催化学报 ›› 2024, Vol. 59: 38-81.DOI: 10.1016/S1872-2067(23)64622-4
宋宁a, 江吉周b,*(
), 洪士欢a, 王赟a, 李春梅a, 董红军a,*()
收稿日期:2023-12-29
接受日期:2024-02-06
出版日期:2024-04-18
发布日期:2024-04-15
通讯作者:
*电子信箱: 基金资助:
Ning Songa, Jizhou Jiangb,*(), Shihuan Honga, Yun Wanga, Chunmei Lia, Hongjun Donga,*()
Received:2023-12-29
Accepted:2024-02-06
Online:2024-04-18
Published:2024-04-15
Contact:
*E-mail: About author:Jizhou Jiang is currently a full Professor in School of Environmental Ecology and Biological Engineering, Wuhan Institute of Technology (WIT). He completed his PhD in the Huazhong University of Science & Technology (HUST) in 2015. This was followed by a period of postdoctoral research at National University of Singapore under the supervision of Prof Andrew T. S. Wee from 2015 to 2017. His current research focuses on the preparation of novel micro/nano-materials, 2D materials, carbon materials and their applications of photo/electro-catalysis.Supported by:摘要：
化石燃料的过度使用导致了严重的环境问题, 因此, 迫切需要人们对能源生产和储存方式进行变革. 电催化在清洁能源转换中发挥着重要的作用, 是推动可持续能源生产技术不断发展的重要驱动力. 单原子催化剂(SACs)因具有独特的物理和化学性质而表现较高的电催化活性, 因而成为研究热点. 通过调控金属单原子的配位环境, 可以有效调节SACs的几何和电子结构, 进而优化电催化效率. 金属有机骨架(MOFs)具有孔结构丰富、表面积大和配体可调节等结构特性, 因此在制备SACs方面表现出巨大潜力. 本文旨在总结以MOFs为前驱体制备SACs的最新进展, 深入探讨单原子空间分布、配位结构和电子结构等局部配位环境对电催化活性的影响. 此外, 对密度泛函理论在研究SACs电催化反应中的应用进行了讨论和分析.
本文系统地介绍了以MOFs为前驱体制备SACs的合成策略、表征方法、电催化应用和反应机理的研究进展, 并对其未来的发展进行了展望. 首先, 概述了以MOFs为原料制备SACs的多种策略, 分析了各自的优缺点及改进方向. 然后, 介绍了SACs的结构表征及电催化反应机理的原位表征技术, 剖析了现有技术面临的挑战. 再后, 重点介绍了一些经典的制备SACs案例, 对以MOFs为源制备的SACs在电催化析氢反应、析氧反应、氧还原反应、CO2还原反应及氮还原消除等的应用进行了系统总结, 并简要回顾了其在光催化、热催化、酶催化方向的应用. 最后, 探讨了SACs面临的挑战及解决方案: (1) 目前采用的以MOFs为源制备SACs方法存在能耗高、污染环境等问题, 应开发出环保可持续的合成方法以降低生产成本, 并将其对环境的影响降到最低. (2) 应利用原子水平控制技术制备双原子或三原子多功能电催化剂, 并根据SACs的应用场景调整其配位结构, 以优化性能. (3) 需研发更先进的测试仪器, 解决测试结果区域化、效率低、测试与实际结果存在偏差以及测试成本较高等问题. (4) 基于SACs的结构特性, 结合先进的测试仪器与理论计算, 深入探究反应机理, 为新一代电催化剂的设计提供指导. (5) 随着信息技术的多维、多样和复杂化发展, 可以借助机器学习, 设计和开发新型SACs, 推动电催化领域的持续创新.
综上, 本文系统地介绍了以MOFs为材料制备SACs的优势、设计原理、表征手段, 并对SACs在电催化应用方面的研究进展与面临的挑战进行了总结, 希望能为SACs相关方面的研究提供有价值的参考和借鉴.
宋宁, 江吉周, 洪士欢, 王赟, 李春梅, 董红军. 以金属有机骨架为源制备单原子电催化剂用于能量转换的最新进展[J]. 催化学报, 2024, 59: 38-81.
Ning Song, Jizhou Jiang, Shihuan Hong, Yun Wang, Chunmei Li, Hongjun Dong. State-of-the-art advancements in single atom electrocatalysts originating from MOFs for electrochemical energy conversion[J]. Chinese Journal of Catalysis, 2024, 59: 38-81.
Fig. 1. The history of SACs development. Reprinted with permission from Ref. [83], Copyright 2007, John Wiley and Sons; Ref. [84], Copyright 2011, Nature Publishing Group; Ref. [85], Copyright 2016, Nature Publishing Group; Ref. [86], Copyright 2017, Nature Publishing Group; Ref. [87], Copyright 2018, Science; Ref. [88], Copyright 2019, Nature Publishing Group; Ref. [89], Copyright 2020, American Chemical Society; Ref. [90], Copyright 2021, Elsevier; Ref. [91], Copyright 2022, Science Advance; Ref. [92], Copyright 2023, John Wiley and Sons.
Fig. 2. Design, schematic preparation, characterization techniques, and SACs originating from MOFs in electrocatalytic energy application. Reprinted with permission from Ref. [129], Copyright 2020, John Wiley and Sons; Ref. [127], Copyright 2022, John Wiley and Sons; Ref. [130], Copyright 2019, John Wiley and Sons.
Fig. 3. (a) Diagram for the synthesis of Zn/NC NSs (a), NiSA-Nx-C (b), and Ru/Pt/Pd@Co-SAs/N-C (c) electrocatalysts. Reprinted with permission from Ref. [133], Copyright 2021, John Wiley and Sons; Ref. [129], Copyright 2020, John Wiley and Sons; Ref. [136], Copyright 2019, Elsevier.
Fig. 4. Diagram of the synthesis of SACs Fe-Co3O4 (a), Fe1-N-C HNRs (b), and NiCo DASs/N-C (c) electrocatalysts. Reprinted with permission from Ref. [141], Copyright 2020, John Wiley and Sons; Ref. [127], Copyright 2022, John Wiley and Sons; Ref. [143], Copyright 2023, John Wiley and Sons.
