Recently, a facile method for the synthesis of size-monodisperse Pt, Pt Sn, and PtSn intermetallic nanoparticles (iNPs) that are confined within a thermally robust mesoporous silica (mSiO ) shell was introduced. These nanomaterials offer improved selectivity, activity, and stability for large-scale catalytic applications. Here we present the first study of parahydrogen-induced polarization NMR on these Pt-Sn catalysts. A 3000-fold increase in the pairwise selectivity, relative to the monometallic Pt, was observed using the PtSn@mSiO catalyst. The results are explained by the elimination of the three-fold Pt sites on the Pt(111) surface. Furthermore, Pt-Sn iNPs are shown to be a robust catalytic platform for parahydrogen-induced polarization for in vivo magnetic resonance imaging.

Pairwise and random addition processes are ordinarily indistinguishable in hydrogenation reactions. The distinction becomes important only when the fate of spin correlation matters, such as in parahydrogen-induced polarization (PHIP). Supported metal catalysts were not expected to yield PHIP signals given the rapid diffusion of H atoms on the catalyst surface and in view of the sequential stepwise nature of the H atom addition in the Horiuti-Polanyi mechanism. Thus, it seems surprising that supported metal hydrogenation catalysts can yield detectable PHIP NMR signals. Even more remarkably, supported Pt and Ir nanoparticles are shown herein to catalyze pairwise replacement on propene and 3,3,3-trifluoropropene. By simply flowing a mixture of parahydrogen and alkene over the catalyst, the scalar symmetrization order of the former is incorporated into the latter without a change in molecular structure, producing intense PHIP NMR signals on the alkene. An important indicator of the mechanism of the pairwise replacement is its stereoselectivity, which is revealed with the aid of density matrix spectral simulations. PHIP by pairwise replacement has the potential to significantly diversify the substrates that can be hyperpolarized by PHIP for biomedical utilization.

The effects of strong metal–support interactions (SMSI) on the pairwise selectivity of propene hydrogenation over metal-oxide-supported Ir nanoparticles were investigated using parahydrogen-enhanced NMR spectroscopy. A ∼20-fold increase in the pairwise selectivity was observed following a reduction treatment of the Ir/TiO2 catalyst at 500 °C. Consistent with SMSI, the effects could be completely reversed by oxidation followed by rereduction at 200 °C. Noninteracting supports, such as Al2O3 and SiO2, did not show this behavior. X-ray photoelectron spectroscopy reveals partial reduction of the TiO2 support, and STEM data reveal flattening of Ir particles after high-temperature reduction. The presence of chloride ions during activation was found to further promote pairwise selectivity but only for the Ir/TiO2 catalyst. The results are interpreted in terms of the electronic and possible geometric blocking effects associated with SMSI.

Intense para-hydrogen-enhanced NMR signals are observed in the hydrogenation of propene and propyne over ceria nanocubes, nano-octahedra, and nanorods. The well-defined ceria shapes, synthesized by a hydrothermal method, expose different crystalline facets with various oxygen vacancy densities, which are known to play a role in hydrogenation and oxidation catalysis. While the catalytic activity of the hydrogenation of propene over ceria is strongly facet-dependent, the pairwise selectivity is low (2.4% at 375 °C), which is consistent with stepwise H atom transfer, and it is the same for all three nanocrystal shapes. Selective semi-hydrogenation of propyne over ceria nanocubes yields hyperpolarized propene with a similar pairwise selectivity of (2.7% at 300 °C), indicating product formation predominantly by a non-pairwise addition. Ceria is also shown to be an efficient pairwise replacement catalyst for propene.

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