催化学报 ›› 2023, Vol. 47: 32-66.DOI: 10.1016/S1872-2067(23)64392-X
詹麒尼, 帅婷玉, 徐慧民, 黄陈金, 张志杰, 李高仁*()
收稿日期:
2022-10-21
接受日期:
2022-12-22
出版日期:
2023-04-18
发布日期:
2023-03-20
通讯作者:
*电子信箱: ligaoren@scu.edu.cn (李高仁).
基金资助:
Qi-Ni Zhan, Ting-Yu Shuai, Hui-Min Xu, Chen-Jin Huang, Zhi-Jie Zhang, Gao-Ren Li*()
Received:
2022-10-21
Accepted:
2022-12-22
Online:
2023-04-18
Published:
2023-03-20
Contact:
*E-mail: ligaoren@scu.edu.cn (G. Li).
About author:
Prof. Gao-Ren Li (College of Materials Science and Engineering, Sichuan University) received his B.A. degree from East China University of Technology in 2000, and Ph.D. degree from Sun Yat-sen University in 2005. From September 2005 to September 2021, he worked in School of Chemistry, Sun Yat-sen Universtiy. Since October 2021, he has been working in College of Materials Science and Engineering, Sichuan University. His current research interests mainly focus on electrocatalysis, especially water splitting and electrochemical conversion of CO2.
Supported by:
摘要:
自2011年张涛院士等首次提出单原子催化剂(SACs)概念以来, 单原子催化迅速成为研究热点. SACs具有最大的原子利用率、独特的结构和性能, 因而在催化领域具有很好的应用前景, 备受关注.
本文首先介绍了基于自下而上和自上而下合成策略的各种SACs制备方法以及近年来相应的研究进展, 其中包括浸渍法、共沉淀法、原子层沉积法等较为传统的催化剂合成策略, 以及缺陷设计法、空间限域法和火焰喷雾热解法等新方法, 并详述了这些制备方法在实际应用中的优缺点. 对于电催化原理分析方面, 较详细地介绍了各电化学能源转换领域相关催化反应的理论计算结果以及各催化反应相应的原理与途径. 然后重点介绍了含贵金属(Pt, Pd, Ir等)和非贵金属(Fe, Cu, Co等)的SACs在析氧反应、析氢反应、氧还原反应、CO2还原反应和氮还原反应中的电催化应用. 最后讨论了SACs的应用前景和未来面临的挑战: (1) 深入进行SACs制备方法的研究, 提高合成策略的实际应用可行性以推进催化剂的工业化进程; (2) 提高SACs中金属负载量, 以提升其催化性能; (3) 结合理论计算, 增强对SACs配位环境、电子结构的精确控制, 进而优化催化剂的催化性能; (4) 由于高原子表面能, 单原子催化剂在催化应用中需解决活性金属单原子容易出现的团聚问题, 因此, 提高催化剂稳定性是SACs催化性能研究的重要方向; (5) 单原子催化剂的结构简单均一, 这非常有利于理论计算研究, 目前仍有很多单原子的催化机理尚未明确, 可基于理论模拟进一步加深对单原子催化机理的研究. 虽然SACs在未来的开发研究中仍面临着诸多亟待解决的问题, 但其未来应用潜力非常令人期待; 经过不断的发展创新, 高性能低成本的单原子催化剂将在工业化生产以及新能源发展中扮演着越来越重要的角色.
詹麒尼, 帅婷玉, 徐慧民, 黄陈金, 张志杰, 李高仁. 单原子催化剂的合成及其在电化学能量转换中的应用[J]. 催化学报, 2023, 47: 32-66.
Qi-Ni Zhan, Ting-Yu Shuai, Hui-Min Xu, Chen-Jin Huang, Zhi-Jie Zhang, Gao-Ren Li. Syntheses and applications of single-atom catalysts for electrochemical energy conversion reactions[J]. Chinese Journal of Catalysis, 2023, 47: 32-66.
