Manganese pyrophosphate with multiple coordinated water molecules for electrocatalytic water oxidation

doi:10.1016/S1872-2067(24)60052-5

Abstract

Abstract:

The coordinated water in the Mn₄CaO₅ clusters in natural water oxidation center is believed to play an important role in promoting water oxidation. However, its specific role is unclear. In this work, based on a new manganese phosphate (Mn₂P₂O₇·3H₂O) with well-defined crystal surfaces (crystalline MnPi) and its amorphous counterpart (amorphous MnPi), the effects of coordinated water molecules on water oxidation have been systematically investigated. There are four coordinated water molecules on one Mn site, which is very rare and valuable to study relevant effects from water coordination. Unusually, the crystalline MnPi outperformed the amorphous MnPi in electrocatalysis. The exposed well-defined surface of the crystalline MnPi contains continuous Mn sites with multiple coordinated water molecules. The kinetics and thermodynamics of surface oxidation have been quantitatively studied based on the appealing catalyst platform. The interaction between adjacent Mn sites leads to a 3H⁺/2e dual site oxidation in crystalline MnPi, while this process is 2H⁺/1e single site conversion in amorphous MnPi. The higher level of charge neutralization of oxygen atoms from continuous H-bond network in crystalline MnPi is helpful for the Mn^II/III oxidation, which subsequently promotes water oxidation. This study provides valuable insight into the role of coordinated water molecules in initiating water oxidation in Mn-based catalytic systems.

Key words: Water oxidation, Structure, Electrocatalysis, Coordinated water molecules, Manganese phosphate

Shujiao Yang, Pengfei Jiang, Kaihang Yue, Kai Guo, Luna Yang, Jinxiu Han, Xinyang Peng, Xuepeng Zhang, Haoquan Zheng, Tao Yang, Rui Cao, Ya Yan, Wei Zhang. Manganese pyrophosphate with multiple coordinated water molecules for electrocatalytic water oxidation[J]. Chinese Journal of Catalysis, 2024, 62: 166-177.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60052-5

https://www.cjcatal.com/EN/Y2024/V62/I7/166

Figures/Tables 5

Fig. 1. The SEM (a,b), TEM (c,d) and HR-TEM (e,f) images of the crystalline MnPi (a,c,e) and amorphous MnPi (b,d,f) samples. (g) The XRD patterns of the MnPi samples, and calculated XRD patterns of MnPi from resolved crystal structure. (h,i) The SEM images and corresponding EDX elemental mapping images of the crystalline MnPi (h) and amorphous MnPi (i) samples.

Fig. 2. (a,b) The XRD patterns of the crystalline MnPi and amorphous MnPi samples treated at different calcination temperatures. The XPS survey scan spectrum (c), the Mn 2p (d) and Mn 3s (e) XPS spectra of the two MnPi samples. The IR spectra (f) and the TGA (g,h) studies of the two MnPi samples. (i) The crystal structures of Mn2P2O7·3H2O (top) and surface atomic configuration of MnPi sample in the (100) crystal plane (bottom).

Fig. 3. LSV (a) and DPV (b) curves of the MnPi samples in 0.05 mol L-1 pH = 7.0 PBS solution. (c) The anodic charging current at 0.84 V plotted against the scan rates, the slope of which is the capacitance of the two samples that is proportional to ECSA. (d,e) The precatalytic oxidation events from DPV of the MnPi samples in electrolytes with different pH values. (f,g) The potential responses of the samples to the pH values of the electrolyte at Epa(MnII/III) (f) and Epa(MnIII/IV) (g).

Fig. 4. (a) The current responses of the electrocatalysts to the KNO3 concentrations in electrolyte under different potentials. (b) DPV curves of the MnPi samples in 0.05 mol L?1 pH = 7.0 PBS solution with 3 mmol L?1 KNO3 concentrations. (c) The potential responses of the electrocatalysts to the KNO3 concentrations of the electrolyte at Epa(MnII/III). (d) Schematic illustration of in-situ EQCM-D experiment. (e) Mass change of the MnPi samples monitored by in-situ EQCM-D experiment in 0.05 mol L?1 pH = 7.0 PBS solution. (f) Bode plots of the MnPi samples at 1.20 V. (g) CA curves obtained from MnPi samples from surface titration by FcDM at 1.20 V substrate potentials. Inset: schematic diagram of the SECM experimental setup. (h) The relative titration charge density from the surface Mn(III) sites. (i) A time-dependent profile for the formation of Mn(III) of the MnPi samples at 1.20 V substrate potentials.

Fig. 5. (a,b) XAS for Mn K-edge of the MnPi samples and standard MnO. (c,d) Mn K-edge EXAFS spectra for the MnPi samples. The insets show details of the denoted boxe areas. (e,f) Proposed Mn(II) to Mn(III) processes of the crystalline MnPi (e) and amorphous MnPi (f) samples. (g) The energy changes for the Mn(II) to Mn(III) of the two samples based on DFT calculations.

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