催化学报 ›› 2024, Vol. 60: 42-67.DOI: 10.1016/S1872-2067(24)60032-X
李沐霖a, 谢一萌a, 宋静婷a, 杨级a,*(), 董金超a, 李剑锋a,b,*()
收稿日期:
2024-03-13
接受日期:
2024-04-02
出版日期:
2024-05-18
发布日期:
2024-05-20
通讯作者:
电子信箱: 基金资助:
Mu-Lin Lia, Yi-Meng Xiea, Jingting Songa, Ji Yanga,*(), Jin-Chao Donga, Jian-Feng Lia,b,*()
Received:
2024-03-13
Accepted:
2024-04-02
Online:
2024-05-18
Published:
2024-05-20
Contact:
E-mail: About author:
Ji Yang graduated with a Ph.D. from Xiamen University in 2022. He carried out postdoctoral research in Jian-Feng Li’s group at Xiamen University from 2022 to 2024. His study focuses on the structural evolution of single-atom catalysts under electrocatalytic process by employing in-situ/operando Raman/XAFS characterizations. He has published more than 26 peer-reviewed papers.Supported by:
摘要:
氨不仅是生产农业肥料和医药分子的关键原料, 同时因其具备高能量密度和零碳排放的特性, 也被视为极具潜力的能源载体. 鉴于当前对环保和可持续发展的迫切需求, 实现氨分子的绿色合成已成为重要任务. 其中, 利用可再生能源驱动的电化学合成氨技术, 因其对环境友好和高效性, 被视为替代传统哈伯-博世工艺的绿色路径, 具有广阔的应用前景. 在电化学催化合成氨的研究中, 单原子催化剂(SAC)因其独特的性质而备受关注. SAC的孤立金属中心不仅提高了金属原子的利用率, 而且有效抑制了氮-氮偶联反应, 从而显著提升了催化合成氨的效率, 成为当前的研究热点.
本文综述了SAC电催化合成氨领域的最新研究进展, 旨在为科研工作者提供基础的理论和实验参考. 系统总结了不同氮源(包括氮气、硝酸根、亚硝酸根及一氧化氮)合成氨的研究进展, 并深入探讨了催化剂的理论和实验设计、催化活性中心的种类及其催化活性, 以及真实反应过程中的催化动态行为. 首先, 介绍了自然和人工固氮系统中的氮循环路径. 自然固氮系统展示了氮气、氮氧化物、氨的循环路径, 为不同氮物种合成氨方法提供了可借鉴的思路; 而人工氮循环则阐述了社会发展、工业生产对自然循环氮平衡的破坏, 凸显了电化学人工固氮的必要性. 随后, 基于理论模拟方法, 在原子和分子尺度上总结了不同氮物种在催化剂表面的反应过程. 例如, 在氮气合成氨过程中探讨了涉及的解离路径、交替缔合及远端缔合路径等. 本文详细阐述了催化活性结构的理论筛选方法的重要性, 并介绍了如何通过结构稳定性评估、反应物种的吸附活性以及催化活性及选择性的综合考量, 来确定最佳的催化活性中心种类及微观结构. 随后, 总结了科研人员基于理论筛选结果, 采用热解策略制备碳载金属SAC的研究进展. 这些策略包括, 碳基底与金属络合物的混合热解策略、金属有机框架衍生策略、金属辅助小分子热解策略、吸附活性策略及模板牺牲辅助策略等. 同时, 系统地总结了不同SAC对四种氮前驱体还原反应的催化活性. 此外, 深入地讨论了催化活性中心如Cu和Fe单原子在合成氨反应过程中的结构动态演化行为, 强调了非原位结构可能仅是单原子前驱体, 而反应过程中演变结构才是真实催化活性中心. 这对于深入理解SAC电催化合成氨的机理和提高催化效率有一定的借鉴意义.
