反应温度对光电极表面气泡动力学及传质特性的影响

doi:10.16085/j.issn.1000-6613.2024-0478

摘要/Abstract

摘要：

与光电分解水有关的一个重大难点是由于电极表面的气泡覆盖而引起的阳极反应速率降低。采用耦合电化学测试与高速摄像的实验系统，实现了TiO₂光电极表面气泡行为的原位观察，研究了温度对反应传质以及气泡动力学的影响规律。结果表明，升高反应温度能够显著提高光电流密度与析气效率。在气泡演化过程中，气泡生长系数随着反应温度的升高而增大，涉及单相自然对流与气液界面扩张微对流的边界层内传质作用增强。其中，尽管单相自然对流占传质的主导作用，但随着反应温度的升高气液界面扩张引起的微对流传质作用逐渐增强。此外，气泡脱离尺寸和生长周期随着反应温度的升高而减小，考虑温度与浓度马兰戈尼力的影响建立气泡生长过程的动力学模型，预测值与实验结果接近。

关键词: 光电催化分解水, 气泡, 温度, 传质, 微对流, 马兰戈尼力

Abstract:

An important challenge related to the photoelectrochemical water splitting is the reduction in the reaction rate caused by the bubble coverage on the electrode surface. In this study, in-situ observation of bubble evolution on the TiO₂ photoanode surface was achieved using an electrochemical system coupled with a high-speed camera system. The effects of reaction temperature on bubble dynamics and mass transfer were systematically explored. It indicated that both the photocurrent and gas evolution efficiency increased as the reaction temperature rise. Furthermore, the bubble growth coefficients during evolution also increased with temperature, consequently enhancing interfacial mass transfer through micro-convection, including single-phase natural convection and micro-convection induced by gas-liquid interface expansion. Although single-phase natural convection played a dominant role in mass transfer, the micro-convection induced by the expansion of gas-liquid interface gradually intensified with rising reaction temperature. Additionally, the bubble detachment size and growth period decreased with increasing reaction temperature. The dynamic model considering the temperature and concentration Marangoni force was established, and the predicted values matched well with the experimental results.

Key words: photoelectrochemical water splitting, bubble, temperature, mass transfer, micro-convection, Marangoni force

中图分类号:

O644.1

佘永璐, 徐强, 罗欣怡, 聂腾飞, 郭烈锦. 反应温度对光电极表面气泡动力学及传质特性的影响[J]. 化工进展, 2025, 44(3): 1243-1252.

SHE Yonglu, XU Qiang, LUO Xinyi, NIE Tengfei, GUO Liejin. Effect of reaction temperature on bubble dynamics and mass transfer characteristics on photoanode surface[J]. Chemical Industry and Engineering Progress, 2025, 44(3): 1243-1252.

图/表 9

图1 实验系统示意图

图2 气泡照片的Matlab程序图像处理和计算过程

图3 不同反应温度下的光电流与气泡变化趋势

图4 不同反应温度下的气泡几何特征的动态变化

表1 不同气泡演化阶段的生长系数β与时间系数α

生长阶段	生长系数β	时间系数α
惯性力控制	$β = (2 K H δ 3 ρ l) 0.5$	1
扩散控制	$β = 2 D 0.5 J a 1 + (1 + 2 π J a) 0.5 2 π$	0.5
化学反应控制	$β = (6 I R T z π F P f g) 0.33$	0.33

表1 不同气泡演化阶段的生长系数β与时间系数α

生长阶段	生长系数β	时间系数α
惯性力控制	$β = (2 K H δ 3 ρ l) 0.5$	1
扩散控制	$β = 2 D 0.5 J a 1 + (1 + 2 π J a) 0.5 2 π$	0.5
化学反应控制	$β = (6 I R T z π F P f g) 0.33$	0.33

