Supporting Information Wiley-VCH 2007 69451 Weinheim, Germany
Aluminum Siting in Silicon-rich Zeolite Frameworks. A Combined High Resolution 27 Al NMR and QM/MM Study of ZSM-5 Stepan Sklenak,* Jiří Dědeček, Chengbin Li, Blanka Wichterlová, Vendula Gábová, Marek Sierka, and Joachim Sauer* * Dr. S. Sklenak, Dr. J. Dědeček, Dr. C. Li, Dr. B. Wichterlová, Dr. V. Gábová; J. Heyrovsky Institute of Physical Chemistry of the Academy of Sciences of the Czech Republic, v.v.i., Dolejskova 3, 182 23 Prague, Czech Republic E-mail: stepan.sklenak@jh-inst.cas.cz Dr. M. Sierka, and Prof. J. Sauer Humboldt-Universität zu Berlin, Institut für Chemie, Unter den Linden 6, 10099 Berlin E-mail: qc.sek@chemie.hu-berlin.de 1
Table S1. Chemical composition of the Na-ZSM-5 samples, framework Si/Al ratio (Si/Al FR ) estimated from 29 Si MAS NMR spectra, maximum exchange capacity of the samples for [Co 2+ (H 2 O) 6 ] 2+ complex (Co MAX /Al), structure directing agent and aluminum, silicon and sodium sources used for the synthesis of the zeolite samples. zeolite Si/Al Na/Al Si/Al FR Co MAX /Al structure directing agent* Na-ZSM-5/A 14.5 0.95 15 0.04 TPA Na-ZSM-5/B 44.0 0.99 45 0.07 Al source Si source Na source mmol/100g Al(NO 3 ) 3 Na-ZSM-5/C 34 1.02 35 0.06 TPA Na-ZSM-5/D 26.0 0.90 25 # 0.13 TPA Na-ZSM-5/E 15.0 1.01 15 0.12 TPA Li-ZSM-5/E 15.2 0.02 15 - H-ZSM-5/E 15.0 0.02 15 - Al isopropoxide NaOH 56 Na-ZSM-5/F 26.0 0.84 25 # 0.15 TPA Na-ZSM-5/G 15.1 0.77 15 0.02 TPA Na-ZSM-5/H 22.5 1.02 25 0.12 Sodium silicate NaOH 6 Na-ZSM-5/I 34.0 0.98 35 0.01 TPA Na-ZSM-5/J 25.0 0.92 26 0.03 TPA bromide Na-ZSM-5/K 13.8 0.98 14 0.11 Na 2 CO 3 56 Na-ZSM-5/B was purchased from Conteca, Na-ZSM-5/H was provided by the Institute of Oil and Hydrocarbon Gases, Slovnaft and ZSM-5/K by the Research Institute of Inorganic Chemistry Inc., Unipetrol Li/Al = 0.97 * TPA tetrapropylammonium # The slightly lower Si/Al FR value compared to Si/Al indicates the limited accuracy of the NMR estimate 2
Synthesis and Characterization XRD, KBr-FTIR and SEM indicated good crystallinity of calcined ion exchanged samples. Moreover, FTIR characterization of acid sites via adsorption of d 3 -acetonitrile as well as 29 Si MAS NMR indicated a negligible amount of extraframework Al atoms. NMR experiments were carried out on a Bruker Avance 500 MHz (11.7 T) Wide Bore spectrometer using 4 mm o.d. ZrO 2 rotors. The two-pulse z-filtered 27 Al 3Q MAS NMR experiments were applied with a π excitation pulse and a π/3 conversion. The aqueous solution of Al(NO 3 ) 3 was used as reference. Table S2. Effect of the counter cations on the 27 Al NMR parameters of the three resonances a of ZSM-5/E zeolite determined from 3Q MAS NMR spectra. Resonance a NMR parameter (ppm) counter cation Na Li H δ F1 54.9 55.0 54.8 III δ F2 52.3 52.3 52.4 δ iso 53.9 54.0 53.9 δ F1 57.1 57.2 57.2 V δ F2 55.6 55.7 55.4 δ iso 56.5 56.6 56.5 δ F1 64.5 64.3 64.6 X δ F2 62.0 62.4 61.7 δ iso 63.6 63.6 63.5 a see Table 1. 3
Computational Part Full reference for Ref. [29] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. Montgomery, J. A., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, J. A. Pople, Gaussian 03, Revision C.02, Gaussian, Inc., Wallingford CT, 2004. 4
Table S3. BLYP GIAO 27 Al NMR shieldings (ppm) and isotropic shifts a (ppm) and average Al-O-Si angles (deg.) for the individual T sites of ZSM-5 T site shielding shift Al-O-Si T site shielding shift Al-O-Si 1 486.3 63.7 143.5 13 490.3 59.7 144.4 2 492.9 57.1 144.8 14 490.7 59.3 142.4 3 488.3 61.7 140.3 15 492.4 57.6 153.5 4 496.6 53.4 151.4 16 492.9 57.1 144.0 5 491.4 58.6 144.7 17 487.5 62.5 140.8 6 494.9 55.1 150.5 18 488.0 62.0 145.2 7 490.0 60.0 143.3 19 490.5 59.5 142.5 8 496.7 53.3 149.1 20 499.3 50.7 154.3 9 491.8 58.2 144.3 21 493.0 57.0 148.2 10 492.3 57.7 146.1 22 491.0 59.0 141.9 11 493.3 56.7 146.6 23 492.8 57.2 145.8 12 489.2 60.8 143.2 24 485.2 64.8 139.8 a The 27 Al NMR isotropic shifts were obtained by a conversion of the BLYP GIAO shieldings using the calculated and measured shielding/shift values 490.0 ppm and 60.0 ppm, respectively, for the chabazite sample (Si/Al = 35). GIAO 27 Al isotropic cheical shift (ppm) 64 60 56 52 R = -0.82 SD = 1.97 140 144 148 152 156 average T-O-T angle (degrees ) Figure S1. GIAO 27 Al isotropic shifts plotted against the average T-O-T angles for the 24 T sites of ZSM-5. 5