具有分级结构的SiC纳米线负载的Pd纳米颗粒光催化芳基卤化物硼化反应

引用本文: 焦志锋, 赵吉晓, 郭晓宁, 郭向云. 具有分级结构的SiC纳米线负载的Pd纳米颗粒光催化芳基卤化物硼化反应[J]. 催化学报, 2020, 41(2): 357-363. doi: S1872-2067(19)63449-2 shu

Citation: Zhi-Feng Jiao, Ji-Xiao Zhao, Xiao-Ning Guo, Xiang-Yun Guo. Photocatalytic C-X borylation of aryl halides by hierarchical SiC nanowire-supported Pd nanoparticles[J]. Chinese Journal of Catalysis, 2020, 41(2): 357-363. doi: S1872-2067(19)63449-2 shu

具有分级结构的SiC纳米线负载的Pd纳米颗粒光催化芳基卤化物硼化反应

a 中国科学院山西煤炭化学研究所煤转化国家重点实验室, 山西太原 030001, 中国;
b 德国维尔茨堡大学无机化学研究所, 硼化学与催化研究所, 维尔茨堡D-97074, 德国;
c 常州大学石油化工学院, 江苏常州 213164, 中国;
d 中国科学院大学材料与光电研究中心, 北京 100049, 中国
基金项目:
国家自然科学基金（21473232，21673271，U1710112）.

摘要: 芳基硼酸酯作为一种重要的有机中间体，在C-C，C-N和C-O键的构筑以及C-X键的转换中有着广泛的应用，其传统合成方法主要是用格氏试剂或有机锂试剂，但该方法的官能团耐受性较差，且对反应环境敏感.在均相催化体系下，过渡金属催化芳烃的C-H和C-X键硼化反应成为合成芳基硼酸酯化合物的重要途径，虽然活性和选择性很高，但催化剂难于分离，且多数反应需要昂贵的配体，限制了其在工业上的大规模应用.多相催化剂体系虽然解决了分离回收的问题，但是催化效率大多较低.近年来，由于光催化能够有效利用太阳能，在温和条件下促使反应进行，并且能够定向的选择性合成目标产物，提高目标产物的产率，因此其在有机合成中的应用引起了广泛的关注.
本文以具有分级结构且能够响应可见光的SiC纳米线为载体，并通过液相还原法制备负载量为3 wt%的Pd/SiC催化剂.TEM照片可以看出，Pd纳米颗粒均地分散在SiC表面，平均粒径为3.7nm.UV-Vis图谱表明，SiC负载Pd以后可明显提高其对可见光的吸收.Pd/SiC在可见光（400-800nm）照射下，在30℃和常压Ar氛围下即可实现碘苯脱碘硼化，苯硼酸频哪醇酯的收率高达95%.Pd/SiC在可见光作用下，对其它碘苯类和溴苯类化合物的光催化硼化均具有较好的的普适性.在暗反应条件下，苯硼酸频哪醇酯的收率仅为5%.并且，转化率能够随着光强度的增强而增加.同时，不同的波长范围对光反应的贡献率也不同，400-450，450-500，500-550，550-600和600-800nm的光反应贡献率分别为34%，22%，16%，13%和5%，这与催化剂的紫外可见吸收光谱相一致，充分说明反应主要为光驱动反应.Pd/SiC催化剂也具有较好的可重复使用性，经过5次循环使用后，催化活性依然保持在较高的水平.
光反应和暗反应活化能的显著差别，说明二者的机理不同.理论研究发现，SiC的功函为4.0eV，低于Pd （5.12eV），当Pd负载在SiC表面时，能够形成Mott-Schottky接触，使SiC吸收可见光生成的光生电子能够迅速的传递到Pd活性位.XPS表征显示，Pd在Pd/SiC催化剂中以金属态Pd⁰的形式存在，并向低结合能方向移动，说明SiC中的电子向Pd迁移，增加了Pd原子周围的电子云密度.同时，光致发光光谱中，Pd/SiC位于400-550nm的特征峰与SiC相比，强度明显减弱，说明光生电子和空穴的分离效率增强.据此我们推断，光生电子迅速从SiC传递到Pd使Pd活性位表面富电子化，进而快速活化和断裂芳基卤化物中的C-I或C-Br键，有效提高催化活性.

关键词:

English

Photocatalytic C-X borylation of aryl halides by hierarchical SiC nanowire-supported Pd nanoparticles

a State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi, China;
b Institut für Anorganische Chemie, and Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany;
c School of Petrochemical Engineering, Changzhou University, Changzhou 213164, Jiangsu, China;
d Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China
Received Date: 17 May 2019
Revised Date: 10 July 2019
Fund Project:
This work was supported by the National Natural Science Foudation of China (21473232, 21673271, U1710112).

Abstract: Hierarchical SiC nanowire-supported Pd nanoparticles showed high photocatalytic activity for the C-X (X=Br, I) borylation of aryl halides at 30℃. The SiC/Pd Mott-Schottky contact enhances the rapid transfer of the photogenerated electrons from SiC to the Pd nanoparticles. As a result, the concentrated energetic electrons in the Pd nanoparticles can facilitate the cleavage of C-I or C-Br bonds, which normally requires high-temperature thermal processes. We show that the present Pd/SiC photocatalyst is capable of catalyzing the transformation of a large variety of aryl halides to their corresponding boronate esters under visible light irradiation, with excellent yields.

Key words:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

具有分级结构的SiC纳米线负载的Pd纳米颗粒光催化芳基卤化物硼化反应

English

Photocatalytic C-X borylation of aryl halides by hierarchical SiC nanowire-supported Pd nanoparticles

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

具有分级结构的SiC纳米线负载的Pd纳米颗粒光催化芳基卤化物硼化反应

English

Photocatalytic C-X borylation of aryl halides by hierarchical SiC nanowire-supported Pd nanoparticles

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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