Diverse effects of ferromagnetic-paramagnetic phase transition on the activity and selectivity of ferromagnetic catalysts

Tuning the catalyst’s activity and selectivity is usually achieved by modifying the electronic structure through strategies such as alloying, doping, strain, and ligand modification, but inevitably accompanied by geometric structure changes of catalysts. It is challenging to modify a catalyst’s electronic structure without changing its geometric structure. Recent studies found that the second-order ferromagnetic to paramagnetic (FM-PM) phase transition could promote catalytic performance without altering the geometric structures of active sites, which was also known as the magneto-catalytic effect (MCE). However, the understanding of the MCE is still incomplete. Herein, we conducted systematic density functional theory (DFT) calculations to clarify the complex reaction mechanisms for conversions of nitrogen-containing small molecules on both FM and PM Ni (1 1 1) surfaces. Our microkinetic modeling (MKM) results demonstrate that FM-PM phase transition promotes the N₂O decomposition activity of FM Ni catalyst but decreases its activity for NO decomposition while showing a negligible influence on the activity of ammonia decomposition. These results indicate the promotion, inhibition, and disappearance mechanisms of MCE on the catalytic activity, which further changes the selectivity of different products. We anticipate the MCE will work as an effective strategy for fine-tuning the activity and selectivity of ferromagnetic catalysts in heterogeneous catalysis, providing an extra basis for rational catalyst design.