Fig. 5. Diagram of the C-FeZIF-4.44-950 (a), SA-Fe-NGM (b) and FeCo-DACs/NC (c) electrocatalysts synthesis process. Reprinted with permission from Ref. [130], Copyright 2019, John Wiley and Sons; Ref. [128], Copyright 2022, American Chemical Society; Ref. [148], Copyright 2021, John Wiley and Sons.
| Electrocatalyst | Synthetic strategy | Loading amounts of SAs (wt%) | Application | Performance | Stability | Characteristic | Ref. |
|---|---|---|---|---|---|---|---|
| Zn/NC NSs | in situ node evolution | 6.39 | CO2RR | FECO 95% | 12 h | twisted Zn-N3+1 model | [ |
| Zn1N-C | in situ node evolution | 15.00 | NRR | FENH3 11.8% yield rate ≈16.1 µg NH3 h-1 | 24 h | Zn-N4, graphitic N | [ |
| NiSA-N2-C | in situ node evolution | 2.83 | CO2RR | FECO 98 % | 10 h | low N coordination number | [ |
| 20Co-NC-1100 | in situ node evolution | 1.41 | ORR | E1/2 = 0.8 V | 100 h | well-dispersed CoN4 active sites | [ |
| Fe1-N-C HNRs | encapsulation confinement | 2.0 | ORR | E1/2 = 0.91 V | 12 h | abundant Fe-N4 active sites | [ |
| Ni-N-C | encapsulation confinement | 0.24 | ORR | E1/2 = 0.938 V | 8 h | Ni-N4 coordination structure | [ |
| NiCo DASs/N-C | encapsulation confinement | Ni: 0.37 Co: 0.43 | ORR HER | E1/2 = 0.880 V η10 = 189 mV | 0.56 h 24 h | proximity electronic effect of Ni/Co DASs | [ |
| CoFe@C | encapsulation confinement | Co: 0.50 Fe: 0.37 | ORR | E1/2 = 0.89 V | 5.56 h | Co and Fe atoms-decorated carbon network | [ |
| C-FeZIF-4.44-950 | anchoring with ligands | 1 | ORR | E1/2 = 0.864 V | 5.56 h | highly dispersed Fe-Nx sites | [ |
| SA-Fe-NGM | anchoring with ligands | 8.36 | ORR | E1/2 = 0.83 V | 5000 cycles | highly loaded Fe SACs and a highly exposed morphology | [ |
| Fe SAC-MOF-5 | anchoring with ligands | 2.35 | ORR | E1/2 = 0.83 V | 7.33 h | high loaded Fe SAs, and ultrahigh specific surface area | [ |
| Co-900-A | anchoring with ligands | 5.87 | HER | η10 = 82 mV | 35k cycles | low-coordinate Co-N2 sites have lower energy barriers | [ |
Table 1 Summary of different preparation strategies for SACs originating from MOFs.
| Electrocatalyst | Synthetic strategy | Loading amounts of SAs (wt%) | Application | Performance | Stability | Characteristic | Ref. |
|---|---|---|---|---|---|---|---|
| Zn/NC NSs | in situ node evolution | 6.39 | CO2RR | FECO 95% | 12 h | twisted Zn-N3+1 model | [ |
| Zn1N-C | in situ node evolution | 15.00 | NRR | FENH3 11.8% yield rate ≈16.1 µg NH3 h-1 | 24 h | Zn-N4, graphitic N | [ |
| NiSA-N2-C | in situ node evolution | 2.83 | CO2RR | FECO 98 % | 10 h | low N coordination number | [ |
| 20Co-NC-1100 | in situ node evolution | 1.41 | ORR | E1/2 = 0.8 V | 100 h | well-dispersed CoN4 active sites | [ |
| Fe1-N-C HNRs | encapsulation confinement | 2.0 | ORR | E1/2 = 0.91 V | 12 h | abundant Fe-N4 active sites | [ |
| Ni-N-C | encapsulation confinement | 0.24 | ORR | E1/2 = 0.938 V | 8 h | Ni-N4 coordination structure | [ |
| NiCo DASs/N-C | encapsulation confinement | Ni: 0.37 Co: 0.43 | ORR HER | E1/2 = 0.880 V η10 = 189 mV | 0.56 h 24 h | proximity electronic effect of Ni/Co DASs | [ |
| CoFe@C | encapsulation confinement | Co: 0.50 Fe: 0.37 | ORR | E1/2 = 0.89 V | 5.56 h | Co and Fe atoms-decorated carbon network | [ |
| C-FeZIF-4.44-950 | anchoring with ligands | 1 | ORR | E1/2 = 0.864 V | 5.56 h | highly dispersed Fe-Nx sites | [ |
| SA-Fe-NGM | anchoring with ligands | 8.36 | ORR | E1/2 = 0.83 V | 5000 cycles | highly loaded Fe SACs and a highly exposed morphology | [ |
| Fe SAC-MOF-5 | anchoring with ligands | 2.35 | ORR | E1/2 = 0.83 V | 7.33 h | high loaded Fe SAs, and ultrahigh specific surface area | [ |
| Co-900-A | anchoring with ligands | 5.87 | HER | η10 = 82 mV | 35k cycles | low-coordinate Co-N2 sites have lower energy barriers | [ |
Fig. 6. Diagram of the FePc||CNTs||NiCo/CP (a), CoFe-N-C (b), Fe/C950 (c), and Co SA@NCF/CNF (d) electrocatalysts. Reprinted with permission from Ref. [108], Copyright 2022, John Wiley and Sons; Ref. [151], Copyright 2022, American Chemical Society; Ref. [152], Copyright 2021, Elsevier; Ref. [153], Copyright 2019, John Wiley and Sons.
Fig. 7. (a) Structural model of CoFe@C electrocatalyst. AC HAADF-STEM images of CoFe@C (b,c), Co@C (d), and Fe@C SACs (e) electrocatalysts. Reprinted with permission from Ref. [145]. Copyright 2019, John Wiley and Sons. (f) Structural model of Co@DMOF-900 electrocatalyst. AC HAADF-STEM (g), corresponding EELS mapping images (h), and AC LAADF-STEM images (i) of Co@DMOF-900 electrocatalyst. Reprinted with permission from Ref. [169]. Copyright 2021, John Wiley and Sons. Structural model of ZnCo-NC-II electrocatalyst (j), corresponding TEM images (k,l) and, AC HAADF-STEM images (m,n). Reprinted with permission from Ref. [170]. Copyright 2022, Elsevier.
Fig. 8. The XANES spectra at the Mo K-edge exhibit somewhat magnified patterns (see insert) (a) and corresponding FT-EXAFS spectra (b) of Mo SACs/N-C and other electrocatalysts. Reprinted with permission from Ref. [191]. Copyright 2020, Elsevier. The XANES (c), and FT Pt L3-edge EXAFS (d) spectra for Pt1/Co1NC electrocatalyst. Reprinted with permission from Ref. [144]. Copyright 2022, Elsevier. (e) In situ XANES normalized difference spectra of the Co K-edge recorded at different voltages. Reprinted with permission from Ref. [192]. Copyright 2018, Nature Publishing Group. (h) In situ Ru K-edge XANES spectra for Ru1-Pt3Cu electrocatalyst. Reprinted with permission from Ref. [88]. Copyright 2019, Nature Publishing Group.
Fig. 9. (a) Schematic diagram of in situ ATR-FTIR measurements. (b) Models of Zn-N4 and Zn-N3+1 electrocatalysts structures. (c) In situ ATR-FTIR spectra recorded during CO2RR on Zn/NC NSs electrocatalyst. Reprinted with permission from Ref. [133]. Copyright 2021, John Wiley and Sons. (d) Schematic diagram of in situ Raman measurements. In situ Raman spectra of Ni-TAPc (e) (Reprinted with permission from Ref. [197]. Copyright 2020, John Wiley and Sons.) and Cu-FeSA (f) (Reprinted with permission from Ref. [198]. Copyright 2022, Nature Publishing Group.) electrocatalysts.
