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过渡金属磷化物基材料在电催化析氢中的改性策略:现状及展望

雷琬莹 吴攀 司渭滨 赵亮 谭自强 杨鑫鑫 乔明涛 张婷婷

雷琬莹, 吴攀, 司渭滨, 等. 过渡金属磷化物基材料在电催化析氢中的改性策略:现状及展望[J]. 复合材料学报, 2024, 41(4): 1737-1749. doi: 10.13801/j.cnki.fhclxb.20231120.002
引用本文: 雷琬莹, 吴攀, 司渭滨, 等. 过渡金属磷化物基材料在电催化析氢中的改性策略:现状及展望[J]. 复合材料学报, 2024, 41(4): 1737-1749. doi: 10.13801/j.cnki.fhclxb.20231120.002
LEI Wanying, WU Pan, SI Weibin, et al. Modification strategies of transition metal phosphide-based materials in electrocatalytic hydrogen evolution: Current status and prospect[J]. Acta Materiae Compositae Sinica, 2024, 41(4): 1737-1749. doi: 10.13801/j.cnki.fhclxb.20231120.002
Citation: LEI Wanying, WU Pan, SI Weibin, et al. Modification strategies of transition metal phosphide-based materials in electrocatalytic hydrogen evolution: Current status and prospect[J]. Acta Materiae Compositae Sinica, 2024, 41(4): 1737-1749. doi: 10.13801/j.cnki.fhclxb.20231120.002

过渡金属磷化物基材料在电催化析氢中的改性策略:现状及展望

doi: 10.13801/j.cnki.fhclxb.20231120.002
基金项目: 国家自然科学基金(51902443);陕西省教育厅重点研究项目(22JY039;22JY037)
详细信息
    通讯作者:

    雷琬莹,博士,副教授,硕士生导师,研究方向为纳米复合材料、能源转化与利用 E-mail: leiwy@xauat.edu.cn

  • 中图分类号: TB331

Modification strategies of transition metal phosphide-based materials in electrocatalytic hydrogen evolution: Current status and prospect

Funds: National Natural Science Foundation of China (51902443); Key Research Project of Shaanxi Education Department (22JY039; 22JY037)
  • 摘要: 氢能作为一种零碳燃料,被认为是替代化石能源的理想能源。电催化析氢(HER)是一种绿色环保技术,可以裂解水分子制备氢气。因此开发低廉高效且稳定性好的非贵金属催化剂对于解决能源危机和可持续发展尤为重要。过渡金属磷化物(TMPs)具有良好的导电性、多变的化学组成、丰富的储量和稳定的理化性质,是HER反应重要的催化剂之一。本文首先介绍了HER反应机制及TMPs的结构特点,然后总结了TMPs的合成方法包括液相合成法和气-固合成法等,接着重点分析了现有TMPs的改性策略如形貌调控、缺陷调控、元素掺杂和界面复合,最后对未来TMPs的发展方向提出了展望。

     

  • 图  1  电催化析氢(HER)反应机制图

    Figure  1.  Diagram of the electrocatalytic hydrogen evolution reaction (HER) reaction mechanism

    图  2  过渡金属磷化物(TMPs)的晶胞示意图

    Figure  2.  Schemtaic of the unit cell for transition metal phosphides (TMPs)

    P—Phosphorus; M—Metal

    图  3  NiP-Pt/Co(OH)2 (a)[30]和CoFeP/还原氧化石墨烯(rGO) (b)的合成过程示意图[32]

    Figure  3.  Schematic illustration of the synthesis process of NiP-Pt/Co(OH)2 (a)[30] and CoFeP/reduced graphene oxide (rGO) (b)[32]

    GO—Graphene oxide; LDH—Layered double hydroxides

    图  4  Fe-CoP (a)[39]和3D WP2 纳米线 (b)[42]的SEM图像;(c) FeP、Mg-FeP和Vc-FeP的(111)晶面的结合能图[43];(d) CoP的线性扫描伏安曲线[44]

