Cyclodextrin-Functionalized Fe₃O₄@TiO₂: Reusable, Magnetic Nanoparticles for Photocatalytic Degradation of Endocrine-Disrupting Chemicals in Water Supplies

Water-dispersible, photocatalytic Fe₃O₄@TiO₂ core–shell magnetic nanoparticles have been prepared by anchoring cyclodextrin cavities to the TiO₂ shell, and their ability to capture and photocatalytically destroy endocrine-disrupting chemicals, bisphenol A and dibutyl phthalate, present in water, has been demonstrated. The functionalized nanoparticles can be magnetically separated from the dispersion after photocatalysis and hence reused. Each component of the cyclodextrin-functionalized Fe₃O₄@TiO₂ core–shell nanoparticle has a crucial role in its functioning. The tethered cyclodextrins are responsible for the aqueous dispersibility of the nanoparticles and their hydrophobic cavities for the capture of the organic pollutants that may be present in water samples. The amorphous TiO₂ shell is the photocatalyst for the degradation and mineralization of the organics, bisphenol A and dibutyl phthalate, under UV illumination, and the magnetism associated with the 9 nm crystalline Fe₃O₄ core allows for the magnetic separation from the dispersion once photocatalytic degradation is complete. An attractive feature of these “capture and destroy” nanomaterials is that they may be completely removed from the dispersion and reused with little or no loss of catalytic activity

Mapping Charge Distribution in Single PbS Core – CdS Arm Nano-Multipod Heterostructures by Off-Axis Electron Holography

We synthesized PbS core–CdS arm nanomultipod heterostructures (NMHs) that exhibit PbS{111}/CdS{0002} epitaxial relations. The PbS–CdS interface is chemically sharp as determined by aberration corrected transmission electron microscopy (TEM) and compared to density functional theory (DFT) calculations. Ensemble fluorescence measurements show quenching of the optical signal from the CdS arms indicating charge separation due to the heterojunction with PbS. A finite-element three-dimensional (3D) calculation of the Poisson equation shows a type-I heterojunction, which would prevent recombination in the CdS arm after optical excitation. To examine charge redistribution, we used off-axis electron holography (OAEH) in the TEM to map the electrostatic potential across an <i>individual</i> heterojunction. Indeed, a built-in potential of 500 mV is estimated across the junction, though as opposed to the thermal equilibrium calculations significant accumulation of positive charge at the CdS side of the interface is detected. We conclude that the NMH multipod geometry prevents efficient removal of generated charge carriers by the high energy electrons of the TEM. Simulations of generated electron–hole pairs in the insulated CdS arm of the NMH indeed show charge accumulation in agreement with the experimental measurements. Thus, we show that OAEH can be used as a complementary methodology to ensemble measurements by mapping the charge distribution in single NMHs with complex geometries