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  • Accepted Manuscript: Heterogeneous hydrogenation of phenylalkynes with parahydrogen: hyperpolarization, reaction selectivity, and kinetics
Title: Heterogeneous hydrogenation of phenylalkynes with parahydrogen: hyperpolarization, reaction selectivity, and kinetics
Parahydrogen-induced polarization (PHIP) is a powerful technique for studying hydrogenation reactions in gas and liquid phases. Pairwise addition of parahydrogen to the hydrogenation substrate imparts nuclear spin order to reaction products, manifested as enhanced 1 H NMR signals from the nascent proton sites. Nanoscale metal catalysts immobilized on supports comprise a promising class of catalysts for producing PHIP effects; however, on such catalysts the percentage of substrates undergoing the pairwise addition route—a necessary condition for observing PHIP—is usually low. In this paper, we present a systematic study of several metal catalysts (Rh, Pt, Pd, and Ir) supported on TiO 2 in liquid-phase hydrogenation of different prototypical phenylalkynes (phenylacetylene, 1-phenyl-1-propyne, and 3-phenyl-1-propyne) with parahydrogen. Catalyst activity and selectivity were found to be affected by both the nature of the active metal and the percentage of metal loading. It was demonstrated that the optimal catalyst for production of hyperpolarized products is Rh/TiO 2 with 4 wt% metal loading, whereas Pd/TiO 2 provided the greatest selectivity for semihydrogenation of phenylalkynes. In a study of liquid-phase hydrogenation reaction kinetics, it was shown that reaction order with respect to hydrogen is nearly the same for pairwise and non-pairwise H 2 addition—consistent with a similar nature more » of the catalytically active sites for these reaction pathways. « less
Authors:
; ; ; ; ; ; ; ;
Award ID(s):
1905341 1904780
Publication Date:
NSF-PAR ID:
10181005
Journal Name:
Physical Chemistry Chemical Physics
Volume:
21
Issue:
48
Page Range or eLocation-ID:
26477 to 26482
ISSN:
1463-9076
Sponsoring Org:
National Science Foundation
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