Atomic-layer deposition (ALD) is a thin-film growth technology that allows for conformal growth of thin films with atomic-level control over their thickness. Although ALD is successful in the semiconductor manufacturing industry, its feasibility for nanoparticle coating has been less explored. Herein, the ALD coating of TiO2 layers on ZnO nanoparticles by employing a specialized rotary reactor is demonstrated. The photocatalytic activity and photostability of ZnO nanoparticles coated with TiO2 layers by ALD and chemical methods were examined by the photodegradation of Rhodamine B dye under UV irradiation. Even though the photocatalytic activity of the presynthesized ZnO nanoparticles is higher than that of commercial P25 TiO2 nanoparticles, their activity tends to decline due to severe photocorrosion. The chemically synthesized TiO2 coating layer on ZnO resulted in severely declined photoactivity despite the improved photostability. However, ultrathin and conformal ALD TiO2 coatings (≈ 0.75-1.5 nm) on ZnO improved its photostability without degradation of photocatalytic activity. Surprisingly, the photostability is comparable to that of pure TiO2, and the photocatalytic activity to that of pure ZnO.
We report the visible-light photocatalytic properties of a composite system consisting of silver quantum clusters [Ag9 (H2 MSA)7 ] (H2 MSA=mercaptosuccinic acid) embedded on graphitic carbon nitride nanosheets (AgQCs-GCN). The composites were prepared through a simple chemical route; their structural, chemical, morphological, and optical properties were characterized by using X-ray diffraction (XRD), energy dispersive X-ray spectroscopy, transmission electron microscopy, UV/Vis diffuse reflectance spectroscopy, and photoluminescence spectroscopy. Embedment of [Ag9 (H2 MSA)7 ] on graphitic carbon nitride nanosheets (GCN) resulted in extended visible-light absorption through multiple single-electron transitions in Ag quantum clusters and an effective electronic structure for hydroxyl radical generation, which enabled increased activity in the photocatalytic degradation of methylene blue and methyl orange dye molecules compared with pristine GCN and silver nanoparticle-grafted GCN (AgNPs-GCN). Similarly, the amount of hydrogen generated by using AgQCs-GCN was 1.7 times higher than pristine GCN. However, the rate of hydrogen generated using AgQCs-GCN was slightly less than that of AgNPs-GCN because of surface hydroxyl radical formation. The plausible photocatalytic processes are discussed in detail.
We demonstrate the conformal coating of an ultrathin Al2 O3 layer on TiO2 nanoparticles through atomic layer deposition by using a specifically designed rotary reactor to eliminate the phototoxicity of the particles for cosmetic use. The ALD reactor is modified to improve the coating efficiency as well as the agitation of the particles for conformal coating. Elemental and microstructural analyses show that ultrathin Al2 O3 layers are conformally deposited on the TiO2 nanoparticles with a controlled thickness. Rhodamine B dye molecules on Al2 O3 -coated TiO2 exhibited a long life time under UV irradiation, that is, more than 2 h, compared to that on bare TiO2 , that is, 8 min, indicating mitigation of photocatalytic activity by the coated layer. The effect of carbon impurities in the film resulting from various deposition temperatures and thicknesses of the Al2 O3 layer on the photocatalytic activity are also thoroughly investigated with controlled experimental condition by using dye molecules on the surface. Our results reveal that an increased carbon impurity resulting from a low processing temperature provides a charge conduction path and generates reactive oxygen species causing the degradation of dye molecule. A thin coated layer, that is, less than 3 nm, also induced the tunneling of electrons and holes to the surface, hence oxidizing dye molecules. Furthermore, the introduction of an Al2 O3 layer on TiO2 improves the light trapping thus, enhances the UV absorption.
A heterojunction of TiO2 grown on g-C3N4 particles is demonstrated using atomic layer deposition (ALD), equipped with a specifically designed rotary reactor for maintaining stable mechanical dispersion of g-C3N4 particles during ALD.
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