Post-synthesis metal (Sn, Zr, Hf) modification of BEA zeolite: Combined Lewis and Brønsted acidity for cascade catalysis

doi:10.1016/S1872-2067(23)64539-5

Abstract

Abstract:

Zeolites modified by Lewis acidic metal centers such as Sn, Zr, and Hf are promising catalysts for numerous reactions relevant to biorefining, such as isomerization of carbohydrates and Meerwein-Ponndorf-Verley (MPV) reduction of furans. Preferred catalysts contain these metal ions in the framework of large-pore BEA zeolite, requiring often complex multistep preparation procedures based on expensive organometallic precursors. Herein, we developed a facile approach for obtaining highly dispersed isolated Sn, Zr, and Hf incorporated in dealuminated BEA zeolite with high metal content (Si/M ratio of 50‒75) via a solid-state grinding approach using simple inorganic metal precursors. The efficient incorporation of isolated metal sites in the BEA framework with high content was achieved by methanol treatment before calcination, which removes excess metal. The Lewis acid sites derive from isolated metal ions in open sites for Sn, Zr, and Hf, while Sn-modified BEA also contains closed Sn sites. The open Sn sites display the highest Lewis acidity. The Brønsted acidity stems from silanols perturbed by Lewis acidic metal ions of open metal sites and the OH group connected to the open metal sites. The metal-modified zeolites are active in the cascade reductive etherification of cinnamaldehyde, involving the MPV reduction to cinnamyl alcohol and the subsequent etherification to cinnamyl propyl ether with the isopropanol solvent over Lewis and Brønsted acid sites, respectively. Sn-modified BEA was the most active sample, which stems from its strongest Lewis acidity, which is crucial for the first MPV step. Sn modification of the optimized solid-state ion-exchange method was applied to various BEA zeolites with different morphologies (nanocrystalline, hierarchical, and conventional BEA), showing that pore hierarchization can further benefit cascade reductive etherification reaction.

Key words: Zeolite, BEA zeolite, Grafting, Metal speciation, Acidity

Peerapol Pornsetmetakul, Ferdy J. A. G. Coumans, Rim C. J. van de Poll, Anna Liutkova, Duangkamon Suttipat, Brahim Mezari, Chularat Wattanakit, Emiel J. M. Hensen. Post-synthesis metal (Sn, Zr, Hf) modification of BEA zeolite: Combined Lewis and Brønsted acidity for cascade catalysis[J]. Chinese Journal of Catalysis, 2023, 55: 200-215.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64539-5

https://www.cjcatal.com/EN/Y2023/V55/I12/200

Figures/Tables 11

Scheme 1. Approach to post-synthesis modification of BEA with Sn, Zr, and Hf.

Fig. 1. (a) XRD patterns of Com-BEA-M, Com-BEA-M(no-wash), and Com-BEA-deal samples. UV-Vis spectra of Zr-modified Com-BEA (b) and Sn-modified Com-BEA (c) samples. STEM-EDX images of Com-BEA-Sn (d) and Com-BEA-Sn(no-wash) (e). Si and Sn are shown in red and green, respectively.

Fig. 2. (a) XRD patterns of Com-BEA zeolites after dealumination and metal modification. (b) Enlargement of (a) 2θ of 21°?24° range. (c) IR spectra of dehydrated Com-BEA-deal and Com-BEA-M zeolites. (d) Enlargement of (c) in the 3600-3850 cm?1 region. (e) XRD patterns of Sn modified BEA zeolites with various morphologies. (f) Enlargement of (e) in the 2θ region of 21°?24° range. (g) STEM-HAADF images of Com-BEA-M zeolites.

Table 1 Elemental composition of BEA zeolites determined by ICP-OES analysis.

Sample	Si/Al	Si/M	Fractional removal or incorporation^a	wt% M	μmol M g^‒1
Com-BEA	13	—	—	—	—
Com-BEA-deal	>1124	—	>99	—	—
Com-BEA-Zr	>1124	53.7	25	2.7	299.3
Com-BEA-Sn	>1124	74.7	18	2.6	216.5
Com-BEA-Hf	>1124	67.3	20	4.2	235.3

Fig. 3. Weight-normalized 29Si MAS NMR (a), 29Si-1H CP MAS NMR (b), weight-normalized 27Al MAS NMR (c) spectra of hydrated zeolites and weight-normalized 1H MAS NMR spectra (d) of Com-BEA, Com-BEA-deal, and Com-BEA-M zeolites. (e) A zoom of 2?8 ppm region of (d).

