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摘要: 本文全面综述了用于电化学反应的炭载单原子催化剂（SAC）的最新进展。首先简要介绍了炭载单原子催化剂的发展和优势，然后详细总结了各种炭载单原子催化剂的合成策略，包括气相传输、高温热解和湿化学方法。随后，回顾了炭载 SAC 的先进表征技术，总结了炭载 SAC 在氧气还原反应、二氧化碳还原反应、氮气还原反应、氢气进化反应和氧气进化反应等不同领域的应用。特别强调了提高炭载SACs电催化性能的改性策略。最后，讨论了利用炭载 SAC 进行电化学反应的前景和挑战。Abstract: Recent advances in the use of carbon-supported single-atom catalysts (SACs) for electrochemical reactions are comprehensively reviewed. The development and advantages of carbon-supported SACs are briefly introduced, followed by a detailed summary of the synthesis strategies used, including vapor phase transport, high temperature pyrolysis and wet chemical methods. Advanced characterization techniques for carbon-supported SACs are also reviewed. The use of carbon-supported SACs in different fields, such as the oxygen reduction reaction, carbon dioxide reduction reaction, nitrogen reduction reaction, hydrogen evolution reaction, and oxygen evolution reaction are summarized. Special emphasis is given to the modification strategies used to enable carbon-supported SACs to have an excellent electrocatalytic performance. Finally, the prospects and challenges associated with using carbon-supported SACs for electrochemical reactions are discussed.
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Key words:
- Single-atom catalysts /
- Carbon /
- Electrochemical reactions /
- Synthesis /
- Modification
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Figure 1. Vapor phase transport methods for SACs preparation. (a) Scheme of the formation isolated copper sites (Cu ISAS/N-C) catalyst. (b) Aberration-corrected high-angle annular dark-field scanning transmission electron microscope (AC HAADF-STEM) image of NC. (c) AC HAADF-STEM image of Cu ISAS/NC. (d) Corresponding EDS mapping of Cu ISAS/NC. (e) Cu K-edge X-ray absorption near-edge structure (XANES) and (f) FT k3-weighted extended X-ray absorption fine structure (EXAFS) spectra of Cu ISAS/NC and the reference samples. (g) Corresponding FT-EXAFS fitting curves of Cu ISAS/NC (Reprinted with permission, Copyright 2019, Springer Nature.)[45]
Figure 2. High temperature pyrolysis methods for SACs preparation. (a) Formation process of single Co atoms with precise N-coordination. (b) TEM, HAADF-STEM and AC-HAADF-STEM images of Co SAs/N-C(800), showing that only Co single atoms are present in Co SAs/N-C. (c) XRD patterns of the as-prepared samples by annealing of Zn1Co1-BMOF at different temperatures. (d) Co K-edge XANES spectra and (e) the k3-weighted χ(k)-function of the EXAFS spectra. The corresponding EXAFS fitting curves for the samples (f) Co SAs/N-C(800) and (g) Co SAs/N-C(900). Insets are the proposed Co-Nx architectures. (h) N2 adsorption and desorption isotherms for Zn1Co1-BMOF, Co SAs/N-C, and Co NPs/N-C. (Reprinted with permission, Copyright 2016, Wiley-VCH)[50]
Figure 3. Wet-chemistry strategies for SAC preparation. (a) Schematic illustration of the preparation and model structure of the atomically dispersed noble metal catalysts. (b) HAADF-STEM images of 5Pt/meso S―C, 10Pt/meso S―C, 20Pt/meso S―C, and 30Pt/meso S―C. (c) XRD patterns of the Pt/meso S―C catalysts. The standard peaks of Pt (JCPDS no. 04-0802) were shown in red lines. (d) Normalized XANES spectra of 10Pt/meso S―C, 30Pt/meso S―C, H2PtCl6/meso S―C and Pt foil at the Pt L3-edge. (e) EXAFS spectra of 10Pt/meso S―C, 30Pt/meso S―C, Pt foil and PtO2. (Reprinted with permission, Copyright 2019, Science Advance.)[55]
