Roles of heteroatoms in electrocatalysts for alkaline water splitting: A review focusing on the reaction mechanism

doi:10.1016/S1872-2067(21)64052-4

Abstract

Abstract:

Alkaline water splitting is a promising technology for “green hydrogen” generation. To improve its efficiency, highly robust catalysts are required to reduce the overpotential for low electrical power consumption. Heteroatom modification is one of the most effective strategies for boosting catalytic performance, as it can regulate the physicochemical properties of host catalysts to improve their intrinsic activity. Herein, aiming to provide an overview of the impact of heteroatoms on catalytic activity at the atomic level, we present a review of the key role of heteroatoms in enhancing reaction kinetics based on the reaction pathways of the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline media. In particular, the introduction of heteroatoms can directly and indirectly optimize the interactions between the active sites and intermediates, thus improving the intrinsic activity. To clearly illustrate this influence in detail, we have summarized a series of representative heteroatom-modified electrocatalysts and discussed the important roles of heteroatoms in the OER and HER reaction pathways. Finally, some challenges and perspectives for heteroatom-modified electrodes are discussed. We hope that this review will be helpful for the development of efficient and low-cost electrocatalysts for water electrolysis and other energy conversion applications.

Key words: Alkaline water splitting, Heteroatom modification, Reaction pathway, Hydrogen evolution reaction, Oxygen evolution reaction

Chuqiang Huang, Jianqing Zhou, Dingshuo Duan, Qiancheng Zhou, Jieming Wang, Bowen Peng, Luo Yu, Ying Yu. Roles of heteroatoms in electrocatalysts for alkaline water splitting: A review focusing on the reaction mechanism[J]. Chinese Journal of Catalysis, 2022, 43(8): 2091-2110.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)64052-4

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Figures/Tables 14

Fig. 1. Schematic illustration for the alkaline HER mechanism (a) and different hydrogen adsorption/desorption behaviors on the catalyst surface (b). (c) A volcano plot of various metals in acidic electrolyte. Reprinted with permission from Ref. [20]. Copyright 2017, American Association for the Advancement of Science. (d) A volcano plot of different metals in alkaline electrolyte. Reprinted with permission from Ref. [57]. Copyright 2013, Royal Society of Chemistry.

Fig. 2. (a) AEM pathway for OER. Reprinted with permission from Ref. [66]. Copyright 2021, Royal Society of Chemistry. (b) Scaling relationship between ΔG*OOH and ΔG*OH on various catalysts. Reprinted with permission from Ref. [67]. Copyright 2016, Nature Publishing Group. (c) A volcano-type relationship between OER activity and the calculated oxygen binding strength (ΔG*O - ΔG*OH). Reprinted with permission from Ref. [68]. Copyright 2011, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. LOM pathways for OER on (d) oxygen site and (e) metal site. Reprinted with permission from Ref. [66]. Copyright 2021, Royal Society of Chemistry. (f) Schematic illustration of the typical band structure of perovskite material, exhibiting the motion of the metal d-band relative to the oxygen p-band when cationic redox becomes anionic redox. Reprinted with permission from Ref. [69]. Copyright 2016, Nature Publishing Group.

Fig. 3. (a) Schematic illustration of orbital hybridization and formed chemical bonding between a transition metal surface and an adsorbate. Reprinted with permission from Ref. [78]. Copyright 2005, Springer Science Business Media, Inc. (b) Schematic illustration of bond formation between a metal surface and adsorbate as well as the density of states (DOS) of Co4N and V-Co4N. (c) ΔG*H comparison of Co4N and V-Co4N. Reprinted with permission from Ref. [79]. Copyright 2018, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. (d) H2 binding energy diagram of various bimetallic Ni-Cu/C catalysts. (e) A volcano-type relationship between overpotentials and calculated hydrogen binding energy. Reprinted with permission from Ref. [80]. Copyright 2020, American Chemical Society. (f) Free energy diagram of CoP and M-CoP (M = Ni, Mn, Fe). (g) Calculated DOS curves of CoP and Ni-CoP. Reprinted with permission from Ref. [81]. Copyright 2018, Elsevier Ltd.