最后, 本文简要探讨了单原子催化剂在合成氨领域所面临的挑战及发展机遇. 主要包括(1)发展更为精准的理论预测方法, 实现从静态计算向动态模拟的转变, 以更准确地预测和解析催化剂在实际反应中的行为机制; (2)积极发展多原子协同位点, 从金属单原子到双甚至三原子团簇, 利用多原子间的协同作用提升催化效率; (3)发展可替代氨合成路径, 如低温等离子体耦合电化学合成氨技术, 以推动氨合成技术的绿色化和高效化; (4)结合动态谱学技术的发展及应用, 通过在原位甚至工况条件下的探究, 深入解析动态反应过程, 为催化剂的进一步优化提供科学依据. 通过发展更为精准的理论预测方法、多原子协同位点、可替代氨合成路径以及结合动态谱学技术的进步, 我们有望推动单原子催化剂在合成氨领域的应用取得更大突破.
李沐霖, 谢一萌, 宋静婷, 杨级, 董金超, 李剑锋. 碳载金属单原子催化剂的电合成氨进展[J]. 催化学报, 2024, 60: 42-67.
Mu-Lin Li, Yi-Meng Xie, Jingting Song, Ji Yang, Jin-Chao Dong, Jian-Feng Li. Ammonia electrosynthesis on carbon-supported metal single-atom catalysts[J]. Chinese Journal of Catalysis, 2024, 60: 42-67.
Fig. 1. The central nitrogen species and corresponding circulation in the natural and artificial ecosystems. In this picture, “a” and “b” symbols correspond to the artificial and biological processes, respectively. Reprinted with permission from Ref. [24]. Copyright 2018, Springer Nature.
Fig. 2. Multiple proposed dinitrogen reduction (N2RR) pathways on heterogeneous catalysts, including dissociative pathway, associative alternating pathway, associative distal pathway, and enzymatic pathway. Reprinted with permission from Ref. [26]. Copyright 2023, Taylor&Francis Group.
Fig. 3. The reaction pathways of NO3--to-NH3, including O-end, N-side, O-side, and N-end pathways, respectively. The N2 formation from NO3RR follows the NO-dimer pathway. Reprinted with permission from Ref. [30]. Copyright 2021, Wiley-VCH Verlag GmbH & Co.
Fig. 4. The proposed five reaction pathways of NO-to-NH3. The “*” represents the catalytic site. Reprinted with permission from Ref. [33]. Copyright 2024, Elsevier.
Fig. 5. (a) The atomic configurations of transitional metal single atoms on pristine g-C3N4 and corresponding adsorption energies. Reprinted with permission from Ref. [38]. Copyright 2018, John Wiley & Sons, Ltd. (b) The atomic structures with M@C3, M@C4, M@N3, and M@N4. Reprinted with permission from Ref. [13]. Copyright 2018, American Chemical Society. (c) The predicted TM atoms and corresponding catalyst structures of p-TM[TCNE] nanosheets (TM = 3d/4d/5d transition metals). Reprinted with permission from Ref. [40]. Copyright 2022, American Chemical Society.
Fig. 6. (a) The binding energy (left) and the difference between binding and cohesive energies (right) of different TM/g-C3N4. Reprinted with permission from Ref. [41]. Copyright 2022, Elsevier. (b) The selected metal atoms and corresponding atomic structure of TM/g-CN (TM = 3d, 4d, and 5d transitional metals). (c) The AIMD time-dependent energy and temperature evolution for Ti/g-CN and Zr/g-CN, respectively. Reprinted with permission from Ref. [30]. Copyright 2021, John Wiley & Sons, Ltd. (d) The atomic models of single atom on g-C3N4 including 3d, 4d, and 5d transition metals. Reprinted with permission from Ref. [42]. Copyright 2021, American Chemical Society
Fig. 7. (a) The N2 adsorption energy (Eads) on TM@C3N with different M-C and M-N coordination structures. (b) The activated N-N bond length (dN-N) vs. Bader charge (Q) transfer from TM@C3N to N2. Reprinted with permission from Ref. [39]. Copyright 2023, Elsevier. (c) The free energies for N2 chemisorption (top section) and the N-N bond length of the adsorbed *N2 (bottom section) on various TM@C9N4. Reprinted with permission from Ref. [44]. Copyright 2021, Elsevier. (d) The ΔGPDS on different SACs. Reprinted with permission from Ref. [13]. Copyright 2018, American Chemical Society.
Fig. 8. (a) The Gibbs free energies of NO3- adsorbed on different TM/g-C3N4 (TM = 3d, 4d, and 5d transitional metals). Reprinted with permission from Ref. [41]. Copyright 2022, Elsevier. (b) The adsorption energy of NO3- on TM/g-C3N4. (c) The charge density difference of Ru/g-C3N4 and NO3- adsorbed on Ru/g-C3N4. Reprinted with permission from Ref. [42]. Copyright 2021, American Chemical Society.