Figure 4. (a) Illustration for the synthesis of Pt1/NCNS. (Reprinted with permission, Copyright 2022, Wiley-VCH.)[56] (b) Schematic of the formation of Pt-SAs/C and Pt-NP/C in the 2 sides of an H-cell under electroplating. (Reprinted with permission, Copyright 2020, The Royal Society of Chemistry.)[57] (c) The solid-phase synthesis of Fe-doped-ZIF-8 crystal and carbonization for final Fe―N―C catalyst. (Reprinted with permission, Copyright 2017, Wiley-VCH.)[58]
Figure 5. Experimental XANES spectra of (a) Co K-edge for Co-SAC, (b) Ni K-edge for Ni-SAC, (c) W L3-edge for W-SAC and first derivative curves (insets) with their reference samples (bulk metal and metal oxide). Fourier transform (FT) magnitudes of EXAFS spectra in R space of (d) Co-SAC, (e) Ni-SAC and (f) W-SAC with their bulk and oxide states respectively. (g–i) Relative comparison between experimentally obtained XANES spectra with the theoretically derived one based on M-N4C4 moieties embedded in the graphene structure (insets). (j-l) STEM images of (j) W-SAC, (k) Co-SAC, and (l) Ni-SAC, respectively, at higher magnification. (Reprinted with permission, Copyright 2019, WILEY-VCH.)[69]
Figure 6. In-situ Raman spectra of Fe SAs-Fe2P NPs/NPCFs-2.5 recorded in O2-saturated (a) 0.5 mol L−1 H2SO4 and (b) 0.1 mol L−1 KOH at room temperature. In-situ ATR-SEIRAS spectra of potential and time difference spectra for the Fe SAs-Fe2P NPs/NPCFs-2.5 recorded in O2-saturated (c–f) 0.5 mol L−1 H2SO4 and (g–j) 0.1 mol L−1 KOH at room temperature. (Reprinted with permission, Copyright 2022, Wiley-VCH)[27]
Figure 7. (a) SEM and TEM images of Cu/Zn―NC. (b) ORR polarization curves of Zn―NC, Cu―NC and Cu/Zn―NC and 20% Pt/C catalysts tested in O2-saturated 0.1 mol L−1 KOH electrolyte with a scanning rate of 5 mV s−1 at 1600 r min−1. (c) Eonset and E1/2 values of different catalysts. (d) The corresponding Tafel curves derived from (b). Free energy diagram for ORR process on the 3 models at the equilibrium potentials of (e) U=0 V and (f) U=1.23 V at pH 14. (g) Proposed ORR mechanism on the Cu−N4/Zn−N4 site (green: Zn atom, orange: Cu atom, blue: N atom, gray: C atom). (Reprinted with permission, Copyright 2021, Wiley-VCH.)[85]
Figure 8. (a) RDE voltammograms of Ru-N/G-Tannealing (Tannealing = 550, 650, 750 or 800 °C) catalysts prepared with different annealing temperatures on glassy carbon electrodes in an O2-saturated 0.1 mol L−1 HClO4 solution at a rotation rate of 1600 r min−1. The catalyst loading was 0.32 mg cm–2 for all samples. (b) RDE voltammograms of Ru-N/G-750 in O2-saturated 0.1 mol L−1 HClO4 solution at a rotation rate of 1600 r min−1, with Fe-N/G-750 and Pt/C as references. The inset shows the enlarged view of ORR currents near the onset region. (c) Free-energy diagram of the ORR on selected nitrogen-coordinated metal moieties embedded on graphene sheets. The proposed associative mechanism involves the following steps: (1) O2+* → O2*; (2) O2* + H+ + e– → OOH*; (3) OOH* + H+ + e– → O* + H2O; (4) O* + H+ + e– → OH*; and (5) OH* + H+ + e– → H2O, where * denotes the adsorption site on the catalyst surface. (d) Proposed reaction scheme of the associative mechanism for the ORR on Ru-oxo-N4 moiety in acidic medium. (Reprinted with permission, Copyright 2017, American Chemical Society.)[82] (e) LSV curves. (f) Onset potential and half-wave potential for Fe SA-NSC-900, Fe SA-NC-900, and Pt/C. The calculated charge density distribution in FeN4 and FeN3S (g). (h) Comparison of free-energy diagram of oxygenated intermediates in ORR on FeN3S and FeN4. (Reprinted with permission, Copyright 2021, American Chemical Society.)[83]
