硅酸盐学报

花球状硫酸根插层镁铝水滑石的制备及其催化Aldol醛酮缩合反应

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张文驰 ¹ , 田旭 ¹ , 陈昕怡 ¹ , 夏鹏飞 ² , 朱琳玉 ¹

硅酸盐学报 | 研究论文 2025,53(4): 998-1006

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硅酸盐学报 |研究论文 2025 , 53 (4) : 998 -1006

花球状硫酸根插层镁铝水滑石的制备及其催化Aldol醛酮缩合反应

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张文驰¹, 田旭¹, 陈昕怡¹, 夏鹏飞², 朱琳玉¹

作者信息

^1．湖州师范学院工学院，浙江湖州 313000

^2．电子科技大学电子科学与工程学院，成都 611731

通讯作者:

朱琳玉（1991—），女，博士，讲师；

夏鹏飞（1989—），男，博士，副教授。

作者简介:

张文驰（2001—），男，硕士研究生。

Synthesis of Flower-like Sulfate Interlayered Magnesium-aluminum Hydrotalcite for Catalytic Aldol Condensation Reaction

Wenchi ZHANG¹, Xu TIAN¹, Xinyi CHEN¹, Pengfei XIA², Linyu ZHU¹

Affiliations

^1.School of Engineering, Huzhou University, Huzhou 313000, Zhejiang, China

^2.School of Electronic Science and Engineering, University of Electronic Science and Technology of China, Chengdu 611731, China

Corresponding Author:

ZHU Linyu (1991-), femal, Ph.D., Lecturer. E-mail: 03115@zjhu.edu.cn;

XIA Pengfei (1989-), male, Ph.D., Associate Professor. forsky@csj.uestc.edu.cn

ZHANG Wenchi (2001-), male, Master candidate. E-mail: 2216015453@qq.com

出版时间: 2025-04-20 doi: 10.14062/j.issn.0454-5648.20240558

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摘要

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Aldol醛酮缩合反应是形成C—C键的关键有机反应之一，在药物合成、天然产物全合成以及工业生产香染料等领域有着广泛的应用。利用水滑石的记忆效应，在进行结构重构的过程中引入过硫酸铵提供阴离子配体，成功制备出花状硫插层镁铝水滑石催化剂（MgAl-SO₄^2--LDH），并对其进行了催化Aldol醛酮反应的研究。通过扫描电子显微镜、能量色散X射线谱仪、X射线衍射和Fourier变换红外光谱仪（FT-IR）等表征手段，详细研究了MgAl-SO₄^2--LDH催化剂的形貌结构、元素分布、晶体结构和表面Brönsted酸性位。结果表明：所制备的MgAl-SO₄^2--LDH催化剂由二维片状结构组装而成的花球状结构，并富含Brönsted酸性催化位点。在丙酮和对硝基苯甲醛的Aldol缩合反应中，改性后的MgAl-SO₄^2--LDH催化缩合转化率为70.5%，且经过再生后，其催化缩合转化率仍可达到64.1%，显示出良好的催化重复性。此外，根据催化产物FT-IR的结果，提出了MgAl-SO₄^2--LDH催化剂表面的Brönsted酸性位催化缩合加成反应的机理。

关键词

水滑石 / 硫酸根插层改性 / 醛酮缩合 / 催化 / 机理

Abstract

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Introduction

The Aldol condensation reaction, as a pivotal organic reaction in forming C-C bonds, plays a crucial role in various fields such as pharmaceutical synthesis, total synthesis of natural products, and the industrial production of perfumes and dyes. Conventional Aldol condensation reactions often rely on liquid alkaline catalysts, which suffer from some issues such as difficulty in recovery, complex waste liquid treatment, strong corrosion to equipment, and severe environmental pollution, thereby restricting their application in industrial production. Therefore, the development of efficient, recyclable, and environmentally friendly solid alkaline catalysts becomes a key to promoting the greening and efficiency of the Aldol condensation reactions. Layered double hydroxides (LDHs), with their unique layered structure and adjustable composition have a great potential in catalysis. Recent research indicates that functional modifications, such as ion exchange, intercalation, and doping, can further enhance their catalytic performance. Among them, sulfate-intercalated magnesium aluminum LDH (MgAl-SO₄^2--LDH) as a special LDH material, through the introduction of sulfate ions, can enhance the structural stability of LDH and introduce additional acidic sites. This makes MgAl-SO₄^2--LDH effectively activate aldehyde or ketone molecules during the catalysis of Aldol condensation reactions, thereby promoting the progress of the condensation reaction. In addition, the morphology of the catalyst has a significant impact on its catalytic performance. The flower-like spherical structure, as a special nanostructure, has attracted much attention in the field of catalysis due to its high specific surface area, abundant pore structure, and superior mass transfer performance. Combining the flower-like spherical structure with MgAl- SO₄^2--LDH can be expected to further improve the catalytic efficiency of the catalyst.

