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Evolution of surface of Pd-Rh bimetallic nanocubes and its correlation with CO oxidation

PdRh双金属纳米立方体表面化学原位研究与CO氧化反应催化性能的关联

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Abstract

Typically, varying pretreatment conditions probably results in the different catalytic performances for the bimetallic catalysts, and this originates from the surface evolution of catalysts during catalytic process. Hence, it is crucial to correlate surface chemistry (e.g., composition, chemical valence, etc.) of bimetallic nanocatalysts with their corresponding performances upon different pretreatments for the fundamental understanding of catalysis. Herein, compositionvaried (100) facet terminated Pd-Rh nanocubes (NCs) with the similar shape and sizes were prepared by a facile one-pot hydrothermal method to exclude the possible size and shape effect. Surface composition and valence state of these Pd0.8 Rh0.2, Pd0.6Rh0.4, and Pd0.2Rh0.8 NCs were tracked under different reaction conditions and during catalysis using a homebuilt ambient pressure X-ray photoelectron spectrometer (APXPS). The correlation of active surface of Pd-Rh NCs and their corresponding catalytic performance was established.

摘要

随着原位表征技术的进步, 最新的研究结果表明, 纳米催化剂在活化或催化反应条件下会发生表面结构或组分的变化, 进而影响其催化性能. 而开展以具有明确结构和组分纳米晶为模型催化剂的原位催化反应研究, 对深入理解催化剂在反应中的活性中心状态和构效关系能起到重要推进作用. 本研究利用水热法制备了具有一系列组成、相似尺寸及相同形貌的PdRh双金属纳米立方体, 针对CO催化氧化反应, 结合原位X射线光电子能谱技术, 研究了不同预处理条件下和不同组成的纳米晶表面化学演化历程. 研究发现Pd0.6Rh0.4和Pd0.8Rh0.2两种组分的纳米晶催化反应活性中心取决于其预活化条件, 而PdRh体系的元素偏析现象仅在Pd0.6Rh0.4一种条件下发生. 因此, 本研究进一步明晰了双金属催化剂表面结构在反应条件下的演变与催化性能的关联.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21573005, 21771009, and 21621061), the National Key Research and Development Program of MOST of China (2016YFB0701100), and Beijing Natural Science Foundation (2162019). Financial aids from the US National Science Foundation (NSF MCB-0824837), and the Georgia Cancer Coalition (GCC) Distinguished Cancer Clinicians and Scientists are also appreciated.

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Authors and Affiliations

  1. Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, PKU-HKU Joint Laboratory in Rare Earth Materials and Bioinorganic Chemistry, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China

    Wei Zhu  (朱威) & Ya-Wen Zhang  (张亚文)

  2. Department of Chemical and Petroleum Engineering and Department of Chemistry, University of Kansas, Lawrence, KS, 66045, USA

    Wei Zhu  (朱威), Junjun Shan  (单军军), Luan Nguyen, Shiran Zhang  (张适然) & Franklin Feng Tao  (陶丰)

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  1. Wei Zhu  (朱威)
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  2. Junjun Shan  (单军军)
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  3. Luan Nguyen
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  4. Shiran Zhang  (张适然)
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  5. Franklin Feng Tao  (陶丰)
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  6. Ya-Wen Zhang  (张亚文)
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Corresponding authors

Correspondence to Franklin Feng Tao  (陶丰) or Ya-Wen Zhang  (张亚文).

Additional information

Wei Zhu received his BSc degree from the Department of Chemistry, Zhejiang University (2009), and his PhD degree from the College of Chemistry and Molecular Engineering, Peking University (2014), guided by Prof. Yawen Zhang and Prof. Chunhua Yan. He participated in an exchange program in Prof. Franklin Tao’s group at University of Notre Dame (2012). Currently, he is working as a postdoc with Prof. Yadong Li and Prof. Chen Chen at the Department of Chemistry, Tsinghua University.

Ya-Wen Zhang is currently a professor and principle investigator at the College of Chemistry and Molecular Engineering, Peking University. His research interest lies in the rational design, controllable synthesis, ordered assembly, catalytic properties and structure-function relationships of rare earth & noble metal nanostructures. He has published more than 130 papers in peer-reviewed scientific journals with a total citation times over 10,000.

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Zhu, W., Shan, J., Nguyen, L. et al. Evolution of surface of Pd-Rh bimetallic nanocubes and its correlation with CO oxidation. Sci. China Mater. 62, 103–114 (2019). https://doi.org/10.1007/s40843-018-9265-0

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