Page 141 - 《精细化工》2021年第8期

第 38 卷第 8 期 精 细 化 工 Vol.38, No.8
202 1 年 8 月 FINE CHEMICALS Aug. 2021

催化与分离提纯技术
镁-三苯胺基金属有机框架的制备及其光/

Lewis 酸协同催化

*
史雨生，宋靖修，张铁欣 ，段春迎
（大连理工大学 精细化工国家重点实验室，辽宁 大连 116024）

2+
摘要：利用水热法将具有 Lewis 酸性的 Mg 和光敏性的三苯胺三羧酸（H 3 TCA）自组装构筑了金属有机框架
Mg-TCA，并通过 SC-XRD 表征了其晶体结构。UV-Vis、FL、CV 等测试表明，Mg-TCA 在可见光区（>400 nm）
具有良好的吸收，其激发态氧化还原电位为–1.95 V（vs. SCE）。以苯乙烯类化合物（0.2 mmol）为底物、N-羟
基邻苯二甲酰亚胺（NHPI）活性酯（0.3 mmol）为自由基前体、Mg-TCA（0.01 mmol）为催化剂、DMSO（2 mL）
为溶剂和氧化剂，氮气保护，在 405 nm LED 下照射 24 h，反应以 30%~82%的产率生成相应的 α-烷基苯乙酮。
催化剂 Mg-TCA 循环使用 2 次后仍保持活性和晶态结构。机理研究表明，在反应过程中发生了光/Lewis 酸协同
催化，Mg-TCA 中具有 Lewis 酸性的镁节点对 NHPI 活性酯的吸附作用拉近了其与光催化中心三苯胺的距离，
从而提升了催化反应的效率。
关键词：金属有机框架；镁；三苯胺；光摧化；Lewis 酸；协同催化
中图分类号：TQ244.2；TQ426 文献标识码：A 文章编号：1003-5214 (2021) 08-1635-09

Preparation of magnesium-triphenylamine based metal organic framework
and its synergistic Lewis acid and photoredox catalysis

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SHI Yusheng, SONG Jingxiu, ZHANG Tiexin , DUAN Chunying
（State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, Liaoning, China）

Abstract: Metal organic framework Mg-TCA was constructed by hydrothermal self-assembly between
2+
Lewis acidic Mg and photosensitive tricarboxytriphenyl amine (H 3TCA). SC-XRD was used to determine
the crystal structure of Mg-TCA. CV, UV-Vis and FL measurements indicated that Mg-TCA had a good
absorption ability in visible light region and its photoexcited redox potential was –1.95 V (vs. SCE).
Mg-TCA could effectively allow access to a wide range of α-alkyl-acetophenones (30%~82%) under the
synergistic Lewis acid and photoredox catalysis, and the reaction conditions was obtained as follows:
styrene compounds (0.2 mmol), N-hydroxyphthalimide (NHPI) ester (0.3 mmol), Mg-TCA (0.01 mmol),
DMSO (2 mL), irradiation under 405 nm LED for 24 h at N 2 atmosphere. The catalyst could be reused for
two times without deactivation, and its structure remained intact before and after use. Mechanism studies
revealed that a synergistic Lewis acid and photoredox catalysis process was carried out within this
transformation, the Lewis acidic nodes of Mg-TCA binded and absorbed NHPI ester, putting the NHPI ester
approximate to the photoredox catalytic center within Mg-TCA, thus improving the catalytic efficiency.
Key words: metal organic framework; magnesium; triphenylaniline; photocatalysis; Lewis acid; synergistic
catalysis

光催化利用光敏剂与底物之间的光致电子或能 量转移，可以在温和条件下实现很多在热反应过程

收稿日期：2021-03-08; 定用日期：2021-04-02; DOI: 10.13550/j.jxhg.20210240
基金项目：国家自然科学基金（21971031，21890381，U1608224）
作者简介：史雨生（1991—），男，博士生，E-mail: 1227405029@qq.com。联系人：张铁欣（1983—），男，副教授，E-mail: zhangtiexin@
dlut.edu.cn。