Fig. 3. (a) EDX elemental analysis diagram corresponding to Pt + Ga overlayer. The top view (b) and diagonal view (c) of the atomic simulation diagram of optimized CO adsorption structure on (PtGa+Pb)-Pt1. (d) The comparison diagram of the three C-H bond cleavage and the free energy barrier of propylene formation during propane conversion on Pt3Sn-Pt3, PtGa-Pt3 and PtGa-Pt1 catalysts. E1, E2 and E3 correspond to a C-H bond cleavage, and Ed represents the activation energy of propylene desorption. Adapted with permission from Ref. [57]. Copyright 2020, Nature Publishing Group. The AC HAADF-STEM image of the Zn La-1/CN SACs (e) and the enlarged view of some of its regions (f), where yellow circles a uniformly dispersed single La atom. Adapted with permission from Ref. [62]. Copyright 2021, American Association for the Advancement of Science.
Fig. 4. (a) XANES full spectra of Pd-ZnO-ZrO2, Pd foil and PdO. Adapted with permission from Ref. [63]. Copyright 2020, Nature Publishing Group. (b) The enlarged XRD patterns of Ni SACs and MgO with different contents at 60°?65°. (c) The change of CO2 adsorption amount (A) and CO formation rate (B) with surface nickel concentration. Adapted with permission from Ref. [64]. Copyright 2019, American Chemical Society. (d) Simulation of the free energy barrier of the reaction process of L-H mechanism of CO oxidation. The AC HAADF-STEM image (e) and the partial enlarged image (f) of 0.02 wt% Au/Ce0.5Zr0.5O2. Adapted with permission from Ref. [68]. Copyright 2021, Elsevier.
Fig. 5. (a) Pd 3d XPS picture of Pd SACs loaded on different carriers. Adapted with permission from Ref. [69]. Copyright 2018, Oxford University Press. The schematic diagram of the deposition process of Ir on the cathode (b) and the anode (c) in KOH electrolyte environment. Adapted with permission from Ref. [73]. Copyright 2020, Nature Publishing Group. (d) The S 2p XPS picture of Cu-0.25V/SNGF-0.4. (e) Synthesis diagram of Cu SACs. Adapted with permission from Ref. [70]. Copyright 2021, Elsevier.
Fig. 6. (a) Concept maps of Pt-SAs/C (top) and Pt-NP/C (bottom) synthesized with or without GOM. (b) During the preparation of Pt-SAs/C, the concentrations of platinum ions on both sides of the GOM surface are close to the counter electrode (green) and the working electrode (red), respectively. (c) The XANES spectra of Pt-SAs/C, PtO2 and Pt foil at the Pt L3-edge. Adapted with permission from Ref. [74]. Copyright 2020, The Royal Society of Chemistry. (d) The simulation diagram of the preparation process of Pd1/graphene SACs, including the selection of the anchoring potential on the surface of the support and the ALD process. (e) Pd1/graphene SACs were tested for 50 h 70% propylene after 50 h durability test without propylene. Adapted with permission from Ref. [77]. Copyright 2015, American Chemical Society. (f) The L3-edge normalized X-ray absorption near edge structure spectra of ALD50Pt/NGNs, ALD100Pt/NGNs and Pt/C catalysts and standard platinum foils were compared and illustrated as the amplified spectra of L3-edge. Adapted with permission from Ref. [50]. Copyright 2016, Nature Publishing Group.
Fig. 7. (a) Synthesis schematic of Pt-Ru dimers loaded on NCNT. (b) The corresponding K2-weighted magnitude of FT spectra of EXAFS for the Pt-Ru dimers and comparison samples. (c) The normalized XANES spectra at the Ru K-edge of the Pt-Ru dimers and Ru-metal. Adapted with permission from Ref. [76]. Copyright 2019, Nature Publishing Group.
Fig. 8. (a) The atomic simulation diagram of Co1Pt1/NCNS prepared by the improved Co ALD method. H, C, N, Co and Pt are represented by white, brown, blue, orange and silver, respectively. HAADF-STEM images of Co1Pt1/NCNS (b), Fe1Pt1/NCNS (c) and Ni1Pt1/NCNS (d), in which the single atom Pt is circled by a white circle, and the single atoms Co, Fe and Ni are marked by red circles in their own images. (e) Comparison of experimental K-edge XANES spectra and theoretical spectra of Co1Pt1/NCNS. The illustration is a coordination structure atom simulation diagram. (f) The theoretical reaction coordinates of CoSACs prepared by Co(Cp)2 with Co ALD method and improved Co ALD method, respectively. Adapted with permission from Ref. [78]. Copyright 2021, Nature Publishing Group.
