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摘要:
通过电化学方法来减少二氧化碳（CO2），同时生产燃料和高附加值化学品，是一种克服全球变暖问题的有效策略，对于缓解能源和环境的双重压力具有重要的现实意义。由于CO2稳定的分子结构，设计高选择性、高能效和低成本的电催化剂是关键。石墨烯及其衍生物因其独特且优异的物理、力学和电学性能，相对较低的成本，使其在CO2电还原方面具有竞争力。此外，石墨烯基材料的表面可以通过使用不同的方法进行改性，包括掺杂、缺陷工程、构建复合结构和包覆形状。首先，本文综述了电化学CO2还原的基本概念、评价标准，以及催化原理和过程。其次，简要介绍了石墨烯基催化剂的制备方法，并按照催化位点的类别，总结了石墨烯基催化剂近年来的研究进展。最后，对CO2电还原技术未来发展方向进行了探讨与展望。
Abstract:The reduction of carbon dioxide (CO2) by electrochemical methods for the production of fuels and value-added chemicals is an effective strategy for overcoming the global warming problem. Due to the stable molecular structure of CO2, the design of highly selective, energy-efficient and cost-effective electrocatalysts is key. For this reason, graphene and its derivatives are competitive for CO2 electroreduction with their unique and excellent physical, mechanical and electrical properties and relatively low cost. In addition, the surface of graphene-based materials can be modified using different methods, including doping, defect engineering, production of composite structures and wrapped shapes. We first review the fundamental concepts and criteria for evaluating electrochemical CO2 reduction, as well as the catalytic principles and processes. Methods for preparing graphene-based catalysts are briefly introduced, and recent research on them is summarized according to the categories of the catalytic sites. Finally, the future development direction of CO2 electroreduction technology is discussed.
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Key words:
- Graphene /
- Carbon dioxide reduction /
- Electrocatalysis /
- Nanomaterials /
- Renewable energy
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图 2 （a）NGQDs的TEM照片，（b）NGQDs的HRTEM照片，（c）NGQDs在不同电势下的法拉第效率图[104]；（d）GQD-NH2-H的TEM照片（插图为HRTEM照片），（e）不同-NH2含量的GQD在不同电势下的CH4法拉第效率图，（f）不同-NH2含量的GQD在不同电势下的CH4部分电流密度图[105]；（g）N-aGQDs-A9的TEM照片，（h）N-aGQDs-A9的HRTEM照片，（i）N-aGQDs-A9在−0.98 V (vs. RHE)的恒定电压下工作的稳定性能图[106]
Figure 2. (a) TEM and (b) HRTEM images of the NGQDs, (c) Faradaic efficiency at various applied potential for NGQDs[104]. (d) TEM and HRTEM images (inset) of the GQD-NH2-H, (e) Faradaic efficiency of CH4, (f) Current density of CH4[105]. (g) TEM and (h) HRTEM images of the N-aGQDs-A9, (i) Stability of N-aGQDs-A9 operated at a constant potential of -0.98 V (vs. RHE)[106]. Reprinted with permission
图 4 （a）N-GRW的合成过程示意图[84]；（b）BN-C-1的合成过程示意图[85]；（c）PGA的合成过程示意图[116]