Fig. 9. (a) The scaling relationship of the free energy changes for the *N2 → *N2H and *NH2 → *NH3 steps. (b) The calculated ΔG*N2 vs. ΔG*H on the 11 promising TM@C9N4 candidates. (c) The theoretical limiting potential for 9 promising TM@C9N4 candidates. Reprinted with permission from Ref. [44]. Copyright 2021, Elsevier.
Fig. 10. (a) The limiting potentials for NO3RR on different TM/g-C3N4. Reprinted with permission from Ref. [41]. Copyright 2022, Elsevier. (b) The limiting potentials on different TM/g-C3N4 for NO3RR. (c) The volcano correlation curve between limiting potential and G*NO3 of different TM/g-C3N4. Reprinted with permission from Ref. [42]. Copyright 2021, American Chemical Society.
Fig. 11. (a) The schematic illustration of the synthetic process of SA-Ag/NC. Reprinted with permission from Ref. [48]. Copyright 2020, American Chemical Society. (b) The schematic of the synthetic process of the Fe-SAs/NSDG. Reprinted with permission from Ref. [49]. Copyright 2022, Elsevier.
Fig. 12. (a) The schematic illustration of the synthetic process of Cu-N-C. Reprinted with permission from Ref. [52]. Copyright 2022, Elsevier. (b) The schematic illustration of the synthetic process of Fe-N/P-C catalyst. Reprinted with permission from Ref. [54]. Copyright 2023, John Wiley & Sons, Ltd.
Fig. 13. (a) The schematic illustration of the synthetic process of Fe1/NC-X. Reprinted with permission from Ref. [57]. Copyright 2023, Elsevier. (b) The schematic illustration of the synthetic process of FeSAs/g-C3N4. Reprinted with permission from Ref. [58]. Copyright 2022, Elsevier. (c) The schematic illustration of the synthetic process of BCN-Cu. Reprinted with permission from Ref. [60]. Copyright 2021, Elsevier.
Fig. 14. (a) The schematic illustration of the Cu-N-C synthetic procedure. Reprinted with permission from Ref. [61]. Copyright 2022, American Chemical Society. (b) The schematic illustration of Fe/Cu-HNG catalyst. Reprinted with permission from Ref. [62]. Copyright 2023, Springer Nature.
Catalyst | Electrolyte | Potential (V vs. RHE) | Production rate | FE | Ref. |
---|---|---|---|---|---|
Ru SAs/N-C | 0.05 mol L-1 H2SO4 | -0.2 | 120.9 μgNH3 h-1 mg-1cat. | 29.6% | [ |
Ru@ZrO2/NC | 0.1 mol L-1 HCl | -0.21 | 3.665 mgNH3 h-1 mg-1Ru | 21% | [ |
Ru SAs/GDY/G | 0.5 mol L-1 Na2SO4 | -0.1 | 4.7 mgNH3 h-1 mg-1Ru | 37.6% | [ |
Rh SA/GDY | 0.005 mol L-1 H2SO4 and 0.1 mol L-1 K2SO4 | -0.2 | 74.15 μg h-1 cm-2 | 20.36% | [ |
Au1/C3N4 | 5 mmol L-1 H2SO4 | -0.1 | 1350 μg h-1 mg-1Au | 11.1% | [ |
AuSAs-NDPCs | 0.1 mol L-1 HCl | -0.2 | 2.32 μg h-1 cm-2 | 12.3% | [ |
SA-Ag/NC | 0.1 mol L-1 HCl | — | 69.4 mg h-1 mg-1Ag at -0.65 V vs. RHE | 21.9% at -0.60 V vs. RHE | [ |
FeSA-N-C | 0.1 mol L-1 KOH | 0.0 | 7.48 μg h-1 mg-1 | 56.55% | [ |
FeSA-NO-C | 0.1 mol L-1 HCl | -0.4 | 31.9 μgNH3 h-1 mg-1cat. | 11.8 % | [ |
FeSA-NSC | 0.1 mol L-1 HCl | -0.4 | 30.4 μg h-1 mg-1cat. | 21.9% | [ |
FeSAs/NSDG | 0.1 mol L-1 KOH | — | 28.89 μg h-1 mg-1cat. at -0.4 V vs. RHE | 23.7% at -0.1 V vs. RHE | [ |
NC-Cu SA | 0.1 mol L-1 KOH | -0.35 | ∼53.3 μgNH3 h-1 mg-1cat. | 13.8% | [ |
0.1 mol L-1 HCl | -0.30 | ∼49.3 μgNH3 h-1 mg-1cat. | 11.7% | ||
Ni-Nx-C-700-3h | 0.1 mol L-1 KOH | — | 115 μg h-1 cm-2 at -0.8 V vs. RHE | 21% at -0.2 V vs. RHE | [ |
Mn−O3N1/PC | 0.1 mol L-1 HCl | -0.35 | 66.41 μg h-1 mg-1cat. | 8.91% | [ |
SA-Mo/NPC | 0.1 mol L-1 KOH | -0.3 | 34 μg h-1 mg-1cat. | 14.6% | [ |
Table 1 The activity comparisons for ammonia synthesis from N2RR on the recently reported SACs.
