Phosphate anions accelerated deprotonation and proton transfer for water-involved electrooxidation

doi:10.1016/S1872-2067(26)65234-5

Abstract

Abstract:

Phosphate anions (Pi)-modified layered double hydroxides (LDH) have long been regarded as promising anodic electrocatalysts, but the effect by which Pi enhances electrooxidative activity remains unclear. Here, we prepare a Pi-intercalated NiFe LDH (Pi-NiFe LDH) to investigate the role of Pi intercalation in electrooxidation processes. Pi anchored at Fe sites facilitates the deprotonation of adjacent hydroxyl groups at Ni sites to form the active NiOOH phase while promoting the deprotonation of reactants to initiate electrooxidation processes. These dual effects collectively lower the thermodynamic energy. Moreover, Pi bridges the interfacial hydrogen-bond (H-bond) network to restore its continuity, ensuring efficient proton transfer and accelerating reaction kinetics. Therefore, Pi-NiFe LDH delivers enhanced activity for both the oxygen evolution reaction and the electrooxidation of various alcohols with reduced overpotentials and elevated yield rates. This study offers mechanistic insights into how anions modulate deprotonation and proton transfer processes, guiding the design of electrooxidation catalysts.

Key words: Electrocatalysis, Electrooxidation, Proton transfer, Hydrogen-bond, NiFe LDH

Junwei Yao, Chuanqi Cheng, Rui Li, Ying Gao, Bin Zhang. Phosphate anions accelerated deprotonation and proton transfer for water-involved electrooxidation[J]. Chinese Journal of Catalysis, 2026, 91: 341-350.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65234-5

https://www.cjcatal.com/EN/Y2026/V91/I12/341

Figures/Tables 5

Fig. 1. Proposed Pi-intercalation strategy for facilitating deprotonation and proton transfer. (a) Process analysis of electrooxidation reactions. (b) The proposed Pi-intercalation strategy.

Fig. 2. Characterization of the Pi-NiFe LDH. Raman spectra (a), Ni 2p XPS spectra (b), Fe 2p XPS spectra (c), Ni K-edge XANES spectra (d), Fe K-edge XANES spectra (e), and O K-edge XANES spectra (f) of NiFe LDH and Pi-NiFe LDH.

Fig. 3. Origin of facilitated deprotonation. (a) CV curves measured in 1 mol L-1 KOH with or without 0.1 mol L-1 CHA at a scan rate of 10 mV s-1. (b) Potential-dependent yield rates and FEs for the CHN of NiFe LDH and Pi-NiFe LDH. Potential-dependent in situ Raman spectra measured in 1 mol L-1 KOH with 0.1 mol L-1 CHA over NiFe LDH (c) and Pi-NiFe LDH (d). Proton transfer barriers of hydroxides to anions (e) and anions to anions (f). Potential-dependent Bode plots measured in 1 mol L-1 KOH with 0.1 mol L-1 CHA over NiFe LDH (g) and Pi-NiFe LDH (h). (i) Free energy diagram for CHA oxidation.

Fig. 4. Origin of facilitated proton transfer. Potential-dependent ATR-FTIR spectra of Pi-NiFe LDH (a) and NiFe LDH (b). (c) Corresponding wavenumbers of the O-H stretching vibration under different potentials. (d) Representative snapshot of the interfacial H-bond networks adjacent to NiFe LDH and Pi-NiFe LDH. (e) Statistical distribution of the intensity of H-bonds. (f) Proton transfer barriers at the interfaces of NiFe LDH and Pi-NiFe LDH. Inset: calculated energy barriers for proton transfer. (g) CHA deprotonation energy barriers at the interfaces of NiFe LDH and Pi-NiFe LDH. Inset: calculated energy barriers for CHA deprotonation. (h) Ea for the CHA electrooxidation of NiFe LDH and Pi-NiFe LDH.

