Since the mid-1990s Hydrogen Isotope Exchange (HIE), consisting in the direct exchange of protium with its isotopes, has witnessed an enormous development (Atzrodt et al. in Angew Chem Int Ed, 57:3022–3047, 2018, [1], Atzrodt in Angew Chem Int Ed, 46:7744–7765, 2007, [2]). HIE reactions can nowadays be performed on a plethora of organic compounds by using both homogeneous and heterogeneous catalysis. Molecular catalysts remain the most commonly used due to their high reliability (Atzrodt et al. in Angew Chem Int Ed, 57:3022–3047, 2018, [1]). However, metallic nanoparticles have started attracting the attention of the scientific community (Asensio et al. in Chem Rev, 120:1042–1084, 2020, [3]) because of their interesting characteristics such as:
1.
their reactivity in between homogeneous and heterogeneous catalysts,
2.
the possibility to deeply influence their chemical properties by varying the stabilizing agent,
3.
the non-negligible advantages of (generally) simple workup procedures.
In this chapter, we will give an overview of the recent advances in HIE. First, we will describe the main applications of protium isotopes. Then, we will briefly discuss the main advances in catalytic HIE reactions in both homogeneous and heterogeneous phase. Finally, we will summarize the examples of HIE catalyzed by metallic nanoparticles that have been described in the literature.