Fig. 9. (a) XPS spectra of C 1s of different Pt catalysts. Adapted with permission from Ref. [79]. Copyright 2019, Elsevier. (b) The R space Ni K-edge spectra of SA-NiNG-NV, and the illustration is the coordination structure of SA-NiNG-NV. (c) Schematic diagram of microwave induced plasma assisted synthesis of SA-NiNG-NV. Adapted with permission from Ref. [80]. Copyright 2021, Wiley-VCH. (d) Mo/Nv-TCN preparation schematic. (e) FTEXAFS fitting curve of Mo K-edge of 10-Mo/Nv-TCN, and the illustration is q-space fitting curve of 10-Mo/Nv-TCN. Adapted with permission from Ref. [81]. Copyright 2022, Elsevier.
Fig. 10. (a) Synthesis simulation diagram of Fe-ISAs/CN. The HAADF-STEM image (b) and enlarged image of part (c) of the Fe-ISAs/CN. Fe single atom sites are prominent in the red circle. Adapted with permission from Ref. [82]. Copyright 2017, Wiley-VCH. (d) XPS spectra of Pt 4f of SA-Pt/g-C3N4 etched by Ar+ plasma. (e) Synthesis process diagram of SA Pt/g-C3N4. Adapted with permission from Ref. [83]. Copyright 2020, Elsevier. (f) In O2-saturated 0.1 mol L?1 KOH solution, ORR polarization curves of Ce/Fe-NCNW prepared at different heat treatment temperatures. Adapted with permission from Ref. [84]. Copyright 2020, American Chemical Society.
Fig. 11. (a) A schematic diagram of the conversion process from Pd NP to Pd SACs. Adapted with permission from Ref. [87]. Copyright 2018, Nature Publishing Group. (b) Fe K-edge EXAFS spectra of SA SA/C samples and control samples. Adapted with permission from Ref. [88]. Copyright 2021, Wiley-VCH. (c) Schematic diagram of synthesis process of Fe-Nx-C. (d) Raman spectra of Fe-Nx-C and N-C. Adapted with permission from Ref. [90]. Copyright 2019, Wiley-VCH. (e) Preparation schematic diagram of Fe/N-G-SAC. (f) ORR Gibbs free energy diagram of FeN4 at edge and in-plane position. Adapted with permission from Ref. [91]. Copyright 2020, Wiley-VCH.
Fig. 12. (a) The schematic diagram of Pd/CeO2 SACs prepared by a single-step FSP method in CO oxidation reaction. Adapted with permission from Ref. [94]. Copyright 2021, Nature Publishing Group. (b) HAADF-STEM images of Cu SAs/NC-900 and the corresponding strength distribution map. (c) EXAFS fitting curves of Cu SAs/NC-800 (top) and Cu SAs/NC-900 (bottom), and illustrations correspond to CuN3 and CuN4 coordination environments, respectively. (d) Speculated simulation diagram of formation mechanism of CuN3 and CuN4. Adapted with permission from Ref. [95]. Copyright 2020, Wiley-VCH.
Fig. 13. (a) The volcanic relationship diagram of each metal for ORR, where Pt is closest to the volcanic peak. Adapted with permission from Ref. [105]. Copyright 2004, Springer American Chemical Society. (b) The process mechanism diagram of AEM mechanism for OER in alkaline conditions. Adapted with permission from Ref. [114]. Copyright 2020, the Royal Society of Chemistry. (c) The process mechanism diagram of LOM mechanism for OER. Adapted with permission from Ref. [118]. Copyright 2020, the Royal Society of Chemistry. (d) The two mechanisms of Volmer-Tafel and Volmer-Heyrovsky in the HER reaction process. Adapted with permission from Ref. [122]. Copyright 2012, American Chemical Society. (e) The volcanic relationship between various metals and MoS2 in HER. Adapted with permission from Ref. [121]. Copyright 2017, American Association for the Advancement of Science.
