Page 167 - 《精细化工》2020年第6期

第 37 卷第 6 期 精 细 化 工 Vol.37, No.6
202 0 年 6 月 FINE CHEMICALS June 2020

催化与分离提纯技术
不同方法制备的铈锰固溶体及其催化醇胺偶联反应

*
符淑钗，刘 鹏，祝德兴，吴华杰，程 高，余 林
（广东工业大学 轻工化工学院，广东省教育厅清洁化学技术重点实验室，广东 广州 510006）

摘要：为了研究不同制备方法对铈锰固溶体形貌、结构及其表面物种等的影响，阐明铈锰固溶体结构与其催化
性能之间的关系，通过纳米铸型法、水热法、共沉淀法、热分解法制备出 4 种理论掺锰量为 15%的铈锰固溶体
〔Ce 0.85 Mn 0.15 O x ，n(Ce)∶n(Mn)=0.85∶0.15〕。采用 XRD、FESEM、TEM、N 2 -吸附脱附、ICP-OES、XPS 对催
化剂进行物化性质表征，并以苯甲醇和苯胺偶联反应作为探针反应来评估其催化性能。结果表明，以纳米铸型
法制备的铈锰固溶体催化剂具有最佳的催化活性，其苯胺转化率达到了 67.9%，N-苄叉苯胺的选择性为 99.4%，
时空产率为 0.56 mmol/(g cat ·h)。与用其他 3 种方法制备的铈锰固溶体相比，纳米铸型法制备的铈锰固溶体具有较
3+
3+
大的表面积、特定的介孔结构，催化剂表面拥有较高相对含量的 Ce 、Mn ，有利于吸附和活化氧分子，这些
因素均有利于催化醇胺偶联反应。
关键词：铈锰固溶体；醇胺偶联反应；亚胺；催化剂；纳米材料
中图分类号：O643.36 文献标识码：A 文章编号：1003-5214 (2020) 06-1233-09

Cerium-manganese solid solutions by different preparation methods and
their catalyzing coupling reaction of alcohols with amines

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FU Shuchai, LIU Peng, ZHU Dexing, WU Huajie, CHENG Gao, YU Lin
（Key Laboratory of Clean Chemistry Technology of Guangdong Regular Higher Education Institutions, School of
Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, Guangdong,
China）

Abstract: In order to explore the effects of different preparation methods on the morphology, structure and
surface species of cerium-manganese solid solution, and clarify the relationship between the structure and
their catalytic performance, four kinds of cerium-manganese solid solution (Ce 0.85Mn 0.15O x) samples with a
theoretical manganese content of 15% [n(Ce)∶n(Mn)=0.85∶0.15] were prepared by nano-casting method,
hydrothermal method, co-precipitation method and thermal decomposition method, respectively. The
physical and chemical properties of the catalysts were characterized by XRD, FESEM, TEM, N 2
adsorption-desorption, ICP-OES and XPS. The coupling reaction of benzyl alcohol and aniline was used as
a probe reaction to evaluate the catalytic performances of the catalysts under air atmosphere. The results
showed that the catalyst prepared by nano-casting method possessed the best catalytic activity. The
conversion of aniline was 67.9%, the selectivity of N-benzylideneaniline was 99.4%, and the time-space
yield was 0.56 mmol/(g cat·h). Compared with those by the other three preparation methods, the
cerium-manganese solid solution prepared by nano-casting method had larger surface area, specific
3+
mesoporous structure, and higher relative content of Ce and Mn 3+ on the catalyst surface, which is
conducive to the adsorption and activation of oxygen molecules. All these factors are conducive to the
coupling reaction of alcohols with amines.
Key words: cerium-manganese solid solution; coupling reaction of alcohols with amines; imines; catalysts;
nanomaterials

收稿日期：2019-12-29; 定用日期：2020-02-26; DOI: 10.13550/j.jxhg.20191217
基金项目：国家自然科学基金（21576054）；广东省教育厅特色与创新项目（2015KTSCX027）；广东省科技创新战略专项资金
（2018A030310563）
作者简介：符淑钗（1995—），女，硕士生，E-mail：Fushuchai@163.com。联系人：余 林（1968—），男，教授。