High-density Ir single sites from rapid ligand transformation for efficient water electrolysis

doi:10.1016/S1872-2067(24)60128-2

Abstract

Abstract:

The development of high-performance oxygen evolution reaction catalysts with low iridium content is the key to the scale-up of proton exchange membrane water electrolyzer (PEMWE) for green hydrogen production. Single-site electrocatalysts with maximized atomic efficiency are held as promising candidates but still suffer from inadequate activity and stability in practical electrolyzer due to the low site density. Here, we proposed a NaNO₃-assistant thermal decomposition strategy for the preparation of high-density Ir single sites on MnO₂ substrate (NaNO₃-H-Ir-MnO₂). Direct spectroscopic evidence suggests the inclusion of NaNO₃ accelerates the transformation of Ir-Cl to Ir-O coordination, thus generating uniform dispersed high-density Ir single sites in the products. The optimized H-Ir-MnO₂ demonstrates not only high intrinsic activity in a three-electrode set-up but also boosted performance in scalable PEMWE, requiring a cell voltage of only 1.74 V to attain a high current density of 2 A cm^-2 at a low Ir loading of 0.18 mg_Ir cm^-2. This work offers a new insight for enhancing the industrial practicality of Ir-based single site catalysts.

Key words: Acidic oxygen evolution reaction, High-density Ir single sites, In situ Raman spectroscopy, Proton exchange membrane electrolyzer, Ligand transformation

Zhaoping Shi, Ziang Wang, Hongxiang Wu, Meiling Xiao, Changpeng Liu, Wei Xing. High-density Ir single sites from rapid ligand transformation for efficient water electrolysis[J]. Chinese Journal of Catalysis, 2024, 66: 223-232.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60128-2

https://www.cjcatal.com/EN/Y2024/V66/I11/223

Figures/Tables 5

Fig. 1. Preparation scheme and the structure of Ir doped MnO2. (a) Schematic illustration of catalyst fabrication method; (b) XRD patterns of γ-MnO2, L-Ir-MnO2, H-Ir-MnO2 and NaNO3-H-Ir-MnO2; (c) TEM and (d) HRTEM image of NaNO3-H-Ir-MnO2; (e,f) HAADF-STEM images of NaNO3-H-Ir-MnO2, the orange box in (f) indicates a randomly selected square with an area of 7 nm × 7 nm and the red circle indicates the Ir sites within that area; (g) the FT-EXAFS and the corresponding fitting results for NaNO3-H-Ir-MnO2 and IrO2.

Fig. 2. In situ Raman analyze. The in situ Raman spectrum of the precursor aqueous containing 100%Mn(NO3)2 (a), 3%H2IrCl6 + 97%Mn(NO3)2 (b), 7%H2IrCl6 + 93%Mn(NO3)2 (c), 7%H2IrCl6 + 93%Mn(NO3)2 + 20%NaNO3 (d). The spectrum obtained after 150 s (e) and 30 s (f) reaction at 220 °C. (g) The evolution of the Raman intensity of Ir-Cl scattering with varied H2IrCl6 and NaNO3 content.

Fig. 3. Schematic diagram of the structure formation process of Ir doped MnO2. Formation process of L-Ir-MnO2 (a), H-Ir-MnO2 (b), and NaNO3-H-Ir-MnO2 (c).

Fig. 4. OER catalytic performance in three-electrode set-up. (a) LSV curves of NaNO3-H-Ir-MnO2 and the controls normalized by the geometric area of electrode; (b) comparison on the mass activity of NaNO3-H-Ir-MnO2 and the recent reported Ir-based catalysts; (c) comparison on the TOF of NaNO3-H-Ir-MnO2 and the recent reported Ir-based catalysts; (d) the Tafel plots and (e) EIS spectrum (@1.445 V vs. RHE) of NaNO3-H-Ir-MnO2 and the controls; (f) Arrhenius plots of NaNO3-H-Ir-MnO2 and the controls; (g) chronopotentiometric responds of NaNO3-H-Ir-MnO2 and Ir-MnO2 at 100 mA cm-2; (h) chronoamperometric responds of NaNO3-H-Ir-MnO2 at 1.5 V and 1.6 V vs. RHE.

Fig. 5. Performance of NaNO3-H-Ir-MnO2 in PEMWE electrolyer. (a) Steady-state polarization curves of electrolyzer constructed with NaNO3-H-Ir-MnO2 at different Ir loading; (b) comparison on the Ir mass activity of the electrolyzer constructed with NaNO3-H-Ir-MnO2 and the recently reported Ir-based catalysts; (c) chronopotentiometry curve of the PEM electrolyzer using NaNO3-H-Ir-MnO2 operated at 0.5 A cm-2 at 60 °C.

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