Resolution of intermediate surface species by combining modulated infrared spectroscopy and chemometrics

In this work, aiming at exploiting the essential particularities of modulation excitation spectroscopy (MES) coupled to phase sensitive detection (PSD) and chemometrics, a data analysis procedure was implemented to analyze phase-resolved infrared (IR) data. The fundamental principle of the proceedin...

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Bibliographic Details
Published in:Analytica chimica acta 2019-02, Vol.1049, p.38-46
Main Authors: Alcaraz, Mirta R., Aguirre, Alejo, Goicoechea, Héctor C., Culzoni, María J., Collins, Sebastián E.
Format: Article
Language:English
Subjects:
Catalysis
Chemometrics
Data analysis
Data processing
Excitation spectra
Infrared analysis
Infrared spectroscopy
Kinetics
Modulation excitation spectroscopy (MES)
Multivariate curve resolution-alternating least squares (MCR-ALS)
Oxalic acid
Phase lag
Phase sensitive detection (PSD)
Reaction kinetics
Spectroscopy
Spectrum analysis
Titanium dioxide
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Summary:In this work, aiming at exploiting the essential particularities of modulation excitation spectroscopy (MES) coupled to phase sensitive detection (PSD) and chemometrics, a data analysis procedure was implemented to analyze phase-resolved infrared (IR) data. The fundamental principle of the proceedings is the application of successive multivariate curve resolution-alternating least squares (MCR-ALS) resolutions to MES-PSD IR data. The applicability of the strategy was evaluated in several cases of simulated data considering the effect of spectral band overlapping and presence of noise. Outcomes related to data-processing are depicted in detail. As a proof of concept, the data resolution approach was validated by resolving an experimental real system related to the adsorption-desorption dynamic of oxalic acid on titanium dioxide by in situ IR spectroscopy in attenuated total reflection (ATR) mode. After data resolution, different oxalate species were assigned to each spectral band and information about the kinetics in terms of phase lag was obtained. In the light of the obtained results, this approach is rather appealing in other research fields, very helpful for the non-chemometric community and foresees manifold applications, specially, in catalytic system investigations. [Display omitted] •Novel proceedings for the analysis of modulation excitation spectroscopy coupled to phase sensitive detection data.•Chemometric data modeling of simulated and experimental systems by MCR-ALS.•Application to the resolution of adsorption-desorption dynamics of oxalic acid on titanium dioxide system.
ISSN:0003-2670
1873-4324
DOI:10.1016/j.aca.2018.10.052