Interfacial charge manipulation enhancing H-bond connectivity for promoted oxygen evolution

doi:10.1016/S1872-2067(26)65070-X

Abstract

Abstract:

Interfacial hydrogen bond connectivity (HBC) of electrical double layer (EDL) has been identified as a critical factor for many electrocatalytic reactions, However, there is a lack of systematic investigation on the correlation between HBC and oxygen evolution reaction (OER) kinetics, and the advanced strategies to rationally manipulate HBC. Herein, we proposed an interfacial charge manipulation (ICM) methodology to engineer HBC and enhance OER kinetic of various electrocatalysts including Ni3FeN and the benchmark oxides (RuO₂, Ni(OH)₂, Co(OH)₂, FeNi LDH, and FeCo LDH). With Ni₃FeN as a model catalyst, we systematically studied the influence of different anion chemisorption (NO₃^-, SO₄^2-, and PO₄^3-) on HBC and establishing a positive correlation between OER activity and the charge of anions. Electrochemical tests show that the modified Ni₃FeN catalysts with NO₃^-, SO₄^2-, and PO₄^3- exhibit 1.1-, 1.4-, and 2.3-fold activity enhancements at 1.5-1.6 V vs. RHE relative to the raw Ni₃FeN, respectively. The in-situ spectroscopy and AIMD reveal that high anion charges increase four-hydrogen-bonded water populations, strengthening HBC to promote proton transfer across the EDL during deprotonations step and lower energy obstacle of the rate-determining step. This work has offered a new paradigm to regulate the interfacial HBC at molecular scale for promoting OER.

Key words: Oxygen evolution reaction, Electrical double layer, Interfacial charge manipulation, Hydrogen bond connectivity, Ni₃FeN, Anions

Jun Ke, Jiaxi Zhang, Longhai Zhang, Chengzhi Zhong, Huiyu Song, Li Du, Yuwei Zhang, Zhiming Cui. Interfacial charge manipulation enhancing H-bond connectivity for promoted oxygen evolution[J]. Chinese Journal of Catalysis, 2026, 86: 290-301.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65070-X

https://www.cjcatal.com/EN/Y2026/V86/I7/290

Figures/Tables 5

Fig. 1. Structure characterization. (A) A schematic illustration of surface reconstruction happened over Ni3FeN. (B) SEM image of Ni3FeN. (C) N 1s XPS spectra of Ni3FeN before and after NO3- modification. (D) S 2p XPS spectra of Ni3FeN before and after SO42- modification. (E) P 2p XPS spectra of Ni3FeN before and after PO43- modification. In-situ Raman spectra of Ni3FeN modified with PO43- (F) and without modification (G) (corresponding raw Raman spectra are provided in Fig. S12). (H) Concentration of PO43- in electrolytes before and after the modification.

Fig. 2. OER evaluation. (A) Difference in OER activity (Δjgeo = jgeo(anion) - jgeo(OH-)) of Ni3FeN in the presence and absence of 5 mmol L-1 anions salts at varying potential. EIS results (B) and Tafel slope (C) for Ni3FeN in 1 mol L-1 KOH with three different anion salts (5 mmol L-1 KNO3, 5 mmol L-1 Na2SO4, and 5 mmol L-1 K3PO4). (D) Difference in specific OER activity (Δjs = js(anion) - js(OH-)) of Ni3FeN with and without 5 mmol L-1 of anions salt at different applied potential. (E) Difference in specific OER activity (Δjs = js(anion) - js(OH-)) of Ni3FeN at 1.6 V vs. RHE in 1 mol L-1 KOH with different concentrations of anion salts. (F) Rate of specific activity for Ni3FeN in 1 mol L-1 KOH with and without 5 mmol L-1 anion salt as a function of potential. (G) Stability test of Ni3FeN in 1 mol L-1 KOH with 5 mmol L-1 K3PO4.