Fig. 4. IR spectra of pyridine adsorbed on Com-BEA (a), Com-BEA-deal (b), Com-BEA-Zr (c), Com-BEA-Sn (d), and Com-BEA-Hf (e).

Fig. 5. CO IR spectra recorded at liquid N2 temperature (hydroxyl stretching vibration region and carbonyl stretching vibration) of Com-BEA (a,f), Com-BEA-deal (b,g), Com-BEA-Sn (c,h), Com-BEA-Zr (d,i), and Com-BEA-Hf (e,j), respectively. CO IR spectra (f?j) in carbonyl stretching region are reference to IR spectra of dehydrated samples.

Fig. 6. (a) 15N CP MAS NMR spectra of pyridine-15N adsorbed on zeolites after adsorption at 50 °C for 0.5 h (dash line) and desorption under evacuation at 150 °C for 1.5 h (solid line). (b) Chemical shift scale and the corresponding species. The spectra were recorded at ambient conditions.

Scheme 2. Cascade conversion of cinnamaldehyde (CAD) into cinnamyl propyl ether (CPE) in isopropanol involving MPV reduction and etherification.

Fig. 7. Catalytic cascade reductive etherification of cinnamaldehyde (a) and etherification of cinnamyl alcohol (b). Reaction conditions: 0.53 mmol (71.1 mg) cinnamaldehyde or cinnamyl alcohol, isopropanol/substrate molar ratio = 97.5 (4 mL isopropanol), catalyst amount = 15 mg, 10 bar He, T = 120 °C for (a) and 150 °C for (b).

Scheme 3. Chemical moieties in metal-modified BEA zeolite giving rise to Lewis and Br?nsted acid sites. Lewis acid sites are derived from isolated metal ions (purple). Br?nsted acid sites (red) are derived from silanols perturbed by Lewis acidic metal ions of open metal sites and the OH group connected to the open metal sites.

