Thermal desorption mass spectroscopy

Electrochemical Thermal Desorption Mass Spectroscopy (ECTDMS). 132... 

The recently developed ex situ analysis of electrode ad-layers by thermal desorption mass spectroscopy has been demonstrated to be a powerful tool for the study of adsorbates [13, 14],... 

Fig. 1.3. Experimental setup for electrochemical thermal desorption mass spectroscopy (ECTDMS). C = electrochemical cell, W = working electrode, El = electrolyte inlet, EO = electrolyte outlet, EH = electrode holder, V = valve, TP = turbo pump, VC = vacuum chamber, L = light source, W = window, P = protective jacket, A = aperture to analysis chamber, GI = grid ion source, S = SEM detector.

Different experimental approaches were applied in the past [6, 45] and in recent years [23, 46] to study the nature of the organic residue. But the results or their interpretation have been contradictory. Even at present, the application of modem analytical techniques and optimized electrochemical instruments have led to different results and all three particles given above, namely HCO, COH and CO, have been recently discussed as possible methanol intermediates [14,15,23,46,47]. We shall present here the results of recent investigations on the electrochemical oxidation of methanol by application of electrochemical thermal desorption mass spectroscopy (ECTDMS) on-line mass spectroscopy, and Fourier Transform IR-reflection-absorption spectroscopy (SNIFTIRS). 

Iwasita et used the similar techniques and confirmed that the adsorbate contains a proton atom but concluded that the adsorbate is C-OHad ie same group executed electrochemical thermal desorption mass spectroscopy, in which the methanol absorbing electrode was washed by the supporting electrolyte, transferred to the UHV environment, heated to desorb the adsorbates to analyze them by mass spectroscopy. They found hydrogen molecules in the desorbed gas as well as CO and the ratio of hydrogen to CO decreased as the concentration of methanol increased. 

Abstract. Gas interstitial fullerenes was produced by precipitation of C6o from the solution in 1,2 dichlorobenzene saturated by O2, N2, or Ar. The structure and chemical composition of the fullerenes was characterized by X-ray powder diffraction analysis, FTIR spectroscopy, thermal desorption mass spectrometry, differential scanning calorimetric and chemical analysis. The images of fullerene microcrystals were analyzed by SEM equipped with energy dispersive X-ray spectroscopy (EDS) attachment. Thermal desorption mass spectroscopy and EDS analysis confirmed the presence of Ar, N and O in C60 specimens. From the diffraction data it has been shown that fullerite with face centered cubic lattice was formed as a result of precipitation. The lattice parameter a was found to enhance for precipitated fullerene microcrystals (a = 14.19 -14.25 A) in comparison with that for pure C60 (a = 14.15 A) due to the occupation of octahedral interstices by nitrogen, oxygen or argon molecules. The phase transition temperature and enthalpy of transition for the precipitated fullerene microcrystals decreased in comparison with pure Cgo- Low temperature wet procedure described in the paper opens a new possibility to incorporate chemically active molecules like oxygen to the fullerene microcrystals. 

UPS Ultraviolet Photoelectron Spectroscopy XPS X-ray Photoelectron Spectroscopy AES Auger Electron Spectroscopy ESCA Electron Spectroscopy for Chemical Analysis TDMS Thermal Desorption Mass Spectroscopy LEED Low-Energy Electron Diffraction RHEED Reflection High-Energy Electron Diffraction EELS Electron Energy Loss Spectroscopy... 

Various mass spectroscopies are applicable ex situ in order to obtain molecular information. Secondary ion mass spectroscopy (SIMS) can be used [124, 125]. Thermal desorption mass spectroscopy is a viable alternative as a less intrusive and more surface sensitive tool [126, 127]. So far, the latter method has been applied exclusively to adsorbed hydrogen and carbon monoxide formed in an electrochemical reaction of organic CHO-compounds. 

Much of the effort on the electrooxidation of ethanol has been devoted mainly to identifying the adsorbed intermediates on the electrode and elucidating the reaction mechanism by means of various techniques, as differential electrochemical mass spectrometry, in situ Fourier transform infrared spectroscopy, and electrochemical thermal desorption mass spectroscopy. The established major products include CO2, acetaldehyde, and acetic acid, and it has been reported that methane and ethane have also been detected. Surface-adsorbed CO is still identified as the leading intermediate in ethanol electrooxidation, as it is in the methanol electrooxidation. Other surface intermediates include various Ci and C2 compounds such as ethoxy and acetyl [102]. There is general agreement that ethanol electrooxidation proceeds via a complex multi-step mechanism, which involves a number of adsorbed intermediates and also leads to different byproducts for incomplete ethanol oxidation, as shown in Figure 1.22. 

Awad et al. [56] reported on the thermal degradation of a series of alkylimidazolium molten salts. Elemental analysis, TGA, and thermal desorption mass spectroscopy (TDMS) were used to characterize the degradation process. A correlation was observed between the chain lengths of the alkyl groups and the thermo-oxidative stability as the chain length increased from propyl, butyl, decyl, hexadecyl, and octadecyl to eicosyl, the stability decreased. Analysis of the decomposition products by FTIR provided information about the decomposition products. It suggested that the thermal decomposition of imidazolium salts followed an SN2 process (Figure 3.12). 

FIGURE 5.11 Thermal desorption mass spectroscopy (TDMS) profiles and hydrogen absorption curves. 

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