Fig. 4. (a) Top view of H adsorption on Co2P (201) (a) and N-Co2P (201) (b) surface, where pink, light blue, blue, and white balls represent P, Co, N, and H atoms, respectively. (c) Lowdin charge analysis of Co atoms. (d) Calculated ΔG*H2O on Co2P and N-Co2P surfaces. (e) Calculated ΔG*H on Co2P (201), Co2P (200), N-Co2P (201), N-Co2P (200), and Pt (111) surfaces. (f) d-Orbital PDOS of Co2P and N-Co2P; Contour plot of the electron density differences of the Co-H bonding region on Co2P (g) and N-Co2P (h) surface. Reprinted with permission from Ref. [84]. Copyright 2019, American Chemical Society.

Fig. 5. (a) Top-view structures of N-NiCo2S4 (100). (b) Electron density difference of NiCo2S4 (100) and N-NiCo2S4 (100). (c) Energy profiles of alkaline HER on NiCo2S4 (100) and N-NiCo2S4 (100) surfaces. Reprinted with permission from Ref. [88]. Copyright 2018, The Author(s). (d) Top-view structures of Fe0.25Co0.75P (101). (e) Electron density differences of (b) CoP (101) and Fe0.25Co0.75P (101). Calculated ΔG*H2O (f) and ΔG*H (g) on CoP (101), Fe0.25Co0.75P (101), Fe0.5Co0.5P (101), and Fe0.75Co0.25P (101) surfaces. Reprinted with permission from Ref. [89]. Copyright 2019, Elsevier Ltd.

Fig. 6. (a) Calculated d-orbital PDOS of CoP, CoP-S1, and S-CoP (002), where CoP-S1 and S-CoP represent S-doped CoP and S-doped CoP with a P-vacancy, respectively. (b) Calculated ΔG*H on (002) and (101) surfaces of CoP, CoP-S1, and S-CoP. (c) Electron density difference of the Co-H bonding region on the CoP (002), CoP-S1 (002), and S-CoP (002) surfaces. (d) Calculated ΔG*H2O on the CoP, CoP-S1, and S-CoP surfaces, where the inset shows photographs of the hydrophilicity test on CoP and S-CoP surfaces. Reprinted with permission from Ref. [90]. Copyright 2020, Elsevier Ltd. (e) Optimized structures of CoSe, CoSe/Ni, CoSe/VCo2, CoSe/Ni-VCo, and CoSe/Ni-VCo2, where orange, purple, brown, and white balls represent Se, Co, Ni, and H atoms, respectively. (f) Calculated ΔG*H2O on these catalyst surfaces. (g,h) Local DOS of CoSe/Ni-VCo2. Reprinted with permission from Ref. [91]. Copyright 2020, Wiley-VCH GmbH.

Fig. 7. (a) Schematic illustration of the alkaline HER mechanism on dual-sites electrode surface. (b) HER activity of dual-site Ni(OH)2/metal (Ni, Ag, and Cu) catalysts in acidic and alkaline electrolytes. Reprinted with permission from Ref. [92]. Copyright 2012, WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim. Calculated ΔG*H2O (c) and ΔG*H (d) on MoN, g-C3N4, and C3N4@MoN surfaces. (e) Schematic illustration of dual-site mechanism of C3N4@MoN. Reprinted with permission from Ref. [94]. Copyright 2018, Elsevier Ltd. (f) Schematic illustration of dual-site mechanism of Ni(OH)2-NiMoOx/NF catalyst. Reprinted with permission from Ref. [95]. Copyright 2019, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fig. 8. (a) Schematic illustration of the alkaline HER mechanism on a dual-site Ni(OH)2/Ni3S2 nanoforest. O 1s XPS spectra of Ni(OH)2/Ni3S2 (b) and Ni3S2 (c) before and after HER. Reprinted with permission from Ref. [96]. Copyright 2018, Elsevier B.V. (d) Top view of optimized c-NiP2, m-NiP2, and c/m-NiP2 structures. Calculated free energy of hydrogen absorption (e) and water dissociation (f) on these catalyst surfaces. (g) Calculated charge density distribution for the c/m-NiP2 catalyst with phase junction. Reprinted with permission from Ref. [97]. Copyright 2020, Wiley-VCH GmbH.

