The modulation of the surface structure of platinum-based single-atom alloys is crucial for improving the catalytic performance in propane dehydrogenation. The optimization of the surface structure of PtCu clusters was attained through regenerative treatment, which significantly improved the propylene yield and catalytic stability, thereby offering a viable strategy for the design of alloy catalysts applicable to various high-temperature dehydrogenation reactions.
A research team, directed by Prof. Guangxu Chen at South China University of Technology in Guangdong, China, recently published a study on the utilization of regenerative treatment to modulate the surface structure of PtCu alloys, thereby effectively enhancing the performance of propane dehydrogenation. The development of Pt-based single-atom alloy catalysts with isolated active sites by introducing a second metal has been extensively investigated. However, this approach continues to encounter significant challenges, including the formation of coke, catalyst regeneration, sintering of Pt species, and, critically, the surface structure of Pt-based single-atom alloys. The present study aims to synthesize well-structured single active site Pt-based alloy catalysts characterized by suitable geometries and electronic structures.
The team published their article in Nano Research on April 18, 2025.
“This article presents the pertinent research conducted by our team on the modulation of the surface structure of PtCu clusters, with a view to effectively enhancing the performance of propane dehydrogenation. We will focus on the preparation, structure, catalytic performance and reaction mechanism of well-configured Pt1Cu30 clusters catalysts, wherein each Pt atom is coordinated to 9 Cu atoms and a thin carbon coating is formed on the cluster surface. Furthermore, we have thoroughly investigated the impact of the thin carbon layer encapsulating the cluster surface on the C-H activation of propane, along with its influence on the desorption and deep dehydrogenation of propylene.” said Chen Guangxu, the senior author of the research paper and a professor at the School of Environment and Energy, South China University of Technology.
“Through multiple characterizations, our research group confirm that that the surface structure of the Pt1Cu30 clusters in the 0.65Pt1Cu30/SiO2 catalysts can be reorganized by regeneration treatment. This reorganization resulted in a structure where nine Cu atoms are coordinated to a single Pt atom, thereby establishing an optimal coordination environment for the Pt1Cu30 cluster on 0.65Pt1Cu30@C/SiO2-450-0.5h catalyst.” Guangxu Chen stated
“The structurally optimized 0.65Pt1Cu30@C/SiO2-450-0.5h catalyst described in this study exhibited excellent catalytic performance, achieving an initial propane conversion of 54.2% and a propylene yield of 50.4%. After 32 h of PDH testing, the deactivation constant of 0.65Pt1Cu30@C/SiO2-450-0.5h catalyst was 0.01 h-1, and the propylene selectivity was as high as 98.2%. This performance was markedly superior to that of the PtCu cluster catalysts prepared under different conditions. These results indicate that structural optimization of the Pt1Cu30 clusters and enhanced performance in propane dehydrogenation via regeneration treatment are indeed feasible.” said Guangxu Chen.
The team further performed a mechanistic analysis of the catalyst, confirming that the structure-optimized 0.65Pt1Cu30@C/SiO2-450-0.5h catalyst exhibits an onset temperature for C-H bond activation that is essentially the same as that of the 0.65Pt1Cu30/SiO2 catalyst. However, it has the lowest propylene desorption temperature and a weaker propylene adsorption strength, which facilitate the avoidance of deep dehydrogenation of propylene and coke deposition, ultimately resulting in a higher propylene yield and enhanced catalytic stability.
Chen Guangxu's team confirmed that after regeneration, the catalyst surface retains a thin carbon cladding layer. “Our team has confirmed through kinetic analysis and theoretical calculations that the presence of this carbon layer on the surface of the PtCu clusters does not impede C-H activation of propane. Instead, it significantly reduces the dissociation energy of propylene on the catalyst surface and raises the energy barrier for in-depth dehydrogenation of propylene, thereby preventing hydrogenolysis and coke formation, ultimately enhancing the stability of propane dehydrogenation.” Chen Guangxu said
The research team expects that this research work to significantly contribute to the understanding of surface structure modulation in Pt-based alloy catalysts, thereby facilitating the development of more efficient Pt-based alloy catalysts and enhancing their activity and stability in various high-temperature dehydrogenation reactions.