Fig. 10. (a) Conformation diagram of Co5Pt-PtSA-2-N2 electrocatalyst. (b) ΔGH* with respect to the center of the PtSA d-band. Reprinted with permission from Ref. [226]. Copyright 2022, John Wiley and Sons. (c) Schematic diagram of the 4e- reaction pathway of the OER occurring over the Ru0.5Ir0.5O2 (120) electrocatalyst (step). (d) ΔG diagram for flat and step surfaces (at 1.23 V). Reprinted with permission from Ref. [227]. Copyright 2021, American Chemical Society. Optimized geometrical models of Zn SAs in ZnN4 (e) and ZnO3C (f) electrocatalysts. (g) The charge density difference in the ZnO3C electrocatalyst model. Reprinted with permission from Ref. [101]. Copyright 2021, John Wiley and Sons. (h) Possible reaction pathways for the CO2RR by SA Ni-NC electrocatalyst. (i) PDOS diagrams of CO adsorbed in the active sites of NiN4 electrocatalyst. Reprinted with permission from Ref. [228]. Copyright 2021, American Chemical Society.
Fig. 11. (a) Schematic diagram of Pt1/Co1NC for electrocatalytic HER. (b) Mass activity and overpotential @10 mA cm-2 plot of Pt1/Co1NC and other electrocatalysts. Reprinted with permission from Ref. [144]. Copyright 2022, Elsevier. (c) Schematic illustration of SGNC hybrids for electrocatalytic HER. (d) Tafel plots for various SGNCs and Pt/C electrocatalysts. Reprinted with permission from Ref. [261]. Copyright 2020, American Chemical Society. (e) Schematic illustration of the preparation process of the Ni-C electrocatalyst. (f,g) LSV curves and EIS spectra of A-Ni-C, HCl-Ni@C, and Pt/C electrocatalysts. Reprinted with permission from Ref. [262]. Copyright 2016, Nature Publishing Group.
Fig. 12. Recently reported overpotential summary plots for classical SACs originating from MOFs at -10 mA cm-2 in the electrocatalytic HER.
Fig. 13. (a) Schematic diagram of the synthesis process of Ir0.06Co2.94O4 electrocatalyst. LSV curves normalized to the surface area of Ir0.06Co2.94O4, and other electrocatalysts (b), compare the mass activity of various electrocatalysts with respect to overpotential (c). Reprinted with permission from Ref. [293]. Copyright 2021, American Chemical Society. (d) Schematic diagram of the synthesis process of Fe-Co3O4 HHNPs electrocatalyst. (e) Corresponding bar graphs of ECSA normalized current density and TOF values, (f) current-time curves of Fe-Co3O4 HHNPs electrocatalyst. Reprinted with permission from Ref. [141]. Copyright 2020, John Wiley and Sons. (g) Schematic diagram of the synthesis of Pt-Ni(OH)x electrocatalyst. (h) The iR-corrected LSVs of Pt-Ni(OH)x and other electrocatalysts. (i) The overall water splitting polarization curves of Pt-Ni(OH)x and other electrocatalysts. Reprinted with permission from Ref. [267]. Copyright 2023, John Wiley and Sons.
Fig. 14. Recently reported overpotential summary plots for classical SACs originating from MOFs at -10 mA cm-2 in the electrocatalytic OER.
Fig. 15. (a) Proposed reaction mechanism of FeN4-O-NC electrocatalyst in electrocatalytic ORR. (b) The comparison of E1/2 and Jk at 0.9 V, and (c) H2O2 yield and electron transfer number (n) for FeN4-O-NCR, and other electrocatalysts in 0.1 mol L-1 KOH. Reprinted with permission from Ref. [339]. Copyright 2022, John Wiley and Sons. (d) Proposed reaction mechanism of Se SA@NC electrocatalyst in electrocatalytic ORR. (e) ORR curves in 0.1 mol L-1 KOH. (f) Tafel plots of various electrocatalysts. Reprinted with permission from Ref. [340]. Copyright 2022, John Wiley and Sons. (g) Schematic diagram of Fe SAs/NC electrocatalyst for electrocatalytic ORR/OER. (h) Overall polarization curves of Fe SAs/NC and other electrocatalysts. Reprinted with permission from Ref. [298]. Copyright 2023, John Wiley and Sons. (i) Schematic diagram of CNT@SAC-Co/NCP electrocatalyst for electrocatalytic ORR. (j) Polarization and power density curves of ZABs using CNT@SAC-Co/NCP, and other electrocatalysts. Reprinted with permission from Ref. [299]. Copyright 2021, John Wiley and Sons.
| Electrocatalyst | Active metals | Electron transfer number | Half-wave potential (V) (vs. RHE)/Electrolyte | Fuel cell/battery power density (mW cm-2) | Characteristic | Pros and cons | Ref. |
|---|---|---|---|---|---|---|---|
| Co-N-C@F127 | Co | ~4 | 0.84 (0.5 mol L-1 H2SO4) | 870 (H2-O2 fuel cell) | CoN4 sites with high atomic dispersion density | good stability/ environmentally unfriendly | [ |
| Fe-N-C | Fe | ~4 | 0.81 (0.1 mol L-1 HClO4) | — | 4 N atoms (plane)-Fe-2O atoms (axial) | good performance/high energy consumption | [ |
| 0.90 (0.1 mol L-1 KOH) | |||||||
| TPI@Z8(SiO2)-650-C | Fe | ~4 | 0.823 (0.5 mol L-1 H2SO4) | 1180 (H2-O2 fuel cell) | high density of Fe-N4 active sites | excellent performance/many steps | [ |
| Fe-SAs/NPS-HC | Fe | 3.90-4.00 | 0.791 (0.5 mol L-1 H2SO4) | 195 (ZAB), 400 (hydrogen-air fuel cell) | S and P modulate the electronic state of N-coordinated Fe SAs | good performance/many steps | [ |
| 0.912 (0.1 mol L-1 KOH) | |||||||
