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Defect engineered 2D mesoporous Mo-Co-O nanosheets with crystalline-amorphous composite structure for efficient oxygen evolution

富含缺陷的非晶态与晶态杂化介孔钴钼纳米片高效 析氧催化剂

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Abstract

Two-dimensional (2D) mesoporous metal-oxide (hydroxide) nanomaterials with defects are promising towards the realization of efficient electrocatalysis. Herein, we report a facile and effective one-pot solvothermal route to synthesize mesoporous Mox-Co-O hybrid nanosheets (NSs) which is composed of crystalline Mo4O11 and amorphous cobalt hydroxide. Due to the corrosion of 1-octylamine at high temperatures, abundant mesoporous holes are created in situ over the Mox-Co-O hybrid NSs during the solvothermal process, which is beneficial to increasing the electrochemical surface area. The dimension of the Mox-Co-O NSs, size of mesoporous and the concentration of defects can be easily modulated by controlling the molar ratio of Mo/Co. Electrochemical measurements reveal that the 2D mesoporous Mox-Co-O NSs show an excellent activity for the oxygen evolution reaction with the highest catalytic activity of η10 = 276 mV at 10 mA cm−2 in 1 mol L−1 KOH. Enhanced adsorption of intermediates and abundant oxygen vacancies achieved by appropriate Mo doping are the two main factors that contribute to the excellent catalytic activity of Mo0.2-Co-O NSs. This work, with the construction of 2D metal-oxide (hydroxide) crystalline-amorphous nanomaterials possessing abundant holes, oxygen vacancies and enhanced adsorption of intermediates, provides important insight on the design of more efficient catalysts.

摘要

构建具有丰富缺陷且缺陷浓度可调的二维(2D)介孔金属氧化物 (氢氧化物)纳米材料作为高效电催化剂仍然是一个巨大的挑战. 本工作 开发了一种简便有效的一锅溶剂热路线来合成由晶体相Mo4O11和准非 晶相氢氧化钴组成的介孔Mox-Co-O杂化纳米片. 由于短链有机胺在高 温下的刻蚀作用, 合成过程中在Mox-Co-O杂化纳米片上原位产生了大 量的介孔空穴, 增加了材料的电化学比表面积. 此外, Mox-Co-O纳米片 的尺寸、介孔和晶相/非晶相纳米片上缺陷(本工作中的氧空位)的浓度 可以通过控制Mo/Co摩尔比调节. 电化学测试表明, 2D介孔Mox-Co-O 纳米片表现出优异的析氧反应活性, 其中Mo0.2-Co-O纳米片表现出最 高的催化活性(在1 mol L−1 KOH中10 mA cm−2处的过电位为276 mV). 研究发现, Mo0.2-Co-O纳米片具有合适的d带中心和最高浓度的氧空 位, 这是促成其优异催化活性的两个主要因素. 本工作构建具有丰富缺 陷(氧空位)和合适d带中心的二维金属氧化物(氢氧化物)的晶相/非晶 杂化纳米材料的方法, 为设计更高效的催化剂提供了重要启发.

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Acknowledgements

This work was financially supported by the National Key R&D Program of China (2020YFB1505802), the Ministry of Science and Technology (2017YFA0208200), the National Natural Science Foundation of China (22025108, U21A20327, and 22121001), and the Start-up Funds from Xiamen University.

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Authors and Affiliations

  1. State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China

    Chuansheng He  (何传生), Lingzheng Bu  (卜令正), Changhong Zhan  (战长宏), Bingyan Xu  (徐冰妍), Leigang Li  (李雷刚) & Xiaoqing Huang  (黄小青)

  2. College of Chemistry, Beijing Normal University, Beijing, 100875, China

    Chuansheng He  (何传生), Xiaochen Hu  (胡晓晨) & Yunchao Li  (李运超)

  3. Graduate School of Integrated Sciences for Life, Hiroshima University, Higashi-Hiroshima, Hiroshima, Japan

    Jia Wang  (王佳)

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  1. Chuansheng He  (何传生)
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Contributions

Huang X conceived and supervised the research. Huang X and He C designed the experiments. He C, Hu X, Wang J, Bu L, Zhan C and Xu B performed most of the experiments and data analysis. Huang X, Li L, He C and Li Y wrote the paper. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Leigang Li  (李雷刚) or Xiaoqing Huang  (黄小青).

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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.

Chuansheng He received his PhD degree (2021) in physical chemistry from Beijing Normal University under the supervision of Prof. Yunchao Li. He is currently a postdoctoral fellow in Prof. Xiaoqing Huang’s group at Xiamen University. His research focuses on the design of nanomaterials and the exploration of the structure-activity relationship between nanomaterials and the electrocatalytic performance.

Leigang Li received his PhD degree in materials science and engineering from Texas A&M University under the supervision of Prof. Haiyan Wang in 2017. He then worked as a postdoctoral research fellow at Purdue University. Since 2018, he has been working as a postdoctoral research fellow in Prof. Xiaoqing Huang’s group. His current research interest focuses on the design and synthesis of metallic nanostructures for electrocatalytic applications.

Xiaoqing Huang is currently a professor at the College of Chemistry and Chemical Engineering, Xiamen University. He obtained his BSc degree in chemistry education from the Southwest Normal University (2005) and PhD degree in inorganic chemistry from Xiamen University (2011) under the supervision of Profs. Nanfeng Zheng and Lansun Zheng. He then worked as a postdoctoral research associate in Profs. Yu Huang and Xiangfeng Duan’s group from 2011 to 2014 at the University of California, Los Angeles. His current research interest focuses on the design and synthesis of nanomaterials for energy-related applications such as electrocatalysis and photocatalysis.

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Defect engineered 2D mesoporous Mo-Co-O nanosheets with crystalline-amorphous composite structure for efficient oxygen evolution

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He, C., Hu, X., Wang, J. et al. Defect engineered 2D mesoporous Mo-Co-O nanosheets with crystalline-amorphous composite structure for efficient oxygen evolution. Sci. China Mater. 65, 3470–3478 (2022). https://doi.org/10.1007/s40843-022-2098-x

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