铈掺杂石墨相氮化碳的合成及可见光光催化性能

doi:10.7503/cjcu20160273

摘要/Abstract

摘要：

以硝酸铈和三聚氰胺为原料, 采用热解法合成系列Ce掺杂石墨相氮化碳(g-C₃N₄). 采用X射线衍射仪(XRD)、透射电子显微镜(TEM)、傅里叶变换红外光谱仪(FTIR)、紫外-可见漫反射光谱仪(UV-Vis DRS)、荧光光谱仪(PL)和X射线光电子能谱仪(XPS)等对样品进行了表征. 结果表明, Ce掺杂使g-C₃N₄晶粒尺寸减小, 比表面积增大, 光生电子/空穴对复合几率降低, 并影响到能带结构. 在可见光下光催化降解亚甲基蓝水溶液的结果表明, Ce掺杂g-C₃N₄的可见光光催化活性远优于纯g-C₃N₄. 其中, 0.10-Ce-C₃N₄样品80 min内对亚甲基蓝的降解率高达98.51%, 速率常数达0.0506 min^-1, 是纯g-C₃N₄的4.9倍.

关键词: 石墨相氮化碳, 光催化, 铈掺杂, 可见光

Abstract:

Graphite carbon nitride(g-C₃N₄) doped with different amounts of Ce were prepared with Ce(NO₃)₃ and melamine as raw materials. The as-prepared samples were characterized by X-ray diffraction(XRD), transmission electron microscopy(TEM), Fourier transform infrared spectroscopy(FTIR), ultraviolet visible diffuse reflectance spectroscopy(DRS), photoluminescence(PL) and X-ray photoelectron spectroscopy(XPS). The results showed that the Ce doped into g-C₃N₄ exists in the form of Ce³⁺ and Ce⁴⁺. Ce dopant could decrease the grain size, increase the electron/hole separation rate and affect the energy band structure. Because of these properties, the obtained Ce doped g-C₃N₄ exhibited an enhanced visible light photocatalytic activity toward degradation of methylene blue when compared with pure g-C₃N₄. In particular, the 0.10-Ce-C₃N₄ sample exhibited the highest activity. The degradation rate of MB over 0.10-Ce-C₃N₄ was 98.51% in 80 min. The rate constant for 0.10-Ce-C₃N₄ reached 0.0506 min^-1, which was 4.9 times that of pure g-C₃N₄. 0.10-Ce-C₃N₄ also displayed good stability with slight decrease of photocatalytic efficiency after five times recycles. A possible mechanism of the improvement of visible light photocatalytic activity was proposed.

Key words: Graphite carbon nitride(g-C3N4), Photocatalysis, Ce doping, Visible light

中图分类号:

O614
O644

TrendMD:

梁瑞钰, 徐冬冬, 查文莹, 齐楫真, 黄浪欢. 铈掺杂石墨相氮化碳的合成及可见光光催化性能. 高等学校化学学报, 2016, 37(11): 1953.

LIANG Ruiyu, XU Dongdong, ZHA Wenying, QI Jizhen, HUANG Langhuan. Preparation of Ce-Doped Graphitic Carbon Nitride with Enhanced Visible-light Photocatalytic Activity^†. Chem. J. Chinese Universities, 2016, 37(11): 1953.

图/表 11

Fig.1 XRD patterns of g-C3N4 and x-Ce-C3N4 photocatalystsa. g-C3N4; b. 0.10-Ce-C3N4; c. 0.50-Ce-C3N4; d. 1.00-Ce-C3N4.

Sample	g-C₃N₄	0.10-Ce-C₃N₄	0.50-Ce-C₃N₄	1.00-Ce-C₃N₄
D/nm	10.0	8.9	8.4	7.9
S_BET/(m²·g^-1)	11	22	21	15

Fig.2 TEM images of g-C3N4(A), 0.10-Ce-C3N4(B), 0.50-Ce-C3N4(C) and 1.00-Ce-C3N4(D)

Fig.3 FTIR spectra of g-C3N4 and x-Ce-C3N4 photocatalystsa. g-C3N4; b. 0.10-Ce-C3N4; c. 0.50-Ce-C3N4; d. 1.00-Ce-C3N4.

Fig.4 UV-Vis DRS spectra of g-C3N4 and x-Ce-C3N4 photocatalystsInset: the plot of [F(R∞)hv]2-hv. a. g-C3N4; b. 0.10-Ce-C3N4; c. 0.50-Ce-C3N4; d. 1.00-Ce-C3N4.

Fig.5 Photoluminescence emission spectra of g-C3N4 and x-Ce-C3N4 photocatalystsa. g-C3N4; b. 0.10-Ce-C3N4; c. 0.50-Ce-C3N4; d. 1.00-Ce-C3N4.

Fig.6 XPS spectra of g-C3N4(A, B) and 0.10-Ce-C3N4(C, D) photocatalysts& (A), (C) C1s; (B), (D) N1s.

Fig.7 XPS spectrum of Ce3d of 0.10-Ce-C3N4 photocatalysts

Fig.8 Photocatalytic performance of g-C3N4 and x-Ce-C3N4 under visible light irradiation(A) and first-order kinetics curves of Methylene blue degradation(B) a. g-C3N4; b. 0.10-Ce-C3N4; c. 0.50-Ce-C3N4; d. 1.00-Ce-C3N4; e. blank.

Fig.9 Cycling times of 0.10-Ce-C3N4 for photodegradation of Methylene blue under visible light

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