{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,25]],"date-time":"2025-10-25T11:51:23Z","timestamp":1761393083693},"reference-count":47,"publisher":"Cambridge University Press (CUP)","issue":"3","license":[{"start":{"date-parts":[[2024,1,1]],"date-time":"2024-01-01T00:00:00Z","timestamp":1704067200000},"content-version":"unspecified","delay-in-days":7519,"URL":"https:\/\/www.cambridge.org\/core\/terms"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Clays and clay miner."],"published-print":{"date-parts":[[2003,6]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The surface acidic properties of pillared clays (PILCs) with Al or Zr oxide pillars (prepared from a natural Portuguese smectite and a synthetic Laponite), and of a protonic NaHY zeolite, were studied by two methods: pyridine adsorption followed by infrared (IR) spectroscopy, and the catalytic transformation of 1-butene. The results of the pyridine adsorption revealed that all the pillared clays studied have mainly Lewis-type acidity, the exception being the clay pillared with Zr oxide, obtained from natural smectite, which also presents a significant number of Br\u00f6nsted acid sites. The results of 1-butene transformation showed that the pillared clays exhibit catalytic properties similar to those of the protonic Y zeolite. The acid character of the solids was confirmed by the values of the <jats:italic>cis\/trans<\/jats:italic> 2-butene isomers ratio. At short reaction times, product distribution showed that the main reaction is oligomerization, followed by cracking. After 15 min the products are mainly the linear isomers, <jats:italic>cis<\/jats:italic> and <jats:italic>trans<\/jats:italic>-2-butene, showing that the majority of the catalytic active sites, are already poisoned after 15 min of reaction. The particular behaviour of Laponite intercalated with Al oxide pillars is discussed. The IR spectra of the pyridine adsorbed on the fresh samples and after the catalytic assays, revealed that Lewis acid sites behave as active sites for 1-butene catalytic transformation. The consistency between the results of the two complementary techniques used for the characterization of the acidity of the solids was proved.<\/jats:p>","DOI":"10.1346\/ccmn.2003.0510311","type":"journal-article","created":{"date-parts":[[2003,5,28]],"date-time":"2003-05-28T22:04:19Z","timestamp":1054159459000},"page":"340-349","source":"Crossref","is-referenced-by-count":24,"title":["Characterization of the Acidity of Al- and Zr-Pillared Clays"],"prefix":"10.1017","volume":"51","author":[{"given":"Ana P.","family":"Carvalho","sequence":"first","affiliation":[]},{"given":"Angela","family":"Martins","sequence":"additional","affiliation":[]},{"given":"Jo\u00e3o M.","family":"Silva","sequence":"additional","affiliation":[]},{"given":"Jo\u00e3o","family":"Pires","sequence":"additional","affiliation":[]},{"given":"Helena","family":"Vasques","sequence":"additional","affiliation":[]},{"given":"M. Brotas","family":"de Carvalho","sequence":"additional","affiliation":[]}],"member":"56","published-online":{"date-parts":[[2024,1,1]]},"reference":[{"key":"S0009860400024836_CR22","doi-asserted-by":"crossref","first-page":"463","DOI":"10.1006\/jcat.1997.1638","article-title":"Tantalum pillared montmorillonite. II. Acidic and catalytic properties","volume":"168","author":"Guiu","year":"(1997)","journal-title":"Journal of Catalysis"},{"key":"S0009860400024836_CR30","doi-asserted-by":"crossref","first-page":"79","DOI":"10.1006\/jcat.1994.1010","article-title":"Transformation of m-xylene over Al-pillared clays and ultrastable