Abstract
Transition metal phosphides (TMPs) have emerged as promising electrocatalysts to enhance the slow kinetic process of oxygen evolution reaction (OER). Framelike hollow nanostructures (nanoframes, NFs) provide the open structure with more accessible active sites and sufficient channels into the interior volume. Here, we report the fabrication of bimetallic Co-Fe phosphide NFs (Co-Fe-P NFs) via an intriguing temperature-controlled strategy for the preparation of precursors followed by phosphidation. The precursors, Co-Fe Prussian blue analogues (Co-Fe PBAs) are prepared by a precipitation method with Co2+ and [Fe(CN)6]3−, which experience a structural conversion from nanocubes to NFs by increasing the aging temperature from 5 to 35°C. The experimental results indicate that this conversion is attributable to the preferentially epitaxial growth on the edges and corners of nanocubes, triggered by intramolecular electron transfer at an elevated aging temperature. The as-prepared Co-Fe-P NFs catalyst shows remarkable catalytic activity toward OER with a low overpotential of 276 mV to obtain a current density of 10 mA cm−2, which is superior to the reference samples (Co-Fe-P nanocubes) and most of the recently reported TMPs-based electrocatalysts. The synthetic strategy can be extended to fabricate Co-Fe dichalcogenide NFs, thereby holding a great promise for the broad applications in energy storage and conversion systems.
摘要
过渡金属磷化物(TMPs)作为一类新型高效水分解电催化剂, 近 年来引起了研究人员的广泛兴趣. 框架型空心纳米结构通过去除内部 非功能性原子而具有独特的开放式结构, 可创造更多的内部反应空间, 提供丰富的活性位点和提升催化剂的原子利用率. 在本文中, 我们合成 了一种钴铁双金属磷化物纳米框架用于高效电催化析氧反应. 该催化 剂材料基于温度调控策略合成钴铁类普鲁士蓝纳米框架前驱体, 随后 通过磷化处理制备. 实验发现, Co2+和[Fe(CN)6]3−共沉淀生成钴铁类普 鲁士蓝前驱体的过程中, 伴随反应温度从5°C升高到35°C, 产物结构由 实心纳米立方体转变为空心纳米框架. 研究表明, 纳米结构的转变与纳 米立方体棱角位置的选择性外延生长相关, 升高反应温度将触发前驱 体分子内的电子转移并诱导结构转变. 所制备的钴铁磷化物纳米框架 表现出优异的电催化析氧活性, 产生10 mA cm–2的催化电流密度仅需 276 mV的过电位, 其性能优于对比样品(钴铁磷化物实心纳米立方体) 和大部分近期报道的TMPs基电催化剂. 本文的合成策略可拓展制备钴 铁硫族化合物(如钴铁硒化物和钴铁硫化物)纳米框架, 因而在能量存储 与转化领域具有广泛的应用前景.
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Acknowledgements
This work was supported by the National Natural Science Foundation of China (21872105 and 22072107) and the Natural Science Foundation of Zhejiang Province (LQ20B030001 and LY20E020002).
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Author contributions Ji L designed this study, conducted the experiment and wrote the paper; Zheng H conducted the experiment and wrote the paper; Wei Y and Gong S did some characterizations; Wang T performed some data analysis; Wang S and Chen Z designed this study and revised the paper. All authors contributed to the general discussion.
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Lvlv Ji is currently a lecturer at Zhejiang Sci-Tech University. He received his BSc degree from Huainan Normal University in 2012, MSc degree from Zhejiang University of Technology in 2015, and PhD degree from Tongji University in 2018. His research interests focus on the synthesis and application of 3D complex hollow structured nanomaterials.
Sheng Wang received his PhD degree from Fukui University, Japan in 2003, and then worked as assistant lecturer at Hokkaido University for 3 years. He joined Zhejiang Sci-Tech University in 2006 and was promoted to a full professor in 2013. His research interests include (1) nano photocatalysis; (2) bio-inspired strategies for functional nanomaterials; and (3) micro/nano fibrous composites.
Zuofeng Chen got his PhD degree at the University of Hong Kong in 2009 and was a postdoctoral fellow at the University of North Carolina at Chapel Hill and Duke University. He has been a full professor at the School of Chemical Science and Engineering of Tongji University since 2014. His research interests focus on new energy materials and the electrocatalysts in energy conversion and storage systems.
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Ji, L., Zheng, H., Wei, Y. et al. Temperature-controlled fabrication of Co-Fe-based nanoframes for efficient oxygen evolution. Sci. China Mater. 65, 431–441 (2022). https://doi.org/10.1007/s40843-021-1743-7
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DOI: https://doi.org/10.1007/s40843-021-1743-7