Figure 4. (a) Schematic illustration of the synthesis process of N-GRW[84]. (b) Schematic illustration of the synthesis process of BN-C-1[85]. (c) Schematic illustration of the synthesis process of PGA[116]. Reprinted with permission
图 5 （a）Fe-N-G-p催化剂的合成过程示意图[87]；（b）Fe/NG催化剂的合成过程示意图[121]；（c）催化剂的合成过程示意图[90]；（d）单原子FeN4和FeN5催化剂的合成路线[89]
Figure 5. (a) Schematic of the synthesis process of the Fe-N-G-p catalyst[87]. (b) Schematic of the synthesis process of the Fe/NG catalyst[121]. (c) Schematic of the synthesis process of the rGO-PVP-ZIFc catalyst[90]. (d) Synthetic route towards single-atom FeN4 and FeN5 catalysts[89]. Reprinted with permission
图 6 （a）CoPc-NVG/CC杂化化合物的合成过程示意图，以及NVG中与氮位相连的CoPc分子的原子构型[118]；（b）DrGO-CoPc的合成过程示意图[119]；（c）N-CoMe2Pc/NRGO合成过程示意图[95]；（d）NapCo@SNG合成过程示意图[102]；（e）Co-u-COF/G的合成过程示意图[103]；（f）CGF-CoTMPyP的合成过程示意图[117]
Figure 6. (a) The schematic illustration of the synthesis process of CoPc-NVG/CC hybrids, and the atomic configurations of a CoPc molecule bonded to the nitrogen site in NVG[118]. (b) Schematic illustration of the synthesis process of DrGO-CoPc[119]. (c) Schematic illustration of the synthesis process of N-CoMe2Pc/NRGO[95]. (d) Schematic illustration of the synthesis process of NapCo@SNG[102]. (e) Schematic illustration of the synthesis process of Co-u-COF/G[103]. (f) Schematic illustration of the synthesis process of CGF-CoTMPyP[117]. Reprinted with permission
图 7 （a）Ni2+@NG催化剂的合成示意图[83]；（b）NiSA-NGA的合成示意图[80]；（c）Ni-N-MEGO的合成示意图[115]；（d）Ni-N-rGO的合成示意图[124]；（e）Ni-B2N4的合成示意图[125]；（f）使用可回收的氯化钠模板大规模生产3D SAM-G催化剂的合成示意图[91]；（g）Ni-NG-acid的合成示意图[81]
Figure 7. (a) Schematic illustration of the synthesis process of Ni2+@NG catalyst[83]. (b) Schematic illustration of the synthesis process of NiSA-NGA[80]. (c) Schematic illustration of the synthesis process of Ni-N-MEGO[115]. (d) Schematic illustration of the synthesis process of Ni-N-rGO[124]. (e) Schematic illustration of the synthesis process of Ni-B2N4[125]. (f) Schematic illustration for mass production of 3D SAM-G catalysts using recyclable NaCl templates[91]. (g) Schematic illustration of the synthesis process of Ni-NG-acid[81]. Reprinted with permission
图 8 （a）Zn-N-G的合成示意图[126]；（b）Mo@NG的合成示意图[128]；（c）Li-N, O/C的合成路线示意图[129]；（d）Ag2-G的合成示意图[130]；（e）Bi单原子的合成示意图[113]；（f）在N掺杂石墨烯上大规模合成单原子Snδ+的合成示意图[82]