Fig. 3. Anion-mediated proton transfer mechanism. (A) A schematic illustration of the proposed mechanism for anion effects on catalyst’s activity and proton transfer process. (B) Gibbs free energy change diagrams for Ni3FeN with different absorbed anions. (C) Kinetic isotope effect of Ni3FeN with different absorbed anions. (D) Equivalent circuit model used for EIS fitting of Ni3FeN. (E) Correlation between the equivalent charge capacity of adsorbed anions (CA) and concentration of anions in the electrolyte. (F) Relationship between the valence charge of anions and specific activity and anion charge capacity. (G) Relationship between specific activity and capacity of anion.

Fig. 4. The role of ICM in HBC. (A) In-situ Raman spectra of PO43- modified Ni3FeN with different interfacial waters (4HB-H2O, 2HB-H2O, and free-H2O) distribution at different potentials vs. Ag/AgCl. (The Ag/AgCl reference was recalibrated against RHE before/after Raman measurements, and its drift in 1.0 mol L-1 KOH was verified to be < 3 mV over 12 h (Fig. S86)) (B,C) Potential-dependent populations of interfacial-water components extracted from Raman peak deconvolution. Data are reported as mean ± s.d. from three independent measurements (n = 3). Deconvolution quality metrics (residuals and RMSE/NRMSE) are provided in Figs. S87-S90.” (Notes: The number indicates difference between maximum and minimum population values). (D) Relationship between the valence charge of anions and the specific activity (at 1.6 V vs. RHE), as well as the population of 4HB-H2O (at 1.55 V vs. RHE) in the corresponding anion-containing electrolytes. (E) Relationship between specific activity and population of 4HB-H2O in corresponding anion electrolytes. (F) Interfacial pH swing calculated from OCP decay transient at different current densities. (G) Total number of H bond obtained from AIMD calculation. Representative snapshots of the EDL structure on NiFeOOH without (H) and with (I) PO43-, along with the corresponding hydrogen distribution profiles and the number of H bonds along the surface normal direction.

Fig. 5. Universality of anion effect. Difference in OER activity (Δjgeo = jgeo(anion) - jgeo(OH-)) of RuO2 (A), Ni(OH)2 (B), Co(OH)2 (C), FeNi LDH (D), and FeCo LDH (E) at 1.65 V vs. RHE in 1 mol L-1 KOH with different concentrations of anion salts. Difference in specific OER activity (Δjs = js(anion) - js(OH-)) of RuO2 (F), Ni(OH)2 (G), OH)2 (H), FeNi LDH (I), and FeCo LDH (J) with and without 5 mmol L-1 of anions salt at different applied potential. Relationship of RuO2 (K), Ni(OH)2 (L), Co(OH)2 (M), FeNi LDH (N), and FeCo LDH (O) between the specific activity (Δjs = js(anion) - js(OH-)) and anion charge capacity (ΔCa = Ca (anion) - Ca (OH-)).

