Authors:Pavel Čičmanec, Roman Bulánek, and Karel Frolich
of NO x by hydrocarbons. The detailed localization of Cu + ions was widely studied by the CO probe molecule adsorption using the FTIR, EXAFS, EPR, UV–Vis, microcalorimetry, and TPD techniques [ 15 – 27 ] assuming the presence of several
Authors:V. Rakić, V. Dondur, R. Hercigonja, and V. Andrić
The active sites of hydrogen-exchanged Y zeolite (HY) and dealuminated (HDY) zeolites are investigated by TPD of carbon monoxide.
Only the high temperature TPD spectra of CO (TM620-690C) were observed, meaning that CO molecules interact with very strong
acid sites. The amounts of CO bonded on these sites are small (less than 1 molecule per unit cell). The strong influence of
dealumination on the coverage degree is found. The calculated values for kinetic parameters indicate chemisorption of CO in
the investigated systems (Edes240 kJ mol-1, A1011 s-1).
Summary Using temperature-programmed desorption (TPD), we have investigated the interaction of carbon dioxide with alkali-metal cation-exchanged faujasite type zeolites (LSX, X and Y). TPD in the temperature range between 300 and 500 K results in desorption profiles of different intensities depending on the kind of cation and the aluminium content of zeolites. For NaX the desorbed amount corresponds to about one percent of the saturation capacity at 298 K. In case of NaX and X type zeolites exchanged with Cs+ ions an additional desorption peak above 500 K could be observed. Taking into account desorption curves of different heating rates, desorption energy distribution functions were calculated by using an extended integral equation. Initial adsorbed CO2 could be assigned to carbonate species in different environments by DRIFT spectroscopy.
) series catalyst by H 2 -TPD, NH 3 /H 2 -TPD and thermodynamic calculations. The results have proved that hydrogen spillover on the catalyst surface is related to the hydrogen of H 3 PW 12 O 40 , and finally the equation H + + ( n − 1)H H n + ( n = 2
Authors:B. Hunger, J. Hoffmann, O. Heitzsch, and M. Hunger
The temperature-programmed desorption (tpd) of the amount of ammonia which is preadsorbed at about 373 K at HZSM-5 zeolites yields a complex desorption curve consisting of two overlapped peaks (Β andγ peak). Parts of the ammonia desorbed can be attributed to SiOHAl groups considering also1H-MAS NMR measurements.
The condensation approximation (CA) and numerical regularization procedure (RP) methods used to solve a Fredholm integral
equation of the first kind describing the adsorption equilibria on a heterogeneous solid surface under isothermal conditions
have been adopted in the present study to evaluate desorption energy distributions from temperature-programmed desorption
(TPD) spectra. From comparisons of the computational results obtained by means of these methods on the basis of simulated
TPD spectra, it follows that the CA gives stable solutions for wide desorption energy distributions and it can be used successfully
for calculations from wide and clear resolved peaks in the TPD spectra. The use of the RP is more advantageous for acquisition
of the distributions from closely related narrow peaks in the TPD spectra.
Curves of the temperature-programmed desorption (TPD) of ammonia from zeolites were evaluated with several kinetic models. An approximately linear correlation was found between the activation energy of desorption or the heat of adsorption of H zeolites with various Si/Al ratios and the intermediate electronegativity of the zeolites, the latter representing a measure of the acid strength.
We have investigated the temperature-programmed desorption (TPD) of ammonia during the activation of NH4Na-mordenites of different
exchange degrees. Using a regularization method, desorption energy distribution functions have been calculated. The obtained
results indicate the heterogeneity of the bridging Si-OH-Al groups in HNa-mordenites. This was concluded from the width of
the distribution functions and from the presence of submaxima. For HNa-mordenites of exchange degrees below 50%, containing
only hydroxyls in the broad channels, two distinct submaxima are present, thus suggesting the presence of at least two kinds
of bridging hydroxyls of various acid strengths. In HNa-mordenites of exchange degrees above 50%, the hydroxyls appear in
narrow channels and the distribution of ammonia desorption energy broadens on the side of higher energies. This may be related
to a strong stabilization of ammonium ions inside narrow channels. The maximum concentrations of hydroxyls of desorption energies
between 95 and 135 kJ mol-1 and between 135 and 165 kJ mol-1 calculated from TPD data were 3.9 and 3.3 OH per unit cell (u.c.). These values agree well with our previous IR results of
concentrations of hydroxyls in broad and in narrow channels (3.7 and 2.8 OH per u.c.). The TPD data obtained for the heterogeneity
of OH groups in HNa-mordenites are in accordance with the IR data concerning ammonia desorption. The IR band of OH groups
restoring upon saturation of all the hydroxyls with ammonia and subsequent step-by-step desorption at increasing temperatures
shifts to lower frequencies indicating that there are hydroxyls of various acid strengths and the less acidic hydroxyls restore
first at lower desorption temperatures.
Authors:B. Hunger, M. v. Szombathely, J. Hoffmann, and P. Bräuer
Desorption energy distributions were calculated for temperature-programmed desorption (TPD) of ammonia from H zeolites of
different type by means of regularization. This method does not require any limiting assumptions about the distribution function.
It could be shown that the desorption energy distributions obtained are nearly independent of the experimental conditions
and therefore they should represent a suitable measure for the distribution of the strength of acidic sites. The calculated
desorption energy distributions for the ammonia desorption from the isolated bridging SiOHAl groups of H zeolites of different
type significantly differ from each other in shape. The increase of the desorption energy of the main range of the distribution
functions correlates well with the increase of the average acid strength of the SiOHAl groups with decreasing Al content of