zeolite Y","volume":"145","author":"Molina","year":"(1994)","journal-title":"Journal of Catalysis"},{"key":"S0009860400024836_CR31","doi-asserted-by":"crossref","first-page":"377","DOI":"10.1016\/0304-5102(86)87085-7","article-title":"New routes to the preparation of pillared montmorillonite catalysts","volume":"35","author":"Occelli","year":"(1986)","journal-title":"Journal of Molecular Catalysis"},{"key":"S0009860400024836_CR35","doi-asserted-by":"crossref","first-page":"345","DOI":"10.1016\/0144-2449(91)80298-E","article-title":"Textural characteristics of Y and ZSM-20 zeolites determined by nitrogen adsorption","volume":"11","author":"Pires","year":"(1991)","journal-title":"Zeolites"},{"key":"S0009860400024836_CR23","doi-asserted-by":"crossref","first-page":"241","DOI":"10.1016\/S0167-2991(08)63605-8","volume-title":"Introduction to Zeolite Science and Practice","author":"Hooff","year":"(1991)"},{"key":"S0009860400024836_CR45","first-page":"55","volume-title":"The Chemistry of Clay Minerals","author":"Weaver","year":"(1975)"},{"key":"S0009860400024836_CR38","doi-asserted-by":"crossref","first-page":"9","DOI":"10.1007\/BF02475309","article-title":"Acidity studies on pillared clays (PILCs) by pyridine adsorption and 1-butanol dehydration","volume":"65","author":"Pires","year":"(1998)","journal-title":"Reaction Kinetics and Catalysis Letters"},{"key":"S0009860400024836_CR24","doi-asserted-by":"crossref","first-page":"1545","DOI":"10.1039\/f19757101545","article-title":"Active sites in zeolites. Part 4. n-butene isomerization over deammoniated and partly hydrolysed NH4Y","volume":"71","author":"Jacobs","year":"(1975)","journal-title":"Journal of the Chemical Society, Faraday Transactions"},{"key":"S0009860400024836_CR15","doi-asserted-by":"crossref","first-page":"515","DOI":"10.1016\/0920-5861(92)85016-F","article-title":"Pillared clays: preparation and characterization of zirconium pillared montmorillonite","volume":"15","author":"Farfan-Torres","year":"(1992)","journal-title":"Catalysis Today"},{"key":"S0009860400024836_CR39","doi-asserted-by":"crossref","first-page":"385","DOI":"10.1346\/CCMN.2000.0480309","article-title":"Heats of adsorption of n-hexane by thermal gravimetry with differential scanning calorimetry (TG-DSC): a tool for textural characterization of pillared clays","volume":"48","author":"Pires","year":"(2000)","journal-title":"Clays and Clay Minerals"},{"key":"S0009860400024836_CR40","unstructured":"Pires, J. , Carvalho, A.P. , Clara, E. and Brotas de Carvalho, M. (2000b) Adsor\u00e7\u00e3o de Compostos Org\u00e2nicos Vol\u00e1teis (VOCs). XVII Ibero American Symposium on Catalysis, Porto, p. 651."},{"key":"S0009860400024836_CR5","doi-asserted-by":"crossref","first-page":"2223","DOI":"10.1021\/j100817a036","article-title":"An infrared study of a silica-alumina surface","volume":"66","author":"Basila","year":"(1962)","journal-title":"The Journal of Physical Chemistry"},{"key":"S0009860400024836_CR36","doi-asserted-by":"crossref","first-page":"107","DOI":"10.1016\/S0144-2449(97)00054-7","article-title":"Aluminium-pillared clays: decomposition of the intercalating species and textural properties","volume":"19","author":"Pires","year":"(1997)","journal-title":"Zeolites"},{"key":"S0009860400024836_CR43","doi-asserted-by":"crossref","first-page":"4","DOI":"10.1016\/0144-2449(87)90108-4","article-title":"Reaction profile of isomerization of n-butenes over zeolite catalysts","volume":"7","author":"Tsuchiya","year":"(1987)","journal-title":"Zeolites"},{"key":"S0009860400024836_CR32","doi-asserted-by":"crossref","first-page":"256","DOI":"10.1016\/0021-9517(84)90253-7","article-title":"Cracking