Ammonia infrared spectroscopy

Still another type of adsorption system is that in which either a proton transfer occurs between the adsorbent site and the adsorbate or a Lewis acid-base type of reaction occurs. An important group of solids having acid sites is that of the various silica-aluminas, widely used as cracking catalysts. The sites center on surface aluminum ions but could be either proton donor (Brpnsted acid) or Lewis acid in type. The type of site can be distinguished by infrared spectroscopy, since an adsorbed base, such as ammonia or pyridine, should be either in the ammonium or pyridinium ion form or in coordinated form. The type of data obtainable is illustrated in Fig. XVIII-20, which shows a portion of the infrared spectrum of pyridine adsorbed on a Mo(IV)-Al203 catalyst. In the presence of some surface water both Lewis and Brpnsted types of adsorbed pyridine are seen, as marked in the figure. Thus the features at 1450 and 1620 cm are attributed to pyridine bound to Lewis acid sites, while those at 1540... 

Deprotonation of H2O2 yields OOH , and hydroperoxides of the alkali metals are known in solution. Liquid ammonia can also effect deprotonation and NH4OOH is a white solid, mp 25° infrared spectroscopy shows the presence of NH4+ and OOH ions in the solid phase but the melt appears to contain only the H-bonded species NH3 and H202. " Double deprotonation yields the peroxide ion 02 , and this is a standard route to transition metal peroxides. 

In order to get the pore system of zeolites available for adsorption and catalysis the template molecules have to be removed. This is generally done by calcination in air at temperatures up to 500 °C. A careful study (ref. 12) of the calcination of as-synthesized TPA-containing MFI-type single crystals by infrared spectroscopy and visible light microscopy showed that quat decomposition sets in around 350 °C. Sometimes special techniques are required, e.g. heating in an ammonia atmosphere (ref. 13) in the case of B-MFI (boron instead of aluminum present) to prevent loss of crystallinity of the zeolite during template quat removal. 

In the case of selective oxidation catalysis, the use of spectroscopy has provided critical Information about surface and solid state mechanisms. As Is well known( ), some of the most effective catalysts for selective oxidation of olefins are those based on bismuth molybdates. The Industrial significance of these catalysts stems from their unique ability to oxidize propylene and ammonia to acrylonitrile at high selectivity. Several key features of the surface mechanism of this catalytic process have recently been descrlbed(3-A). However, an understanding of the solid state transformations which occur on the catalyst surface or within the catalyst bulk under reaction conditions can only be deduced Indirectly by traditional probe molecule approaches. Direct Insights Into catalyst dynamics require the use of techniques which can probe the solid directly, preferably under reaction conditions. We have, therefore, examined several catalytlcally Important surface and solid state processes of bismuth molybdate based catalysts using multiple spectroscopic techniques Including Raman and Infrared spectroscopies, x-ray and neutron diffraction, and photoelectron spectroscopy. 

Widespread medicinal use of colloidal bismuth subcitrate (CBS) has prompted extensive studies of bismuth compounds involving the citrate anion. Bismuth citrate is essentially insoluble in water, but a dramatic increase in solubility with increasing pH has been exploited as a bio-ready source of soluble bismuth, a material referred to as CBS. Formulation of these solutions is complicated by the variability of the bismuth anion stoichiometry, the presence of potassium and/ or ammonium cations, the susceptibility of bismuth to oxygenation to Bi=0, and the incorporation of water in isolated solids. Consequently, a variety of formulas are classified in the literature as CBS. Solids isolated from various, often ill-defined combinations of bismuth citrate, citric acid, potassium hydroxide, or ammonium hydroxide have been assigned formulas on the basis of elemental analysis data or by determination of water and ammonia content, but are of low significance in the absence of complementary data other than thermal analysis (163), infrared spectroscopy (163), or NMR spectroscopy (164). In this context, the Merck index lists the chemical formula of CBS as KgfNHJaBieOafOHMCeHsCbh in the 11th edition (165), but in the most recent edition provides a less precise name, tripotassium dicitrato bismuthate (166). 

Acid properties. The acid properties of zeolites, including those of aluminum-deficient zeolites, have been described in several reviews (e.g. 33-35). The methods used to study the acidity of aluminum-deficient Y zeolites include infrared spectroscopy (primarily pyridine and ammonia sorption studies), n-butylamine titrations in the presence of Hammett or arylmethanol indicators, and to a lesser extent potentiometric titrations and calorimetric measurements. 