References

[1]	B. R. Caes, R. E. Teixeira, K. G. Knapp, R. T. Raines, ACS Sustainable Chem. Eng., 2015, 3, 2591-2605.
[2]	M. Moliner, Dalton Trans., 2014, 43, 4197-4208.
[3]	Y. Roman-Leshkov, M. E. Davis, ACS Catal., 2011, 1, 1566-1580.
[4]	A. Corma, M. E. Domine, L. Nemeth, S. Valencia, J. Am. Chem. Soc., 2002, 124, 3194-3195.
[5]	B. A. Johnson, J. R. Di Iorio, Y. Roman-Leshkov, J. Catal., 2021, 404, 607-619.
[6]	A. Corma, L. T. Nemeth, M. Renz, S. Valencia, Nature, 2001, 412, 423-425.
[7]	Y. N. Palai, A. Shrotri, A. Fukuoka, ACS Catal., 2022, 12, 3534-3542.
[8]	M. Moliner, Y. Román-Leshkov, M. E. Davis, Proc. Natl. Acad. Sci. U. S. A., 2010, 107, 6164.
[9]	X. Yang, J. Bian, J. Huang, W. Xin, T. Lu, C. Chen, Y. Su, L. Zhou, F. Wang, J. Xu, Green Chem., 2017, 19, 692-701.
[10]	W. N. P. van der Graaff, G. Li, B. Mezari, E. A. Pidko, E. J. M. Hensen, ChemCatChem, 2015, 7, 1152-1160.
[11]	C. M. Lew, N. Rajabbeigi, M. Tsapatsis, Microporous Mesoporous Mater., 2012, 153, 55-58.
[12]	E. M. Albuquerque, P. N. Paulino, R. Sadek, L. Valentin, J.-M. Krafft, S. Dzwigaj, M. A. Fraga, Appl. Catal. A, 2020, 604, 117766.
[13]	Y. Zhu, G.-K. Chuah, S. Jaenicke, J. Catal., 2006, 241, 25-33.
[14]	J. Luo, J. Yu, R. J. Gorte, E. Mahmoud, D. G. Vlachos, M. A. Smith, Catal. Sci. Technol., 2014, 4, 3074-3081.
[15]	J. D. Lewis, S. Van de Vyver, A. J. Crisci, W. R. Gunther, V. K. Michaelis, R. G. Griffin, Y. Roman-Leshkov, ChemSusChem, 2014, 7, 2255-2265.
[16]	Y. Zhu, G. Chuah, S. Jaenicke, J. Catal., 2004, 227, 1-10.
[17]	M. Boronat, A. Corma, M. Renz, J. Phys. Chem. B, 2006, 110, 21168-21174.
[18]	Z. Zhu, H. Xu, J. Jiang, Y. Guan, P. Wu, J. Catal., 2017, 352, 1-12.
[19]	Z. Zhu, H. Xu, B. Wang, J. Yin, J. Jiang, H. Lü, P. Wu, Chem. Commun., 2019, 55, 14279-14282.
[20]	C.-C. Chang, H. J. Cho, Z. Wang, X. Wang, W. Fan, Green Chem., 2015, 17, 2943-2951.
[21]	H. J. Cho, N. S. Gould, V. Vattipalli, S. Sabnis, W. Chaikittisilp, T. Okubo, B. Xu, W. Fan, Microporous Mesoporous Mater., 2019, 278, 387-396.
[22]	J. Dijkmans, D. Gabriëls, M. Dusselier, F. de Clippel, P. Vanelderen, K. Houthoofd, A. Malfliet, Y. Pontikes, B. F. Sels, Green Chem., 2013, 15, 2777-2785.
[23]	J. Dijkmans, J. Demol, K. Houthoofd, S. Huang, Y. Pontikes, B. Sels, J. Catal., 2015, 330, 545-557.
[24]	J. Wang, K. Okumura, S. Jaenicke, G.-K. Chuah, Appl. Catal. A, 2015, 493, 112-120.
[25]	P. Wolf, C. Hammond, S. Conrad, I. Hermans, Dalton Trans., 2014, 43, 4514-4519.
[26]	B. Tang, W. Dai, X. Sun, N. Guan, L. Li, M. Hunger, Green Chem., 2014, 16, 2281-2291.
[27]	B. Tang, W. Dai, G. Wu, N. Guan, L. Li, M. Hunger, ACS Catal., 2014, 4, 2801-2810.
[28]	B. Tang, W. Dai, X. Sun, G. Wu, N. Guan, M. Hunger, L. Li, Green Chem., 2015, 17, 1744-1755.
[29]	C. Hammond, S. Conrad, I. Hermans, Angew. Chem. Int. Ed., 2012, 51, 11736-11739.
[30]	P. Li, G. Liu, H. Wu, Y. Liu, J.-G. Jiang, P. Wu, J. Phys. Chem. C, 2011, 115, 3663-3670.
