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Research Article | Open Access

Surface structure engineering of PtCu clusters enhances the performance of propane dehydrogenation

Jiajin Lin1, Jin Yang1, Tan Li2 (), Shuaiqi Zhao3, Wei-Hsiang Huang4, Chi-Liang Chen4, Yun Zhao1, Shumin Liu1, Lin Gu5, Leneng Yang6, Yongcai Qiu1, Guangxu Chen1 ()
School of Environment and Energy, State Key Laboratory of Luminescent Materials and Devices, Guangdong Provincial Key Laboratory of Atmospheric Environment and Pollution Control, South China University of Technology, Guangzhou 510000, China
Faculty of Chemical Engineering, Kunming University of Science and Technology, Kunming 650500, China
School of Chemistry and Chemical Engineering, Wuhan Textile University, Wuhan 430200, China
"National Synchrotron Radiation Research Center", Graduate Institute of Applied Science and Technology, "National Taiwan University of Science and Technology" (NTUST), Hsinchu 30076
National Center of Electron Microscopy in Beijing, School of Materials Science and Engineering, Tsinghua University, Beijing 100190, China
Guangdong Chengyi Environmental Technology Corp., Shaoguan 512158, China
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A surface structure engineering strategy was developed to prepare the well structured Pt1Cu30 cluster catalysts with the single Pt atom coordinated by 9 Cu atoms and coated with a thin carbon layer. The prepared catalysts exhibited excellent propane C–H cleavage activity and promoted propylene desorption, significantly improving propylene yield and catalytic stability at high temperatures.

Abstract

Highly dispersed Pt-based single-atom alloys have been extensively studied in heterogeneous catalysis, particularly for propane dehydrogenation (PDH). However, Pt-based single-atom alloys still suffer from sintering and coke deposition in high-temperature dehydrogenation reactions. Additionally, the atomic structure of the active sites of Pt-based single-atom alloys for PDH remains elusive, and the solid chemistry occurring on the catalyst surface is still under debate. In this work, we discovered that the coordination environment of the single Pt atom for Pt1Cu30 cluster catalysts, encapsulated with a carbon layer, can be regulated by sequential heat treatment under air and H2 atmosphere. The Pt1Cu30 cluster catalyst, with a single Pt atom coordinated by 9 Cu atoms, is similar to the surface structure of Pt1Cu3 (111) and exhibits excellent catalytic activity and stability at high temperatures, maintaining propane conversion of 43.5% and propylene selectivity of 98.2%, with a deactivation constant (Kd) of 0.01 h−1, even after 32 h of testing at 600 °C. The combination of structural characterizations and temperature programmed analysis reveal that the single Pt atom coordinated by around 9 Cu atoms of the Pt1Cu30 cluster catalyst, serves as the vital active sites for C–H cleavage of propane and propylene desorption due to their electron-rich and geometrically isolated Pt atom structure. Furthermore, the thin carbon layer coated on the surface of Pt1Cu30 clusters can effectively reduce the desorption energy of propylene, thereby avoiding further dehydrogenation and improving the propylene yield and catalytic stability.

Keywords

single-atom alloysPtCu alloysurface structurepropane dehydrogenationcatalyst regeneration

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Nano Research
Volume 18 Issue 5,
May 2025
Article number: 94907357
DOI: 10.26599/NR.2025.94907357
Cite this article:
Lin J, Yang J, Li T, et al. Surface structure engineering of PtCu clusters enhances the performance of propane dehydrogenation. Nano Research, 2025, 18(5): 94907357. https://doi.org/10.26599/NR.2025.94907357
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