图5 不同反应温度下气泡生长过程的析气效率分布

图6 微对流传质的瞬态传质系数分布

图7 气泡生长过程的微对流传质计算

图8 气泡脱离与脱离尺寸预测

参考文献 41

1	CHENG Wenhui, DE LA CALLE Alberto, ATWATER Harry A, et al. Hydrogen from sunlight and water: A side-by-side comparison between photoelectrochemical and solar thermochemical water-splitting[J]. ACS Energy Letters, 2021, 6(9): 3096-3113.
2	ZHOU Peng, NAVID Ishtiaque Ahmed, MA Yongjin, et al. Solar-to-hydrogen efficiency of more than 9% in photocatalytic water splitting[J]. Nature, 2023, 613(7942): 66-70.
3	HISATOMI Takashi, KUBOTA Jun, DOMEN Kazunari. Recent advances in semiconductors for photocatalytic and photoelectrochemical water splitting[J]. Chemical Society Reviews, 2014, 43(22): 7520-7535.
4	DORFI Anna E, WEST Alan C, ESPOSITO Daniel V. Quantifying losses in photoelectrode performance due to single hydrogen bubbles[J]. The Journal of Physical Chemistry C, 2017, 121(48): 26587-26597.
5	Isaac HOLMES-GENTLE, Franky BEDOYA-LORA, ALHERSH Faye, et al. Optical losses at gas evolving photoelectrodes: Implications for photoelectrochemical water splitting[J]. The Journal of Physical Chemistry C, 2019, 123(1): 17-28.
6	QIN Jingshan, XIE Tianhui, ZHOU Daojin, et al. Kinetic study of electrochemically produced hydrogen bubbles on Pt electrodes with tailored geometries[J]. Nano Research, 2021, 14(7): 2154-2159.
7	HERNÁNDEZ S, BARBERO G, SARACCO G, et al. Considerations on oxygen bubble formation and evolution on BiVO₄ porous anodes used in water splitting photoelectrochemical cells[J]. The Journal of Physical Chemistry C, 2015, 119(18): 9916-9925.
8	陈娟雯, 郭烈锦, 胡晓玮, 等. TiO₂光电极表面气泡相互作用规律研究[J]. 工程热物理学报, 2018, 39(3): 550-554.
	CHEN Juanwen, GUO Liejin, HU Xiaowei, et al. Study on bubble interaction on TiO₂ photoelectrode[J]. Journal of Engineering Thermophysics, 2018, 39(3): 550-554.
9	HU Xiaowei, CAO Zhenshan, WANG Yechun, et al. Single photogenerated bubble at gas-evolving TiO₂ nanorod-array electrode[J]. Electrochimica Acta, 2016, 202: 175-185.
10	WANG Mengsha, NIE Tengfei, SHE Yonglu, et al. Study on the behavior of single oxygen bubble regulated by salt concentration in photoelectrochemical water splitting[J]. International Journal of Hydrogen Energy, 2023, 48(61): 23387-23401.
11	XU Qiang, LIANG Liang, NIE Tengfei, et al. Effect of electrolyte pH on oxygen bubble behavior in photoelectrochemical water splitting[J]. The Journal of Physical Chemistry C, 2023, 127(11): 5308-5320.
12	LUO Xinyi, XU Qiang, NIE Tengfei, et al. Influence of subatmospheric pressure on bubble evolution on the TiO₂ photoelectrode surface[J]. Physical Chemistry Chemical Physics, 2023, 25(23): 16086-16104.
13	LI Mingbo, MA Xiaotong, EISENER Julian, et al. How bulk nanobubbles are stable over a wide range of temperatures[J]. Journal of Colloid and Interface Science, 2021, 596: 184-198.
14	MA Benchi, LIN Hua, ZHU Yizhou, et al. A new Concentrated Photovoltaic Thermal-Hydrogen system with photocatalyst suspension as optical liquid filter[J]. Renewable Energy, 2022, 194: 1221-1232.
15	冯浩, 张莹, 刘东, 等. 光电化学反应中界面气泡多尺度作用机制的研究进展[J]. 科学通报, 2023, 68(25): 3275-3292.
	FENG Hao, ZHANG Ying, LIU Dong, et al. Advances in multiscale interaction of interfacial gas bubble evolution in photoelectrochemical reactions[J]. Chinese Science Bulletin, 2023, 68(25): 3275-3292.
16	VOGT H. On the gas-evolution efficiency of electrodes Ⅰ-Theoretical[J]. Electrochimica Acta, 2011, 56(3): 1409-1416.
17	VOGT H. On the gas-evolution efficiency of electrodes. Ⅱ‍-Numerical analysis[J]. Electrochimica Acta, 2011, 56(5): 2404-2410.
18	CAO Zhenshan, ZHANG Bo, FENG Yuyang, et al. Mass transfer mechanism during bubble evolution on the surface of photoelectrode[J]. Electrochimica Acta, 2022, 434: 141293.
19	CAO Zhenshan, FENG Yuyang, ZHANG Bo, et al. Distribution characteristics of multiphysics around the bubble on the surface of photoelectrode[J]. Journal of the Electrochemical Society, 2022, 169(12): 126504.
20	郭烈锦, 曹振山, 王晔春, 等. 太阳能光催化分解水气泡动力学研究进展[J]. 西安交通大学学报, 2023, 57(3): 1-22.
