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Surface controllable anchoring of Cu onto nanostructured PtNi for efficient electrochemical hydrogen evolution from seawater

Cu在纳米结构PtNi上的表面可控锚定用于高效海水产氢

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Abstract

Composition adjustment and establishment of multifunctional sites are promising routes to enhance the performance of Pt nanoalloys. A new strategy, involving surface controllable anchoring of Cu on nanostructured PtNi (named as Cu/PtNi), has been developed to enable precise control of stoichiometric elements. The nanostructured material contains oxophilic Ni that promotes fast water dissociation, Pt for superior H adsorption and efficient H2 production, and Cu to give positive Gibbs free-energy of active hydrogen adsorption for H2 desorption. The new Cu/PtNi electrocatalyst displays superior activity in the electrocatalytic hydrogen evolution reaction, associated with an overpotential of 23 mV at 10 mA cm−2 in alkaline seawater that is five times higher than the mass activity of commercial Pt/C (at 70 mV overpotential). Results of density functional theory calculations verify that key processes including H2O dissociation, H* adsorption and H2 desorption involved in the hydrogen evolution reaction pathway in alkaline seawater are facilitated by Pt, Ni, and Cu multifunctional metal sites.

摘要

表面组分调控及建立多功能活性位点是提高Pt基催化剂性能的有效途径. 通过将Cu可控地锚定在纳米结构PtNi表面(Cu/PtNi)可以精确控制Pt基催化剂表面元素的化学计量比, 其中亲氧的非贵金属Ni能加速水的解离, Pt由于具有适中的H吸附能, 可有效地将游离态的H转换成氢气, Cu由于具有正的H吸附吉布斯自由能(ΔGH*), 有助于H2的脱附. 其中具有最优组分比例的Cu/PtNi电催化剂在海水中表现出优异的电化学析氢活性和稳定性, 在碱性海水中, 10 mA cm−2下的过电位为23 mV (在70 mV过电位下, 其质量活性是商用Pt/C的5倍). 同时, 密度泛函理论结果进一步验证了在碱性海水中Pt, Ni和Cu多功能金属活性位点可提高HER的H2O解离、 H*吸附和H2脱附的过程.

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Acknowledgements

This work was supported by the National Key Research and Development Program of China (2022YFB3805600, 2022YFB3805604, and 2022YFB3806800), the National Natural Science Foundation of China (22293020), the National 111 project (B20002), the Program Fund of Non-Metallic Excellence and Innovation Center for Building Materials (2023TDA1-1), the Program for Changjiang Scholars and Innovative Research Team in University (PCSIRT) (IRT_15R52), Guangdong Basic and Applied Basic Research Foundation (2022A1515010137, 2022A1515010504, and 2021A1515111131), Shenzhen Science and Technology Program (GJHZ20210705143204014, JCYJ20210324142010029, and KCXFZ20211020170006010), Hubei Province Key Research and Development Program (2023BAB101), and the Fundamental Research Funds for the Central Universities (WUT: 2023IVA095 and 2023IV030h). We thank the Nanostructure Research Centre (NRC) for performing the S/TEM imaging. Mark D. Symes thanks the Royal Society for a University Research Fellowship (UF150104, URFR211007).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. State Key Laboratory of Advanced Technology for Materials Synthesis and Processing & Shenzhen Research Institute & International School of Materials Science and Engineering and Processing, Wuhan University of Technology, Wuhan, 430070, China

    Xiong Yang  (杨雄), Jiang-Bo Chen  (陈江波), Fei Yu  (余菲), Ge Tian  (田歌), Fu-Fei Pu  (蒲福飞), Song Zhang  (章嵩) & Xiao-Yu Yang  (阳晓宇)

  2. School of Chemical Engineering and Technology, Sun Yat-sen University, Zhuhai, 519082, China

    Yu-Xuan Xiao  (肖宇轩)

  3. Instituto de Química, Universidade de Sao Paulo, Av. Prof. Lineu Prestes 748, 05508-080, São Paulo, SP, Brazil

    Susana I. Córdoba de Torresi

  4. WestCHEM, School of Chemistry, University of Glasgow, Glasgow, G12 8QQ, UK

    Mark D. Symes

  5. Institut für Anorganische Chemie und Strukturchemie, Heinrich-Heine-Universität Düsseldorf, Düsseldorf, 40204, Germany

    Christoph Janiak

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  1. Xiong Yang  (杨雄)
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  2. Yu-Xuan Xiao  (肖宇轩)
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Contributions

Author contributions Yang X performed the experiments related to the synthesis and electrocatalytic performance. Yang X, Xiao YX, and Yang XY conceived the project, provided the ideas and designed the experiments. Tian G performed TEM and EDX characterizations. Chen JB and Yu F performed DFT calculation and analysis. Pu FF provided guidance for material synthesis. Yang X, Xiao YX, and Yang XY wrote and revised the paper. de Torresi SIC, Symes MD, Zhang S, and Janiak C revised the paper. All the authors discussed the results, analyzed the data, and gave their approval for the submission of the final version of the manuscript.

Corresponding author

Correspondence to Xiao-Yu Yang  (阳晓宇).

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

Additional information

Xiong Yang received his Bachelor degree in materials science from Wuhan University of Technology in 2019. He is currently a PhD candidate under the supervision of Prof. Xiaoyu Yang at Wuhan University of Technology. His research interest focuses on Pt-based metal compounds for applications in the electrocatalysis field.

Yu-Xuan Xiao received his PhD degree from Wuhan University of Technology in 2021. Currently, he is a postdoctoral fellow at Sun Yat-sen University. His research interest is focused on the design and synthesis of metal nanomaterials, as well as their applications in electrocatalysis.

Xiao-Yu Yang earned his BS degree from Jilin University in 2000 and his joint PhD degree from Jilin University, China and Facultes Universitaires Notre-Dame de la Paix (FUNDP), Belgium (co-education) in 2007. After a post-doctoral fellowship at FUNDP, he worked as a “Chargé de Recherches” at Le Fonds de la Recherche Scientifique (F.N. R.S.) of Belgium. He is currently working as a full professor at the State Key Laboratory of Advanced Technology for Material Synthesis and Processing and a visiting professor at Harvard University.

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

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Surface controllable anchoring of Cu onto nanostructured PtNi for efficient electrochemical hydrogen evolution from seawater

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Yang, X., Xiao, YX., Chen, JB. et al. Surface controllable anchoring of Cu onto nanostructured PtNi for efficient electrochemical hydrogen evolution from seawater. Sci. China Mater. 66, 3887–3894 (2023). https://doi.org/10.1007/s40843-023-2566-y

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