Catalyst | Electrolyte | Potential (V vs. RHE) | Production rate | FE | Ref. |
---|---|---|---|---|---|
Ru SAs/N-C | 0.05 mol L-1 H2SO4 | -0.2 | 120.9 μgNH3 h-1 mg-1cat. | 29.6% | [ |
Ru@ZrO2/NC | 0.1 mol L-1 HCl | -0.21 | 3.665 mgNH3 h-1 mg-1Ru | 21% | [ |
Ru SAs/GDY/G | 0.5 mol L-1 Na2SO4 | -0.1 | 4.7 mgNH3 h-1 mg-1Ru | 37.6% | [ |
Rh SA/GDY | 0.005 mol L-1 H2SO4 and 0.1 mol L-1 K2SO4 | -0.2 | 74.15 μg h-1 cm-2 | 20.36% | [ |
Au1/C3N4 | 5 mmol L-1 H2SO4 | -0.1 | 1350 μg h-1 mg-1Au | 11.1% | [ |
AuSAs-NDPCs | 0.1 mol L-1 HCl | -0.2 | 2.32 μg h-1 cm-2 | 12.3% | [ |
SA-Ag/NC | 0.1 mol L-1 HCl | — | 69.4 mg h-1 mg-1Ag at -0.65 V vs. RHE | 21.9% at -0.60 V vs. RHE | [ |
FeSA-N-C | 0.1 mol L-1 KOH | 0.0 | 7.48 μg h-1 mg-1 | 56.55% | [ |
FeSA-NO-C | 0.1 mol L-1 HCl | -0.4 | 31.9 μgNH3 h-1 mg-1cat. | 11.8 % | [ |
FeSA-NSC | 0.1 mol L-1 HCl | -0.4 | 30.4 μg h-1 mg-1cat. | 21.9% | [ |
FeSAs/NSDG | 0.1 mol L-1 KOH | — | 28.89 μg h-1 mg-1cat. at -0.4 V vs. RHE | 23.7% at -0.1 V vs. RHE | [ |
NC-Cu SA | 0.1 mol L-1 KOH | -0.35 | ∼53.3 μgNH3 h-1 mg-1cat. | 13.8% | [ |
0.1 mol L-1 HCl | -0.30 | ∼49.3 μgNH3 h-1 mg-1cat. | 11.7% | ||
Ni-Nx-C-700-3h | 0.1 mol L-1 KOH | — | 115 μg h-1 cm-2 at -0.8 V vs. RHE | 21% at -0.2 V vs. RHE | [ |
Mn−O3N1/PC | 0.1 mol L-1 HCl | -0.35 | 66.41 μg h-1 mg-1cat. | 8.91% | [ |
SA-Mo/NPC | 0.1 mol L-1 KOH | -0.3 | 34 μg h-1 mg-1cat. | 14.6% | [ |
Catalyst | Electrolyte | Potential (V vs. RHE) | Production rate | FE | Ref. |
---|---|---|---|---|---|
Cu-PTCDA | 0.1 mol L-1 PBS and 500 ppm NO3- | -0.4 | 436 μgNH3 h-1 cm-2 | 77% | [ |
Cu-N-C | 50 mg L-1 NO3- and 0.5 M Na2SO4 | 1.5 V vs. SCE | 9.23 mg h-1 mg-1cat. | 94% | [ |
Cu MNC-7 | 50 mL Na2SO4 and 100 mg-N mL-1 NaNO3 | -0.64 | 5466 mmol h-1 g-1Cu | 94.8% | [ |
Cu-cis-N2O2 | 1000 ppm N-KNO3/0.5 mol L-1 Na2SO4 | -1.6 | 28.73 mg h-1 cm-2 | 77% | [ |
PR-CuNC | 0.1 mol L-1 KOH and 0.1 mol L-1 KNO3 | -0.5 | 130.71 mg h-1 mg-1Cu | 94.61% | [ |
BCN-Cu | 0.1 mol L-1 KOH and 0.1 mol L-1 KNO3 | -0.6 | 1900.07 μg h-1 cm-2 | 97.37% | [ |
Fe-PPy SACs | 0.1 mol L-1 KOH and 0.1 mol L-1 KNO3 | — | 2.75 mg h-1 cm-2 at -0.7V | 100% at -0.3 V | [ |
