The successful synthesis of hierarchically structured titanium silicalite-1 (TS-1) with large intracrystalline macropores by steam-assisted crystallisation of mesoporous silica particles is reported. The macropore topology was imaged in 3D by using electron tomography and synchrotron radiation-based ptychographic X-ray computed tomography, revealing interconnected macropores within the crystals accounting for about 30 % of the particle volume. The study of the macropore formation mechanism revealed that the mesoporous silica particles act as a sacrificial macropore template during the synthesis. Silicon-to-titanium ratio of the macroporous TS-1 samples was successfully tuned from 100 to 44. The hierarchically structured TS-1 exhibited high activity in the liquid phase epoxidation of 2-octene with hydrogen peroxide. The hierarchically structured TS-1 surpassed a conventional nano-sized TS-1 sample in terms of alkene conversion and showed comparable selectivity to the epoxide. The flexible synthesis route described here can be used to prepare hierarchical zeolites with improved mass transport properties for other selective oxidation reactions.

Department of Physical and Macromolecular Chemistry Charles University Hlavova 8 128 43 Prague 2 Czech Republic

Department Physik Universität Hamburg Luruper Chaussee 149 22761 Hamburg Germany

Deutsches Elektronen Synchrotron DESY Notkestraße 85 22607 Hamburg Germany

Institute for Chemical Technology and Polymer Chemistry Karlsruhe Institute of Technology Engesserstr 20 76131 Karlsruhe Germany

Institute of Catalysis Research and Technology Karlsruhe Institute of Technology Hermann von Helmholtz Platz 1 76344 Eggenstein Leopoldshafen Germany

Institute of Chemical Reaction Engineering University of Erlangen Nuremberg Egerlandstr 3 91058 Erlangen Germany

Institute of Micro and Nanostructure Research University of Erlangen Nuremberg Cauerstr 6 91058 Erlangen Germany

J Heyrovsky Institute of Physical Chemistry Czech Academy of Sciences Dolejškova 2155 3 18223 Prague 8 Czech Republic

Johnson Matthey Catalysts GmbH Bahnhofstr 43 96257 Redwitz Germany

Johnson Matthey Technology Centre PO Box 1 Belasis Avenue Billingham TS23 1LB UK

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M. Taramasso, G. Perego, B. Notari, Google Patents, 1983.

J. Přech, Catal. Rev. 2018, 60, 71-131.

P. Bassler, M. Weidenbach, H. Goebbel, Mech. Chem. Eng. Trans. 2010, 21, 571-576;

P. Roffia, G. Leofanti, A. Cesana, M. Mantegazza, M. Padovan, G. Petrini, S. Tonti, P. Gervasutti, in Studies in Surf. Sci. and Catalysis, Vol. 55 (Eds.: G. Centi, F. Trifiro), Elsevier, Amsterdam, 1990, pp. 43-52.

J. Jiang, J. Yu, A. Corma, Angew. Chem. Int. Ed. 2010, 49, 3120-3145;

Angew. Chem. 2010, 122, 3186-3212.

L.-H. Chen, X.-Y. Li, J. C. Rooke, Y.-H. Zhang, X.-Y. Yang, Y. Tang, F.-S. Xiao, B.-L. Su, J. Mater. Chem. 2012, 22, 17381-17403;

D. Schneider, D. Mehlhorn, P. Zeigermann, J. Kärger, R. Valiullin, Chem. Soc. Rev. 2016, 45, 3439-3467.

W. Schwieger, A. G. Machoke, B. Reiprich, T. Weissenberger, T. Selvam, M. Hartmann, in Zeolites in Catalysis: Properties and Applications (Eds.: J. Čeijka, R. E. Morris, P. Nachtigall), The Royal Society of Chemistry, 2017, pp. 103-145;

M. V. Opanasenko, W. J. Roth, J. Cejka, Catal. Sci. Technol. 2016, 6, 2467-2484.

L. Tosheva, V. P. Valtchev, Chem. Mater. 2005, 17, 2494-2513.

W. Schwieger, A. G. Machoke, T. Weissenberger, A. Inayat, T. Selvam, M. Klumpp, A. Inayat, Chem. Soc. Rev. 2016, 45, 3353-3376.

