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无定形CoxHyPO4复合NiCo2S4核壳结构设计及其电催化析氧性能

蔡晓燕 陈自豪 毛梁

蔡晓燕, 陈自豪, 毛梁. 无定形CoxHyPO4复合NiCo2S4核壳结构设计及其电催化析氧性能[J]. 复合材料学报, 2024, 41(11): 5993-6002. doi: 10.13801/j.cnki.fhclxb.20240717.002
引用本文: 蔡晓燕, 陈自豪, 毛梁. 无定形CoxHyPO4复合NiCo2S4核壳结构设计及其电催化析氧性能[J]. 复合材料学报, 2024, 41(11): 5993-6002. doi: 10.13801/j.cnki.fhclxb.20240717.002
CAI Xiaoyan, CHEN Zihao, MAO Liang. Core-shell structured CoxHyPO4/NiCo2S4 composites towards electrocatalytic oxygen evolution[J]. Acta Materiae Compositae Sinica, 2024, 41(11): 5993-6002. doi: 10.13801/j.cnki.fhclxb.20240717.002
Citation: CAI Xiaoyan, CHEN Zihao, MAO Liang. Core-shell structured CoxHyPO4/NiCo2S4 composites towards electrocatalytic oxygen evolution[J]. Acta Materiae Compositae Sinica, 2024, 41(11): 5993-6002. doi: 10.13801/j.cnki.fhclxb.20240717.002

无定形CoxHyPO4复合NiCo2S4核壳结构设计及其电催化析氧性能

doi: 10.13801/j.cnki.fhclxb.20240717.002
基金项目: 国家自然科学基金 (22309204;22209203);博士后科学基金(2023M733742);中国矿业大学材料科学与工程学科引导基金(CUMTMS202202;CUMTMS202207)
详细信息
    通讯作者:

    蔡晓燕,博士,副教授,硕士生导师,研究方向为光/电功能材料 E-mail: xycai@cumt.edu.cn

  • 中图分类号: TB332

Core-shell structured CoxHyPO4/NiCo2S4 composites towards electrocatalytic oxygen evolution

Funds: National Natural Science Foundation of China (22309204; 22209203); China Postdoctoral Science Foundation (2023M733742); Material Science and Engineering Discipline Guidance Fund of China University of Mining and Technology (CUMTMS202202; CUMTMS202207)
  • 摘要: 探索具有优异活性和稳定性的非贵金属析氧反应(OER)电催化剂是电解水制氢的关键。本文采用光还原沉积方法将无定形的非晶物质磷酸氢钴(CoxHyPO4,简称Co-Pi)沉积在多孔NiCo2S4 (NCS)蛋黄-蛋壳微球表面,成功制备出具有核壳结构的Co-Pi/NCS复合材料。密度泛函理论(DFT)计算与实验研究相结合,探究Co-Pi的引入对NCS电子结构和电催化性能的影响。异质界面的形成及化学键的重构可以提升Co-Pi/NCS的电导率,调节催化剂与反应中间体之间的电荷转移,从而改变吸附强度和反应的吉布斯自由能,最终优化OER催化活性。因此,Co-Pi/NCS表现出良好的催化活性和耐久性,在10 mA·cm−2电流密度下的过电位仅为335 mV,并且在1 mol/L的KOH溶液中能保持14 h的长时稳定性。这项工作可以促进过渡金属硫化物在电化学制氧过程中的应用。

     

  • 图  1  (a) NiCo2S4 (NCS)和CoxHyPO4/NiCo2S4 (Co-Pi/NCS)样品的XRD图谱;(b) NCS和1%Co-Pi/NCS的FTIR图谱

    Figure  1.  (a) XRD patterns of NiCo2S4 (NCS) and CoxHyPO4/NiCo2S4 (Co-Pi/NCS) samples; (b) FTIR spectra of NCS and 1%Co-Pi/NCS

    图  2  NiCo-MOF (a) 和NCS (b) 的SEM图像;NCS的N2等温吸脱附曲线和孔径分布图 (c);0.7%Co-Pi/NCS (d)、1%Co-Pi/NCS (e)、2%Co-Pi/NCS (f) 的SEM图像;NCS (g) 和1%Co-Pi/NCS (h) 的TEM图像;1%Co-Pi/NCS的HRTEM图像 (i) 和EDS元素分布图(j)

    Figure  2.  SEM images of NiCo-MOF (a) and NCS (b); N2 isothermal adsorption curves and pore size distribution of NCS (c); SEM images of 0.7%Co-Pi/NCS (d), 1%Co-Pi/NCS (e) and 2%Co-Pi/NCS (f); TEM images of NCS (g) and 1%Co-Pi/NCS (h); HRTEM image (i) and EDS elemental mapping (j) of 1%Co-Pi/NCS