Fig. 5. Universality and utility of Pi-NiFe LDH. FEs of electrooxidation of isopropanol (a), ethylene glycol (b), and glycerol electrooxidation (c) at a current density of 100 mA cm-2 over NiFe LDH and Pi-NiFe LDH. (d) Schematic diagram of the cascade system for cyclohexanone oxime electrosynthesis. (e) FE and full-cell voltage of anodic CHN electrosynthesis and cathodic cyclohexanone oxime electrosynthesis. (f) 1H NMR spectra of the obtained cyclohexanone oxime.

References

[1]	Y. Jiao, Y. Zheng, M. Jaroniec, S.-Z. Qiao, Chem. Soc. Rev., 2015, 44, 2060-2086.
[2]	C. Liu, F. Chen, B.-H. Zhao, Y. Wu, B. Zhang, Nat. Rev. Chem., 2024, 8, 277-293.
[3]	H. Li, Y. Lin, J. Duan, Q. Wen, Y. Liu, T. Zhai, Chem. Soc. Rev., 2024, 53, 10709-10740.
[4]	F. Liu, X. Gao, Z. Guo, E. C. M. Tse, Y. Chen, J. Am. Chem. Soc., 2024, 146, 15275-15285.
[5]	S. M. Hashmi, Y. Wang, N. Rehman, X. Tan, J. García-Martínez, U. Aiman, M. Sajid, Z. Sun, Chin. J. Catal., 2026, 82, 1-41.
[6]	M. Gao, W. Sheng, Z. Zhuang, Q. Fang, S. Gu, J. Jiang, Y. Yan, J. Am. Chem. Soc., 2014, 136, 7077-7084.
[7]	J. Suntivich, K. J. May, H. A. Gasteiger, J. B. Goodenough, Y. Shao-Horn, Science, 2011, 334, 1383-1385.
[8]	J. Yao, R. Yang, C. Liu, B.-H. Zhao, B. Zhang, Y. Wu, ACS Cent. Sci., 2024, 10, 155-162.
[9]	Z.-P. Wu, X.-F. Lu, S.-Q. Zang, X. W. D. Lou, Adv. Funct. Mater., 2020, 30, 1910274.
[10]	F. Wu, F. Tian, M. Li, S. Geng, L. Qiu, L. He, L. Li, Z. Chen, Y. Yu, W. Yang, Y. Hou, Angew. Chem. Int. Ed., 2025, 64, e202413250.
[11]	Y. Liu, H. Hu, K. Wang, J. Huang, D. Wang, Adv. Energy Mater., 2026, 16, e04101.
[12]	X. Sun, W. Shen, H. Liu, P. Xi, M. Jaroniec, Y. Zheng, S.-Z. Qiao, Nat. Commun., 2024, 15, 10351.
[13]	H. Sun, L. Li, H.-C. Chen, D. Duan, M. Humayun, Y. Qiu, X. Zhang, X. Ao, Y. Wu, Y. Pang, K. Huo, C. Wang, Y. Xiong, Sci. Bull., 2022, 67, 1763-1775.
[14]	H. Zhang, G. Shen, X. Liu, B. Ning, C. Shi, L. Pan, X. Zhang, Z.-F. Huang, J.-J. Zou, Chin. J. Catal., 2021, 42, 1732-1741.
[15]	X. Cui, Y. Ding, F. Zhang, X. Cao, Y. Guo, L. Sun, B. Zhang, Nat. Chem., 2026, 18, 120-127.
[16]	S. Qi, J. You, X. Liufu, Y. Zhang, R. Chen, J. Zhuang, T. Liang, L. Li, Q. Huo, C. Shang, X. Zhang, H. Yang, Q. Hu, C. He, Adv. Mater., 2026, 38, e12188.
