In Situ Synchrotron X‐ray Diffraction Studies of the Mechanochemical Synthesis of ZnS from its Elements. Issue 49 (9th July 2021)

• Record Type: Journal Article
• Authors: Petersen, Hilke; Reichle, Steffen; Leiting, Sebastian; Losch, Pit; Kersten, Wolfgang; Rathmann, Tobias; Tseng, Jochi; Etter, Martin; Schmidt, Wolfgang; Weidenthaler, Claudia
• Is Part Of: Chemistry. Volume 27:Issue 49(2021)
• Page Start: 12558
• Page End: 12565
• Publication Date: 2021-07-09
• Subjects: in situ investigations -- kinetic study -- material synthesis -- mechanochemistry -- synchrotron study; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202101260
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Mechanochemistry, as a synthesis tool for inorganic materials, became an ever‐growing field in material chemistry. The direct energy transfer by collision of the educts with the milling media gives the possibility to design environmental‐friendly reactions. Nevertheless, the underlying process of energy transfer and hence the kinetics of mechanosynthesis remain unclear. Herein, we present in situ synchrotron X‐ray diffraction studies coupled with pressure measurements performed during the formation of ZnS and the subsequent phase transition (PT) from the hexagonal to the cubic modification. Milling Zn and S8 results in the sublimation of S8, observed by a sudden pressure increase. Simultaneously, the hexagonal metastable ZnS‐modification (wurtzite) forms. Via detection of the pressure maximum, the exact start of the wurtzite formation can be determined. Immediately after the formation of wurtzite, the structural PT to the thermodynamic stable cubic modification sphalerite takes place. This PT can be described by the Prout‐Tompkins equation for autocatalytic reactions, similar to thermally induced PT in sulfur vapor at high temperatures (T>1133 K). The increase in the reactivity of the wurtzite formation is explained by the reaction in sulfur vapor and the induction of defect structures by the collisions with the milling media. Abstract : A detailed in situ investigation of the mechanosynthesis of the hexagonal ZnS modification (wurtzite) from its elements combining synchrotron powder diffraction and pressure measurements is presented. In addition, the subsequent phase transition from the hexagonal to the cubic structure (sphalerite) was investigated and the kinetics was explored.