Probing the Brønsted Acidity of the External Surface of Faujasite-Type Zeolites

We outline two methodologies to selectively characterize the Brønsted acidity of the external surface of FAU-type zeolites by IR and NMR spectroscopy of adsorbed basic probe molecules. The challenge and goal are to develop reliable and quantitative IR and NMR methodologies to investigate the accessibility of acidic sites in the large pore FAU-type zeolite Y and its mesoporous derivatives often referred to as ultra-stable Y (USY). The accessibility of their Brønsted acid sites to probe molecules (n-alkylamines, n-alkylpyridines, n-alkylphosphine- and phenylphosphine-oxides) of different molecular sizes is quantitatively monitored either by IR or ³¹P NMR spectroscopy. It is now possible, for the first time to quantitatively discriminate between the Brønsted acidity located in the microporosity and on the external surface of large pore zeolites. For instance, the number of external acid sites on a Y (LZY-64) zeolite represents 2 % of its total acid sites while that of a USY (CBV760) represents 4 % while the latter has a much lower framework Si/Al ratio.     

Quantum chemical investigation of the adsorption of methanol on a cluster model of faujasite

The adsorption of methanol in zeolites of the faujasite type with sodium and calcium counter ions is studied with quantum chemical methods. The zeolite is represented with a cluster model allowing calculations at the Møller-Plesset as well as the DFT level of theory. An adsorption energy of −62.4 kJ/mol is calculated at the MP2/TZVP//BP86/TZVP level of theory for one methanol molecule at one site II sodium cation. Insight into the adsorption process is obtained with a three-body decomposition which reveals a strong destabilisation of the adsorption strength by large, positive three-body terms, which is important for force field development.     

富硅超稳八面沸石研究：制备,表征,稳定性,羟基酸性及催化活性

用(NH_4)_2SiF_6二次合成法制备了Si/Al=4.2～7.1、结晶度大于94％的系列八面沸石(FSY样品),再于500℃水热处理得到相应的US-SY样品。XRD、DTA及IR研究发现US-SY样品较FSY样品有更高的热稳定性、骨架稳定性和酸强度,其裂解、歧化活性也优于FSY样品。     

The use of X-ray fluorescence (XRF) analysis in predicting the alkaline hydrothermal conversion of fly ash precipitates into zeolites

The use and application of synthetic zeolites for ion exchange, adsorption and catalysis has shown enormous potential in industry. In this study, X-ray fluorescence (XRF) analysis was used to determine Si and Al in fly ash (FA) precipitates. The Si and Al contents of the fly ash precipitates were used as indices for the alkaline hydrothermal conversion of the fly ash compounds into zeolites. Precipitates were collected by using a co-disposal reaction wherein fly ash is reacted with acid mine drainage (AMD). These co-disposal precipitates were then analysed by XRF spectrometry for quantitative determination of SiO₂ and Al₂O₃. The [SiO₂]/[Al₂O₃] ratio obtained in the precipitates range from 1.4 to 2.5. The [SiO₂]/[Al₂O₃] ratio was used to predict whether the fly ash precipitates could successfully be converted to faujasite zeolitic material by the synthetic method of [J. Haz. Mat. B 77 (2000) 123]. If the [SiO₂]/[Al₂O₃] ratio is higher than 1.5 in the fly ash precipitates, it favours the formation of faujasite. The zeolite synthesis included an alkaline hydrothermal conversion of the co-disposal precipitates, followed by aging for 8 h and crystallization at 100 °C. Different factors were investigated during the synthesis of zeolite to ascertain their influence on the end product. The factors included the amount of water in the starting material, composition of fly ash related starting material and the FA:NaOH ratio used for fusing the starting material. The mineralogical and physical analysis of the zeolitic material produced was performed by X-ray diffraction (XRD) and nitrogen Brunauer-Emmett-Teller (N₂ BET) surface analysis. Scanning electron microscopy (SEM) was used to determine the morphology of the zeolites, while inductively coupled mass spectrometry (ICP-MS), Fourier transformed infrared spectrometry (FT-IR) and Cation exchange capacity (CEC) [Report to Water Research Commission, RSA (2003) 15] techniques were used for chemical characterisation. The heavy and trace metal concentrations of the zeolite products were compared to that of the post-synthesis filtrate and of the precipitate materials used as Si and Al feed stock for zeolite formation, in order to determine the trends (increase or decrease) and ultimate fate of any toxic metals incorporated in the co-disposed precipitated residues.     

Xenon Adsorption and Xe-129 NMR on Faujasite Zeolites

Faujasites of Si/Al = 2–5 were obtained by direct synthesis and (NH₄)SiF₆ dealumination. The dependence of their Xe-129 NMR and xenon adsorption isotherm on Al content was used to monitor the inhomogeneous distribution of Al in synthesized samples of faujasite.     

