~1H MAS NMR characterization of hydrogen over silica-supported rhodium catalyst

Hydrogen species in both SiO2 and Rh/SiO2catalysts pretreated in different atmospheres (H2, O2, helium or air) at different temperatures (773 or 973 K) were investigated by means of1H MAS NMR. In SiO2 and O2-pretreated catalysts, a series of downfield signals at ～7.0, 3.8–4.0, 2.0 and 1.5–1.0 were detected. The first two signals can be attributed to strongly adsorbed and physisorbed water and the others to terminal silanol (SiOH) and SiOH under the screening of oxygen vacancies in SiO2lattice, respectively. Besides the above signals, both upfield signal at ～?110 and downfield signals at 3.0 and 0.0 were also detected in H2-pretreated catalyst, respectively. The upfield signal at ～?110 originated from the dissociative adsorption of H2 over rhodium and was found to consist of both the contributions of reversible and irreversible hydrogen. There also probably existed another dissociatively adsorbed hydrogen over rhodium, which was known to be β hydrogen and in a unique form of “delocalized hydrogen”. It was presumed that the β hydrogen had an upfield shift of ca. ?20–?50, though its1H NMR signals, which, having been masked by the spinning sidebands of Si-OH, failed to be directly detected out. The downfield signal at 3.0 was assigned to spillover hydrogen weakly bound by the bridge oxygen of SiO2. Another downfield signal at 0.0 was assigned to hydrogen held in the oxygen vacancies of SiO2 (Si-H species), suffering from the screening of trapped electrons. Both the spillover hydrogen and the Si-H resulted from the migration of the reversible hydrogen and the β hydrogen from rhodium to SiO2 in the close vicinity. It was proved that the above migration of hydrogen was preferred to occur at higher temperature than at lower temperature.

Qualitative and quantitative analysis of Brønsted and Lewis acid sites in zeolites:A combined probe-assisted ^(1)H MAS NMR and NH_(3)-TPD investigation

Zeolite is one of the most important heterogeneous catalysts in acid catalytic reactions.Considering that the catalytic behaviors of zeolites are mostly related to their acidic characteristics,extensive attention has been attracted to the measurements of acid type,strength and concentration in zeolites.Numerous techniques including Fourier-transform infrared(FTIR)spectroscopy,probe-assisted^(1)H,^(13)C and^(31)P magic angle spinning nuclear magnetic resonance spectroscopy(MAS NMR)as well as temperature programmed desorption of ammonia(NH_(3)-TPD)have been developed for determining the acid sites.Nevertheless,a single approach is defective to characterize the acid sites comprehensively.Herein,combining the probe-assisted(e.g.,NH_(3)and CD_(3)CN)^(1)H MAS NMR and NH_(3)-TPD,the acid sites in different zeolites including the acid type,density and strength were determined.The commonly utilized NH_(3)-TPD to determine the acid strength of zeolite samples with different topologies should be rigorously considered owing to zeolite confinement effect.Controlling the desorption temperature of NH_(3)probe molecules,the acid type(Le.,Brønsted acid sites(BAS)and Lewis acid sites(LAS))and the corresponding density could be determined by NH_(3)probe-assisted^(1)H MAS NMR spectroscopy,while the acid strength could be investigated via CD_(3)CN probe-assisted^(1)H MAS NMR spectroscopy.