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Synthesis of single-crystal hyperbranched rhodium nanoplates with remarkable catalytic properties

超支化Rh单晶纳米薄片的合成及其催化性能研究

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Abstract

The catalytic properties of noble metal nanocrystals can be tuned via engineering their structures. Nanocrystals with fractal structures are fascinating catalysts regarding their large surface area-to-volume ratios, large numbers of edges and corners, which can be tuned simultaneously by their hierarchical ordering. However, it is still a great challenge to control the hierarchical ordering of noble metal fractal nanocrystals and their formation mechanism is not fully understood. Herein, we report a facile solvothermal method for the direct preparation of a unique single-crystal Rh-hyperbranched structure, which consists of hierarchically ultrathin nanoplates with threefold symmetry, large surface area and high density of low-coordinated edge/corner sites. Importantly, the hierarchical ordering can be readily tuned by changing the composition of solvent. In addition, we found the as-prepared single-crystal hyperbranched Rh nanoplates possessed great structure stability, and exhibited better catalytic performance towards both ethanol electrooxidation and hydrogenation of styrene than the commercial Rh black, which can be attributed to the large surface area and high-dentisty of edge/corner sites.

摘要

贵金属纳米晶的催化性质与其结构密切相关. 比表面积越大、配位不饱和的边角原子密度越高, 贵金属纳米晶在催化反应过程中表现出的性能往往越优异. 相比于常见的具有完整几何形貌的贵金属纳米晶, 具有多重分级结构特征的超支化贵金属纳米晶拥有更大的比表面积以及更丰富的配位不饱和的活性位点, 因此被认为是一种潜在的性能优异的催化剂. 但这种具有多重分级结构特征的超支化贵金属纳米晶无论是在生长机理研究还是可控制备上都还存在巨大的挑战. 本文通过简单的湿化学法成功制备出一种具有多重分级结构特征的超支化Rh纳米薄片. 该产物由三角形纳米片在扩散限制条件下分级生长形成, 整体呈现三次对称性的单晶特征. 研究表明, 该纳米结构不仅具有出色的结构稳定性, 而且其生长级数可通过反应溶剂比例的简单调节进行调控, 从而实现Rh纳米薄片比表面积和位于边/角活性位点的原子比例的调控. 由于拥有更大的比表面积以及更为丰富的配位不饱和的活性位点, 这种具有多重分级结构的超支化Rh纳米薄片在乙醇电催化氧化和苯乙烯催化加氢催化反应中展现出了比目前主流商业催化剂Rh黑更为优异的催化活性.

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Acknowledgements

This work was supported by the National Basic Research Program of China (2015CB932301), the National Natural Science Foundation of China (21333008, 21671163, 21603178 and J1310024), and China Postdoctoral Science Foundation (2016M602066 and 2017T100468). We particularly appreciate Shilong Liu at the University of Science and Technology of China for the analysis of fractal dimensions.

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Authors and Affiliations

  1. State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry, College of Chemistry and Chemical Engineering Xiamen University, Xiamen, 361005, China

    Jiawei Zhang  (张嘉伟), Meishan Chen  (陈梅珊), Jiayu Chen  (陈佳煜), Huiqi Li  (李慧齐), Suheng Wang  (王苏恒), Qin Kuang  (匡勤), Zhenming Cao  (曹振明) & Zhaoxiong Xie  (谢兆雄)

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  1. Jiawei Zhang  (张嘉伟)
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  2. Meishan Chen  (陈梅珊)
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  6. Qin Kuang  (匡勤)
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  7. Zhenming Cao  (曹振明)
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  8. Zhaoxiong Xie  (谢兆雄)
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Correspondence to Qin Kuang  (匡勤) or Zhaoxiong Xie  (谢兆雄).

Additional information

Author contributions Kuang Q and Xie Z proposed the research direction and guided the whole project. Zhang J designed and performed the experiments and wrote the manuscript; Chen M, Chen J, Li H and Wang S helped draft the manuscript and analyze the data. All authors contributed to the general discussion and reviewed the manuscript.

Conflict of interset The authors declare that they have no conflict of interest.

Supplementary information Experimental details are available in the online version of the paper.

Jiawei Zhang received his BSc degree from Jinan University in 2009. Then he joined the Department of Chemistry at Xiamen University as a graduate and obtained his PhD degree under the supervision of Prof. Zhaoxiong Xie in 2015. He is currently working as a postdoctoral research fellow in Prof. Xie’s group. His research focuses on the controlled synthesis of noble metal nanocrystals, and their applications in catalysis and fuel cells.

Qin Kuang received his BSc degree in 2001 and PhD degree in 2008 from Xiamen University, China. Thereafter, he joined the Department of Chemistry as an assistant professor in Xiamen University and was promoted to associate professor in 2009. His current research focuses on the surface/interface engineering of inorganic functional nanomaterials and their applications in energy and environmental fields.

Zhaoxiong Xie received his BSc degree (1987) in chemistry, MSc degree (1990), and PhD degree (1995) in physical chemistry from Xiamen University, China. He worked as a postdoctoral fellow at the Centre d’Etudes de Saclay in France from 1997 to 1998. Since 2002, he has been a professor of physical chemistry at Xiamen University. His current research is focused on the surface/interface chemistry of inorganic nanomaterials.

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Zhang, J., Chen, M., Chen, J. et al. Synthesis of single-crystal hyperbranched rhodium nanoplates with remarkable catalytic properties. Sci. China Mater. 60, 685–696 (2017). https://doi.org/10.1007/s40843-017-9073-9

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