常压低温等离子体有效去除催化CO氧化的金原子团簇的保护剂

doi:10.1016/S1872-2067(18)63018-9

催化学报 ›› 2018, Vol. 39 ›› Issue (5): 929-936.DOI: 10.1016/S1872-2067(18)63018-9

常压低温等离子体有效去除催化CO氧化的金原子团簇的保护剂

谭媛^a,b, 刘华^a,b, 刘晓艳^a, 王爱琴^a, 刘昌俊^c, 张涛^a,b

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, 能源材料化学协同创新中心, 金催化中心, 辽宁大连 116023;
b 中国科学院大学, 北京 100049;
c 天津大学化学化工协同创新中心, 天津 300072

收稿日期:2017-11-27 修回日期:2017-12-27 出版日期:2018-05-18 发布日期:2018-04-19
通讯作者: 刘晓艳
基金资助:
国家自然科学基金（21476227，21522608，21776271）；中国科学院战略性先导科技专项（XDB17020100）；国家重点研发计划"纳米科技"重点专项（2016YFA0202801）；中国科学院青年创新促进会（2014163）；辽宁省科技厅（2015020086-101）.

Effective removal of the protective ligands from Au nanoclusters by ambient pressure nonthermal plasma treatment for CO oxidation

Yuan Tan^a,b, Hua Liu^a,b, Xiao Yan Liu^a, Aiqin Wang^a, Changjun Liu^c, Tao Zhang^a,b

a State Key Laboratory of Catalysis, iChEM(Collaborative Innovation Center of Chemistry for Energy Materials), Gold Catalysis Research Center, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
b University of Chinese Academy of Sciences, Beijing 100049, China;
c Collaborative Innovation Center of Chemical Science and Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China

Received:2017-11-27 Revised:2017-12-27 Online:2018-05-18 Published:2018-04-19
Contact: 10.1016/S1872-2067(18)63018-9
Supported by:
This work was supported by the National Natural Science Foundation of China (21476227, 21522608, 21776271), the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB17020100), the National Key Research & Development Program of China (2016YFA0202801), the Youth Innovation Promotion Association CAS (2014163), and the Department of Science and Technology of Liaoning Province under contract of 2015020086-101.

摘要/Abstract

摘要：

采用介质阻挡放电等离子体技术可以在低温、常压下实现对纳米金催化剂中保护基团的有效去除.本文通过对不同保护基团（聚乙烯吡咯烷酮和半胱氨酸）保护的金催化剂进行等离子体预处理，发现采用该技术能有效去除载体中的层间阴离子，还可能将金原子与保护基团之间的化学键打断.通过X射线粉末衍射对等离子体处理后的样品和未经处理的样品进行表征，发现经等离子体处理后的样品，载体从水滑石结构变为复合氧化物结构，这说明等离子体处理可将载体中的羟基和羰基除去，从而引起载体结构变化.热重分析结果显示，经等离子体处理后的样品失重量（19%-23%）与未处理样品的失重量（31%）相比差10%左右，这说明采用该方法可以在一定程度上去除纳米金表面保护基团和载体的层间阴离子.用紫外-可见光谱和高角环形暗场像-扫描透射电子显微镜对催化剂中金颗粒的尺寸分布和平均粒径进行分析，发现金颗粒在等离子体处理过后其粒径没有发生严重聚集，平均粒径由未处理时的1.4-1.7nm轻微长大至2.4-3.7nm.
以含硫醇化合物（半胱氨酸）保护的金原子团簇催化剂为例考察了等离子体不同处理时间的影响，发现随着处理时间从25min延长至150min，样品的颜色从浅紫色变为暗紫色.结合XRD和TGA等结果可知，随着处理时间的延长，催化剂中保护基团的去除度逐渐提高.CO氧化反应活性评价结果显示，与未经处理的样品相比，经等离子体处理后的样品催化CO氧化反应活性有明显提高，且随预处理时间延长，活性有提高的趋势.动力学测试结果表明，经等离子体处理后的样品催化CO氧化的表观活化能低至1.2-2.9kJ/mol，接近于文献中报道的Au/TiO₂催化剂.这说明作为一种催化剂处理方法，介质阻挡放电等离子体技术可以有效去除催化剂中的保护剂，且因其处理条件相对温和，可在一定程度上保持金颗粒尺寸的稳定，这对于控制合成负载型小尺寸的金催化剂具有重要意义.

关键词: 金原子团簇, 等离子体, 纳米金催化剂, 有机保护基团, 一氧化碳氧化

Abstract:

We used a dielectric barrier discharge (DBD) plasma technique to eliminate the protective ligand of ZnAl-hydrotalcite-supported gold nanoclusters. We used X-ray powder diffraction, ultraviolet-visible spectrophotometry, thermogravimetric analysis, and high angle annular dark-field-scanning transmission electron microscopy characterization to show that the samples pretreated with/without DBD-plasma displayed different performances in CO oxidation. The enhanced activity was obtained on the plasma-treated samples, implying that the protective ligand was effectively removed via the plasma technique. The crystal structure of the plasma-treated samples changed markedly, suggesting that the plasma treatment could not only break the chemical bond between the gold and the protective agent but could also decompose the interlayer ions over the hydrotalcite support. The particle sizes of the gold after DBD-plasma treatment implied that it was a good way to control the size of the gold nanoparticles under mild conditions.

Key words: Gold cluster, Plasma, Supported gold catalyst, Protective ligand, Carbon monoxide oxidation

谭媛, 刘华, 刘晓艳, 王爱琴, 刘昌俊, 张涛. 常压低温等离子体有效去除催化CO氧化的金原子团簇的保护剂[J]. 催化学报, 2018, 39(5): 929-936.

Yuan Tan, Hua Liu, Xiao Yan Liu, Aiqin Wang, Changjun Liu, Tao Zhang. Effective removal of the protective ligands from Au nanoclusters by ambient pressure nonthermal plasma treatment for CO oxidation[J]. Chinese Journal of Catalysis, 2018, 39(5): 929-936.

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常压低温等离子体有效去除催化CO氧化的金原子团簇的保护剂

Effective removal of the protective ligands from Au nanoclusters by ambient pressure nonthermal plasma treatment for CO oxidation

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