Parahydrogen-induced polarization (PHIP) is an NMR hyperpolarization
technique with the ability to increase the NMR sensitivity by serval
orders. The generation of hyperpolarization in hydrogenation reactions
is associated with a pairwise addition behavior, which is sensitive
to the properties of catalysts and the reaction process, making it
a powerful tool for the characterization of catalyst properties and
elucidation of reaction mechanisms. In this Perspective, we provide
an in-depth overview of the heterogeneous PHIP (HET-PHIP) technique
and its application in heterogeneous catalytic hydrogenation. The
fundamentals of HET-PHIP are introduced. We describe how HET-PHIP
can be used to obtain information about the morphology and electronic
properties of supported monometallic catalysts, bimetallic catalysts,
and zeolites as well as the facet effect and strong metal–support
interaction (SMSI) effect in hydrogenation. Advances in the mechanistic
understanding of catalytic hydrogenations by using HET-PHIP are discussed
with representative work. We propose the current limitations and prospects
of the HET-PHIP technique in catalytic hydrogenation reactions.