Department of Chemistry, University of California, Davis, California 95616, USA.
Nat Mater. 2010 Jan;9(1):11-9. doi: 10.1038/nmat2585. Epub 2009 Nov 17.
Our understanding of mineral and glass dissolution has advanced from simple thermodynamic treatments to models that emphasize adsorbate structures. This evolution was driven by the idea that the best understanding is built at the molecular level. Now, it is clear that the molecular questions cannot be answered uniquely with dissolution experiments. At the surface it is unclear which functional groups are present, how they are arranged, and how they interact with each other and with solutes as the key bonds are activated. An alternative approach has developed whereby reactions are studied with nanometre-sized aqueous oxide ions that serve as models for the more complicated oxide interface. For these ions, establishing the structure is not a research problem in itself, and bond ruptures and dissociations can be followed with much confidence. We review the field from bulk-dissolution kinetics to the new isotope-exchange experiments in large oxide ions.
我们对矿物和玻璃溶解的理解已经从简单的热力学处理发展到强调吸附物结构的模型。这种演变的驱动力是这样一种观点,即最好的理解是在分子水平上建立的。现在,很明显,分子问题不能仅通过溶解实验来回答。在表面上,不清楚存在哪些官能团,它们是如何排列的,以及它们如何与彼此以及与溶质相互作用,因为关键键被激活。已经开发出一种替代方法,通过用纳米级大小的水合氧化物离子研究反应来研究更复杂的氧化物界面。对于这些离子,确定结构本身并不是一个研究问题,并且可以非常有信心地跟踪键的断裂和离解。我们从体相溶解动力学综述到新的同位素交换实验在大型氧化物离子。