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Manipulating the electronic structure of platinum via alloying with ruthenium to boost photocatalytic selective hydrogenation with water as a proton source

通过与钌合金化来调控铂的电子结构促进以水为质 子源的光催化选择性加氢

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Abstract

Regulating the electronic structure of metal sites to develop high-performance catalysts for selective hydrogenation reactions is very important for sustainable organic synthesis, yet still challenging. Herein, we adopt a facile method to rationally design an ultrafine PtRu alloy cocatalyst on CdS nanorods (PtRu/CdS) for the efficient photocatalytic hydrogenation reaction with water as a proton source. The ultrafast transient absorption spectroscopy studies uncover that alloying promotes the separation of photoexcited carriers, and density functional theory calculations demonstrate that alloying reduces the energy barrier of the rate-determining step, thus enhancing the hydrogenation activity. This work opens a new avenue to rationally design highly-active metal-modified photocatalysts via modulating electronic structures of co-catalysts.

摘要

调控金属活性位点的电子结构来发展高活性的选择性加氢反应 催化剂对于可持续有机合成非常重要. 但时至今日, 这仍然是非常具有 挑战性的课题. 在本文中, 我们将具有电子结构调节特性的超细PtRu合 金纳米颗粒负载在CdS纳米棒上, 成功构建了PtRu/CdS复合催化剂并 研究了其光催化芳香族硝基化合物氢化还原性能. 我们发现当以水为 质子源时, 所得复合催化剂表现出高效的光催化加氢活性. 超快光谱研 究和密度泛函理论计算揭示了合金的形成促进了光生载流子的分离并 降低了氢化还原反应中决速步的能垒, 从而显著提高了加氢活性. 本研 究通过合金化效应调节助催化剂的电子结构, 为高活性助催化剂/光催 化剂体系的理性设计开辟了一条新途径.

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Acknowledgements

This work was supported by the University Annual Scientific Research Plan of Anhui Province (2022AH010013).

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Author notes

  1. These authors contributed equally to this work.

Authors and Affiliations

  1. College of Chemistry and Materials Science, Key Laboratory of Functional Molecular Solids, Ministry of Education, Anhui Laboratory of Molecule-Based Materials, Anhui Key Laboratory of Functional Molecular Solids, Anhui Normal University, Wuhu, 241002, China

    Manman Shi  (施曼曼), Dian Luo  (罗点), Peng Wu  (吴鹏), Jieding Wei  (魏杰顶), Saiya Guo  (郭赛雅), Yucheng Huang  (黄玉成) & Yonghong Ni  (倪永红)

  2. School of Physics and Electronic Information, Anhui Normal University, Wuhu, 241002, China

    Yarong Shen  (沈娅蓉) & Zhou Lu  (陆洲)

Authors
  1. Manman Shi  (施曼曼)
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  2. Dian Luo  (罗点)
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  3. Peng Wu  (吴鹏)
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  7. Zhou Lu  (陆洲)
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  8. Yucheng Huang  (黄玉成)
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  9. Yonghong Ni  (倪永红)
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Contributions

Author contributions Ni Y directed this project. Shi M and Luo D conceived and designed the experiments. Shi M, Wei J, and Guo S carried out the syntheses, characterizations and performance tests of the materials. Wu P performed the DFT calculations and Huang Y reviewed the calculation results. Shen Y performed the ultrafast TA measurements and Lu Z analyzed the TA data. Shi M wrote the original draft and Ni Y revised and reviewed the manuscript. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Zhou Lu  (陆洲), Yucheng Huang  (黄玉成) or Yonghong Ni  (倪永红).

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

Additional information

Supplementary information Supporting data are available in the online version of the paper.

Manman Shi is currently pursuing a PhD degree at the College of Chemistry and Materials Science, Anhui Normal University. Her research interest focuses on the synthesis of functional nanomaterials and their applications in solar energy conversion.

Dian Luo is a PhD student at Anhui Normal University. His current interests focus on the synthesis of nanocrystals and their applications in energy conversion.

Peng Wu is a Master student at the College of Chemistry and Materials Science, Anhui Normal University. His current interest focuses on the theoretical computation of materials for catalysis.

Yucheng Huang received his PhD degree from Nanjing University. He joined Anhui Normal University in 2005, and now is a professor of the College of Chemistry and Materials Science. His current interests focus on the theoretical computation of materials for catalysis and theoretical studies of the optical, electrical and magnetic properties of functional nanomaterials.

Zhou Lu graduated from the University of California, San Diego in 2007 with a PhD degree. He worked as a postdoctoral researcher at the University of Southern California and the Pacific Northwest National Laboratory from 2007 to 2013, and as a researcher at the Institute of Chemistry, Chinese Academy of Sciences from 2013 to 2019. In 2019, he joined the School of Physics and Electronic Information, Anhui Normal University as a Professor. His research interests include ultrafast spectroscopy, interfacial nonlinear spectroscopy and microscopic reaction kinetics.

Yonghong Ni received his PhD degree from the University of Science and Technology of China in 2001. He worked as a postdoctoral researcher at the National Key Laboratory of Coordination Chemistry, Nanjing University from 2002 to 2004. In 2004, he joined the chemistry faculty at Anhui Normal University. In 2005, he was promoted to professor in chemistry. His research is primarily on the development of functional inorganic micro/nano-materials that are both fundamentally important and potentially useful for environmental detection and protection, clean and renewable energy applications.

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Manipulating the electronic structure of platinum via alloying with ruthenium to boost photocatalytic selective hydrogenation with water as a proton source

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Shi, M., Luo, D., Wu, P. et al. Manipulating the electronic structure of platinum via alloying with ruthenium to boost photocatalytic selective hydrogenation with water as a proton source. Sci. China Mater. 67, 824–832 (2024). https://doi.org/10.1007/s40843-023-2739-4

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