With respect to the considerations above, research is split into three parts. The first is connected to the kinetic description of the release of ammonia from the biomass as function of temperature. This research employs infrared spectroscopy using a tunable diode laser. Here very small biomass particles are used that are heated up very rapidly in a small reactor, which ensures that transport effects are virtually excluded from the kinetic release effects. Since ammonia is released in very small quantities it is quite hard to detect. Therefore, we first measure CO release, which is easier. In the second part we investigate the propagation of a conversion front in biomass layers. Here we perform experiments and try to establish a modeling approach for the propagation by analytical and numerical approaches. In the third part the gas-phase conversion processes are described in terms of... 

The catalytically active sites of isomorphous substituted MFI structures (Al-Sil and In-Sil) have been characterized by infrared spectroscopy and microcalorimetric measurements using ammonia and acetonitrile as probes [261]. The hrst derivative of the heat of adsorption curves, dg/dfl, as function of the loading, a, gave maxima at about 140 and 100 kJ/mol for Al-Sil and In-Sil, respectively. Janchen and colleagues... 

There is considerable evidence that surface acidity influences the catalytic activity of iron molybdate [254]. It was found by studying the adsorption of ammonia using infrared spectroscopy that, under reaction conditions, the acidity is due to Lewis sites. The conclusion is that surface acidity is a necessary, but not a sufficient, property. 

Moffat and Neeleman (139) investigated the adsorption of ammonia on boron phosphate by means of infrared spectroscopy. Ammonia appear to dissociate on this solid. Although absorption bands arising from NH4+ and coordinated ammonia were obtained, the authors feel that the presence of NH + does not necessarily indicate that Br0nsted sites were initially present on the BP04 surface. Hydroxyl groups that might be formed when ammonia dissociates could react with dry ammonia to form NHi+. 

Tolbutamide exists in two polymorphs, one was obtained either by crystallization of tolbutamide from benzene solution after addition of hexane, or by precipitation from solution in aqueous ammonia by addition of acetic acid, and the other, metastable form was obtained from ethanolic solution after addition of water. The two forms were characterized by infrared spectroscopy, x-ray diffraction and d.t.a.(l)... 

Ammonia is a strong Lewis base and it is small in size. The various forms of ammonia expected to occur on surfaces due to specific interactions (see Table I) can be detected by infrared spectroscopy. Interactions should be quite strong since ammonia is a fairly hard base. Thus, criteria a-d (see Section II.C.l) could hopefully be fulfilled. 

Thus, adsorption of NH3 on alumina resembles that of water in many respects. Both molecules are adsorbed molecularly at low temperatures but are chemisorbed dissociatively at higher temperatures. Ammonia is held strongly on A1203 surfaces and cannot be removed completely even on desorption at 500°C. Various species occur simultaneously, their relative importance being determined by the OH content of the surface. Furthermore, displacement adsorptions may take place. Thus, NH2" ions readily replaced chloride ions on surfaces of chlo-rided aluminas (166). One has, therefore, to conclude that ammonia retention on aluminas cannot be an acceptable measure of surface acidity and can hardly be related to catalytic activity. Ammonia adsorption on aluminas as studied by infrared spectroscopy, perhaps combined with TPD experiments (173), gives ample information on surface properties but ammonia cannot be used as a specific poison on alumina. 

Catalysts Characterization. Following pretreatment of the SAPO molecular sieves, the catalysts were characterized by temperature programmed desorption (TPD) of ammonia and infrared spectroscopy. To assess the acidity of the samples, the desorption of ammonia from the catalysts was performed in a manner similar to that described by van Hooff et. al. [11]. For the ammonia TPD experiments, typically 0.1 gram of the molecular sieve sample was supported on quartz wool inside a 9 mm O.D. quartz reactor equipped with axial thermowell which contacted the top of the... 

Characterization of the catalyst acid sites by infrared spectroscopy correlated well with the results of ammonia desorption experiments. The transmission spectra of HZSM-5 (Figure 2a), and SAPO-34 (Figure 2b) following in vacuo pretreatment at 650 K all showed absorbance bands near 3610 cm. Since these two molecular sieves were the only samples to show high-temperature NH3 desorption peaks... 

Infrared spectroscopy has been used for many years to probe acid sites in zeolites. Typically, strong bases such as ammonia or pyridine are adsorbed, and the relative or absolute intensities of bands due to Lewis acid adducts or protonated Bronsted acid adducts are measured. The basicity of ammonia or pyridine is however much stronger than that of most hydrocarbon reactants in zeolite catalysed reactions. Such probe molecules therefore detect all of the acid sites in a zeolite, including those weaker acid sites which do not participate in the catalytic reaction. Interest has recently grown in using much more weakly basic probe molecules which will be more sensitive to variations in acid strength. It is also important in studying smaller pore zeolites to use probe molecules which can easily access all of the available pore volume. 