    Figure  4.  SEM images of Fe-CoP (a)[39]and 3D WP2 nanowire (b)[42]; (c) Free energy diagram of FeP, Mg-FeP and Vc-FeP of (111) crystal plane[43]; (d) Liner sweep voltammetry curves of CoP[44]

    Vc-FeP—Fe-vacancy-rich FeP; F-CoP-Vp—F doping and P vacancies CoP; U—Voltage; RHE—Reversible hydrogen electrode

    图  5  (a) W-NiCoP/镍泡沫(NF)的HER机制图[49];(b) Cu-CoP材料不同位点的HER反应能垒图[50];(c) H和金属位之间态密度图[51];(d) 恒电位下C-Co2P的原位拉曼光谱及等值线图[72]

    Figure  5.  (a) HER mechanism for W-NiCoP/nickel foam (NF)[49]; (b) HER free energy diagrams for various sites on Cu-CoP[50]; (c) Partial density of states between H and active metallic site[51]; (d) In-situ Raman spectra and corresponding contour plots of C-Co2P at constant potentials[72]

    OCP—Open circuit potential; DOS—Density of states

    图  6  CoP3/Fe2P@NF (a)[23]和CoP-WP/rGO (b)[77]的HRTEM图像;(c) CoP3/Fe2P@NF的线性扫描伏安曲线[23];(d) CoP-WP/rGO的结合能图[77]

    Figure  6.  HRTEM images of CoP3/Fe2P@NF (a)[23] and CoP-WP/rGO (b)[77]; (c) Liner sweep voltammetry curves of CoP3/Fe2P@NF[23];(d) Free-energy diagram of CoP-WP/rGO[77]

    表  1  通过缺陷调控改善TMPs 基电催化剂的HER性能的总结

    Table  1.   Summary of the HER performance for TMPs-based electrocatalysts by vacancy creation

    Catalyst Vacancy
    Substrate Current density/
    (mA·cm−2)
    Overpotential/
    mV
    Tafel slope/
    (mV·dec−1)
    Ref.
    WP Cationic vacancies Glassy carbon electrode 100 175 58 [18]
    Vc-FeP Cationic vacancy Ti foils 10 108 33 [43]
    F-CoP-Vp Anion vacancies Carbon fiber cloth 10 108 88.9 [44]
    V-Ni2P/NF Cationic vacancy Nickel foam (NF) 10 81 48 [45]
    WP Cationic vacancies Glassy carbon electrode 300 80.6 52 [46]
    S-CoP-p P vacancies Ti mesh 100 114 58.4 [47]
    下载: 导出CSV

    表  2  通过元素掺杂改善TMPs 基电催化剂的HER性能的总结

    Table  2.   Summary of the HER performance for TMPs-based electrocatalysts by elemental doping

