Microstructure and catalytic properties of Fe3O4/BN, Fe3O4(Pt)/BN, and FePt/BN heterogeneous nanomaterials in CO2 hydrogenation reaction: Experimental and theoretical insights

• The size of Fe 3 O 4 nanoparticles on the h-BN surfaces can be controlled by small Pt additions into synthesis media. • FePt/BN is high-productive catalyst in CO 2 hydrogenation reaction. • In situ TEM annealing revealed a unique mechanism of FePt/BN core–shell structure formation. • According to MD bimetallic FePt nanoparticles formation can be induced by Pt atoms diffusion toward the surface of Fe@Pt core–shell system. Hexagonal boron nitride ( h -BN) nanosheets are a promising material for various applications including catalysis. Herein, h -BN-supported Fe-based catalysts are characterised with respect to CO 2 hydrogenation reaction. Heterogeneous Fe 3 O 4 /BN, Fe 3 O 4 (Pt)/BN, and FePt/BN nanostructures are obtained via polyol synthesis in ethylene glycol. The sizes of Fe 3 O 4 nanoparticles and their distributions over h -BN surfaces depend on the amount of H 2 PtCl 6 added to the synthesis media. Bimetallic FePt nanoparticles are formed when Pt content is high enough. In situ TEM analysis shows the formation of core–shell h -BN@FePt nanoparticles during heating that prevents FePt NPs from further sintering during the catalytic process. The mechanism of Fe and Pt interaction is elucidated based on the molecular dynamic simulations. The FePt/BN nanomaterials show significantly higher CO 2 conversion rate compared to the Fe 3 O 4 /BN and Fe 3 O 4 (Pt)/BN heterogeneous nanomaterials and exhibit almost 100% selectivity to carbon monoxide. The Fe 3 O 4 /BN and Fe 3 O 4 (Pt)/BN nanomaterials show better selectivity to hydrocarbons. The possible reaction pathways are discussed based on the calculated sorption energies of all reactants, intermediate compounds, and reaction products. The study highlights pronounced catalytic properties of the developed system and reveals a unique interaction mechanism between its components increasing their stability.