Fig. 14. (a) Volcano diagram associated with theoretical limit potential and DFT calculated ΔECO. Adapted with permission from Ref. [121]. Copyright 2017, American Association for the Advancement of Science. (b) A schematic diagram of the CO2RR reaction atom starting from the intermediate *H2C2OH to show the difference in reaction pathways for the preparation of ethylene and ethanol. Adapted with permission from Ref. [133]. Copyright 2013, Wiley-VCH. (c) Three possible reaction pathways of NRR on metal-based electrocatalysts. Adapted with permission from Ref. [135]. Copyright 2018, The Royal Society of Chemistry. (d) The intermediate adsorption energy distribution of NRR at the edge site of MoS2. Adapted with permission from Ref. [141]. Copyright 2018, Wiley-VCH. (e) Volcano diagrams of NRR (blue) and HER (purple) for each metal. Adapted with permission from Ref. [121]. Copyright 2017, American Association for the Advancement of Science.
SACs | Electrolyte | Overpotential (mV, j = 10 mA cm-1) | Tafel slope (mV dec-1) | Ref. |
---|---|---|---|---|
Ru1/D-NiFe LDH | 1 mol L‒1 KOH | 189 | 31 | [ |
Co-SAC/RuO2 | 1 mol L‒1 KOH | 200 | 110 | [ |
Ni-SA@NCA | 1 mol L‒1 KOH | 280 | 89.8 | [ |
Ru/Co-N-C-800 °C | 1 mol L‒1 KOH | 276 | — | [ |
Ir1Co13.3O20.1 | 1 mol L‒1 KOH | 152 | 60.5 | [ |
Co1/TaS2-3 | 1 mol L‒1 KOH | 330 | 70 | [ |
CoFe-N-C DAC | 1 mol L‒1 KOH | 360 | 67.7 | [ |
Fe1(OH)x/P-C | 1 mol L‒1 KOH | 320 | 41 | [ |
IrSA-Ni2P | 1 mol L‒1 KOH | 149 | 90.1 | [ |
IrSA-Ni12P5 | 1 mol L‒1 KOH | 178 | 91.3 | [ |
Ir1-Ni(OH)2 | 1 mol L‒1 KOH | 260 | 78 | [ |
Ni SAs@S/N-CMF | 1 mol L‒1 KOH | 285 | 50.8 | [ |
WCx-FeNi | 1 mol L‒1 KOH | 237 | 44 | [ |
W-NiS0.5Se0.5 | 1 mol L‒1 KOH | 171 | 41 | [ |
Ir0.08Co2.92O4 NWs | 0.5 mol L‒1 H2SO4 | 189.5 | 22.32 | [ |
NiSAFeSA-Ni50Fe/CNT | 1 mol L‒1 KOH | 227 | 41.8 | [ |
Table 1 The development of metal-based SACs for OER in recent years.
SACs | Electrolyte | Overpotential (mV, j = 10 mA cm-1) | Tafel slope (mV dec-1) | Ref. |
---|---|---|---|---|
Ru1/D-NiFe LDH | 1 mol L‒1 KOH | 189 | 31 | [ |
Co-SAC/RuO2 | 1 mol L‒1 KOH | 200 | 110 | [ |
Ni-SA@NCA | 1 mol L‒1 KOH | 280 | 89.8 | [ |
Ru/Co-N-C-800 °C | 1 mol L‒1 KOH | 276 | — | [ |
Ir1Co13.3O20.1 | 1 mol L‒1 KOH | 152 | 60.5 | [ |
Co1/TaS2-3 | 1 mol L‒1 KOH | 330 | 70 | [ |
CoFe-N-C DAC | 1 mol L‒1 KOH | 360 | 67.7 | [ |
Fe1(OH)x/P-C | 1 mol L‒1 KOH | 320 | 41 | [ |
IrSA-Ni2P | 1 mol L‒1 KOH | 149 | 90.1 | [ |
IrSA-Ni12P5 | 1 mol L‒1 KOH | 178 | 91.3 | [ |
Ir1-Ni(OH)2 | 1 mol L‒1 KOH | 260 | 78 | [ |
