高活性方形氧化铅与可视化电解槽协同促进电催化臭氧生产

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

催化学报 ›› 2024, Vol. 57: 80-95.DOI: 10.1016/S1872-2067(23)64614-5

高活性方形氧化铅与可视化电解槽协同促进电催化臭氧生产

刘佳^a^,¹, 王式彬^a^,¹, 蔡锦福^a^,¹, 武立振^b, 刘云^b, 贺佳辉^a, 许在祥^a, 彭小革^a, 钟兴^a^,^*(), 安亮^b^,^*(), 王建国^a^,^*()

^a浙江工业大学化工学院, 工业催化研究所, 绿色化学合成技术国家重点实验室培育基地, 浙江杭州 310032
^b香港理工大学机械工程系, 香港九龙

收稿日期:2023-09-21 接受日期:2023-12-11 出版日期:2024-02-18 发布日期:2024-02-10
通讯作者: * 电子信箱: zhongx@zjut.edu.cn (钟兴),liang.an@polyu.edu.hk (安亮),jgw@zjut.edu.cn (王建国).
作者简介:¹共同第一作者.
基金资助:
国家重点研发计划(2022YFA1504200);国家重点研发计划(2021YFA1500903);浙江省自然科学基金(LR22B060003);国家自然科学基金(22322810);国家自然科学基金(22078293);国家自然科学基金(22141001);国家自然科学基金(22008211)

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

Jia Liu^a^,¹, Shibin Wang^a^,¹, Jinfu Cai^a^,¹, Lizhen Wu^b, Yun Liu^b, Jiahui He^a, Zaixiang Xu^a, Xiaoge Peng^a, Xing Zhong^a^,^*(), Liang An^b^,^*(), Jianguo Wang^a^,^*()

^aInstitute of Industrial Catalysis, State Key Laboratory Breeding Base of Green-Chemical Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, Zhejiang, China
^bDepartment of Mechanical Engineering, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong SAR, China

Received:2023-09-21 Accepted:2023-12-11 Online:2024-02-18 Published:2024-02-10
Contact: * E-mail: zhongx@zjut.edu.cn (X. Zhong), liang.an@polyu.edu.hk (L. An), jgw@zjut.edu.cn (J. Wang).
About author:¹ Contributed equally to this work.
Supported by:
National Key R&D Program of China(2022YFA1504200);National Key R&D Program of China(2021YFA1500903);Zhejiang Provincial Natural Science Foundation(LR22B060003);National Natural Science Foundation of China(22322810);National Natural Science Foundation of China(22078293);National Natural Science Foundation of China(22141001);National Natural Science Foundation of China(22008211)

摘要/Abstract

摘要：

臭氧是一种环境友好型氧化剂, 可直接用于消毒、杀菌和废水处理, 对于维护和促进公共卫生安全至关重要. 由于臭氧容易分解, 不利于储存, 因此需要现制即用. 目前臭氧生成技术主要包括: 电晕放电法和电催化臭氧生产(EOP)技术. 相较于电晕放电法, EOP是一种本质安全的臭氧生产技术. 然而, 该工艺相较于电晕放电技术电能消耗量大, 为了使其更具商业可行性, 有必要开发高活性且低成本的电催化剂. 此外, 合理的电解槽设计对于实现高效EOP过程也至关重要. 然而, 目前研究主要集中在提高EOP催化剂活性方面, 对电解槽的结构设计优化的关注较少. 本文通过开发高效电催化剂进而将其应用于结构优化后的电解槽中, 实现了更加高效的EOP过程.

