Oxygen vacancy-mediated Mn 2 O 3 catalyst with high efficiency and stability for toluene oxidation

被引:6
|
作者
Yang, Xueqin [1 ]
Ma, Ziqing [1 ]
Wang, Dadao [1 ]
Yu, Xiaolin [2 ]
Zhu, Xiuhong [1 ]
Wang, Ting [1 ]
Yuan, Yuan [1 ]
Guo, Yucong [3 ]
Shi, Bo [4 ]
Ge, Maofa [3 ]
Ru, Guangxin [1 ]
机构
[1] Henan Agr Univ, Coll Forestry, Zhengzhou 450046, Peoples R China
[2] Univ Sci & Technol Beijing, Sch Energy & Environm Engn, Beijing 100083, Peoples R China
[3] Chinese Acad Sci, Inst Chem, Res Educ Ctr Excellence Mol Sci,Beijing Natl Lab M, State Key Lab Struct Chem Unstable & Stable Specie, Beijing 100190, Peoples R China
[4] Hebei Normal Univ, Coll Chem & Mat Sci, Hebei Key Lab Inorgan Nanomat, Shijiazhuang 050024, Peoples R China
关键词
Toluene oxidation; Defect engineering; Oxygen vacancy; Molecular oxygen activation; High stability; DENSITY-FUNCTIONAL THEORY; BIRNESSITE-TYPE MNO2; FORMALDEHYDE OXIDATION; ALPHA-MN2O3; NANOCRYSTALS; MANGANESE OXIDES; CO OXIDATION; ADSORPTION; DEHYDROGENATION; COMBUSTION; MECHANISM;
D O I
10.1016/j.jcis.2024.07.066
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Oxygen vacancy engineering in transition metal oxides is an effective strategy for improving catalytic performance. Herein, defect-enriched Mn 2 O 3 catalysts were constructed by controlling the calcination temperature. The high content of oxygen vacancies and accompanying Mn 4+ ions were generated in Mn 2 O 3 catalysts calcined at low temperature, which could greatly improve the low-temperature reducibility and migration of surface oxygen species. DFT theoretical calculations further confirmed that molecular oxygen and toluene were easily adsorbed over defective alpha-Mn 2 O 3 (222) facets with an energy of-0.29 and-0.48 eV, respectively, and corresponding O - O bond length is stretched to 1.43 & Aring;, resulting in the highly reactive oxygen species. Mn 2 O 3-300 catalyst with abundant oxygen vacancies exhibited the highest specific reaction rate and lowest activation energy. Furthermore, the optimized catalyst possessed the outstanding stability, water tolerance and CO 2 yield. In comparison with the fresh Mn 2 O 3-300 catalyst, the physical structure and surface property of the used catalyst remained almost unchanged regardless of whether undergoing the stability test at consecutive catalytic runs as well as high temperature, and water resistance test. In situ DRIFTS spectra further elucidated that introducing the water vapor had little effect on the reaction intermediates, indicating the excellent durability of the defectenriched catalyst.
引用
收藏
页码:815 / 824
页数:10
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