TiHAP@g-C3N4异质结的制备及光催化降解甲基橙

doi:10.15541/jim20220413

摘要/Abstract

摘要：

通过水热法合成了钛羟基磷灰石(TiHAP)与g-C₃N₄复合光催化剂(TiHAP@g-C₃N₄), 并对其结构和光学特性进行表征, 通过甲基橙(MO)降解实验评价其光催化活性。结果表明：样品中短棒状TiHAP生长在g-C₃N₄表面, 均保持原有晶型和化学结构; 制备的TiHAP@g-C₃N₄纯度高, 比表面积达107.92 m²/g, 较TiHAP、g-C₃N₄分别增大约135%、44%; 在TiHAP@g-C₃N₄添加量为1.0 g/L、pH 7条件下, 120 min内MO降解率达96.35%; 3次循环实验降解率保持在80.02%以上, TiHAP@g-C₃N₄光催化性能良好且结构稳定。空穴(h⁺)在MO降解过程中作用最大, ·O₂^-与·OH的作用递减。TiHAP@g-C₃N₄异质结的构建, 增强了对光的吸收, 提高了光生电子-h⁺的分离效率, 保留了氧化还原性更强的TiHAP价带h⁺和g-C₃N₄导带电子, 从而提升了光催化性能。

关键词: 紫外光催化, TiHAP@g-C₃N₄, 甲基橙, 异质结, 光生电子-空穴

Abstract:

A composite photocatalyst (TiHAP@g-C₃N₄) consisting of Ti doped hydroxyapatite and g-C₃N₄was synthesized through hydrothermal route. Its structure and optical property were characterized by various means and photocatalytic activity was evaluated through methyl orange (MO) degradation experiments. Results show that short rod-shaped TiHAP in the sample grows on the surface of g-C₃N₄. Both TiHAP and g-C₃N₄ maintain their original crystal shape and chemical structure. As-prepared TiHAP@g-C₃N₄ is of high purity with specific surface area of 107.92 m²/g, which is increased about 135% and 44% as compared with sole TiHAP and sole g-C₃N₄, respectively. The highest MO degradation rate of 96.35% is achieved within 120 min by TiHAP@g-C₃N₄ at the concentration of 1.0 g/L and pH 7. More than 80.02% of MO was removed in every of three cyclic tests, demonstrating good and stable photocatalytic performance of TiHAP@g-C₃N₄. Holes (h⁺) play the largest role in the MO degradation process, followed by ·O₂^- and ·OH. The constructed TiHAP@g-C₃N₄ heterojunction enhances light absorption, improves separation efficiency of photoelectrons-h⁺, and preserves more redox-prone TiHAP valence band h⁺ and g-C₃N₄ conduction band electrons. Therefore, as-synthesized TiHAP@g-C₃N₄ can be a promising catalyst in photocatalytic degradation.

Key words: ultraviolet photocatalysis, TiHAP@g-C₃N₄, methyl orange, heterojunction, photoelectron-hole

中图分类号:

X522

伍林, 胡明蕾, 王丽萍, 黄少萌, 周湘远. TiHAP@g-C₃N₄异质结的制备及光催化降解甲基橙[J]. 无机材料学报, 2023, 38(5): 503-510.

WU Lin, HU Minglei, WANG Liping, HUANG Shaomeng, ZHOU Xiangyuan. Preparation of TiHAP@g-C₃N₄ Heterojunction and Photocatalytic Degradation of Methyl Orange[J]. Journal of Inorganic Materials, 2023, 38(5): 503-510.