Ni SAs@S/N-CMF | 1 mol L‒1 KOH | 285 | 50.8 | [ |
WCx-FeNi | 1 mol L‒1 KOH | 237 | 44 | [ |
W-NiS0.5Se0.5 | 1 mol L‒1 KOH | 171 | 41 | [ |
Ir0.08Co2.92O4 NWs | 0.5 mol L‒1 H2SO4 | 189.5 | 22.32 | [ |
NiSAFeSA-Ni50Fe/CNT | 1 mol L‒1 KOH | 227 | 41.8 | [ |
Fig. 15. (a) Preparation schematic diagram of Ir-SA@Fe@NCNT. (b) CV curves of Ir-SA@Fe@NCNT before and after CA test. Adapted with permission from Ref. [159]. Copyright 2020, American Chemical Society. (c) The chronoamperometric curve of Ni-O-G SACs for 50-h durability test was obtained at a constant overpotential of 400 mV in 1 mol L-1 KOH. The illustration is the HAADF-STEM image of Ni-O-G SAC after durability test, where single atom Pt is highlighted by red circles. Adapted with permission from Ref. [160]. Copyright 2020, WILEY-VCH. (d) Energy distribution curve of *OH diffusion from the nearest Ni atom to Ir atom. In the illustration, O, H, Ni and Ir atoms are represented in red, pink green, and egg yolk, respectively. Adapted with permission from Ref. [161]. Copyright 2020, American Chemical Society. (e) OER polarization curve of NiFe-CNG at different Ni/Fe ratios. (f) The Bode phase plot of NiFe-CNG. (g) In different environments, Fe K-edge XANES of NiFe-CNG. The illustration is the locally amplified XANES spectrum. Adapted with permission from Ref. [162]. Copyright 2021, Nature Publishing Group.
SACs | Electrolyte | Overpotential (mV, j = 10 mA cm-1) | Tafel slope (mV dec-1) | Ref. |
---|---|---|---|---|
NiRu0.13-BDC | 1 mol L‒1 KOH | 34 | 32 | [ |
Pt-SAs/MoSe2 | 1 mol L‒1 KOH | 29 | 41 | [ |
Ru0.10@2H-MoS2 | 1 mol L‒1 KOH | 51 | 64.9 | [ |
Ru1/D-NiFe LDH | 1 mol L‒1 KOH | 18 | 29 | [ |
Co-SA@NCA | 1 mol L‒1 KOH | 78.6 | 109.6 | [ |
Ni-SA@NCA | 1 mol L‒1 KOH | 35.6 | 117.2 | [ |
Mo-SA@NCA | 1 mol L‒1 KOH | 74.5 | 126.7 | [ |
CC@WS2/Ru-450 | 1 mol L‒1 KOH | 32.1 | 53.2 | [ |
PtSA-Ni3S2@Ag NWs | 1 mol L‒1 KOH | 33 | 34.7 | [ |
Rh@NG | 1 mol L‒1 KOH | 33 | 30 | [ |
Co-NC-AF | 0.5 mol L‒1 H2SO4 | 87 | 67.6 | [ |
CoSAs-MoS2/ TiN NRs | 0.5 mol L‒1 H2SO4 | 187.5 | 165.5 | [ |
Pt-HNCNT | 0.5 mol L‒1 H2SO4 | 15 | 29.1 | [ |
NiCo-SAD-NC | 0.5 mol L‒1 H2SO4 | 54.7 | 31.5 | [ |
Pt1/Co1NC | 0.5 mol L‒1 H2SO4 | 4.15 | 17 | [ |
PtSA/C-Air | 0.5 mol L‒1 H2SO4 | 8 | 27 | [ |
Ti3C2Tx-PtSA | 0.5 mol L‒1 H2SO4 | 38 | 45 | [ |
Ru/Co-N-C-800 °C | 0.5 mol L‒1 H2SO4 | 17 | 27.8 | [ |
Pt0.8@CN-1000 | 1 mol L‒1 HClO4 | 13 | 34 | [ |
Pt0.4@CN-1000 | 1 mol L‒1 HClO4 | 50 | 55 | [ |
Table 2 The development of metal-based SACs for HER in recent years.
