锌铜复合氧化物负载的金纳米粒子在无碱条件下催化多种醇高效选择性氧化

引用本文: 汪伟, 谢妍, 张少华, 刘星, 张历云, 张炳森, 春田正毅, 黄家辉. 锌铜复合氧化物负载的金纳米粒子在无碱条件下催化多种醇高效选择性氧化[J]. 催化学报, 2019, 40(12): 1924-1933. doi: S1872-2067(19)63429-7 shu

Citation: Wei Wang, Yan Xie, Shaohua Zhang, Xing Liu, Liyun Zhang, Bingsen Zhang, Masatake Haruta, Jiahui Huang. Highly efficient base-free aerobic oxidation of alcohols over gold nanoparticles supported on ZnO-CuO mixed oxides[J]. Chinese Journal of Catalysis, 2019, 40(12): 1924-1933. doi: S1872-2067(19)63429-7 shu

锌铜复合氧化物负载的金纳米粒子在无碱条件下催化多种醇高效选择性氧化

汪伟 ^a,b, ,
谢妍 ^a, ,
张少华 ^a, ,
刘星 ^a, ,
张历云 ^c, ,
张炳森 ^c, ,
春田正毅 ^a,d, ,
黄家辉 ^a,

a 中国科学院大连化学物理研究所, 催化基础国家重点实验室, 金催化研究中心, 辽宁大连 116023, 中国;
b 中国科学院大学, 北京 100049, 中国;
c 中国科学院金属研究所, 沈阳材料科学国家研究中心, 辽宁沈阳 110016, 中国;
d 首都大学东京, 大学院都市环境科学研究科, 金化学研究中心, 八王子市, 东京192-0397, 日本
基金项目:
国家自然科学基金（21606219）；中国科学院战略性先导科技专项变革性洁净能源关键技术与示范（XDA21030900）.

摘要: 醇选择性氧化为醛和酮是化学工业上的重要反应.醛和酮是广泛应用于合成医药、农药和香料等精细化学品的重要化学中间体.过去常用化学计量的氧化剂来实现醇的选择性氧化，但会带来严重的环境污染.目前，很多研究工作致力于发展环境友好的催化体系，利用分子氧来实现醇的高效选择性氧化.
在过去的30年里，金催化剂在多种气相和液相反应中的催化性能和反应机理已被深入研究.近年来，金催化剂在醇选择性氧化反应中表现出高的催化活性和特殊的选择性.设计和制备合适的载体对金催化剂取得优异的醇氧化催化活性有至关重要的作用.先前的研究工作报道氧化锌是一种碱性材料，其表面没有酸性位.Au/ZnO催化剂在苯甲醇氧化反应中表现出高的苯甲醛选择性和低的苯甲醇转化率.在本研究工作中，我们向ZnO载体中掺杂Cu元素，制备出一系列ZnO-CuO复合氧化物，并进一步负载金用于催化苯甲醇氧化反应.研究结果表明，在无碱的反应条件下，Au/ZnO-CuO催化剂比Au/ZnO和Au/CuO催化剂具有更高的苯甲醇氧化催化活性，其中Au/Zn_0.7Cu_0.3O催化剂表现出最优的催化活性.我们还研究了反应温度和氧气压力对Au/Zn_0.7Cu_0.3O催化苯甲醇选择性氧化活性的影响，探索了Au/Zn_0.7Cu_0.3O催化剂对多种醇氧化反应的普遍适用性，考察了Au/Zn_0.7Cu_0.3O催化剂对醇氧化反应的催化循环性能.我们发现Au/Zn_0.7Cu_0.3O催化剂在无碱温和的反应条件下可以将1-苯基乙醇、对甲基苯甲醇、对异丙基苯甲醇、二苯甲醇、环丙基苯甲醇和肉桂醇高效选择性氧化为对应的羰基化合物，但对正辛醇氧化反应表现出相对较低的催化活性.此外，Au/Zn_0.7Cu_0.3O催化剂在苯甲醇氧化反应的催化循环中容易失活，而在1-苯基乙醇氧化反应的催化循环中则表现出较好的稳定性.
利用X射线衍射、氮气吸脱附、氢气程序升温还原、透射电子显微镜、二氧化碳程序升温脱附和氧气程序升温脱附等方法对金催化剂的物化性质进行了表征，并提出了金催化苯甲醇选择性氧化可能的反应机理.我们认为Au/Zn_0.7Cu_0.3O催化剂优异的催化活性与其小的金粒径、好的低温还原性能、高的表面氧物种含量、表面酸碱性及金粒子与载体的协同效应等密切相关.

关键词:

English

Highly efficient base-free aerobic oxidation of alcohols over gold nanoparticles supported on ZnO-CuO mixed oxides

a Gold Catalysis Research Center, State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
b University of Chinese Academy of Sciences, Beijing 100049, China;
c Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, Liaoning, China;
d Research Center for Gold Chemistry, Department of Applied Chemistry, Graduate School of Urban Environmental Sciences, Tokyo Metropolitan University, Hachioji, Tokyo 192-0379, Japan
Received Date: 29 April 2019
Revised Date: 23 June 2019
Fund Project:
This work was supported by the National Natural Science Foundation of China (21606219), and the "Transformational Technologies for Clean Energy and Demonstration", Strategic Priority Research Program of the Chinese Academy of Sciences (XDA21030900).

Abstract: The design and preparation of suitable supports are of great importance for gold catalysts to attain excellent catalytic performance for alcohol oxidation. In this work, we found that ZnO-CuO mixed oxides supported gold catalysts showed much better catalytic activity for base-free aerobic oxidation of benzyl alcohol than Au/ZnO and Au/CuO catalysts, and among them Au/Zn_0.7Cu_0.3O displayed the best catalytic performance. In addition, the Au/Zn_0.7Cu_0.3O catalyst could selectively catalyze the aerobic oxidation of a wide range of alcohols to produce the corresponding carbonyl compounds with high yields under mild conditions without base. Further characterizations indicated that the outstanding catalytic performance of Au/Zn_0.7Cu_0.3O was correlated with the small size of Au nanoparticles (NPs), good low-temperature reducibility, high concentration of surface oxygen species, and collaborative interaction between Au NPs and mixed oxide.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

锌铜复合氧化物负载的金纳米粒子在无碱条件下催化多种醇高效选择性氧化

English

Highly efficient base-free aerobic oxidation of alcohols over gold nanoparticles supported on ZnO-CuO mixed oxides

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

锌铜复合氧化物负载的金纳米粒子在无碱条件下催化多种醇高效选择性氧化

English

Highly efficient base-free aerobic oxidation of alcohols over gold nanoparticles supported on ZnO-CuO mixed oxides

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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