Etude infrarouge des sites d'adsorption des alcools sur alumine

M Benaïssa, O Saur, J.-C Lavalley
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引用次数: 9

Abstract

The adsorption of different alcohols ((CF3)3 COH, (CF3)2 CHOH, CF3 CH2 OH, CH3 OH) has been studied by gravimetry and infrared spectroscopy. Gravimetric results show that the irreversibly and reversibly adsorbed quantities increase with alcohols basicity. Infrared spectra of the irreversible species formed on alumina samples activated at 1120 K provide evidence for alcoholate species. Moreover additional species are present in the case of methanol and 2-propanol: they are coordinated to Lewis acid sites. The reversible species are mainly hydrogen bonded. Poisoning experiments with bases ((CH3)2 O and (CH3)3 CC ≡ N) lead us to conclude that the number of acid sites not involved in the irreversible adsorption of alcohols increases from (CH3)2 CHOH to (CF3)3 COH. Use of CD3 OCD2H shows that these unoccupied sites are strong Lewis acid ones. These results with those obtained from the coadsorption of two alcohols show the heterogeneity of alumina surface sites; basic O2− - weak Lewis acid Al3+ pair sites are involved in the adsorption of the different alcohols. Moreover the surface presents other sites such as O2+ — strong Lewis acid Al3+ pair sites or strong Lewis acid Al3+ sites which are also involved in the adsorption of alcohols with high pka.

醇在氧化铝上吸附位点的红外研究
用重量法和红外光谱法研究了不同醇类((CF3)3COH、(CF3,2CHOH、CF3CH2-OH、CH3-OH)的吸附性能。重量分析结果表明,不可逆吸附量和可逆吸附量随醇碱度的增加而增加。在1120K下活化的氧化铝样品上形成的不可逆物种的红外光谱为醇化物物种提供了证据。此外,在甲醇和2-丙醇的情况下还存在额外的物种:它们与路易斯酸位点配位。可逆物种主要是氢键。碱((CH3)2O和(CH3。CD3-OCD2H的使用表明这些未被占据的位点是强路易斯酸位点。这些结果与从两种醇的共吸附获得的结果显示了氧化铝表面位点的不均匀性;碱性O2-弱路易斯酸Al3+对位参与了不同醇的吸附。此外,表面存在其他位点,如O2+-强路易斯酸Al3+对位点或强路易斯酸Al 3+位点,它们也参与具有高pka的醇的吸附。
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