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Size-engineered noble metal nanoclusters synthesized by impregnation for size-dependent catalysis

浸渍法制备尺寸均一可调的贵金属纳米团簇及其尺 寸依赖的催化性质

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Abstract

Noble metal nanoclusters, as a bridge between atoms and nanoparticles, show extraordinary catalytic activities because of their unique electronic structures. Such nanoclusters are usually synthesized by a wet chemical approach through unfavorable surface passivation by ligands and have not been obtained by an impregnation approach with satisfactory size uniformity. Herein, we report highly uniform ligand-free noble metal nanoclusters, such as Pd nanoclusters, synthesized each in a silica capsule by an impregnation strategy, with their size accurately engineerable in the range of 0.9–2.9 nm. The key is to ensure the impregnation synthesis with strict control over the nucleation and growth of noble metal nanoclusters by involving hollow silica nanoreactors and non-noble metal competitor ions, thereby showing unprecedented advantages of operational simplicity, scalability, and excellent size controllability. These Pd nanoclusters exhibit a strong size effect on catalysis exemplified by the alcohol oxidation-Knoevenagel condensation sequential reaction, with those of 1.3 nm exhibiting the highest catalytic activity. We believe this novel strategy opens new opportunities for rationally designing efficient noble metal nanocluster-type catalysts for a broad range of important reactions and bringing laboratory-quality nanoclusters into large-scale applications.

摘要

贵金属纳米团簇作为原子和纳米颗粒的中间形态, 表现出特殊 的电子结构和优异的催化性能. 目前, 这类纳米团簇通常通过湿化学法 合成, 其表面常被配体所钝化, 而通过浸渍法合成的贵金属纳米团簇通 常表现出较宽的尺寸分布. 本研究以钯为例, 发展了基于浸渍法精准合 成尺寸介于0.9和2.9 nm、无表面配体的贵金属纳米团簇的新范式. 该 方法关键在于采用二氧化硅纳米胶囊为纳米反应器并引入非贵金属竞 争吸附离子, 从而达到严格控制贵金属纳米团簇成核和生长的目的, 因 此具有操作便利、合成可放大及纳米团簇尺寸精准可调等优势. 钯纳 米团簇在醇氧化-Knoevenagel缩合连续反应中表现出显著的尺寸效应, 其中1.3 nm的钯纳米团簇具有最优的催化活性. 这一新颖的合成策略 为贵金属纳米团簇型催化剂的开发提供了新思路, 为实验室级高品质 纳米团簇催化剂的规模应用提供了可行方案.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (22071191), the Key Research and Development Projects of Shaanxi Province (2021GXLH-Z-022), the Fundamental Research Funds for the Central Universities, and the Key Scientific and Technological Innovation Team of Shaanxi Province (2020TD-001). Liu K acknowledges China Postdoctoral Science Foundation (2019TQ0249) and the Natural Science Basic Research Plan in Shaanxi Province (2022JQ-100). The authors thank the Instrument Analysis Center of Xi’an Jiaotong University for the assistance with HRTEM and XPS measurements.

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Authors and Affiliations

  1. Frontier Institute of Science and Technology, Xi’an Jiaotong University, Xi’an, 710054, China

    Zhibin Wen  (文智斌), Shumeng Zhang  (张树蒙), Zhaojun Liu  (刘钊钧), Zhixue Zhang  (张志学), Zhun Qiao  (乔准), Kai Liu  (刘凯) & Chuanbo Gao  (高传博)

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  1. Zhibin Wen  (文智斌)
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  2. Shumeng Zhang  (张树蒙)
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  3. Zhaojun Liu  (刘钊钧)
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  4. Zhixue Zhang  (张志学)
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  5. Zhun Qiao  (乔准)
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  6. Kai Liu  (刘凯)
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  7. Chuanbo Gao  (高传博)
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Contributions

Gao C conceived the idea and supervised the project. Wen Z conducted the synthesis, characterization, and catalysis. Zhang S, Liu Z, Zhang Z, Qiao Z, and Liu K assisted in materials characterizations. Wen Z and Gao C wrote the manuscript. All authors discussed the results and revised the manuscript.

Corresponding author

Correspondence to Chuanbo Gao  (高传博).

Additional information

Zhibin Wen received his BS degree from the Northwest A&F University in 2016 and then obtained his MS degree from the Southwest University in 2019. He is currently a PhD candidate at the Frontier Institute of Science and Technology, Xi’an Jiaotong University. His research interest is the synthesis of noble metal nanoclusters for catalysis.

Chuanbo Gao received his PhD degree in applied chemistry in 2009 from Shanghai Jiao Tong University and carried out his postdoctoral research at the University of California, Riverside. Since 2012 he has been a professor at the Frontier Institute of Science and Technology, Xi’an Jiaotong University. His research interest is the precision synthesis of noble metal-based nanomaterials for catalysis and energy conversion.

Conflict of interest

The authors declare that they have no conflict of interest.

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Experimental details and supporting data are available in the online version of the paper.

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Wen, Z., Zhang, S., Liu, Z. et al. Size-engineered noble metal nanoclusters synthesized by impregnation for size-dependent catalysis. Sci. China Mater. 66, 1417–1426 (2023). https://doi.org/10.1007/s40843-022-2247-0

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