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In situ electrochemically converting Fe2O3-Ni(OH)2 to NiFe2O4-NiOOH: a highly efficient electrocatalyst towards water oxidation

Fe2O3-Ni(OH)2原位电化学转化为NiFe2O4-NiOOH用于高效电解水产氧 张

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Abstract

To develop low-cost, earth-abundant NiFebased materials as highly efficient oxygen evolution reaction (OER) electrocatalysts and to probe new catalytic species are still great challenges to now. Here, an in situ formation of OER active NiFe2O4-NiOOH nanosheet arrays is demonstrated as a highly efficient OER electrocatalyst by the anodization of Fe2O3 domains anchored on Ni(OH)2 nanosheet arrays. The as-converted product can deliver the current density of 30 mA cm−2 with a small overpotential of 240 mV, and only requires an overpotential of 410 mV to achieve an amazing huge current density of 3000 mA cm−2. In situ potential-dependent Raman spectroscopy reveals that Ni(OH)2 in the composite is easier to be oxidized to NiOOH than pure Ni(OH)2, and the newly formed NiOOH reacts with the nearby Fe2O3 to produce hybrid NiFe2O4-NiOOH. It is found that the cooperative effect of the in situ formed NiFe2O4 and NiOOH as well as the hydrophilic and aerophobic electrode surface make main contribution to the outstanding OER activity of the catalyst. This work will bring new perspectives to the recognition of the origin of NiFe composite materials for OER and provide a mild method to synthesize amorphous spinel materials at room temperature.

摘要

探索新的催化活性物种和开发价格低廉、来源广泛的镍铁基电催化剂对实现高效电解水产氧有着重要意义. 本文报道了一种通过 阳极化镶嵌Fe2 O3颗粒的Ni(OH)2纳米片阵列, 使其原位电化学转化成NiFe2O4-NiOOH纳米片阵列用于高效电解水产氧的复合催化剂. 电化 学产氧测试表明: 这种复合材料催化剂在电流密度达到30 mA cm−2时仅需240 mV的过电势, 且只需要410 mV的过电势就可使电流密度达 到3000 mA cm−2. 电化学原位拉曼光谱测试表明: 这种镶嵌有Fe2O3颗粒的Ni(OH)2纳米片中的Ni(OH)2拥有更高的反应活性, 从而使其不仅 更容易氧化生成NiOOH, 同时新生成的NiOOH可以在正电流的刺激下与Fe2O3颗粒反应原位生成非晶的NiFe2O4-NiOOH复合材料. 该复合 材料的高电化学产氧活性主要归因于NiFe2O4和NiOOH的协同作用, 以及由于纳米片阵列结构所导致的超疏气与超亲水表面. 这项工作不 仅从全新的角度解读了镍铁基催化剂高电催化产氧活性的起源, 同时还提供了一种温和的室温合成方法用以制备具有非晶结构的尖晶石 类材料. 此外, 该项工作还有助于研究者关注异质催化剂在电催化过程中的物质转化行为, 从而更好地设计和发展新型高效催化体系.

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Acknowledgments

This work was supported by the National Natural Science Foundation of China (21422104) and the Key Project of Natural Science Foundation of Tianjin City (16JCZDJC30600). We acknowledge Prof. Bin Ren for kind discussion.

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Authors and Affiliations

  1. Department of Chemistry, School of Science, and Tianjin Key Laboratory of Molecular Optoelectronic Science, Tianjin University, and Collaborative Innovation Center of Chemical Science and Engineering, Tianjin, 300072, China

    Fang Zhang  (张芳), Yanmei Shi  (史艳梅), Jingfang Zhang  (张競方), Yu Liang  (梁瑜) & Bin Zhang  (张兵)

  2. Analysis Center of Tianjin University, Tianjin University, Tianjin, 300072, China

    Tao Xue  (薛涛)

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  1. Fang Zhang  (张芳)
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Correspondence to Bin Zhang  (张兵).

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These authors contributed equally to this work.

Fang Zhang is currently a Master candidate at Tianjin University under the supervision of Prof. Bin Zhang. She received her BSc degree from the College of Chemistry, Chemical Engineering and Materials Science from Shandong Normal University in 2014. Her research interests include the development of non-noble metal electrocatalysts for oxygen evolution reaction.

Yanmei Shi received her BSc degree in applied chemistry from Tianjin University in 2013. She is currently working on her PhD degree at Tianjin University under the supervision of Prof. Bin Zhang. Her research focuses on the development of non-noble metal electrocatalysts for hydrogen and oxygen evolution reactions.

Bin Zhang received his PhD degree from the University of Science and Technology of China in 2007. He carried out postdoctoral research in the University of Pennsylvania (2007.7–2008.7) and worked as an Alexander von Humboldt fellow in Max Planck Institute of Colloids and Interfaces (2008.8–2009.7). Currently, he is a professor in the Chemistry Department at Tianjin University and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin). His research mainly focuses on the development of chemical transformation strategy to prepare porous and ultrathin nanomaterials, and their hybrids for energy catalytic applications. Fe2O3-

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In situ electrochemically converting Fe2O3-Ni(OH)2 to NiFe2O4-NiOOH: a highly efficient electrocatalyst towards water oxidation

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Zhang, F., Shi, Y., Xue, T. et al. In situ electrochemically converting Fe2O3-Ni(OH)2 to NiFe2O4-NiOOH: a highly efficient electrocatalyst towards water oxidation. Sci. China Mater. 60, 324–334 (2017). https://doi.org/10.1007/s40843-017-9017-6

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