Studies on the solid acidity of heated and cation-exchanged montmorillonite using n-butylamine titration in non-aqueous system and diffuse reflectance Fourier transform infrared (DRIFT) spectroscopy
Tóm tắt
The effects of heating and cation exchange on the solid acidity of montmorillonite were investigated using n-butylamine titration in non-aqueous system and diffuse reflectance Fourier transform infrared spectroscopy. The number of total, Brønsted, and Lewis acid sites showed the same modulation tendency with increasing heating temperature, reaching a maximum at 120 °C and subsequently decreasing until it reaches a minimum at 600 °C. The Lewis acid sites result from unsaturated Al3+ cations, and their number increased with the heating temperature due to the dehydration and dehydroxylation of montmorillonite. The generation and evolution of Brønsted acidity were mainly related to interlayer-polarized water molecules. Water adsorbed on the unsaturated Al3+ ions also acted as a Brønsted acid. The acid strength of the Brønsted acid sites was dependent on the polarization ability of the exchangeable cation, the amount of interlayer water, and the degree of dissociation of the interlayer water coordinated to exchangeable cations. All cation-exchanged montmorillonites exhibited different numbers of acid sites and various distributions of acid strength. Brønsted acidity was predominant in Al3+-exchanged montmorillonite, whereas the Na+- and K+-exchanged montmorillonites showed predominantly Lewis acidity. Moreover, Mg2+- and Li+-exchanged montmorillonites exhibited approximately equal numbers of Brønsted and Lewis acid sites. The Brønsted acidity of cation-exchanged montmorillonite was positively correlated with the charge-to-radius ratios of the cations, whereas the Lewis acidity was highly dependent on the electronegativity of the cations. The acid strengths of Al3+- and Mg2+-exchanged montmorillonites were remarkably higher than those of monovalent cation-exchanged montmorillonites, showing the highest acid strength (H
0 ≤ −3.0). Li+- and Na+-exchanged montmorillonites exhibited an acid strength distribution of −3.0 < H
0 ≤ 4.8, with the acid strength ranging primarily from 1.5 to 3.3 in Li+-exchanged montmorillonite, whereas only weaker-strength acid sites (1.5 < H
0 ≤ 4.8) were present in K+-exchanged montmorillonite. The results of the catalysis experiments indicated that montmorillonite promoted the thermal decomposition of the model organic. The catalytic activity showed a positive correlation with the solid acidity of montmorillonite and was affected by cation exchange, which occurs naturally in geological processes.
Tài liệu tham khảo
Adams J, McCabe R (2006) Clay minerals as catalysts. In: Bergaya F, Theng BKG, Lagaly G (eds) Handbook of clay science, vol 1. Elsevier, Amsterdam, pp 541–581
Akçay M (2005) The surface acidity and characterization of Fe-montmorillonite probed by in situ FT-IR spectroscopy of adsorbed pyridine. Appl Catal A Gen 294(2):156–160
Arena F, Dario R, Parmaliana A (1998) A characterization study of the surface acidity of solid catalysts by temperature programmed methods. Appl Catal A Gen 170(1):127–137
Benesi H (1957) Acidity of catalyst surfaces. II. Amine titration using Hammett indicators. J Phys Chem 61(7):970–973
Bhattacharyya KG, Gupta SS (2008) Adsorption of a few heavy metals on natural and modified kaolinite and montmorillonite: a review. Adv Colloid Interface 140(2):114–131. doi:10.1016/j.cis.2007.12.008
Billingham J, Breen C, Yarwood J (1996) In situ determination of Brønsted/Lewis acidity on cation-exchanged clay mineral surfaces by ATR-IR. Clay Miner 31(4):513–522
