核桃壳粉负载纳米Cu催化剂的制备及

doi:10.3969/j.issn.0253-2417.2019.02.015

林产化学与工业 ›› 2019, Vol. 39 ›› Issue (2): 103-108.doi: 10.3969/j.issn.0253-2417.2019.02.015

核桃壳粉负载纳米Cu催化剂的制备及

熊兴泉(),王彦龙,廖旭,赖石林,张辉

华侨大学材料科学与工程学院, 福建厦门 361021

收稿日期:2018-09-05 出版日期:2019-04-25 发布日期:2019-05-08
作者简介:熊兴泉(1980—),男,湖南平江人,副教授,博士,硕士生导师,研究方向为生物质化学与应用; E-mail:xxqluli@hqu.edu.cn
基金资助:
福建省自然科学基金资助项目(2016J01063);福建省“高校新世纪优秀人才支持计划”资助项目(2012FJ-NCET-ZR03);“华侨大学中青年教师科研提升资助计划”资助项目(ZQN-YX103)

Preparation of Walnut Shell Powders-supported Cu Nanoparticles and Its Application in Ynones Synthesis

Xingquan XIONG(),Yanlong WANG,Xu LIAO,Shilin LAI,Hui ZHANG

College of Materials Science and Engineering, Huaqiao University, Xiamen 361021, China

Received:2018-09-05 Online:2019-04-25 Published:2019-05-08
Supported by:
福建省自然科学基金资助项目(2016J01063);福建省“高校新世纪优秀人才支持计划”资助项目(2012FJ-NCET-ZR03);“华侨大学中青年教师科研提升资助计划”资助项目(ZQN-YX103)

摘要/Abstract

摘要：

以核桃壳粉(WSPs)为载体，采用还原沉淀法制备了WSPs负载的铜催化剂(WSPs-Cu)，采用红外(FT-IR)、热重分析(TGA)、X射线衍射分析(XRD)、扫描电镜结合X射线能谱(SEM/EDS)等对WSPs-Cu进行表征，结果表明：成功制备出Cu较均匀分布在WSPs表面的WSPs-Cu催化剂，WSPs-Cu的含铜量为3.386 %，同时WSPs-Cu在100~200 ℃范围内具有较好的热稳定性。以WSPs-Cu为异相催化剂，催化苯甲酰氯及其衍生物与苯乙炔之间的偶联反应，制备出炔酮类化合物，结果表明:在无溶剂的条件下，以三乙胺为缚酸剂，微波辐射以及40 ℃下反应30 min，WSPs-Cu催化合成了5种炔酮化合物(产率61%~90%)。WSPs-Cu循环使用5次后仍保留较高活性，催化合成产物的产率为79%。将模型反应由微量放大到常量，投料量为80 mmol时，WSPs-Cu催化合成炔酮的产率可达到82%。

关键词: 核桃壳粉, 炔酮化合物, 异相催化剂, 微波

Abstract:

Walnut shell powders(WSPs), which were grinded from walnut shell, was used as supporter for the preparation of WSPs-supported copper catalyst(WSPs-Cu) by adsorption method. The heterogeneous catalyst WSPs-Cu was characterized by FT-IR, thermogravimetric analysis(TGA), X-ray diffraction analysis(XRD) and scanning electron microscopy/energy dispersive X-ray spectroscopy(SEM/EDS). The results showed that the WSPs-Cu catalyst was successfully prepared by this method. Copper were well distributed on the surface of WSPs. The copper content of the catalyst was 3.386% with good thermal stability within 100-200 ℃. The WSPs-Cu catalyst was used to prepare five ynones from benzoyl chloride derivatives and phenylacetylene via copper-catalyzed coupling reaction. The results revealed that ynones were synthesized under microwave irradiation and solvent-free conditions for 30 min at 40 ℃ by using triethylamine as acid-binding agent(61%-90%). The recyclability of WSPs-Cu was studied. It was found that the WSPs-Cu has high activity after using for five times and the yield was 79%. As the model reaction was amplified from trace to constant and the dosage of substrate was 80 mmol, the yield of ynone catalyzed by WSPs-Cu reached 82%.

Key words: walnut shell powders, ynones, heterogeneous catalyst, microwave

中图分类号:

TQ35

熊兴泉,王彦龙,廖旭,赖石林,张辉. 核桃壳粉负载纳米Cu催化剂的制备及[J]. 林产化学与工业, 2019, 39(2): 103-108.

Xingquan XIONG,Yanlong WANG,Xu LIAO,Shilin LAI,Hui ZHANG. Preparation of Walnut Shell Powders-supported Cu Nanoparticles and Its Application in Ynones Synthesis[J]. Chemistry and Industry of Forest Products, 2019, 39(2): 103-108.

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催化剂 catalyst	传统油浴加热 heating by traditional oil bath		微波辅助加热 microwave assistant heating
催化剂 catalyst	时间/min time	产率/% yield	时间/mintime	产率/%yield
WSPs-Cu	480	81	30	90
WSPs-Ru	480	0	30	0
WSPs-Ni	480	0	30	0
WSPs-Fe	480	0	30	0
CaCO₃-Cu	480	73	30	78
C-Cu	480	70	30	74

酰氯 acyl chloride	产物 product	产率/% yield
苯甲酰氯benzoyl chloride	1, 3-二苯-2-炔丙基-1-酮1, 3-diphenylprop-2-yn-1-one	90
4-硝基苯甲酰氯4-nitrobenzoyl chloride	1-(4-硝基-苯基)-3-苯基炔酮1-(4-nitrophenyl)-3-phenylprop-2-yn-1-one	75
4-甲氧基苯甲酰氯4-methoxybenzoyl chloride	1-(4-甲氧基-苯基)-3-苯基炔酮1-(4-methoxyphenyl)-3-phenylprop-2-yn-1-one	85
特戊酰氯pivaloyl chloride	4, 4-二甲基-1-苯戊基-1-炔-3-酮4, 4-dimethyl-1-phenylpent-1-yn-3-one	70
2-呋喃甲酰氯furan-2-carbonyl chloride	1-呋喃-3-苯基丙基-2-炔-1-酮1-(furan-2-yl)-3-phenylprop-2-yn-1-one	61

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核桃壳粉负载纳米Cu催化剂的制备及

Preparation of Walnut Shell Powders-supported Cu Nanoparticles and Its Application in Ynones Synthesis

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