A key issue in the chemistry and catalysis of basic molecules reacting in acid zeolites is the extent to which proton transfer occurs from the Bronsted site to the basic molecule. For strongly basic molecules like ammonia or pyridine, infrared spectroscopy clearly identifies the protonated adduct (NH4+ or PyH+) from its characteristic vibrational frequencies. For trimethylphosphine, also a strong base, both infrared and NMR evidence for complete proton transfer are convincing[37]. For molecules which are less strongly basic, the question is not so easily answered. 

Infrared spectroscopy measurements were performed using a Perkin Elmer 580 apparatus. The acid strength distribution of the samples was measured using both calorimetric and volumetric gas-solid titration. Ammonia, pyridine, and branched pyridines (2,6-lutidine and 3,5-lutidine) were the selected probes. They were further dried over activated 3A molecular sieve extrudates and were purified by freeze-thaw techniques. 

Dealuminated M-Y zeolites (Si/Al = 4.22 M NH4, Li, Na, K, Cs) were prepared using the dealumination method developed by Skeels and Breck and the conventional ion exchange technique. These materials were characterised by infrared spectroscopy (IR) with and without pyridine adsorption, temperature-programmed desorption (t.p.d.) of ammonia. X-ray difiracto-metry (XRD) and differential thermoanalysis (DTA). They were used for encapsulation of Mo(CO)5. Subsequent decarbonylation and ammonia decomposition was monitored by mass spectrometry (MS) as a function of temperature. The oxidation numbers of entrapped molybdenum as well as the ability for ammonia decomposition were correlated to the overall acidity of the materials. It was found that the oxidation number decreased with the overall acidity (density and/or strength of Bronsted and Lewis acidity). Reduced acidity facilitated ammonia decomposition. 

Figure 11 Measured Brensted acid site density as a function of the nominal concentration from ammonium ion exchange, (o) infrared spectroscopy ( ) 2-propanol dehydration ) TPD of ammonia. Line represents perfect agreement. ...

M. J. McShane and G. L. Cote, Near-Infrared Spectroscopy for Determination of Glucose, Lactate, and Ammonia in Cell Culture Media, Appl. Spectrosc., 52(8), 1073 (1998). 

Ammonia adsorption on Lewis sites is stronger than that on Bronsted sites [97]. In situ infrared spectroscopy has been used to monitor surface coverages by various species under reaction conditions. Temperature programmed desorption shows that no NO decomposition occurs in the temperature range 100-600 K. By means of in situ FTIR spectroscopy it was observed that the fractional surface coverages by ammonia on the Bronsted and Lewis acid sites were 0.26 and 0.39, respectively, at 573 K. No adsorption of NO was found. Moreover, it was stated that water does not block the sites for ammonia adsorption. 

The powder X-ray diffraction patterns were measured in a D-500 SIEMENS diffractometer with a graphite seeondary beam monochromator and CuKoj contribution was eliminated by the DIFFRAC/AT software to obtain a monochromatic CuKa,. The Unit Cell Size (UCS) was measured following the ASTM D-3942-90 procedure. The Surface areas were measured by nitrogen adsorption at 75 K on a Micromeritics Accusorb 2100 E equipment using the ASTM method D-3663-78. Temperature Programmed Desorption (TPD) of ammonia and pyridine adsorption by Infrared Spectroscopy (IR) were used to characterize the acidity of the zeolites. For IR-Pyridine the spectra were recorded each 100°C and the characteristic bands of Lewis and Bronsted acid sites (1444 cm" and 1540 cm, respectively) were integrated in order to obtain the total acid sites. 

In-situ FTIR of CO (and other molecules as site specific probes) was studied on the H-form and hydrothermally treated samples of H-ZSM-5. These results have been more thoroughly reported elsewhere [10] but are sununarized here for comparison with experimental data from other techniques. Zeolites have been traditionally examined using infrared spectroscopy of N-containing adsorbates such as ammonia and pyridine to assess Bronsted acidity. The use of weaker Lewis bases allows a more discriminating approach to assessing the strength and quantity of Bronsted sites arising from the partial and sequential dealumination of framework A1 in H-ZSM-5. 

T emperature-programmed desorption (TPD) of ammonia and infrared spectroscopy (IR) of adsorbed pyridine are probably the most extensively used methods for characterising acidity (number, strength and nature of acid sites) in zeolites [17,18]. Fig. 1 shows the diffuse-reflectance infrared spectra of pyridine adsorbed on H-Y, H-Y(d5o%) and H-Y(d64%) samples at... 

Water has a negative effect on the SCR reaction because it competes with ammonia for chemisorption. In the presence and absence of water the rate constants at 673K are about 17 and 27cm g s, respectively. It was suggested that sulfation increases both Lewis and Bronsted acidity. The existence of Lewis sites was proved by adding water to the catalyst which results in an increase in Bronsted acidity. Bronsted sites were observed by means of infrared spectroscopy. 

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