	GUO Liejin, CAO Zhenshan, WANG Yechun, et al. Review of bubble dynamics in solar photocatalytic water splitting[J]. Journal of Xi’an Jiaotong University, 2023, 57(3): 1-22.
21	YANG Xuegeng, KARNBACH Franziska, UHLEMANN Margitta, et al. Dynamics of single hydrogen bubbles at a platinum microelectrode[J]. Langmuir, 2015, 31(29): 8184-8193.
22	ZENG Binglin, CHONG Kai Leong, WANG Yuliang, et al. Periodic bouncing of a plasmonic bubble in a binary liquid by competing solutal and thermal Marangoni forces[J]. Proceedings of the National Academy of Sciences, 2021, 118(23): e2103215118.
23	NIE Tengfei, LI Zhiqing, LUO Xinyi, et al. Single bubble dynamics on a TiO₂ photoelectrode surface during photoelectrochemical water splitting[J]. Electrochimica Acta, 2022, 436: 141394.
24	NATH Saurabh, RICARD Guillaume, JIN Panlin, et al. Thermal Marangoni bubbles[J]. Soft Matter, 2022, 18(38): 7422-7426.
25	LIU Ya, JIANG Jiangang, XU Quan, et al. Photoelectrochemical performance of CdS nanorods grafted vertically aligned TiO₂ nanorods[J]. Materials Research Bulletin, 2013, 48(11): 4548-4554.
26	FALLISCH Arne, SCHELLHASE Leon, FRESKO Jan, et al. Hydrogen concentrator demonstrator module with 19.8% solar-to-hydrogen conversion efficiency according to the higher heating value[J]. International Journal of Hydrogen Energy, 2017, 42(43): 26804-26815.
27	Damaris FERNÁNDEZ, MAURER Paco, MARTINE Milena, et al. Bubble formation at a gas-evolving microelectrode[J]. Langmuir, 2014, 30(43): 13065-13074.
28	BRANDON N P, KELSALL G H. Growth kinetics of bubbles electrogenerated at microelectrodes[J]. Journal of Applied Electrochemistry, 1985, 15(4): 475-484.
29	MATSUSHIMA Hisayoshi, KIUCHI Daisuke, FUKUNAKA Yasuhiro, et al. Single bubble growth during water electrolysis under microgravity[J]. Electrochemistry Communications, 2009, 11(8): 1721-1723.
30	SCRIVEN L E. On the dynamics of phase growth[J]. Chemical Engineering Science, 1959, 10(1/2): 1-13.
31	ZUBKOV Tykhon, STAHL Dirk, THOMPSON Tracy L, et al. Ultraviolet light-induced hydrophilicity effect on TiO₂(110)(1 × 1). dominant role of the photooxidation of adsorbed hydrocarbons causing wetting by water droplets[J]. The Journal of Physical Chemistry B, 2005, 109(32): 15454-15462.
32	CAPUTO Gianvito, NOBILE Concetta, KIPP Tobias, et al. Reversible wettability changes in colloidal TiO₂ nanorod thin-film coatings under selective UV laser irradiation[J]. The Journal of Physical Chemistry C, 2008, 112(3): 701-714.
33	GAO Yanfeng, MASUDA Yoshitake, KOUMOTO Kunihito. Light-excited superhydrophilicity of amorphous TiO₂ thin films deposited in an aqueous peroxotitanate solution[J]. Langmuir, 2004, 20(8): 3188-3194.
34	CHEN Juanwen, GUO Liejin. Nanoscale capillarity for mitigating gas bubble adhesion on arrayed photoelectrode during photoelectrochemical water splitting[J]. Applied Physics Letters, 2019, 114(23): 231604.
35	VOGT H. The role of single-phase free convection in mass transfer at gas evolving electrodes—‍Ⅱ. Experimental verification[J]. Electrochimica Acta, 1993, 38(10): 1427-1431.
36	VOGT H. On the various types of uncontrolled potential increase in electrochemical reactors—The anode effect[J]. Electrochimica Acta, 2013, 87: 611-618.
37	LOCHIEL A C, CALDERBANK P H. Mass transfer in the continuous phase around axisymmetric bodies of revolution[J]. Chemical Engineering Science, 1964, 19(7): 471-484.
38	LIU Hongbo, PAN Liangming, WEN Jian. Numerical simulation of hydrogen bubble growth at an electrode surface[J]. The Canadian Journal of Chemical Engineering, 2016, 94(1): 192-199.
39	LAX M. Temperature rise induced by a laser beam[J]. Journal of Applied Physics, 1977, 48(9): 3919-3924.
40	VOGT H. Interfacial supersaturation at gas evolving electrodes[J]. Journal of Applied Electrochemistry, 1993, 23(12): 1323-1325.
41	VOGT H. The concentration overpotential of gas evolving electrodes as a multiple problem of mass transfer[J]. Journal of the Electrochemical Society, 1990, 137(4): 1179-1184.