本文采用水热方法成功制备了一种具有较高EOP活性的方形氧化铅(PbO_x-CTAB-120)电催化剂. 在标准三电极测试系统中, 电流密度为50 mA cm^-2的测试条件下, 法拉第效率(FE)可达20.7%, 与商用β-PbO₂(17.1%)相比提高了21.1%. 此外, 设计了具有平行流场的可视化EOP电解槽, 该可视化电解槽在传质和传热方面具有明显优势, 有利于实现更加高效的EOP过程. 将催化剂PbO_x-CTAB-120组装至可视化电解槽中, 在1.0 A cm^-2的测试电流密度下, 电解液为超纯水, 该体系气态臭氧产量可以达到588 mg h^-1 g^-1_catalyst, 比能量消耗(P_EOP)为56 Wh g^-1_{gaseous ozone}. 体系臭氧产量约为商用β-PbO₂在传统电解槽中产量的2倍, 并且P_EOP降低率超过62%. 原位¹⁸O同位素标记差分电化学质谱和密度泛函理论计算结果表明, PbO_x-CTAB-120电催化剂在EOP过程中遵循晶格氧机理路径, 晶格氧迁移产生的氧空位能有效稳定OOH^*和O₂^*反应中间体, 因此有利于催化剂在EOP过程中保持较好的反应活性和稳定性. 同时, 还利用先进的高速摄像可视化工具和计算流体力学(CFD)仿真模拟研究了平行流场EOP电解槽的运行过程和高效传质传热的原理. CFD模拟结果表明, 与传统流场模型相比, 平行流场对应的出口气泡停留时间更长, 说明平行流场更有利于产物气泡从出口逸出, 即气泡容易快速扩散, 与实验结果一致. 因此, PbO_x-CTAB-120电催化剂与新型可视化电解槽相结合, 有助于在超纯水中实现较好的气态臭氧产率和较低比能耗. 此外, 二者的结合充分发挥了电催化剂的EOP活性和电解槽的传质特性所带来的优势, 实现了反应性和传输性的协同增强, 从而极大促进了原位有机污染物降解效率.

综上所述, 本文在制备高效阳极催化剂的基础上, 同时利用优化电解槽结构实现了提升臭氧产率和降低过程能耗, 为高活性电催化剂与优化的电解槽耦合以实现高效EOP过程及其有效应用提供参考.

关键词: PbO_x-CTAB-120, 可视化电解槽, 电催化臭氧生产, 计算流体力学模拟, 原位降解

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

刘佳, 王式彬, 蔡锦福, 武立振, 刘云, 贺佳辉, 许在祥, 彭小革, 钟兴, 安亮, 王建国. 高活性方形氧化铅与可视化电解槽协同促进电催化臭氧生产[J]. 催化学报, 2024, 57: 80-95.

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.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(23)64614-5

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

图/表 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.

