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钴掺杂铜基复合材料的制备及其电催化析氧性能

张海成 杨邦志 张娇 高鹏 向万夏 郭婷 徐海涛

张海成, 杨邦志, 张娇, 等. 钴掺杂铜基复合材料的制备及其电催化析氧性能[J]. 复合材料学报, 2024, 41(4): 1923-1933. doi: 10.13801/j.cnki.fhclxb.20230814.006
引用本文: 张海成, 杨邦志, 张娇, 等. 钴掺杂铜基复合材料的制备及其电催化析氧性能[J]. 复合材料学报, 2024, 41(4): 1923-1933. doi: 10.13801/j.cnki.fhclxb.20230814.006
ZHANG Haicheng, YANG Bangzhi, ZHANG Jiao, et al. Synthesis and electrocatalytic oxygen evolution performance of cobalt doped copper-based composites[J]. Acta Materiae Compositae Sinica, 2024, 41(4): 1923-1933. doi: 10.13801/j.cnki.fhclxb.20230814.006
Citation: ZHANG Haicheng, YANG Bangzhi, ZHANG Jiao, et al. Synthesis and electrocatalytic oxygen evolution performance of cobalt doped copper-based composites[J]. Acta Materiae Compositae Sinica, 2024, 41(4): 1923-1933. doi: 10.13801/j.cnki.fhclxb.20230814.006

钴掺杂铜基复合材料的制备及其电催化析氧性能

doi: 10.13801/j.cnki.fhclxb.20230814.006
基金项目: 陕西省自然科学基金(2022JQ-148);陕西省教育厅基金(22JK0311);陕西理工大学人才启动项目(SLGRCQD2108);陕西省大学生创新创业训练计划(S202210720094);秦巴生物资源与生态环境国家重点实验室(培育)“市校共建”科研专项 (SXJ-2304)
详细信息
    通讯作者:

    郭婷,博士,讲师,研究方向为纳米材料合成与环境催化应用 E-mail: guotingjob@163.com

    徐海涛,博士,讲师,研究方向为无机纳米材料合成与电催化应用 E-mail: xuhaitao@snut.edu.cn

  • 中图分类号: TB333

Synthesis and electrocatalytic oxygen evolution performance of cobalt doped copper-based composites

Funds: Shaanxi Provincial Natural Science Foundation (2022JQ-148); Shaanxi Provincial Department of Education Project (22JK0311); Doctor Research Start Foundation of Shaanxi University of Technology (SLGRCQD2108); Shaanxi University Student Innovation and Entrepreneurship Training Program (S202210720094); State Key Laboratory of Qinba Bio-Resource and Ecological Environment, Scientific Research Project of City-University Co-construction of Shaanxi Province (SXJ-2304)
  • 摘要: 铜基纳米材料在电催化方面受到广泛关注,但其存在催化活性低和稳定性差的问题,探索简单高效的策略解决上述问题具有重要的实际意义。本文在室温条件下,采用Co-MOF材料在CuCl2溶液中水解刻蚀策略成功在泡沫镍基底上构筑了钴掺杂的碱式氯化铜/氯化亚铜复合材料。通过改变Co-MOF在CuCl2溶液中的水解刻蚀时间,从而调控物种和复合物的形貌结构。最优催化剂仅需238 mV的过电位便能够驱动100 mA·cm−2的电流密度。经过50 h的稳定性测试,电流密度几乎没有下降,表明其具有良好的稳定性。优异的电催化析氧反应(OER)性能可归属于Co原子的掺杂优化了Cu原子周围电子环境,激活碱式氯化铜和氯化亚铜的催化活性及CuCl2对泡沫镍的刻蚀增加了活性位点。本文为铜基电催化材料的制备和电催化OER活性增强提供了新的思路和策略。

     

  • 图  1  钴掺杂的碱式氯化铜/氯化亚铜(Co-CuCO)/泡沫镍(NF)的制备过程示意图和Co-MOF结构示意图(a)、反应过程中的Co-MOF/NF照片(b)和Co-CuCO/NF的照片(c)

    Figure  1.  Schematic diagram of the preparation of cobalt-doped Cu2Cl(OH)3/CuCl (Co-CuCO)/NF and the structure diagram of Co-MOF (a), digital photographs of Co-MOF/NF (b) and Co-CuCO/NF (c) during the reaction