Figure 8. (a) Schematic illustration of the synthesis process of Zn-N-G[126]. (b) Schematic illustration of the synthesis process of Mo@NG[128]. (c) Schematic illustration of the synthetic route leading to Li-N, O/C[129]. (d) Schematic illustration of the synthesis process of Ag2-G[130]. (e) Schematic illustration of the synthesis process of Bi single atom[113]. (f) Scheme illustration for large-scale synthesis of the single-atom Snδ+ on N-doped graphene[82]. Reprinted with permission
图 11 （a）不同炭材料（CB、GA和NGAhdrz）负载的铋催化剂的合成过程和CO2RR性能示意图[107]；（b）具有多层结构的In/N-dG催化剂制备示意图[136]
Figure 11. (a) Schematic diagram of the synthesis process and the CO2RR performance of Bismuth catalysts supported on different carbon materials (CB, GA, and NGAhdrz)[107]. (b) Schematic diagram illustrating the preparation of In/N-dG catalyst with multilayer structure[136]. Reprinted with permission
图 12 （a）Cu-In/PNGC的合成示意图[137]；（b）CuSn-NP/NG的合成示意图[138]；（c）CuSn-LIG的合成示意图[114]
Figure 12. (a) Schematic illustration of the synthesis process of Cu-In/PNGC[137]. (b) Schematic illustration of the synthesis process of CuSn-NP/NG[138]. (c) Schematic illustration of the synthesis process of CuSn-LIG[114]. Reprinted with permission
图 14 （a）SnO2/tert-GO的合成示意图[142]；（b）Bi2O3/p-rGO的合成示意图[143]；（c）In2O3
$\supset $ NC@GO的合成示意图[144]；（d）NG-Co3O4和RG-Co3O4电催化剂的合成示意图[145]；（e）rGO-Co3O4的合成示意图[146]Figure 14. (a) Schematic illustration of the synthesis process of SnO2/tert-GO[142]. (b) Schematic illustration of the synthesis of Bi2O3/p-rGO[143]. (c) Schematic illustration of the synthesis of In2O3
$\supset $ NC@GO[144]. (d) Schematic illustration of the synthesis of NG-Co3O4 and RG-Co3O4 catalysts[145]. (e) Schematic illustration of the synthesis of rGO-Co3O4[146]. Reprinted with permission
图 15 （a）CG electrodes的合成示意图[147]；（b）Cu2O/Cu@C/NG的合成示意图[148]；（c）Cu2O/NRGO的合成示意图[149]；（d）CuO/NG_AN的合成示意图[150]；（e）NG/Cu、rGO/Cu和BG/Cu的合成及CO2RR选择性示意图[151]
Figure 15. (a) Schematic illustration of the synthesis process of CG electrodes[147]. (b) Schematic illustration of the synthesis of Cu2O/Cu@C/NG[148]. (c) Schematic illustration of the synthesis of Cu2O/NRGO[149]. (d) Schematic illustration of the synthesis of CuO/NG_AN[150]. (e) Schematic illustration of the difference in selectivity over NG/Cu, rGO/Cu, and BG/Cu in electrochemical CO2RR[151]. Reprinted with permission
图 17 （a）CuS/N, S-rGO的合成示意图[108]；（b）2D In2S3-rGO的合成示意图[109]；（c）Ag2S/N-S-doped rGO的合成示意图[154]；（d）rGO-PEI-MoSx的合成示意图[155]
Figure 17. (a) Schematic illustration of the synthesis process of CuS/N, S-rGO[108]. (b) Schematic illustration of the synthesis of 2D In2S3-rGO[109]. (c) Schematic illustration of the synthesis process of Ag2S/N-S-doped rGO[154]. (d) Schematic illustration of the synthesis process of rGO-PEI-MoSx[155]. Reprinted with permission