图/表 17

图1 HAP、TiHAP、g-C3N4和TiHAP@g-C3N4的XRD图谱

Fig. 1 XRD patterns of HAP, TiHAP, g-C3N4, and TiHAP@g-C3N4

图S1 TiHAP、g-C3N4和TiHAP@g-C3N4的FT-IR谱

Fig. S1 FT-IR spectra of TiHAP, g-C3N4 and TiHAP@g-C3N4

图2 (a)TiHAP、(b)g-C3N4和(c, d)TiHAP@g-C3N4的FESEM照片

Fig. 2 FESEM images of (a) TiHAP, (b) g-C3N4 and (c, d) TiHAP@g-C3N4

图3 TiHAP、g-C3N4和TiHAP@g-C3N4的(a)N2吸附-脱附曲线及(b)孔径分布图

Fig. 3 (a) N2 adsorption-desorption curves and (b) pore size distributions of TiHAP, g-C3N4 and TiHAP@g-C3N4

表1 TiHAP、g-C3N4和TiHAP@g-C3N4的BET比表面积及孔结构数据

Table 1 BET specific surface area and pore structure of TiHAP, g-C3N4 and TiHAP@g-C3N4

Sample	S_BET/ (m²·g^-1)	Pore volume/ (cm³·g^-1)	Average pore/ nm
TiHAP	46.02	0.1368	11.89
g-C₃N₄	74.99	0.1370	7.30
TiHAP@g-C₃N₄	107.92	0.3107	11.52

图4 TiHAP、g-C3N4和TiHAP@g-C3N4的UV-Vis漫反射光谱

Fig. 4 UV-Vis diffuse reflectance spectra of TiHAP, g-C3N4 and TiHAP@g-C3N4

图S2 (a)TiHAP和(b)g-C3N4的带隙估算

Fig. S2 Band gap estimation of (a) TiHAP and (b) g-C3N4

图S3 (a)TiHAP和(b)g-C3N4的莫特-肖特基曲线

Fig. S3 Mott-Schottky plots of (a) TiHAP and (b) g-C3N4

表2 TiHAP和g-C3N4的能带位置

Table 2 Band position of TiHAP and g-C3N4

Sample	Band gap energy/eV	Conduction band edge/V(vs. NHE)	Valence band gap/ V(vs. NHE)
TiHAP	3.88	-0.70	3.18
g-C₃N₄	2.90	-1.09	1.82

图5 TiHAP和g-C3N4的(a)暂态光电流响应曲线和(b)奈奎斯特图

Fig. 5 (a) Transient photocurrent response curves and (b) Nyquist plots of TiHAP, g-C3N4 and TiHAP@g-C3N4

图6 TiHAP、g-C3N4和TiHAP@g-C3N4的PL谱

Fig. 6 PL spectra of TiHAP, g-C3N4 and TiHAP@g-C3N4

图7 (a)TiHAP@g-C3N4添加量和(b)pH对MO降解的影响

Fig. 7 Effect of (a) TiHAP@g-C3N4 dosage and (b) initial pH on MO degradation

图S4 TiHAP@g-C3N4添加量为0.5 g/L、pH 5时甲基橙浓度和总有机碳(TOC)变化

Fig. S4 Change of methyl orange concentration and TOC in solution with TiHAP@g-C3N4 dosage of 0.5 g/L and pH 5

图8 TiHAP@g-C3N4降解MO的循环实验结果

Fig. 8 Cyclic experimental results of MO degradation by TiHAP@g-C3N4

图S5 TiHAP@g-C3N4光催化反应前后的(a)XRD图谱和(b)FT-IR谱图

Fig. S5 (a) XRD patterns and (b) FT-IR spectra of TiHAP@g-C3N4 before (fresh) and after (used) photocatalytic reactions

图9 不同自由基清除剂对MO降解效果的影响

Fig. 9 Effects of different radical trapping agents on MO degradation

图10 紫外光照下TiHAP@g-C3N4光催化降解MO的机理示意图

Fig. 10 Schematic mechanism of MO degradation process by TiHAP@g-C3N4 under UV light irradiation

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TiHAP@g-C₃N₄异质结的制备及光催化降解甲基橙

Preparation of TiHAP@g-C₃N₄ Heterojunction and Photocatalytic Degradation of Methyl Orange

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