Bjølykke K (1998) Clay mineral diagenesis in sedimentary basins–a key to the prediction of rock properties. Examples from the North Sea Basin. Clay Miner 33(1):15–34
Breen C (1991a) Thermogravimetric and infrared study of the desorption of butylamine, cyclohexylamine and pyridine from Ni-and Co-exchanged montmorillonite. Clay Miner 26(4):487–496
Breen C (1991b) Thermogravimetric study of the desorption of cyclohexylamine and pyridine from an acid-treated Wyoming bentonite. Clay Miner 26(4):473–486
Breen C, Moronta AJ (2001) Influence of exchange cation and layer charge on the isomerization of α-pinene over SWy-2, SAz-1 and Sap-Ca. Clay Miner 36(4):467–472. doi:10.1180/0009855013640001
Breen C, Deane A, Flynn J (1987) The acidity of trivalent cation-exchanged montmorillonite. Temperature-programmed desorption and infrared studies of pyridine and n-butylamine. Clay Miner 22(2):169–178
Brown DR, Rhodes CN (1997) Brønsted and Lewis acid catalysis with ion-exchanged clays. Catal Lett 45(1):35–40. doi:10.1023/a:1019038806333
Cseri T, Békássy S, Figueras F, Rizner S (1995) Benzylation of aromatics on ion-exchanged clays. J Mol Catal A Chem 98(2):101–107. doi:10.1016/1381-1169(95)00016-x
Dontsova KM, Norton LD, Johnston CT, Bigham JM (2004) Influence of exchangeable cations on water adsorption by soil clays. Soil Sci Soc Am J 68(4):1218–1227. doi:10.2136/sssaj2004.1218
Flessner U, Jones DJ, Rozière J, Zajac J, Storaro L, Lenarda M, Pavan M, Jiménez-López A, Rodríguez-Castellón E, Trombetta M, Busca G (2001) A study of the surface acidity of acid-treated montmorillonite clay catalysts. J Mol Catal A Chem 168(1–2):247–256. doi:10.1016/s1381-1169(00)00540-9
Frenkel M (1974) Surface acidity of montmorillonites. Clays Clay Miner 22(5–6):435–441
Fripiat J, Cruz-Cumplido M (1974) Clays as catalysts for natural processes. Annu Rev Earth Plant Sci 2:239
Geatches DL, Clark SJ, Greenwell HC (2010) Role of clay minerals in oil-forming reactions. J Phys Chem A 114(10):3569–3575. doi:10.1021/jp9096869
Hart MP, Brown DR (2004) Surface acidities and catalytic activities of acid-activated clays. J Mol Catal A Chem 212(1–2):315–321. doi:10.1016/j.molcata.2003.11.013
He H, Yang D, Yuan P, Shen W, Frost RL (2006) A novel organoclay with antibacterial activity prepared from montmorillonite and Chlorhexidini Acetas. J Colloid Interface Sci 297(1):235–243. doi:10.1016/j.jcis.2005.10.031
Heller-Kallai L (2006) Thermally modified clay minerals. In: Bergaya F, Theng BKG, Lagaly G (eds) Handbook of clay science, vol 1. Elsevier, Amsterdam, pp 289–308
Hetényi M (1995) Simulated thermal maturation of type I and III kerogens in the presence, and absence, of calcite and montmorillonite. Org Geochem 23(2):121–127. doi:10.1016/0146-6380(94)00120-p
Jankovič Ľ, Komadel P (2003) Metal cation-exchanged montmorillonite catalyzed protection of aromatic aldehydes with Ac2O. J Catal 218(1):227–233. doi:10.1016/s0021-9517(03)00138-6
Jerónimo D, Guil JM, Corbella BM, Vasques H, Miranda A, Silva JM, Lobato A, Pires J, Carvalho AP (2007) Acidity characterization of pillared clays through microcalorimetric measurements and catalytic ethylbenzene test reaction. Appl Catal A Gen 330:89–95. doi:10.1016/j.apcata.2007.07.013
Johns WD (1979) Clay mineral catalysis and petroleum generation. Annu Rev Earth Plant Sci 7:183
Johns WD, Shimoyama A (1972) Clay minerals and petroleum-forming reactions during burial and diagenesis. AAPG Bull 56(11):2160–2167
Khaorapapong N, Ontam A, Youngme S, Ogawa M (2008) Solid-state intercalation and in situ formation of cadmium sulfide in the interlayer space of montmorillonite. J Phys Chem Solids 69(5–6):1107–1111
Larter SR, Douglas AG (1982) Pyrolysis methods in organic geochemistry: an overview. J Anal Appl Pyrol 4(1):1–19. doi:10.1016/0165-2370(82)80023-5
Liu D, Yuan P, Liu H, Cai J, Qin Z, Tan D, Zhou Q, He H, Zhu J (2011) Influence of heating on the solid acidity of montmorillonite: a combined study by DRIFT and Hammett indicators. Appl Clay Sci 52(4):358–363. doi:10.1016/j.clay.2011.03.016
Madejová J, Komadel P (2001) Baseline studies of the clay minerals society source clays: infrared methods. Clays Clay Miner 49(5):410–432
Mahmoud S, Hammoudeh A, Al-Noaimi M (2003) Pretreatment effects on the catalytic activity of Jordanian bentonite. Clays Clay Miner 51(1):52–57. doi:10.1346/ccmn.2003.510106
Mortland M, Raman K (1968) Surface acidity of smectites in relation to hydration, exchangeable cation, and structure. Clays Clay Miner 16(5):393–398
Motokura K, Nakagiri N, Mizugaki T, Ebitani K, Kaneda K (2007) Nucleophilic substitution reactions of alcohols with use of montmorillonite catalysts as solid Brønsted acids. J Org Chem 72(16):6006–6015. doi:10.1021/jo070416w
Noyan H, Önal M, Sarikaya Y (2006) The effect of heating on the surface area, porosity and surface acidity of a bentonite. Clays Clay Miner 54(3):375–381. doi:10.1346/ccmn.2006.0540308
Reddy CR, Iyengar P, Nagendrappa G, Jai Prakash BS (2005) Esterification of succinic anhydride to di-(p-cresyl) succinate over Mn + -montmorillonite clay catalysts. J Mol Catal A Chem 229(1–2):31–37. doi:10.1016/j.molcata.2004.10.044
Reddy CR, Nagendrappa G, Jai Prakash BS (2007) Surface acidity study of Mn + -montmorillonite clay catalysts by FT-IR spectroscopy: correlation with esterification activity. Catal Commun 8(3):241–246
Reddy CR, Bhat YS, Nagendrappa G, Jai Prakash BS (2009) Brønsted and Lewis acidity of modified montmorillonite clay catalysts determined by FT-IR spectroscopy. Catal Today 141(1–2):157–160
Rupert JP, Granquist WT, Pinnavaia TJ (1987) Catalytic properties of clay minerals. Chemistry of clays and clay minerals. Longman scientific and technical, New York
Shimizu K-i, Higuchi T, Takasugi E, Hatamachi T, Kodama T, Satsuma A (2008) Characterization of Lewis acidity of cation-exchanged montmorillonite K-10 clay as effective heterogeneous catalyst for acetylation of alcohol. J Mol Catal A Chem 284(1–2):89–96. doi:10.1016/j.molcata.2008.01.013
Singh B, Patial J, Sharma P, Agarwal SG, Qazi GN, Maity S (2007) Influence of acidity of montmorillonite and modified montmorillonite clay minerals for the conversion of longifolene to isolongifolene. J Mol Catal A Chem 266(1–2):215–220
Tyagi B, Chudasama CD, Jasra RV (2006) Characterization of surface acidity of an acid montmorillonite activated with hydrothermal, ultrasonic and microwave techniques. Appl Clay Sci 31(1–2):16–28
Ursu AV, Jinescu G, Gros F, Nistor ID, Miron ND, Lisa G, Silion M, Djelveh G, Azzouz A (2011) Thermal and chemical stability of Romanian bentonite. J Therm Anal Calorim 106(3):965–971. doi:10.1007/s10973-011-1414-z
Vaccari A (1999) Clays and catalysis: a promising future. Appl Clay Sci 14(4):161–198
Varma RS (2002) Clay and clay-supported reagents in organic synthesis. Tetrahedron 58(7):1235–1255
Walling C (1950) The acid strength of surfaces. J Am Chem Soc 72(3):1164–1168
Wattel-Koekkoek EJW, van Genuchten PPL, Buurman P, van Lagen B (2001) Amount and composition of clay-associated soil organic matter in a range of kaolinitic and smectitic soils. Geoderma 99(1–2):27–49. doi:10.1016/s0016-7061(00)00062-8
Zheng Y, Zaoui A, Shahrour I (2010) Evolution of the interlayer space of hydrated montmorillonite as a function of temperature. Am Mineral 95(10):1493–1499. doi:10.2138/am.2010.3541
Zhou CH (2011) Clay mineral-based catalysts and catalysis. Appl Clay Sci 53(2):85