Mesoporous MnCeOx solid solutions for low temperature and selective oxidation of hydrocarbons

Pengfei Zhang; Hanfeng Lu; Ying Zhou; Li Zhang; Zili Wu; Shize Yang; Hongliang Shi; Qiulian Zhu; Yinfei Chen; Sheng Dai

doi:10.1038/ncomms9446

Mesoporous MnCeO_x solid solutions for low temperature and selective oxidation of hydrocarbons

Pengfei Zhang, Hanfeng Lu, Ying Zhou, Li Zhang, Zili Wu, Shize Yang, Hongliang Shi, Qiulian Zhu, Yinfei Chen, Sheng Dai

Research output: Contribution to journal › Article › peer-review

274 Scopus citations

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%). 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 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.

Original language	English
Article number	8446
Journal	Nature Communications
Volume	6
DOIs	https://doi.org/10.1038/ncomms9446
State	Published - Oct 15 2015

Funding

P.F.Z., L.Z., Z.L.W. and S.D. were supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division. The DRIFTS study was conducted at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility. H.L.S. was supported by the Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division. H.F.L, Y.Z., Q.L.Z. and Y.F.C. were supported by the Natural Science Foundation of China (NO. 21107096, 21506194), the Natural Science Foundation of Zhejiang province (No. LY14E080008) and the commission of Science and Technology of Zhejiang province (No. 2013C03021).

Funders	Funder number
U.S. Department of Energy
Office of Science
Basic Energy Sciences
Division of Materials Sciences and Engineering
Chemical Sciences, Geosciences, and Biosciences Division
National Natural Science Foundation of China	21107096, 21506194
Natural Science Foundation of Zhejiang Province

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title = "Mesoporous MnCeOx 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 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%). 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.",

author = "Pengfei Zhang and Hanfeng Lu and Ying Zhou and Li Zhang and Zili Wu and Shize Yang and Hongliang Shi and Qiulian Zhu and Yinfei Chen and Sheng Dai",

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T1 - Mesoporous MnCeOx solid solutions for low temperature and selective oxidation of hydrocarbons

AU - Zhang, Pengfei

AU - Lu, Hanfeng

AU - Zhou, Ying

AU - Zhang, Li

AU - Wu, Zili

AU - Yang, Shize

AU - Shi, Hongliang

AU - Zhu, Qiulian

AU - Chen, Yinfei

AU - Dai, Sheng

PY - 2015/10/15

Y1 - 2015/10/15

N2 - 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%). 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.

AB - 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%). 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.

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VL - 6

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Mesoporous MnCeO_x solid solutions for low temperature and selective oxidation of hydrocarbons

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