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Research Article

Revealing the surface atomic arrangement of noble metal alkane dehydrogenation catalysts by a stepwise reduction-oxidation approach

Chenliang Ye1,2,§, Mao Peng3,§, Tingting Cui1, Xinxin Tang4, Dingsheng Wang1, Miaolun Jiao3( ), Jeffrey T. Miller2( ), Yadong Li1( )
Department of Chemistry, Tsinghua University, Beijing 100084, China
Davidson School of Chemical Engineering, Purdue University, 480 Stadium Mall Drive, West Lafayette, IN 47907, USA
School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China
Institute of Microbial Chemistry, (BIKAKEN), Tokyo 141-0021, Japan

§ Chenliang Ye and Mao Peng contributed equally to this work.

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Graphical Abstract

This work provides a conceptional model for determination of the surface structure in noble metal nanoparticles by determination of the difference EXAFS of reduced and oxidized samples.

Abstract

Surface characterization of metal nanoparticles is a critical need in nanocatalysis for in-depth understanding of the structure–function relationships. The surface structure of nanoparticles is often different from the subsurface, and it is challenging to separately characterize the surface and the subsurface. In this work, theoretical calculations and extended X-ray absorption fine structure (EXAFS) analysis illustrate that the surface atoms of noble metals (Pt and Pd) are oxidized in the air, while the subsurface atoms are not easily oxidized. Taking advantage of the oxidation properties, we suggest a stepwise reduction–oxidation approach to determine the surface atomic arrangement of noble metal nanoparticles, and confirm the rationality of this approach by identifying the surface structure of typical 2–3 nm Pt and Pd nanoparticles. The reduction–oxidation approach is applied to characterize the surface structure of model Pd-Sb bimetallic catalyst, which illustrates that the surface Pd is well isolated by Sb atoms with short bond distance at 2.70 Å, while there are still Pd–Pd bonds in the subsurface. Density functional theory (DFT) calculations and Pd L edge X-ray absorption near edge structure (XANES) indicate that the isolation of surface Pd significantly decreases the adsorption energies of Pd-hydrocarbon, which leads to the high propylene selectivity and turnover frequency Pd-Sb bimetallic catalyst for propane dehydrogenation.

Keywords

surface characterizationstepwise reduction–oxidation approachpropane dehydrogenationPd-Sb bimetallic catalyst

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Nano Research
Volume 16 Issue 4,
April 2023
Pages 4499-4505
DOI: 10.1007/s12274-021-3636-0
Cite this article:
Ye C, Peng M, Cui T, et al. Revealing the surface atomic arrangement of noble metal alkane dehydrogenation catalysts by a stepwise reduction-oxidation approach. Nano Research, 2023, 16(4): 4499-4505. https://doi.org/10.1007/s12274-021-3636-0
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Special Issue of Xiamen University Centennial CelebrationAccelerating clean energy innovations via nanotechnology toward achieving circular economy

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Received: 18 April 2021
Revised: 23 May 2021
Accepted: 30 May 2021
Published: 02 July 2021
© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2021
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