Synergistic promotion by highly active square-shaped lead oxide and visualized electrolyzer for enhanced electrochemical ozone production

doi:10.1016/S1872-2067(23)64614-5

Abstract

Abstract:

Electrochemical ozone production (EOP) is an intrinsically safe technology compared to Corona discharge methods for ozone generation. However, EOP technology exhibits higher electrical utility demand. Herein, a square-shaped lead oxide (PbO_x-CTAB-120) electrocatalyst with outstanding EOP activity has been successfully prepared by a simple method. Then the PbO_x-CTAB-120 was assembled into a newly visualized EOP electrolyzer (with parallel flow field) at 1.0 A cm^-2 in ultrapure water. The gaseous ozone yield reached 588 mg h^-1 g^-1_catalyst, corresponding to a specific energy consumption (P_EOP) of 56 Wh g^-1_{gaseous ozone}. In-situ ¹⁸O isotope-labelled differential electrochemical mass spectrometry reveals that PbO_x-CTAB-120 undergoes phase shuttling to β-PbO₂ via the lattice oxygen oxidation mechanism pathway. Furthermore, density functional theory calculations for multiple reaction pathways on the Pb₃O₄ (110) surface also demonstrated the participance of lattice oxygen in the EOP process, with the results show that the oxygen vacancy generated from lattice oxygen migration could effectively stabilize the OOH* and O₂* reaction intermediate in contrast to the adsorbate evolution mechanism. Therefore, the presence of highly stabilized surfaces Pb₃O₄(110) on PbO_x-CTAB-120 before phase shuttling and the stabilization of β-PbO₂ (101) and β-PbO₂(110) crystalline surfaces after phase shuttling allowed PbO_x-CTAB-120 to maintain its excellent EOP activity and stability. Moreover, based on computational fluid dynamics simulations and experimental observations, the parallel flow field design facilitated efficient mass transfer of the gaseous product (O₂+O₃) and effective thermal dissipation of the system. In addition, the high activity electrocatalyst coupled with the optimized EOP electrolyzer enabled efficient in-situ degradation of organic species.

Key words: PbO_x-CTAB-120, Visualized electrolyzer, Electrochemical ozone production, Computational fluid dynamics, simulation, In-situ degradation

Jia Liu, Shibin Wang, Jinfu Cai, Lizhen Wu, Yun Liu, Jiahui He, Zaixiang Xu, Xiaoge Peng, Xing Zhong, Liang An, Jianguo Wang. Synergistic promotion by highly active square-shaped lead oxide and visualized electrolyzer for enhanced electrochemical ozone production[J]. Chinese Journal of Catalysis, 2024, 57: 80-95.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64614-5

https://www.cjcatal.com/EN/Y2024/V57/I2/80

Figures/Tables 6

Fig. 1. Synthesis process and morphological characterization of square-shaped PbOx. (a) Scheme of square-shaped PbOx synthesis. (b) An illustration of different square-shaped PbOx. Electrocatalysts morphological characterization obtained using different surfactants under hydrothermal conditions at 120 °C: CTAB (c), PVP (d), PEG (e), F127 (f), and P123 (g). Electrocatalysts morphological characterization obtained at various hydrothermal reaction temperatures using CTAB as surfactant: 100 °C (h), 110 °C (i), 130 °C (j) and 140 °C (k)).

Fig. 2. XRD patterns of square-shaped PbOx and the standard patterns of β-PbO2 (PDF # 41-1492) and Pb3O4 (PDF # 41-1493). (a) The electrocatalysts obtained using different surfactants at 120 °C hydrothermal conditions were named PbOx-CTAB-120, PbOx-PVP-120, PbOx-PEG-120, PbOx-F127-120, and PbOx-P123-120, respectively. (b) The electrocatalysts obtained using CTAB as a surfactant at different hydrothermal reaction temperatures were named PbOx-CTAB-120, PbOx-CTAB-100, PbOx-CTAB-110, PbOx-CTAB-130, and PbOx-CTAB-140, respectively.

Fig. 3. Electrochemical performance of electrocatalysts in saturated K2SO4 solution. (a,b) LSV curves of series PbOx. LSV curves (c), Tafel slopes (d), ECSA obtained by Cdl testing (e) and Nyquist plots (f) of PbOx-CTAB-120, commercial Pb3O4 and commercial β-PbO2. (g) Gaseous ozone productivity of series PbOx. (h) The total FE (%) of PbOx-CTAB-120, commercial Pb3O4 and commercial β-PbO2 at constant current density (50 mA cm-2). (i) EOP performance comparison of different electrocatalysts in neutral media.

Fig. 4. DEMS and theoretical calculation results. (a) DEMS signals of O2 and O3 from the reaction products cycled in saturated K2SO4 (H218O) by in-situ DEMS of PbOx-CTAB-120 at 2.4 V vs. RHE. (b) DEMS signals of 32O2, 34O2, 36O2, 48O, 50O3, 52O3 and 54O3 on PbOx-CTAB-120 during OER and EOP process at 2.4 V vs. RHE. (c) Constituent content of 16O16O16O (m/z = 48), 16O18O16O (m/z = 50), 18O18O16O (m/z = 52) and 18O18O18O (m/z = 54) through DEMS measurements. (d) XRD patterns of PbOx-CTAB-120, commercial Pb3O4 and the standard patterns of Pb3O4 (PDF # 41-1493). (e) DFT calculated potential energy diagram for the EOP process via the AEM under various applied potential conditions (electro-neutral, 1.23 V vs. SHE and 1.51 V vs. SHE). (f) DFT calculated potential energy diagram for the EOP process via the LOM under various applied potential conditions (electro-neutral, 1.23 V vs. SHE and 1.51 V vs. SHE).

Fig. 5. Design of visualized EOP electrolyzer with a parallel flow field. (a) Schematic of the novel EOP electrolyzer. (b) Photograph of the EOP electrolyzer. Anode gas flow rate (L h-1) (c), Electrolyzer temperature (°C) (d) and Faradic efficiency of gaseous ozone (%) (e) for the two different flow fields at various current density. (f) Photographs of bubble distribution in the flow fields during EOP operation at different current density taken with a high-speed camcorder. (g,h) CFD simulation results of the bubble trajectories in parallel (g) and spot (h) flow fields (see Methods section for specific simulation details).

Fig. 6. In-situ electrochemical degradation of organic pollutants by means of the novel EOP electrolyzer with parallel flow fields. (a) Experimental setup for in-situ electrochemical degradation under flow conditions. In-situ electrochemical degradation of tetracycline (b), carbaryl (c), bisphenol A (d), ciprofloxacin (e), phenol (f) and chloramphenicol (g). (h) In-situ cyclic degradation performance of tetracycline in the novel EOP electrolyzer.

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