SACs | Electrolyte | Overpotential (mV, j = 10 mA cm-1) | Tafel slope (mV dec-1) | Ref. |
---|---|---|---|---|
NiRu0.13-BDC | 1 mol L‒1 KOH | 34 | 32 | [ |
Pt-SAs/MoSe2 | 1 mol L‒1 KOH | 29 | 41 | [ |
Ru0.10@2H-MoS2 | 1 mol L‒1 KOH | 51 | 64.9 | [ |
Ru1/D-NiFe LDH | 1 mol L‒1 KOH | 18 | 29 | [ |
Co-SA@NCA | 1 mol L‒1 KOH | 78.6 | 109.6 | [ |
Ni-SA@NCA | 1 mol L‒1 KOH | 35.6 | 117.2 | [ |
Mo-SA@NCA | 1 mol L‒1 KOH | 74.5 | 126.7 | [ |
CC@WS2/Ru-450 | 1 mol L‒1 KOH | 32.1 | 53.2 | [ |
PtSA-Ni3S2@Ag NWs | 1 mol L‒1 KOH | 33 | 34.7 | [ |
Rh@NG | 1 mol L‒1 KOH | 33 | 30 | [ |
Co-NC-AF | 0.5 mol L‒1 H2SO4 | 87 | 67.6 | [ |
CoSAs-MoS2/ TiN NRs | 0.5 mol L‒1 H2SO4 | 187.5 | 165.5 | [ |
Pt-HNCNT | 0.5 mol L‒1 H2SO4 | 15 | 29.1 | [ |
NiCo-SAD-NC | 0.5 mol L‒1 H2SO4 | 54.7 | 31.5 | [ |
Pt1/Co1NC | 0.5 mol L‒1 H2SO4 | 4.15 | 17 | [ |
PtSA/C-Air | 0.5 mol L‒1 H2SO4 | 8 | 27 | [ |
Ti3C2Tx-PtSA | 0.5 mol L‒1 H2SO4 | 38 | 45 | [ |
Ru/Co-N-C-800 °C | 0.5 mol L‒1 H2SO4 | 17 | 27.8 | [ |
Pt0.8@CN-1000 | 1 mol L‒1 HClO4 | 13 | 34 | [ |
Pt0.4@CN-1000 | 1 mol L‒1 HClO4 | 50 | 55 | [ |
Fig. 16. (a) HER polarization diagrams of various catalysts with and without SCN- ions. Adapted with permission from Ref. [178]. Copyright 2019, Nature Publishing Group. (b) High resolution core level spectrum. (c) Polarization curves of SA Pt-GDY1, SA Pt-GDY2 and commercial Pt/C. Adapted with permission from Ref. [179]. Copyright 2018, WILEY-VCH. (d) Comparison of mass activity of Pt/C, Ir-SA@Fe@NCNT and Ir-NP@Fe@NCNT. (e) Comparison of LSV curves of Ir-SA@Fe@NCNT before and after 5000 potential cycles. The illustration is the corresponding timing current test at -26 mV relative to RHE. Adapted with permission from Ref. [159]. Copyright 2020, American Chemical Society. (f) HER mechanism diagram of Ru/Ni-MoS2 under alkaline conditions. Adapted with permission from Ref. [182]. Copyright 2021, Elsevier. (g) Schematic diagram of Pt1-O2-Fe1-N4-C12. (h) LSV curves of Pt1@Fe-N-C under different Pt loadings. (i) Tafel plot of Pt1@Fe-N-C and other catalysts in 0.5 mol L?1 H2SO4. Adapted with permission from Ref. [183]. Copyright 2018, Wiley-VCH.
