Co-Cr-O复合氧化物上丙烷低温完全氧化:结构效应、反应动力学和原位光谱研究

引用本文: 廖文敏, 赵培培, 岑丙横, 贾爱平, 鲁继青, 罗孟飞. Co-Cr-O复合氧化物上丙烷低温完全氧化:结构效应、反应动力学和原位光谱研究[J]. 催化学报, 2020, 41(3): 442-453. doi: S1872-2067(19)63480-7 shu

Citation: Wen-Min Liao, Pei-Pei Zhao, Bing-Heng Cen, Ai-Ping Jia, Ji-Qing Lu, Meng-Fei Luo. Co-Cr-O mixed oxides for low-temperature total oxidation of propane: Structural effects, kinetics, and spectroscopic investigation[J]. Chinese Journal of Catalysis, 2020, 41(3): 442-453. doi: S1872-2067(19)63480-7 shu

Co-Cr-O复合氧化物上丙烷低温完全氧化:结构效应、反应动力学和原位光谱研究

浙江师范大学物理化学研究所, 教育部先进催化材料重点实验室, 浙江金华 321004
基金项目:
国家自然科学基金（21773212，21872124）.

摘要: 低碳烷烃是一类主要的挥发性有机污染物（VOCs），广泛生成于汽车尾气以及各种工业过程如煤处理、石油精炼以及天然气处理等.随着对环保要求的日益提高，对高效VOCs消除技术的需求愈加迫切.催化完全氧化（催化燃烧）技术具有起燃温度低、能耗低、净化效果好（无二次污染）等优点，因而极具应用潜力.对于低碳烷烃的催化燃烧，贵金属催化剂如Pt和Pd等具有很高的反应活性，但存在价格昂贵并易中毒等缺陷限制了其商业应用.另一方面，过渡金属氧化物由于其价格低廉、抗中毒性能优异及热稳定性好等特点受到广泛关注.Cu，Mn，Co，Fe等氧化物都具有良好的催化活性，其中Co氧化物由于其在丙烷催化燃烧中的高活性受到关注.而在Co氧化物中添加第二金属更能促进其反应性能.因此本文制备了一系列不同Co/Cr比例的复合氧化物用于丙烷催化燃烧，考察了催化剂结构和表面性质对其反应行为的影响，并通过反应动力学和原位光谱技术对反应机理进行了探索.
实验结果表明，随着Co/Cr比例的变化，催化剂的晶相结构、颗粒尺寸、比表面积、表面酸性以及氧化还原性等特性均发生了明显变化，进而影响了其反应行为.当Co/Cr比例为1/2时（1Co2Cr），催化剂为尖晶石结构并具有最大的比表面积.该催化剂上具有最高的反应活性（250℃时反应速率为1.38μmol g^-1 s^-1），可归因于其最高的表面酸性和低温氧化还原性能的协同作用.反应动力学结果表明，1Co2Cr催化剂上丙烷和氧气的反应级数分别为0.58 ±0.03和0.34 ±0.05，低于2Co1Cr（分别为0.77 ±0.02和0.98 ±0.16）和1Co5Cr（分别为0.66 ±0.05和1.30 ±0.11），表明1122Cr催化剂相比后二者具有更高的丙烷和氧气表面覆盖度，得益于其更高的表面酸性和更好的低温氧化还原性能.此外，原位红外光谱表明，在反应过程中，1Co2Cr催化剂上的主要表面物种为多齿碳酸盐，该物种在低温时（< 250℃）在表面积聚，但在高温时被分解.

关键词:

English

Co-Cr-O mixed oxides for low-temperature total oxidation of propane: Structural effects, kinetics, and spectroscopic investigation

Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua 321004, Zhejiang, China
Received Date: 07 July 2019
Revised Date: 02 August 2019
Fund Project:
This work was financially supported by the National Natural Science Foundation of China (21773212, 21872124).

Abstract: A series of Co-Cr-O mixed oxides with different Co/Cr molar ratios are synthesized and tested for the total oxidation of propane. The reaction behaviors are closely related to the structural features of the mixed oxides. The catalyst with a Co/Cr molar ratio of 1:2 (1Co2Cr) and a spinel structure has the best activity (with a reaction rate of 1.38 μmol g^-1 s^-1 at 250℃), which is attributed to the synergistic roles of its high surface acidity and good low-temperature reducibility, as evidenced by the temperature-programmed desorption of ammonia, reduction of hydrogen, and surface reaction of propane. Kinetic study shows that the reaction orders of propane and oxygen on the 1Co2Cr catalyst (0.58 ± 0.03 and 0.34 ±0.05, respectively) are lower than those on the 2Co1Cr catalyst (0.77 ±0.02 and 0.98 ±0.16, respectively) and 1Co5Cr (0.66 ±0.05 and 1.30 ±0.11, respectively), indicating that the coverages of propane and oxygen on 1Co2Cr are higher than those on the other catalysts due to its higher surface acidity and higher reducibility. In addition, in-situ diffuse reflectance infrared spectroscopic investigation reveals that the main surface species on 1Co2Cr during the reaction are polydentate carbonate species, which accumulate on the surface at low temperatures (< 250℃) but decompose at relatively high temperatures.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

Co-Cr-O复合氧化物上丙烷低温完全氧化:结构效应、反应动力学和原位光谱研究

English

Co-Cr-O mixed oxides for low-temperature total oxidation of propane: Structural effects, kinetics, and spectroscopic investigation

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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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

Co-Cr-O复合氧化物上丙烷低温完全氧化:结构效应、反应动力学和原位光谱研究

English

Co-Cr-O mixed oxides for low-temperature total oxidation of propane: Structural effects, kinetics, and spectroscopic investigation

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

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