selectivity of a delaminated clay catalyst","volume":"90","author":"Occelli","year":"(1984)","journal-title":"Journal of Catalysis"},{"key":"S0009860400024836_CR46","doi-asserted-by":"crossref","first-page":"256","DOI":"10.1016\/0021-9517(74)90269-3","article-title":"The polymerisation and aromatic alkylation of butene-1 with calcined ammonium type Y zeolite","volume":"33","author":"Weeks","year":"(1974)","journal-title":"Journal of Catalysis"},{"key":"S0009860400024836_CR26","doi-asserted-by":"crossref","first-page":"241","DOI":"10.1016\/1381-1169(95)00281-2","article-title":"Surface characteristics and catalytic activity of Al-pillared (AZA) and Fe-Al-pillared (FAZA) clays for isopropanol decomposition","volume":"106","author":"Ladavos","year":"(1996)","journal-title":"Journal of Molecular Catalysis"},{"key":"S0009860400024836_CR33","doi-asserted-by":"crossref","first-page":"4584","DOI":"10.1021\/la980209e","article-title":"Zirconium pillared clays for carbon dioxide\/methane separation. 1. Preparation of adsorbent materials and pure gas adsorption","volume":"14","author":"Pereira","year":"(1998)","journal-title":"Langmuir"},{"key":"S0009860400024836_CR1","doi-asserted-by":"crossref","first-page":"24","DOI":"10.1016\/0144-2449(92)90005-A","article-title":"Synthesis, properties, and catalytic behaviour of zeolite EU-12","volume":"12","author":"Araya","year":"(1992)","journal-title":"Zeolites"},{"key":"S0009860400024836_CR27","doi-asserted-by":"crossref","first-page":"43","DOI":"10.1023\/A:1019175803068","article-title":"Acidity in pillared clays: origin and catalytic manifestations","volume":"4","author":"Lambert","year":"(1997)","journal-title":"Topics in Catalysis"},{"key":"S0009860400024836_CR42","doi-asserted-by":"crossref","first-page":"85","DOI":"10.1016\/S0926-860X(98)00052-0","article-title":"PLS vs. Zeolites as sorbents and catalysts. 5. Evidence for Br\u00f8nsted\/Lewis acid crossover and high acidity in conversions of C1\u20133 alcohols in some alumina-pillared smectite clays","volume":"171","author":"Raimond","year":"(1998)","journal-title":"Applied Catalysis A: General"},{"key":"S0009860400024836_CR7","doi-asserted-by":"crossref","first-page":"65","DOI":"10.1016\/0927-6513(95)00089-5","article-title":"Characterization of clays and aluminium pillared clays by adsorption of probe molecules","volume":"6","author":"de Brotas Carvalho","year":"(1996)","journal-title":"Microporous Materials"},{"key":"S0009860400024836_CR6","doi-asserted-by":"crossref","first-page":"175","DOI":"10.1016\/S0926-860X(98)00328-7","article-title":"Toluene methylation on Al13- and GaAl12-pillared clay catalysts","volume":"180","author":"Benito","year":"(1999)","journal-title":"Applied Catalysis A: General"},{"key":"S0009860400024836_CR11","doi-asserted-by":"crossref","first-page":"1309","DOI":"10.1039\/f19817701309","article-title":"Adsorption of butanes on NaY and dehydroxylated Y zeolites by infrared spectroscopy","volume":"77","author":"Datka","year":"(1981)","journal-title":"Journal of Chemical Society Faraday Transactions I"},{"key":"S0009860400024836_CR29","doi-asserted-by":"crossref","first-page":"91","DOI":"10.1016\/0021-9517(75)90136-0","article-title":"Isomerization of butene over alumina","volume":"37","author":"Medema","year":"(1975)","journal-title":"Journal of Catalysis"},{"key":"S0009860400024836_CR2","doi-asserted-by":"crossref","first-page":"23","DOI":"10.1016\/0926-860X(93)80064-W","article-title":"Pillared clays: characterization of acidity and catalytic properties and comparision