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Nano Research 2022, 15(2): 1366-1374 https://doi.org/10.1007/s12274-021-3669-4
Research Article | Open Access | Issue | Published: 03 August 2021

Continuous dimethyl carbonate synthesis from CO2 and methanol over BixCe1-xOδ monoliths: Effect of bismuth doping on population of oxygen vacancies, activity, and reaction pathway

Show Author's Information Yongdong Chen1( ),  Yue Li1,  Wei Chen1,  Wen Wu Xu2( ),  Zhong-kang Han3,  Ammara Waheed4,  Zhongbin Ye1,  Gao Li4( ),  Alfons Baiker5( )
College of Chemistry and Chemical Engineering Southwest Petroleum University Chengdu 610500 China
School of Physical Science and Technology Ningbo University Ningbo 315211 China
Center for Energy Science and Technology Skolkovo Institute of Science and Technology Skolkovo Innovation Center Moscow 143026 Russia
State Key Laboratory of Catalysis Dalian Institute of Chemical Physics Chinese Academy of Sciences Dalian 116023 China
ETH Zurich Department of Chemistry and Applied Biosciences Institute for Chemical and BioengineeringChinese Academy of Sciences, Hönggerberg, HCl, CH-8093 Zurich Switzerland
Keywords:
oxygen vacancies, reaction mechanism, dimethyl carbonate synthesis, bismuth-cerium oxides, monolithic catalyst
Topics:
Nanocatalysts
Cite this article:
Chen Y, Li Y, Chen W, et al. Continuous dimethyl carbonate synthesis from CO2 and methanol over BixCe1-xOδ monoliths: Effect of bismuth doping on population of oxygen vacancies, activity, and reaction pathway. Nano Research, 2022, 15(2): 1366-1374. https://doi.org/10.1007/s12274-021-3669-4
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Abstract Full text Electronic supplementary material About this article

We evaluated bismuth doped cerium oxide catalysts for the continuous synthesis of dimethyl carbonate (DMC) from methanol and carbon dioxide in the absence of a dehydrating agent. BixCe1-xOδ nanocomposites of various compositions (x = 0.06-0.24) were coated on a ceramic honeycomb and their structural and catalytic properties were examined. The incorporation of Bi species into the CeO2 lattice facilitated controlling of the surface population of oxygen vacancies, which is shown to play a crucial role in the mechanism of this reaction and is an important parameter for the design of ceria-based catalysts. The DMC production rate of the BixCe1-xOδ catalysts was found to be strongly enhanced with increasing OV concentration. The concentration of oxygen vacancies exhibited a maximum for Bi0.12Ce0.88Oδ, which afforded the highest DMC production rate. Long-term tests showed stable activity and selectivity of this catalyst over 45 h on-stream at 140 ℃ and a gas-hourly space velocity of 2,880 mL·gcat-1·h-1. In-situ modulation excitation diffuse reflection Fourier transform infrared spectroscopy and first-principle calculations indicate that the DMC synthesis occurs through reaction of a bidentate carbonate intermediate with the activated methoxy (-OCH3) species. The activation of CO2 to form the bidentate carbonate intermediate on the oxygen vacancy sites is identified as highest energy barrier in the reaction pathway and thus is likely the rate-determining step.


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About this article

Continuous dimethyl carbonate synthesis from CO2 and methanol over BixCe1-xOδ monoliths: Effect of bismuth doping on population of oxygen vacancies, activity, and reaction pathway

Show Author's information Yongdong Chen1( ), Yue Li1, Wei Chen1, Wen Wu Xu2( ), Zhong-kang Han3, Ammara Waheed4, Zhongbin Ye1, Gao Li4( ), Alfons Baiker5( )
College of Chemistry and Chemical Engineering Southwest Petroleum University Chengdu 610500 China
School of Physical Science and Technology Ningbo University Ningbo 315211 China
Center for Energy Science and Technology Skolkovo Institute of Science and Technology Skolkovo Innovation Center Moscow 143026 Russia
State Key Laboratory of Catalysis Dalian Institute of Chemical Physics Chinese Academy of Sciences Dalian 116023 China
ETH Zurich Department of Chemistry and Applied Biosciences Institute for Chemical and BioengineeringChinese Academy of Sciences, Hönggerberg, HCl, CH-8093 Zurich Switzerland

Abstract

We evaluated bismuth doped cerium oxide catalysts for the continuous synthesis of dimethyl carbonate (DMC) from methanol and carbon dioxide in the absence of a dehydrating agent. BixCe1-xOδ nanocomposites of various compositions (x = 0.06-0.24) were coated on a ceramic honeycomb and their structural and catalytic properties were examined. The incorporation of Bi species into the CeO2 lattice facilitated controlling of the surface population of oxygen vacancies, which is shown to play a crucial role in the mechanism of this reaction and is an important parameter for the design of ceria-based catalysts. The DMC production rate of the BixCe1-xOδ catalysts was found to be strongly enhanced with increasing OV concentration. The concentration of oxygen vacancies exhibited a maximum for Bi0.12Ce0.88Oδ, which afforded the highest DMC production rate. Long-term tests showed stable activity and selectivity of this catalyst over 45 h on-stream at 140 ℃ and a gas-hourly space velocity of 2,880 mL·gcat-1·h-1. In-situ modulation excitation diffuse reflection Fourier transform infrared spectroscopy and first-principle calculations indicate that the DMC synthesis occurs through reaction of a bidentate carbonate intermediate with the activated methoxy (-OCH3) species. The activation of CO2 to form the bidentate carbonate intermediate on the oxygen vacancy sites is identified as highest energy barrier in the reaction pathway and thus is likely the rate-determining step.

Keywords: oxygen vacancies, reaction mechanism, dimethyl carbonate synthesis, bismuth-cerium oxides, monolithic catalyst

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Received: 19 March 2021
Revised: 17 May 2021
Accepted: 09 June 2021
Published: 03 August 2021
Issue date: February 2022

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© The Author(s) 2021

Acknowledgements

Acknowledgements

We acknowledged the financial supported by the National Natural Science Foundation of China (Nos. 21773189 and 11974195) and Department of Science and Technology of Sichuan Province (19ZDZX0113) and Liaoning Revitalization Talents Program (XLYC1807121).

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