Pd-based bimetallic catalysts for parahydrogen-induced polarization in heterogeneous hydrogenations

Abstract. Production of hyperpolarized catalyst-free gases and liquids by heterogeneous hydrogenation with parahydrogen can be useful for various technical as well as biomedical applications, including in vivo studies, investigations of mechanisms of industrially important catalytic processes, enrichment of nuclear spin isomers of polyatomic gases, and more. In this regard, the wide systematic search for heterogeneous catalysts effective in pairwise H2 addition required for the observation of parahydrogen-induced polarization (PHIP) effects is crucial. Here in this work we demonstrate the competitive advantage of Pd-based bimetallic catalysts for PHIP in heterogeneous hydrogenations (HET-PHIP). The dilution of catalytically active Pd with less active Ag or In atoms provides the formation of atomically dispersed Pd1 sites on the surface of Pd-based bimetallic catalysts, which are significantly more selective toward pairwise H2 addition compared to the monometallic Pd. Furthermore, the choice of the dilution metal (Ag or In) has a pronounced effect on the efficiency of bimetallic catalysts in HET-PHIP, as revealed by comparing Pd-Ag and Pd-In bimetallic catalysts.