Ammonia surface basicity

In the present work low temperature adsoi ption of fluoroform and CO, were used to characterize surface basicity of silica, both pure and exposed to bases. It was found that adsorption of deuterated ammonia results in appearance of a new CH stretching vibration band of adsorbed CHF, with the position typical of strong basic sites, absent on the surface of pure silica. Low-frequency shift of mode of adsorbed CO, supports the conclusion about such basicity induced by the presence of H-bonded bases. 

In the course of mixture separation, the composition and properties of both mobile phase (MP) and stationary phase (SP) are purposefully altered by means of introduction of some active components into the MP, which are absorbed by it and then sorbed by the SP (e.g. on a silica gel layer). This procedure enables a new principle of control over chromatographic process to be implemented, which enhances the selectivity of separation. As a possible way of controlling the chromatographic system s properties in TLC, the pH of the mobile phase and sorbent surface may be changed by means of partial air replacement by ammonia (a basic gaseous component) or carbon dioxide (an acidic one). 

In most recent calorimetric studies of the acid-base properties of metal oxides or mixed metal oxides, ammonia and n-butylamine have been used as the basic molecule to characterize the surface acidity, with a few studies using pyridine, triethylamine, or another basic molecule as the probe molecule. In some studies, an acidic probe molecule like CO2 or hexafluoroisopropanol have been used to characterize the surface basicity of metal oxides. A summary of these results on different metal oxides will be presented throughout this article. Heats of adsorption of the basic gases have been frequently measured near room temperature (e.g., 35, 73-75, 77, 78,81,139-145). As demonstrated in Section 111, A the measurement of heats of adsorption of these bases at room temperature might not give accurate quantitative results owing to nonspecific adsorption. 

Bautista, FM Campelo, JM (iarcia. A Luna. D Marinas. JM Romero. A A. Aluminum phosphatc atumina catalysts with low alumina content. III. Surface basicity of catalysts obtained in aqueous ammonia. ( V/r /v.v/.v/.ei/er.v, 1993 19. 137-142. 

This effect will be even more pronounced when a high number of nitrogen atoms is present on the surface, i.e. when tlie surface basicity of the carbon increases [81]. Given the impregnation process of whetlerites (see section 4.2.2.1), it is clear that the residual ammonia from the impregnation solution will enhance the capacity of the carbon for SO2 adsorption. The presence of the basic TEDA molecules will reinforce this effect. 

Rivera-Utrilla and coworkers carried out adsorption studies of Co(ll) ions from aqueous solutions using activated carbons prepared from almond shell activated to different degrees by activation in CO2 at 1123 K, and after the formation of carbon-oxygen acidic surface groups on treatment with nitric acid, hydrogen peroxide, and in air, and carbon-nitrogen basic surface groups on treatment with ammonia. The surface acidity and the surface basicity of each carbon was determined by titration with sodium hydroxide and HCl solutions, respectively. The adsorption isotherms of Co(II) ions on three typical samples of carbons, namely commercial... 

The probe molecules that are used to investigate surface acidity should be chosen accordingly to their ability to accept proton from the surface active site, or to donate electron pair to the solid surface. The molecules that fulfil these demands are, for example, ammonia, pyridine, or hydrocarbons. Similarly, the probe molecules that can be used to trace the basic site of solid catalysts must be able either to donate a proton or to accept electron(s). Importantly, many species (that even do not contain hydrogen in their formula, which is a demand according to Lowry-Brdnsted theory) can function as Lewis acid, accepting electron pair. Hence, the molecules that could be chosen to investigate surface basicity are, for example, dioxides of carbon or sulphur. 

In gas separation with membranes, a gas mixture at an elevated pressure is passed across the surface of a membrane that is selectively permeable to one component of the mixture. The basic process is illustrated in Figure 16.4. Major current applications of gas separation membranes include the separation of hydrogen from nitrogen, argon and methane in ammonia plants the production of nitrogen from ah and the separation of carbon dioxide from methane in natural gas operations. Membrane gas separation is an area of considerable research interest and the number of applications is expanding rapidly. 

Ammonia activation by Pt, to be discussed in the next section, is an interesting example, because it illustrates the basic principle that provides chemical direction to the identification of surface topologies that give low reaction barriers in surface reactions. This holds specifically for elementary reactions that require a surface ensemble of atoms. 

New aluminophosphate oxynitrides solid basic catalysts have been synthesised by activation under ammonia of an AIPO4 precursor. When the nitrogen content increases, XPS points out two types of nitrogen phosphorus bonding. The conversions in Knoevenagel condensation are related to the surface nitrogen content. Platinum supported on aluminophosphate oxynitride is an active catalyst for isobutane dehydrogenation. 

Temperature Programmed Desorption (TPD). Chemisorbed molecules are bonded to the surface by forces dependent on the nature of the sites. For instance, ammonia will be strongly adsorbed on acid sites, whereas it is only weakly adsorbed on basic sites. Consequently, the adsorbate complex formed with the basic sites will decompose at lower temperatures than that formed with the acid sites. The following example regarding the NH.i-zeolite H-ZSM-5 system will illustrate this. 

As stated above, when probes with specific adsorption characteristics are used, additional chemical information can be extracted from adsorption-desorption experiments. Temperature-programmed desorption (TPD) in particular is often employed to obtain information about specific sites in catalysts [55,56], The temperature at which desorption occurs indicates the strength of adsorption, whereas either the amount of gas consumed in the uptake or the amount of desorption upon heating attests to the concentration of the surface sites. The most common molecules used in TPD are NH3 and C02, which probe acidic and basic sites, respectively, but experiments with pyridine, Oz, H2, CO, H20, and other molecules are often performed as well [57-59], As an example, the ammonia... 

Another thermal analysis method available for catalyst characterization is microcalorimetiy, which is based on the measurement of the heat generated or consumed when a gas adsorbs and reacts on the surface of a solid [66-68], This information can be used, for instance, to determine the relative stability among different phases of a solid [69], Microcalorimetiy is also applicable in the measurement of the strengths and distribution of acidic or basic sites as well as for the characterization of metal-based catalysts [66-68], For instance, Figure 1.10 presents microcalorimetry data for ammonia adsorption on H-ZSM-5 and H-mordenite zeolites [70], clearly illustrating the differences in both acid strength (indicated by the different initial adsorption heats) and total number of acidic sites (measured by the total ammonia uptake) between the two catalysts. 

Figure 3. Principles of photochemical modification of polymer (e.g. PTFE) by ultraviolet (UV) light in ammonia or acetylene atmosphere (A-B). Basic processes of photochemical modification of polymer by UV light (hv) in atmosphere are (a) surface reactions, (b) reactions in atmosphere and (c) reactions in polymer. [5].

Ammonia TPD is very simple and versatile. The use of propylamine as a probe molecule is starting to gain some popularity since it decomposes at the acid site to form ammonia and propene directly. This eliminates issues with surface adsorption observed with ammonia. The conversion of the TPD data into acid strength distribution can be influenced by the heating rate and can be subjective based on the selection of desorption temperatures for categorizing acid strength. Since basic molecules can adsorb on both Bronsted and Lewis acid sites, the TPD data may not necessarily be relevant for the specific catalytic reaction of interest because of the inability to distinguish between Bronsted and Lewis acid sites. 

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