    图  3  NCS和1%Co-Pi/NCS样品的Ni2p (a)、Co2p (b)、P2p (c)、S2p (d) 高分辨XPS图谱

    Sat.—Satellite peak

    Figure  3.  High resolution XPS spectra of Ni2p (a), Co2p (b), P2p (c), and S2p (d) of NCS and 1%Co-Pi/NCS

    图  4  NCS和Co-Pi/NCS样品的LSV曲线(a)、Tafel斜率(b)、EIS曲线(c)和电化学双层电容 (Cdl) (d);NCS和1%Co-Pi/NCS样品在10 mA·cm−2电流密度下的计时电位曲线(e)及800 min测试前后的LSV曲线(f)

    J—Current density; Z'—Real part of impedance; Z''—Imaginary part of impedance; RHE—Reversible hydrogen electrode

    Figure  4.  LSV curves (a), Tafel slopes (b), EIS plots (c), and electrochemical double layer capacitance (Cdl) (d) of NCS and Co-Pi/NCS samples; Chronopotential curves under current density of 10 mA·cm−2 (e) and LSV curves before and after 800 min testing (f) of NCS and 1%Co-Pi/NCS

    图  5  NCS(100) (a)、CoPO4(010) (b)和CoPO4/NCS (c)的晶体结构模型;CoPO4/NCS的差分电荷密度(d);NCS (e)、CoPO4 (f)和CoPO4/NCS (g)的态密度;NCS (h)、CoPO4 (i)和CoPO4/NCS (j)表面吸附中间体的稳定结构和自由能;NCS (k)、CoPO4 (l)和CoPO4/NCS (m)表面吸附O原子的Bader电荷

    Efermi—Fermi energy; TDOS—Total density of state

    Figure  5.  Crystal structures of NCS(100) (a), CoPO4(010) (b) and CoPO4/NCS (c); Differential charge density of CoPO4/NCS (d); Densities of state of NCS (e), CoPO4 (f) and CoPO4/NCS (g); Stable structures and adsorption free energies of intermediates on NCS (h), CoPO4 (i) and CoPO4/NCS (j); Bader charges of NCS (k), CoPO4 (l) and CoPO4/NCS (m) adsorbed O atom

    表  1  CoxHyPO4复合NiCo2S4核壳结构(Co-Pi/NCS)样品制备参数

    Table  1.   Preparation parameter for CoxHyPO4 complex NiCo2S4 core-shell structure (Co-Pi/NCS) sample

    Sample mNCS/mg VPBS/mL VCo/μL Co-Pi content/wt%
    0.7%Co-Pi/NCS 10 15 26.25 0.7
    1%Co-Pi/NCS 10 15 37.5 1
    2%Co-Pi/NCS 10 15 75 2
    Notes: mNCS—Mass of NCS; VPBS—Volume of phosphate buffer solution (0.1 mol/L); VCo—Volume of Co(NO3)2·6H2O solution (0.5 mmol/L).
    下载: 导出CSV

    表  2  CoxHyPO4/NiCo2S4 (Co-Pi/NCS)与已报道的析氧反应(OER)电催化剂在10 mA·cm−2电流密度下的过电位比较

    Table  2.   Comparison of the overpotentials to achieve the oxygen evolution reaction (OER) current density of 10 mA·cm−2 for CoxHyPO4/NiCo2S4 (Co-Pi/NCS) with reported electrocatalysts

    Electrocatalyst Electrolyte P/mV Ref.
    CoxHyPO4/NiCo2S4 1 mol/L KOH 335 This work
    NiCo2S4@double-layered carbon nanospheres 1 mol/L KOH 344 [16]
    P-doped MnCo2O4 1 mol/L KOH 364 [28]
    CoO/CoxP 1 mol/L KOH 370 [29]
    In-doped CoO/CoP 1 mol/L KOH 365 [30]
    Co6Ni4P/nickel foam 1 mol/L KOH 373 [31]
    Co9S8/MnS sulfur/nitrogen nitrogen co-doped carbon nanosheets 1 mol/L KOH 360 [32]
    P-doped (Zn0.33Ni0.33Mn0.33)Co2O4 1 mol/L KOH 349 [33]
    NiO/NiCo2O4 1 mol/L KOH 350 [34]
    NiCo2S4/reduced graphene oxide 1 mol/L KOH 366 [35]
    P-doped manganese-cobalt oxide 1 mol/L KOH 520 [36]
    NiCo2O4/N-doped carbon nanotubes/NiCo 1 mol/L KOH 350 [37]
    Note: P—Overpotential at the OER current density of 10 mA·cm−2.
    下载: 导出CSV
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  • 收稿日期:  2024-05-07
  • 修回日期:  2024-07-03
  • 录用日期:  2024-07-05
  • 网络出版日期:  2024-07-18
  • 刊出日期:  2024-11-15

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