Parahydrogen-induced Polarization in Heterogeneous Catalytic Processes

Parahydrogen-induced polarization of nuclear spins provides enhancements of NMR signals for various nuclei of up to four to five orders of magnitude in magnetic fields of modern NMR spectrometers and even higher enhancements in low and ultra-low magnetic fields. It is based on the use of parahydrogen in catalytic hydrogenation reactions which, upon pairwise addition of the two H atoms of parahydrogen, can strongly enhance the NMR signals of reaction intermediates and products in solution. A recent advance in this field is the demonstration that PHIP can be observed not only in homogeneous hydrogenations but also in heterogeneous catalytic reactions. The use of heterogeneous catalysts for generating PHIP provides a number of significant advantages over the homogeneous processes, including the possibility to produce hyperpolarized gases, better control over the hydrogenation process, and the ease of separation of hyperpolarized fluids from the catalyst. The latter advantage is of paramount importance in light of the recent tendency toward utilization of hyperpolarized substances in in vivo spectroscopic and imaging applications of NMR. In addition, PHIP demonstrates the potential to become a useful tool for studying mechanisms of heterogeneous catalytic processes and for in situ studies of operating catalytic reactors. Here, the known examples of PHIP observations in heterogeneous reactions over immobilized transition metal complexes, supported metals, and some other types of heterogeneous catalysts are discussed and the applications of the technique for hypersensitive NMR imaging studies are presented.