Methods

The flower-like MgAl-SO₄^2--LDH catalyst was prepared in the molar ratios of n(Mg)∶n(Al)=2∶1 and n(urea)∶n(NO₃^-)=1∶1. In the preparation, magnesium nitrate hexahydrate (Mg(NO₃)₂·6H₂O), aluminum nitrate nonahydrate (Al(NO₃)₃·9H₂O) and urea were mixed and dissolved in deionized water under stirring. The mixed solution was then transferred to a hydrothermal reaction vessel and reacted at 120 ℃ for 6 h. The resulting product was washed with deionized water for several times and then dried thoroughly in an oven. The dried material was calcined in a muffle furnace at 500 ℃ for 8 h to obtain the magnesium-aluminum composite oxide (LDO). Subsequently, a series of ammonium persulfate solutions ((NH₄)₂S₂O₈) with different concentrations (i.e., 0, 0.05, 0.10, 0.15 mol/L, and 0.20 mol/L) were prepared. The reaction was proceeded in a nitrogen atmosphere at room temperature for a certain period, and the solvent was removed through filtration and drying, yielding the S₂O₈^2- intercalated magnesium-aluminum hydrotalcite compounds (i.e., S₂O₈^2-/LDH). Finally, the prepared S₂O₈^2-/LDH was calcined in a muffle furnace at 550 ℃ for 8 h to obtain the modified magnesium-aluminum composite oxide. The modified magnesium-aluminum composite oxide was uniformly dispersed in deionized water, and the hydration-reduction process was repeated when sulfate ions were introduced to replace persulfate ions. A final catalyst MgAl-SO₄^2--LDH was obtained after completing the hydration-reduction and subsequent treatment.

Results and Discussion

MgAl- SO₄^2--LDH catalyst prepared has a flower-like spherical structure assembled from two-dimensional MgAl-SO₄^2--LDH sheets with a uniform morphology and a diameter of 2 μm. The SEM images reveal that, in contrast to the irregular shape of traditional MgAl-LDH catalysts, the MgAl-SO₄^2--LDH sample after sulfate ion intercalation modification exhibits a flower-like spherical structure. This interconnected sheet structure divides the catalyst surface into numerous small chambers, which provides abundant reaction sites for the catalytic reaction and promotes the mass transfer process between reactants and products, thereby contributing to an enhanced catalytic performance. The results of EDS analysis confirm that sulfate ions are introduced into the catalyst structure and distributed uniformly.

The XRD patterns indicate that the crystallinity of MgAl-SO₄^2--LDH catalyst is inferior to that of the MgAl-LDH, exposing more active sites due to the intercalation of sulfate ions. The FTIR spectra reveal that MgAl-SO₄^2--LDH catalyst contains a rich number of Brönsted acid sites, enhancing the activation of acetone and p-nitrobenzaldehyde, thus effectively improving catalytic performance. The optimized MgAl-SO₄^2--LDH catalyst has a p-nitrobenzaldehyde conversion rate of 70.5%, and after one regeneration the catalytic conversion rate remains 64.03%, demonstrating a good reusability. The FTIR spectra of the reaction products indicate a mixture of 4-(4-nitrophenyl)-3-hydroxy-2-butanone and 4-(4-nitrophenyl)-3-penten-2-one.

Conclusions

The study prepared a flower-like sulfate-intercalated MgAl-SO₄^2--LDH catalyst with a uniform microstructure and a diameter of 2 μm, assembled from two-dimensional MgAl-SO₄^2--LDH sheet structures. The catalyst showed an improved surface activity due to the intercalation of sulfate ions, thus increasing the number of active sites. The FTIR spectra confirmed the abundance of the Brönsted acid sites in MgAl-SO₄^2--LDH catalyst, which significantly enhanced the activation of acetone and p-nitrobenzaldehyde, effectively improving catalytic performance. The optimized catalyst showed a high conversion rate of 70.5% for the aldol condensation of acetone with p-nitrobenzaldehyde, and after regeneration it maintained a conversion rate of 64.03%, indicating a good reusability. The reaction products consisted of a mixture of 4-(4-nitrophenyl)-3-hydroxy-2-butanone and 4-(4-nitrophenyl)-3-penten-2-one, indicating a possible mechanism involving the Brönsted acid sites on MgAl-SO₄^2--LDH catalyst facilitating the nucleophilic addition reaction between the activated enol of acetone and the protonated aldehyde group of p-nitrobenzaldehyde.

Key words

hydrotalcite / sulfate intercalation modification / aldol condensation / catalysis / mechanism

引用本文

张文驰, 田旭, 陈昕怡, 夏鹏飞, 朱琳玉. 花球状硫酸根插层镁铝水滑石的制备及其催化Aldol醛酮缩合反应. 硅酸盐学报, 2025 , 53 (4) : 998 -1006 . DOI: 10.14062/j.issn.0454-5648.20240558

Wenchi ZHANG, Xu TIAN, Xinyi CHEN, Pengfei XIA, Linyu ZHU. Synthesis of Flower-like Sulfate Interlayered Magnesium-aluminum Hydrotalcite for Catalytic Aldol Condensation Reaction[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (4) : 998 -1006 . DOI: 10.14062/j.issn.0454-5648.20240558

基金

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国家自然科学基金项目(22202033)
国家级大学生创新创业训练计划项目(202310347048)
浙江省大学生创新创业训练计划项目(S202310347032)
浙江省自然科学基金资助项目(ZCLQN25B0301)

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2025年第53卷第4期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240558

接收时间：2024-08-27
首发时间：2026-10-22
出版时间：2025-04-20

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收稿日期：2024-08-27
修回日期：2024-09-25

基金

国家自然科学基金项目(22202033)

国家级大学生创新创业训练计划项目(202310347048)

浙江省大学生创新创业训练计划项目(S202310347032)

浙江省自然科学基金资助项目(ZCLQN25B0301)

作者信息

^1．湖州师范学院工学院，浙江湖州 313000

^2．电子科技大学电子科学与工程学院，成都 611731

通讯作者:

朱琳玉（1991—），女，博士，讲师；

夏鹏飞（1989—），男，博士，副教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240558

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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