H. Xin, J. Zhao, S. Xu, J. Li, W. Zhang, X. Guo, E. J. Hensen, Q. Yang, C. Li, J. Phys. Chem. C 2010, 114, 6553-6559.

D. Serrano, R. Sanz, P. Pizarro, I. Moreno, Chem. Commun. 2009, 1407-1409.

D.-Y. Ok, N. Jiang, E. A. Prasetyanto, H. Jin, S.-E. Park, Microporous Mesoporous Mater. 2011, 141, 2-7.

Y. Zhu, Z. Hua, X. Zhou, Y. Song, Y. Gong, J. Zhou, J. Zhao, J. Shi, RSC Adv. 2013, 3, 4193-4198.

M. B. Yue, M. N. Sun, F. Xie, D. D. Ren, Microporous Mesoporous Mater. 2014, 183, 177-184;

X. Wang, G. Li, W. Wang, C. Jin, Y. Chen, Microporous Mesoporous Mater. 2011, 142, 494-502;

W. Wang, G. Li, L. Liu, Y. Chen, Microporous Mesoporous Mater. 2013, 179, 165-171;

W. Wang, G. Li, W. Li, L. Liu, Chem. Commun. 2011, 47, 3529-3531.

S. S. Li, A. F. Zhang, M. Liu, X. W. Guo, Chin. Chem. Lett. 2011, 22, 303-305;

S. Du, Q. Sun, N. Wang, X. Chen, M. Jia, J. Yu, J. Mater. Chem. A 2017, 5, 7992-7998;

S. Du, F. Li, Q. Sun, N. Wang, M. Jia, J. Yu, Chem. Commun. 2016, 52, 3368-3371;

Y. Cheneviere, F. Chieux, V. Caps, A. Tuel, J. Catal. 2010, 269, 161-168.

L. Lakiss, M. Rivallan, J.-M. Goupil, J. El Fallah, S. Mintova, Catal. Today 2011, 168, 112-117.

D. P. Serrano, R. Sanz, P. Pizarro, I. Moreno, Appl. Catal. A 2012, 435-436, 32-42;

D. P. Serrano, R. Sanz, P. Pizarro, A. Peral, I. Moreno, Microporous Mesoporous Mater. 2013, 166, 59-66;

D. P. Serrano, R. Sanz, P. Pizarro, I. Moreno, Topics in Catalysis 2010, 53, 1319-1329.

B. Wang, M. Lin, B. Zhu, X. Peng, G. Xu, X. Shu, Catal. Commun. 2016, 75, 69-73;

S.-T. Tsai, P.-Y. Chao, T.-C. Tsai, I. Wang, X. Liu, X.-W. Guo, Catal. Today 2009, 148, 174-178;

A. Silvestre-Albero, A. Grau-Atienza, E. Serrano, J. García-Martínez, J. Silvestre-Albero, Catal. Commun. 2014, 44, 35-39;

S. Du, X. Chen, Q. Sun, N. Wang, M. Jia, V. Valtchev, J. Yu, Chem. Commun. 2016, 52, 3580-3583;

P.-Y. Chao, S.-T. Tsai, T.-C. Tsai, J. Mao, X.-W. Guo, Topics in Catalysis 2009, 52, 185-192.

N. Wilde, M. Pelz, S. G. Gebhardt, R. Glaser, Green Chem. 2015, 17, 3378-3389;

B. Wang, M. Lin, X. Peng, B. Zhu, X. Shu, RSC Adv. 2016, 6, 44963-44971.

S. Mitchell, N.-L. Michels, K. Kunze, J. Pérez-Ramírez, Nat. Chem. 2012, 4, 825;

J. Zečević, K. P. de Jong, P. E. de Jongh, Curr. Opin. Solid State Mater. Sci. 2013, 17, 115-125.

J. Zečević, C. J. Gommes, H. Friedrich, P. E. de Jongh, K. P. de Jong, Angew. Chem. Int. Ed. 2012, 51, 4213-4217;

Angew. Chem. 2012, 124, 4289-4293.

J. Ihli, R. R. Jacob, M. Holler, M. Guizar-Sicairos, A. Diaz, J. C. da Silva, D. Ferreira Sanchez, F. Krumeich, D. Grolimund, M. Taddei, W. C. Cheng, Y. Shu, A. Menzel, J. A. van Bokhoven, Nat. Commun. 2017, 8, 809.