| A-CoPt-NC | Pt, Co | 3.6 | 0.96 (0.1 mol L-1 KOH) | — | synergetic effect of the Pt and Co SAs | high mass activity / low yield | [ |
| CoFe@C | Fe, Co | 3.98 | 0.89 (0.1 mol L-1 KOH) | — | Co and Fe atoms-decorated carbon network | extraordinary catalytic performance / many steps | [ |
| Se@NC-1000 | Se | 3.91 | 0.85 (0.1 mol L-1 KOH) | 176.6 (ZAB) | Se SAs can modulate local electronic configurations | metal-free SACs/high energy consumption | [ |
| SA-Fe-NGM | Fe | 3.95 | 0.83 (0.5 mol L-1 H2SO4) | 634 (H2-O2 fuel cell) | highly loaded Fe SACs and a highly exposed morphology | high metal loadings (8.36 wt%)/many steps | [ |
| NiCo DASs/N-C | Ni, Co | 3.9 | 0.754 (0.5 mol L-1 H2SO4) | — | Ni-N4 site adjust the electronic localization of Co-N4 site | superior activity/high energy consumption | [ |
| 3.7 | 0.880 (0.1 mol L-1 KOH) | ||||||
| Fe/C950 | Fe | ~4 | 0.84 (0.1 mol L-1 HClO4) | — | highly dispersed single atom sites | highly dispersed SAs (0.72 wt%)/high energy consumption | [ |
| FeN4-O-NCR | Fe | 3.96 | 0.942 (0.1 mol L-1 KOH) | 214.2 (ZAB) | 4 N atoms (plane)-Fe-1O atoms (axial) | outstanding intrinsic activity/many steps | [ |
| Fe1-N-C HNRs | Fe | ~4 | 0.8 (0.1 mol L-1 HClO4) | 208 (ZAB) | highly porous and open carbon hollow architecture | superior activity and stability/many steps | [ |
| 3.97-3.99 | 0.91 (0.1 mol L-1 KOH) | ||||||
| Co@DMOF-900 | Co | 3.85 | 0.866 (0.1 mol L-1 KOH) | 158 (ZAB) | high surface area, N doping, Co-N4 sites, and rich defects | high TOF/high energy consumption | [ |
| 20Co-NC-1100 | Co | — | 0.80 (0.5 mol L-1 H2SO4) | 560 (H2-O2 fuel cell) | well-dispersed CoN4 active sites embedded in 3D porous carbon particles | respectable activity and stability/high energy consumption | [ |
| Mn/C-NO | Mn | 3.95 | 0.86 (0.1 mol L-1 KOH) | 120 (ZAB) | abundant Mn SAs cofactors in the graphene frameworks | excellent performance/high energy consumption | [ |
| 55%100@30 | Fe | — | 0.86 (0.5 mol L-1 H2SO4) | 750 (H2-O2 fuel cell) | perfect size combination, hierarchical porosity | exceptional activity/high energy consumption | [ |
| 340 (H2-air fuel cell) | |||||||
| Fe1/d-CN | Fe | 3.7-4.00 | 0.781 (0.5 mol L-1 H2SO4) | 78 (ZAB) | rich defects and hierarchical porous features | remarkable durability/ many steps | [ |
| 0.95 (0.1 mol L-1 KOH) | |||||||
| 0.605 (0.1 mol L-1 PBS) | |||||||
| Ni-N-C-0.1 | Ni | — | 0.938 (0.1 mol L-1 KOH) | 178 (ZAB) | Ni-N4-C10 coordination site | excellent activity and stability/high energy consumption | [ |
| Co-SAs/3D GFs | Co | 3.99 | 0.901 (0.1 mol L-1 KOH) | 206 (ZAB) | dense single metal sites with high accessibility dispersed | excellent activity/many steps | [ |
| ZIF/MIL-10-900 | Fe | ~4 | 0.78 (0.1 mol L-1 HClO4) | 83 (direct methanol fuel cell) (DMFC) | abundant FeN4 sites | excellent stability/high energy consumption | [ |
| PtCo2/Zn6Co NPs | Co | — | 0.858 (0.1 mol L-1 HClO4) | — | Pt-rich shell and the PtCo@Pt structure | good stability/many steps | [ |
| Fe SAC-MOF-5 | Fe | 3.98 | 0.83 (0.5 mol L-1 H2SO4) | 840 (H2-O2 fuel cell) | high density of single Fe atoms | high density of Fe SAs/high energy consumption | [ |
| Fe SAC-MIL101-1000 | Fe | 3.9-4.0 | 0.94 (0.1 mol L-1 KOH) | 192.3 (ZAB) | high utilization of the Fe SAs sites | outstanding activity/ environmentally unfriendly | [ |
| Ru-SSC | Ru | ~4 | 0.824 (0.1 mol L-1 HClO4) | 640 (H2-O2 fuel cell) | unique single-atom site configuration | excellent activity and stability/high energy consumption | [ |
| Fe-S-Phen/CNT | Fe | ~4 | 0.914 (0.1 mol L-1 KOH) | 760 (anion-exchange membrane fuel cell) (AEMFC) | Method for preparing Fe-Nx catalysts: almost no Fe-based particles | high activity/many steps | [ |
| Co-SAs/SNPs@NC | Co | 3.92-3.99 | 0.898 (0.1 mol L-1 KOH) | 223.5 (ZAB) | the synergistic effect of Co-SAs and Co-SNPs | outstanding activity and remarkable stability/high energy consumption | [ |
| Cu-N-C-ICHP NDs | Cu | 3.9 | 0.85 (0.1 mol L-1 KOH) | — | hierarchical porous Cu-N-C NDs catalyst | good stability/many steps | [ |
| Co@FeSAC-N2P/C | Fe | ~4 | 0.92 (0.1 mol L-1 KOH) | 179 (ZAB) | N and P dual-coordinated Fe SAs with N unsaturated coordination | good stability/many steps | [ |
| Pt SAs-ZIF-NC | Pt | 3.79 | 0.875 (0.1 mol L-1 HClO4) | — | low-coordination | high activity/high energy consumption | [ |
| ZnCo-NC-II | Zn, Co | - | 0.79 (0.5 mol L-1 H2SO4) | 164.85 (ZAB) | high-density ZnN4 and CoN4 sites | high metal loadings (Zn and Co: 1.41 wt% and 1.43 wt%)/low yield | [ |
| 0.86 (0.1 mol L-1 KOH) | |||||||
| Co-NCS-2 | Co | ~ 4 | 0.90 (0.1 mol L-1 KOH) | 292 (ZAB) | Co NPs change the electronic structure of the Co-Nx | superior performance/high energy consumption | [ |
| Co-MOF@rGO-3 | Co | 3.9 | 0.74 (PBS (pH = 7)) | — | introduction of carbon support materials could tune the electronic architecture | good activity/many steps | [ |
Table 2 Summary of SACs originating from MOFs for the ORR.