with some zeolites","volume":"97","author":"Auer","year":"(1993)","journal-title":"Applied Catalysis. A: General"},{"key":"S0009860400024836_CR17","doi-asserted-by":"crossref","first-page":"4274","DOI":"10.1021\/ja01501a039","article-title":"Stereoselective catalytic isomerization of n-butenes","volume":"82","author":"Foster","year":"(1959)","journal-title":"Journal of American Chemical Society"},{"key":"S0009860400024836_CR4","doi-asserted-by":"crossref","first-page":"359","DOI":"10.1016\/0021-9517(74)90217-6","article-title":"The isomerization of cis-2-butene over silica-alumina catalysts. III. Dependence on alumina content","volume":"35","author":"Ballivet","year":"(1974)","journal-title":"Journal of Catalysis"},{"key":"S0009860400024836_CR34","doi-asserted-by":"crossref","first-page":"14","DOI":"10.1016\/0021-9517(76)90195-0","article-title":"Catalytic isomerization of ethylenic hydrocarbons","volume":"41","author":"Perot","year":"(1976)","journal-title":"Journal of Catalysis"},{"key":"S0009860400024836_CR44","first-page":"187","volume-title":"Pillared Clays: Catalysis Today","author":"Vaughan","year":"(1988)"},{"key":"S0009860400024836_CR14","first-page":"337","volume-title":"Preparation of Catalysts V","author":"Farfan-Torres","year":"(1991)"},{"key":"S0009860400024836_CR8","doi-asserted-by":"crossref","first-page":"27","DOI":"10.1016\/0927-6513(95)00080-1","article-title":"Preparation and characterization of zirconium pillared laponite and hectorite","volume":"6","author":"Cool","year":"(1996)","journal-title":"Microporous Materials"},{"key":"S0009860400024836_CR28","doi-asserted-by":"crossref","first-page":"363","DOI":"10.1346\/CCMN.1990.0380405","article-title":"Synthesis of highly microporous hydrophilic alumina-pillared montmorillonite: Water-sorption properties","volume":"38","author":"Malla","year":"(1990)","journal-title":"Clays and Clay Minerals"},{"key":"S0009860400024836_CR47","doi-asserted-by":"crossref","first-page":"34","DOI":"10.1006\/jcat.1994.1320","article-title":"Selective conversion of n-butene to isobutylene at extremely high space velocities on ZSM-23 zeolites","volume":"150","author":"Xu","year":"(1994)","journal-title":"Journal of Catalysis"},{"key":"S0009860400024836_CR41","doi-asserted-by":"crossref","first-page":"277","DOI":"10.1016\/S1387-1811(01)00207-4","article-title":"Adsorption of volatile organic compounds in Y zeolites and pillared clays","volume":"43","author":"Pires","year":"(2001)","journal-title":"Microporous and Mesoporous Materials"},{"key":"S0009860400024836_CR3","doi-asserted-by":"crossref","first-page":"1101","DOI":"10.1021\/cm00032a013","article-title":"FTIR surface site analysis of pillared clays using pyridine probe species","volume":"5","author":"Bagshaw","year":"(1993)","journal-title":"Chemistry of Materials"},{"key":"S0009860400024836_CR13","doi-asserted-by":"crossref","first-page":"347","DOI":"10.1006\/jcat.1993.1145","article-title":"Determination of integrated molar extinction coefficients for infrared absorption bands of pyridine adsorbed on solid acid catalysts","volume":"141","author":"Emeis","year":"(1993)","journal-title":"Journal of Catalysis"},{"key":"S0009860400024836_CR20","first-page":"209","volume-title":"Adsorption, Surface Area and Porosity","author":"Gregg","year":"(1982)"},{"key":"S0009860400024836_CR9","doi-asserted-by":"crossref","first-page":"207","DOI":"10.1016\/S1381-1169(98)00365-3","article-title":"Activity-acidity relationship in zeolite Y. Part 1. Transformation of light olefins","volume":"144","author":"Costa","year":"(1999)","journal-title":"Journal of Molecular