S. A. Bagshaw, E. Prouzet, T. J. Pinnavaia, Science 1995, 269, 1242-1244.

H. Yang, G. Novk, N. Coombs, I. Sokolov, G. A. Ozin, J. Mater. Chem. 1998, 8, 743-750.

Q. Gao, Y. Xu, D. Wu, Y. Sun, X. Li, J. Phys. Chem. C 2009, 113, 12753-12758.

P. Wu, T. Tatsumi, T. Komatsu, T. Yashima, J. Phys. Chem. B 2001, 105, 2897-2905;

P. Ratnasamy, D. Srinivas, H. Knözinger, in Advances in Catalysis, Vol. 48, Academic Press, San Diego, 2004, pp. 1-169;

F. Geobaldo, S. Bordiga, A. Zecchina, E. Giamello, G. Leofanti, G. Petrini, Catal. Lett. 1992, 16, 109-115;

T. Blasco, M. Camblor, A. Corma, J. Perez-Pariente, J. Am. Chem. Soc. 1993, 115, 11806-11813.

A. G. Machoke, A. M. Beltrán, A. Inayat, B. Winter, T. Weissenberger, N. Kruse, R. Güttel, E. Spiecker, W. Schwieger, Adv. Mater. 2015, 27, 1066-1070.

M. Holler, M. Guizar-Sicairos, E. H. R. Tsai, R. Dinapoli, E. Müller, O. Bunk, J. Raabe, G. Aeppli, Nature 2017, 543, 402.

J. D. Grunwaldt, J. B. Wagner, R. E. Dunin-Borkowski, ChemCatChem 2013, 5, 62-80.

A. Diaz, P. Trtik, M. Guizar-Sicairos, A. Menzel, P. Thibault, O. Bunk, Phys. Rev. B 2012, 85, 020104.

Y. Fam, T. L. Sheppard, A. Diaz, T. Scherer, M. Holler, W. Wang, D. Wang, P. Brenner, A. Wittstock, J. D. Grunwaldt, ChemCatChem 2018, 10, 2858-2867;

A. M. Wise, J. N. Weker, S. Kalirai, M. Farmand, D. A. Shapiro, F. Meirer, B. M. Weckhuysen, ACS Catal. 2016, 6, 2178-2181.

Y. Zhang, L. Xu, J. Zhang, P. Li, Y. Yuan, H. Guo, X. Zhang, L. Xu, Catal. Sci. Technol. 2018, 8, 4526-4536.

R. Millini, E. Previde Massara, G. Perego, G. Bellussi, J. Catal. 1992, 137, 497-503.

A. Thangaraj, M. J. Eapen, S. Sivasanker, P. Ratnasamy, Zeolites 1992, 12, 943-950;

A. J. H. P. van der Pol, J. H. C. van Hooff, Appl. Catal. A 1992, 92, 93-111.

T. Weissenberger, B. Reiprich, A. G. F. Machoke, K. Klühspies, J. Bauer, R. Dotzel, J. L. Casci, W. Schwieger, Catal. Sci. Technol. 2019, 9, 3259-3269.

J. Přech, M. Kubů, J. Čejka, Catal. Today 2014, 227, 80-86.

L. Gueudré, M. Milina, S. Mitchell, J. Pérez-Ramírez, Adv. Funct. Mater. 2014, 24, 209-219;

S. Mitchell, A. B. Pinar, J. Kenvin, P. Crivelli, J. Kärger, J. Pérez-Ramírez, Nat. Commun. 2015, 6, 8633;

D. Schneider, D. Kondrashova, R. Valiullin, A. Bunde, J. Kaerger, Chem. Ing. Tech. 2015, 87, 1794-1809.

J. Přech, D. Vitvarová, L. Lupínková, M. Kubů, J. Čejka, Microporous Mesoporous Mater. 2015, 212, 28-34.

C. G. Schroer, M. Seyrich, M. Kahnt, S. Botta, R. Döhrmann, G. Falkenberg, J. Garrevoet, M. Lyubomirskiy, M. Scholz, A. Schropp, F. Wittwer, Proc. SPIE 2017, 10389, 10389E.

A. M. Maiden, J. M. Rodenburg, Ultramicroscopy 2009, 109, 1256-1262.

D. Gürsoy, F. De Carlo, X. Xiao, C. Jacobsen, J. Synchrotron Radiat. 2014, 21, 1188-1193.

V. Novák, F. Štěpánek, P. Kočí, M. Marek, M. Kubíček, Chem. Eng. Sci. 2010, 65, 2352-2360.