The hydrogenolysis of N-benzylcyclohexylamine (NBCA) was carried out at low temperature and pressure using series of Pd/SiO2 catalysts having Pd contents between 0.5 and 10%. Three different silica supports were used, two of them having pore diameters of 60A and 40A and one an amorphous material. In the hydrogenolysis of NBCA over the Pd/SiO2 (60A) series of catalysts there was a slight increase in the reaction rate on gong from the 10% Pd to the 2% Pd catalysts. This was followed by significant rate increases using the 1% Pd, 0.75% Pd and 0.5% Pd catalysts. It is proposed that this unexpectedly large rate increase observed using the catalysts having the smallest Pd particles was the result of a true ‘nano effect’. The rates of debenzylations run over the Pd/SiO2 (40A) series of catalysts steadily increased with the use of the 10% Pd to the 2% Pd catalysts, a trend observed for some Structure Sensitive reactions, though, in this case, there was also a rate decrease using the 1% Pd catalyst even though the Pd particles in this catalyst were smaller than the others. No relationship was observed between reaction rate and Pd composition of the amorphous silica supported catalysts. It is commonly accepted that the nano effect is the result of an interaction between the small catalyst particles and the support so the electronic character of the support could have an influence on the surface electrons of the catalyst and, thus, modify its reaction capabilities.
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Connor R, Adkins H (1932) J Am Chem Soc 54:4678
Augustine RL (1996) Heterogeneous catalysis for the synthetic chemist. Marcel Dekker Inc, New York
Bremner JGM, Keeys RKF (1949) J Chem Soc 1663
Lukes RM, Wilson CL (1951) J Am Chem Soc 73:4790
Bonner WA, Zderic JA (1956) J Am Chem Soc 78:3218
Garbisch EW Jr, Schreader L, Frankel JJ (1967) J Am Chem Soc 89:4233
Murchu CO (1969) Tetrahedron Lett 3231
Khan AM, McQuilin FJ, Jardine I (1967) J Chem Soc (C) 136
Mitsui S, Inoue N, Kasahara A (1951) Nippon Kagaku Zasshi 71:203
Mitsui S, Imaizumi S (1961) Bull Chem Soc 34:774
Mitsui S, Senda Y, Konno, K (1963) Chem Ind 1354
Mitsui S, Imaizumi S (1963) Bull Chem Soc 36:855
Kieboom APG, De Kreuk JF, Van Bekkum H (1971) J Catal 20:58
Harvey FM, Bochet CG (2020) J Org Chem 85:7511
Smith GV, Roth JA (1966) J Am Chem Soc 88:3879
Sandee AJ, Chintada TJ, Groen C, Donkervoort JG, Terorde RJAM (2013) Chim Oggi 31:20
Pitchai R, Wong SS, Takahashi N, Butt JB, Burwell RL Jr, Cohen JB (1985) J Catal 94:478
Ostgard D, Notheisz F, Zsigmond AG, Smith GV, Bartok M (1991) J. Catal. 129:519
Boudjahem AG, Bouderbala W, Soltani A (2013) Metal Org Nano Metal Chem 43:1397
Boudjahem A-G, Redjel A, Mokrane T (2012) J Indus Eng Chem 18:303
Wilson OM, Knecht MR, Garcia-Martinez JC, Crooks RM (2006) J Am Chem Soc 128:4510
Ruta M, Semegina N, Kiwi-Minsker L (2008) J Phys Chem C 112:13635
Borodzinski A (2001) Catal Lett 71:169
Weerachawanasak P, Mekasuwandumrong O, Arai M, Fujita S-I, Praserthdam P, Panpranot J (2009) J Catal 262:199
Hu J, Zhou Z, Zhang R, Li L, Cheng Z (2014) J Mol Catal A Chem 381:61
Tardy B, Noupa C, Leclercq C, Bertolini JC, Hoareau A, Treileuz M, Faure JP, Nihoul G (1991) J Catal 129:1
Albano G, Evangelisti C, Aronica LA (2017) Chem Select 2:384
Bond GC, Sermon PA, Webb G, Buchanan DA, Wells PB (1973) Chem Commun 444
Mekasuwandumrong O, Somboonthanaki S, Praserthdam P, Panpranot J (2009) J Ind Eng Chem Res 48:2819
Meschke RW, Hartung WH (1960) J Org Chem 25:137
Campbell CT (2012) Nat Chem 4:597
Bruix A, Rodriguez JA, Ramírez PJ, Senanayak SD, Evans J, Park JB, Stacchiola D, Liu P, Hrbek J, Illas F (2012) J Am Chem Soc 134:8968
Figueras F, Gomez R, Primet M (1973) Adv Chem 121:480
Bond GC (1985) Surf Sci 156:966
Telkar MM, Rode CV, Chaudhari RV, Joshi SS, Nalawade AM (2001) Appl Catal A 273:11
Augustine RL, Thompson MM (1987) J Org Chem 52:1911
Augustine RL, Warner RW (1983) J Catal 80:358
Augustine RL, Warner RW, Melnick MJ (1984) J Org Chem 49:4853
Moss RL, Pope D, Davis BJ, Edwards DH (1979) J Catal 58:206
Numwong N, Prabnasak P, Prayoonpunratn P, Triphatthanaphong P, Sooknoi T (2020) Fuel Process Technol 203:106393
Yang F, Deng D, Pan X, Fu Q, Bao X (2015) Natl Sci Rev 2:183
Tanielyan SK, Alvez G, Marin N, Augustine RL (2014) Top Catal 57:1359
We thank Prof. Alex Fadeev of the department of Chemistry and Biochemistry at Seton Hall University for providing the nitrogen adsorption derived pore volume.
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Augustine, R.L., Tanielyan, S.K., Bhagat, R. et al. Hydrogenolysis of N-Benzylcyclohexylamine: A Support Specific ‘Nano Effect’. Catal Lett (2021). https://doi.org/10.1007/s10562-021-03536-5
- Nano effect
- Support effect