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Nano Research 2023, 16(5): 6951-6959 https://doi.org/10.1007/s12274-023-5407-6
Research Article | Issue | Published: 10 February 2023

Morphology effects in MnCeOx solid solution-catalyzed NO reduction with CO: Active sites, water tolerance, and reaction pathway

Show Author's Information Quanquan Shi1,§( ),  Yifei Zhang2,3,§,  Zhiwen Li3,  Zhongkang Han4( ),  Liangliang Xu5,  Alfons Baiker6( ),  Gao Li3( )
College of Science & College of Material Science and Art Design, Inner Mongolia Agricultural University, Hohhot 010018, China
College of Chemistry and Chemical Engineering, Shenyang Normal University, Shenyang 110034, China
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
School of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, China
Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology, Daejeon 34141, Republic of Korea
Department of Chemistry and Applied Biosciences, Institute for Chemical and Bioengineering, ETH Zurich, Hönggerberg, HCl, CH-8093 Zurich, Switzerland

§ Quanquan Shi and Yifei Zhang contributed equally to this work.

Keywords:
active sites, reaction mechanism, NO reduction with CO, manganese-ceria solid solution, morphology effects
Topics:
Cerium oxideNanostructured materials
Cite this article:
Shi Q, Zhang Y, Li Z, et al. Morphology effects in MnCeOx solid solution-catalyzed NO reduction with CO: Active sites, water tolerance, and reaction pathway. Nano Research, 2023, 16(5): 6951-6959. https://doi.org/10.1007/s12274-023-5407-6
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Abstract Full text Electronic supplementary material About this article

Morphological effects of nanoparticles are crucial in many solid-catalyzed chemical transformations. We herein prepared two manganese-ceria solid solutions, well-defined MnCeOx nanorods and MnCeOx-nanocubes, exposing preferentially (111) and (100) facets of ceria, respectively. The incorporation of Mn dopant into ceria lattice strongly enhanced the catalytic performance in the NO reduction with CO. MnCeOx (111) catalyst outperformed MnCeOx (100) counterpart due to its higher population density of oxygen vacancy defects. In-situ infrared spectroscopy investigations indicated that the reaction pathway over MnCeOx and pristine CeO2 is similar and that besides the direct pathway, an indirect pathway via adsorbed hyponitrite as an intermediate cannot be ruled out. X-ray photoelectron and Raman spectroscopies as well as first-principles density functional theory (DFT) calculations indicate that the enhanced catalytic performance of MnCeOx can be traced back to its “Mn–OL(VÖ)–Mn–OL(VÖ)–Ce” connectivities. The Mn dopant strongly facilitates the formation of surface oxygen vacancies (VÖ) by liberating surface lattice oxygen (OL) via CO* + OL → CO2* + VÖ and promotes the reduction of NO, according to NO* + VÖ → N* + OL and 2N* → N2. The Mn dopant impact on both the adsorption of CO and activation of OL reveals that a balance between these two effects is critical for facilitating all reaction steps.


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About this article

Morphology effects in MnCeOx solid solution-catalyzed NO reduction with CO: Active sites, water tolerance, and reaction pathway

Show Author's information Quanquan Shi1,§( ), Yifei Zhang2,3,§, Zhiwen Li3, Zhongkang Han4( ), Liangliang Xu5, Alfons Baiker6( ), Gao Li3( )
College of Science & College of Material Science and Art Design, Inner Mongolia Agricultural University, Hohhot 010018, China
College of Chemistry and Chemical Engineering, Shenyang Normal University, Shenyang 110034, China
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
School of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, China
Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology, Daejeon 34141, Republic of Korea
Department of Chemistry and Applied Biosciences, Institute for Chemical and Bioengineering, ETH Zurich, Hönggerberg, HCl, CH-8093 Zurich, Switzerland

§ Quanquan Shi and Yifei Zhang contributed equally to this work.

Abstract

Morphological effects of nanoparticles are crucial in many solid-catalyzed chemical transformations. We herein prepared two manganese-ceria solid solutions, well-defined MnCeOx nanorods and MnCeOx-nanocubes, exposing preferentially (111) and (100) facets of ceria, respectively. The incorporation of Mn dopant into ceria lattice strongly enhanced the catalytic performance in the NO reduction with CO. MnCeOx (111) catalyst outperformed MnCeOx (100) counterpart due to its higher population density of oxygen vacancy defects. In-situ infrared spectroscopy investigations indicated that the reaction pathway over MnCeOx and pristine CeO2 is similar and that besides the direct pathway, an indirect pathway via adsorbed hyponitrite as an intermediate cannot be ruled out. X-ray photoelectron and Raman spectroscopies as well as first-principles density functional theory (DFT) calculations indicate that the enhanced catalytic performance of MnCeOx can be traced back to its “Mn–OL(VÖ)–Mn–OL(VÖ)–Ce” connectivities. The Mn dopant strongly facilitates the formation of surface oxygen vacancies (VÖ) by liberating surface lattice oxygen (OL) via CO* + OL → CO2* + VÖ and promotes the reduction of NO, according to NO* + VÖ → N* + OL and 2N* → N2. The Mn dopant impact on both the adsorption of CO and activation of OL reveals that a balance between these two effects is critical for facilitating all reaction steps.

Keywords: active sites, reaction mechanism, NO reduction with CO, manganese-ceria solid solution, morphology effects

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Acknowledgements

Publication history

Received: 22 September 2022
Revised: 04 December 2022
Accepted: 15 December 2022
Published: 10 February 2023
Issue date: May 2023

Copyright

© Tsinghua University Press 2023

Acknowledgements

Acknowledgements

We thank financial support from the National Natural Science Foundation of China (Nos. 22065029 and 22172167) and the Natural Science Foundation of Inner Mongolia Autonomous Region (No. 2022MS02002).

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