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Ultrathin PtNiW@WOx core-shell nanowires for enhanced CO-tolerant hydrogen oxidation: three-in-one catalyst design

三合一设计策略促进超细PtNiW@WOx核壳纳米线氢氧化电催化剂的CO耐受性

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Abstract

Platinum (Pt) is the state-of-the-art electrocatalyst for anodic hydrogen oxidation reaction (HOR) in proton exchange membrane fuel cells (PEMFCs). However, a critical drawback of PEMFCs is the extreme sensitivity of Pt catalyst to CO (impurity in industrial hydrogen), which markedly damages the device’s performance. Therefore, enhancing the CO-tolerant performance of Pt catalysts is crucial for the commercialization of PEMFCs. Herein, we constructed PtNiW@amorphous WOx core-shell nanowires to improve the CO-tolerance of Pt. Mechanistically, it is demonstrated that the surface amorphous WOx shell can kinetically hinder the accessibility of CO over Pt sites by acting as a selective molecular-sieving layer. Besides, thermodynamically, the electronic effect from the alloying of Ni and W elements could weaken the CO adsorption on Pt sites by downshifting the d-band center. In addition, the oxyphilic W elements can accelerate the dissociation of water to provide more OH species, promoting the oxidation of CO. As a consequence, the as-designed PtNiW@WOx NWs can maintain over 90% HOR current density after 4000 s in 1000 ppm CO/H2, exceeding most of the Pt-based catalysts reported ever.

摘要

铂(Pt)是质子交换膜燃料电池(PEMFCs)阳极氢氧化反应(HOR) 中最先进的电催化剂. 然而, Pt催化剂对CO (工业低成本氢燃料中的杂 质)极度敏感从而中毒, 这会引起器件性能的急剧衰退, 导致器件运行 成本高. 因此, 提高Pt催化剂的CO耐受性对PEMFCs的商业化推广至关 重要. 在此, 我们设计合成了一种独特的PtNiW@WOx核壳纳米线来提 高Pt基催化剂对CO的耐受能力. 机理研究表明, 表面无定形的WOx壳 层可以作为分子围栏, 在动力学上阻碍CO扩散到达Pt位点. 在热力学 上, Ni和W元素合金化产生的电子效应可以使Pt的d带中心降低, 减弱 CO在Pt位点上的化学吸附. 此外, 亲氧W元素可以加速水的解离, 提供 更多OH活性物种, 促进CO的氧化脱附. 因此, 在1000 ppm CO/H2条件 下, 所设计的PtNiW@WOx核壳纳米线催化剂表现出优异的HOR抗CO 中毒性能, 在4000 s后仍能保持超过90%的HOR电流密度, 超过了原始 的PtNi纳米线和目前报道的绝大多数Pt基催化剂.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (22322902, U22A20396, 22102052, 22309050, and 22211540385), the National Key Research and Development Program of China (2021YFA1502000), the Science and Technology Innovation Program of Hunan Province (2021RC3065), Jiebang Guashuai Project of Changsha City (kq2301009), Shenzhen Science and Technology Program (JCYJ20210324120800002, JCYJ20220818100012025, and JCYJ20230807122007015), and China Postdoctoral Science Foundation (2023T160205).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. College of Materials Science and Engineering, Hunan University, Changsha, 410082, China

    Wei Liu  (刘巍), Furong Yang  (杨馥榕), Chenming Huang  (黄晨明), Wenchuan Lai  (赖文川), Lei Gao  (高磊) & Hongwen Huang  (黄宏文)

  2. Center for Electron Microscopy, State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology and College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, 310014, China

    Tulai Sun  (孙土来)

  3. College of Chemistry and Materials Science, Nanjing Normal University, Nanjing, 210023, China

    Wenchuan Lai  (赖文川)

  4. 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

    Jiafeng Du  (杜佳峰) & Jinyu Ye  (叶进裕)

  5. Key Laboratory of Optoelectronic Devices and Systems of Ministry of Education and Guangdong Province, College of Physics and Optoelectronic Engineering, Shenzhen University, Shenzhen, 518060, China

    Yujia Zeng  (曾昱嘉)

  6. Shenzhen Research Institute of Hunan University, Shenzhen, 518055, China

    Hongwen Huang  (黄宏文)

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  1. Wei Liu  (刘巍)
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Contributions

Author contributions Huang H provided guidance and revised the manuscript. Sun T and Lai W performed and analyzed the HAADF-STEM characterizations. Liu W designed this work, carried out the experiments, analyzed the results, and wrote this paper. Yang F carried out the DFT simulations. Huang C, Du J and Ye J conducted the in-situ FTIR. Zeng Y performed the XPS analyses. Gao L carried out the XRD measurements. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Tulai Sun  (孙土来), Wenchuan Lai  (赖文川) or Hongwen Huang  (黄宏文).

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

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

Wei Liu received his Bachelor’s degree from Hunan Institute of Technology in 2021. Currently, he is pursuing a Master’s degree at Hunan University, focusing on the control of synthesis and application of precious metal nanocrystals.

Fongrong Yang completed her BS degree at Hunan University in 2021. She is currently pursuing a Master’s degree at Hunan University. Her research focuses on controlling the synthesis of precious metal nanocrystals assistented by DFT.

Tulai Sun is an associate researcher at Zhejiang University of Technology. He received his PhD degree in materials science and engineering from Zhejiang University and then worked as a postdoctoral fellow at the Center for Electron Microscopy, Zhejiang University. His research primarily revolves around the development of electron microscopy techniques and their applications in understanding the structure-activity relationships of functional materials.

Wenchuan Lai obtained his PhD degree from Sichuan University in 2020. Then he joined Hongwen Huang’s group as a post-doctoral fellow at Hunan University. Now, he is an associate professor at Nanjing Normal University. His research is focused on the chemistry and applications of graphene, nanotechnology as well as polymer nanocomposites.

Hongwen Huang is now a full professor at Hunan University. He received his Bachelor’s degree in materials science and engineering from the South China University of Technology in 2009 and his PhD degree in materials science and engineering from Zhejiang University in 2015. From 2012 to 2014, he studied at Georgia Institute of Technology under the supervision of Prof. Younan Xia. After graduation, he worked at the University of Science and Technology of China as a postdoctoral fellow from 2015 to 2017 and joined Hunan University in 2017. His research interests include the controlled growth of nanocrystals and their applications in energy-related electrocatalysis.

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Liu, W., Yang, F., Sun, T. et al. Ultrathin PtNiW@WOx core-shell nanowires for enhanced CO-tolerant hydrogen oxidation: three-in-one catalyst design. Sci. China Mater. 67, 1866–1875 (2024). https://doi.org/10.1007/s40843-023-2804-9

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