RESUMO
ZnO-Cu2O composites were made as photocatalysts in a range of different amounts using an easy, cheap, and environment-friendly coprecipitation method due to their superior visible light activity to remove pollutants from the surrounding atmosphere. X-ray diffraction and Fourier transform infrared spectroscopy (FT-IR) have demonstrated that ZnO-Cu2O catalysts are made of highly pure hexagonal ZnO and cubic Cu2O. X-ray photoelectron spectroscopy has confirmed that there is a substantial interaction between the two phases of the resultant catalyst. The optical characterizations of the synthesized ZnO-Cu2O composite were done via UV-vis reflectance spectroscopy. Due to the doping on ZnO, the absorption range of the ZnO-Cu2O catalyst is shifted from the ultraviolet to the visible region due to diffuse reflection. The degradation efficiency is affected by the Ratio of ZnO: Cu2O and ZnO-Cu2O composite with a proportion of 90:10 exhibited the most prominent photocatalytic activity on Acid Red 114, with a pseudo-first-order rate constant of 0.05032 min-1 that was 6 and 11 times greater than those of ZnO and Cu2O, respectively. The maximum degradation efficiency is 97 %. The enhanced photocatalytic activity of the composite is caused by the synergistic interaction of ZnO and Cu2O, which improves visible light absorption by lowering band gap energy and decreasing the rate at which the electron-hole pairs recombine. The scavenging experiment confirmed that hydroxyl radical was the dominant species for the photodegradation of Acid Red 114. Notably, the recycling test demonstrated the ZnO-Cu2O photocatalyst was highly stable and recyclable. These results suggest that the ZnO-Cu2O mix might be able to clean up environmental pollutants when it meets visible light.
RESUMO
Condensation of 2-hydroxybenzaldehyde (salicylaldehyde) or 2-hydroxy-1-naphthaldehyde with 2-ethylaniline yields the Schiff base compound of (E)-2-(((2-ethylphenyl)imino)methyl)phenol (HL1) or (E)-1-(((2-ethylphenyl)imino)methyl)naphthalen-2-ol (HL2), which in turn react with the dinuclear complex of [Rh(η4-cod)(µ-O2CCH3)]2 (cod = cycloocta-1,5-diene) to afford the mononuclear (η4-cod){(E)-2-(((2-ethylphenyl)imino)methyl)phenolato-κ2N,O}rhodium(I), [Rh(η4-cod)(L1)] (1) or (η4-cod){(E)-1-(((2-ethylphenyl)imino)methyl)naphthalen-2-olato-κ2N,O}rhodium(I), [Rh(η4-cod)(L2)] (2) (L1 or L2 = deprotonated Schiff base ligand). The X-ray structure determination revealed that the HL2 exists in the solid state not as the usual (imine)N···H-O(phenol) form (enolamine form) but as the zwitterionic (imine)N-H+···-O(phenol) form (ketoamine form). 1H NMR spectra for HL2 in different solvents demonstrated the existence of keto-enol tautomerism (i.e., keto â enol equilibrium) in solution. The structure for 1 and 2 showed that the deprotonated Schiff base ligand coordinates to the Rh(η4-cod)-fragment as a six-membered N^O-chelate around the rhodium atom with a close-to-square-planar geometry. Two symmetry-independent molecules (with Rh1 and Rh2) were found in the asymmetric unit in 1 in a structure with Z' = 2. The supramolecular packing in HL2 was organized by π-π and C-H···π contacts, while only two recognized C-H···π contacts were revealed in 1 and 2. Remarkably, there were reciprocal or pairwise C-H···π contacts between a pair of each of the symmetry-independent molecules in 1. This pairwise C-H contact to the Rh-N^O chelate (metalloaromatic) ring may be a reason for the two symmetry-independent molecules in 1. Differential scanning calorimetry (DSC) analyses revealed an irreversible phase transformation from the crystalline-solid to the isotropic-liquid phase and subsequently confirmed the thermal stability of the compounds. Absorption spectra in solution were explained by excited state properties from DFT/TD-DFT calculations.