Sonically modified hierarchical FAU-type zeolites as active catalysts for the production of furan from furfural

In this study, the sonochemical-assisted desilication method was applied as a special and innovative way of preparing hierarchical zeolites. The physicochemical properties of the hierarchical zeolites prepared using the sonochemical route were compared with those prepared using the conventional desilication method. Commercial zeolite with FAU-type structure was desilicated with a sodium and tetrabutylammonium hydroxide aqueous solution (NaOH/TBAOH) for 30 min. The ultrasound treatment process was performed using a QSonica Q700 sonicator (Church Hill Rd, Newtown, CT, USA) equipped with a ½″ diameter horn. The average power of sonication was 60 W, and the frequency was 20 kHz. During the sonication procedure, the alkaline solution with the catalyst precursor and sonicator probe were placed in an ice bath to keep them at room temperature. The prepared catalyst samples were examined by ICP-OES, XRD, SEM, NMR, and nitrogen sorption techniques. The acidic properties of the prepared hierarchical zeolite samples were assessed by means of IR spectroscopy with ammonia and carbon monoxide sorption as probe molecules. All catalysts were studied in the decarbonylation of furfural into furan.Independently of the application of ultrasonic irradiation, desilication of zeolites with an NaOH/TBAOH mixture extracts comparable amounts of silicon, resulting in comparable crystallinity and acidity. On the other hand, the samples prepared in the presence of ultrasounds revealed higher both mesoporosity and enhanced catalytic properties in the reaction of decarbonylation of furfural into furan in comparison with their counterparts prepared using the conventional method.     

Faujasite zeolites as solid electrolyte for low temperature fuel cells

In this work, the potential use of faujasite zeolites as a solid electrolyte material was evaluated with a particular focus on their endurance in acid environment, and on the influence played by the zeolites' chemical and textural properties on the degree of hydration and proton conductivity. Three faujasites with different initial Si/Al ratio were exposed to 6 mol dm⁻³ HCl solution and the exposure time was varied up to 7000 h for selected samples. Faujasite dealumination is a very fast process occurring mainly within 24 h of exposure. X-ray diffraction patterns show the faujasite structure was preserved, although N₂ sorption measurements indicate a possible partial collapse of the pore structure for samples dealuminated for 4500 and 7000 h.The proton conductivity of the faujasites is in the order of 10⁻⁸ S cm^-1 at 10% relative humidity, 10⁻⁶ S cm^-1 at 90% relative humidity, and 10⁻⁴ S cm^-1 for samples immersed in liquid water. The correlation between the proton conductivity and the zeolites' properties shows the predominant influence of the Al content at low relative humidity, and of the water content and micropore and mesopore volumes at high relative humidity. In particular, the expected increase of the proton conductivity with the mesopore volume at high relative humidity and for samples saturated with water was not observed.     

New experimental set-ups for studying nanoconfined water on the AILES beamline at SOLEIL

Three ensembles designed to investigate condensed matter in complex environments have been developed recently on the AILES beamline at SOLEIL. They have been exploited for studies aiming at understanding the properties of water molecules and their network in various confining systems, namely:

• -a hydration and temperature-controlled cell for the study of water confined in nanoporous Vycor,
• -a high pressure set-up allowing the study of the evolution of water molecules network trapped in Faujasite through the pressure-induced amorphisation of the matrix material,
• -a temperature resolved electrochemical cell used to record FIR difference spectra of metalloproteins interacting with water molecules.

By combining the high infrared flux and collimation of the AILES beamline with these optimized sample environments, it is possible to measure the infrared and THz spectra for minute quantities of samples in precise physical conditions.     

Synthesis of NaX and NaY Zeolites from Tunisian Kaolinite as Base Catalysts: An Investigation of Knoevenagel Condensation

The synthesis of Faujasite‐type zeolites with high purity has been successfully performed from Tunisian kaolinite and the effects of different crystallization parameters on the final products were widely investigated. The alkaline fusion of kaolinite followed by hydrothermal treatment lead to zeolite NaX synthesis whereas the classic hydrothermal transformation of metakaolinite produces NaY zeolite. The results show that an increase in the synthesis temperature and time has improved the crystallization process of the zeolite NaX whereas the SiO₂/Al₂O₃ and the Na₂O/SiO₂ molar ratios were the key parameters to obtain a pure zeolite NaY. The highest specific surface areas obtained with the optimal crystallization conditions were 554 m2 g^?1 and 592 m2 g^?1 for respectively NaX and NaY zeolites. The basic properties of NaX and NaY zeolites were explored in the Knoevenagel condensation of benzaldehyde with ethyl cyanoacetate at 140 °C as a test reaction in the absence of solvent. The influence of ion exchange with cesium cation on the catalytic activity of prepared catalysts was also investigated. It was found that the NaX provided higher activity than that of NaY catalyst due to its lower Si/Al ratio whereas a cesium exchange conferred higher basicity to the prepared Na‐faujasite.     

Propylene/propane mixture adsorption on faujasite sorbents

The adsorption of propylene and propane on zeolite NaX with and without a saturated (36 wt%) amount of CuCl have been investigated. The single component adsorption isotherms could be well described with a Dual-Site Langmuir model. The dispersion of CuCl results in a decrease of the maximum adsorption capacity of the zeolite for both components. For propylene a strong adsorption via π-complexation with CuCl is present, increasing the adsorption selectivity of the zeolite. The binary mixture (50:50) adsorption was determined via breakthrough/desorption experiments at 318, 358 and 408 K with a partial pressure of the two components between 0.8–54 kPa. For NaX the mixture loading could be well described with the IAS-theory and the single component isotherms, both qualitatively and quantitatively. A transition from an enthalpy controlled adsorption at lower loadings to an entropy affected adsorption at higher loadings was observed. The IAS-theory could only qualitatively describe the trends in the observed mixture adsorption for the CuCl/NaX adsorbent. The dispersion of CuCl in NaX results in a modest improvement of the adsorption selectivity for propylene over propane (from 3–7 to 15–30) but at the expense of a reduced capacity.