Jin Yuzhen, Zong Lukuan, Wang Xiangyu, Wei Huijuan
Green Catalysis Center, and College of Chemistry, Zhengzhou University, Zhengzhou 450001, P. R. China.
Zhejiang Medicine Co, Ltd., Changhai Biological Branch, Shaoxing 312000, P.R. China.
ACS Omega. 2022 Jul 19;7(30):26289-26297. doi: 10.1021/acsomega.2c02031. eCollection 2022 Aug 2.
Ga-doped ZSM-5 zeolites were directly synthesized by a facile one-step hydrothermal method without organic templates and calcination and then investigated in the cyclohexene hydration reaction. The structure, component, textural properties, and acidity of the as-prepared samples were examined by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray fluorescence (XRF), Brunauer-Emmett-Teller (BET), ammonia temperature-programmed desorption (NH-TPD), pyridine-chemisorbed IR (Py-IR), and Ga, Al, Si, and H magic-angle spinning (MAS) NMR techniques. The characterization results showed that the introduction of Ga atoms into the ZSM-5 zeolite framework is much easier than Al atoms and beneficial to promote the formation of small-sized crystals. The number of Brønsted acid sites of Ga-doped ZSM-5 samples obviously increased compared with Ga0-ZSM-5. Additionally, the highest cyclohexanol yield (10.1%) was achieved over the Ga3-ZSM-5 sample, while the cyclohexanol yield of the Ga0-ZSM-5 sample was 8.6%. This result indicated that the improved catalytic performance is related to its larger external surface area, smaller particle size, and more Brønsted acid sites derived from Si-OH-Al and Si-OH-Ga of Ga3-ZSM-5. Notably, the green route reduces harmful gas emission and provides a basis for doping other heteroatoms to regulate the catalytic performance of zeolites, especially in industrial production.
采用简便的一步水热法直接合成了无有机模板且无需煅烧的Ga掺杂ZSM-5沸石,然后对其在环己烯水合反应中的性能进行了研究。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、X射线荧光(XRF)、布鲁诺尔-埃米特-泰勒(BET)法、氨程序升温脱附(NH-TPD)、吡啶化学吸附红外光谱(Py-IR)以及Ga、Al、Si和H魔角旋转(MAS)核磁共振技术对所制备样品的结构、组成、织构性质和酸性进行了表征。表征结果表明,将Ga原子引入ZSM-5沸石骨架比引入Al原子更容易,且有利于促进小尺寸晶体的形成。与Ga0-ZSM-5相比,Ga掺杂ZSM-5样品的布朗斯台德酸位数量明显增加。此外,Ga3-ZSM-5样品的环己醇产率最高(10.1%),而Ga0-ZSM-5样品的环己醇产率为8.6%。该结果表明,催化性能的提高与其更大的外表面积、更小的粒径以及Ga3-ZSM-5中源自Si-OH-Al和Si-OH-Ga的更多布朗斯台德酸位有关。值得注意的是,这种绿色合成路线减少了有害气体排放,并为掺杂其他杂原子以调节沸石的催化性能提供了依据,尤其是在工业生产中。