Application of matrix‐assisted laser desorption/ionization in the studies of phosphotungstic acid.

Rationale: Phosphorotungstic acid (PTA) has many applications, especially in the field of catalysis, due to its structural properties. However, the structure of PTA is studied mainly using theoretical methods. Matrix‐assisted laser desorption/ionization (MALDI) has the potential to be an effective method for the experimental study of heteropolyacids. Limitations of MALDI are the high molecular weight of the particles and the complex distribution of isotopic peak intensities. Both problems can be solved by automatically identifying observed signals by generating hypothetical molecular formulas and estimating their isotopic distributions. Methods: Phosphotungstic acid was studied under conditions of laser desorption/ionization in the absence and in the presence of the matrix. Three types of matrices were used: 2,5‐dihydroxybenzoic acid in water, α‐cyano‐4‐hydroxycinnamic acid in acetonitrile, and sinapic acid (SA) in tetrahydrofuran. Part of the peaks in the resulting mass spectra was identified using in‐house developed software that implements the automated isotopic distribution brute force. Results: The most informative mass spectra were obtained using SA as the matrix, which enabled the detection of particles containing PTA dimers for the first time. The compositions of particles incorporating PTA dimers were determined in an automated manner and can be written as [H3PW12O40]2·2H2O (m/z = 5791.2 Da) and [H3PW12O40]2·4H2O (m/z = 5836.5 Da). Other observed species included (WO3)n·PO3−, HPO2·(WO3)n, and WO2·(WO3)n clusters, with the latter containing W in mixed oxidation states. Conclusions: The combined use of MALDI and an automated identification procedure provided valuable experimental data on the structure and fragmentation of phosphotungstic acid. To the best of our knowledge, this study was the first to report on particles containing phosphotungstic acid dimers. [ABSTRACT FROM AUTHOR]