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Valence electrons are one of the main players in solid catalysts and in catalytic reactions, since they are involved in several correlated phenomena like chemical bonding, magnetism, chemisorption, and bond activation. This is particularly true in the case of solid catalysts containing d-transition metals, which exhibit a wide range of magnetic phenomena, from paramagnetism to collective behaviour. Indeed, the electrons of the outer d-shells are, on one hand, involved in the formation of bonds within the structure of a catalyst and on its surface, and, on the other, they are accountable for the magnetic properties of the material. For this reason, the relationship between magnetism and heterogeneous catalysis has been a source of great interest since the mid-20th century. The subject has gained a lot of attention in the last decade, thanks to the orbital engineering of quantum spin–exchange interactions and to the widespread application of external magnetic fields as boosting tools in several catalytic reactions. The topic is discussed here through experimental examples and evidences of the interplay between magnetism and covalent bonding in the structure of solids and during the chemisorption process. Covalent bonding is discussed since it represents one of the strongest contributions to bonds encountered in materials.

Magnetism in a chemical compound is the macroscopic result of the couplings of the spins of electrons within in it [...]

The relationship between magnetism and catalysis has been an important topic since the mid-20th century. At present time, the scientific community is well aware that a full comprehension of this relationship is required to face modern challenges, such as the need for clean energy technology. The successful use of (para-)magnetic materials has already been corroborated in catalytic processes, such as hydrogenation, Fenton reaction and ammonia synthesis. These catalysts typically contain transition metals from the first to the third row and are affected by the presence of an external magnetic field. Nowadays, it appears that the most promising approach to reach the goal of a more sustainable future is via ferromagnetic conducting catalysts containing open-shell metals (i.e., Fe, Co and Ni) with extra stabilization coming from the presence of an external magnetic field. However, understanding how intrinsic and extrinsic magnetic features are related to catalysis is still a complex task, especially when catalytic performances are improved by these magnetic phenomena. In the present review, we introduce the relationship between magnetism and catalysis and outline its importance in the production of clean energy, by describing the representative case of 3d metal Pt-based alloys, which are extensively investigated and exploited in PEM fuel cells.