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Spatial construction of ultrasmall Pt-decorated 3D spinel oxide-modified N-doped graphene nanoarchitectures as high-efficiency methanol oxidation electrocatalysts

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Abstract

Direct methanol fuel cell technology recently becomes the focus of both academic and engineering circles, which stimulates the exploitation and utilization of advanced electrode catalysts with high activity and long lifespan. Herein, we demonstrate a robust bottom-up approach to the spatial construction of three-dimensional (3D) spinel manganese-cobalt oxide-modified N-doped graphene nanoarchitectures decorated with ultrasmall Pt nanoparticles (Pt/MnCo2O4-NG) via a controllable self-assembly process. The incorporation of MnCo2O4 nanocrystals provides abundant hydroxyl sources to promote the oxidative removal of CO-like byproducts on Pt sites, while the existence of 3D porous N-doped graphene networks facilitates the transportation of both ions and electrons in the hybrid system, thus giving rise to remarkable synergetic coupling effects during the methanol oxidation process. Consequently, the optimized Pt/MnCo2O4-NG nanoarchitecture expresses exceptional electrocatalytic properties with a large electrochemically active surface area of 99.5 m2·g−1, a high mass activity of 1508.3 mA·mg−1, strong toxicity resistance and reliable long-term durability, which have obvious competitive advantages over those of conventional Pt/carbon black, Pt/carbon nanotube, Pt/graphene, and Pt/N-doped graphene catalysts with the same Pt usage.

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摘要

直接甲醇燃料电池技术在近年来成为了学术界和工业界的关注热点，这也推动了高活性、长寿命的先进电极催化剂的开发与利用。在本文中，我们展示了一种“自下而上”的方法通过自组装过程实现了小尺寸铂修饰的三维尖晶石氧化物改性氮掺杂石墨烯（Pt/MnCo2O4-NG）纳米结构的空间构筑。钴酸锰纳米晶的引入提供了丰富的羟基物种，促进了铂活性位点上副产物的氧化去除，同时三维多孔氮掺杂石墨烯网络的存在促进了杂化体系中离子和电子的输运，从而在甲醇氧化过程中产生了显著的协同耦合效应。研究结果表明，经过组分优化后，Pt/MnCo2O4-NG纳米结构的电化学活性表面积可达 99.5 m2·g-1，甲醇氧化质量活性为 1508.3 mA·mg-1，并具有较强的抗毒性和可靠的长期稳定性，相比于传统的铂/炭黑、铂/碳纳米管、铂/石墨烯和铂/氮掺杂石墨烯催化剂具有明显的竞争优势。

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Nos. 22209037 and 51802077) and the Fundamental Research Funds for the Central Universities (No. B220202042).

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Authors and Affiliations

  1. College of Mechanics and Materials, Hohai University, Nanjing, 210098, China

    Qi Zhang, Min-Min Yan, Wen-Fa Du, Chen-Yu Yin, Lu Yang, Hai-Yan He & Hua-Jie Huang

  2. New Energy Technology Engineering Lab of Jiangsu Province, College of Science, Nanjing University of Posts & Telecommunications (NUPT), Nanjing, 210023, China

    Jian Zhang

  3. International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science, Tsukuba, 305-0044, Ibaraki, Japan

    Yun-Qing Kang

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  1. Qi Zhang
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Correspondence to Hai-Yan He or Hua-Jie Huang.

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Zhang, Q., Yan, MM., Du, WF. et al. Spatial construction of ultrasmall Pt-decorated 3D spinel oxide-modified N-doped graphene nanoarchitectures as high-efficiency methanol oxidation electrocatalysts. Rare Met. 43, 186–197 (2024). https://doi.org/10.1007/s12598-023-02418-6

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