Ali Saima, Granbohm Henrika, Lahtinen Jouko, Hannula Simo-Pekka
Department of Chemistry and Materials Science, Aalto University School of Chemical Engineering, P.O. Box 16100, FI-00076, Espoo, Finland.
Department of Applied Physics, School of Science, Aalto University, P.O. Box 15100, FI 00076, Espoo, Finland.
Nanoscale Res Lett. 2018 Jun 14;13(1):179. doi: 10.1186/s11671-018-2591-5.
Titania nanotube (TNT) powder was prepared by rapid breakdown anodization (RBA) in a perchloric acid electrolyte. The photocatalytic efficiency of the as-prepared and powders annealed at temperatures between 250 and 550 °C was tested under UV and natural sunlight irradiation by decolorization of both anionic and cationic organic dyes, i.e., methyl orange (MO) and rhodamine B (RhB), as model pollutants. The tubular structure of the nanotubes was retained up to 250 °C, while at 350 °C and above, the nanotubes transformed into nanorods and nanoparticles. Depending on the annealing temperature, the TNTs consist of anatase, mixed anatase/brookite, or anatase/rutile phases. The bandgap of the as-prepared nanotubes is 3.04 eV, and it shifts towards the visible light region upon annealing. The X-ray photoelectron spectroscopy (XPS) results show the presence of titania and impurities including chlorine on the surface of the TNTs. The atomic ratio of Ti/O remains unchanged for the annealed TNTs, but the concentration of chlorine decreases with temperature. The photoluminescence (PL) indicate high electron-hole recombination for the as-prepared TNTs, probably due to the residual impurities, low crystallinity, and vacancies in the structure, while the highest photocurrent was observed for the TNT sample annealed at 450 °C. The TNTs induce a small degradation of the dyes under UV light; however, contrary to previous reports, complete decolorization of dyes is observed under sunlight. All TNT samples showed higher decolorization rates under sunlight irradiation than under UV light. The highest reaction rate for the TNT samples was obtained for the as-prepared TNT powder sample under sunlight using RhB (κ = 1.29 h). This is attributed to the bandgap, specific surface area and the crystal structure of the nanotubes. The as-prepared TNTs performed most efficiently for decolorization of RhB and outperformed the reference anatase powder under sunlight irradiation. This could be attributed to the abundance of reactive sites, higher specific surface area, and degradation mechanism of RhB. These RBA TNT photocatalyst powders demonstrate a more efficient use of the sunlight spectrum, making them viable for environmental remediation.
通过在高氯酸电解质中进行快速击穿阳极氧化(RBA)制备了二氧化钛纳米管(TNT)粉末。以阴离子和阳离子有机染料,即甲基橙(MO)和罗丹明B(RhB)作为模型污染物,在紫外光和自然阳光照射下,测试了所制备的以及在250至550℃之间退火的粉末的光催化效率。纳米管的管状结构在250℃以下得以保留,而在350℃及以上,纳米管转变为纳米棒和纳米颗粒。根据退火温度的不同,TNT由锐钛矿相、锐钛矿/板钛矿混合相或锐钛矿/金红石相组成。所制备的纳米管的带隙为3.04 eV,退火后向可见光区域移动。X射线光电子能谱(XPS)结果表明,TNT表面存在二氧化钛和包括氯在内的杂质。退火后的TNT中Ti/O原子比保持不变,但氯的浓度随温度降低。光致发光(PL)表明,所制备的TNT存在高电子 - 空穴复合,这可能是由于结构中的残留杂质、低结晶度和空位所致,而在450℃退火的TNT样品观察到最高的光电流。TNT在紫外光下会使染料发生少量降解;然而,与先前的报道相反,在阳光下观察到染料完全脱色。所有TNT样品在阳光照射下的脱色率均高于在紫外光下。使用RhB时,在阳光下所制备的TNT粉末样品的TNT样品获得了最高反应速率(κ = 1.29 h⁻¹)。这归因于纳米管的带隙、比表面积和晶体结构。所制备的TNT在RhB脱色方面表现最为高效,并且在阳光照射下优于参考锐钛矿粉末。这可能归因于丰富的活性位点、更高的比表面积以及RhB的降解机制。这些RBA TNT光催化剂粉末展示了对太阳光光谱更有效的利用,使其在环境修复方面具有可行性。