Unconventional metastable cubic 2D LaMnO3 for efficient alkaline seawater oxygen evolution

doi:10.1016/S1872-2067(25)64667-5

Abstract

Abstract:

The electrolysis of alkaline seawater is critical for sustainable hydrogen production but is hindered by the sluggish oxygen evolution reaction in saline environments. Advanced electrocatalysts with tailored structures and electronic properties are essential, and phase engineering provides a transformative approach by modulating crystallographic symmetry and electronic configurations. Two-dimensional (2D) LaMnO₃ perovskites show promise due to their exposed active sites and tunable electronic properties. However, the conventional stable rhombohedral phase limits oxygen diffusion despite good electron transport. Unconventional metastable phases with superior symmetry enhance lattice oxygen activity in saline environments but are challenging to synthesize. Herein, we propose a microwave shock method incorporating Co atoms to rapidly produce 2D LaMnO₃ in rhombohedral, hexagonal, and metastable cubic phases. This strategy circumvents the limitations of high-temperature synthesis, preserving the 2D morphology while enabling the formation of metastable cubic phases. The metastable cubic phase exhibits superior OER activity and stability even in alkaline seawater due to optimal symmetry, interlayer spacing, and Mn-O covalency. X-ray absorption spectroscopy and theoretical calculations further highlight its balanced oxygen adsorption and desorption. This work underscores the role of metastable phase engineering in advancing seawater electrolysis and establishes a scalable route for designing high-performance 2D electrocatalysts.

Key words: Metastable phase, Phase engineering, Two-dimensional material, Microwave, Seawater oxygen evolution

Ji’ao Dai, Jinglin Xian, Kaisi Liu, Zhiao Wu, Miao Fan, Shutong Qin, Huiyu Jiang, Weilin Xu, Huanyu Jin, Jun Wan. Unconventional metastable cubic 2D LaMnO₃ for efficient alkaline seawater oxygen evolution[J]. Chinese Journal of Catalysis, 2025, 74: 228-239.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64667-5

https://www.cjcatal.com/EN/Y2025/V74/I7/228

Figures/Tables 5

Fig. 1. Microwave-induced phase engineering for enhanced OER catalysis. (A) Transformation of crystal phase structure under microwave shock method. (B) Relationship between interlayer spacing and charge transfer energy. (C) The OER performance comparison of different catalysts.

Fig. 2. Synthesis of LaCo0.5Mn0.5O3 and detailed structural characterization of LMO-xCo. (A) Schematic diagram of LaCo0.5Mn0.5O3 synthesis by traditional hydrothermal method. (B) Schematic diagram of the synthesis of 2D LaMnO3 nanosheets by microwave shock method, followed by refined XRD analysis of LMO-xCo (x = 0, 0.3, 0.5, 0.7). (C) Variation in metal-O-metal bond length and metal-O-metal angle for R-LMO-0Co, C-LMO-0.5Co and H-LMO-0.7Co. TEM images of R-LMO-0Co (D), C-LMO-0.5Co (E), and H-LMO-0.7Co (F). HRTEM images of R-LMO-0Co (G), C-LMO-0.5Co (H), and H-LMO-0.7Co (I) with inset the corresponding SAED patterns images.

Fig. 3. Electrocatalytic performance of LMO-xCo catalysts in OER. (A) LSV curves of LMO-xCo (x = 0, 0.3, 0.5, 0.7) and RuO? based catalyst supported on a glass carbon electrode in an N2-saturated 1 mol L-1 KOH solution. Inset, Tafel plots extracted from LSV curves. (B) Overpotential and Tafel data of catalysts. (C) Mass activities and TOF of catalysts at 1.55 V. (D) Bandgap of LMO-xCo (x = 0, 0.3, 0.5, 0.7). (E) Diagram of the bandgap change between R-LMO-0Co and C-LMO-0.5Co. (F) E-t plots of LMO-xCo (x = 0, 0.3, 0.5, 0.7) at 10 mA cm-2 with inset showing durability test of C-LMO-0.5Co.

Fig. 4. Electronic structure and reaction mechanisms of LMO-xCo catalysts. (A) Mn K-edge XANES spectra of LMO-xCo (x = 0, 0.5, 0.7). (B) O K-edge XANES spectra of LMO-xCo (x = 0, 0.5, 0.7). (C) LOM reaction mechanism diagram. (D-F) WT-EXAFS plots of LMO-xCo (x = 0, 0.5, 0.7). (G) PDOS of O 2p orbitals in LMO-xCo. (H) PDOS of Mn (and Co) 3d orbitals in LMO-xCo. (I) Trend analysis of variations in the d-band center and p-band center for LMO-xCo. The inset illustrates the schematic of the density of states for perovskite oxides.

Fig. 5. Catalytic performance of C-LMO-0.5Co for seawater electrolysis. (A) LSV curves for simulated and real seawater electrolysis. (B) Corresponding Tafel plots for the electrolysis of simulated and real seawater. (C) Overpotential summary at 100 and 400 mA cm-2 for electrolysis in simulated and real seawater. (D) Performance advantages of C-LMO-0.5Co and overpotential comparison of various catalysts for seawater electrolysis at 100 mA cm-2. (E) Stability test of C-LMO-0.5Co at 400 mA cm-2 current density. (F) ICP-MS analysis of La, Mn, and Co elemental content in the electrolyte after stability testing.

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Unconventional metastable cubic 2D LaMnO₃ for efficient alkaline seawater oxygen evolution

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