Understanding Copper Activation and Xanthate Adsorption on Sphalerite by Time-of-Flight Secondary Ion Mass Spectrometry, X‑ray Photoelectron Spectroscopy, and in Situ Scanning Electrochemical Microscopy

Abstract

In situ scanning electrochemical microscopy (SECM) was applied for the first time to study the copper activation and subsequent xanthate adsorption on sphalerite. The corresponding surface compositions were analyzed by time-of-flight secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS). The probe approach curve (PAC) using SECM shows that unactivated and activated sphalerite surfaces have negative current feedback and partially positive current feedback, respectively, suggesting that Cu_<i>x</i>S is formed on the sphalerite after copper activation. The copper activation of sphalerite strongly depends on the surface heterogeneity (e.g., presence of polishing defects, chemical composition), impacting the subsequent xanthate adsorption process. The SECM, ToF-SIMS, and XPS analyses show that during the copper activation the polishing defects, which have high excess surface energy, tend to consume more copper ions, resulting in Cu-rich regions by forming CuS-like species, while Fe oxide/hydroxide forms at Fe-rich regions. The XPS spectra further confirm that the CuS-like species involve Cu­(I) and S­(−I). The SECM imaging shows that after xanthate adsorption the current response at the Cu-rich regions decreases because of the formation of cuprous xanthate (CuX) and dixanthogen (X₂) while increases at the Fe-rich regions mainly due to the chemisorption of xanthate on Fe oxide/hydroxide. Our results shed light on the fundamental understanding of the electrochemical processes on sphalerite surface associated with its copper activation and subsequent xanthate adsorption in flotation