孔结构对纳米浇注的中孔钙钛矿上甲醇氧化反应动力学的影响

引用本文: Mahesh M. Nair, Freddy Kleitz, Serge Kaliaguine. 孔结构对纳米浇注的中孔钙钛矿上甲醇氧化反应动力学的影响[J]. 催化学报, 2016, 37(1): 32-42. doi: 10.1016/S1872-2067(15)60909-3 shu

Citation: Mahesh M. Nair, Freddy Kleitz, Serge Kaliaguine. Pore structure effects on the kinetics of methanol oxidation over nanocast mesoporous perovskites[J]. Chinese Journal of Catalysis, 2016, 37(1): 32-42. doi: 10.1016/S1872-2067(15)60909-3 shu

孔结构对纳米浇注的中孔钙钛矿上甲醇氧化反应动力学的影响

1.
a 拉瓦尔大学化学系Matériaux Avancés研究中心(CERMA), 魁北克, G1V 0A6, 加拿大;
2.
b 拉瓦尔大学化工系, 魁北克, G1V 0A6, 加拿大

通讯作者: Serge Kaliaguine

基金项目:
This work was supported by the the National Science and Engineering Research Council (Canada) (Canada)

and the Fonds Qué

cois de la Recherche sur la Nature et les Technologies (Province of Quebec). (Province of Quebec)

摘要: 限制工业有毒气体(如挥发性有机化合物)的排放是当今社会主要的挑战之一.因此,迫切需要开发出消除污染物、且不造成二次污染的环境友好技术.其中热燃烧技术比较有效,但通常该过程会采用贵金属催化剂以实现低温高活性.由于贵金属催化剂的成本较高,不利于工业应用,因此,人们一直致力于研究和开发新型材料以替代贵金属催化剂.研究发现,在许多部分氧化或完全氧化反应(特别是烃类或挥发性有机物的氧化反应)中,钙钛矿类复合金属氧化物(ABO₃)具有与贵金属类似的催化性能.但是该材料的制备需在高温(>700ºC)条件下进行,使得其比表面积(<30m²/g)很低,因而限制了其应用.可见,欲使该材料在工业上得到广泛应用,必须在制备技术上实现很大的突破,即制得高比表面积的钙钛矿类材料.已有人通过在200℃下焙烧成功地制备了比表面积为100m²/g的钙钛矿氧化物,但继续提高焙烧温度,所制样品的比表面积下降.
在过去20年中,中孔氧化硅及随后众多中孔材料的成功制备,使得合成具有极高比表面积的非硅基材料(如碳,金属氧化物,和碳化物等)成为可能.在这些材料的制备方法中,纳米浇铸法因其特别适用于制备具有高比表面积的单金属或单金属氧化物而备受青睐.采用纳米浇铸法已经成功制得一系列材料,并用于很多催化反应中.但文献报道大多只局限于温度、催化剂组成或比表面积对其活性的影响.为了能将这些材料成功用于工业应用,需要对其表面反应机理和相关反应动力学进行深入的研究.
最近,本课题组采用纳米浇铸法制备了高比表面积的中孔钙钛矿类氧化物,并考察了它们的催化性能.结果表明,在各种气相反应中,所制纳米浇注的钙钛矿类氧化物具有比相应体相氧化物更高的催化效率.基于此,本文以在不同温度老化的SBA-15为硬模板,采用纳米浇铸法制备高比表面积的LaMnO₃材料,运用X-射线衍射、N₂吸附-脱附、透射电镜、程序升温还原和O₂-程序升温脱附等方法分析所制材料的晶相、织构、表面和氧化还原等性质,考察了其孔结构参数对其催化甲醇完全氧化反应性能和动力学的影响,以深入理解该类材料的催化性能.结果表明,以35,100,140℃老化制得的SBA-15为模板剂,成功地制得了La在A位,Mn在B位的一系列LaMnO₃材料,它们具有可调控的比表面积(80-190m²/g);同时,材料的比表面积与所用硬模板剂的老化温度存在很好的关联,且比表面积最大的样品具有最高的催化活性.测量了各催化剂在不同空速(19500-78200h^-1)条件下甲醇氧化反应结果,从而得到了各催化剂的速率常数,发现它们随着催化剂的比表面积而变化.再结合阿伦尼乌斯方程,采用线性回归法测得了所制备的三个催化剂上该方程的指前因子和表观活化能;发现在所考察的反应条件下,所有催化剂上反应的表观活化能较低,且保持不变.另外,指前因子与催化剂比表面积之间存在线性关系,表明尽管各催化剂的比表面积不同,但单位比表面积的甲醇氧化的比活性是相同的.由于在制备过程中很难除去残余的Si物种,因此未来工作中我们将进一步考察残余物种对纳米浇注的钙钛矿类材料性质的影响.

关键词:

English

Pore structure effects on the kinetics of methanol oxidation over nanocast mesoporous perovskites

1.
a Department of Chemistry and Centre de Recherche sur les Matériaux Avancés (CERMA), Université Laval, Quebec City, G1V 0A6, Canada;
2.
b Department of Chemical Engineering, Université Laval, Quebec City, G1V 0A6, Canada

Corresponding author: Serge Kaliaguine

Received Date: 21 March 2015
Fund Project:
This work was supported by the the National Science and Engineering Research Council (Canada)

and the Fonds Qué

cois de la Recherche sur la Nature et les Technologies (Province of Quebec).

Abstract: Mesoporous LaMnO₃ perovskite catalysts with high surface area were synthesized by using the recently developed hard templating method designated as “nanocasting”. Ordered mesoporous silica designated as SBA-15 was used as the hard template. It was found that the surface area of the nanocast perovskites can be tuned (80-190 m²/g) by varying the aging temperature of the SBA-15 template. Nanocast LaMnO₃ catalysts showed high conversion efficiencies for the total oxidation of methanol under steady state conditions, the one with the highest value of surface area being the best catalysts, as expected. Kinetic studies were performed for all of the synthesized catalysts. Rate constants were found to vary in accordance with the specific surface area of the nanocast catalyst which depends on the aging temperature of the parent template. From the rate constants obtained from experimental conversions at various space velocities (19500 to 78200 h^-¹), values of activation energy and pre-exponential factor for the three nanocast LaMnO₃ catalysts were determined by the linear regression of the Arrhenius plot. It is observed that the activation energy for all the catalysts remain constant irrespective of the variation in specific surface area. Further, a linear relationship was found to exist between the pre-exponential factor and specific surface areas of the catalysts indicating that the rates per unit surface area remains the same for all the catalysts.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

孔结构对纳米浇注的中孔钙钛矿上甲醇氧化反应动力学的影响

通讯作者: Serge Kaliaguine

English

Pore structure effects on the kinetics of methanol oxidation over nanocast mesoporous perovskites

Corresponding author: Serge Kaliaguine

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

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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

孔结构对纳米浇注的中孔钙钛矿上甲醇氧化反应动力学的影响

通讯作者: Serge Kaliaguine

English

Pore structure effects on the kinetics of methanol oxidation over nanocast mesoporous perovskites

Corresponding author: Serge Kaliaguine

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

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs