Effect of Surface Functionalization on the Magnetization of Fe3O4 Nanoparticles by Hybrid Density Functional Theory Calculations

by E. Bianchetti and C. Di Valentin
J. Phys. Chem. Lett. 2022, 13, 40, pp 9348-9354 View at Publisher
DOI: 10.1021/acs.jpclett.2c02186



Surface functionalization is found to prevent the reduction of saturation magnetization in magnetite nanoparticles, but the underlying mechanism is still to be clarified. Through a wide set of hybrid density functional theory (HSE06) calculations on Fe3O4 nanocubes, we explore the effects of the adsorption of various ligands (containing hydroxyl, carboxylic, phosphonic, catechol, and silanetriol groups), commonly used to anchor surfactants during synthesis or other species during chemical reactions, onto the spin and structural disorder, which contribute to the lowering of the nanoparticle magnetization. The spin canting is simulated through a spin-flip process at octahedral Fe ions and correlated with the energy separation between O 2p and FeOct 3d states. Only multidentate bridging ligands hamper the spin canting process by establishing additional electronic channels between octahedral Fe ions for an enhanced ferromagnetic superexchange interaction. The presence of anchoring organic acids also interferes with structural disorder, by disfavoring surface reconstruction.