Modeling the Effect of Dissolved Hydrogen Sulfide on Mg2+鈥揥ater Complex on Dolomite {104} Surfaces

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• 作者：Zhizhang Shen ; Yun Liu ; Philip E. Brown ; Izabela Szlufarska ; Huifang Xu
• 刊名：Journal of Physical Chemistry C
• 出版年：2014
• 出版时间：July 24, 2014
• 年：2014
• 卷：118
• 期：29
• 页码：15716-15722
• 全文大小：305K
• ISSN：1932-7455

文摘

The key kinetic barrier to dolomite formation is related to the surface Mg²⁺鈥揌₂O complex, which hinders binding of surface Mg²⁺ ions to the CO₃^{2鈥?/sup> ions in solution. It has been proposed that this reaction can be catalyzed by dissolved hydrogen sulfide. To characterize the role of dissolved hydrogen sulfide in the dehydration of surface Mg2+ ions, ab initio simulations based on density functional theory (DFT) were carried out to study the thermodynamics of competitive adsorption of hydrogen sulfide and water on dolomite (104) surfaces from solution. We find that water is thermodynamically more stable on the surface with the difference in adsorption energy of 鈭?3.6 kJ/mol (in vacuum) and 鈭?2.8 kJ/mol (in aqueous solution). However, aqueous hydrogen sulfide adsorbed on the surface increases the Mg2+鈥揌₂O distances on the surrounding surface sites. Two possible mechanisms were proposed for the catalytic effects of adsorbed hydrogen sulfide on the anhydrous Ca鈥揗g carbonate crystallization at low temperature.}