新型无氢胺化催化剂PdHx-Pd/C的水合肼还原法制备及形成机制研究

doi:10.3724/SP.J.1077.2013.13011

无机材料学报 ›› 2013, Vol. 28 ›› Issue (10): 1072-1078.DOI: 10.3724/SP.J.1077.2013.13011

新型无氢胺化催化剂PdH_x-Pd/C的水合肼还原法制备及形成机制研究

郇昌永, 马磊, 吕德义, 郑遗凡, 季来军, 李小年

(浙江工业大学工业催化研究所, 绿色化学合成技术国家重点实验室培育基地, 杭州 310032)

收稿日期:2013-01-07 修回日期:2013-02-17 出版日期:2013-10-20 网络出版日期:2013-09-18
作者简介:郇昌永(1979-), 男, 博士研究生. E-mail: huanmy2006@163.com
基金资助:
国家重点基础研究发展计划(2011CB710800)

Preparation and Formation Mechanism of New PdH_x-Pd/C Catalyst through Hydrazine-reducing Method under Atmospheric Pressure and H₂-free Conditions

HUAN Chang-Yong, MA Lei, L- De-Yi, ZHENG Yi-Fan, JI Lai-Jun, LI Xiao-Nian

(Institute of Industrial Catalysis, Zhejiang University of Technology, Hangzhou 310032, China)

Received:2013-01-07 Revised:2013-02-17 Published:2013-10-20 Online:2013-09-18
About author:HUAN Chang-Yong. E-mail: huanmy2006@163.com
Supported by:
Key Project of Chinese National Programs for Fundamental Research and Development(2011CB710800)

摘要/Abstract

摘要： PdH_x是Pd/C催化剂中重要的活性物种, 在常温无氢的条件下不能稳定存在。在常压无氢条件下, 以PdO作前驱体, 用水合肼还原法可制备出PdH_x含量较高, 且能够稳定存在的PdH_x-Pd/C催化剂。通过XRD、XPS和TEM等表征方法研究了PdH_x和Pd颗粒的微观结构、形貌及化学状态; 提出了水合肼还原法生成PdH_x的机理。实验结果表明: PdH_x颗粒的平均粒径为3.9 nm, PdH_x(111)晶面间距比Pd(111)稍大; PdH_x生成于水合肼对PdO的还原过程, 且其晶粒大小与前驱体PdO的粒度大小及结构不完整性密切相关。将该催化剂应用于无氢条件下胺化法合成2, 6-二甲基苯胺的反应中, 其催化性能明显优于普通的Pd/C催化剂。

关键词: 钯, 活性炭, 表征, PdH_x

Abstract: PdH_x is an important reactive species for the Pd/C catalyst. Without H₂, it can not exist stably at room temperature. This species is usually prepared through reaction of Pd with H₂ under certain pressure. PdH_x-Pd/C catalyst was prepared through hydrazine-reducing method under atmospheric pressure and H₂-free conditions. The microstructure, morphology and chemical state of PdHx and Pd particles were investigated by XRD, TEM and XPS characterization methods. The formation mechanism of PdH_x particles in the hydrazine-reducing method was proposed. Experimental results show that the average particle size of PdH_x is 3.9 nm, and the d spacing of PdH_x(111) is slightly larger than that of Pd(111). The PdH_x particles derive from the reduction process of PdO by hydrazine. Their particle size is closely related to the particle size and structural imperfection of PdO. The PdH_x-Pd/C catalyst demonstrates better catalytic performance than the conventional Pd/C catalyst in the amination reaction to produce 2, 6-dimethylaniline under H₂-free condition.

Key words: Pd, activated carbon, characterization, PdH_x

中图分类号:

TQ174

郇昌永, 马磊, 吕德义, 郑遗凡, 季来军, 李小年. 新型无氢胺化催化剂PdH_x-Pd/C的水合肼还原法制备及形成机制研究[J]. 无机材料学报, 2013, 28(10): 1072-1078.

HUAN Chang-Yong, MA Lei, L- De-Yi, ZHENG Yi-Fan, JI Lai-Jun, LI Xiao-Nian. Preparation and Formation Mechanism of New PdH_x-Pd/C Catalyst through Hydrazine-reducing Method under Atmospheric Pressure and H₂-free Conditions[J]. Journal of Inorganic Materials, 2013, 28(10): 1072-1078.

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新型无氢胺化催化剂PdH_x-Pd/C的水合肼还原法制备及形成机制研究

Preparation and Formation Mechanism of New PdH_x-Pd/C Catalyst through Hydrazine-reducing Method under Atmospheric Pressure and H₂-free Conditions

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新型无氢胺化催化剂PdHx-Pd/C的水合肼还原法制备及形成机制研究

Preparation and Formation Mechanism of New PdHx-Pd/C Catalyst through Hydrazine-reducing Method under Atmospheric Pressure and H2-free Conditions

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新型无氢胺化催化剂PdH_x-Pd/C的水合肼还原法制备及形成机制研究

Preparation and Formation Mechanism of New PdH_x-Pd/C Catalyst through Hydrazine-reducing Method under Atmospheric Pressure and H₂-free Conditions