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光电催化与人工光合作用还原CO2研究进展

刘金瑞 张妍 孙诗书 石建军 孙天一 史载锋

刘金瑞, 张妍, 孙诗书, 等. 光电催化与人工光合作用还原CO2研究进展[J]. 复合材料学报, 2024, 41(10): 5049-5067. doi: 10.13801/j.cnki.fhclxb.20240204.003
引用本文: 刘金瑞, 张妍, 孙诗书, 等. 光电催化与人工光合作用还原CO2研究进展[J]. 复合材料学报, 2024, 41(10): 5049-5067. doi: 10.13801/j.cnki.fhclxb.20240204.003
LIU Jinrui, ZHANG Yan, SUN Shishu, et al. Advances in photoelectrocatalysis and artificial photosynthesis for the reduction of CO2[J]. Acta Materiae Compositae Sinica, 2024, 41(10): 5049-5067. doi: 10.13801/j.cnki.fhclxb.20240204.003
Citation: LIU Jinrui, ZHANG Yan, SUN Shishu, et al. Advances in photoelectrocatalysis and artificial photosynthesis for the reduction of CO2[J]. Acta Materiae Compositae Sinica, 2024, 41(10): 5049-5067. doi: 10.13801/j.cnki.fhclxb.20240204.003

光电催化与人工光合作用还原CO2研究进展

doi: 10.13801/j.cnki.fhclxb.20240204.003
基金项目: 国家自然科学基金(22168017);海南省自然科学基金(420QN259;222CXTD513;420QN251)
详细信息
    通讯作者:

    孙天一,博士,讲师,硕士生导师,研究方向为光催化 E-mail: tianyi870328@163.com

    史载锋,博士,教授,博士生导师,研究方向为材料化学 E-mail: zaifengshi@163.com

  • 中图分类号: TB333

Advances in photoelectrocatalysis and artificial photosynthesis for the reduction of CO2

Funds: National Natural Science Foundation of China (22168017); Hainan Provincial Natural Science Foundation of China (420QN259; 222CXTD513; 420QN251)
  • 摘要: 随着工业化的不断发展,化石燃料的过度使用产生的CO2导致了温室效应等问题,已经引起国际社会的高度关注,并制定了一系列应对措施。因此,对大气中CO2的还原回收技术研发具有迫切性和重要意义。光电催化是目前可用于还原CO2的具有良好应用前景的技术之一,为了对该技术进行更深入的研究,推动其实际应用,本文首先阐述了光催化、电催化、光电催化还原CO2的基本原理和优缺点,并举例介绍了各类催化剂还原CO2的效率。由于光催化是光合作用中的重要步骤之一,接着重点分析了光合作用在还原CO2研究现状和前景,提出人工光合作用还原CO2可行性与潜力。本文旨在为人工光合作用还原CO2提供新思路和参考,为减少大气中CO2的积累和应对当前的环境挑战提供新的见解和视角。

     

  • 图  1  用于CO2催化还原/转化为增值产品的常见光催化剂的分类[8]

    Figure  1.  Classification of common photocatalysts for CO2 catalytic reduction/conversion to value-added products[8]

    ZIF—Zeolitic imidazolate framework; PMOF—Polymeric metal-organic frameworks; MIL—Materials of institut lavoisier; MOF—Metal-organic frameworks

    图  2  用于CO2催化还原/转化为增值产品的常见电催化剂的分类[8]

    Figure  2.  Classification of common electrocatalysts for CO2 catalytic reduction/conversion to value-added products[8]

    图  3  叶绿素a与叶绿素b结构示意图

    Figure  3.  Structure diagram of chlorophyll a and chlorophyll b

    图  4  卟啉-石墨烯复合材料光生电子的转移过程[136]

    Figure  4.  Photogenerated electron transfer process of porphyrin-graphene composites[136]

    图  5  光合作用反应序列:明暗反应

    Figure  5.  Photosynthetic reaction sequence: Light-dark reaction

    NADP—Nicotinamide adenine dinucleotide phosphate; ADP—Adenosine diphosphate; NADPH—Nicotinamide adenine dinucleotide phosphate; ATP—Adenosine triphosphate

    表  1  部分非金属或金属负载半导体光催化剂复合材料用于CO2还原

    Table  1.   Several non-metallic or metal supported semiconductor photocatalyst composites for CO2 reduction