表 1 CO2电化学还原的热力学反应及其相应的标准氧化还原电势[35]
Table 1. The electrochemical thermodynamic reactions for CO2 reduction and their corresponding standard redox potentials[35]. Reprinted with permission
Products Acid Base Equation E0/V Equation E0/V H2 2H++2e−→H2 0.000 2H2O+2e−→H2+2OH− −0.828 CO CO2+2H++2e−→CO+H2O −0.104 CO2+H2O+2e−→CO+2OH− −0.932 CH4 CO2+8H++8e−→CH4+2H2O 0.169 CO2+6H2O+8e−→CH4+8OH− −0.659 CH3OH CO2+6H++6e−→CH3OH+H2O 0.016 CO2+5H2O+6e−→CH3OH+6OH− −0.812 HCOOH CO2+2H++2e−→HCOOH −0.171 CO2+H2O+2e−→HCOO−+OH− −0.639 C2H4 2CO2+12H++12e−→C2H4+4H2O 0.085 2CO2+8H2O+12e−→C2H4+12OH− −0.743 C2H6 2CO2+14H++14e−→C2H6+4H2O 0.144 2CO2+10H2O+14e−→C2H6+14OH− −0.685 CH3CH2OH 2CO2+12H++12e−→CH3CH2OH+3H2O 0.084 2CO2+9H2O+12e−→CH3CH2OH+12OH− −0.744 CH3COOH 2CO2+8H++8e−→CH3COOH+2H2O 0.098 2CO2+5H2O+8e−→CH3COO−+7OH− −0.653 C3H7OH 3CO2+18H++18e−→CH3CH2CH2OH+5H2O 0.095 3CO2+13H2O+18e−→CH3CH2CH2OH+18OH− −0.733 
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表 2 CO2RR对不同产物的标准电极电势（pH=7）[63-65]
Table 2. Standard electrode potentials of CO2RR towards different products at pH=7[63-65]
Reaction E0(vs. RHE)/V Products CO2 + 2H+ + 2e− → CO + H2O −0.10 CO CO2 + 2H+ + 2e− → HCOOH −0.19 HCOOH 2H+ + 2e− → H2 0 H2 CO2 + 6H+ + 6e− → CH3OH + H2O 0.03 CH3OH 2CO2 + 12H+ + 12e− → C2H4 + 4H2O 0.08 C2H4 2CO2 + 12H+ + 12e− → C2H5OH + 3H2O 0.09 C2H5OH 3CO2 + 18H+ + 18e− → C3H7OH + 5H2O 0.10 C3H7OH 2CO2 + 8H+ + 8e− → CH3COOH + 2H2O 0.11 CH3COOH 2CO2 + 14H+ + 14e− → C2H6 + 4H2O 0.14 C2H6 CO2 + 8H+ + 8e− → CH4 + 2H2O 0.17 CH4
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表 3 石墨烯基电催化材料在CO2RR中的电催化性能
Table 3. The electrocatalytic performance of recent graphene-based catalysts in electrochemical CO2RR
Catalysts Electrolyte Onset
potential
(vs. RHE)/VApplied
potential
(vs. RHE)/VCurrent density/
(mA·cm−2)Main product Faradaic
efficiencyStability Reference NGQDs 1.0 M KOH −0.3 −0.8 90.3 Total
C2H490.0%
31.0%[104] GQD-NH2−H 1.0 M KOH −0.6 −1.0 200.0 CH4 70.0% 10 h [105] N-aGQDs-A9 1.0 M KOH −0.6 −1.0 176.0 CH4 50.0% 35 h [106] NG-800 Foam 0.1 M KHCO3 −0.3 −0.6 1.8 CO 85.0% 5 h [111] N-GRW 0.5 M KHCO3 −0.2 −0.4 6.9 CO 87.6% 10 h [84] BN-C-1 0.1 M KHCO3 −0.4 −0.5 0.3 CH4 68.0% 12 h [85] N-Graphene(NG) 0.5 M KHCO3 −0.3 −0.8 7.5 HCOO− 73.0% 12 h [86] N-functionalized GO 0.1 M KHCO3 −0.4 0.7 C2H5OH 37.0% [93] PGA 0.5 M KHCO3 −0.5 −0.8 4.7 C2H5OH 