Determination of Si/Al molar ratios in microporous zeolites using calibration-free laser induced breakdown spectroscopy

In this paper, the potential application of a calibration-free laser-induced breakdown spectroscopy (CF-LIBS) method for the determination of the silicon-to-aluminum molar ratio in microporous zeolites (with both intermediate and high silica contents) is discussed. Three different zeolite types, i.e., mordenite and zeolites type Y and ZSM-5, were analyzed in this study and were shown to have Si/Al molar ratios in the range between 2.3 and 51.8. Many ionic and neutral atomic spectral lines of silicon and aluminum were detected in the measured LIBS spectra in the spectral range 200–1000 nm, but not all of the observed spectral lines are convenient for a CF-LIBS analysis. To increase the accuracy of the results, only lines with no or low self-absorption probability were selected. A systematic method is proposed to select spectral lines based on three main parameters: the transition probability (Einstein coefficient), the lower level energy of the observed transition and the number density ratio between singly ionized and neutral species (as calculated for Si and Al for the measured electron density and electron temperature). The calculated Si/Al molar ratios were close to that determined by wet chemical analysis with an average relative standard deviation of approximately 5% (maximum less than 15%). Our results point to the possibility of using CF-LIBS for analysis of these types of materials and for determination of Si/Al molar ratios.