[17]	A. Moysiadou, S. Lee, C.-S. Hsu, H.-M. Chen, X. Hu, J. Am. Chem. Soc., 2020, 142, 11901-11914.
[18]	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.
[19]	Z.-F. Huang, J. Song, Y. Du, S. Xi, S. Dou, J. M. V. Nsanzimana, C. Wang, Z. J. Xu, X. Wang, Nat. Energy, 2019, 4, 329-338.
[20]	Y. Jia, Z. Chen, B. Gao, Z. Liu, T. Yan, Z. Gui, X. Liao, W. Zhang, Q. Gao, Y. Zhang, X. Xu, Y. Tang, J. Am. Chem. Soc., 2024, 146, 1282-1293.
[21]	H. Zhou, Z. Li, S.-M. Xu, L. Lu, M. Xu, K. Ji, R. Ge, Y. Yan, L. Ma, X. Kong, L. Zheng, H. Duan, Angew. Chem. Int. Ed., 2021, 60, 8976-8982.
[22]	W. Li, Y. Ding, Y. Zhao, Z. Li, G. Lin, L. Wang, L. Sun, Angew. Chem. Int. Ed., 2025, 64, e202505924.
[23]	Z. Li, Y. Lin, M. N. Garaga, S. G. Greenbaum, M. Liao, J. Ruan, Q. Li, Y. Li, D. Sun, K. Xu, F. Fang, F. Wang, Nat. Mater., 2025, 24, 1968-1977.
[24]	P. Li, Y. Jiang, Y. Hu, Y. Men, Y. Liu, W. Cai, S. Chen, Nat. Catal., 2022, 5, 900-911.
[25]	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. Goddard, Y. Yan, Q. Jia, Nat. Energy, 2023, 8, 859-869.
[26]	M. Yan, R. Yang, C. Liu, Y. Gao, B. Zhang, J. Am. Chem. Soc., 2025, 147, 6698-6706.
[27]	X. Li, C. Cheng, Q. Ruan, Y. Gao, L. Kong, Y. Shi, B. Zhang, J. Am. Chem. Soc., 2025, 147, 24984-24992.
[28]	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.
[29]	Y. Li, J. Liu, S. Li, S. Peng, ACS Catal., 2024, 14, 4807-4819.
[30]	P. Zhang, S. Liu, L. Cai, J. Jiang, X. Zhao, X. Wu, B. Li, B.-Y. Xia, Y. Liu, Angew. Chem. Int. Ed., 2026, 65, e24529.
[31]	R. Fan, C. Liu, Z. Li, H. Huang, J. Feng, Z. Li, Z. Zou, Nat. Sustain., 2024, 7, 158-167.
[32]	X. He, Y. Yao, M. Zhang, Y. Zhou, L. Zhang, Y. Ren, K. Dong, H. Tang, J. Nan, X. Zhou, H. Luo, B. Ying, Q. Yu, F. Luo, B. Tang, X. Sun, Nat. Commun., 2025, 16, 5541.
[33]	M.-Y. Xie, J.-R. Huang, H. Wan, J. Nie, M.-H. Xian, Z.-Y. Ou-Yang, G.-F. Huang, W.-Q. Huang, Appl. Phys. Lett., 2025, 126, 153901.
[34]	Z. Cai, J. Liang, Z. Li, T. Yan, C. Yang, S. Sun, M. Yue, X. Liu, T. Xie, Y. Wang, T. Li, Y. Luo, D. Zheng, Q. Liu, J. Zhao, X. Sun, B. Tang, Nat. Commun., 2024, 15, 6624.
[35]	G. Liu, T. Nie, Z. Song, X. Sun, T. Shen, S. Bai, T. Yu, L. Zheng, Y.-F. Song, Adv. Funct. Mater., 2024, 34, 2411284.
