Homogeneity of Surface Sites in Supported Single-Site Metal Catalysts: Assessment with Band Widths of Metal Carbonyl Infrared Spectra

摘要

Determining and controlling the uniformity of isolated metal sites on surfaces of supports are central goals in investigations of single-site catalysts because well-defined species provide opportunities for fundamental understanding of the surface sites. CO is a useful probe of surface metal sites, often reacting with them to form metal carbonyls, the infrared spectra of which provide insights into the nature of the sites and the metal support interface. Metals bonded to various support surface sites give broad bands in the spectra, and when narrow bands are observed, they indicate a high degree of uniformity of the metal sites. Much recent work on single-site catalysts has been done with supports that are inherently nonuniform, giving supported metal species that are therefore nonuniform. Herein we summarize values of vco data characterizing supported iridium gem-dicarbonyls, showing that the most nearly uniform of them are those supported on zeolites and the least uniform are those supported on metal oxides. Guided by vco data of supported iridium gem-dicarbonyls, we have determined new, general synthesis methods to maximize the degree of uniformity of iridium species on zeolites and on MgO. We report results for a zeolite HY-supported iridium gem-dicarbonyl with full width at half-maximum values of only 4.6 and 5.2 cm(-1) characterizing the symmetric and asymmetric CO stretches and implying that this is the most nearly uniform supported single-site metal catalyst.