RESUMO
CO2 photoreduction using a semiconductor-based photocatalyst is a promising option for completing a new carbon-neutral cycle. The short lifetime of charges generated owing to light energy is one of the most critical problems in further improving the performance of semiconductor-based photocatalysts. This study shows the structure, electron transmission, and stability of Ti3C2Xy (X = oxo, OH, F, or Cl) MXene combined with a ZrO2 photocatalyst. Using H2 as a reductant, the photocatalytic CO formation rate increased by 6.6 times to 4.6 µmol h-1 gcat-1 using MXene (3.0 wt %)-ZrO2 compared to that using ZrO2, and the catalytic route was confirmed using 13CO2 to form 13CO. In clear contrast, using H2O (gas) as a reductant, CH4 was formed as the major product using Ti3C2Xy MXene (5.0 wt %)-ZrO2 at the rate of 3.9 µmol h-1 gcat-1. Using 13CO2 and H2O, 12CH4, 12C2H6, and 12C3H8 were formed besides H212CO, demonstrating that the C source was the partial decomposition and hydrogenation of Ti3C2Xy. Using the atomic force and high-resolution electron microscopies, 1.6 nm thick Ti3C2Xy MXene sheets were observed, suggesting â¼3 stacked layers that are consistent with the Ti-C and Ti···Ti interatomic distances of 0.218 and 0.301 nm, respectively, forming a [Ti6C] octahedral coordination, and the major component as the X ligand was suggested to be F and OH/oxo, with the temperature increasing by 116 K or higher owing to the absorbed light energy, all based on the extended X-ray absorption fine structure analysis.
RESUMO
The elution of pharmaceutical products such as metformin at higher concentrations than the safe level in aquatic systems is a serious threat to human health and the ecosystem. Photocatalytic technology using TiO2 semiconductors potentially fixes this problem. This study aims to synthesize triphasic anatase-rutile-brookite TiO2 using ultrasound assisted sol-gel technique in the presence of acid and its application to photodegradation of metformin under UV light irradiation. Based on X-ray diffraction analysis, a TiO2 sample consisted of anatase (76%), rutile (7%), and brookite (17%) polymorph (A76R7B17) that was fully crystallized. Scanning electron microscopy (EM)-energy dispersive X-ray spectra results showed agglomerated triphasic A76R7B17 with irregular spherical clusters. Transmission EM results revealed that the crystal size of A76R7B17 was 4-14 nm. The Brunauer-Emmett-Teller analysis showed the sample's specific surface area of 149 m2 g-1. The degradation test of metformin demonstrated that the A76R7B17 exhibited a 75.4% degradation efficiency after 120 min under UV light irradiation, significantly higher than using biphasic and single-phase TiO2 photocatalysts. This difference could be attributed to the heterojunction effect of triphasic materials that effectively reduced electron-hole recombination rate as well as the combination of effective electron transfer from conduction band of brookite and anatase and the utilization of wider range of UV-visible light using rutile.