杂原子(Zr,Y)掺杂的铈基催化剂中氧物种与其催化CH3SH分解的活性/稳定性之间的关系

doi:10.1016/S1872-2067(18)63146-8

催化学报 ›› 2018, Vol. 39 ›› Issue (12): 1929-1941.DOI: 10.1016/S1872-2067(18)63146-8

杂原子(Zr,Y)掺杂的铈基催化剂中氧物种与其催化CH₃SH分解的活性/稳定性之间的关系

陈定凯^a, 张德华^a, 何德东^a,b, 陆继长^a, 钟丽萍^a, 韩彩云^a, 罗永明^a

a 昆明理工大学环境科学与工程学院, 云南昆明 650500;
b 昆明理工大学化学工程学院, 云南昆明 650500

收稿日期:2018-05-29 修回日期:2018-07-23 出版日期:2018-12-18 发布日期:2018-09-26
通讯作者: 张德华, 罗永明
基金资助:
国家自然科学基金（21667016，21267011，U1402233）.

Relationship between oxygen species and activity/stability in heteroatom (Zr, Y)-doped cerium-based catalysts for catalytic decomposition of CH₃SH

Dingkai Chen^a, Dehua Zhang^a, Dedong He^a,b, Jichang Lu^a, Liping Zhong^a, Caiyun Han^a, Yongming Luo^a

a Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming 650500, Yunnan, China;
b Faculty of Chemical Engineering, Kunming University of Science and Technology, Kunming 650500, Yunnan, China

Received:2018-05-29 Revised:2018-07-23 Online:2018-12-18 Published:2018-09-26
Contact: 10.1016/S1872-2067(18)63146-8
Supported by:
This work was supported by the National Natural Science Foundation of China (21667016, 21267011, U1402233).

摘要/Abstract

摘要：

铈基催化剂因其优异的储放氧能力被广泛地应用于多种催化反应.铈基材料作为催化剂在CH₃SH（甲硫醇）分解反应中的应用也因其产物简单、易处理而受到越来越多的关注.本课题组在前期研究中发现，纳米二氧化铈在CH₃SH催化分解反应中表现出较高的催化活性，然而催化剂却在很短时间内快速失活.为进一步提高铈基氧化物的稳定性，我们通过引入稀土元素对氧化铈催化剂进行改性，结果发现其稳定性明显提高；同时催化剂稳定性与氧空位数量有关，氧空位数量越多，催化剂越稳定.然而，目前关于氧空位对催化CH₃SH分解反应的具体作用，CH₃SH在铈基材料上的失活机理以及氧物种与催化行为之间的相互关系尚不清楚.因此，有必要进一步研究氧空位对提高催化稳定性的贡献并揭示催化行为与氧物种之间的相互关系.
本文通过微波辅助柠檬酸络合法制备一系列杂原子（Zr，Y）掺杂的铈基催化剂CeO₂，Ce_1-xZr_xO₂，Ce_1-xY_xO_2-δ（x=0.25，0.50，0.75，1.00），通过考察锆、钇杂原子价态和离子半径对CH₃SH催化分解活性和稳定性的影响来探索铈基催化剂中氧空位的作用及氧物种与催化行为之间的关系.其中，氧物种与催化行为之间的关系可包括两类：（1）表面晶格氧与催化活性之间的关系；（2）体相晶格氧迁移与催化稳定性之间的关系.
催化性能和表征结果表明，铈基氧化物中表面晶格氧对CH₃SH催化转化起着至关重要的作用.Ce_0.75Zr_0.25O₂在CH₃SH的催化分解中表现出更高的催化活性，这是由于Ce_0.75Zr_0.25O₂有更多的表面晶格氧、活性氧物种及良好的氧化还原性能.Ce_0.75Y_0.25O_2-δ也表现出更好的催化稳定性，这是由于催化剂中有更多的氧空位，它们会促进体相晶格氧迁移到催化剂表面以补充表面晶格氧.此外，Ce与杂原子之间化学价差极大地影响着表面晶格氧含量以及催化剂中体相氧的迁移率，进而影响铈基催化剂的活性和稳定性.

关键词: 铈基催化剂, 杂原子, 表面晶格氧, 甲硫醇分解, 体相氧迁移

Abstract:

CeO₂,Ce_1-xZr_xO₂, and Ce_1-xY_xO_2-δ(x=0.25, 0.50, 0.75, and 1.00) have been rapidly synthesized to estimate their catalytic behavior in decomposing CH₃SH. The role of oxygen vacancies, and the relationship between the oxygen species and catalytic properties of CeO₂ andZr-doped and Y-doped ceria-based materials are investigated in detail. Combining the observed catalytic performance with the characterization results, it can be deemed that surface lattice oxygenplays a critical role in methanethiol catalytic conversion over cerium oxides. Ce_0.75Zr_0.25O₂ shows higher catalytic activity for CH₃SH decomposition due to the large amount of surface lattice oxygen,readily available oxygen species, and excellent redox properties. Ce_0.75Y_0.25O_2-δ displays better catalytic stability owing to the greater number of oxygen vacancies that would promote bulk lattice oxygen migration to the surface of the catalyst in order to replenish surface lattice oxygen. In addition, the results show that the difference in chemical valence between Ce and the heteroatoms would strongly influence the amount of surface lattice oxygen as well as the mobility of bulk-phase oxygen in these catalysts, thus affecting their activity and stability.

Key words: Cerium-base catalyst, Heteroatom, Surface lattice oxygen, CH₃SH decomposition, Bulk oxygen migration

陈定凯, 张德华, 何德东, 陆继长, 钟丽萍, 韩彩云, 罗永明. 杂原子(Zr,Y)掺杂的铈基催化剂中氧物种与其催化CH₃SH分解的活性/稳定性之间的关系[J]. 催化学报, 2018, 39(12): 1929-1941.

Dingkai Chen, Dehua Zhang, Dedong He, Jichang Lu, Liping Zhong, Caiyun Han, Yongming Luo. Relationship between oxygen species and activity/stability in heteroatom (Zr, Y)-doped cerium-based catalysts for catalytic decomposition of CH₃SH[J]. Chinese Journal of Catalysis, 2018, 39(12): 1929-1941.

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杂原子(Zr,Y)掺杂的铈基催化剂中氧物种与其催化CH₃SH分解的活性/稳定性之间的关系

Relationship between oxygen species and activity/stability in heteroatom (Zr, Y)-doped cerium-based catalysts for catalytic decomposition of CH₃SH

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