Incorporation of NiO into SiO2, TiO2, Al2O3, and Na4.2Ca2.8(Si6O18) Matrices: Medium Effect on the Optical Properties and Catalytic Degradation of Methylene Blue

Abstract

The medium effect of the optical and catalytic degradation of methylene blue was studied in the NiO/SiO2, NiO/TiO2, NiO/Al2O3, and NiO/Na4.2Ca2.8(Si6O18) composites, which were prepared by a solid-state method. The new composites were characterized by XRD (X-ray diffraction of powder), SEM/EDS, TEM, and HR-TEM. The size of the NiO nanoparticles obtained from the PSP-4-PVP (polyvinylpyrrolidone) precursors inside the different matrices follow the order of SiO2 > TiO2 > Al2O3. However, NiO nanoparticles obtained from the chitosan precursor does not present an effect on the particle size. It was found that the medium effect of the matrices (SiO2, TiO2, Al2O3, and Na4.2Ca2.8(Si6O18)) on the photocatalytic methylene blue degradation, can be described as a specific interaction of the NiO material acting as a semiconductor with the MxOy materials through a possible p-n junction. The highest catalytic activity was found for the TiO2 and glass composites where a favorable p-n junction was formed. The isolating character of Al2O3 and SiO2 and their non-semiconductor behavior preclude this interaction to form a p-n junction, and thus a lower catalytic activity. NiO/SiO2 and NiO/Na4.2Ca2.8(Si6O18) showed a similar photocatalytic behavior. On the other hand, the effect of the matrix on the optical properties for the NiO/SiO2, NiO/TiO2, NiO/Al2O3, and NiO/Na4.2Ca2.8(Si6O18) composites can be described by the different dielectric constants of the SiO2, TiO2, Al2O3, Na4.2Ca2.8(Si6O18) matrices. The maxima absorption of the composites (λmax) exhibit a direct relationship with the dielectric constants, while their semiconductor bandgap (Eg) present an inverse relationship with the dielectric constants. A direct relationship between λmax and Eg was found from these correlations. The effect of the polymer precursor on the particle size can explain some deviations from this relationship, as the correlation between the particle size and absorption is well known. Finally, the NiO/Na4.2Ca2.8(Si6O18) composite was reported in this work for the first time.

Solventless Preparation of Thoria and Its Inclusion into SiO2 and TiO2: A Luminescence and Photocatalysis Study

“…The photocatalytic activity toward methylene blue degradation follows the order of ThO 2 > ThO 2 /TiO 2 > ThO 2 /SiO 2 and was attributed to the encapsulation of the ThO 2 into the different matrices. Similar results on the effect of the SiO 2 , TiO 2 , and Al 2 O 3 on the nanostructured NiO have recently appeared …”

“…Similar results on the effect of the SiO 2 , TiO 2 , and Al 2 O 3 on the nanostructured NiO have recently appeared. 33 ■ ASSOCIATED CONTENT * sı Supporting Information…”

Solid-State Preparation of Metal and Metal Oxides Nanostructures and Their Application in Environmental Remediation

“…The method reported here allowed us to prepare NiO from inexpensive and commercially available polymer and Ni salts. Using chitosan•(NiCl 2 •H 2 O) x and PS-co-4-PVP•(NiCl 2 •6H 2 O) x precursors [65] and by thermal treatment at 800 • C under air, pure NiO phase was obtained. The band-gap of the as-prepared NiO is 4.15 eV for the one obtained from both Chitosan and PS-co-4-PVP precursors [60].…”

“…On the other hand, NiO as well as their NiO/SiO 2 , NiO/TiO 2 , NiO/Al 2 O 3 nanocomposites presenting band-gap values in the range 5.0-5.6 eV, see Table 2, predicts that they can be used as appropriate photocatalyst using UV irradiation [65]. In fact, NiO and their NiO/SiO 2 , NiO/TiO 2 , NiO/Al 2 O 3 nanocomposites exhibit a satisfactory efficient photocatalytic behavior [65]. The higher methylene blue efficiency was for the NiO/TiO 2 composite arising from the chitosan (NiCl 2 .6H 2 O) x //TiO 2 precursor, see Table 3.…”