| Electrocatalyst | Active metals | Electron transfer number | Half-wave potential (V) (vs. RHE)/Electrolyte | Fuel cell/battery power density (mW cm-2) | Characteristic | Pros and cons | Ref. |
|---|---|---|---|---|---|---|---|
| Co-N-C@F127 | Co | ~4 | 0.84 (0.5 mol L-1 H2SO4) | 870 (H2-O2 fuel cell) | CoN4 sites with high atomic dispersion density | good stability/ environmentally unfriendly | [ |
| Fe-N-C | Fe | ~4 | 0.81 (0.1 mol L-1 HClO4) | — | 4 N atoms (plane)-Fe-2O atoms (axial) | good performance/high energy consumption | [ |
| 0.90 (0.1 mol L-1 KOH) | |||||||
| TPI@Z8(SiO2)-650-C | Fe | ~4 | 0.823 (0.5 mol L-1 H2SO4) | 1180 (H2-O2 fuel cell) | high density of Fe-N4 active sites | excellent performance/many steps | [ |
| Fe-SAs/NPS-HC | Fe | 3.90-4.00 | 0.791 (0.5 mol L-1 H2SO4) | 195 (ZAB), 400 (hydrogen-air fuel cell) | S and P modulate the electronic state of N-coordinated Fe SAs | good performance/many steps | [ |
| 0.912 (0.1 mol L-1 KOH) | |||||||
| A-CoPt-NC | Pt, Co | 3.6 | 0.96 (0.1 mol L-1 KOH) | — | synergetic effect of the Pt and Co SAs | high mass activity / low yield | [ |
| CoFe@C | Fe, Co | 3.98 | 0.89 (0.1 mol L-1 KOH) | — | Co and Fe atoms-decorated carbon network | extraordinary catalytic performance / many steps | [ |
| Se@NC-1000 | Se | 3.91 | 0.85 (0.1 mol L-1 KOH) | 176.6 (ZAB) | Se SAs can modulate local electronic configurations | metal-free SACs/high energy consumption | [ |
| SA-Fe-NGM | Fe | 3.95 | 0.83 (0.5 mol L-1 H2SO4) | 634 (H2-O2 fuel cell) | highly loaded Fe SACs and a highly exposed morphology | high metal loadings (8.36 wt%)/many steps | [ |
| NiCo DASs/N-C | Ni, Co | 3.9 | 0.754 (0.5 mol L-1 H2SO4) | — | Ni-N4 site adjust the electronic localization of Co-N4 site | superior activity/high energy consumption | [ |
| 3.7 | 0.880 (0.1 mol L-1 KOH) | ||||||
| Fe/C950 | Fe | ~4 | 0.84 (0.1 mol L-1 HClO4) | — | highly dispersed single atom sites | highly dispersed SAs (0.72 wt%)/high energy consumption | [ |
| FeN4-O-NCR | Fe | 3.96 | 0.942 (0.1 mol L-1 KOH) | 214.2 (ZAB) | 4 N atoms (plane)-Fe-1O atoms (axial) | outstanding intrinsic activity/many steps | [ |
| Fe1-N-C HNRs | Fe | ~4 | 0.8 (0.1 mol L-1 HClO4) | 208 (ZAB) | highly porous and open carbon hollow architecture | superior activity and stability/many steps | [ |
| 3.97-3.99 | 0.91 (0.1 mol L-1 KOH) | ||||||
| Co@DMOF-900 | Co | 3.85 | 0.866 (0.1 mol L-1 KOH) | 158 (ZAB) | high surface area, N doping, Co-N4 sites, and rich defects | high TOF/high energy consumption | [ |
| 20Co-NC-1100 | Co | — | 0.80 (0.5 mol L-1 H2SO4) | 560 (H2-O2 fuel cell) | well-dispersed CoN4 active sites embedded in 3D porous carbon particles | respectable activity and stability/high energy consumption | [ |
| Mn/C-NO | Mn | 3.95 | 0.86 (0.1 mol L-1 KOH) | 120 (ZAB) | abundant Mn SAs cofactors in the graphene frameworks | excellent performance/high energy consumption | [ |
| 55%100@30 | Fe | — | 0.86 (0.5 mol L-1 H2SO4) | 750 (H2-O2 fuel cell) | perfect size combination, hierarchical porosity | exceptional activity/high energy consumption | [ |
| 340 (H2-air fuel cell) | |||||||
| Fe1/d-CN | Fe | 3.7-4.00 | 0.781 (0.5 mol L-1 H2SO4) | 78 (ZAB) | rich defects and hierarchical porous features | remarkable durability/ many steps | [ |
| 0.95 (0.1 mol L-1 KOH) | |||||||
| 0.605 (0.1 mol L-1 PBS) | |||||||
| Ni-N-C-0.1 | Ni | — | 0.938 (0.1 mol L-1 KOH) | 178 (ZAB) | Ni-N4-C10 coordination site | excellent activity and stability/high energy consumption | [ |
| Co-SAs/3D GFs | Co | 3.99 | 0.901 (0.1 mol L-1 KOH) | 206 (ZAB) | dense single metal sites with high accessibility dispersed | excellent activity/many steps | [ |
| ZIF/MIL-10-900 | Fe | ~4 | 0.78 (0.1 mol L-1 HClO4) | 83 (direct methanol fuel cell) (DMFC) | abundant FeN4 sites | excellent stability/high energy consumption | [ |
| PtCo2/Zn6Co NPs | Co | — | 0.858 (0.1 mol L-1 HClO4) | — | Pt-rich shell and the PtCo@Pt structure | good stability/many steps | [ |
| Fe SAC-MOF-5 | Fe | 3.98 | 0.83 (0.5 mol L-1 H2SO4) | 840 (H2-O2 fuel cell) | high density of single Fe atoms | high density of Fe SAs/high energy consumption | [ |
| Fe SAC-MIL101-1000 | Fe | 3.9-4.0 | 0.94 (0.1 mol L-1 KOH) | 192.3 (ZAB) | high utilization of the Fe SAs sites | outstanding activity/ environmentally unfriendly | [ |
| Ru-SSC | Ru | ~4 | 0.824 (0.1 mol L-1 HClO4) | 640 (H2-O2 fuel cell) | unique single-atom site configuration | excellent activity and stability/high energy consumption | [ |
| Fe-S-Phen/CNT | Fe | ~4 | 0.914 (0.1 mol L-1 KOH) | 760 (anion-exchange membrane fuel cell) (AEMFC) | Method for preparing Fe-Nx catalysts: almost no Fe-based particles | high activity/many steps | [ |
| Co-SAs/SNPs@NC | Co | 3.92-3.99 | 0.898 (0.1 mol L-1 KOH) | 223.5 (ZAB) | the synergistic effect of Co-SAs and Co-SNPs | outstanding activity and remarkable stability/high energy consumption | [ |
| Cu-N-C-ICHP NDs | Cu | 3.9 | 0.85 (0.1 mol L-1 KOH) | — | hierarchical porous Cu-N-C NDs catalyst | good stability/many steps | [ |
| Co@FeSAC-N2P/C | Fe | ~4 | 0.92 (0.1 mol L-1 KOH) | 179 (ZAB) | N and P dual-coordinated Fe SAs with N unsaturated coordination | good stability/many steps | [ |
| Pt SAs-ZIF-NC | Pt | 3.79 | 0.875 (0.1 mol L-1 HClO4) | — | low-coordination | high activity/high energy consumption | [ |
| ZnCo-NC-II | Zn, Co | - | 0.79 (0.5 mol L-1 H2SO4) | 164.85 (ZAB) | high-density ZnN4 and CoN4 sites | high metal loadings (Zn and Co: 1.41 wt% and 1.43 wt%)/low yield | [ |
| 0.86 (0.1 mol L-1 KOH) | |||||||
| Co-NCS-2 | Co | ~ 4 | 0.90 (0.1 mol L-1 KOH) | 292 (ZAB) | Co NPs change the electronic structure of the Co-Nx | superior performance/high energy consumption | [ |
| Co-MOF@rGO-3 | Co | 3.9 | 0.74 (PBS (pH = 7)) | — | introduction of carbon support materials could tune the electronic architecture | good activity/many steps | [ |
Fig. 16. Recently reported E1/2 summary plots for classical SACs originating from MOFs in the electrocatalytic ORR.
