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Nano Research 2023, 16(5): 6670-6678 https://doi.org/10.1007/s12274-023-5450-3
Research Article | Issue | Published: 07 March 2023

Selective and effective oxidation of 5-hydroxymethylfurfural by tuning the intermediates adsorption on Co-Cu-CNx

Show Author's Information Tianyun Jing1,§,  Shaokang Yang1,§,  Yonghai Feng1,†( ),  Tingting Li2,  Yunpeng Zuo3( ),  Dewei Rao1( )
School of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013, China
Institute of Surface Micro and Nano Materials, Xuchang University, Xuchang 461002, China
Regional Centre of Advanced Technologies and Materials, Czech Advanced Technology and Research Institute, Palacký University, 77900 Olomouc, Czech Republic
Present address: Pharmaceutical Sciences Laboratory and Turku Bioscience Center, Åbo Akademi University, Turku 20520, Finland

§ Tianyun Jing and Shaokang Yang contributed equally to this work.

Keywords:
d-band center, Co-based materials, electronegativity offset, 5-hydroxymethylfurfural (HMF) oxidative activity, 2,5-furandicarboxylic acid (FDCA) selectivity
Topics:
Catalysts
Cite this article:
Jing T, Yang S, Feng Y, et al. Selective and effective oxidation of 5-hydroxymethylfurfural by tuning the intermediates adsorption on Co-Cu-CNx. Nano Research, 2023, 16(5): 6670-6678. https://doi.org/10.1007/s12274-023-5450-3
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Abstract Full text Electronic supplementary material About this article

Co-based catalysts are promising alternatives to precious metals for the selective and effective oxidation of 5-hydroxymethylfurfural (HMF) to the higher value-added 2,5-furandicarboxylic acid (FDCA). However, these catalysts still suffer from unsatisfactory activity and poor selectivity. A series of N-doped carbon-supported Co-based dual-metal nanoparticles (NPs) have been designed, among which the Co-Cu1.4-CNx exhibits enhanced HMF oxidative activity, achieving FDCA formation rates 4 times higher than that of pristine Co-CNx, with 100% FDCA selectivity. Density functional theory (DFT) calculations evidenced that the increased electron density on Co sites induced by Cu can mediate the positive electronegativity offset to downshift the d-band center of Co-Cu1.4-CNx, thus reducing the energy barriers for the conversion of HMF to FDCA. Such findings will support the development of superior non-precious metal catalysts for HMF oxidation.


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Electronic supplementary material
About this article

Selective and effective oxidation of 5-hydroxymethylfurfural by tuning the intermediates adsorption on Co-Cu-CNx

Show Author's information Tianyun Jing1,§, Shaokang Yang1,§, Yonghai Feng1,†( ), Tingting Li2, Yunpeng Zuo3( ), Dewei Rao1( )
School of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013, China
Institute of Surface Micro and Nano Materials, Xuchang University, Xuchang 461002, China
Regional Centre of Advanced Technologies and Materials, Czech Advanced Technology and Research Institute, Palacký University, 77900 Olomouc, Czech Republic
Present address: Pharmaceutical Sciences Laboratory and Turku Bioscience Center, Åbo Akademi University, Turku 20520, Finland

§ Tianyun Jing and Shaokang Yang contributed equally to this work.

Abstract

Co-based catalysts are promising alternatives to precious metals for the selective and effective oxidation of 5-hydroxymethylfurfural (HMF) to the higher value-added 2,5-furandicarboxylic acid (FDCA). However, these catalysts still suffer from unsatisfactory activity and poor selectivity. A series of N-doped carbon-supported Co-based dual-metal nanoparticles (NPs) have been designed, among which the Co-Cu1.4-CNx exhibits enhanced HMF oxidative activity, achieving FDCA formation rates 4 times higher than that of pristine Co-CNx, with 100% FDCA selectivity. Density functional theory (DFT) calculations evidenced that the increased electron density on Co sites induced by Cu can mediate the positive electronegativity offset to downshift the d-band center of Co-Cu1.4-CNx, thus reducing the energy barriers for the conversion of HMF to FDCA. Such findings will support the development of superior non-precious metal catalysts for HMF oxidation.

Keywords: d-band center, Co-based materials, electronegativity offset, 5-hydroxymethylfurfural (HMF) oxidative activity, 2,5-furandicarboxylic acid (FDCA) selectivity

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Publication history
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Acknowledgements

Publication history

Received: 03 November 2022
Revised: 23 December 2022
Accepted: 24 December 2022
Published: 07 March 2023
Issue date: May 2023

Copyright

© Tsinghua University Press 2023

Acknowledgements

Acknowledgements

The work is supported by the National Natural Science Foundation of China (Nos. 51902281, 51801075, and 82160421), the Natural Science Foundation of Jiangsu Province (No. BK20211322), and the Scientific and Technological Projects of Henan Province (No. 212102210293).

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