Temperature-programmed desorption sites

TPD Temperature-programmed desorption [171, 172] The surface is heated and chemisorbed species desorb at characteristic temperatures Characterization of surface sites and desorption kinetics... 

Studies to determine the nature of intermediate species have been made on a variety of transition metals, and especially on Pt, with emphasis on the Pt(lll) surface. Techniques such as TPD (temperature-programmed desorption), SIMS, NEXAFS (see Table VIII-1) and RAIRS (reflection absorption infrared spectroscopy) have been used, as well as all kinds of isotopic labeling (see Refs. 286 and 289). On Pt(III) the surface is covered with C2H3, ethylidyne, tightly bound to a three-fold hollow site, see Fig. XVIII-25, and Ref. 290. A current mechanism is that of the figure, in which ethylidyne acts as a kind of surface catalyst, allowing surface H atoms to add to a second, perhaps physically adsorbed layer of ethylene this is, in effect, a kind of Eley-Rideal mechanism. 

The SCR catalyst is considerably more complex than, for example, the metal catalysts we discussed earlier. Also, it is very difficult to perform surface science studies on these oxide surfaces. The nature of the active sites in the SCR catalyst has been probed by temperature-programmed desorption of NO and NH3 and by in situ infrared studies. This has led to a set of kinetic parameters (Tab. 10.7) that can describe NO conversion and NH3 slip (Fig. 10.16). The model gives a good fit to the experimental data over a wide range, is based on the physical reality of the SCR catalyst and its interactions with the reacting gases and is, therefore, preferable to a simple power rate law in which catalysis happens in a black box . Nevertheless, several questions remain unanswered, such as what are the elementary steps and what do the active site looks like on the atomic scale ... 

This clearly indicates that the support is able to convert a fraction of methane but contributes primarily to coking To investigate the role of acid sites in the conversion of methane to coke and hydrogen, the acid sites of the catalysts were characterized by sorption and temperature programmed desorption (t.p.d) of pyridine T.p.d. of pyridine (see Fig. 4) suggest a higher... 

Accessibility to Cu sites was determined by temperature programmed desorption of NO (NO TPD), using an experimental setup similar to that used for TPR, except the detector was a quadrupole mass spectrometer (Balzers QMS421) calibrated on standard mixtures. The samples were first activated in air at 673 K, cooled to room temperature in air, and saturated with NO (NO/He 1/99, vol/vol). They were then flushed with He until no NO could be detected in the effluent, and TPD was started up to 873 K at a heating rate of 10 K/min with an helium flow of 50 cm min. The amount of NO held on the surface was determined from the peak area of the TPD curves. 

Temperature-programmed desorption of mesitylene shows a marked difference to the catalysts prepared on MgCl2 surfaces. The spectrum contains only one desorption peak at aroimd 250 K. Due to the similar desorption temperature to the peak observed for MgCl2-based films, this peak was assigned to desorption from low coordinated or defect sites [118]. 

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. 

It has been known for some time that the spectroscopic signature of Ob-vacs can be healed by exposure to 02 [42-46], In addition, Epling etal. [47] show that temperature-programmed desorption (TPD) spectra of water and ammonia are perturbed when the surface is predosed with 02. This implies that oxygen is left on the surface in some form when Ob-vacs are healed by 02, As such, Epling et al. proposed that one Ob-vac is healed per 02 molecule with the other O atom being adsorbed at a Ti5c site (Oad), a dissociation mechanism supported by theoretical calculations [48, 49]. 

Such a possibility has been recognized by early workers,9 but in spite of this intriguing possibility, only recently has such a metal surface been created. Chiral kink sites were created on Ag single crystal surfaces to produce the enantiomeric surfaces Ag(643)s and Ag(643)R however, no differences between (R)- and (S)-2-butanol were observed for either the temperature-programmed desorption from the clean surfaces or the dehydrogenation (to 2-butanone) from preoxidized surfaces.10 Unfortunately, Ag exhibits few catalytic properties, so only a limited array of test reactions is available to probe enantioselectivity over this metal. It would be good if this technique were applied to a more catalytically active metal such as Pt. 

