The Influence of Mineral Matter on X-Ray Photoelectron Spectroscopy Characterization of Surface Oxides on Carbon

The chemical structure of coal is very composite, consisting of a heterogeneous carbonaceous matrix with variable degrees of “turbostratic” order and the inclusion and/or exclusion of mineral matter (ash). The formation of surface oxides on carbon has long been recognized as a key to understanding many chemical and physical properties of carbon materials relevant to their consolidated or emerging applications. The extent and nature of surface oxides can effectively be assessed by high-resolution X-ray photoelectron spectroscopy (XPS), which provides excellent insight into the functional nature of C-O moieties. However, the XPS analysis of ash-bearing carbons may be biased by the interfering effects of inorganics with the most relevant spectral ranges, namely the core levels O1s and C1s. The effect of ash components on the spectroscopic characterization of carbon is scrutinized here with reference to a sub-bituminous coal characterized by a fairly large ash content. The coal is subjected to different treatments, including devolatilization, milling, and oxidation. A synthetic carbon (Carboxen) is used as a reference sample for the correct assignment of the carbon–oxygen functionalities in the core-level XPS spectra (C1s and O1s) in the absence of mineral matter. On the opposite side, fly ash from an industrial coal boiler is analyzed to investigate the effects of mineral matter. It is shown that the establishment of non-uniform charging of the sample induced by ash provides a key to the interpretation of the XPS spectra of ash-bearing carbon samples. The positive charge on the surface, referred to as the charging effect, brings about a shift of the core-level binding energies towards higher values. Grinding of the samples or partial combustion emphasizes the charging effect. XPS analysis of the fly ash, where carbon is largely consumed and dispersed in the inorganic matter, confirms that charging arises from non-conductive aluminosilicates. These effects may induce remarkable changes in carbon and oxygen peak shapes and need to be accounted for to obtain correct interpretations of the XPS spectra of ash-rich carbonaceous fuels.