| Electrocatalyst | Active metals | Potential (J = 10 mA cm-2) (V vs. RHE) | Half-wave potential (V vs. RHE)/ Electrolyte | Fuel cell/battery power density (mW cm-2) | Characteristic | Pros and cons | Refs. |
|---|---|---|---|---|---|---|---|
| Mo SACs/N-C | Mo | 1.48 | 0.83 (0.1 mol L-1 KOH) | 112 (ZAB) | Mo site in Mo1N1C2 favors the reaction | good activity/high energy consumption | [ |
| CoNi-SAs/NC | Co, Ni | 1.57 | 0.76 (0.1 mol L-1 KOH) | 101.4 (ZAB) | synergistic interaction of Co SAs and Co-Ni sites lowers the reaction energy barrier | outstanding performance/many steps | [ |
| Fe2/Co1-GNCL | Fe, Co | 1.58 | 0.846 (1 mol L-1 KOH) | 218 (ZAB) | stabilized Fe dimer is formed | excellent activity/high energy consumption | [ |
| CoFe-N-C | Fe, Co | 1.59 | 0.897 (0.1 mol L-1 KOH) | 142.1 (ZAB) | two neighboring metal atoms can adjust the electronic structure of the active site | exceptional activities/ environmentally unfriendly | [ |
| NiFe-LDH@Fe/CNP | Fe | 1.594 | 0.867 (1 mol L-1 KOH) | — | flexible dimension control | long-term cycling stability/high energy consumption | [ |
| FeNi SAs/NC | Ni, Fe | 1.50 | 0.84 (0.1 mol L-1 KOH) | 42.22 (ZAB) | Ni site regulates the electronic structure of the central Fe site | extraordinary activity/ environmentally unfriendly | [ |
| FeCo-DACs/NC | Fe, Co | 1.60 | 0.877 (1 mol L-1 KOH) | 175 (ZAB) | dual atoms optimize the d-band center of the reaction site | excellent performance/ high energy consumption | [ |
| Fe SAs/NC | Fe | 1.55 | 0.83 (0.5 mol L-1 H2SO4) | 306.1 (ZAB) | engineered electronic structure of active sites modulates Fe charge distribution | remarkable activity/ high energy consumption | [ |
| 0.93 (0.1 mol L-1 KOH) | |||||||
| 0.75 (0.1 mol L-1 PBS) | |||||||
| CNT@SAC-Co/NCP | Co | 1.61 | 0.87 (0.1 mol L-1 KOH) | 172 (ZAB) | hierarchical porous structure, independent single-atom and nanosized phases, and conductive networks | excellent activity/high energy consumption | [ |
| SCoNC | Co | 1.54 | 0.91 (0.1 mol L-1 KOH) | 194 (ZAB) | high-density dispersed Co SAs | excellent activity/high energy consumption | [ |
| UNT Co SAs/N-C | Co | 1.61 | 0.89 (0.1 mol L-1 KOH) | — | high-quality SAs, precise local coordination of CoN4, and well-aligned carbon matrix | superior performance/environmentally unfriendly | [ |
| FeNx-PNC | Fe | 1.625 | 0.86 (0.1 mol L-1 KOH) | 278 (ZAB) | abundant active sites and high intrinsic activity | superior activity/high energy consumption | [ |
| CoDNi-N/C | Co, Ni | 1.59 | 0.81 (0.1 mol L-1 KOH) | — | homogeneous Co/Ni double atoms and abundant content of micropores and nitrogen | good performance/high energy consumption | [ |
| Co SA@NCF/CNF | Co | 1.63 | 0.88 (1 mol L-1 KOH) | — | single-atom active sites and hierarchically porous architectures | excellent activity/many steps | [ |
Table 3 Summary of SACs originating from MOFs for the OER/ORR.
| Electrocatalyst | Active metals | Potential (J = 10 mA cm-2) (V vs. RHE) | Half-wave potential (V vs. RHE)/ Electrolyte | Fuel cell/battery power density (mW cm-2) | Characteristic | Pros and cons | Refs. |
|---|---|---|---|---|---|---|---|
| Mo SACs/N-C | Mo | 1.48 | 0.83 (0.1 mol L-1 KOH) | 112 (ZAB) | Mo site in Mo1N1C2 favors the reaction | good activity/high energy consumption | [ |
| CoNi-SAs/NC | Co, Ni | 1.57 | 0.76 (0.1 mol L-1 KOH) | 101.4 (ZAB) | synergistic interaction of Co SAs and Co-Ni sites lowers the reaction energy barrier | outstanding performance/many steps | [ |
| Fe2/Co1-GNCL | Fe, Co | 1.58 | 0.846 (1 mol L-1 KOH) | 218 (ZAB) | stabilized Fe dimer is formed | excellent activity/high energy consumption | [ |
| CoFe-N-C | Fe, Co | 1.59 | 0.897 (0.1 mol L-1 KOH) | 142.1 (ZAB) | two neighboring metal atoms can adjust the electronic structure of the active site | exceptional activities/ environmentally unfriendly | [ |
| NiFe-LDH@Fe/CNP | Fe | 1.594 | 0.867 (1 mol L-1 KOH) | — | flexible dimension control | long-term cycling stability/high energy consumption | [ |
| FeNi SAs/NC | Ni, Fe | 1.50 | 0.84 (0.1 mol L-1 KOH) | 42.22 (ZAB) | Ni site regulates the electronic structure of the central Fe site | extraordinary activity/ environmentally unfriendly | [ |
| FeCo-DACs/NC | Fe, Co | 1.60 | 0.877 (1 mol L-1 KOH) | 175 (ZAB) | dual atoms optimize the d-band center of the reaction site | excellent performance/ high energy consumption | [ |
| Fe SAs/NC | Fe | 1.55 | 0.83 (0.5 mol L-1 H2SO4) | 306.1 (ZAB) | engineered electronic structure of active sites modulates Fe charge distribution | remarkable activity/ high energy consumption | [ |
| 0.93 (0.1 mol L-1 KOH) | |||||||
| 0.75 (0.1 mol L-1 PBS) | |||||||
| CNT@SAC-Co/NCP | Co | 1.61 | 0.87 (0.1 mol L-1 KOH) | 172 (ZAB) | hierarchical porous structure, independent single-atom and nanosized phases, and conductive networks | excellent activity/high energy consumption | [ |
| SCoNC | Co | 1.54 | 0.91 (0.1 mol L-1 KOH) | 194 (ZAB) | high-density dispersed Co SAs | excellent activity/high energy consumption | [ |
| UNT Co SAs/N-C | Co | 1.61 | 0.89 (0.1 mol L-1 KOH) | — | high-quality SAs, precise local coordination of CoN4, and well-aligned carbon matrix | superior performance/environmentally unfriendly | [ |
| FeNx-PNC | Fe | 1.625 | 0.86 (0.1 mol L-1 KOH) | 278 (ZAB) | abundant active sites and high intrinsic activity | superior activity/high energy consumption | [ |
| CoDNi-N/C | Co, Ni | 1.59 | 0.81 (0.1 mol L-1 KOH) | — | homogeneous Co/Ni double atoms and abundant content of micropores and nitrogen | good performance/high energy consumption | [ |
| Co SA@NCF/CNF | Co | 1.63 | 0.88 (1 mol L-1 KOH) | — | single-atom active sites and hierarchically porous architectures | excellent activity/many steps | [ |
Fig. 17. (a) Proposed reaction mechanism of Sn/NCNFs and NCNFs electrocatalysts in electrocatalytic CO2RR. JCO (b) and Tafel slops (c) of Sn/NCNFs, and other electrocatalysts. Reprinted with permission from Ref. [157]. Copyright 2023, John Wiley and Sons. (d) Proposed reaction mechanism of Ni-SAs/HMMNC-800 electrocatalyst in electrocatalytic CO2RR. (e) Current-time response of Ni-SAs/HMMNC-800 electrocatalyst at a constant potential of -0.7 V (inset is FECO at a different time). Reprinted with permission from Ref. [391]. Copyright 2022, John Wiley and Sons. (f) Proposed reaction mechanism of Ni/Cu-N-C electrocatalyst in electrocatalytic CO2RR. (g) TOF for Ni/Cu-N-C, and other electrocatalysts at different potentials. Reprinted with permission from Ref. [392]. Copyright 2021, American Chemical Society.
