Page 46 - 精细化工2020年第2期

第 37 卷第 2 期 精 细 化 工 Vol.37, No.2
202 0 年 2 月 FINE CHEMICALS Feb. 2020

功能材料
锆基 MOFs 的合成与表征及催化制备生物柴油

1
1*
杨子飞 ，曹 阳 1,2 ，李 进
（1. 海南大学 化学工程与技术学院 南海海洋资源利用国家重点实验室，海南 海口 570228；2. 琼台师
范学院，海南 海口 571127）

摘要：采用不同有机配体（对苯二甲酸、2-硝基对苯二甲酸、2-氨基对苯二甲酸、2-羟基对苯二甲酸），利用溶
剂热合成法合成锆基 MOFs 结构 UiO-66 及其衍生物，添加不同的调节剂（甲酸、乙酸、苯甲酸和盐酸）调节锆
基 MOFs 结构。采用 XRD、SEM 和 FTIR 等对锆基 MOFs 材料进行表征，考察了不同调节剂和添加量对锆基
MOFs 形貌特征和结构性质的影响。研究发现，不同调节剂对锆基 MOFs 结构形成产生不同影响，盐酸和乙酸
混合调节剂能显著提高 UiO-66 的结晶度，当 n(调节剂)∶n(ZrCl 4 )=30∶1 时，苯甲酸为调节剂可以获得尺寸为
500 nm 结构规整的 UiO-66 八面体晶体，甲酸为调节剂将 UiO-66 的比表面积由 1173.3 m²/g 提高到 1973.8 m²/g。
选择 3 种乙酸为调节剂的锆基 MOFs 作为麻疯树油的酯化反应催化剂，UiO-66-NH 2 催化活性较好，其游离脂肪
酸转化率为 50.7%，用 KOH 催化酯化油反应得到的生物柴油产率为 51.6%，脂肪酸甲酯含量达 99%以上。
关键词：UiO-66；调节；表征；催化；生物柴油；功能材料
中图分类号：TQ426.81 文献标识码：A 文章编号：1003-5214 (2020) 02-0248-09

Synthesis and characterization of zirconium-based MOFs and
catalytic preparation of biodiesel

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1,2
1*
Yang Zifei , Cao Yang , Li Jin
（1. State Key Laboratory of Marine Resource Utilization in South China Sea1, College of Chemical Engineering and
Technology, Hainan University, Haikou 570228, Hainan, China; 2. Qiongtai Normal University, Haikou 571127, Hainan,
China）

Abstract: UiO-66 and its derivatives were synthesized by solvothermal synthesis of different organic
ligands, such as terephthalic acid, 2-nitroterephthalic acid, 2-aminoterephthalic acid and 2-hydroxyterephthalic
acid. In the synthesis, formic acid, acetic acid, benzoic acid and hydrochloric acid were used as different
modulators to modulate the structure of zirconium-based MOFs. The zirconium-based MOFs were
characterized by XRD, SEM and FTIR. The effects of different modulators and additions on the
morphology and structure of zirconium-based MOFs were investigated. It was found that the different
modulators have different effects on the formation of zirconium-based MOFs. The hydrochloric acid and
acetic acid mixture modulators can significantly improve the crystallinity of UiO-66. When the molar ratio
of the regulator to ZrCl 4 was 30, the benzoic acid modulator can obtain uniform UiO-66 octahedral crystal
with dimensions of 500 nm, the formic acid modulators increased the specific surface area of UiO-66 from
2
2
1173.3 m /g to 1973.8 m /g. Three kinds of zirconium-based MOFs were selected as esterification reaction
catalysts to obtain esterified oil. UiO-66-NH 2 has good catalytic activity, and its free fatty acid conversion
rate was 50.7%. The yield of biodiesel obtained by the reaction of KOH catalyzed esterification oil was
51.6%, and the methyl ester rate was as high as 99% or more.
Key words: UiO-66; modulation; characterization; catalytic; biodiesel; functional materials

收稿日期：2019-05-06; 定用日期：2019-07-09; DOI: 10.13550/j.jxhg.20190406
基金项目：海南省重点项目（ZDYF2018134）
作者简介：杨子飞（1993—），男，硕士生，E-mail：1937563184@qq.com。联系人：李 进（1974—），男，副教授，E-mail：
316800681@qq.com。