TPD-MASS

Keywords cell surface, nanoparticle, MALDI, TPD, mass spectrometry 1. Introduction... 

Strauss, W. S., Lukens, J. A., Young, F. K., and Bingham, F. B., Oxygen enrichment of combustion air in a 360 TPD mass bum refuse-fired waterwall furnace, in Proceedings of the 1988 National Waste Processing Conference, 13th Bi-Annual Conference, Philadelphia, May 1-4, 1988, 315. 

The Kinetic Parameters Obtained on the Basis of the Data from TPD Mass Spectrometry during Thermal Destruction of Modified Silica... 

FIGURE 4.11 TPD mass spectra for heated carbosil prepared by phenylethanol carbonization at a silica gel surface. (Adapted from Carbon, 37, Pokrovskiy, V.A., Leboda, R., Turov, V.V., Charmas, B., and Ryczkowski, J., Temperature programmed desorption mass spectrometry of carbonized silica surface, 1039-1047, 1999, Copyright 1999, with permission from Elsevier.)... 

Thenual desorption spectroscopy (TDS) or temperature progranuned desorption (TPD), as it is also called, is a simple and very popular teclmique in surface science. A sample covered with one or more adsorbate(s) is heated at a constant rate and the desorbing gases are detected with a mass spectrometer. If a reaction takes place diirmg the temperature ramp, one speaks of temperature programmed reaction spectroscopy (TPRS). 

TPD is frequently used to detenuine (relative) surface coverages. The area below a TPD spectrum of a certain species is proportional to the total amount that desorbs. In this way one can detennine uptake curves that correlate gas exposure to surface coverage. If tire pumping rate of the UHV system is sufiBciently high, the mass spectrometer signal for a particular desorption product is linearly proportional to the desorption rate of the adsorbate [20, 21] ... 

Figure 7.6 shows a schematic set up for TPD. The crystal, mounted on a manipulator in an ultrahigh vacuum chamber, is heated such that the temperature increases linearly in time. The concentration of desorbing species is monitored with a mass spectrometer or with a simple pressure gauge. 

In principle, TPD can also be applied to high-surface area catalysts in plug-flow reactors. Often, however, the curves are seriously broadened by mass-transport phenomena. Hence, the use of single crystals or particles on planar supports offers great advantages for these investigations. 

The scanning transmission electron microscope (STEM) was used to directly observe nm size crystallites of supported platinum, palladium and first row transition metals. The objective of these studies was to determine the uniformity of size and mass of these crystallites and when feasible structural features. STEM analysis and temperature programmed desorption (TPD) of hydrogen Indicate that the 2 nm platinum crystallites supported on alumina are uniform In size and mass while platinum crystallites 3 to 4 nm in size vary by a factor of three-fold In mass. Analysis by STEM of platinum-palladium dn alumina established the segregation of platinum and palladium for the majority of crystallites analyzed even after exposure to elevated temperatures. Direct observation of nickel, cobalt, or iron crystallites on alumina was very difficult, however, the use of direct elemental analysis of 4-6 nm areas and real time Imaging capabilities of up to 20 Mx enabled direct analyses of these transition metals to be made. Additional analyses by TPD of hydrogen and photoacoustic spectroscopy (PAS) were made to support the STEM observations. 

Supported platinum. The STEM and TPD data for platinum supported on alumina and silica are summarized In Table I. The platlnum-slllca samples show a high degree of variability In size and mass. This variability Is Indicative of the mobility of platinum on silica at elevated temperatures, l.e., 500°C. These samples were of little... 

Specific surface areas of the catalysts used were determined by nitrogen adsorption (77.4 K) employing BET method via Sorptomatic 1900 (Carlo-Erba). X-ray difiraction (XRD) patterns of powdered catalysts were carried out on a Siemens D500 (0 / 20) dififactometer with Cu K monochromatic radiation. For the temperature-programmed desorption (TPD) experiments the catalyst (0.3 g) was pre-treated at diflferent temperatures (100-700 °C) under helium flow (5-20 Nml min ) in a micro-catalytic tubular reactor for 3 hours. The treated sample was exposed to methanol vapor (0.01-0.10 kPa) for 2 hours at 260 °C. The system was cooled at room temperature under helium for 30 minutes and then heated at the rate of 4 °C min . Effluents were continuously analyzed using a quadruple mass spectrometer (type QMG420, Balzers AG). 