参考文献

[1]	C. Tizaoui, R. Stanton, E. Statkute, A. Rubina, E. Lester-Card, A. Lewis, P. Holliman, D. Worsley, J. Hazard. Mater., 2022, 428, 128251.
[2]	C. M. Morrison, S. Hogard, R. Pearce, D. Gerrity, U. von Gunten, E. C. Wert, Water Res., 2022, 214, 118206.
[3]	I. Bavasso, D. Montanaro, E. Petrucci, Curr. Opin. Electrochem., 2022, 34, 101017.
[4]	L. G. De Sousa, D. V. Franco, L. M. Da Silva, J. Environ. Chem. Eng., 2016, 4, 418-427.
[5]	P. A. Christensen, T. Yonar, K. Zakaria, Ozone Sci. Eng., 2013, 35, 149-167.
[6]	M. Rodriguez-Pena, J. A. Barrios Perez, J. Llanos, C. Saez, C. E. Barrera-Diaz, M. A. Rodrigo, Chemosphere, 2022, 289, 133141.
[7]	M. Rodríguez-Peña, J. A. B. Pérez, J. Llanos, C. Saez, C. E. Barrera-Díaz, M. A. Rodrigo, Electrochim. Acta, 2021, 376, 138033.
[8]	M. Rodríguez-Peña, J. A. Barrios Pérez, J. Llanos, C. Saez, C. E. Barrera-Díaz, M. A. Rodrigo, Sep. Purif. Technol., 2021, 267, 118672.
[9]	P. A. Christensen, W. F. Lin, H. Christensen, A. Imkum, J. M. Jin, G. Li, C. M. Dyson, Ozone Sci. Eng., 2009, 31, 287-293.
[10]	Y. Gu, S. Wang, H. Shi, J. Yang, S. Li, H. Zheng, W. Jiang, J. Liu, X. Zhong, J. Wang, ACS Catal., 2021, 11, 5438-5451.
[11]	Q. Zhang, Y. Cao, Y. Yan, B. Yuan, H. Zheng, Y. Gu, X. Zhong, J. Wang, J. Mater. Chem. A, 2020, 8, 2336-2342.
[12]	P. A. Christensen, K. Zakaria, T. P. Curtis, Ozone Sci. Eng., 2012, 34, 49-56.
[13]	B. Yuan, Z. Yao, C. Qiu, H. Zheng, Y. Yan, Q. Zhang, X. Sun, Y. Gu, X. Zhong, J. Wang, J. Energy Chem., 2020, 51, 312-322.
[14]	H. Y. Li, C. Deng, L. Zhao, C. H. Gong, M. F. Zhu, J. W. Chen, Water Supply, 2022, 22, 3993-4005.
[15]	J. L. Lansing, L. Zhao, T. Siboonruang, N. H. Attanayake, A. B. Leo, P. Fatouros, S. M. Park, K. R. Graham, J. A. Keith, M. Tang, AlChE J., 2021, 67, e17486.
[16]	M. Rodríguez-Peña, J. A. Barrios Pérez, J. Llanos, C. Sáez, M. A. Rodrigo, C. E. Barrera-Díaz, Curr. Opin. Electrochem., 2021, 27, 100697.
[17]	W. Li, G. Feng, J. Liu, X. Zhong, Z. Yao, S. Deng, S. Wang, J. Wang, Chin. J. Struct. Chem., 2022, 41, 2212051-2212059.
[18]	Y. Yan, Y. Gao, H. Zheng, B. Yuan, Q. Zhang, Y. Gu, G. Zhuang, Z. Wei, Z. Yao, X. Zhong, X. Li, J. Wang, Appl. Catal. B, 2020, 266, 118632.
[19]	W. Jiang, S. Wang, J. Liu, H. Zheng, Y. Gu, W. Li, H. Shi, S. Li, X. Zhong, J. Wang, J. Mater. Chem. A, 2021, 9, 9010-9017.
[20]	X. Luo, C. Ren, J. Song, H. Luo, K. Xiao, D. Zhang, J. Hao, Z. Deng, C. Dong, X. Li, J. Mater. Sci. Technol., 2023, 146, 19-41.
[21]	C. Wu, Q. Huang, B. Gong, J. Zhou, G. Xia, F. He, Y. Wang, Y. Yan, Y. Chen, J. Mater. Sci. Technol., 2023, 163, 1-16.
[22]	J. Liu, S. Wang, Z. Yang, C. Dai, G. Feng, B. Wu, W. Li, L. Shu, K. Elouarzaki, X. Hu, X. Li, H. Wang, Z. Wang, X. Zhong, Z. J. Xu, J.-G. Wang, EES Catal., 2023, 1, 301-311.
