Infrared absorption spectroscopy characterization of liquid solid interfaces: The case of chiral modification of catalysts

SURFACE SCIENCE

卷:669

Article

Zaera, Francisco^1,2 

[1] Univ Catalysis, Dept Chem, Riverside, CA 92521 USA

[2] Univ Catalysis, UCR Ctr Catalysis, Riverside, CA 92521 USA

关键词: Infrared absorption spectroscopy;    Liquid-solid interfaces;    Chiral modifiers;    Hydrogenation catalysis;    Platinum surface;    Cinchona alkaloids;   

DOI  :  10.1016/j.susc.2017.11.004

来源: Elsevier

【 摘 要 】

An overview is provided here of our work on the characterization of chiral modifiers for the bestowing of enantioselectivity to metal-based hydrogenation catalysts, with specific reference to the so-called Onto reaction. We start with a brief discussion of the use of infrared absorption spectroscopy (IR) for the characterization of chemical species at liquid solid interfaces, describing the options available as well as the information that can be extracted from such experiments and the advantages and disadvantages associated with the technique. We then summarize the main results that we have reported to date from our IR study of the adsorption of cinchona alkaloids and related compounds from solutions onto platinum surfaces. Several observations are highlighted and placed in context in terms of the existing knowledge and their relevance to catalysis. Key conclusions include the uniqueness of the nature of the adsorbed species when in the presence of the solvent (versus when the uptake is done under vacuum, or versus the pure or dissolved molecules), the fact that each modifier adopts unique and distinct adsorption geometries on the surface and that those change with the concentration of the solution in ways that correlate well with the performance of the catalyst, the potential tendency of at least some of these chiral modifiers to bind to the surface primarily via the nitrogen atom of the amine group, not the aromatic ring as it is often assumed, and the observation that the ability of one modifier to dominate the catalytic chemistry in solutions containing mixtures of two or more of those is linked to their capacity for displacing each other from the surface, which in turn is determined by a balance between the strength of their binding to the surface and their solubility in the liquid solvent. (C) 2017 Elsevier B.V. All rights reserved.

【 授权许可】

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