| Electrocatalyst | Active metal | Value-added products | FEs (%)/ Potential (V vs. RHE) | Characteristic | Pros and cons | Refs. |
|---|---|---|---|---|---|---|
| Ni-N-C | Ni | CO | 99 (-0.67) | adjusting the d-band center distribution of Ni using local dynamic behavior | promising performance and excellent robustness/high energy consumption | [ |
| Co-POMOFs | Co | CO | 99 (-1.0) | POM enhances electron transfer | excellent performance/environmentally unfriendly | [ |
| Zn/NC NSs | Zn | CO | 98.2 (-0.5) | unique coordination environment and atomic dispersion | outstanding FECO/high energy consumption | [ |
| Fe-N-C | Fe | CO | 90 (-0.8) | adjustment of Fe-N bond length and local strain | good performance / high energy consumption | [ |
| NiSA-N2-C | Ni | CO | 98 (-0.8) | lowest N coordination number | high FECO/high energy consumption | [ |
| Sn/NCNFs | Sn | CO | 96.5 (-0.7) | isolated Sn-N active sites | outstanding activity/high energy consumption | [ |
| O-Fe-N-C | Fe | CO | 95 (-0.5) | axial O-coordination regulates the binding energy of intermediates | excellent activity / high energy consumption | [ |
| Ni-SAs/HMMNC-800 | Ni | CO | 99.5 (-0.7) | Ni-N3 sites cooperating with defects reducing reaction energy barriers | excellent activity and selectivity, wide potential range/high energy consumption | [ |
| Ni/Cu-N-C | Cu, Ni | CO | 99.2 (-0.79) | adjacent NiN4 and CuN4 moieties lowering the overall reaction barriers | high FECO, wide potential range/high energy consumption | [ |
| Ni/Fe-N-C | Fe, Ni | CO | 98 (-0.39) | nearby Ni and Fe weaken the bonding energy of the CO2RR intermediates | exclusive selectivity/high energy consumption | [ |
| In-SAs/NC | In | HCOO- | 96 (-0.65) | isolated Inδ+-N4 atomic interface sites | extremely large TOF/high energy consumption | [ |
| Fe1N2O2/NC | Fe | CO | 99.7 (-0.5) | high-precision manipulation of coordinating atoms to boost the performances | high FECO, wide potential range/high energy consumption | [ |
| Cu-In-NC | Cu, In | CO | 96 (-0.7) | neighboring In sites modify the electronic structure of Cu sites | high FECO/high energy consumption | [ |
| 2Bn-Cu@UiO-67 | Cu | CH4 | 81 (-1.5) | σ donation of NHC enriches the surface electron density of Cu SAS | outstanding FECH4/many steps | [ |
| SA Ni-NC | Ni | CO | 95 (-0.8) | NiN4 site facilitates the rapid desorption of CO | record-high CO yield rate/high energy consumption | [ |
| Ni-N3-C | Ni | CO | 95.6 (-0.65) | lower Ni coordination number in Ni-N3-C | ultrahigh FECO and TOF/high energy consumption | [ |
| Cu-DBC | Cu | CH4 | 80 (-0.9) | Cu-O4 sites lower the reaction energy barrier | high FECH4/low yield | [ |
| Co-SAs/Zr-CPF | Co | CO | 76.8 (-0.8) | rich Co-N4 active centers and hierarchical porous structure | highest activity and selectivity/low yield | [ |
| Ni/N-CNTs | Ni | CO | 96 (-0.67) | placement of polymers in MOF pores | high activity, selectivity, and stability / high energy consumption | [ |
| HNTM-Au-SA | Au | CO | 94.2 (-0.9) | placement of polymers in MOF pores | high TOF and FECO/low yield | [ |
| Ni(NC)-1 | Ni | CO | >99 (-0.75 ~ -0.80) | regulating the surface environment of Ni species | high performances and FECO/high energy consumption | [ |
| Fe1NC/S1-1000 | Fe | CO | 96 (-0.5) | size modulation and the redistribution of doped N species | superior performance, FECO, TOF, and outstanding stability / high energy consumption | [ |
| CoNC | Co | CO | >90 (-0.57 ~ -0.88) | depending on the type, charge, spin, and coordination layers of the metal atoms, different configurations have been investigated | good performances, wide potential range/high energy consumption | [ |
| Ni1-N-C | Ni | CO | 96.8 (-0.8) | catalytic properties of different SAs in similar support site environments | high FECO/high energy consumption | [ |
| Co1-N4 | Co | CO | 82 (-0.8) | pyrolysis temperature regulates different coordination environments | excellent performance, remarkable stability/high energy consumption | [ |
| FeSAs/CNF-900 | Fe | CO | 86.9 (-0.47) | introduction of a large number of large mesopores in a nano-framework | remarkable activity and selectivity/high energy consumption | [ |
| M-AuPd(20) | Au | HCOO- | 99 (-0.25) | localized disorder on the catalyst surface by atomic modulation | excellent activity, selectivity, and stability/environmentally unfriendly | [ |
| Fe1-Ni1-N-C | Fe, Ni | CO | 96.2 (-0.5) | neighboring Ni SAs can activate Fe SAs through non-bonding interactions | superior performance with excellent CO selectivity and durability/high energy consumption | [ |
Table 4 Summary of SACs originating from MOFs for the CO2RR.