References

[1]	J. Zhang, X. Zhao, L. Du, Y. Li, L. Zhang, S. Liao, J. B. Goodenough, Z. Cui, Nano Lett., 2019, 19, 7457-7463.
[2]	X. Qiao, X. Yin, L. Wen, X. Chen, J. Li, H. Ye, X. Huang, W. Zhao, T. Wang, Chem, 2022, 8, 3241-3251.
[3]	K. Yue, R. Lu, M. Gao, F. Song, Y. Dai, C. Xia, B. Mei, H. Dong, R. Qi, D. Zhang, J. Zhang, Z. Wang, F. Huang, B.-Y. Xia, Y. Yan, Science, 2025, 388, 430-436.
[4]	F. Qian, L. Peng, D. Cao, W. Jiang, C. Hu, J. Huang, X. Zhang, J. Luo, S. Chen, X. Wu, L. Song, Q. Chen, Joule, 2024, 8, 2425.
[5]	Z. Li, G. Lin, L. Wang, H. Lee, J. Du, T. Tang, G. Ding, R. Ren, W. Li, X. Cao, S. Ding, W. Ye, W. Yang, L. Sun, Nat. Catal., 2024, 7, 944-952.
[6]	W. T. Hong, K. A. Stoerzinger, Y.-L. Lee, L. Giordano, A. Grimaud, A. M. Johnson, J. Hwang, E. J. Crumlin, W. Yang, Y. Shao-Horn, Energy Environ. Sci., 2017, 10, 2190-2200.
[7]	P.-C. Yu, X.-L. Zhang, T.-Y. Zhang, X.-Y.-N. Tao, Y. Yang, Y.-H. Wang, S.-C. Zhang, F.-Y. Gao, Z.-Z. Niu, M.-H. Fan, M.-R. Gao, J. Am. Chem. Soc., 2024, 146, 20379-20390.
[8]	Y. Ding, Z. Wang, Z. Liang, X. Sun, Z. Sun, Y. Zhao, J. Liu, C. Wang, Z. Zeng, L. Fu, M. Zeng, L. Tang, Adv. Mater., 2025, 37, 2302860.
[9]	N. Wang, P. Ou, R.-K. Miao, Y. Chang, Z. Wang, S.-F. Hung, J. Abed, A. Ozden, H.-Y. Chen, H.-L. Wu, J. E. Huang, D. Zhou, W. Ni, L. Fan, Y. Yan, T. Peng, D. Sinton, Y. Liu, H. Liang, E. H. Sargent, J. Am. Chem. Soc., 2023, 145, 7829-7836.
[10]	S. Jo, J. I. Jeon, K. H. Shin, L. Zhang, K. B. Lee, J. Hong, J. I. Sohn, Adv. Mater., 2024, 36, 2314211.
[11]	S. Li, T. Liu, W. Zhang, M. Wang, H. Zhang, C. Qin, L. Zhang, Y. Chen, S. Jiang, D. Liu, X. Liu, H. Wang, Q. Luo, T. Ding, T. Yao, Nat. Commun., 2024, 15, 3416.
[12]	J. Han, H. Wang, Y. Wang, H. Zhang, J. Li, Y. Xia, J. Zhou, Z. Wang, M. Luo, Y. Wang, N. Wang, E. Cortés, Z. Wang, A. Vomiero, Z.-F. Huang, H. Ren, X. Yuan, S. Chen, D. Feng, X. Sun, Y. Liu, H. Liang, Angew. Chem. Int. Ed., 2024, 63, e202405839.
[13]	L. Wu, W. Huang, D. Li, H. Jia, B. Zhao, J. Zhu, H. Zhou, W. Luo, Angew. Chem. Int. Ed., 2025, 64, e202413334.
[14]	S. Zhu, R. Yang, H. J. W. Li, S. Huang, H. Wang, Y. Liu, H. Li, T. Zhai, Angew. Chem. Int. Ed., 2024, 63, e202319462.
[15]	T. Wang, Y. Zhang, B. Huang, B. Cai, R. R. Rao, L. Giordano, S.-G. Sun, Y. Shao-Horn, Nat. Catal., 2021, 4, 753-762.
[16]	B. Tang, Y. Fang, S. Zhu, Q. Bai, X. Li, L. Wei, Z. Li, C. Zhu, Chem. Sci., 2024, 15, 7111-7120.
[17]	Y.-H. Wang, S. Zheng, W.-M. Yang, R.-Y. Zhou, Q.-F. He, P. Radjenovic, J.-C. Dong, S. Li, J. Zheng, Z.-L. Yang, G. Attard, F. Pan, Z.-Q. Tian, J.-F. Li, Nature, 2021, 600, 81-85.
[18]	P. Li, Y. Jiang, Y. Hu, Y. Men, Y. Liu, W. Cai, S. Chen, Nat. Catal., 2022, 5, 900-911.
[19]	P. Li, Y.-L. Jiang, Y. Men, Y.-Z. Jiao, S. Chen, Nat. Commun., 2025, 16, 1844.