    图  2  (a) Co-CuCO-10 h/NF复合材料的XRD图谱;(b) Co-CuCO-2 h/NF、Co-CuCO-4 h/NF、Co-CuCO-8 h/NF、Co-CuCO-12 h/NF复合材料的XRD图谱;Co-MOF (c)和裸泡沫镍(d)的XRD图谱

    Figure  2.  (a) XRD patterns of Co-CuCO-10 h/NF composites; (b) XRD patterns of Co-CuCO-2 h/NF, Co-CuCO-4 h/NF, Co-CuCO-8 h/NF, Co-CuCO-12 h/NF composites; XRD patterns of Co-MOF powder sample (c) and bare nickel foam (d)

    图  3  Co-MOF ((a), (b))、Co-MOF在CuCl2溶液中分别反应4 h ((c), (d))、10 h ((e), (f))和12 h ((g), (h))的SEM图像

    Figure  3.  SEM images of Co-MOF ((a), (b)), Co-MOF reacted in CuCl2 solution for 4 h ((c), (d)), 10 h ((e), (f)) and 12 h ((g), (h)), respectively

    图  4  Co-CuCO-10 h/NF复合材料的TEM (a)、HRTEM (b)、元素分布图((c), (d))和EDS能谱(e)

    Figure  4.  TEM (a), HRTEM (b) and corresponding elemental mapping images ((c), (d)) and EDS spectrum (e) of Co-CuCO-10 h/NF composites

    图  5  Co-CuCO-10 h/NF复合材料的XPS图谱:全谱(a)、Cu2p (b)、O1s (c)、Cl2p (d)、Co2p (e)和N1s (f)

    Figure  5.  XPS spectra of the Co-CuCO-10 h/NF composites: Survey (a), Cu2p (b), O1s (c), Cl2p (d), Co2p (e), and N1s (f)

    Sat.—Satellite peak

    图  6  Co-CuCO-2 h/NF、Co-CuCO-4 h/NF、Co-CuCO-8 h/NF、Co-CuCO-10 h/NF、Co-CuCO-12 h/NF、CuCl2-10 h/NF、Co-MOF/NF和NF的极化曲线(a)、在电流密度100 mA·cm−2下的过电位比较(b)和Tafel斜率(c);(d) Co-CuCO-10 h/NF、Co-MOF/NF和NF的电化学阻抗谱;Co-CuCO-10 h/NF电极的稳定性测试(e)和反应50 h之后的SEM图像((f), (g))

    Figure  6.  LSV polarization curves (a), overpotentials at a current density of 100 mA·cm−2 (b) and Tafel slopes (c) of Co-CuCO-2 h/NF, Co-CuCO-4 h/NF, Co-CuCO-8 h/NF, Co-CuCO-10 h/NF, Co-CuCO-12 h/NF, CuCl2-10 h/NF, Co-MOF/NF, and NF; (d) Nyquist plots for Co-CuCO-10 h/NF, Co-MOF/NF, and NF; Stability test (e) and SEM images ((f), (g)) after 50 h of reaction for the Co-CuCO-10 h/NF electrode

    图  7  Co-CuCO-10 h/NF ((a), (b))、Co-MOF/NF ((c), (d))和NF ((e), (f))在非法拉第电位区间的循环伏安曲线和相应的双电层电容曲线

    Figure  7.  Cyclic voltammetry curves in the non-Faradaic potential region and corresponding the capacitive current densities plotted against scan rate of Co-CuCO-10 h/NF ((a), (b)), Co-MOF/NF ((c), (d)) and NF ((e), (f))

    ja—Anodic current density; jc—Cathodic current density

    表  1  刻蚀不同时间所制备的复合材料的组分

    Table  1.   Components of composites prepared by etching for different time

    Abbreviation of
    sample name
    Reaction time/hComponent
    Co-CuCO-2 h/NF 2CuCl, Co-MOF
    Co-CuCO-4 h/NF 4CuCl, Co-MOF
    Co-CuCO-8 h/NF 8CuCl, Co-MOF,Cu2Cl(OH)3
    Co-CuCO-10 h/NF10CuCl, Cu2Cl(OH)3
    Co-CuCO-12 h/NF12CuCl, Cu2Cl(OH)3
    Note: NF—Nickel foam.
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出版历程
  • 收稿日期:  2023-06-21
  • 修回日期:  2023-07-28
  • 录用日期:  2023-08-03
  • 网络出版日期:  2023-08-15
  • 刊出日期:  2024-04-15

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