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Iron has long been recognized as an ideal catalytic material for sustainable chemistry. However, conventional iron catalysts employed in liquid-phase hydrogenation reactions suffer from poor activity and air instability, severely restricting their wide applicability in practical use. Herein, we present the development of highly active and air-stable iron phosphide nanocrystal immobilized on zirconia (Fe 2 P NC/ZrO 2 ) for the reductive amination of aldehydes and ketones. The Fe 2 P NC/ZrO 2 catalyst demonstrated broad substrate applicability, high recyclability, and scalability in both gram-scale and continuous-flow processes. This catalyst leverages the synergistic metal–support effect of Fe 2 P NCs and ZrO 2 support, leading to activity 313 times higher than that of conventional iron nanoparticle catalysts. In-depth mechanistic studies elucidated that the distinctive interplay between Fe 2 P and ZrO 2 significantly accelerates ammonolysis of Schiff bases, a key step for boosting reaction efficiency. This study sets a new benchmark for iron-based catalysis, offering a robust alternative to precious metals, thereby contributing significantly to sustainable chemical manufacturing and green organic synthesis.
Tsuda et al. (Wed,) studied this question.