48.7% 70 h [116] Fe-N-G-p 0.1 M KHCO3 −0.3 −0.6 4.5 CO 94.0% 9 h [87] Fe/NG 0.1 M KHCO3 −0.3 −0.6 2.5 CO 80.0% 10 h [121] FePc-G 0.1 M KHCO3 −0.3 −0.5 1.1 CO 90.0% 10 h [75] FePGF 0.1 M KHCO3 −0.5 −0.5 1.7 CO 98.7% 10 h [79] FeN5 0.1 M KHCO3 −0.3 −0.5 1.8 CO 97.0% 24 h [89] rGO-PVP-ZIFc 0.5 M KHCO3 −0.4 −0.6 6.5 CO 98.6% 8 h [90] CoPc-NVG/CC 0.1 M KHCO3 −0.6 −0.8 14.0 CO 97.5% 10 h [118] DrGO-CoPc 0.1 M KHCO3 −0.4 −0.6 12.0 CO 90.2% 20 h [119] CoN4/G 0.1 M KHCO3 −0.3 −0.8 10.5 CO 95.0% 15 h [96] VitB12@rGO 0.5 M KHCO3 −0.5 −0.8 6.2 CO 94.5% 10 h [122] N-CoMe2Pc/NRGO 0.5 M KHCO3 −0.4 −0.8 9.7 CO 90.0% 5 h [95] CPF-Co@LGO 0.5 M KHCO3 −0.4 −0.7 21.0 CO 97.6% 24 h [123] NapCo@SNG 0.1 M KHCO3 −0.4 −0.8 2.3 CO 97.0% 2.5 h [102] Co-u-COF/G 0.5 M KHCO3 −0.5 −0.7
−1.28.2
191.0CO 97.0%
99.0%30 h
[103] rGO-CoTMPyP 0.1 M Na2CO3 −0.5 −0.7 3.2 CO
HCOO−45.0%
24.3%6 h [97] CGF-CoTMPyP 0.1 M NaHCO3 −0.6 −0.7 1.8 CO
CH440.0%
20.0%1.5 h [117] Ni2+@NG 0.5 M KHCO3 −0.4 −0.7 10.2 CO 92.0% 20 h [83] NiSA-NGA 0.5 M KHCO3 −0.4 −0.8 5.0 CO 90.2% 6 h [80] Ni-N-MEGO 0.5 M KHCO3 −0.3 −0.7 26.8 CO 92.1% 21 h [115] Ni-N-Gr 0.1 M KHCO3 −0.5 −0.7 0.2 CO 80.0% 5 h [88] Ni-N-rGO 0.5 M KHCO3 −0.4 −0.8 23.0 CO 97.0% [124] Ni-B2N4 0.5 M KHCO3 −0.5 −0.8 10.5 CO 98.0% 20 h [125] 3D SANi-G 0.5 M KHCO3 −0.4 −0.7 25.0 CO 96.0% 35 h [91] A-Ni-NSG 0.5 M KHCO3 −0.2 −0.8 23.5 CO 97.0% 100 h [56] Ni-NG-acid 0.5 M KHCO3 −0.5 −0.9 27.2 CO 97.0% 10 h [81] Cu-N4−NG 0.1 M KHCO3 −0.4 −1.0 5.0 CO 80.6% 1 h [92] Zn-N-G 0.5 M KHCO3 −0.4 −0.8 11.2 CO 91.0% 15 h [126] MoC@NG-BW 0.1 M KHCO3 −0.2 −0.9 43.5 CH4 89.0% 50 h [127] Mo@NG EmimBF4 −0.3 −1.4 193.0 HCOO− 8 h [128] Li-N, O/C 0.5 M KHCO3 −0.4 −0.6 12.5 CO 98.8% 10 h [129] Ag2−G 0.5 M KHCO3 −0.3 −0.7 11.9 CO 93.4% 36 h [130] Bi-C
Bi-NC0.5 M KHCO3
0.1 M KHCO3−0.5
−0.3−1.0
−0.529.3
16.5HCOO−
CO82.6%
81.8%40 h
[113] Single-atom Snδ+ on N-doped graphene 0.25 M KHCO3 −0.3 −1.1 11.7 HCOO− 75.1% 200 h [82] Ni@N-C/rGO(4,4′-bipy) 0.5 M KHCO3 −0.3 −1.0 20.0 CO 88.0% 10 h [131] PO-5nm Co/SL-NG 0.1 M NaHCO3 −0.2 −0.5 4.0 CH3OH 71.4% 10 h [132] Ag-G-NCF 0.1 M KHCO3 −0.4 −0.5 0.4 C2H5OH 79.1% 10 h [133] ET-L 0.1 M KHCO3 −0.5 −1.0 4.0 HCOO− 84.1% 7.5 h [98] GO-VB6−Cu 0.1 M KHCO3 0.1 −0.3 7.5 C2H5OH 56.3% 24 h [78] Note: M: mol L−1
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3 石墨烯基电催化材料在CO2RR中的电催化性能 (续)
3. The electrocatalytic performance of recent graphene-based catalysts in electrochemical CO2RR (Continued)
Catalysts Electrolyte Onset
