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NMR spectroscopic investigations of surface and interlayer species on minerals, clays and other oxides

Cygan, Randall T.

The behavior of chemical species adsorbed on solid surfaces and exchanged into clay interlayers plays a significant role in controlling many natural and technologically important processes, including rheological behavior, catalysis, plant growth, transport in natural pore fluids and those near anthropogenic hazardous waste sites, and water-mineral interaction. Adsorption and exchange reactions have been the focus of intense study for many decades. Only more recently, however, have there been extensive spectroscopic studies of surface species. Among the spectroscopic methods useful for studying surface and exchanged species (e.g., infrared, X-ray photoelectron spectroscopy [XPS] and X-ray absorption spectroscopy [XAS]), nuclear magnetic resonance spectroscopy (NMR) has the considerable advantage of providing not only structural information via the chemical shift and quadrupole coupling constant but dynamical information in the Hz-mHz range via lineshape analysis and relaxation rate measurements. It is also possible to obtain data in the presence of a separate fluid phase, which is essential for many applications. This paper illustrates the range of applications of NMR methods to surface and exchanged species through review of recent work from our laboratory on Cs in clay interlayers and Cs, Na and phosphate adsorbed on oxide surfaces. The substrate materials used for these experiments and our long-term objectives are related to problems of geochemical interest, but the principals and techniques are of fundamental interest and applicable to a wide range of technological problems.