SACs | Electrolyte | Eonset (V vs. RHE) | E1/2 (V vs. RHE) | Tafel slope (mV dec-1) | Ref. |
---|---|---|---|---|---|
Fe/OES | 0.1 mol L‒1 KOH | 1.00 | 0.85 | — | [ |
Fe-N4-C | 0.1 mol L‒1 KOH | 1.02 | 0.89 | 72 | [ |
FNC1/5 | 0.1 mol L‒1 HClO4 | 0.96 | 0.79 | — | [ |
Ru-SAS/SNC | 0.1 mol L‒1 KOH | 0.998 | 0.861 | 57.6 | [ |
Co2/Fe-N@CHC | 0.1 mol L‒1 KOH | — | 0.915 | 62 | [ |
Fe-N@CHC | 0.1 mol L‒1 KOH | — | 0.894 | 68 | [ |
Se@NC-1000 | 0.1 mol L‒1 KOH | 0.95 | 0.85 | 52 | [ |
Fe-N-GDY | 0.1 mol L‒1 KOH | 1.05 | 0.89 | — | [ |
FeN4-O-NCR | 0.1 mol L‒1 KOH | 1.05 | 0.942 | 54.3 | [ |
SACs-Mn-1000@g-C3N4 | 0.1 mol L‒1 KOH | 0.95 | 0.863 | 79 | [ |
Pt1@Co/NC | 0.1 mol L‒1 HClO4 | — | 0.89 | — | [ |
Fe1Se1-NC | 0.1 mol L‒1 KOH | 1.00 | 0.88 | — | [ |
Ag1-h-NPClSC | 0.1 mol L‒1 KOH | 0.998 | 0.896 | 55 | [ |
Pt1@Pt/NBP | 0.1 mol L‒1 HClO4 | — | 0.867 | — | [ |
Zn-N4P/C | 0.1 mol L‒1 KOH | 1.01 | 0.86 | 81 | [ |
Table 3 The development of metal-based SACs for ORR in recent years.
SACs | Electrolyte | Eonset (V vs. RHE) | E1/2 (V vs. RHE) | Tafel slope (mV dec-1) | Ref. |
---|---|---|---|---|---|
Fe/OES | 0.1 mol L‒1 KOH | 1.00 | 0.85 | — | [ |
Fe-N4-C | 0.1 mol L‒1 KOH | 1.02 | 0.89 | 72 | [ |
FNC1/5 | 0.1 mol L‒1 HClO4 | 0.96 | 0.79 | — | [ |
Ru-SAS/SNC | 0.1 mol L‒1 KOH | 0.998 | 0.861 | 57.6 | [ |
Co2/Fe-N@CHC | 0.1 mol L‒1 KOH | — | 0.915 | 62 | [ |
Fe-N@CHC | 0.1 mol L‒1 KOH | — | 0.894 | 68 | [ |
Se@NC-1000 | 0.1 mol L‒1 KOH | 0.95 | 0.85 | 52 | [ |
Fe-N-GDY | 0.1 mol L‒1 KOH | 1.05 | 0.89 | — | [ |
FeN4-O-NCR | 0.1 mol L‒1 KOH | 1.05 | 0.942 | 54.3 | [ |
SACs-Mn-1000@g-C3N4 | 0.1 mol L‒1 KOH | 0.95 | 0.863 | 79 | [ |
Pt1@Co/NC | 0.1 mol L‒1 HClO4 | — | 0.89 | — | [ |
Fe1Se1-NC | 0.1 mol L‒1 KOH | 1.00 | 0.88 | — | [ |
Ag1-h-NPClSC | 0.1 mol L‒1 KOH | 0.998 | 0.896 | 55 | [ |
Pt1@Pt/NBP | 0.1 mol L‒1 HClO4 | — | 0.867 | — | [ |
Zn-N4P/C | 0.1 mol L‒1 KOH | 1.01 | 0.86 | 81 | [ |
Fig. 17. (a) The schematic diagram of catalyst preparation. (b) Fe K-edge EXAFS of Fe-CNT catalyst with metal loading of 0.2 atom%. (c) Curves of H2O2 selectivity and electron transfer number in potential scanning. Adapted with permission from Ref. [200]. Copyright 2019, Nature Publishing Group. (d) In 0.1 mol L-1 KOH, LSV curves at various rotating speeds of catalysts of Fe/OES. Adapted with permission from Ref. [187]. Copyright 2020, Wiley-VCH. (e) Linear combination XANES fitting diagram of Mo1/OSG-H. Adapted with permission from Ref. [221]. Copyright 2020, Wiley-VCH.
