Columnar assembly of luminescent 3,5-dimethyl pyrazolate complexes/titanium oxide composites with different metal ions has shown significant improvement in its photocatalytic activity for the removal and degradation of 2, 4-dichlorophenoxyacetic acid (2,4-D). Since photocatalytic activity of semiconductor titanium oxide (TiO2) with an anatase phase can be improved by calcination temperature, we report the effect of heat treatments on the preparation of copper(I) 3,5-dimethyl pyrazolate complex/titanium oxide composite ([Cu3Pz3]/TiO2) for the removal and degradation of 2,4-D. Photocatalyst composites [Cu3Pz3]/TiO2 were successfully prepared using an impregnation method with different calcination temperature at 373, 473 and 573 K. Although, the activity of photocatalyst composites [Cu3Pz3]/TiO2 was significantly improved with increasing of calcination temperature on pure TiO2, it was slightly reduced with an increase of calcined temperature to 473 and 573 K. These results showed that [Cu3Pz3]/TiO2 was unstable at high temperature due to the decomposition of molecular structure of [Cu3Pz3] during the preparation of the photocatalyst. Hence, suitable calcination temperature is an important parameter to increase photocatalytic activity of photocatalyst composites [Cu3Pz3]/TiO2.
The methodical study of trinuclear copper(I) metal complexes phosphorescent vapochromic chemosensor via metal-metal interactions for sensing various volatile organic compounds has piqued the interest of many researchers. Herein, we highlighted the performance of chemosensors trinuclear copper(I) pyrazolate complexes (2Pz1‒2Pz5) with different molecular design short alkyl side chains from the respective pyrazole ligands. The synthesized complexes had demonstrated a high phosphorescent sensing capacity of various alcohol derivatives. Due to weak metal-metal interactions, the complexes give emission bands centered around 553-644 nm at an excitation of 280 nm. We found that the only 2Pz3 chemosensors showed quenching phenomena with a significant decrease in its emission intensity of 100% for exposure in 5 minutes with irreversible performance. Interestingly, we also found that the shifting of the emission center due to the disruption of metal-metal interaction performed by chemosensor 2Pz5 resulting in the best detection performance of methanol and ethanol (∆λ= 60 nm) and propanol (∆λ = 22 nm) showing autonomous recovery within 15 minutes. Based on the findings, the specific balance, such as rigidity and amphiphilicity in the molecular design of chemosensors, is important for the detection of vapors via supramolecular interactions.
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