CeO<sub>2</sub>纳米管负载Pd纳米颗粒催化CO低温氧化

引用本文: 吴静谧, 曾亮, 程党国, 陈丰秋, 詹晓力, 巩金龙. CeO₂纳米管负载Pd纳米颗粒催化CO低温氧化[J]. 催化学报, 2016, 37(1): 83-90. doi: 10.1016/S1872-2067(15)60913-5 shu

Citation: Jingmi Wu, Liang Zeng, Dangguo Cheng, Fengqiu Chen, Xiaoli Zhan, Jinlong Gong. Synthesis of Pd nanoparticles supported on CeO₂ nanotubes for CO oxidation at low temperatures[J]. Chinese Journal of Catalysis, 2016, 37(1): 83-90. doi: 10.1016/S1872-2067(15)60913-5 shu

CeO₂纳米管负载Pd纳米颗粒催化CO低温氧化

吴静谧 ^a, ,
曾亮 ^b, ,
程党国 ^{a,
,} ,
陈丰秋 ^a, ,
詹晓力 ^a, ,
巩金龙 ^{b,
,}

1.
a 浙江大学化学工程与生物工程学院, 生物质化工教育部重点实验室, 浙江杭州310027;
2.
b 天津大学化工学院, 绿色合成与转化教育部重点实验室, 天津化学化工协同创新中心, 天津300072

通讯作者: 程党国, 巩金龙; 程党国, 巩金龙

基金项目:
国家自然科学基金(21376209, 21376169) (21376209, 21376169)

浙江省自然科学重点基金(LZ13B060004) (LZ13B060004)

浙江省重点科技创新团队计划(2013TD07) (2013TD07)

高等学校学科创新引智计划(B06006). (B06006)

摘要: 高效负载型Pd催化剂的制备及其在CO低温氧化反应中的机理探究是近年来的研究热点.普遍认为,Pd催化剂上的CO氧化反应遵循Langmuir-Hinshelwood机理:首先,CO吸附于Pd物种表面; 然后,CO与催化剂表面的晶格氧发生反应转化为CO₂,反应发生在金属-载体界面.另外,高分散的Pd活性物种有利于CO氧化反应.同时载体的形貌、暴露的晶面、氧空位以及孔结构等都是影响催化剂活性的重要因素.CeO₂纳米管具有独特的管状特征和较高的比表面积,是一种潜在的CO低温氧化催化剂载体.
本文利用乙醇还原法,以CeO₂纳米管为载体,制备不同Pd含量的Pd/CeO₂-nanotube纳米催化剂,并利用N₂吸附脱附、X射线衍射(XRD)、透射电子显微镜(TEM)、CO程序升温脱附(CO-TPD)、X射线光电子能谱(XPS)等表征手段,探索纳米催化剂载体形貌对CO氧化反应活性的影响.氮气吸脱附结果表明,Pd/CeO₂-nanotube具有较高的比表面积(58.0m²/g),且存在介孔结构.XRD表征发现,Pd/CeO₂-nanotube的衍射峰对应立方萤石型结构的CeO₂的(111),(200),(220),(311)等晶面.TEM结果表明,Pd/CeO₂-nanotube具有均匀的纳米管形貌,其外径为40-60nm,Pd纳米颗粒均匀分散在其表面.CO-TPD结果表明,Pd/CeO₂-nanotube在110ºC附近具有很强的脱附峰,在370ºC和600ºC附近分别具有较宽和较弱的脱附峰,这表明该催化剂具有较多的吸附位,且具有很强的CO吸附能力; CO不可逆吸附量计算结果表明,该催化剂上的Pd具有很高的表面分散度(23.3%),Pd颗粒尺寸为7.3nm.XPS表征显示,Pd以Pd²⁺的形式分散于CeO₂纳米管的表面,且与载体发生相互作用,存在Pd-O-Ce键;同时该催化剂表面存在丰富的Ce³⁺,为反应提供更多的氧空位.0.9Pd/CeO₂-nanotube纳米催化剂在CO氧化反应中表现出优良的活性,能在100℃实现CO的完全转化; 通过计算发现,该催化剂具有较高的TOF值(0.63s^-1),由Arrhenius曲线可得到该催化剂的活化能为26.5kJ/mol.
综上可见:金属活性组分的尺寸和分散度、载体的结构特征、CO吸附能力以及金属-载体间的相互作用决定催化剂的性能.Pd/CeO₂-nanotube的高比表面积有利于Pd的分散; 其强CO吸附能力有利于CO吸附于Pd物种表面; 催化剂表面丰富的Ce³⁺能为反应提供更多的氧空位,Pd-O-Ce键的形成能增强金属-载体间的相互作用,有利于CO与催化剂表面晶格氧发生反应.同时催化剂介孔结构有利于反应气体和产物气体的吸附和扩散,因此,Pd/CeO₂-nanotube纳米催化剂在CO氧化反应中表现出优良的活性.

关键词:

English

Synthesis of Pd nanoparticles supported on CeO₂ nanotubes for CO oxidation at low temperatures

1.
a Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China;
2.
b Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University; Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300072, China

Corresponding author: 程党国, 巩金龙; 程党国, 巩金龙

Received Date: 30 April 2015
Fund Project:
国家自然科学基金(21376209, 21376169)

浙江省自然科学重点基金(LZ13B060004)

浙江省重点科技创新团队计划(2013TD07)

高等学校学科创新引智计划(B06006).

Abstract: Developing efficient supported Pd catalysts and understanding their catalytic mechanism in CO oxidation are challenging research topics in recent years. This paper describes the synthesis of Pd nanoparticles supported on CeO₂ nanotubes via an alcohol reduction method. The effect of the support morphology on the catalytic reaction was explored. Subsequently, the performance of the prepared catalysts was investigated toward CO oxidation reaction and characterized by Nitrogen sorption, X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, and CO-temperature-programmed desorption techniques. The results indicated that the catalyst of Pd on CeO₂ nanotubes exhibits excellent activity in CO oxidation at low temperatures, due to its large surface area, the high dispersion of Pd species, the mesoporous and tubular structure of the CeO₂-nanotube support, the abundant Ce³⁺, formation of Pd-O-Ce bonding, and enhanced metal-support interaction on the catalyst surface.

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

CeO₂纳米管负载Pd纳米颗粒催化CO低温氧化

通讯作者: 程党国, 巩金龙; 程党国, 巩金龙

English

Synthesis of Pd nanoparticles supported on CeO₂ nanotubes for CO oxidation at low temperatures

Corresponding author: 程党国, 巩金龙; 程党国, 巩金龙

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中国化学会秘书处

CeO2纳米管负载Pd纳米颗粒催化CO低温氧化

通讯作者: 程党国, 巩金龙; 程党国, 巩金龙

English

Synthesis of Pd nanoparticles supported on CeO2 nanotubes for CO oxidation at low temperatures

Corresponding author: 程党国, 巩金龙; 程党国, 巩金龙

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

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CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CeO₂纳米管负载Pd纳米颗粒催化CO低温氧化

Synthesis of Pd nanoparticles supported on CeO₂ nanotubes for CO oxidation at low temperatures

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