二氧化钛负载的镍氧化态对乙腈气相加氢的影响

引用本文: 夏龙飞, 江治, 上官文峰, 顾顺超, 平野真一. 二氧化钛负载的镍氧化态对乙腈气相加氢的影响[J]. 物理化学学报, 2015, 31(5): 941-947. doi: 10.3866/PKU.WHXB201503051 shu

Citation: XIA Long-Fei, JIANG Zhi, SHANGGUAN Wen-Feng, GU Shun-Chao, HIRANO Shinichi. Influence of Oxidation State of Nickel Supported on TiO₂ on Gas-Phase Hydrogenation of Acetonitrile[J]. Acta Physico-Chimica Sinica, 2015, 31(5): 941-947. doi: 10.3866/PKU.WHXB201503051 shu

二氧化钛负载的镍氧化态对乙腈气相加氢的影响

基金项目:
花王株式会社(日本)项目资助 (日本)

摘要:

采用浸渍法制备了二氧化钛负载镍催化剂. 通过控制还原温度(200-400 ℃), 在TiO₂上得到不同氧化态的镍颗粒. 结果发现, 乙腈气相加氢反应受镍氧化态的影响, 300 ℃下还原的催化剂表现出最高的乙腈转化活性, 100 ℃时将乙腈完全转化. 产物产率受到Ni/TiO₂催化剂酸性的影响, 而催化剂的酸性不仅受到TiO₂载体的影响, 还受到负载物Ni 颗粒性质的影响. 随着催化剂还原温度升高, 金属态镍逐渐出现在催化剂表面, 降低了催化剂的酸性强度, 使三乙胺的最大产率升高(从34%升高到48%左右). 研究还发现在Ni/TiO₂催化乙腈加氢反应中, 三乙胺是初始产物. Ni 的状态不仅影响乙腈的转化, 还影响产物的脱附. 提出了乙腈加氢的第一步反应机理.

关键词:

English

Influence of Oxidation State of Nickel Supported on TiO₂ on Gas-Phase Hydrogenation of Acetonitrile

1.
1 School of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai 200240, P. R. China;
2 School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, P. R. China;
3 Hirano Institute for Materials Innovation, Shanghai Jiao Tong University, Shanghai 200240, P. R. China
Received Date: 09 December 2014
Available Online: 08 May 2015
Fund Project:
花王株式会社(日本)项目资助

Abstract:

Nickel catalysts supported on TiO₂ were prepared using an impregnation method. Changes in the reduction temperature from 200 to 400 ℃ resulted in dispersion of nickel with different oxidation states on TiO₂. The gas-phase hydrogenation of acetonitrile was found to be influenced by the nickel oxidation state. Nickel reduced at 300 ℃ gave the highest acetonitrile conversion ratio, i.e., about 100%, when the reaction temperature was 100 ℃. The product yields depend on the amount of acidic sites on Ni/TiO₂ catalysts; this can be influenced not only by the TiO₂ support, but also by the properties of the supported nickel nanoparticles. The triethylamine yield increased to a maximum (from 34% to about 48%) with increasing reduction temperature; this corresponded to the gradual appearance of Ni⁰ in Ni/TiO₂ and a decrease in the intrinsic acidity of the Ni/TiO₂ catalyst. Triethylamine was the initial product in the hydrogenation of acetonitrile with Ni/TiO₂. The oxidation state of nickel influenced not only the conversion of acetonitrile but also desorption of the final products. Amechanism for the first step in this reaction is proposed.

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

二氧化钛负载的镍氧化态对乙腈气相加氢的影响

English

Influence of Oxidation State of Nickel Supported on TiO₂ on Gas-Phase Hydrogenation of Acetonitrile

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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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

二氧化钛负载的镍氧化态对乙腈气相加氢的影响

English

Influence of Oxidation State of Nickel Supported on TiO2 on Gas-Phase Hydrogenation of Acetonitrile

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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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

Influence of Oxidation State of Nickel Supported on TiO₂ on Gas-Phase Hydrogenation of Acetonitrile

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs