Controlling Hydrogenation–Ammonolysis Competition in the Selective Reductive Amination of Biomass‐Derived Furfural Over Pt–Ni Catalysts

Understanding the factors controlling selectivity in the reductive amination of biomass‐derived furfural remains a major challenge for the rational design of sustainable catalytic processes. Herein, selective reductive amination of biomass‐derived furfural to furfurylamine (FAM) was achieved over TiO ₂ ‐supported Pt–Ni nanoparticles derived from carbonyl clusters as well‐defined bimetallic precursors. Tuning the Pt/Ni ratio enabled the identification of Pt ₂ Ni ₄ /TiO ₂ as the most efficient catalyst, reaching 92% furfurylamine selectivity and a productivity of 92 molFAM molmetal ⁻¹  h ⁻¹ under mild conditions. This study integrates kinetic analysis with density functional theory (DFT) to provide qualitative support for Ni‐to‐Pt electron redistribution and suggests that the bimetallic interface facilitated furfural activation, in agreement with the experimentally observed enhancement in catalytic performance. DFT calculations reveal that Ni incorporation induces a significant electronic redistribution, promoting electron transfer toward Pt surface sites and substantially lowering the activation barrier of the hydrogenation step to 0.37 eV. Furthermore, we establish that FAM selectivity emerges from a dynamic interplay where surface ammonia coverage dictates the competition between difurfurylimine hydrogenation and ammonolysis. We also identify the non‐innocent role of methanol via the formation of methoxyimine intermediates, which bypass traditional reaction pathways under hydrogen‐limited conditions. These findings demonstrate that selective reductive amination is governed by coverage‐dependent intermediate equilibria on the bimetallic surface rather than by metal identity alone. This work provides general design principles for controlling the hydrogenation–ammonolysis competition in the sustainable upgrading of renewable platform molecules.