Fig. 9. (a) Calculated Bader charges for Co4 of Co4N (111) and Cr4 of Cr-Co4N (111), where the inset is the electron density plot of water molecule. Calculated free energy of water absorption (b) and water dissociation (c) on the Co4N and Cr-Co4N surfaces. Reprinted with permission from Ref. [98]. Copyright 2019, WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim. (d) Calculated Pun values of several transition metal dopants (V, Cr, Mo, Mn, Fe, Co, Ni, and Cu). (e) Relationship between overpotentials for alkaline HER and Pun values for these dopants. (f) Calculated ΔG*H2O of M-CoP vs. Pun of the dopants. Reprinted with permission from Ref. [99]. Copyright 2020, The Author(s).

Fig. 10. (a) Schematic representation of the orbital hybridization between metal 3d and O 2p of La1-xSrxCoO3-δ. (b) OER free energy of LOM and AEM on La1-xSrxCoO3-δ. Reprinted with permission from Ref. [100]. Copyright 2016, the Author(s). (c) Schematic diagram of Co 3d-O 2p hybridization for LaCoO3 and LaCo0.9Fe0.1O3. Reprinted with permission from Ref. [101]. Copyright 2017, American Chemical Society. (d) Fe Mössbauer spectra tested at 298 K. (e) Schematic illustration of Fe 3d orbital degeneration. Reprinted with permission from Ref. [102]. Copyright 2018, Elsevier Ltd. (f) Crystal structure of La0.5Sr1.5NiO4. (g) Computed values of O p-band center, B-B’ overlap, and overlap center of different catalysts. Reprinted with permission from Ref. [103]. Copyright © 2018, The Author(s).

Fig. 11. (a) Crystal structures of Ni-doped ZnCo2O4. (b) Calculated formation energy of ZnCo2-xNixO4 and energy difference between the O p-band center and Moh d-band center of ZnCo2-xNixO4. Reprinted with permission from Ref. [108]. Copyright 2019, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fig. 12. (a) Free energy diagram of the LOM on an (FeCoCrNi)OOH catalyst. (b) Energy comparison of RLS following LOM and AEM on (FeCoCrNi)OOH and (CoCrNi)OOH models. (c) HER activity of various catalysts at different pH values. (d) Detected MS signals of oxygen products using 18O isotope-labeled catalysts. Reprinted with permission from Ref. [110]. Copyright 2020, the Author(s).

Fig. 13. Single-site OER route (a) and the corresponding free energy on FeN4(OH)@CNT (b) and CrN4(OH)@CNT (c) catalysts. Dual-site OER route (d) and the corresponding free energy on FeN4(OH)@CNT (e) and CrN4(OH)@CNT (f) catalysts. Reprinted with permission from Ref. [112]. Copyright 2020, Royal Society of Chemistry.

Fig. 14. (a) Wavelet transform diagram from the k3-weighted EXAFS signal for Ni K-edge of Ni(OH)2 and Ir/Ni(OH)2 as well as Ir LIII-edge of Ir NPs and Ir/Ni(OH)2 after OER. Reprinted with permission from Ref. [114]. Copyright 2020, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. (b) Free energy diagram for OER following the single-site route (Fe-NHGF, Co-NHGF and Ni-NHGF) and dual-site route (Ni-NHGF). Reprinted with permission from Ref. [115]. Copyright 2018, The Author(s). (c,d) Schematic illustration of the dual-site OER mechanism at the S1 site of the NiO/NiFe LDH intersection; (e) Schematic illustration of the single-site OER mechanism. (f) Free energy diagram of the OER pathway on S1 and L1 sites. Reprinted with permission from Ref. [116]. Copyright 2019, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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