potential
(vs. RHE)/VApplied
potential
(vs. RHE)/VCurrent density/
(mA·cm−2)Main product Faradaic
efficiencyStability Reference Cu NCbs-rGO 0.1 M KHCO3 −0.5 −0.9 3.2 C2H5OH 76.8% [99] Sn/rGO 0.1 M KHCO3 −0.5 −0.8 9.9 HCOO− 98.0% [134] SL-NG@Sn 0.5 M KHCO3 −0.5 −1.0 21.3 HCOO− 92.0% 20 h [135] Bi/NGAhdrz 0.5 M KHCO3 −0.5 −1.0 51.4 HCOO− 96.4% 24 h [107] Bi/rGO 0.1 M KHCO3 −0.7 −0.8 2.0 HCOOH 98.0% 12 h [76] Bi-rGO 0.1 M KHCO3 −0.6 −0.9 4.0 HCOO− 98.0% 24 h [100] SbNS-G 0.5 M NaHCO3 −0.5 −1.0 7.5 HCOO− 88.5% 12 h [101] In/N-dG 1.0 M KOH −0.4 −0.7 700.0 HCOOH 100.0% 14 h [136] PdTe/FLG 0.1 M KHCO3 −0.6 −0.8 3.5 CO 90.0% 5 h [77] Cu-In/PNGC 0.5 M KHCO3 −0.5 −0.7 136.4 CO 91.3% 20 h [137] CuSn-NP/NG 0.5 M KHCO3 −0.5 −1.0 9.0 CO+HCOO− 93.0% 15 h [138] Ag-Sn/rGO 0.5 M NaHCO3 −0.6 −0.9 21.3 HCOO− 88.3% 6 h [139] CuSn-LIG 0.5 M KHCO3 −0.6 −1.0 26.0 HCOOH 99.0% [114] CuNi@C/N-npG 0.5 M KHCO3 −0.3 −0.8 38.0 C2H5OH 84.0% 36 h [112] NiO/NLG 0.1 M KHCO3 −0.6 −0.7 10.0 CO 87.5% 12 h [140] R-ZnO/rGO 0.5 M KHCO3 −0.8 −1.0 3.8 CO 94.3% 21 h [141] SnO2/tert-GO 0.1 M KHCO3 −0.6 −1.0 4.5 HCOO− 84.4% 12 h [142] Bi2O3/p-rGO 0.1 M KHCO3 −0.7 −1.1 16.8 HCOOH 94.3% 39 h [143] In2O3$ \supset $NC@GO 0.5 M KHCO3 −0.4 −0.8 40.4 HCOO− 91.2% 10 h [144] NG-Co3O4 0.1 M KHCO3 −0.2 −0.3 10.5 HCOOH 83.0% 8 h [145] rGO-Co3O4 0.5 M KHCO3 −0.2 −0.4 3.2 C2H5OH
C2H445.9%
28.8%9 h [146] CG electrodes 1.0 M KOH −0.3 −1.0 54.8 CO 93.2% 8 h [147] Cu2O/Cu@C/NG 0.1 M KHCO3 −0.4 −0.8 8.0 HCOO− 82.1% 30 h [148] Cu2O/NRGO 0.1 M KHCO3 −1.0 −1.4 12.0 C2H4 19.7% 2.8 h [149] CuO/NG_AN 0.1 M KHCO3 −1.0 −1.3 12.5 C2H4 30.0% 4.2 h [150] NG/Cu 1.0 M KOH −0.2 −1.5 150.0 C2+ 68.0% 24 h [151] Cu/Cu2O@NG 0.2 M KI −1.0 −1.9 19.0 C2~C3 56.0% 1.25 h [152] CuZnx/NGN 0.1 M KHCO3 −0.4 −0.8 4.0 C2H5OH
n-C3H7OH34.3%
12.4%24 h [110] GN/ZnO/Cu2O 0.5 M NaHCO3 −0.2 −0.3 0.8 n-C3H7OH 30.0% [153] CuS/N, S-rGO 0.5 M KHCO3 −0.3 −0.6 4.5 HCOO− 82.0% 20 h [108] In2S3−rGO 0.1 M KHCO3 −0.4 −1.2 10.9 HCOO− 91.0% 14 h [109] Ag2S/N-S-doped rGO 0.1 M KHCO3 −0.3 −0.8 0.1 CO 87.4% 40 h [154] rGO-PEI-MoSx 0.5 M NaHCO3 −0.3 −0.7 5.0 CO 85.1% 1.7 h [155] Fe-N-G/bC 0.1 M KHCO3 −0.4 −0.7 7.5 CO 95.0% 12 h [120] N-Fe3C/rGO NPs 0.5 M KHCO3 −0.2 −0.3 0.5 CO 33.0% 24 h [156] CsPbI3/rGO 0.1 M KHCO3 −1.1 −1.5 12.7 HCOO− 92.0% 10.5 h [157] Ni-AlO(OH)3@rGO 0.1 M KHCO3 −0.2 −0.9 5.1 CO 92.2% 3 h [158] SnSe2−graphene 0.1 M KHCO3 −0.3 −0.9 11.8 HCOOH 95.1% 16 h [159] Note: M: mol L−1
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