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

doi:10.15541/jim20220413

Abstract

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

CLC Number:

X522

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.

Figures/Tables 17

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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