Abstract
Characteristics of the non-stoichiometric near-surface layers formed at reacted chalcopyrite are important for understanding its behavior as the main mineral of copper and for various materials applications. Here, we measured Cu L-, Fe L-, and S L-edge TEY XANES, and conventional XPS from chalcopyrite electrochemically polarized in 1M HCl solution. The spectra of copper, in contrast to those of Fe and S, remain almost unchanged on the first potential cycle despite strongly varying composition of the Fe-depleted near-surface regions. The Cu L-XANES spectra of chalcopyrite electrochemically pre-reduced and then anodized, and of that first anodized and then cathodically reduced, show the same leading peak but post-edge features indicative of covellite CuS and bornite Cu5FeS4, respectively. We suggest that the invariability of the Cu L-edge XANES and Cu 2p spectra is due to tetrahedral coordination CuS4 units stable even in the highly distorted non-stoichiometric structures.
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