Raman spectroscopy zeolites

Vibrational Spectroscopy. Infrared absorption spectra may be obtained using convention IR or FTIR instrumentation the catalyst may be present as a compressed disk, allowing transmission spectroscopy. If the surface area is high, there can be enough chemisorbed species for their spectra to be recorded. This approach is widely used to follow actual catalyzed reactions see, for example. Refs. 26 (metal oxide catalysts) and 27 (zeolitic catalysts). Diffuse reflectance infrared reflection spectroscopy (DRIFT S) may be used on films [e.g.. Ref. 28—Si02 films on Mo(llO)]. Laser Raman spectroscopy (e.g.. Refs. 29, 30) and infrared emission spectroscopy may give greater detail [31]. 

The diffusion, location and interactions of guests in zeolite frameworks has been studied by in-situ Raman spectroscopy and Raman microscopy. For example, the location and orientation of crown ethers used as templates in the synthesis of faujasite polymorphs has been studied in the framework they helped to form [4.297]. Polarized Raman spectra of p-nitroaniline molecules adsorbed in the channels of AIPO4-5 molecular sieves revealed their physical state and orientation - molecules within the channels formed either a phase of head-to-tail chains similar to that in the solid crystalline substance, with a characteristic 0J3 band at 1282 cm , or a second phase, which is characterized by a similarly strong band around 1295 cm . This second phase consisted of weakly interacting molecules in a pseudo-quinonoid state similar to that of molten p-nitroaniline [4.298]. 

Though as yet in its infancy, the application of laser Raman spectroscopy to the study of the nature of adsorbed species appears certain to provide unusually detailed information on the structure of oxide surfaces, the adsorptive properties of natural and synthetic zeolites, the nature of adsorbate-adsorbent interaction, and the mechanism of surface reactions. 

In this chapter we have limited ourselves to the most common techniques in catalyst characterization. Of course, there are several other methods available, such as nuclear magnetic resonance (NMR), which is very useful in the study of zeolites, electron spin resonance (ESR) and Raman spectroscopy, which may be of interest for certain oxide catalysts. Also, all of the more generic tools from analytical chemistry, such as elemental analysis, UV-vis spectroscopy, atomic absorption, calorimetry, thermogravimetry, etc. are often used on a routine basis. 

IR and Raman spectroscopy can fulfill these requirements and they are also robust enough for in situ silicate analysis in plant reactors [7]. Both of these techniques have been used for identifying the symmetric (s) and asymmetric (as), stretching (va, vas) and bending (5a, 5as) O-Si-O vibrations in aqueous alkaline silicate solutions which are the cheapest hence most frequently used ingredients for zeolite synthesis [8, 9 and references herein]. However, this information has to be "translated" into siloxane ring... 

V-Mo-Zeolite catalysts prepared by solid-state ion exchange were studied in the selective catalytic reduction of NOx by ammonia. The catalysts were characterized by chemical analysis, X-ray powder diffraction, N2 adsorption (BET), DRIFT, UV-Vis and Raman, spectroscopy and H2 TPR. Catalytic results show that upon addition of Mo to V-ZSM-5, catalytic performance was enhanced compared to V-ZSM-5. 

Many of the characterization techniques described in this chapter require ambient or vacuum conditions, which may or may not be translatable to operational conditions. In situ or in opemndo characterization avoids such issues and can provide insight and information under more realistic conditions. Such approaches are becoming more common in X-ray adsorption spectroscopy (XAS) methods ofXANES and EXAFS, in NMR and in transmission electron microscopy where environmental instruments and cells are becoming common. In situ MAS NMR has been used to characterize reaction intermediates, organic deposits, surface complexes and the nature of transition state and reaction pathways. The formation of alkoxy species on zeolites upon adsorption of olefins or alcohols have been observed by C in situ and ex situ NMR [253]. Sensitivity enhancement techniques play an important role in the progress of this area. In operando infrared and RAMAN is becoming more widely used. In situ RAMAN spectroscopy has been used to online monitor synthesis of zeolites in pressurized reactors [254]. Such techniques will become commonplace. 

McNicol et al. (49) used luminescence and Raman spectroscopy to study structural and chemical aspects of gel growth of A and faujasite-type crystals. Their results are consistent with a solid-phase transformation of the solid amorphous network into zeolite crystals. Beard (50) used infrared spectroscopy to determine the size and structure of silicate species in solution in relationship to zeolite crystallization. 

The crystallization of zeolites from alkaline aluminosilicate gels was studied by luminescence and Raman spectroscopy. Trace amounts of Fe3+ ions substituted for Al3+in the tetrahedral aluminosilicate gel framework exhibit characteristic phosphorescence spectra, which have been used to follow the buildup of the zeolite framework. Phosphorescence spectra of exchanged Eui+ cations and Raman spectra of (CH N+ cations present in the solid phase of the gel indicate that no zeolitic cages exist in this phase during the induction period. Raman spectra of the liquid phase of the gel system show only the presence of Si02-(0H)2 and Al(OH)a anions. Our results demonstrate that crystallization of zeolites occurs within the solid phase of the gel, which is believed to consist of amorphous tetrahedral alumino-... 