[31]	D. Padovan, L. Botti, C. Hammond, ACS Catal., 2018, 8, 7131-7140.
[32]	H. Joshi, C. Ochoa-Hernandez, E. Nürenberg, L. Kang, F. R. Wang, C. Weidenthaler, W. Schmidt, F. Schüth, Microporous Mesoporous Mater., 2020, 309, 110566.
[33]	J. Dijkmans, M. Dusselier, D. Gabriëls, K. Houthoofd, P. C. M. M. Magusin, S. Huang, Y. Pontikes, M. Trekels, A. Vantomme, L. Giebeler, S. Oswald, B. F. Sels, ACS Catal., 2015, 5, 928-940.
[34]	W. N. P. van der Graaff, C. H. L. Tempelman, E. A. Pidko, E. J. M. Hensen, Catal. Sci. Technol., 2017, 7, 3151-3162.
[35]	J. C. Vega-Vila, R. Gounder, ACS Catal., 2020, 10, 12197-12211.
[36]	M. Boronat, P. Concepción, A. Corma, M. Renz, S. Valencia, J. Catal., 2005, 234, 111-118.
[37]	S. L. Suib, J. Prech, E. Szaniawska, J. Cejka, Chem. Rev., 2022, 123, 877-917.
[38]	J. S. Bates, B. C. Bukowski, J. W. Harris, J. Greeley, R. Gounder, ACS Catal., 2019, 9, 6146-6168.
[39]	J. W. Harris, J. S. Bates, B. C. Bukowski, J. Greeley, R. Gounder, ACS Catal., 2020, 10, 9476-9495.
[40]	A. Corma, M. E. Domine, S. Valencia, J. Catal., 2003, 215, 294-304.
[41]	P. Y. Dapsens, C. Mondelli, J. Pérez-Ramirez, Chem. Soc. Rev., 2015, 44, 7025-7043.
[42]	V. L. Sushkevich, A. Vimont, A. Travert, I. I. Ivanova, J. Phys. Chem. C, 2015, 119, 17633-17639.
[43]	W. Dai, Q. Lei, G. Wu, N. Guan, M. Hunger, L. Li, ACS Catal., 2020, 10, 14135-14146.
[44]	J. Dijkmans, M. Dusselier, W. Janssens, M. Trekels, A. Vantomme, E. Breynaert, C. Kirschhock, B. F. Sels, ACS Catal., 2016, 6, 31-46.
[45]	S. Tolborg, A. Katerinopoulou, D. D. Falcone, I. Sadaba, C. M. Osmundsen, R. J. Davis, E. Taarning, P. Fristrup, M. S. Holm, J. Mater. Chem. A, 2014, 2, 20252-20262.
[46]	S. Shetty, S. Pal, D. G. Kanhere, A. Goursot, Chem. Eur. J., 2006, 12, 518-523.
[47]	G. Qi, Q. Wang, J. Xu, Q. Wu, C. Wang, X. Zhao, X. Meng, F. Xiao, F. Deng, Commun. Chem., 2018, 1, 22.
[48]	V. L. Sushkevich, P. A. Kots, Y. G. Kolyagin, A. V. Yakimov, A. V. Marikutsa, I. I. Ivanova, J. Phys. Chem. C, 2019, 123, 5540-5548.
[49]	G. Yang, L. Zhou, X. Han, J. Mol. Catal. A, 2012, 363- 364, 371-379.
[50]	R. Otomo, R. Kosugi, Y. Kamiya, T. Tatsumi, T. Yokoi, Catal. Sci. Technol., 2016, 6, 2787-2795.
[51]	P. Treu, P. Huber, P. N. Plessow, F. Studt, E. Saraci, Catal. Sci. Technol., 2022, 12, 7439-7447.
[52]	W. R. Gunther, V. K. Michaelis, R. G. Griffin, Y. Roman-Leshkov, J. Phys. Chem. C, 2016, 120, 28533-28544.
[53]	Q. Yu, Y. Guo, X. Wu, Z. Yang, H. Wang, Q. Ge, X. Zhu, ACS Sustainable Chem. Eng., 2021, 9, 7982-7992.
[54]	L. Botti, S. A. Kondrat, R. Navar, D. Padovan, J. S. Martinez-Espin, S. Meier, C. Hammond, Angew. Chem. Int. Ed., 2020, 59, 20017-20023.
[55]	F. Hemmann, G. Scholz, K. Scheurell, E. Kemnitz, C. Jaeger, J. Phys. Chem. C, 2012, 116, 10580-10585.
[56]	H. Jiang, L. Yi, G. Yang, L. Wang, Catal. Sci. Technol., 2023, 13, 245-256.