Other contributors include Jiajin Lin, Jin Yang, Shumin Liu, Yun Zhao, and Yongcai Qiu from the School of Environment and Energy, South China University of Technology in Guangdong, China; Tan Li from the School of Chemical Engineering, Kunming University of Science and Technology in Yunnan, China; Shuaiqi Zhao from the School of Chemistry and Chemical Engineering, Wuhan Textile University in Wuhan, China; Chi-Liang Chen and Wei-Hsiang Huang from the National Center for Synchrotron Radiation Research, Institute of Applied Science and Technology, National Taiwan University of Science and Technology in Taiwan; Gu Lin from the National Center for Electron Microscopy Beijing and the School of Materials Science and Engineering at Tsinghua University in Beijing, China, and Yang Leneng from Guangdong Cheng Yi Environmental Protection Technology Co in Guangdong, China.
This work was supported by the National Key Research and Development Program of China (No. 2024YFC3908700), the National Natural Science Foundation of China (No. 21971070, 22176063), Guangdong Innovative and Entrepreneurial Research Team Program (No. 2019ZT08L075), Guangdong Pearl River Talent Program (No. 2019QN01L159), the Natural Science Foundation of Guangdong Province (No. 2022A1515012047), Foshan Innovative and Entrepreneurial Research Team Program (No. 2018IT100031), Yunnan Fundamental Research Projects (No. 202401AU070180), Guangdong Basic and Applied Basic Research Foundation (No. 2021A1515110427).
About the Authors
Guangxu Chen is a professor at the School of Environment and Energy at South China University of Technology, where he also serves as a doctoral supervisor. He obtained his Ph.D. from the School of Chemistry and Chemical Engineering at Xiamen University, under the supervision of Prof. Nanfeng Zheng, in 2014. Following this, he worked as a postdoctoral researcher at the Collaborative Innovation Center for Chemistry of Energy Materials at Xiamen University from 2014 to 2015. He subsequently conducted postdoctoral research in Prof. Yi Cui's group at Stanford University from 2015 to 2019. In 2018, he was selected for the Overseas High-level Introduced Talents Youth Program. He primarily focuses on fundamental research related to the precise and efficient conversion of energy and environmental small molecules, including the controlled synthesis of functional nanomaterials, structural characterization, electrically/thermally catalytic properties, reaction mechanisms, as well as the design and development of reaction systems. To date, he has published over 60 papers in reputable journals, including Science, Nat. Mater., Nat. Catal., JACS, Nat. Commun., ACS Nano, Small, ACS Catal., ACS AMI, EST, Nano Lett., Nano Res. Among these publications, seven are recognized as highly cited papers in the ESI. His works have garnered more than 14,000 citations according to Google Scholar, resulting in an h-index of 44.
About Nano Research
Nano Research is a peer-reviewed, open access, international and interdisciplinary research journal, sponsored by Tsinghua University and the Chinese Chemical Society, published by Tsinghua University Press on the platform SciOpen. It publishes original high-quality research and significant review articles on all aspects of nanoscience and nanotechnology, ranging from basic aspects of the science of nanoscale materials to practical applications of such materials. After 18 years of development, it has become one of the most influential academic journals in the nano field. Nano Research has published more than 1,000 papers every year from 2022, with its cumulative count surpassing 7,000 articles. In 2024 InCites Journal Citation Reports, its 2024 IF is 9.0 (8.7, 5 years), and it continues to be the Q1 area among the four subject classifications. Nano Research Award, established by Nano Research together with TUP and Springer Nature in 2013, and Nano Research Young Innovators (NR45) Awards, established by Nano Research in 2018, have become international academic awards with global influence.
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