The Ti02 (001) surface was cleaned and reduced by cycles of ion bombardment as previously described [3]. The distribution of titanium oxidation states was determined from cxirve fitting the Ti(2p3/2) envelope in x-ray photoelectron spectra [3]. After surface preparation, reaction experiments were conducted in either the TPD or steady state mode. TPD experiments have been described [1]. XPS spectra were also obtained following a saturation exposure of the sample using the same procedure as that for the TPD experiments. After pump down, the crystal was placed under the Mg X-ray source and the Ti(2p), 0(ls), and C(ls) regions were scanned. For steady-state experiments a dosing needle was aligned perpendicular to the axis of the mass spectrometer. It was used to direct a steady beam of methylacetylene (Linde, 95%) at the crystal surface when the sample was placed at the aperture of the mass spectrometer. Steady state reaction experiments were... 

Steady-state molecular beam studies of the reaction of methylacetylene on reduced Ti02 (001) surfaces were undertaken to determine whether this reaction could be performed catalytically under UHV conditions. A representative experiment is presented in Figure 1. Prior to each experiment, the surface was sputtered and annealed to a temperature between 400 K and 550 K surfaces prepared in this manner have the highest fraction of Ti(+2) sites (ca. 30% of all surface cations) of any surface we have been able to create by initial sputtering [3]. Thus these are the surfaces most active for cyclotrimerization in TPD experiments [1]. Steady-state production of trimethylbenzene (as indicated by the m/e 105 signal detected by the mass spectrometer) was characterized by behavior typical of more traditional catalysts a jump in activity upon initial exposure of the crystal to the molecular beam, followed by a decay to a lower, constant level of activity over a longer time scale. Experiments of up to 6 hours in duration showed... 

This study presents kinetic data obtained with a microreactor set-up both at atmospheric pressure and at high pressures up to 50 bar as a function of temperature and of the partial pressures from which power-law expressions and apparent activation energies are derived. An additional microreactor set-up equipped with a calibrated mass spectrometer was used for the isotopic exchange reaction (DER) N2 + N2 = 2 N2 and the transient kinetic experiments. The transient experiments comprised the temperature-programmed desorption (TPD) of N2 and H2. Furthermore, the interaction of N2 with Ru surfaces was monitored by means of temperature-programmed adsorption (TPA) using a dilute mixture of N2 in He. The kinetic data set is intended to serve as basis for a detailed microkinetic analysis of NH3 synthesis kinetics [10] following the concepts by Dumesic et al. [11]. 

Figure 1 Mass spectrometer (MS) intensities versus surface temp ature in a rqnesentadve temperature programmed desorpticm (TPD) profile of methyl on a clean Ni(lOO) surface. Total exposure was 1 L. Adsorption temperature was 105 K and heating rate was 3 K/s. Methane is produced near 225 K.

The pretreatment conditions were the same as those for IR study of adsorbed pyridine. The sample pretreated in a vacuum was exposed to ca. 300Torr D2 at different temperatimes for 1 h. After cooling to room temperature, the sample was outgassed for 10 min prior to TPD run. TPD was run at a heating rate of lOK min 1, and the desorbed gases were analyzed by mass spectrometry. 

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 (TPD) of NH3 adsorbed on the samples was carried out on an Altamira TPD apparatus. NH3 adsorption was performed at 50°C on the sample that had been heat-treated at 120°C in a helium flow. After flushing with helium, the sample was subjected to TPD from 50 to 600°C (AT = 10°C min 1). The evolved NH3, H20 and N2 were monitored by mass spectroscopy by recording the mass signals of m/e = 16, 18 and 28, respectively using a VG Trio-1 mass spectrometer. 

After the catalyst was saturated with carbon dioxide, a temperature programmed desorption (TPD) was carried out by heating the sample in helium (40 cm3min 1) from room temperature to 873 K (10 Kmin 1). The mass spectrometer was used to follow water (mass 18), carbon monoxide (mass 28), carbon dioxide (mass 44) and oxygen (mass 32). 

TPD and static secondary ion mass spectrometry (SSIMS) data suggest that methanol dissociatively adsorbs at Ob-vacs and molecularly at the Ti5c sites [52, 53]. There is also some evidence that methanol also dissociates at other sites apart from Ob-vacs, presumably Tisc sites [53-55]. Similar conclusions have been reached for a series of short-chain (C2-C8) aliphatic alcohols [56-58]. 

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