[57]	P. Wolf, W.-C. Liao, T.-C. Ong, M. Valla, J. W. Harris, R. Gounder, W. N. P. van der Graaff, E. A. Pidko, E. J. M. Hensen, P. Ferrini, J. Dijkmans, B. Sels, I. Hermans, C. Copéret, Helv. Chim. Acta, 2016, 99, 916-927.
[58]	R. Bermejo-Deval, M. Orazov, R. Gounder, S.-J. Hwang, M. E. Davis, ACS Catal., 2014, 4, 2288-2297.
[59]	W. Hu, Z. Chi, Y. Wan, S. Wang, J. Lin, S. Wan, Y. Wang, Catal. Sci. Technol., 2020, 10, 2986-2993.
[60]	E. Peeters, G. Pomalaza, I. Khalil, A. Detaille, D. P. Debecker, A. P. Douvalis, M. Dusselier, B. F. Sels, ACS Catal., 2021, 11, 5984-5998.
[61]	V. L. Sushkevich, I. I. Ivanova, A. V. Yakimov, J. Phys. Chem. C, 2017, 121, 11437-11447.
[62]	V. L. Sushkevich, D. Palagin, I. I. Ivanova, ACS Catal., 2015, 5, 4833-4836.
[63]	N. O. Popovych, P. I. Kyriienko, Y. Millot, L. Valentin, J. Gurgul, R. P. Socha, J. Żukrowski, S. O. Soloviev, S. Dzwigaj, Microporous Mesoporous Mater., 2018, 268, 178-188.
[64]	L. Ford, A. Spanos, N. A. Brunelli, ACS Catal., 2023, 13, 11422-11432.
[65]	T. Lu, X. You, Y. Zong, Y. Xu, X. Yang, L. Zhou, Fuel, 2023, 332, 126262.
[66]	F. Gonell, M. Boronat, A. Corma, Catal. Sci. Technol., 2017, 7, 2865-2873.
[67]	A. Al-Nayili, K. Yakabi, C. Hammond, J. Mater. Chem. A, 2016, 4, 1373-1382.
[68]	G. Li, L. Gao, Z. Sheng, Y. Zhan, C. Zhang, J. Ju, Y. Zhang, Y. Tang, Catal. Sci. Technol., 2019, 9, 4055-4065.
[69]	M. Paniagua, G. Morales, J. A. Melero, J. Iglesias, C. López-Aguado, N. Vidal, R. Mariscal, M. López-Granados, I. Martinez-Salazar, Catal. Today, 2021, 367, 228-238.
[70]	J. Dijkmans, W. Schutyser, M. Dusselier, B. F. Sels, Chem. Commun., 2016, 52, 6712-6715.
[71]	H. Li, S. Zhao, W. Zhang, H. Du, X. Yang, Y. Peng, D. Han, B. Wang, Z. Li, Fuel, 2023, 342, 127786.
[72]	J. Zhang, L. Wang, G. Wang, F. Chen, J. Zhu, C. Wang, C. Bian, S. Pan, F.-S. Xiao, ACS Sustainable Chem. Eng., 2017, 5, 3123-3131.
[73]	M. Choi, K. Na, R. Ryoo, Chem. Commun., 2009, 2845-2847.
[74]	V. P. S. Caldeira, A. Peral, M. Linares, A. S. Araujo, R. A. Garcia-Muñoz, D. P. Serrano, Appl. Catal. A, 2017, 531, 187-196.
[75]	K. Na, M. Choi, R. Ryoo, J. Mater. Chem., 2009, 19, 6713-6719.
[76]	R. Baran, Y. Millot, T. Onfroy, J.-M. Krafft, S. Dzwigaj, Microporous Mesoporous Mater., 2012, 163, 122-130.
[77]	L. Qi, Y. Zhang, M. A. Conrad, C. K. Russell, J. Miller, A. T. Bell, J. Am. Chem. Soc., 2020, 142, 14674-14687.
[78]	Y. Wan, M. Zhuang, S. Chen, W. Hu, J. Sun, J. Lin, S. Wan, Y. Wang, ACS Catal., 2017, 7, 6038-6047.
[79]	I. C. Medeiros-Costa, E. Dib, N. Nesterenko, J.-P. Dath, J.-P. Gilson, S. Mintova, Chem. Soc. Rev., 2021, 50, 11156-11179.
[80]	A. Astafan, M. A. Benghalem, Y. Pouilloux, J. Patarin, N. Bats, C. Bouchy, T. J. Daou, L. Pinard, J. Catal., 2016, 336, 1-10.
[81]	I. C. Medeiros-Costa, E. Dib, F. Dubray, S. Moldovan, J.-P. Gilson, J.-P. Dath, N. Nesterenko, H. A. Aleksandrov, G. N. Vayssilov, S. Mintova, Inorg. Chem., 2022, 61, 1418-1425.
[82]	J. Pérez-Pariente, J. Sanz, V. Fornes, A. Corma, J. Catal., 1990, 124, 217-223.