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... 

In the case of alkenes, 1-pentene reactions were studied over a catalyst with FAU framework (Si/Al2 = 5, ultrastable Y zeoHte in H-form USHY) in order to establish the relation between acid strength and selectivity [25]. Both fresh and selectively poisoned catalysts were used for the reactivity studies and later characterized by ammonia temperature programmed desorption (TPD). It was determined that for alkene reactions, cracking and hydride transfer required the strongest acidity. Skeletal isomerization required moderate acidity, whereas double-bond isomerization required weak acidity. Also an apparent correlation was established between the molecular weight of the hard coke and the strength of the acid sites that led to coking. 

The number of acid sites on pillared clays was determined by means of temperature programmed desorption (TPD) of ammonia. In each TPD experiment, a sample weighing about 0.5 g was treated in vacuo for 1 h at a given temperature in the range 400 - 600°C. Ammonia was adsorbed at a desired temperature (100-300°C) for 30 min and evacuated for 30 min. This sample was heated to 700°C at a rate of 10°C/min and desorbed ammonia was monitored by thermal conductivity detector. As water was desorbed simultaneously with ammonia, the ammonia TPD spectrum was obtained by point-by-point subtraction of the water desorption spectrum obtained with the sample which had not adsorbed ammonia. 

Catalyst base site densities inj,) were measured by Temperature-Programmed Desorption (TPD) of CO2 pre-adsorbed at room temperature. Samples were pretreated in situ in a N2 flow at 773 K, eooled down to room temperature and then exposed to a flowing mixture of 3 % of CO2 in N2 until surface saturation. Weakly adsorbed CO2 was removed by flushing in N2. Finally, temperature was raised up to 773 K at 10 K/min. The desorbed CO2 was converted to CH4 over a methanation catalyst (Ni/Kieselghur) and then analyzed with a flame ionization detector. 

CO/Rh(100). - This system forms an example where we have determined lateral interactions by fitting temperature-programmed desorption spectra that were simulated using kinetic Monte Carlo to experimental spectra. For coverages below 5ML CO adsorbs at top sites, which form a square grid. CO desorption has a rate constant... 

The technique is temperature programmed desorption and reaction, or more generally, thermal desorption and reaction. The principle of the technique is simple. A reactant molecule is adsorbed at low temperatures on an active site. The temperature is then raised in a controlled manner and the evolution of the reaction products is monitored. If the various products are evolved independent of each other, they must be formed on independent sites. 

The technique was applied to a-Fe203 (5). cis-2-Butene was introduced to the catalyst at 25°C for equilibration with the active site. After equilibration and removal of the gas-phase butene, temperature programmed desorption... 

Fig. 1. The temperature programmed desorption profiles for a-Fe203 (a) Blank desorption without adsorbates (b) ris-2-butene adsorption (c) butadiene adsorption (d) cis-2-butene adsorption from a catalyst depleted of selective oxidation sites. From ref. 5, reprinted with permission, copyright 1979 by the American Chemical Society.

The temperature programmed desorption profile for the adsorption of butadiene in place of cis-2-butene is shown in Fig. 1, curve c. Two sets of products are observed. The product below 210°C is unreacted butadiene, and the products above 210°C are carbon dioxide and water. The similarity in the evolution of the combustion products of butene and butadiene is an indication that their combustion proceeds via similar reaction mechanisms. The similarity in the desorption of butadiene suggests that in butene adsorption, butadiene desorption is desorption limited. Indeed, that both butene and butadiene adsorb on the same type of sites has been confirmed by sequential adsorption experiments. The results are shown in Table III. It was found that if the C4 hydrocarbons are adsorbed sequentially without thermal desorption between adsorptions, the amounts of the final desorption products are the same as those in experiments where only the first hydrocarbon... 

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