[36]	A. Seijas-Da Silva, A. Hartert, V. Oestreicher, J. Romero, C. Jaramillo-Hernández, L. J. J. Muris, G. Thorez, B. J. C. Vieira, G. Ducourthial, A. Fiocco, S. Legendre, C. Huck-Iriart, M. Mizrahi, D. López-Alcalá, A. T. S. Freiberg, K. J. J. Mayrhofer, J. C. Waerenborgh, J. J. Baldoví, S. Cherevko, M. Varela, S. Thiele, V. Lloret, G. Abellán, Nat. Commun., 2025, 16, 6138.
[37]	L. Xia, B. F. Gomes, W. Jiang, D. Escalera-López, Y. Wang, Y. Hu, A. Y. Faid, K. Wang, T. Chen, K. Zhao, X. Zhang, Y. Zhou, R. Ram, B. Polesso, A. Guha, J. Su, C. M. S. Lobo, M. Haumann, R. Spatschek, S. Sunde, L. Gan, M. Huang, X. Zhou, C. Roth, W. Lehnert, S. Cherevko, L. Gan, F. P. García de Arquer, M. Shviro, Nat. Mater., 2025, 24, 753-761.
[38]	N. Zhang, X. Feng, D. Rao, X. Deng, L. Cai, B. Qiu, R. Long, Y. Xiong, Y. Lu, Y. Chai, Nat. Commun., 2020, 11, 4066.
[39]	J. Nie, J. Shi, L. Li, M.-Y. Xie, Z.-Y. Ouyang, M.-H. Xian, G.-F. Huang, H. Wan, W. Hu, W.-Q. Huang, Adv. Funct. Mater., 2025, 35, 2414493.
[40]	Y. Huang, Z. Wang, H. Xiao, Q. Liu, X. Wang, J. Am. Chem. Soc., 2024, 146, 29006-29016.
[41]	M. Klingenhof, H. Trzesniowski, S. Koch, J. Zhu, Z. Zeng, L. Metzler, A. Klinger, M. Elshamy, F. Lehmann, P. W. Buchheister, A. Weisser, G. Schmid, S. Vierrath, F. Dionigi, P. Strasser, Nat. Catal., 2024, 7, 1213-1222.
[42]	R. Ge, Y. Wang, Z. Li, M. Xu, S.-M. Xu, H. Zhou, K. Ji, F. Chen, J. Zhou, H. Duan, Angew. Chem. Int. Ed., 2022, 61, e202200211.
[43]	J. Huang, Y. Li, Y. Zhang, G. Rao, C. Wu, Y. Hu, X. Wang, R. Lu, Y. Li, J. Xiong, Angew. Chem. Int. Ed., 2019, 58, 17458-17464.
[44]	W. Chen, C. Xie, Y. Wang, Y. Zou, C.-L. Dong, Y.-C. Huang, Z. Xiao, Z. Wei, S. Du, C. Chen, B. Zhou, J. Ma, S. Wang, Chem, 2020, 6, 2974-2993.
[45]	D. Marx, M. E. Tuckerman, J. Hutter, M. Parrinello, Nature, 1999, 397, 601-604.
[46]	X. Kang, F. Yang, Z. Zhang, H. Liu, S. Ge, S. Hu, S. Li, Y. Luo, Q. Yu, Z. Liu, Q. Wang, W. Ren, C. Sun, H.-M. Cheng, B. Liu, Nat. Commun., 2023, 14, 3607.
[47]	Y. Tian, P. Hou, Y. Zhou, Q. Li, J. Am. Chem. Soc., 2025, 147, 35118-35127.
[48]	Y. X. Chen, S. Z. Zou, K. Q. Huang, Z. Q. Tian, J. Raman Spectrosc., 1998, 29, 749-756.
[49]	J. Yao, C. Cheng, Y. Wu, C. Liu, S. Guo, Y. Gao, B. Zhang, J. Am. Chem. Soc., 2025, 147, 8024-8031.
[50]	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.
[51]	Y. Wu, X. Liu, R. Yang, C. Cheng, Z. Song, B. Zhang, Nat. Synth., 2025, 4, 1504-1512.