwman E, Reedijk J (2004) Appl Catal A 259:101
Ramanathan A, Hamdy MS, Parton R, Maschmeyer T, Jansen JC, Hanefeld U (2009) Appl Catal A 355:78
Hmady MS, Ramanathan A, Maschmeyer T, Hanefled U, Jansen JC (2006) Chem Eur J 12:1782
Conte M, Miyamura H, Kobayashi S, Chechik V (2009) J Am Chem Soc 131:7189
Conte M, Wilson K, Chechik V (2007) Org Biomol Chem 7:1361
Novak M, Brodeur BA (1984) J Org Chem 49:1142
Baum SL, Anderson IGM, Baker RR, Murphy DM, Rowlands CC (2003) Anal Chim Acta 481:1
Davies MJ, Slater TF (1986) Biochem J 240:789
Janzen EG, Evans CA, Liu JP (1973) J Magn Reson 9:513
Conte M, Wilson K, Chechik V (2010) Rev Sci Instrum 81:104102
Ionita P, Conte M, Gilbert BC, Chechik V (2007) Org Biomol Chem 5:3504
Conte M, Liu X, Murphy DM, Whiston K, Hutchings GJ (2012) Phys Chem Chem Phys 14:16279
Silke EJ, Pitz WJ, Westbrook CK, Ribaucour M (2007) J Phys Chem A 111:3761
Lee SO, Raja R, Harris KDM, Thomas JM, Brian BFG, Sankar G (2003) Angew Chem Int Ed 42:1520
Jensen RK, Korcek S, Mahoney LR, Zinbo M (1981) J Am Chem Soc 103:1742
Modén B, Zhan BZ, Dakka J, Santiesteban JG, Iglesia E (2006) J Catal 239:390
Stark MS (2002) J Am Chem Soc 122:4162
Acknowledgments
The authors wish to acknowledge the support of INVISTA Textiles (UK) Limited, INVISTA Intermediates and INVISTA Technologies S. à r. l.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Conte, M., Liu, X., Murphy, D.M. et al. Insights into the Reaction Mechanism of Cyclohexane Oxidation Catalysed by Molybdenum Blue Nanorings. Catal Lett 146, 126–135 (2016). https://doi.org/10.1007/s10562-015-1660-y
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10562-015-1660-y