TiN/TiO2复合光电极的构建及TiN的等离激元光热作用

doi:10.15541/jim20250483

摘要/Abstract

摘要：

TiN纳米颗粒具有显著的等离激元光热特性, 但其与TiO₂光电极的光热性能还有待研究。本研究以尿素为氮源, 采用溶胶-凝胶法可控制备了TiN纳米颗粒, 通过调控TiN分散液的旋涂用量制备了一系列TiN/TiO₂复合光电极。研究表明, 控制尿素/四氯化钛摩尔比为8可制得粒径10~30 nm的TiN颗粒。采用该颗粒的200 μL 2%(质量分数)乙醇分散液, 通过旋涂法制备TiN/TiO₂复合光电极, 其在模拟太阳光照射下光电流密度达到1.47 mA·cm⁻², 开路光电压达到0.69 V, 较纯TiO₂光电极分别提升75%和57%, 并可稳定输出3 h以上。引入TiN增强了材料在可见光区吸收, 在光照下TiN纳米颗粒快速升温, 热量有效传递至TiO₂基底, 促进界面电荷转移与表面反应动力学, 说明TiN的光热效应可提升光电极表面局域温度以增强光电极水分解性能。

关键词: TiN纳米材料, 溶胶-凝胶法, TiN/TiO₂复合光电极, 光电化学, 等离激元光热作用

Abstract:

TiN nanoparticles exhibit significant plasmonic photothermal properties, yet their role within TiN/TiO₂ composite photoanodes remains unclear. In this work, TiN nanoparticles were controllably synthesized via a Sol-Gel method using urea as the nitrogen source. A series of TiN/TiO₂ composite photoanodes were fabricated by adjusting the spin-coating volume of the TiN dispersion. The results show that TiN nanoparticles with size in the range of 10-30 nm can be obtained by controlling the urea/TiCl₄ molar ratio to 8. The TiN/TiO₂ composite photoelectrode, fabricated by spin-coating 200 μL of 2% (in mass) ethanol dispersion of these nanoparticles, achieves a photocurrent density of 1.47 mA·cm^-2 and an open-circuit photovoltage of 0.69 V under simulated solar illumination, enhanced by 75% and 57%, respectively, compared to pristine TiO₂ photoelectrode, and the electrode maintains stable performance for over 3 h. Introduction of TiN enhances visible light absorption of material. Therefore, under illumination, TiN nanoparticles undergo rapid heating, and the generated heat is efficiently transferred to the TiO₂ substrate, promoting interfacial charge transfer and surface reaction kinetics. These findings demonstrate that the photothermal effect of TiN can elevate the local temperature at the photoelectrode surface, thereby enhancing photoelectrochemical water splitting performance.

Key words: TiN nanomaterial, Sol-Gel method, TiN/TiO₂ composite photoanode, photoelectrochemistry, plasmonic photothermal effect

中图分类号:

TQ116

李扬扬, 桑丽霞, 陈梦佳, 杜春旭. TiN/TiO₂复合光电极的构建及TiN的等离激元光热作用[J]. 无机材料学报, 2026, 41(9): 1229-1237.

LI Yangyang, SANG Lixia, CHEN Mengjia, DU Chunxu. Construction of TiN/TiO₂ Composite Photoanodes and the Plasmonic Photothermal Effect of TiN[J]. Journal of Inorganic Materials, 2026, 41(9): 1229-1237.

图/表 8

表1 复合光电极参数设计

Table 1 Parameter design of composite photoanodes

Sample	Urea/TiCl₄ (in molar)	TiN dispersion/μL
TiN4/TiO₂-100	4	100
TiN6/TiO₂-100	6	100
TiN8/TiO₂-100	8	100
TiN10/TiO₂-100	10	100
TiN8/TiO₂-200	8	200
TiN8/TiO₂-300	8	300

图1 TiNR的XRD图谱

Fig. 1 XRD patterns of TiNR

图2 (a) TiO2纳米棒阵列的正面与侧面(插图)SEM照片; (b) TiN8的TEM照片; (c~e) TiN8/TiO2-x复合光电极的SEM照片; (f) TiN8/TiO2-200复合光电极的能谱图及Ti、O、N元素面分布图

Fig. 2 (a) Top-view and cross-sectional (inset) SEM images of the TiO2 nanorod array; (b) TEM image of TiN8; SEM images of (c-e) TiN8/TiO2-x composite photoanodes; (f) Energy dispersive spectrum and corresponding elemental mappings of Ti, O, and N for TiN8/TiO2-200 composite photoanode (c) TiN8/TiO2-100; (d) TiN8/TiO2-200; (e) TiN8/TiO2-300

图3 (a) TiNR/TiO2-100复合光电极的J-t曲线; (b) TiO2纳米棒光电极及TiN8/TiO2-x的J-t曲线; (c) TiN8/TiO2-200复合光电极的J稳定性测试

Fig. 3 (a) J-t curves of TiNR/TiO2-100; (b) J-t curves of the pristine TiO2 photoanode and TiN8/TiO2-x; (c) J stability test of the TiN8/TiO2-200 composite photoanode under illumination

图4 (a) TiO2纳米棒光电极及TiN8/TiO2-x复合光电极的Eoc-t曲线; (b) TiN8、TiO2纳米棒光电极及TiN8/TiO2-x复合光电极的紫外-可见光吸收光谱图; TiO2纳米棒光电极及TiN8/TiO2-200复合光电极的(c) J-Eapp曲线和(d) ABPE曲线

Fig. 4 (a) Eoc-t curves of pristine TiO2 and TiN8/TiO2-x composite photoanodes; (b) UV-Vis absorption spectra of TiN8, pristine TiO2 and TiN8/TiO2-x composite photoanodes; (c) J-Eapp curves and (d) ABPE curves of TiO2 nanorod photoanode and TiN8/TiO2-200 composite photoanode

图5 TiO2纳米棒光电极及TiN8/TiO2-200复合光电极在模拟太阳光辐照下的红外热成像图

Fig. 5 Infrared thermal images of pristine TiO2 nanorod photoanode and TiN8/TiO2-200 composite photoanode under simulated solar illumination Colorful figure is available on website

图6 (a) TiN8/TiO2-200复合光电极的温度-时间曲线和(b~d)简化模型光热效应示意图

Fig. 6 (a) Temperature-time curves and (b-d) schematic diagrams of the simplified photothermal model for TiN8/TiO2-200 composite photoanode(b) Structural side view; (c) Isothermal distribution; (d) Conductive heat flux. Colorful figures are available on website

图7 TiN8/TiO2-200复合光电极等效模型时域温度场仿真结果

Fig. 7 Temporal temperature field simulation results of TiN8/TiO2-200 composite photoanode equivalent model Colorful figure is available on website

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TiN/TiO₂复合光电极的构建及TiN的等离激元光热作用

Construction of TiN/TiO₂ Composite Photoanodes and the Plasmonic Photothermal Effect of TiN

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