Fe SAC | 0.50 mol L-1 KNO3/0.10 mol L-1 K2SO4 | -0.66 | 20000 μg h−1 mg−1cat. | 75% | [ |
FeSAs/g-C3N4 | 50 mg N/L NO3--N and 0.1 mol L-1 Na2SO4 | -0.65 | — | 77.3% | [ |
Fe1/N-C-900 | 0.1 mol L-1 K2SO4 and 0.5 mol L-1 KNO3 | — | 18.8 mgNH3 h-1 mg-1cat. at -0.9 V | 86% at -0.7 V | [ |
Fe-N/P-C SAC | 0.1 mol L-1 KOH and 0.1 mol L-1 KNO3 | — | 17980 μg h-1 mg-1cat. at -0.8 V | 90.3% at -0.4 V | [ |
Table 2 The activity comparisons for ammonia synthesis from NO3RR on the recently reported SACs.
Catalyst | Electrolyte | Potential (V vs. RHE) | Production rate | FE | Ref. |
---|---|---|---|---|---|
Cu-PTCDA | 0.1 mol L-1 PBS and 500 ppm NO3- | -0.4 | 436 μgNH3 h-1 cm-2 | 77% | [ |
Cu-N-C | 50 mg L-1 NO3- and 0.5 M Na2SO4 | 1.5 V vs. SCE | 9.23 mg h-1 mg-1cat. | 94% | [ |
Cu MNC-7 | 50 mL Na2SO4 and 100 mg-N mL-1 NaNO3 | -0.64 | 5466 mmol h-1 g-1Cu | 94.8% | [ |
Cu-cis-N2O2 | 1000 ppm N-KNO3/0.5 mol L-1 Na2SO4 | -1.6 | 28.73 mg h-1 cm-2 | 77% | [ |
PR-CuNC | 0.1 mol L-1 KOH and 0.1 mol L-1 KNO3 | -0.5 | 130.71 mg h-1 mg-1Cu | 94.61% | [ |
BCN-Cu | 0.1 mol L-1 KOH and 0.1 mol L-1 KNO3 | -0.6 | 1900.07 μg h-1 cm-2 | 97.37% | [ |
Fe-PPy SACs | 0.1 mol L-1 KOH and 0.1 mol L-1 KNO3 | — | 2.75 mg h-1 cm-2 at -0.7V | 100% at -0.3 V | [ |
Fe SAC | 0.50 mol L-1 KNO3/0.10 mol L-1 K2SO4 | -0.66 | 20000 μg h−1 mg−1cat. | 75% | [ |
FeSAs/g-C3N4 | 50 mg N/L NO3--N and 0.1 mol L-1 Na2SO4 | -0.65 | — | 77.3% | [ |
Fe1/N-C-900 | 0.1 mol L-1 K2SO4 and 0.5 mol L-1 KNO3 | — | 18.8 mgNH3 h-1 mg-1cat. at -0.9 V | 86% at -0.7 V | [ |
Fe-N/P-C SAC | 0.1 mol L-1 KOH and 0.1 mol L-1 KNO3 | — | 17980 μg h-1 mg-1cat. at -0.8 V | 90.3% at -0.4 V | [ |
Catalyst | Electrolyte | Potential (V vs. RHE) | Production rate | FE | Ref. |
---|---|---|---|---|---|
Ru SA-NC | 1 mol L‒1 KOH and 0.5 mol L‒1 NO2- | -0.6 V | 0.69 mmol h−1 cm−2 | 97.8% | [ |
Nb-SA/BNC | 0.1 mol L‒1 HCl | -0.6 V | 8.2 × 10-8 mol cm-2 s-1 | 77% | [ |
Ce-SA/NHCS | 0.05 mol L‒1 HCl | -0.7V | 1023 μg h-1 mg-1cat. | 91% | [ |
SA-Ni/graphene | 0.5 mol L‒1 K2SO4 and H2SO4 (pH = 1) | — | 1.6 mmol mg-1 h-1 at -0.68 V | 81.2% at -0.51 V | [ |
Table 3 The activity comparisons for ammonia synthesis from NO2RR and NORR on the recently reported SACs.
