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Research Article

Alkali ion-promoted palladium subnanoclusters stabilized on porous alumina nanosheets with enhanced catalytic activity for benzene oxidation

Zhijun Li1( ), Minghui Di1, Wei Wei1, Leipeng Leng1, Zhijun Li2( ), Cheng He3, Qiang Tan3, Qian Xu4( ), J. Hugh Horton1,5( ), Li Li6, Junfa Zhu4
Joint International Research Laboratory of Advanced Chemical Catalytic Materials & Surface Science, College of Chemistry and Chemical Engineering, Northeast Petroleum University, Daqing 163318, China
Key Laboratory of Functional Inorganic Materials Chemistry (Ministry of Education), School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, China
State Key Laboratory for Mechanical Behavior of Materials, School of Material Science and Engineering, Xi’an Jiaotong University, Xi’an 710049, China
National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029, China
Department of Chemistry, Queen’s University, Kingston K7L 3N6, Canada
College of Chemistry and Chemical Engineering, Qiqihar University, Qiqihar 161006, China
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Graphical Abstract

Herein, we report on alkali ion-promoted Pd subnanoclusters supported over defective γ-Al2O3 nanosheets. This catalyst presents exceptional catalytic efficacy for benzene oxidation and excellent anti-sintering ability. Density functional theory calculations reveal that the addition of alkali ion can significantly impact the catalyst’s structure and electronic properties, and ultimately promote its activity and stability.

Abstract

Catalytic C−H bond activation is one of the backbones of the chemical industry. Supported metal subnanoclusters consisting of a few atoms have shown attractive properties for heterogeneous catalysis. However, the creation of such catalyst systems with high activity and excellent anti-sintering ability remains a grand challenge. Here, we report on alkali ion-promoted Pd subnanoclusters supported over defective γ-Al2O3 nanosheets, which display exceptional catalytic activity for C−H bond activation in the benzene oxidation reaction. The presence of Pd subnanoclusters is verified by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy. This catalyst shows excellent catalytic activity, with a turnover frequency of 280 h−1 and yield of 98%, in benzene oxidation reaction to give phenol under mild conditions. Moreover, the introduction of alkali ion greatly retards the diffusion and migration of metal atoms when tested under high-temperature sintering conditions. Density functional theory (DFT) calculations reveal that the addition of alkali ion to Pd nanoclusters can significantly impact the catalyst’s structure and electronic properties, and eventually promote its activity and stability. This work sheds light on the facile and scalable synthesis of highly active and stable catalyst systems with alkali additives for industrially important reactions.

Keywords

Pd subnanoclustersγ-Al2O3 nanosheets heterogeneous catalysisbenzene oxidationcatalytic activity

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Nano Research
Volume 15 Issue 7,
July 2022
Pages 5912-5921
DOI: 10.1007/s12274-022-4250-5
Cite this article:
Li Z, Di M, Wei W, et al. Alkali ion-promoted palladium subnanoclusters stabilized on porous alumina nanosheets with enhanced catalytic activity for benzene oxidation. Nano Research, 2022, 15(7): 5912-5921. https://doi.org/10.1007/s12274-022-4250-5
Topics:
Catalysis

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Received: 21 January 2022
Revised: 17 February 2022
Accepted: 17 February 2022
Published: 08 March 2022
© Tsinghua University Press 2022
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