[20]	S. Zhou, W. Cao, L. Shang, Y. Zhao, X. Xiong, J. Sun, T. Zhang, J. Yuan, Nat. Commun., 2025, 16, 1849.
[21]	Q. Sun, N. J. Oliveira, S. Kwon, S. Tyukhtenko, J. J. Guo, N. Myrthil, S. A. Lopez, I. Kendrick, S. Mukerjee, L. Ma, S. N. Ehrlich, J. Li, W. A. III Goddard, Y. Yan, Q. Jia, Nat. Energy, 2023, 8, 859-869.
[22]	Y. Huang, Y. Gao, B. Zhang, Chem, 2025, 11, 102533.
[23]	Z. Cui, G. Fu, Y. Li, J. B. Goodenough, Angew. Chem. Int. Ed., 2017, 56, 9901-9905.
[24]	J. Zhang, Y. Tu, L. Zhang, S. He, C. Zhong, J. Ke, L. Wang, C. Cui, H. Song, L. Du, Z. Cui, ACS Nano, 2024, 18, 32077-32087.
[25]	A. Sivanantham, P. Ganesan, A. Vinu, S. Shanmugam, ACS Catal., 2020, 10, 463-493.
[26]	J. Zhang, Y. Tu, X. Xu, J. Ke, L. Zhang, C. Zhong, Y. Zhang, L. Du, S.-P. Jiang, Z. Shao, Z. Cui, Adv. Mater., 2025, 37, 2509042.
[27]	H. Liao, T. Luo, P. Tan, K. Chen, L. Lu, Y. Liu, M. Liu, J. Pan, Adv. Funct. Mater., 2021, 31, 2102772.
[28]	H. Sun, J. Sun, Y. Song, Y. Zhang, Y. Qiu, M. Sun, X. Tian, C. Li, Z. Lv, L. Zhang, ACS Appl. Mater. Interfaces, 2022, 14, 22061-22070.
[29]	W. Liu, X. Ding, J. Cheng, J. Jing, T. Li, X. Huang, P. Xie, X. Lin, H. Ding, Y. Kuang, D. Zhou, X. Sun, Angew. Chem. Int. Ed., 2024, 63, e202406082.
[30]	L. Luciani, A. Nocera, M. Raimondi, G. Ciattaglia, S. Spinsante, E. Gambi, R. Galassi, ACS Meas. Sci. Au, 2025, 5, 443-460.
[31]	M. C. O. Monteiro, F. Dattila, B. Hagedoorn, R. García-Muelas, N. López, M. T. M. Koper, Nat. Catal., 2021, 4, 654-662.
[32]	W. Wen, S. Fang, Y. Zhou, Y. Zhao, P. Li, X.-Y. Yu, Angew. Chem. Int. Ed., 2024, 63, e202408382.
[33]	P. Feng, D. Xu, K. Song, G. Yin, G. Jiang, Y. Yang, Y. He, J. Supercrit. Fluids, 2025, 226, 106732.
[34]	H. Hu, X. Wang, Z. Zhang, J. Liu, X. Yan, X. Wang, J. Wang, J. P. Attfield, M. Yang, Adv. Mater., 2025, 37, 2415421.
[35]	B. Zhang, L. Wang, Z. Cao, S. M. Kozlov, F. P. García de Arquer, C. T. Dinh, J. Li, Z. Wang, X. Zheng, L. Zhang, Y. Wen, O. Voznyy, R. Comin, P. De Luna, T. Regier, W. Bi, E. E. Alp, C.-W. Pao, L. Zheng, Y. Hu, Y. Ji, Y. Li, Y. Zhang, L. Cavallo, H. Peng, E. H. Sargent, Nat. Catal., 2020, 3, 985-992.
[36]	S. S. Jeon, P. W. Kang, M. Klingenhof, H. Lee, F. Dionigi, P. Strasser, ACS Catal., 2023, 13, 1186-1196.
[37]	A. S. Bandarenka, A. Maljusch, V. Kuznetsov, K. Eckhard, W. Schuhmann, J. Phys. Chem. C, 2014, 118, 8952-8959.
[38]	P. Córdoba-Torres, T. J. Mesquita, R. P. Nogueira, J. Phys. Chem. C, 2015, 119, 4136-4147.
[39]	S. Yang, X. Li, Y. Li, Y. Wang, X. Jin, L. Qin, W. Zhang, R. Cao, Angew. Chem. Int. Ed., 2023, 62, e202215594.
[40]	M. Liu, N. Li, X. Wang, J. Zhao, D.-C. Zhong, W. Li, X.-H. Bu, Angew. Chem. Int. Ed., 2023, 62, e202300507.
[41]	E. R. Sauvé, B. Y. Tang, N. K. Razdan, W. L. Toh, S. Weng, Y. Surendranath, Joule, 2024, 8, 728-745.