Fourier transform infrared spectroscopy acid zeolites

Vibrational spectroscopy of adsorbed probe molecules is one of the most powerful tools to assess the acidic properties of catalysts. Acidity studies of dealumi-nated Y zeolites (main active component of FCC catalysts) or other zeolitic catalysts are reported using mostly Fourier Transform Infrared Spectroscopy (FTIR) with CO adsorption at 77 K or FTIR-pyridine/substituted pyridines adsorption at 425 K [22-26]. FTIR acidity studies of commercial FCC catalysts are even more scarce... 

Recently, we reported that an Fe supported zeolite (FeHY-1) shows high activity for acidic reactions such as toluene disproportionation and resid hydrocracking in the presence of H2S [1,2]. Investigations using electron spin resonance (ESR), Fourier transform infrared spectroscopy (FT-IR), MiJssbauer and transmission electron microscopy (TEM) revealed that superfine ferric oxide cluster interacts with the zeolite framework in the super-cage of Y-type zeolites [3,4]. Furthermore, we reported change in physicochemical properties and catalytic activities for toluene disproportionation during the sample preparation period[5]. It was revealed that the activation of the catalyst was closely related with interaction between the iron cluster and the zeolite framework. In this work, we will report the effect of preparation conditions on the physicochemical properties and activity for toluene disproportionation in the presence of 82. ... 

I. Mirsojew, S. Ernst, J. Weitkamp, and H. Knozinger, Characterization of acid properties of [Al] - and [Ga] - HZSM - 5 zeolites by low temperature Fourier transform infrared spectroscopy of adsorbed carbon monoxide, Catal. Lett. 24, 235-248 (1994). 

Characterization of catalysts The zeolite structure was checked by X-ray diffraction patterns recorded on a CGR Theta 60 instrument using Cu Ka, filtered radiation. The chemical composition of the catalysts was determined by atomic absorption analysis after dissolution of the sample (SCA-CNRS, Solaize, France). Micropore volumes were measured by N2 adsorption at 77 K using a Micromeritics ASAP 2000 apparatus and by adsorption of cyclohexane (at P/Po=0.15) using a microbalance apparatus SET ARAM SF 85. Incorporation of tetrahedral cobalt (II) in the framework of Co-Al-BEA and Co-B-BEA was confirmed by electronic spectroscopy [18] using a Perkin Elmer Lambda 14 UV-visible diffuse reflectance spectrophotometer. Acidity measurements were performed by Fourier transform infrared spectroscopy (FT-IR, Nicolet FTIR 320) after pyridine adsorption. Self-supported wafer of pure zeolite (20 mg/cm ) was outgassed at 673 K for 6 hours at a pressure of lO Pa. After cooling at 423 K, the zeolite was saturated with pyridine vapour (30 kPa) for 5 min, evacuated at this temperature for 30 min and the IR spectrum was recorded. 

We have investigated the photooxidation of toluene in several different zeolite hosts (BaX, BaY, CaY, BaZSM-5, and NaZSM-5) using in-situ Fourier Transform Infrared (FT-IR) spectroscopy and ex-situ Gas Chromatography (GC) to analyze product formation and product yields. This combined approach allows for a more detailed analysis of the product distribution. The product selectivity in these reactions appears to be governed by the presence of a small number of acid sites rather than by the framework composition or topology of the zeolite host. 

The study of the dynamics of N isotope transfer under adsorption-desorption equilibrium (NO -1- O2 + He) revealed two types of NOx complexes, and their concentrations and formation rates (depending on NO and O2 concentrations) were estimated. According to in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) data, these complexes are assigned to nitrite-nitrate (1520 cm" ) and N02 species (2130 cm" ). Note that nitrite-nitrates and N02 differ clearly in the rates of their formation. Under the reaction conditions, the concentrations of both active species drop considerably. Therefore, two parallel reaction pathways were proposed that involve both active complexes. The rates of NOx complexes interaction with methane were also calculated, and the reaction with participation of N02 species was shown to proceed about 2.5 times faster than that of nitrite-nitrate. The N02 species was determined to form at the interface between CoO clusters and acid OH groups in zeolite (or at the paired Co -OH sites). This finding agrees well with in situ DRIFTS data that indicates that the N02 formation correlates with a drop in the acid OH group band intensity. 

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