    Catalyst Substrate Current density/(mA·cm−2) Overpotential/mV Tafel slope/(mV·dec−1) Ref.
    MnCoP/CC Carbon cloth (CC) 10 65 46.16 [29]
    Fe-CoP@CC Carbon cloth 10 49 149 [39]
    W-NiCoP/NF Nickel foam (NF) 10 29.6 38 [49]
    Cu-CoP NAs/CP Carbon paper (CP) 10 81 83.5 [50]
    S-WP2 Carbon cloth 10 115 75 [51]
    Zn/F-NiCoP/NF Nickel foam 10 59 81.03 [52]
    V-CoxP@NC Carbon paper 10 106 93 [53]
    Mn-CoP Glassy carbon electrode 10 148 61 [54]
    CoP-N/Co foam Co foam 50 100 50.9 [55]
    W, Ru-NiP2 Nickel foam 10 17.8 67.5 [56]
    F0.25CP-G Graphene (G) 10 66 61 [57]
    O-CoP Glassy carbon electrode 10 98 59.9 [58]
    Mo-CoFeP/NC Glassy carbon electrode 10 145 68 [59]
    pCoMo-P/ NF Nickel foam 10 49 55.02 [60]
    O-CoP Glassy carbon electrode 10 116 59 [61]
    Mn-doped CoP/NF Nickel foam 10 60 56.7 [62]
    V-Ni5P4 Nickel foam 10 13 [63]
    Co-Cu3P/CF Cu foam (CF) 100 250 75 [64]
    CoFeP/C Graphene 10 42.1 59 [65]
    V-CoP/CC Carbon cloth 10 71 67.6 [66]
    Mn-CoP PMFs/CC Carbon cloth 10 90 86.1 [67]
    V-doped CoP/NF Nickel foam 10 84.6 79.2 [68]
    CoFeP/NF Nickel foam 10 29.8 68.4 [69]
    Ga-CoP NSs/CFP Carbon fiber paper (CFP) 10 44 62 [70]
    Nb-CoP Glassy carbon electrode 10 99 59.4 [71]
    Notes: NAs—Nanosheet arrays; PMFs—Peony-like micro-flower; NSs—Nanosheets; NC—Nitrogen doped carbon.
    下载: 导出CSV

    表  3  界面复合调控TMPs 基电催化剂的HER性能的总结

    Table  3.   Summary of the HER performance for TMPs-based catalysts by interface engineering

    Catalyst Substrate Current density/(mA·cm−2) Overpotential/mV Tafel slope/(mV·dec−1) Ref.
    NiCoP@FePx 10 82.5 69.1 [17]
    CoP3/Fe2P@NF Nickel foam 10 81 104.4 [23]
    Co2P&CoP@NC Nickel foam 10 62.8 60 [33]
    NiP-Pt/Co(OH)2 Nickel foam 10 40 49.85 [30]
    CoFeP/rGO Glassy carbon electrode 10 101 169 [32]
    CoFeP NS@Fe-CoP Nickel foam 10 78 73 [73]
    NiFe LDH/CoFeP/NF Nickel foam 50 198 75.2 [74]
    CoP/NiCoP N-doped carbon 10 75 64 [75]
    Cu3P/NiCoP Nickel-cobalt foam 10 51 89 [76]
    CoP-WP/rGO Nickel foam 10 138 62 [77]
    g-C3N4/Cu3P Cu foil 10 67 45 [78]
    W2C/WP@NC Glassy carbon electrode 10 116.37 59.07 [79]
    NiP/Wood Pristine wood 10 83 73.2 [80]
    Cu3P@NPC Copper foam 10 81.94 81.25 [81]
    CoFeP NFs/NPCNT Glassy carbon electrode 10 132 62.9 [82]
    CoP/Mo2CTx Glassy carbon electrode 10 78 66 [83]
    N-CoO@CoP Nickel foam 100 201 37 [84]
    Fe2O3-TiO2/rGO Reduced graphene oxide 10 96 98 [85]
    Ni2P@NPCNFs Carbon cloth 10 63.2 56.7 [86]
    CoFeP NS@NCNF Nickel foam 10 113 108 [87]
    CoFeOH/CoFeP/IF Iron foam (IF) 100 114.9 128.37 [88]
    Notes: NPC—Nitrogen and phosphorus co-doped carbon; NPCNT—Nitrogen and phosphorus co-doped carbon nanotubes; NPCNFs—Nitrogen-doped porous carbon nanofibers; NCNF—Nitrogen-doped carbon nanofiber; NFs—Nanoframes; MoCT—Molybdenum carbide (T is the surface terminal group).
    下载: 导出CSV
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出版历程
  • 收稿日期:  2023-09-05
  • 修回日期:  2023-11-03
  • 录用日期:  2023-11-09
  • 网络出版日期:  2023-11-21
  • 刊出日期:  2024-04-15

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