C元素修饰g-C3N4对TiO2的调控及复合材料光催化产氢性能研究

doi:10.11949/0438-1157.20241261

摘要/Abstract

摘要：

光催化剂的光吸收范围窄以及光生电子-空穴对的快速复合是影响光催化制氢性能的重要因素，通过掺杂改性可有效改善其催化性能。利用热缩合和煅烧法制备出C/g-C₃N₄-TiO₂复合材料，C修饰g-C₃N₄不仅调控了TiO₂的能带结构，还显著增强了TiO₂对可见光的吸收能力。进一步探究了不同C/g-C₃N₄含量的C/g-C₃N₄-TiO₂分解水制氢的光催化性能。实验结果表明，C/g-C₃N₄的引入显著增强了TiO₂在可见光区域的吸收能力，并拓宽了其光响应范围。当C/g-C₃N₄-TiO₂质量比为0.10时，三元复合物的产氢速率最高[4.66 mmol/(g·h)]，是TiO₂的2.31倍，是C/g-C₃N₄的7.17倍，且经过七次循环后，仍具有较好的稳定性。这主要得益于C/g-C₃N₄与TiO₂之间的协同作用，有效促进了光生载流子的分离和传输，减少了电子-空穴对的复合，从而提高了光催化产氢效率。因此，通过合理设计和优化光催化剂的复合结构，可以显著提升其在水分解制氢过程中的性能，为高效光催化剂的开发提供新的思路和方向。

关键词: 催化剂, g-C₃N₄, TiO₂, 光催化, 制氢

Abstract:

The narrow light absorption range of photocatalysts and the rapid complexation of photogenerated electron-hole pairs are important factors affecting the photocatalytic hydrogen production performance. Doping modification is an effective method to improve it. The C/g-C₃N₄-TiO₂ composites were synthesized by hydrothermal and calcination methods, and the C-doped g-C₃N₄ not only modulated the energy band structure of g-C₃N₄, but also significantly enhanced the visible light absorption ability of TiO₂. Then the photocatalytic performance of C/g-C₃N₄-TiO₂ with different C/g-C₃N₄ contents in decomposing water to hydrogen was further explored. The experimental results showed that the introduction of C/g-C₃N₄ significantly enhanced the absorption ability of TiO₂ in the visible region and broadened its photoresponse range. When the mass ratio of C/g-C₃N₄-TiO₂ was 0.1, the ternary complex showed the highest hydrogen production rate [4.66 mmol/(g·h)], which was 2.31 times that of TiO₂ and 7.17 times that of C/g-C₃N₄. And it still has certain enough stability after seven cycles. This is mainly due to the synergistic effect between C/g-C₃N₄ and TiO₂, which effectively promotes the separation and transport of photogenerated carriers and reduces the complexation of electron-hole pairs, thus improving the photocatalytic efficiency. Therefore, by rationally designing and optimizing the composite structure of photocatalysts, their performance in the process of water splitting for hydrogen production can be significantly enhanced, providing new insights and directions for the development of efficient photocatalysts.

Key words: catalyst, g-C₃N₄, TiO₂, photocatalysis, hydrogen production

中图分类号:

TK 91

宋粉红, 王文光, 郭亮, 范晶. C元素修饰g-C₃N₄对TiO₂的调控及复合材料光催化产氢性能研究[J]. 化工学报, 2025, 76(6): 2983-2994.

Fenhong SONG, Wenguang WANG, Liang GUO, Jing FAN. Modulation of TiO₂ by C-element modified g-C₃N₄ and photocatalytic hydrogen production performance of composites[J]. CIESC Journal, 2025, 76(6): 2983-2994.

图/表 11

图1 样品的SEM、TEM图以及0.10CCN0.1-TiO2的元素映射图和EDS能谱图

Fig.1 SEM and TEM images of the samples; Elemental mapping and EDS image of 0.10CCN0.1-TiO2

图2 CCN0.1、TiO2和yCCN0.1-TiO2复合物的XRD谱图

Fig.2 XRD patterns of CCN0.1, TiO2 and yCCN0.1-TiO2 composites

图3 0.10CCN0.1-TiO2的XPS全谱图

Fig.3 XPS full spectra of 0.10CCN0.1-TiO2

图4 TiO2、CCN0.1和0.10CCN0.1-TiO2的XPS谱图

Fig.4 XPS spectra of TiO2, CCN0.1 and 0.10CCN0.1-TiO2

图5 样品的N2吸附-脱附曲线以及孔径分布曲线

Fig.5 N2 adsorption-desorption curves and pore size distribution curves of samples

表1 样品的表面结构性质

Table 1 Surface structural properties of the samples

样品	比表面积/(m²/g)	孔径/nm
CCN_0.1	36.0032	19.9325
TiO₂	81.1675	13.7842
0.10CCN_0.1-TiO₂	64.7460	16.4268

图6 样品的光学性能分析

Fig.6 Optical property analysis of samples

图7 样品的光催化水解制氢性能表征

Fig.7 Characterization of Photocatalytic Hydrogen Production by Hydrolysis of Samples

图8 样品的电化学性质

Fig.8 Electrochemical properties of samples

图9 样品的EPR谱图

Fig.9 EPR spectra of samples

图10 0.10CCN0.1-TiO2光生载流子转移路线示意图

Fig.10 Schematic illustration for possible photogenerated charge carriers transfer route for 0.10CCN0.1-TiO2

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C元素修饰g-C₃N₄对TiO₂的调控及复合材料光催化产氢性能研究

Modulation of TiO₂ by C-element modified g-C₃N₄ and photocatalytic hydrogen production performance of composites

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