Abstract Dumbbell-like ZnO micro-nanomaterials with uniform morphology were prepared with tetrasulfonatomethyl-n-hexyl calix[ 4 ]resorcinarene tetrasodium salt (THCRT) by a simple reflux method. The ZnO samples were characterized by X-ray diffraction, field emission scanning electron microscope, transmission electron microscopy, high-resolution transmission electron microscopy, thermogravimetric analysis, Brunauer-Emmett-Teller technique, Fourier transform infrared spectroscopy, ultraviolet-visible diffuse reflectance spectra, and Photoluminescence. The as-prepared ZnO micro-nanomaterials with a hexagonal wurtzite structure exhibited dumbbell-like morphology with a length of 700-900 nm and a hemisphere diameter of 500-700 nm. The THCRT was involved in the formation of ZnO nanostructure framework during the assembly and stacking of ZnO nanoparticles. The as-obtained dumbbell-like micro-nanomaterials possessed obvious mesoporous structure after the calcination at 500oC and 650oC, which is due to the rigid hydrophobic cavity of THCRT as hard template. The effects of the zinc sources, amount of THCRT, surfactants and amount of ammonia on the size and morphology of the ZnO samples were studied. The results indicate that THCRT with multi-head and multi-tail as soft template has a good protective effect on the growth of ZnO crystals. This study shows that the as-prepared ZnO product has a dumbbell-like mesoporous micro-nanostructure due to the special structure of THCRT which consists of rigid cup cavity, hydrophilic heads and hydrophobic tails. The evolution process of the dumbbell-like ZnO micro-nanostructures was investigated by FE-SEM, and a possible formation mechanism was proposed. The as-prepared ZnO micro-nanomaterials exhibited good adsorption capacity without calcination and excellent photocatalytic activity for degradation of methyl violet after calcination. Due to the excellent properties of micro-nanoscale, suitable pore size, high specific surface and good photoabsorption, the as-prepared dumbbell-like mesoporous ZnO micro-nanomaterials exhibit potential application as photocatalyst.

中文翻译：

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以四磺化甲基-正己基杯[]间苯二酚四钠盐为软硬模板的哑铃状介孔ZnO微纳米材料的合成及光催化活性

摘要 以四磺化甲基-正己基杯[4]间苯二酚四钠盐(THCRT)为原料，采用简单的回流法制备了形貌均匀的哑铃状ZnO微纳米材料。ZnO 样品通过 X 射线衍射、场发射扫描电子显微镜、透射电子显微镜、高分辨率透射电子显微镜、热重分析、Brunauer-Emmett-Teller 技术、傅里叶变换红外光谱、紫外-可见漫反射光谱、和光致发光。所制备的具有六方纤锌矿结构的 ZnO 微纳米材料表现出哑铃状形态，长度为 700-900 nm，半球直径为 500-700 nm。在 ZnO 纳米粒子的组装和堆叠过程中，THCRT 参与了 ZnO 纳米结构框架的形成。得到的哑铃状微纳米材料在 500oC 和 650oC 煅烧后具有明显的介孔结构，这是由于 THCRT 的刚性疏水腔作为硬模板。研究了锌源、THCRT 用量、表面活性剂和氨用量对 ZnO 样品尺寸和形貌的影响。结果表明，以多头多尾为软模板的THCRT对ZnO晶体的生长具有良好的保护作用。该研究表明，由于 THCRT 具有由刚性杯腔、亲水头和疏水尾组成的特殊结构，所制备的 ZnO 产品具有哑铃状介孔微纳米结构。通过FE-SEM研究了哑铃状ZnO微纳米结构的演化过程，并提出了可能的形成机制。所制备的ZnO微纳米材料无需煅烧即可表现出良好的吸附能力和煅烧后降解甲基紫的优异光催化活性。由于微纳米级的优异性能、合适的孔径、高比表面积和良好的光吸收性，所制备的哑铃状介孔ZnO微纳米材料具有作为光催化剂的潜在应用。所制备的ZnO微纳米材料无需煅烧即可表现出良好的吸附能力和煅烧后降解甲基紫的优异光催化活性。由于微纳米级的优异性能、合适的孔径、高比表面积和良好的光吸收性，所制备的哑铃状介孔ZnO微纳米材料具有作为光催化剂的潜在应用。所制备的ZnO微纳米材料无需煅烧即可表现出良好的吸附能力和煅烧后降解甲基紫的优异光催化活性。由于微纳米级的优异性能、合适的孔径、高比表面积和良好的光吸收性，所制备的哑铃状介孔ZnO微纳米材料具有作为光催化剂的潜在应用。