In contrast, recent work (4-12) has shown that Raman spectroscopy can be used to study Ti) adsorption on oxides, oxide supported metals and on bulk metals [including an unusual effect sometimes termed "enhanced Raman scattering" wherein signals of the order of 10 - 106 more intense than anticipated have been reported for certain molecules adsorbed on silver], (ii) catalytic processes on zeolites, and (iii) the surface properties of supported molybdenum oxide desulfurization catalysts. Further, the technique is unique in its ability to obtain vibrational data for adsorbed species at the water-solid interface. It is to these topics that we will turn our attention. We will mainly confine our discussion to work since 1977 (including unpublished work from our laboratory) because two early reviews (13,14) have covered work before 1974 and two short recent reviews have discussed work up to 1977 (15,16). 

In a different application of Raman spectroscopy to studies of zeolites, Cooney and Tsai (6) have investigated the adsorption of bromine on alkali exchanged zeolites X, NaY and NaA, and the... 

Finally, in a brief communication Saperstain and Rein (26) have reported that Raman spectroscopy can even be used to detect the presence of physically adsorbed N2 and O2 on a 4A zeolite, and the results are discussed in terms of the chromatographic ability of the A zeolites to separate N2 from other gases. This ability to detect adsorbed gases on zeolite might prove useful for in situ catalytic studies, but thus far no additional uses of the technique have been reported. 

There have been few Raman investigations of catalyst preparation (of oxides, zeolites, or metals). Such experiments deliver information about molecular structures, and the formation of crystalline phases is detected at earlier stages by Raman spectroscopy than by XRD. Moreover, cells that allow for variable conditions are easily constructed. 

Appearance of Fluorescence in Raman Spectroscopy of Calcined Zeolites (24)... 

Similar tests of the fiuidized-bed method have been successful with a variety of molecular adsorbates and catalysts (other zeolites, supported oxides, naphthalene, pyridine, methanol, alkanes, alkenes, acetonitrile, ammonia, etc.) (25). We believe that this fiuidized-bed method is a major step forward for measurements of working catalysts with UV Raman spectroscopy. It should also be a useful method for measurements of catalytic kinetics by reducing heat and mass transfer effects that arise when catalysts are used in the form of pellets. In the limit of low conversions... 

The formation of hydrocarbons from methanol catalyzed by zeolite H-MFI has been investigated extensively 60,61). As with many hydrocarbon conversions, the catalytic activity of the methanol-to-hydrocarbons reaction decreases over time as a result of the buildup of high-molecular-weight carbonaceous deposits (coke). UV Raman spectroscopy was employed to characterize the accumulation and chemical nature of deposited hydrocarbons as a function of time and reaction temperature with both methanol and dimethyl ether as reactants and with zeolite MFI of various Si/Al atomic ratios as catalysts the first account of this work reported results for a zeolite MFI with low acid content (Si/Al = 90) (62). Both polyolefin and a cyclopentadienyl species were observed as intermediates during the formation of polyaromatic retained hydrocarbons. These observations strongly confirm the mechanism of coke formation proposed by Schulz and Wei (63) involving aromatic formation via a five-membered ring... 

Li, C. and Stair, P.C. (1997) Ultraviolet Raman spectroscopy characterization of coke formation in zeolites. Catalysis Today, 33 (1-3), 353-60. 

The reaction of water with low-loaded [Ru(bpy)3] + entrapped in zeolite Y has been reported [152]. Since translational mobility of the Ru molecules cannot occur in the zeolite, the multimolecular degradation step observed in solution is no longer possible. Instead, O2 was found to be formed from the reaction of [Ru(bpy)3] with water. It was possible to examine the evolution of this reaction at various pHs by spectroscopic methods, such as EPR, diffuse reflectance and Raman spectroscopy. Figure 30 shows the evolution of the diffuse reflectance spectra after exposure of Ru(bpy)3 +-zeolite Y to water at pH 7 [152]. Trace e is the spectrum of the... 

Transition-metal containing zeolites such as CoY and NiY (but not the Cu, Mn and Zn forms) polymerize acetylene to give trans-polyacetylene with relatively short conjugation length, as indicated by resonance Raman spectroscopy.70 The pol3nmerization products appeared to be restricted to the zeolite crystal surfaces. The authors also point to die importance of Lewis acidic centers for the polymerization. 

The polymerization of pyrrole over Cu(II)-exchanged ZSM-5 zeolites was studied with resonance Raman spectroscopy. The authors found that a critical concentration of cupric ions must be exceeded to observe polymerization. Hosts with low Si/Al ratios gave partially oxidized pol5rpyrrole (having quinoidal and aromatic structures) and pyrrole monomer. The quinoidal structure was associated with the charge carriers. Residual oxygen degraded the polymer. 

Introduction EPR spectroscopy Infrared spectroscopy Raman spectroscopy UV-Visible spectroscopy X-ray absorption spectroscopy Mass spectrometry of zeolites References... 

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