[83]	E. B. Lami, F. Fajula, D. Anglerot, T. Des Courieres, Microporous Mater., 1993, 1, 237-245.
[84]	C. Jia, P. Massiani, D. Barthomeuf, J. Chem. Soc., Faraday Trans., 1993, 89, 3659-3665.
[85]	R. Hajjar, Y. Millot, P. P. Man, M. Che, S. Dzwigaj, J. Phys. Chem. C, 2008, 112, 20167-20175.
[86]	A. A. Gabrienko, I. G. Danilova, S. S. Arzumanov, A. V. Toktarev, D. Freude, A. G. Stepanov, Microporous Mesoporous Mater., 2010, 131, 210-216.
[87]	J. Weitkamp, Solid State Ionics, 2000, 131, 175-188.
[88]	R. Buzzoni, S. Bordiga, G. Ricchiardi, C. Lamberti, A. Zecchina, G. Bellussi, Langmuir, 1996, 12, 930-940.
[89]	L. Meng, X. Zhu, B. Mezari, R. Pestman, W. Wannapakdee, E. J. M. Hensen, ChemCatChem, 2017, 9, 3942-3954.
[90]	J. Datka, A. M. Turek, J. M. Jehng, I. E. Wachs, J. Catal., 1992, 135, 186-199.
[91]	B. D. Montejo-Valencia, J. L. Salcedo-Pérez, M. C. Curet-Arana, J. Phys. Chem. C, 2016, 120, 2176-2186.
[92]	A. Zecchina, S. Bordiga, G. Spoto, D. Scarano, G. Petrini, G. Leofanti, M. Padovan, C. O. Areàn, J. Chem. Soc. Faraday Trans., 1992, 88, 2959-2969.
[93]	A. Zecchina, S. Bordiga, G. Spoto, L. Marchese, G. Petrini, G. Leofanti, M. Padovan, J. Phys. Chem., 1992, 96, 4991-4997.
[94]	M. Maache, A. Janin, J. C. Lavalley, J. F. Joly, E. Benazzi, Zeolites, 1993, 13, 419-426.
[95]	K. Hadjiivanov, Adv. Catal., 2014, 57, 99-318.
[96]	L. Kubelková, S. Beran, J. A. Lercher, Zeolites, 1989, 9, 539-543.
[97]	M. A. Makarova, K. M. Al-Ghefaili, J. Dwyer, J. Chem. Soc., Faraday Trans., 1994, 90, 383-386.
[98]	A. Zecchina, E. E. Platero, C. O. Arean, J. Catal., 1987, 107, 244-247.
[99]	W. Hu, Y. Wan, L. Zhu, X. Cheng, S. Wan, J. Lin, Y. Wang, ChemSusChem, 2017, 10, 4715-4724.
[100]	N. Sergent, P. Gélin, L. Perier-Camby, H. Praliaud, G. Thomas, Phys. Chem. Chem. Phys., 2002, 4, 4802-4808.
[101]	A. Jystad, H. Leblanc, M. Caricato, J. Phys. Chem. C, 2020, 124, 15231-15240.
[102]	I. G. Shenderovich, G. Buntkowsky, A. Schreiber, E. Gedat, S. Sharif, J. Albrecht, N. S. Golubev, G. H. Findenegg, H.-H. Limbach, J. Phys. Chem. B, 2003, 107, 11924-11939.
[103]	H. Zhu, A. Ramanathan, J.-F. Wu, B. Subramaniam, ACS Catal., 2018, 8, 4848-4859.
[104]	Z.-K. Gao, Y.-C. Hong, Z. Hu, B.-Q. Xu, Catal. Sci. Technol., 2017, 7, 4511-4519.
[105]	M. Lashdaf, V.-V. Nieminen, M. Tiitta, T. Venäläinen, H. Österholm, O. Krause, Microporous Mesoporous Mater., 2004, 75, 149-158.
[106]	B. C. Bukowski, J. S. Bates, R. Gounder, J. Greeley, J. Catal., 2018, 365, 261-276.
[107]	L. Botti, S. Meier, C. Hammond, ACS Catal., 2021, 11, 1296-1308.
[108]	A. Rodriguez-Fernandez, J. R. Di Iorio, C. Paris, M. Boronat, A. Corma, Y. Román-Leshkov, M. Moliner, Chem. Sci., 2020, 11, 10225-10235.
[109]	J. Jae, E. Mahmoud, R. F. Lobo, D. G. Vlachos, ChemCatChem, 2014, 6, 508-513.
[110]	A. Corma, M. Renz, Angew. Chem. Int. Ed., 2007, 46, 298-300.
[111]	H. Y. Luo, D. F. Consoli, W. R. Gunther, Y. Román-Leshkov, J. Catal., 2014, 320, 198-207.