Promoting interfacial free water supply through the hydration of single-atom lanthanide doping for acidic water oxidation

doi:10.1016/S1872-2067(26)65111-X

Abstract

Abstract:

Interfacial free water plays a vital role in accelerating electrocatalytic water splitting. However, the low proportion of free water at the interface significantly limits the reaction rate. Herein, we demonstrate a new strategy to increase the interfacial free water supply by doping single lanthanide atoms into Co₃O₄ for acidic oxygen evolution (OER). Taking La as an example, the doped La at the surface of Co₃O₄ spontaneously captures water molecules from the electrolyte through hydration, providing a sufficient free water supply for the OER. In addition, La doping strengthens Co-O bonding, affording strong structural stability. As a result, La-doped Co₃O₄ has a small overpotential of 288 mV at a current density of 10 mA cm^-2 and can remain stable for 230 h. Except for La, other lanthanide elements, such as Sm and Pr, also have similar effects on the OER. Our work not only develops efficient electrocatalysts for the acidic OER but also provides a universal strategy to increase the interfacial free water supply.

Key words: Acidic oxygen evolution reaction, Structure of interfacial water, Doping, Lanthanides, Lattice oxygen

Xiaoshan Hao, Shanshan Lu, Chuanqi Cheng, Qingqing Ruan, Bin Zhang, Yanmei Shi. Promoting interfacial free water supply through the hydration of single-atom lanthanide doping for acidic water oxidation[J]. Chinese Journal of Catalysis, 2026, 89: 196-206.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65111-X

https://www.cjcatal.com/EN/Y2026/V89/I10/196

Figures/Tables 6

Fig. 1. Theoretical predictions of La doping into Co3O4. (a) Calculation models of La-Co3O4 for different OER steps. The red, dark blue, pink, and green balls represent O, Co, H, and La, respectively. The O and H in the OER intermediates are highlighted in cyan and light blue, respectively. (b) Calculated density of H2O (top) and O species (bottom) at the surface of Co3O4 and La-Co3O4. (c) Free energy diagrams of the OER over Co3O4 and La-Co3O4 at a bias of 0 V. (d) -pCOHP analysis of Co3O4 and La-Co3O4.

Fig. 2. Preparation and morphology of La-Co3O4. (a) Illustration of the preparation of La-Co3O4. (b) LSV curves of Co3O4 scanning in electrolytes with different La3+ concentrations. (c) XRD patterns of Co3O4 and La-Co3O4. Peaks labeled by asterisk (*) arise from Ti as the substrate. (d) Magnified view of the marked region in (c). (e) TEM image of La-Co3O4. (f) Aberration-corrected HAADF-STEM image of La-Co3O4. (g) HAADF-STEM and corresponding elemental distributing mapping images of La-Co3O4.

Fig. 3. Spectroscopic characterizations of La-Co3O4. (a) Co 2p XPS spectra of Co3O4 and La-Co3O4. (b) La 3d5/2 spectrum of La-Co3O4. (c) Raman spectra of Co3O4 and La-Co3O4. (d) Co K-edge XANES spectra of Co3O4 and La-Co3O4. The Co foil and CoO data are shown for comparison. The inset is the corresponding pre-edge region in (d). (e) Co K-edge EXAFS spectra of Co3O4 and La-Co3O4. (f) O K-edge soft X-ray absorption spectra of Co3O4 and La-Co3O4.

Fig. 4. Electrocatalytic OER performance and reaction mechanism. (a) LSV curves of Co3O4, La-Co3O4, and RuO2. (b) Tafel plots of Co3O4 and La-Co3O4. (c) Nyquist plots of Co3O4 and La-Co3O4 at 1.6 V vs. RHE. (d) I-t curves of Co3O4, La-Co3O4, and RuO2 at 10 mA cm-2. (e) Co 2p XPS spectra of the counter electrode used for Co3O4 and La-Co3O4. (f) Current densities of Co3O4 and La-Co3O4 at 1.7 V as a function of pH. (g) Proportion of 34O2 and 36O2 generated from 18O-labeled Co3O4 and La-Co3O4 tested in H216O. (h) Raman spectra of Co3O4 and La-Co3O4 with the addition of TMA+ at the OCP and 1.7 V.

Fig. 5. In-situ investigations of the effect of La doping. In-situ Raman spectra of Co3O4 (a) and La-Co3O4 (b) in the range of 550-770 cm-1. (c) Corresponding Raman shifts of F2g at different potentials for Co3O4 and La-Co3O4. In-situ Raman spectra of Co3O4 (d) and La-Co3O4 (e) in the range of 2800-4000 cm-1. Corresponding proportion (f) and Raman shift (g) of free water for Co3O4 and La-Co3O4.

Fig. 6. Universality of the performance promotion through other lanthanide-element doping. (a) LSV curves of Co3O4, Sm-Co3O4, and Pr-Co3O4. (b) I-t curves of Co3O4, Sm-Co3O4, and Pr-Co3O4 at 10 mA cm-2. In-situ Raman spectra of Sm-Co3O4 (c) and Pr-Co3O4 (d) in the range of 2800-4000 cm-1. Corresponding proportion (e) and Raman shift (f) of free water for Sm-Co3O4 and Pr-Co3O4.

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