Catalysis A: Chemical"},{"key":"S0009860400024836_CR10","doi-asserted-by":"crossref","first-page":"2633","DOI":"10.1039\/f19817702633","article-title":"Transformations of butanes on dehydroxylated Y zeolites studied by infrared spectroscopy","volume":"77","author":"Datka","year":"(1981)","journal-title":"Journal of Chemical Society Faraday Transactions I"},{"key":"S0009860400024836_CR12","doi-asserted-by":"crossref","first-page":"551","DOI":"10.1021\/ie50519a029","article-title":"Review of olefin isomerization","volume":"45","author":"Dunning","year":"(1953)","journal-title":"Industrial and Engineering Chemistry"},{"key":"S0009860400024836_CR16","doi-asserted-by":"crossref","first-page":"323","DOI":"10.1016\/S0926-860X(97)00362-1","article-title":"The influence of the composition on the thermal and acid characteristics of multi-component oxide pillared montmorillonite","volume":"168","author":"Flego","year":"(1998)","journal-title":"Applied Catalysis A: General"},{"key":"S0009860400024836_CR18","doi-asserted-by":"crossref","first-page":"111","DOI":"10.1016\/S1381-1169(96)00455-4","article-title":"Solid acid catalysts from clays: cumene synthesis by benzene alkylation with propene catalyzed by cation exchanged aluminum pillared clays","volume":"121","author":"Geatti","year":"(1997)","journal-title":"Journal of Molecular Catalysis A: Chemical"},{"key":"S0009860400024836_CR37","doi-asserted-by":"crossref","first-page":"1465","DOI":"10.1039\/a800891d","article-title":"Porosity and thermal stability of PILCs prepared with clays from different origins and different metal-polyhydroxycationic species of Al and Al\/Ce","volume":"8","author":"Pires","year":"(1998)","journal-title":"Journal of Materials Chemistry"},{"key":"S0009860400024836_CR21","doi-asserted-by":"crossref","first-page":"166","DOI":"10.1016\/0021-9517(77)90088-4","article-title":"Catalytic isomerization of ethylenic hydrocarbons. XIV. Effect of drying and reaction temperature on the isomerization of deuterated butenes over alumina","volume":"48","author":"Guisnet","year":"(1977)","journal-title":"Journal of Catalysis"},{"key":"S0009860400024836_CR19","doi-asserted-by":"crossref","first-page":"145","DOI":"10.1081\/CR-100100261","article-title":"Recent advances in the synthesis and catalytic applications of pillared clays","volume":"42","author":"Gil","year":"(2000)","journal-title":"Catalysis Reviews \u2014 Science and Engineering"},{"key":"S0009860400024836_CR25","doi-asserted-by":"crossref","first-page":"50","DOI":"10.1006\/jcat.1996.0304","article-title":"Chemical mechanism of hydrocarbon cracking over solid acidic catalysts","volume":"163","author":"Kissin","year":"(1996)","journal-title":"Journal of Catalysis"}],"container-title":["Clays and Clay Minerals"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.cambridge.org\/core\/services\/aop-cambridge-core\/content\/view\/S0009860400024836","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2024,3,11]],"date-time":"2024-03-11T10:56:07Z","timestamp":1710154567000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.cambridge.org\/core\/product\/identifier\/S0009860400024836\/type\/journal_article"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2003,6]]},"references-count":47,"journal-issue":{"issue":"3","published-print":{"date-parts":[[2003,6]]}},"alternative-id":["S0009860400024836"],"URL":"https:\/\/doi.org\/10.1346\/ccmn.2003.0510311","relation":{},"ISSN":["0009-8604","1552-8367"],"issn-type":[{"value":"0009-8604","type":"print"},{"value":"1552-8367","type":"electronic"}],"subject":[],"published":{"date-parts":[[2003,6]]}}}