| Electrocatalyst | Active metal | Value-added products | FEs (%)/ Potential (V vs. RHE) | Characteristic | Pros and cons | Refs. |
|---|---|---|---|---|---|---|
| Ni-N-C | Ni | CO | 99 (-0.67) | adjusting the d-band center distribution of Ni using local dynamic behavior | promising performance and excellent robustness/high energy consumption | [ |
| Co-POMOFs | Co | CO | 99 (-1.0) | POM enhances electron transfer | excellent performance/environmentally unfriendly | [ |
| Zn/NC NSs | Zn | CO | 98.2 (-0.5) | unique coordination environment and atomic dispersion | outstanding FECO/high energy consumption | [ |
| Fe-N-C | Fe | CO | 90 (-0.8) | adjustment of Fe-N bond length and local strain | good performance / high energy consumption | [ |
| NiSA-N2-C | Ni | CO | 98 (-0.8) | lowest N coordination number | high FECO/high energy consumption | [ |
| Sn/NCNFs | Sn | CO | 96.5 (-0.7) | isolated Sn-N active sites | outstanding activity/high energy consumption | [ |
| O-Fe-N-C | Fe | CO | 95 (-0.5) | axial O-coordination regulates the binding energy of intermediates | excellent activity / high energy consumption | [ |
| Ni-SAs/HMMNC-800 | Ni | CO | 99.5 (-0.7) | Ni-N3 sites cooperating with defects reducing reaction energy barriers | excellent activity and selectivity, wide potential range/high energy consumption | [ |
| Ni/Cu-N-C | Cu, Ni | CO | 99.2 (-0.79) | adjacent NiN4 and CuN4 moieties lowering the overall reaction barriers | high FECO, wide potential range/high energy consumption | [ |
| Ni/Fe-N-C | Fe, Ni | CO | 98 (-0.39) | nearby Ni and Fe weaken the bonding energy of the CO2RR intermediates | exclusive selectivity/high energy consumption | [ |
| In-SAs/NC | In | HCOO- | 96 (-0.65) | isolated Inδ+-N4 atomic interface sites | extremely large TOF/high energy consumption | [ |
| Fe1N2O2/NC | Fe | CO | 99.7 (-0.5) | high-precision manipulation of coordinating atoms to boost the performances | high FECO, wide potential range/high energy consumption | [ |
| Cu-In-NC | Cu, In | CO | 96 (-0.7) | neighboring In sites modify the electronic structure of Cu sites | high FECO/high energy consumption | [ |
| 2Bn-Cu@UiO-67 | Cu | CH4 | 81 (-1.5) | σ donation of NHC enriches the surface electron density of Cu SAS | outstanding FECH4/many steps | [ |
| SA Ni-NC | Ni | CO | 95 (-0.8) | NiN4 site facilitates the rapid desorption of CO | record-high CO yield rate/high energy consumption | [ |
| Ni-N3-C | Ni | CO | 95.6 (-0.65) | lower Ni coordination number in Ni-N3-C | ultrahigh FECO and TOF/high energy consumption | [ |
| Cu-DBC | Cu | CH4 | 80 (-0.9) | Cu-O4 sites lower the reaction energy barrier | high FECH4/low yield | [ |
| Co-SAs/Zr-CPF | Co | CO | 76.8 (-0.8) | rich Co-N4 active centers and hierarchical porous structure | highest activity and selectivity/low yield | [ |
| Ni/N-CNTs | Ni | CO | 96 (-0.67) | placement of polymers in MOF pores | high activity, selectivity, and stability / high energy consumption | [ |
| HNTM-Au-SA | Au | CO | 94.2 (-0.9) | placement of polymers in MOF pores | high TOF and FECO/low yield | [ |
| Ni(NC)-1 | Ni | CO | >99 (-0.75 ~ -0.80) | regulating the surface environment of Ni species | high performances and FECO/high energy consumption | [ |
| Fe1NC/S1-1000 | Fe | CO | 96 (-0.5) | size modulation and the redistribution of doped N species | superior performance, FECO, TOF, and outstanding stability / high energy consumption | [ |
| CoNC | Co | CO | >90 (-0.57 ~ -0.88) | depending on the type, charge, spin, and coordination layers of the metal atoms, different configurations have been investigated | good performances, wide potential range/high energy consumption | [ |
| Ni1-N-C | Ni | CO | 96.8 (-0.8) | catalytic properties of different SAs in similar support site environments | high FECO/high energy consumption | [ |
| Co1-N4 | Co | CO | 82 (-0.8) | pyrolysis temperature regulates different coordination environments | excellent performance, remarkable stability/high energy consumption | [ |
| FeSAs/CNF-900 | Fe | CO | 86.9 (-0.47) | introduction of a large number of large mesopores in a nano-framework | remarkable activity and selectivity/high energy consumption | [ |
| M-AuPd(20) | Au | HCOO- | 99 (-0.25) | localized disorder on the catalyst surface by atomic modulation | excellent activity, selectivity, and stability/environmentally unfriendly | [ |
| Fe1-Ni1-N-C | Fe, Ni | CO | 96.2 (-0.5) | neighboring Ni SAs can activate Fe SAs through non-bonding interactions | superior performance with excellent CO selectivity and durability/high energy consumption | [ |
Fig. 18. Recently reported overpotentials and the corresponding Faraday efficiencies of the product summary plots for classical SACs originating from MOFs in the electrocatalytic CO2RR.
Fig. 19. (a) Schematic diagram of Ru@ZrO2/NC electrocatalyst for electrocatalytic NRR. (b) The FEs of Ru@ZrO2/NC and other electrocatalysts at various applied potentials. Reprinted with permission from Ref. [425]. Copyright 2019, Elsevier. (c) Schematic illustration of ISAS-Fe/NC electrocatalyst for electrocatalytic NRR. (d)NH3 yield rate at the different potentials of ISAS-Fe/NC electrocatalyst. Reprinted with permission from Ref. [426]. Copyright 2019, Elsevier. (e) Proposed reaction mechanism of Zn1N-C electrocatalyst in electrocatalytic NRR. (f) LSV curves of Zn1N-C electrocatalyst. (g) FE values and NH3 yields of Zn1N-C electrocatalyst at various potentials. Reprinted with permission from Ref. [134]. Copyright 2022, John Wiley and Sons.
Fig. 20. (a) Schematic diagram of the synthesis process of Ru SAs/N-C catalyst. In quinoline hydrogenation reactions of Ru SAs/N-C (b) and Ru NCs/C (c) catalysts for catalytic activity and selectivity. Reprinted with permission from Ref. [432]. Copyright 2017, American Chemical Society. (d) Proposed reaction mechanism of 1.5 wt% CuSA-TiO2 photocatalyst in photocatalytic H2 evolution. (e) Photocatalytic H2 evolution performance of TiO2 and TiO2 loaded with different ratios of Cu SACs photocatalysts. Reprinted with permission from Ref. [433]. Copyright 2022, Nature Publishing Group. (f) Schematic illustration of FeN3P-SAzyme. (g) Time curves of FeN3P-SAzyme, FeN4-SAzyme, and Fe3O4 nanozyme catalyzing the TMB colorimetric reaction. Reprinted with permission from Ref. [434]. Copyright 2021, Nature Publishing Group.
Fig. 21. Proposed reaction mechanism of (a) Fe1(OH)x/P-C electrocatalyst in electrocatalytic OER, (The white, red, green, and blue spheres represent H, O, Ru, and Ir atoms, respectively.) (b) Ni-N-C electrocatalyst in electrocatalytic ORR. (c) HNTM-Au-SA electrocatalyst in electrocatalytic CO2RR. (d) UNT Co SAs/N-C electrocatalyst in electrocatalytic ORR/OER. Reprinted with permission from Ref. [443], Copyright 2021, American Chemical Society; Ref. [142], Copyright 2021, John Wiley and Sons; Ref. [404], Copyright 2019, Nature Publishing Group; Ref. [301], Copyright 2019, Elsevier.
Fig. 22. Outlooks of SACs originating from MOFs.
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