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Tailoring the electronic structure of ZnCo2O4 by incorporating anions with low electronegativity to improve the water oxidation activity

低电负性阴离子掺杂调控钴酸锌的电子结构以提高析氧反应活性

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Abstract

Electron configurations and conductivity are significant descriptors/characteristics for the oxygen evolution reaction (OER), which can be modulated with heteroatom doping. Given that metal substitution usually reduces the number of active sites of spinel electrocatalysts, the effect of anion doping on the electronic structure has been investigated by using ZnCo2O4 (ZCO) as a demonstration. Compared with Co3+-dominated ZCO, the substitution of oxygen with less electronegative sulfur raises the portion of Co2+ in the low-spin states (t2g6eg1), which is more OER-active than Co3+ (t2g6eg0). Co2+ in the sulfur-doped ZCO (ZCO-S) is associated with the redistribution of electron density from S toward Co due to the high covalent interaction of Co-S. The Co-S interaction also induces a fast charge transfer. ZCO-S outperforms pristine ZCO by 11 times in terms of specific OER activity at 1.65 V versus reversible hydrogen electrode. In contrast, doping fluorine with higher electronegativity and valence deteriorates OER activity. Our work establishes the correlation between the electronegativity of anion dopants and OER intrinsic activity in spinel oxides and provides a simple and effective method to modulate the electronic structure of spinel oxides by doping anions with different electronegativities, which can be a new avenue for the rational design of high-performance spinel electrocatalysts.

摘要

电子结构和电导率是析氧反应活性的重要描述符, 它们可以通过掺杂来调节. 鉴于金属掺杂通常会减少电催化剂的活性位点数量, 本工作探究了阴离子掺杂对尖晶石钴酸锌(ZCO)电子结构及其析氧活性的影响. 与三价钴为主的ZCO相比, 用电负性较低的硫取代氧会提高低自旋态(t2g6eg1)二价钴的占比, 其析氧活性要高于低自旋态的三价钴(t2g6eg0). 掺硫钴酸锌(ZCO-S)中钴离子和阴离子之间的电子密度的再分布导致了二价钴的增多, 而且钴和硫离子间的强共价作用也会加速电荷迁移. ZCO-S在1.65伏(相对于可逆氢电极)下的比活性比原始ZCO高11倍. 相反, 掺入具有较高电负性和价态的氟(F)并不能有效地改善电子结构, 最终导致材料析氧活性的降低. 本工作建立了所掺阴离子的电负性与钴酸锌本征析氧活性之间的联系, 并提供了一种通过掺杂不同电负性的阴离子来调控尖晶石氧化物的电子结构的简单有效的方法,这为合理设计高性能尖晶石电催化剂提供了新途径.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (U2032154), the Key Research and Development Program of Anhui (202004a05020072), Anhui Initiative in Quantum Information Technologies (AHY100000), and Anhui Provincial Natural Science Foundation (1908085ME119).

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Authors and Affiliations

  1. CAS Key Laboratory of Materials for Energy Conversion, Department of Materials Science and Engineering, University of Science and Technology of China, Hefei, 230026, China

    Bing Xiong  (熊兵), Liangbing Ge  (葛良兵), Xueyan Lei  (雷雪颜), Yangkai Wang  (汪扬凯), Jiwen Yang  (杨吉文), Weiwei Li  (李威威), Zhengping Fu  (傅正平) & Yalin Lu  (陆亚林)

  2. Institute for Superconducting and Electronic Materials (ISEM), University of Wollongong, Wollongong, 2500, Australia

    Xiaoning Li  (李晓宁) & Zhenxiang Cheng  (程振祥)

  3. Anhui Laboratory of Advanced Photon Science and Technology, University of Science and Technology of China, Hefei, 230026, China

    Zhengping Fu  (傅正平) & Yalin Lu  (陆亚林)

  4. Synergetic Innovation Center of Quantum Information & Quantum Physics, Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, 230026, China

    Zhengping Fu  (傅正平) & Yalin Lu  (陆亚林)

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  1. Bing Xiong  (熊兵)
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  2. Liangbing Ge  (葛良兵)
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  3. Xueyan Lei  (雷雪颜)
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Contributions

Lu Y, Fu Z, and Cheng Z conceived the project. Xiong B fabricated the samples. Ge L conducted the Bader charge analysis. Lei X and Li W performed the XAS characterization. Wang Y and Yang J performed the UV-vis experiments. Xiong B wrote the manuscript. Li X and Fu Z revised the manuscript. All the authors discussed the results and contributed to the manuscript preparation.

Corresponding authors

Correspondence to Xiaoning Li  (李晓宁), Zhengping Fu  (傅正平) or Yalin Lu  (陆亚林).

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Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary information

Supporting data are available in the online version of the paper.

Bing Xiong received his BSc degree (2020) from Hefei University of Technology under the supervision of Prof. Yong Zhang. Now, he is a PhD candidate at the University of Science and Technology of China (USTC). His research mainly focuses on the modulation of electronic structure and magnetic property for energy conversion applications.

Zhengping Fu is an associate professor at the USTC. He graduated from the Department of Materials Science and Engineering, USTC in 1999 with a PhD degree. Then he has been working at the USTC. He did post-doctoral research at Tsing Hua University (Hsinchu) from 2003 to 2004. His research is on new functional materials and electrocatalysts.

Xiaoning Li is an associate research fellow at the Institute for Superconducting and Electronic Materials (ISEM), University of Wollongong. She obtained her PhD degree in material physics and chemistry from the University of Science and Technology of China in 2016. Currently, she is focusing on the correlation of crystal and electrontic structure, physical property, and the energy conversion efficiency of electrocatalysts for energy conversion applications.

Yalin Lu is the distinguished professor at the USTC and the director of Anhui Laboratory of Advanced Photon Science and Technology. He received a PhD degree in physics from Nanjing University in 1991. He was a professor at the Air Force Academy, Tufts University and Lawrence Berkeley National Laboratory. His research focuses on THz optics and materials, optoelectronics, materials physics of complex oxides, and materials for energy conversion.

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Tailoring the electronic structure of ZnCo2O4 by incorporating anions with low electronegativity to improve the water oxidation activity

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Xiong, B., Ge, L., Lei, X. et al. Tailoring the electronic structure of ZnCo2O4 by incorporating anions with low electronegativity to improve the water oxidation activity. Sci. China Mater. 66, 1793–1800 (2023). https://doi.org/10.1007/s40843-022-2335-1

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