    Photocatalyst Main product Photocatalytic activity Ref.
    m-CeO2/g-C3N4 CH4 and CO CH4: 13.88 µmol·h−1·g−1; CO: 11.8 µmol·h−1·g−1 [54]
    SrCO3/SrTiO3 CO CO: 23.82 (100) μmol·h−1·g−1 [55]
    Fe2O3/Cu2O CO 5.0 μmol·g·cat−1 [56]
    Cu2ZnSnS4-ZnO CH4 138.90 μmol·g−1·L−1 [57]
    TiO2-SiO2 CH4 2.42 μmol·g−1 [58]
    Cu/TiO2 CH3OH 1.8 μmol·cm−2·h−1 [59]
    Sulfur-doped g-C3N4 CH3OH 1.12 μmol·g−1 [60]
    ZnPc/TiO2 HCOOH 978.6 μmol·g·cat−1 [61]
    GO-TiO2 CH3OH/C2H5OH 47.0 μmol·g−1·h−1/144.7 μmol·g−1·h−1 [62]
    Bi2S3 HC(O)OCH3 300.94 μmol·g−1 [63]
    Notes: m-CeO2—Mesoporous-CeO2; GO—Graphene oxide; ZnPc—Zinc-phthalocyanine.
    下载: 导出CSV

    表  2  一些用于CO2还原的选择性电催化剂

    Table  2.   Some selective electrocatalysts for CO2 reduction

    Electrocatalyst Electrolyte Main product Corresponding overpotential Ref.
    Fe-N4O 0.1 mol/L KHCO3, pH=6.8 CO 470 mV [88]
    In(OH)3-Cu2O 0.7 mol/L KHCO3 CO 290 mV [89]
    BiOI 0.5 mol/L NaHCO3, pH=6 HCOOH −0.40 V [90]
    Pyridoxine modification
    graphene oxide (GO-VB6-Cu)
    0.1 mol/L KHCO3, pH=6.8 CH3CH2OH 0.14 V [84]
    Graphite/carbon nanoparticle (NPs)/
    Cu/polytetrafluoroethylene (PTFE)
    7 mol/L KOH, pH>14 C2H4 −0.63 V [91]
    Cu2O/ZnO/Graphene(GN) 0.5 mol/L NaHCO3 C3H7OH −0.90 V [92]
    Cu/TiO2/GN 0.2 mol/L KI, pH=6.62 C2H5OH 0.84 V [93]
    Bi nanosheet 0.1 mol/L KHCO3, pH=6.8 HCOOH 420 mV [94]
    Nanoporous Au-Sn (NPAS) 0.5 mol/L KHCO3, pH=7.2 CO 0.45 V [95]
    下载: 导出CSV

    表  3  CO2还原的主要产物及其对应电位(pH=7)

    Table  3.   Main products of CO2 reduction and their corresponding potentials (pH=7)

    Reaction Eo(vs NHE)/V Product
    CO2 + e→·$\text{CO}_{2}^{-} $ −1.90 ·$\text{CO}_{2}^{-} $ anion radical
    2CO2 + 2H+ + 2e → H2C2O4 −0.87 Oxalate
    CO2 + 2H+ + 2e → HCOOH −0.61 Formic acid
    CO2 + 2H+ + 2e → CO + H2O −0.53 Carbon monoxide
    CO2 + 4H+ + 4e → HCHO + H2O −0.48 Formaldehyde
    CO2 + 6H+ + 6e → CH3OH + H2O −0.38 Methanol
    2CO2 + 12H+ + 12e → C2H5OH + 3H2O −0.33 Ethanol
    2CO2 + 14H+ + 14e → C2H6 + 4H2O −0.27 Ethane
    CO2 + 8H+ + 8e → CH4 + 2H2O −0.24 Methane
    Notes: Eo—Standard electrode potential; NHE—Normal hydrogen electrode.
    下载: 导出CSV

    表  4  用于CO2还原的几种光电催化界面

    Table  4.   Several photoelectrocatalytic interfaces for CO2 reduction

    Catalyst Number of electrons transferred Main product Yield/(μmol·gcat−1·h−1) Ref.
    Pt/TiO2 8 CH4 1361 [108]
    Cu@TiO2-Au 2 HCOOH N.A. [100]
    Au-ZnTe/ZnO 2 CO N.A. [109]
    Rh grain boundaries (GBs)/TiO2 12 C2H5OH 12.1 [110]
    NH3/g-C3N4 8, 6 CH4, CH3OH 1.39, 1.87 [111]
    NH2-C/Cu2O 2 HCOOH 138.65 [112]
    Co-ZIF9/g-C3N4 2 CO 495 [113]
    UiO-66/MoS2 8 CH3COOH 39 [114]
    Ni(II) MOF/g-C3N4 2, 8 CO, CH4 13.6 [115]
    Note: N.A.—Not available.
    下载: 导出CSV
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  • 收稿日期:  2023-11-13
  • 修回日期:  2024-01-16
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