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Title: Mesoporous MnCeO x solid solutions for low temperature and selective oxidation of hydrocarbons

Abstract

The development of noble-metal-free heterogeneous catalysts that can realize the aerobic oxidation of C–H bonds at low temperature is a profound challenge in the catalysis community. Here we report the synthesis of a mesoporous Mn 0.5Ce 0.5O x solid solution that is highly active for the selective oxidation of hydrocarbons under mild conditions (100–120 °C). Notably, the catalytic performance achieved in the oxidation of cyclohexane to cyclohexanone/cyclohexanol (100 °C, conversion: 17.7%) is superior to those by the state-of-art commercial catalysts (140–160 °C, conversion: 3-5%). Finally, the high activity can be attributed to the formation of a Mn 0.5Ce 0.5O x solid solution with an ultrahigh manganese doping concentration in the CeO 2 cubic fluorite lattice, leading to maximum active surface oxygens for the activation of C–H bonds and highly reducible Mn 4+ ions for the rapid migration of oxygen vacancies from the bulk to the surface.

Authors:
 [1];  [2];  [2];  [1];  [1];  [1];  [1];  [2];  [2];  [3]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Zhejiang Univ. of Technology, Hangzhou (China)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1259683
Grant/Contract Number:  
21107096; 21506194; LY14E080008; 2013C03021
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 6; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Zhang, Pengfei, Lu, Hanfeng, Zhou, Ying, Zhang, Li, Wu, Zili, Yang, Shize, Shi, Hongliang, Zhu, Qiulian, Chen, Yinfei, and Dai, Sheng. Mesoporous MnCeOx solid solutions for low temperature and selective oxidation of hydrocarbons. United States: N. p., 2015. Web. doi:10.1038/ncomms9446.
Zhang, Pengfei, Lu, Hanfeng, Zhou, Ying, Zhang, Li, Wu, Zili, Yang, Shize, Shi, Hongliang, Zhu, Qiulian, Chen, Yinfei, & Dai, Sheng. Mesoporous MnCeOx solid solutions for low temperature and selective oxidation of hydrocarbons. United States. doi:10.1038/ncomms9446.
Zhang, Pengfei, Lu, Hanfeng, Zhou, Ying, Zhang, Li, Wu, Zili, Yang, Shize, Shi, Hongliang, Zhu, Qiulian, Chen, Yinfei, and Dai, Sheng. Thu . "Mesoporous MnCeOx solid solutions for low temperature and selective oxidation of hydrocarbons". United States. doi:10.1038/ncomms9446. https://www.osti.gov/servlets/purl/1259683.
@article{osti_1259683,
title = {Mesoporous MnCeOx solid solutions for low temperature and selective oxidation of hydrocarbons},
author = {Zhang, Pengfei and Lu, Hanfeng and Zhou, Ying and Zhang, Li and Wu, Zili and Yang, Shize and Shi, Hongliang and Zhu, Qiulian and Chen, Yinfei and Dai, Sheng},
abstractNote = {The development of noble-metal-free heterogeneous catalysts that can realize the aerobic oxidation of C–H bonds at low temperature is a profound challenge in the catalysis community. Here we report the synthesis of a mesoporous Mn0.5Ce0.5Ox solid solution that is highly active for the selective oxidation of hydrocarbons under mild conditions (100–120 °C). Notably, the catalytic performance achieved in the oxidation of cyclohexane to cyclohexanone/cyclohexanol (100 °C, conversion: 17.7%) is superior to those by the state-of-art commercial catalysts (140–160 °C, conversion: 3-5%). Finally, the high activity can be attributed to the formation of a Mn0.5Ce0.5Ox solid solution with an ultrahigh manganese doping concentration in the CeO2 cubic fluorite lattice, leading to maximum active surface oxygens for the activation of C–H bonds and highly reducible Mn4+ ions for the rapid migration of oxygen vacancies from the bulk to the surface.},
doi = {10.1038/ncomms9446},
journal = {Nature Communications},
number = ,
volume = 6,
place = {United States},
year = {2015},
month = {10}
}

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