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Defect engineering of carbon-based electrocatalysts for the CO2 reduction reaction: A review

LU Yan-kun CHENG Bai-xue ZHAN Hao-yu ZHOU Peng

卢衍堃, 程白雪, 战浩宇, 周鹏. 碳基电催化剂缺陷工程用于CO2还原反应. 新型炭材料(中英文), 2024, 39(1): 17-41. doi: 10.1016/S1872-5805(24)60833-4
引用本文: 卢衍堃, 程白雪, 战浩宇, 周鹏. 碳基电催化剂缺陷工程用于CO2还原反应. 新型炭材料(中英文), 2024, 39(1): 17-41. doi: 10.1016/S1872-5805(24)60833-4
LU Yan-kun, CHENG Bai-xue, ZHAN Hao-yu, ZHOU Peng. Defect engineering of carbon-based electrocatalysts for the CO2 reduction reaction: A review. New Carbon Mater., 2024, 39(1): 17-41. doi: 10.1016/S1872-5805(24)60833-4
Citation: LU Yan-kun, CHENG Bai-xue, ZHAN Hao-yu, ZHOU Peng. Defect engineering of carbon-based electrocatalysts for the CO2 reduction reaction: A review. New Carbon Mater., 2024, 39(1): 17-41. doi: 10.1016/S1872-5805(24)60833-4

碳基电催化剂缺陷工程用于CO2还原反应

doi: 10.1016/S1872-5805(24)60833-4
基金项目: 山东省自然科学青年基金项目(ZR2023QB235);催化材料制备及应用湖北省重点实验室开放基金项目(202306404);山东省泰山学者工程项目
详细信息
    通讯作者:

    周 鹏,博士,副教授. E-mail:pengzhou@qdu.edu.cn

  • 中图分类号: TQ127.1+1

Defect engineering of carbon-based electrocatalysts for the CO2 reduction reaction: A review

Funds: This work was financially supported by the Natural Science Foundation of Shandong Province (ZR2023QB235), Open Fund of Hubei Key Laboratory of Processing and Application of Catalytic Materials (202306404) and the Taishan Scholar Program of Shandong Province
More Information
  • 摘要: 电催化二氧化碳(CO2)还原是通过电能将温室气体CO2转化为高附加值化学品。碳基材料因其成本低、活性高的特点,被广泛应用于包括电催化CO2还原在内的多种电化学反应中。近年来,通过缺陷工程在碳基材料中构建不对称中心优化材料的物理化学性质,提高电催化活性这一策略引起了研究人员的广泛关注。本文综述了缺陷碳基材料的类型、构建方法和缺陷表征方法,并进一步梳理了缺陷工程的优势、各种缺陷构建方法和表征方法的优缺点。最后,对缺陷碳基材料在电催化CO2还原中面临的挑战和机遇进行了展望。相信本文能为缺陷碳基材料在CO2还原中的发展提供针对性的建议。
  • FIG. 2910.  FIG. 2910.

    FIG. 2910..  FIG. 2910.

    .  Scheme 1. Schematic illustration for the types of the defective in carbon materials

    Figure  1.  (a) The synthesis process of the K-defect-carbon; (b, c) The adsorption free energy change and the values of UL(CO2RR)−UL(HER) on V0, V1, V10, and V12 sites[46]. Copyright 2022, Wiley-VCH. (d) The theoretical computational model molecule of the F-doped defect carbon; (e, f) The free energy change of different catalysts for ECRR and the related schematic of ECRR pathway[48]. Copyright 2018, Wiley-VCH. (g) The N-doped, P-doped, and N,P-co-doped carbon configurations. (h) Difference in limiting potentials for ECRR and HER over a simulated N,P-co-doped carbon configuration[49]. Copyright 2020, Wiley-VCH

    Figure  2.  (a) The synthesis process diagram; (b) electron energy loss spectrum; (c) scanning transmission electron microscopy and energy dispersive mapping spectra; (d, e) low and high-angle toroidal dark-field scanning transmission electron microscopy of the Fe-N-C-750 material[50]. Copyright 2018, Wiley-VCH. (f) The reaction mechanism diagram; (g, h) The low and high-angle toroidal dark-field scanning transmission electron microscopy (the inset exhibits the related energy dispersive mapping spectrum of Zn); (i, j) X-ray absorption near edge structure and extended X-ray absorption fine structure spectra of the Zn-microporous N-doped carbon catalyst[55]. Copyright 2020, American Chemical Society. (k) The linear sweep curve; (l) electrochemical impedance spectra; m) schematic of the catalytic enhancement mechanism of various catalysts including defective carbon[59]. Copyright 2020, American Chemical Society

