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Molecular iron phthalocyanine catalysts on morphology-engineered graphene towards the oxygen reduction reaction

石墨烯负载分子铁酞菁催化剂的形貌结构调控与氧还原催化应用

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Abstract

Molecular catalysts dispersed on nanocarbon substrates represent a unique class of single atom catalysts (SACs) for their well-defined active sites and tailorable structures, and are promising substitutes to precious metals for catalyzing the technologically important oxygen reduction reaction (ORR). Herein, we develop a highly active ORR catalyst consisting of iron phthalocyanine uniformly and densely dispersed on puff-like graphene (FePc/PG). With the unique crumpled and spheroid morphology, the graphene carrier possesses a large surface area and multiscale porosity, benefiting the high-density loading of FePc, exposure of the active sites and mass transfer efficiency during catalysis. When evaluated by a rotating disk electrode, FePc/PG presents a high half-wave potential of 0.909 V vs. the reversible hydrogen electrode. Furthermore, when employed as the gas diffusion electrode, FePc/PG exhibits outstanding high-rate and highpower capabilities at practically high current densities. This work provides efficient strategies to engineer the morphology of the nanocarbon substrates to design high-performance heterogeneous molecular catalysts toward applications in diverse energy conversion and storage technologies.

摘要

分散在纳米碳基底上的分子催化剂由于具有明确的活性位点和结构可调的特点, 成为了一类独特的单原子催化剂, 有望代替贵金属催化剂用于电催化氧还原反应. 本文中, 我们开发了一种高活性氧还原催化剂, 该催化剂由均匀且密集分散在泡芙状石墨烯载体上的铁酞菁(FePc/PG)构成. 泡芙状石墨烯载体由于具有独特的皱褶和球状形貌, 具有较大的比表面积和多尺度的孔结构, 有利于FePc的高密度负载、 活性位点的暴露和催化过程中传质效率的提高. 当用旋转圆盘电极评估性能时, FePc/PG表现出优异的半波电位, 达0.909 V (相对于可逆氢电极). 此外, 当用作气体扩散电极时, FePc/PG在高电流密度下表现出优异的高倍率和高功率性能. 这项工作为设计纳米碳材料的形貌以及高性能异相分子催化剂提供了有效的策略, 有望在多种能源转换和存储技术中得到应用.

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Acknowledgements

Fei H acknowledges the financial support from the National Natural Science Foundation of China (92163116) and the Major Program of the Natural Science Foundation of Hunan Province (2021JC0006). Ye G acknowledges the support from the National Natural Science Foundation of China (22209043).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Advanced Catalytic Engineering Research Center of the Ministry of Education, State Key Laboratory for Chemo/Biosensing and Chemometrics, and College of Chemistry and Chemical Engineering, Hunan University, Changsha, 410082, China

    Man Gao  (高曼), Jingjing Liu  (刘静静), Gonglan Ye  (叶龚兰), Jianbin Liu  (柳建斌), Guanchao He  (何观朝), Zhichao Gong  (龚智超), Kang Huang  (黄康) & Huilong Fei  (费慧龙)

  2. The Harold & Inge Marcus Department of Industrial & Manufacturing Engineering, Materials Research Institute (MRI), The Pennsylvania State University, University Park, Pennsylvania, 16802, USA

    Zhongkun Zhao  (赵忠坤) & Hongtao Sun  (孙洪涛)

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  1. Man Gao  (高曼)
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Contributions

Author contributions Fei H, Sun H and Ye G conceived the concept and supervised the research. Gao M and Liu J performed the experiments, analyzed the data, and wrote the original draft. He G, Gong Z and Huang K carried out SEM, XRD, ICP-MS tests. Zhao Z and Liu J conducted partial data analysis. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Gonglan Ye  (叶龚兰), Hongtao Sun  (孙洪涛) or Huilong Fei  (费慧龙).

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

Additional information

Man Gao received her BE degree from the North University of China in 2020. She is currently studying for a Master’s degree at the College of Chemistry and Chemical Engineering, Hunan University, China. Her main research directions are graphene-based oxygen reduction electrocatalysts and their applications.

Jingjing Liu is currently a PhD student at the College of Chemistry and Chemical Engineering, Hunan University, China. She received her MS degree from the College of Chemistry and Chemical Engineering, Central South University in 2019. Her research focuses on the design of functional nanocarbon materials for ORR in metal-air batteries and hydrogen peroxide production.

Gonglan Ye is currently an associate professor at the College of Chemistry and Chemical Engineering, Hunan University, China. She received her BS degree (2010) in materials chemistry from China University of Geoscience (Wuhan) and PhD degree (2016) in materials science and nanoengineering from Rice University. Before she joined Hunan University, she had worked as a senior packaging engineer at Intel in Chandler, Arizona (2017–2019). Her scientific interest focuses on the controllable synthesis of two-dimensional (2D) materials for energy storage and conversion.

Hongtao Sun is an assistant professor at Harold and Inge Marcus Department of Industrial and Manufacturing Engineering, Pennsylvania State University, University Park, USA. He obtained his PhD degree in mechanical engineering from Rensselaer Polytechnic Institute (RPI) in 2014. He was previously a postdoc researcher at the University of California, Los Angeles. His current research interests focus on the co-design of materials, structures, and manufacturing processes with a particular emphasis on their applications in the field of energy.

Huilong Fei is currently a professor at the College of Chemistry and Chemical Engineering, Hunan University, China. He received his BS degree in materials chemistry from China University of Geosciences (Wuhan) in 2011, and his PhD degree in chemistry from Rice University in 2015. He was previously a postdoc researcher at the University of California, Los Angeles, before joining Hunan University in 2018. His current research interests focus on the controllable synthesis and rational design of nanocarbon-supported single atom catalysts for energy and environmental applications.

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Gao, M., Liu, J., Ye, G. et al. Molecular iron phthalocyanine catalysts on morphology-engineered graphene towards the oxygen reduction reaction. Sci. China Mater. 66, 3865–3874 (2023). https://doi.org/10.1007/s40843-023-2554-x

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