[23]	L. Ding, J. Zhao, Z. Bao, S. Zhang, H. Shi, J. Liu, G. Wang, X. Peng, X. Zhong, J. Wang, J. Mater. Chem. A, 2023, 11, 3454-3463.
[24]	H. Shi, G. Feng, S. Li, J. Liu, X. Yang, Y. Li, Y. Lu, X. Zhong, S. Wang, W. Jianguo, J. Mater. Chem. A, 2022, 10, 5430-5441.
[25]	R. J. Nikhil, G. Latha, J. M. Catherine, Adv. Mater., 2001, 13, 1389-1393.
[26]	M. Cao, C. Hu, G. Peng, Y, Qi, E. Wang, J. Am. Chem. Soc., 2003, 125, 4982-4983.
[27]	G. Xi, Y. Peng, L. Xu, M. Zhang, W. Yu, Y. Qian, Inorg. Chem. Commun., 2004, 7, 607-610.
[28]	Y. Yan, H. Yang, F. Zhang, B. Tu, D. Zhao, Small, 2006, 2, 517-521.
[29]	L. Shi, Y. Xu, Q. Li, Cryst. Growth Des., 2008, 8, 3521-3525.
[30]	H. Arami, M. Mazloumi, R. Khalifehzadeh, S. K. Sadrnezhaad, J. Alloys Compd., 2008, 466, 323-325.
[31]	J. Liu, C. Qiu, Z. Xu, M. Xue, J. Cai, H. Shi, L. Ding, X. Li, X. Zhong, J. Wang, Chem. Eng. J., 2023, 468, 143504.
[32]	C. Zhang, Y. Xu, P. Lu, X. Zhang, F. Xu, J. Shi, J. Am. Chem. Soc., 2017, 139, 16620-16629.
[33]	Q. Wu, Q. Gao, L. Sun, H. Guo, X. Tai, D. Li, L. Liu, C. Ling, X. Sun, Chin. J. Catal., 2021, 42, 482-489.
[34]	C. Wei, Z. J. Xu, Chin. J. Catal., 2022, 43, 148-157.
[35]	G. Feng, W. Li, J. Liu, X. Zhong, Z. Yao, S. Deng, W. Zhang, S. Wang, J. Wang, J. Chem. Phys., 2022, 157, 184105.
[36]	H. Jiang, J. Gu, X. Zheng, M. Liu, X. Qiu, L. Wang, W. Li, Z. Chen, X. Ji, J. Li, Energy Environ. Sci., 2019, 12, 322-333.
[37]	W. Li, G. Feng, S. Wang, J. Liu, X. Zhong, Z. Yao, S. Deng, J. Wang, J. Phys. Chem. C, 2022, 126, 8627-8636.
[38]	Y. Wang, Q. Cheng, T. Yuan, Y. Zhou, H. Zhang, Z. Zou, J. Fang, H. Yang, Chin. J. Catal., 2016, 37, 1089-1095.
[39]	S. Authayanun, K. Im-orb, A. Arpornwichanop, Chin. J. Catal., 2015, 36, 473-483.
[40]	B. L. Loeb, Ozone Sci. Eng., 2017, 40, 3-20.
[41]	B. Zhu, X.-S. Li, P. Sun, J.-L. Liu, X.-Y. Ma, X. Zhu, A.-M. Zhu, Chin. J. Catal., 2017, 38, 1759-1769.
[42]	H. Ye, Y. Liu, S. Chen, H. Wang, Z. Liu, Z. Wu, Chin. J. Catal., 2019, 40, 631-637.
[43]	A. Heebner, B. Abbassi, J. Water Process. Eng., 2022, 46, 102638.
[44]	D. Zhi, J. Wang, Y. Zhou, Z. Luo, Y. Sun, Z. Wan, L. Luo, D. C. W. Tsang, D. D. Dionysiou, Chem. Eng. J., 2020, 383, 123149.
[45]	Y. Wang, X. Duan, Y. Xie, H. Sun, S. Wang, ACS Catal., 2020, 10, 13383-13414.
[46]	B. Kasprzyk-Hordern, M. Ziólek, J. Nawrocki, Appl. Catal. B, 2003, 46, 639-669.
[47]	Y. Wang, H. Cao, C. Chen, Y. Xie, H. Sun, X. Duan, S. Wang, Chem. Eng. J., 2019, 355, 118-129.
[48]	Z. Song, M. Wang, Z. Wang, Y. Wang, R. Li, Y. Zhang, C. Liu, Y. Liu, B. Xu, F. Qi, Environ. Sci. Technol., 2019, 53, 5337-5348.
[49]	X. Fan, J. Restivo, J. J. M. Órfão, M. F. R. Pereira, A. A. Lapkin, Chem. Eng. J., 2014, 241, 66-76.

高活性方形氧化铅与可视化电解槽协同促进电催化臭氧生产

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

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 6

参考文献

相关文章 0

编辑推荐

Metrics