Catalyst | Electrolyte | Potential (V vs. RHE) | Production rate | FE | Ref. |
---|---|---|---|---|---|
Ru SA-NC | 1 mol L‒1 KOH and 0.5 mol L‒1 NO2- | -0.6 V | 0.69 mmol h−1 cm−2 | 97.8% | [ |
Nb-SA/BNC | 0.1 mol L‒1 HCl | -0.6 V | 8.2 × 10-8 mol cm-2 s-1 | 77% | [ |
Ce-SA/NHCS | 0.05 mol L‒1 HCl | -0.7V | 1023 μg h-1 mg-1cat. | 91% | [ |
SA-Ni/graphene | 0.5 mol L‒1 K2SO4 and H2SO4 (pH = 1) | — | 1.6 mmol mg-1 h-1 at -0.68 V | 81.2% at -0.51 V | [ |
Fig. 15. (a) The HAADF-STEM image of Ru SAs/N-C. (b) The FT-EXAFS fitting curve for Ru SAs/N-C. The FE (c) and yield rate (d) of NH3 production at different working potentials on Ru SAs/N-C and Ru NPs/N-C. Reprinted with permission from Ref. [70]. Copyright 2018, John Wiley & Sons, Ltd. FE (e) and yield rate (f) of NH3 over Ru@ZrO2/NC and the other controlled samples. (g) ΔGPDS for NRR on various active structures. Reprinted with permission from Ref. [55]. Copyright 2019, Cell Press. (h) The NH3 yield and FE of Ru SAs/GDY/G at different applied potentials. (i) The NH3 yield rate normalized by the mass of Ru for Ru SAs/GDY/G at different potentials. Reprinted with permission from Ref. [63]. Copyright 2023, American Chemical Society.
Fig. 16. (a) The FT-EXAFS spectra of Au1/C3N4 and the other standard samples. The FE (b) and yield rate (c) of NH3 for Au1/C3N4 at different potentials. (d) The free energy profile of NRR on Au1/C3N4 and Au (211). Reprinted with permission from Ref. [75]. Copyright 2018, Elsevier. (e) The HADDF-STEM image of SA-Ag/NC. (f) The FE-EXAFS fitting curve of SA-Ag/NC. (g) The FE and yield rate of NH3 over SA-Ag/NC. The cycling tests (h) and chronoamperometry result (i) of SA-Ag/NC. Reprinted with permission from Ref. [48]. Copyright 2020, American Chemical Society.
Fig. 17. (a) The HAADF-STEM image of FeSA-N-C, scale bar, 2 nm. (b) The FE-EXAFS spectra of FeSA-N-C and Fe foil. (c) The comparison of linear sweep voltammograms between FeSA-N-C and N-C. (d) The NH3 FE and yield rate at different potentials. (e) The mean force (PMF) potential for N2 adsorption on FeSA-N-C in 0.1 mol L-1 KOH electrolyte. (f) The energy barriers of the adsorption of hydrogen and nitrogen. Reprinted with permission from Ref. [68]. Copyright 2019, Springer Nature.