    Figure  3.  (a-c) The linear sweep curves. (d) Faraday efficiency. (e, f) C K-edge X-ray absorption near edge structure spectra and related expanded view; (g) theoretical computational model molecule; (h) free energy change of the different N-doped carbon materials[61]. Copyright 2019, Wiley-VCH. (i) The Faraday efficiency; (j) current density of the NRMC-800, NRMC-900 and NRMC-1000 materials at different applied potentials; (k) The N element content; (l) ID/IG with FECO for NRMC-800, NRMC-900 and NRMC-1000 at the applied potential of −0.7 V; (m) The Faraday efficiency; (n) current density of the NRMC-900. NRMC-900-2 and NRMC-900-3 materials at different applied potentials; (o) The EPR spectra; (p) Double-integrated intensity of defects in EPR spectra for NMC and NRMC catalysts[62]. Copyright 2018, American Chemical Society

    Figure  4.  (a) The nitrogen dopants model system of reactive molecular dynamics (RMD) simulation, i.e., pyridinic-N, pyrrolic-N, and graphitic-N. (b) The structural evolution of the active site in ECRR process. (c) The free energy diagram for ECRR at N-doped sites, penta-hole, and 585-1 sites. (d) The partial charge distribution at defect sites[64]. Copyright 2020, Wiley-VCH. (e) The N-doped structure model of pyridinic-N, pyrrolic-N and graphitic-N.[71] Copyright 2017, Wiley-VCH. (f) The structural model of N-doped carbon and the correspondence between Tafel value and N content[74]. Copyright 2016, Wiley-VCH. (g) The structural model of N-doped carbon nanotube[75]. Copyright 2015, American Chemical Society. (h) The structural model of pyrrolic-N, graphitic-N, S-doped carbon nanosheet[88]. Copyright 2018, Wiley-VCH

    Figure  5.  (a) The schematic diagram of the process of converting wood into defective carbon material by pyrolysis method[91]. Copyright 2019, Wiley-VCH. (b) The schematic diagram of the preparation process of the N-doped carbon nanotube by pyrolysis[97]. Copyright 2019, Wiley-VCH. (c) The schematic diagram of the preparation process of the defective carbon materials by nitrogen removal pyrolysis method[98]. Copyright 2021, American Chemical Society. (d) The model structure of the P-modified carbon material prepared by chemical vapor deposition[103]. Copyright 2018, Royal Society of Chemistry

    Figure  6.  (a) The schematic diagram of structural evolution of the defective carbon materials prepared by ball milling method[106]. Copyright 2019, Wiley-VCH. (b) The schematic diagram of the preparation of the defective graphene by chemical etching[110]. Copyright 2019, American Chemical Society. (c) The schematic diagram of the preparation of the defective graphene by plasma etching method[115]. Copyright 2016, Royal Society of Chemistry. (d) The schematic diagram of the self-supporting defective carbon material prepared by plasma treatment[116]. Copyright 2017, Wiley-VCH

    Figure  7.  (a, b) STEM images of the defective carbon material. (c) Raman spectra and (d) C 1s XPS spectrum of the defective carbon material[120]. Copyright 2019, Wiley-VCH. (e) The comparison of elemental content ratio of different defective carbon materials. (f-l) C 1s XPS spectra of different defective carbon materials. (m) The comparison of AC-sp3/AC-sp2 ratio of different defective carbon materials. (n-p) HRTEM images of different defective carbon materials[121]. Copyright 2023, Springer Nature Publishing Group. (q, r) TEM and STEM images of the defective graphene. (s) Raman spectrum; and (t) C1s XPS spectrum of the defective graphene[122]. Copyright 2017, Wiley-VCH

    Figure  8.  (a, b) STM and related fast fourier transform images of the defective graphene material[125]. Copyright 2022, American Physical Society. (c) EXAFS spectrum and (d) EPR spectrum of the defective carbon material[99]. Copyright 2023, American Chemical Society. (e) C K-edge XANES spectrum of the defective carbon material[128]. Copyright 2018, American Chemical Society. (f) The EPR spectrum of ECM-800[129]. Copyright 2022, Wiley-VCH. (g) PAS spectrum of the defective PBA-60. (h, i) The schematic diagram of positron capture[130]. Copyright 2019, Springer Nature Publishing Group

