Zhang Qiuyun, Luo Qizhi, Wu Yaping, Yu Rongfei, Cheng Jingsong, Zhang Yutao
School of Chemistry and Chemical Engineering, Anshun University Anshun 561000 Guizhou China
College Rural Revitalization Research Center of Guizhou Anshun 561000 Guizhou China.
RSC Adv. 2021 Oct 13;11(53):33416-33424. doi: 10.1039/d1ra06023f. eCollection 2021 Oct 8.
This work reports the one-pot solvothermal synthesis of a Keggin heteropolyacid (phosphomolybdic acid, tungstophosphoric acid, or silicotungstic acid) immobilized on Ni-MOF composite catalysts for esterification of fatty acids, and the composites were further analyzed by XRD, FTIR, NH-TPD, SEM, TEM, N adsorption/desorption, and XPS. Among the contrastive syntheses (, HPW/Ni-MOF, HSiW/Ni-MOF, and HPMo/Ni-MOF), HPMo/Ni-MOF exhibits the most active catalyst toward fatty acids esterification, and the characterization results also revealed that HPMo/Ni-MOF has a strong acidity, large specific surface area, and appropriate average pore size. More significantly, this catalyst exhibits a good catalytic performance (86.1% conversion) during esterification under the optimized reaction conditions, and the HPMo/Ni-MOF catalyst can remain stable after the tenth cycle with a conversion of 73.5%. Intriguingly, the esterification reaction kinetics was studied, and the activation energy was found to be 64.6 kJ mol. The results indicated that the esterification of fatty acids using the HPMo/Ni-MOF catalyst is a chemically controlled reaction.
本工作报道了一种用于脂肪酸酯化的负载在镍基金属有机框架(Ni-MOF)复合催化剂上的Keggin杂多酸(磷钼酸、钨磷酸或硅钨酸)的一锅溶剂热合成法,并用X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)、程序升温脱附(NH-TPD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、氮吸附/脱附以及X射线光电子能谱(XPS)对复合材料进行了进一步分析。在对比合成(磷钨酸/镍基金属有机框架、硅钨酸/镍基金属有机框架和磷钼酸/镍基金属有机框架)中,磷钼酸/镍基金属有机框架对脂肪酸酯化表现出最具活性的催化剂,表征结果还表明磷钼酸/镍基金属有机框架具有强酸性、大比表面积和合适的平均孔径。更显著的是,该催化剂在优化反应条件下的酯化反应中表现出良好的催化性能(转化率86.1%),并且磷钼酸/镍基金属有机框架催化剂在第十次循环后仍能保持稳定,转化率为73.5%。有趣的是,研究了酯化反应动力学,发现活化能为64.6 kJ/mol。结果表明,使用磷钼酸/镍基金属有机框架催化剂进行脂肪酸酯化是一个化学控制反应。