[1]	赖俊华, 潘大伟, 巨晓洁, 刘壮, 谢锐, 汪伟, 褚良银. 光栅结构对智能凝胶光栅传感器检测性能的影响规律[J]. 化工进展, 2025, 44(3): 1578-1587.
[2]	李昊阳, 李洪伟, 谭建宇. 瞬态振荡加热条件下沸腾气泡运动特性[J]. 化工进展, 2025, 44(2): 735-742.
[3]	白依冉, 翟玉玲, 戴晶慧, 李舟航. 微纳尺度池沸腾表面润湿性的气泡成核及强化传热机制[J]. 化工进展, 2025, 44(2): 743-751.
[4]	罗小平, 贾梦帆, 李世珍. 电场和改性PVDF膜相分离结构协同作用下逆流微细通道压降特性[J]. 化工进展, 2025, 44(2): 646-659.
[5]	苏瑶, 陈占秀, 杨历, 邢赫威, 呼和仓, 李源华. 热源温度对非对称纳米通道流动换热的影响[J]. 化工进展, 2024, 43(S1): 144-153.
[6]	熊建华, 段志刚, 陈剑峰, 于乐, 康玉阳, 孙韶峰, 秦远智, 黄启玉. 低含水阶段含蜡原油不加热集油温度下限确定[J]. 化工进展, 2024, 43(S1): 255-267.
[7]	郑庆雨, 金光远, 冯文凯, 朱正山, 周逸凡, 滕厚场, 李臻峰, 宋春芳, 宋飞虎, 李静. 一种混沌C型几何流动混合耦合电磁热特性数值分析[J]. 化工进展, 2024, 43(8): 4262-4272.
[8]	宋占龙, 汤涛, 潘蔚, 赵希强, 孙静, 毛岩鹏, 王文龙. 微纳米气泡强化臭氧氧化降解含酚废水[J]. 化工进展, 2024, 43(8): 4614-4623.
[9]	杨磊, 邱广薇, 李思言, 葛宏程, 孙园园, 王菲, 范晓光. 基于温度和葡萄糖双重响应性共聚物微囊的胰岛素控释载体[J]. 化工进展, 2024, 43(6): 3277-3284.
[10]	赵伟, 江雨寒, 李振, 李毅红, 周安宁, 王宏. 煤岩显微组分电浮选分离与制氢过程中氢/氧气泡的影响机制[J]. 化工进展, 2024, 43(5): 2428-2435.
[11]	谢小金, 张晓雪, 刘晓玲, 崇明本, 程党国, 陈丰秋. 单晶多级孔ZSM-5分子筛酸性质对正庚烷催化裂解反应传质性能的影响[J]. 化工进展, 2024, 43(5): 2661-2672.
[12]	武西宁, 张宁, 秦佳敏, 徐龙, 魏朝阳, 马晓迅. 低冷量下强化CO₂吸收的甲醇基纳米流体性能[J]. 化工进展, 2024, 43(5): 2811-2822.
[13]	祝妍妮, 王维, 孙闫晨昊, 魏岗, 张大为. 基于单液滴蒸发的离心喷雾干燥数值模拟[J]. 化工进展, 2024, 43(4): 1700-1710.
[14]	何发超, 刘海龙, 李昌烽, 王军锋. 非均匀电场对高黏流体中气泡分散特性的影响[J]. 化工进展, 2024, 43(4): 1774-1782.
[15]	杨东晓, 熊启钊, 王毅, 陈杨, 李立博, 李晋平. 多级孔MOF的制备及其吸附分离应用研究进展[J]. 化工进展, 2024, 43(4): 1882-1896.