    Table  1.   Summary of defect category, defect effect, synthesis strategy and performance of reported electrocatalysts

    ElectrocatalystsDefect categoryDefect effectSynthesis strategyPerformance
    K-defect-C[46] Vacancy defect Enhance CO2 adsorption and the formation of COOH intermediate Pyrolysis method FE up to 99% at −0.45 V vs. RHE
    D-C-X[61] Vacancy defect Optimization the adsorption of COOH intermediate Pyrolysis method (nitrogen removal) FE up to 94.5% at −0.6 V vs. RHE
    NRMC-X[62] Edge defect Optimization the adsorption of COOH intermediate; Inhibition of H intermediate adsorption Pyrolysis method FE up to 80% at −0.49 V vs. RHE
    NPC[64] Topological defect Enhance CO2 adsorption and the formation of COOH intermediate; Inhibition of H intermediate adsorption Pyrolysis method (nitrogen removal) FE up to 95.2% at −0.6 V vs. RHE
    Fe2C-Cs@DC[65] Topological defect Promote CO desorption Pyrolysis method FE up to 97.1% at −0.7 V vs. RHE
    DNG-SAFe[66] Topological defect Optimization the adsorption of COOH and CO; Inhibition of H adsorption; Promote the charge transfer Pyrolysis method FE up to 90% at −0.75 V and −0.85 V vs. RHE
    Fe+-N-C[5] Doping defect Enhance CO2 adsorption; Reduce CO adsorption Pyrolysis
    method
    FE higher than 90% at −0.45 V vs. RHE
    F-CPC[57] Doping defect Improve electrical conductivity and the adsorption of CO2 and K+; Reduce the CO2 conversion energy barrier Pyrolysis method FE up to 88.3% at −1.0 V vs. RHE
    CNFs[67] Doping defect Increase the binding energies between the CO2 intermediates and the CNF Pyrolysis method FE up to 98% at −0.573 V vs. RHE
    NC@Ni/C[68] Doping defect Enhance CO2 adsorption and the formation of COOH intermediate Pyrolysis method FE up to 97% at −1.05 V vs. RHE
    Fe-N-C[70] Doping defect Optimization the adsorption of COOH intermediate; Inhibition of H intermediate adsorption Pyrolysis method FE up to 99% at −0.24 V vs. RHE
    CN-CNTs[71] Doping defect Inhibition of H intermediate adsorption CVD FE up to 88% at −0.5 V vs. RHE
    Co@Pc/C[72] Doping defect Optimization the adsorption of COOH intermediate Pyrolysis method FE up to 84% at −0.9 V vs. RHE
    NPC[73] Doping defect Optimization the adsorption of COOH and CO Pyrolysis method FE up to 98.4% at −0.55 V vs. RHE
    NCNTs[74] Doping defect Stabilization of the key intermediate CO2·- Pyrolysis method FE up to 90% at −0.9 V vs. RHE
    1D/2D NR/CS-X[83] Doping defect Optimization the adsorption of COOH and CO Pyrolysis method FE up to 94.2% at −0.45 V vs. RHE
    N doped ultra nano-crystalline diamond[84] Doping defect Optimization the adsorption of COOH and CO CVD FE up to 82% at −1.1 V vs. RHE
    N,B-co-doped graphitic carbon loaded with Co nanoparticles[86] Doping defect Increase electrical conductivity, active area, charge density distribution Pyrolysis method FE up to 97.9% at −2.4 V vs. Ag/Ag+
    N,F co-doped carbon nanosheet[87] Doping defect Improve electrical conductivity and charge density distribution; Optimization the adsorption of COOH intermediate Pyrolysis method FE up to 90% at −0.49 V vs. RHE
    NSHCF[88] Doping defect Reduce the CO2 conversion energy barrier; Increase active area Pyrolysis method FE up to 94% at −0.7 V vs. RHE
    P-OLC[103] Doping defect Optimization the adsorption of COOH intermediate; Improve electrical conductivity CVD FE up to 81% at −0.9 V vs. RHE
    BDD[104] Doping defect Formation of sp3-bonded carbon; Improve electrical conductivity and durability CVD FE up to 74% at −1.7 V vs. Ag/Ag+
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  • 收稿日期:  2023-10-13
  • 录用日期:  2023-11-27
  • 修回日期:  2023-11-27
  • 网络出版日期:  2023-12-06
  • 刊出日期:  2024-02-01

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