Fig. 18. (a) The FT-EXAFS fitting curve and atomic structure of FeSA-NSC-900. (b) The comparison of the FE values and NH3 yields for FeSA-NSC-900 with other reported state-of-the-art Fe SACs and Fe-based compounds. (c) The free energy profiles of FeN3S1 and FeN4 models at -0.4 V are presented by gray and red lines, respectively. Reprinted with permission from Ref. [59]. Copyright 2022, John Wiley & Sons, Ltd.
Fig. 19. (a) The HAADF-STEM image of NC-Cu SA. (b) The FT-EXAFS fitting curve for the NC-Cu SA. NH3 yield rate and FE at different potentials for NC-Cu SA in 0.1 mol L-1 KOH (c) and 0.1 mol L-1 HCl (d). Reprinted with permission from Ref. [78]. Copyright 2019, American Chemical Society. (e) NH3 yield rate (red) and FE (blue) at different potentials for SA-Mo/NPC. (f) The chronoamperometric curve and FE stability for SA-Mo/NPC. Reprinted with permission from Ref. [69]. Copyright 2019, John Wiley & Sons, Ltd.
Fig. 20. (a) The FE of NH3 (blue) and NO2- (mauve) of various elements incorporated in PTCDA at the potential of -0.4 V vs. RHE. (b) The NH3 yield rate at different potentials at the second hour. (c) NH3 FE at different potentials at the second hour. H (d) and NO3- (e) adsorption energies. Reprinted with permission from Ref. [84]. Copyright 2020, Springer Nature.
Fig. 21. (a) The FT-EXAFS fitting curve and atomic model of Cu MNC-7. (b) The charge density difference of NC, Cu(I)-N3C1, and Cu(II)-N4. (c) The activation energy for NO3RR using Cu(I)-N3C1 and Cu(II)-N4 as models. (d) The NO3- conversion and nitrogen product selectivity of different catalysts. Reprinted with permission from Ref. [67]. Copyright 2022, American Chemical Society.
Fig. 22. The HAADF-STEM image (a) and corresponding local EELS (b) of Fe-PPy SACs. (c) The LSVs of the Fe-PPy SACs, Fe NPs, and PPy with and without adding NO3- in the electrolytes. (d) The yield rate of the three catalysts at high overpotentials. (e) The NH3 FE over three catalysts. Reprinted with permission from Ref. [88]. Copyright 2021, Royal society of chemistry. (f) The FT-EXAFS fitting curve and atomic configuration of Fe SAC. (g) The NH3 FE of Fe SAC at different potentials. (h) The NH3 yield rate and partial current density of Fe SAC, Fe NP/NC, and NC. (i) The NH3 yield rate of Fe SAC, Co SAC, and Ni SAC. Reprinted with permission from Ref. [66]. Copyright 2021, Springer Nature.
Fig. 23. (a) Selection of 3d/4d/5d/f metals synthesized via the sacrificial support method. (b) The Schematic of the nitrogen-coordinated metal active site (M-N4) on a prototype carbon matrix illustrates in-plane and out-of-plane configurations. (c) Electrochemical NO2RR for M-N-C catalysts in 0.05 mol L?1 PBS?+?0.01 mol L?1 KNO2 for 0.5?h. The bottom section shows the corresponding NH3 yield rate. Reprinted with permission from Ref. [91]. Copyright 2023, Springer Nature.
Fig. 24. (a) The HAADF-STEM image of Nb-SA/BNC. (b) The FT-EXAFS fitting curve and corresponding atomic structure of Nb-SA/BNC. (c) The NH3 yield rate of NORR for NB-SA/BNC and the other controlled samples. Reprinted with permission from Ref. [93]. Copyright 2020, Elsevier. (d) The NH3 FE and yield rate of NORR over Ce-SA/NHCS. Reprinted with permission from Ref. [94]. Copyright 2023, Elsevier.
Fig. 25. (a) The first-order derivatives of the XANES spectra were recorded at different cathodic potentials in nitrate electrolysis. (b) Corresponding Cu K edge FT-EXAFS spectra at different potentials from fresh, 0.00 to -1.00 V vs. RHE. (c) The XAS comparisons of electrolysis of Cu-N-C at -1.00 V vs. RHE with and without nitrate. (d) Corresponding FT-EXAFS spectra and HAADF-STEM image (inset) after durability measurements. (e) Identical-location electron microscopic characterizations. Reprinted with permission from Ref. [61]. Copyright 2022, American Chemical Society.
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