NH3-probe X-ray photoelectron spectroscopy method to characterize solid acidity of clay minerals

Accurate determination of solid acidity is essential for evaluating the catalytic activity of clay minerals. However, the conventional Fourier-transform infrared (FTIR) method using NH₃ as the probe encounters challenges in measuring the solid acidity owing to the presence of water on the surface or within interlayer spaces of clay minerals as well as the influence of environmental water during the detection process. To mitigate water interference, a NH₃-probe X-ray photoelectron spectroscopy (XPS) approach was adopted as an alternative to the FTIR method for the identification and semi-quantification of solid acidity of clay minerals. Following NH₃ adsorption, the types of solid acid sites in clay minerals were identified through the chemical shift in N1s XPS spectra. The ratio of Brønsted and Lewis acid sites in a given sample and the relative concentration of acid sites across different samples were determined by examining the specific N1s peak area ratio. According to the XPS data, the ratios of Brønsted and Lewis acid sites in Ca-montmorillonite (SAz-2) and Na-montmorillonite (SWy-2) were nearly 1:1, whereas that for the illite–smectite mixed-layer mineral (ISCz-1) was 4. The acid site contents in SAz-2 were more than twice those of SWy-2. This work highlights the promising application prospects of the NH₃-probe XPS method in solid acidity investigations of clay minerals.