Fig. 18. (a) Synthesis schematic of Cr SACs. (b) The pore size distribution of ZIF-8 and Cr-ZIF. (c) Polarization curve of Cr/N/C-950 initially and after 20000 test cycles. Adapted with permission from Ref. [222]. Copyright 2019, Wiley-VCH. (d) FT-EXAFS curves of Ru-SA/Ti3C2Tx. (e) Geometric area normalized LSV curves of Ru-SA/Ti3C2Tx, Pt/C, Ti3C2Tx and Ru-NP/Ti3C2Tx for ORR in O2-saturated 0.1 mol L?1 HClO4 aqueous solution. (f) The comparison of the free energy of each process of ORR on Ti3C2Tx and Ru-SA/Ti3C2Tx. Adapted with permission from Ref. [226]. Copyright 2020, Wiley-VCH.
Fig. 19. In the CO2RR process, metal-based SACs catalyze CO2 and select ways to produce corresponding products. The atomic model of the intermediate adds additional bonds to the atoms bound to the active site to distinguish the product from the intermediate. PCET, the proton coupled electron transfer, refers to different amounts of electron transfer.
Fig. 20. (a) Comparison of CO Faraday efficiency between Ni SACs-NGO catalyst and graphene supported Ni Nanoparticles in CO2-saturated 0.5 mol L?1 KHCO3 solution. (b) EXAFS contrast diagram of Ni SACs-NGO before and after stability test. Adapted with permission from Ref. [228]. Copyright 2018, The Royal Society of Chemistry. (c) A comparison of the K-edge EXAFS of Ni-SACs and other Ni metal samples. (d) The preparation diagram of mol L?1 SACs. (e) The comparison curves of Faradaic efficiency of different metals bases SACs in CO2RR. Adapted with permission from Ref. [229]. Copyright 2019, Nature Publishing Group. (f) EXAFS signal fitting curve of ZnNx/C catalyst at R space. (g) ECSA changes of ZnNx/C after long-term durability test. Adapted with permission from Ref. [230]. Copyright 2018, Wiley-VCH. (h) The FT spectra of CuSAs/TCNFs, CuO and Cu foil at R space. (i) The free energy change process of CO conversion to CH3OH. H, C, N, O and Cu atoms are represented by light blue sphere, gray, dark blue, red and orange, respectively. Adapted with permission from Ref. [231]. Copyright 2019, American Chemical Society. (j) Diagram of Ni single atom distribution in Ni-N-MEGO. (k) In N2 and CO2 saturated 0.5 mol L?1 KHCO3 solution, LSV curves of Ni-N-MEGO. (l) Reaction energy distribution maps corresponding to different Ni-N sites. Adapted with permission from Ref. [232]. Copyright 2019, Elsevier.
Fig. 21. (a) Comparison of reaction free energies of 23 kinds of SACs (M@C3, M@C4, M@N3 and M@N4) at PDS. Horizontal virtual lines represent ΔGPDS on Ru (0001) ladder surfaces. Adapted with permission from Ref. [234]. Copyright 2018, American Chemical Society. (b) Mo SAs/NPC model diagram (left) and atomic structure diagram (right). (c) At different potentials in 0.1 mol L-1 KOH, NH3 yield (red) and FE curve (blue) of Mo SAs/NPC. Adapted with permission from Ref. [235]. Copyright 2019, Wiley-VCH. (d) the PDOS of N2 adsorption on Fe SAs-NC. Adapted with permission from Ref. [236]. Copyright 2019, Elsevier. (e) Curves of NH3 yield and FE of Cu SAs-NC at different potentials in 0.1 mol L-1 KOH. Adapted with permission from Ref. [237]. Copyright 2019, American Chemical Society. (f) Preparation schematic diagram of Fe SAs-NC. Adapted with permission from Ref. [236]. Copyright 2019, Elsevier. (g) Optimized structure diagram of Cu-N2 adsorption by N*H-NH2 (a), N*H2-NH2 (b), N*N* (c), N*-N*H (d), N*H-N*H (e), and N*H-N*H2 (f). Adapted with permission from Ref. [237]. Copyright 2019, American Chemical Society. (h) Crystal structure of Fe SAs-MoS2. (i) With or without applied potential, performances of Fe SAs-MoS2 in the cycle of N2-Ar. (j) Synthesis schematic diagram of Fe SAs-MoS2. Adapted with permission from Ref. [238]. Copyright 2020, Elsevier.
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