Figure 9. (a) Typical HAADF-STEM image of the optimal ZnNx/C catalyst. (b) EXAFS signal in R-space for the adsorbed ZnNx/C catalyst. (c) The proposed reaction pathways for complete CO2RR on carbon supported Zn―N4 active site and (d) the free energy diagrams for this process on ZnN4/C, N4/C and ZnC4. (e) Top: pH-corrected LSV of N-C and ZnNx/C in N2-saturated KH2PO4/K2HPO4 (pH 7.0) and CO2-saturated (pH 7.2) 0.5 mol L−1 KHCO3 solution; bottom: Comparison of LSV results for C, N―C, Zn―C, and ZnNx/C catalysts in CO2-saturated 0.5 mol L−1 KHCO3. (f) FEs of CO and H2 at various applied potentials on ZnNx/C catalyst. (g) TOFs of ZnNx/C catalyst at different applied potentials. (h) Long-term stability of ZnNx/C at a potential load of −0.43 V and the corresponding FEs of CO and H2. (Reprinted with permission, Copyright 2018, Wiley-VCH.)[109]
Figure 10. (a) LSV curves measured in the CO2 saturated 0.5 mol L−1 KHCO3 electrolyte. (b) FE curves for CO. (c) The proposed reaction pathways and free energy diagrams for electrochemical reduction of CO2 to CO. (Reprinted with permission, Copyright 2022, Elsevier.)[113] (d) Atomic-resolution AC-STEM image and corresponding enlarged AC-STEM image. Atomic-level dispersed Ni species are displaying in the form of bright dots highlighted by yellow circles. (e) Polarization curves of Ni―N4―O/C (red), Ni―N4/C (black), and NC (blue) in CO2-saturated (Solid) and Ar-saturated (Dash) 0.5 mol L−1 KHCO3 solutions. (f) CO FEs at different potentials for Ni―N4―O/C, Ni―N4/C, and NC. (g)DFT-based potential barriers for the optimized Ni―Nx―O/C (x=1, 2, 3 and 4) models: from the CO2* transition to COOH*, from the COOH* transition to CO* during the CO2RR, and the H2O* transition to H* during the water dissociation process. (Reprinted with permission, Copyright 2021, Wiley-VCH.)[111]
Figure 11. (a) The optimized structure of pristine g-C3N4 monolayer and the possible sites for the single metal atoms to adsorb on the g-C3N4 substrate. (b) The computed Gibbs free energy changes (∆G) of potential-determining step of NRR on various single metal atoms supported on g-C3N4 surface. (Reprinted with permission, Copyright 2019, Wiley-VCH.)[143] (c) Gibbs free energy diagram of NRR at different applied potentials on Fe2N4@graphene by the distal pathway. (Reprinted with permission, Copyright 2021, American Chemical Society.)[144] (d) Top and side views of the atomic structure of NiCo@GDY. (e) Free energy profiles for the NRR on the FeCo@GDY catalyst through the distal pathway at different applied potentials of the reaction intermediates. (Reprinted with permission, Copyright 2021, Elsevier.)[139]
Figure 12. (a) Atomic-resolution HAADF-STEM images for Pt-GDY1 and Elemental mapping for Pt-GDY2. (b) The polarization curves for Pt-GDY1, Pt-GDY2, and commercial Pt/C in 0.5 mol L−1 H2SO4 solution, with a scan rate of 5 mV s−1. (c) Tafel plots of Pt/C, Pt-GDY1, and Pt-GDY2 for HER. (d) The configuration of Pt-GDY2 with hydrogen adsorbed on and the calculated Gibbs free energy diagram for hydrogen evolution on different catalysts. (Reprinted with permission, Copyright 2018, Wiley-VCH.)[149]
Figure 13. (a) Configuration of the TM/pyrrolic-N4-G monolayer. (b) The scaling relationship of OER overpotential (η) versus (εd) on TM/pyrrolic-N4-G. (c) Representative HAADF-STEM image of Ru―N―C catalyst. (Reprinted with permission, Copyright 2019, Nature Communications.)[162] (d) Optimized structure of pristine g-CN and the possible sites for TM atoms adsorption on g-CN with the binding energies of TM atoms. (e) Free energy diagram for HER under standard conditions. (f) HER volcano curve of exchange current as a function of the Gibbs free energy (ΔGH*) of hydrogen adsorption on TM/g-CN. (Reprinted with permission, Copyright 2020, Elsevier.)[164]
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