Abstract
Designing cost-effective and high-performance carbon-based oxygen reduction reaction (ORR) electrocatalysts is crucial in the development of Zn-air batteries (ZABs). In this study, a facile one-pot synthesis approach is engineered to construct Zn/Co-N-C carbonaceous polyhedrons interconnected with self-catalyzed-grown carbon nanotubes (CNTs) from zeolitic imidazolium frameworks linked with graphene oxide nanosheets. The special N-doped three-dimensional (3D) carbon matrix allows manipulating the exposure of active sites and the synergistic interaction between metal nanoparticles and CNTs. The as-synthesized catalyst features impressive ORR activity in 0.1 mol L−1 KOH (E1/2 = 0.83 V) and 0.5 mol L−1 H2SO4 (E1/2 = 0.73 V), satisfactory cycling stability and methanol resistance comparable to those of the benchmark Pt/C catalyst (E1/2 = 0.80 V in 0.1 mol L−1 KOH, E1/2 = 0.75 V in 0.5 mol L−1 H2SO4). Furthermore, the as-established ZAB demonstrates a competitive peak power density (90 mW cm−2) and prominent long-term stability, which are better than those of devices based on the commercial Pt/C catalyst (82 mW cm−2). This work provides promising guidance for fabricating highly effective ORR catalysts with in situ formed CNTs, which can be applied in portable ZAB-related devices.
摘要
开发高性价比、 高性能碳基氧还原反应(ORR)电催化剂对于锌空气电池发展至关重要. 本工作通过一锅合成法构建自催化生长碳纳米管(CNTs)交联的Zn/Co-N-C碳质多面体, 该碳纳米管由氧化石墨烯纳米片连接的沸石咪唑框架(ZIF-8)衍生而来. 该特殊氮掺杂三维碳基体可以调控活性中心暴露以及金属纳米粒子和碳纳米管的协同作用. 该催化剂在0.1 mol L−1 KOH (E1/2 = 0.83 V)和0.5 mol L−1 H2SO4 (E1/2 = 0.73 V)中均表现出优良的ORR活性、 循环稳定性和耐甲醇性, 性能与Pt/C相当(0.1 mol L−1 KOH, E1/2=0.80 V; 0.5 mol L−1 H2SO4, E1/2 = 0.75 V). 由该催化剂组装的锌空气电池表现出高功率密度 (90 mW cm−2)和优异的循环稳定性, 优于Pt/C (82 mW cm−2). 本工作为原位合成高效碳纳米管ORR催化剂提供了有力指导, 并为便携式锌空气电池器件研究提供了良好借鉴.
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Acknowledgements
This work was supported by the National Natural Science Foundation of China (51872076 and U1804255), the Program for Innovative Research Team of Henan Scientific Committee (CXTD2014033), the Project of Central Plains Science and Technology Innovation Leading Talents of Henan Province (194200510001) and the Scientific and Technological Research Project of Henan province (212102210651).
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Author contributions Gao S, Liu X and Zhang J conceived and designed the experiments. Zhang J, Chen Y and Liu Y performed the experiments and characterizations. Gao S, Liu X and Zhang J wrote the paper. All authors participated in the general discussion.
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The authors declare that they have no conflict of interest.
Jing Zhang is a postgraduate student in Prof. Shuyan Gao’s group at Henan Normal University. Her current research interest includes carbon-based electrocatalysts and their application in Zn-air battery.
Xupo Liu received his PhD degree from China University of Geosciences (Wuhan) in 2018. He worked as a postdoctoral researcher under the supervision of Prof. Deli Wang at Huazhong University of Science and Technology from July 2018 to July 2020. He is currently a lecturer at Henan Normal University. His research interests focus on carbon materials, nonnoble metal electrocatalysts, self-supporting electrodes, and their applications for fuel cells and water splitting.
Shuyan Gao received her PhD degree from Changchun Institute of Applied Chemistry, Chinese Academy of Sciences in 2006. She worked as a Japan Science Promotion Society research fellow at the National Institute of Advanced Industrial Science and Technology (2007–2009). Afterward, she was a specially appointed professor at Hokkaido University. She is currently a professor at Henan Normal University. Her research includes the utilization of environmental waste resources to build energy storage and conversion materials, additive manufacturing of triboelectric nanogenerators, and their applications in self-power electrocatalysis field.
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Self-catalyzed growth of Zn/Co-N-C carbon nanotubes derived from metal-organic frameworks as efficient oxygen reduction catalysts for Zn-air battery
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Zhang, J., Chen, Y., Liu, Y. et al. Self-catalyzed growth of Zn/Co-N-C carbon nanotubes derived from metal-organic frameworks as efficient oxygen reduction catalysts for Zn-air battery. Sci. China Mater. 65, 653–662 (2022). https://doi.org/10.1007/s40843-021-1775-2
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DOI: https://doi.org/10.1007/s40843-021-1775-2