Bi2MoO6/Ni-Fe LDH复合材料的制备及可见光催化性能

doi:10.15541/jim20140675

摘要/Abstract

摘要：

采用水热法和共沉淀法结合制备Bi₂MoO₆/Ni-Fe LDH复合材料, 通过XRD、FT-IR、SEM、TEM、XPS和N₂物理吸附等对样品的结构和形貌进行表征。以甲基橙、亚甲基蓝、罗丹明B和苯酚为目标降解物, 在可见光下进行复合材料的光催化性能测试, 以降解甲基橙溶液为例研究复合材料的光催化反应机理。结果表明, 复合材料的BET比表面积随着Ni-Fe LDH含量的增加而增大, 光催化活性明显提高。Bi₂MoO₆/Ni-Fe LDH复合材料中Ni-Fe LDH的含量为4.5%时具有最好的光催化效果, 可见光照射60 min, 甲基橙的降解率达91%, 较Bi₂MoO₆和Ni-Fe LDH分别提高52%和16%。Bi₂MoO₆/Ni-Fe LDH复合材料具有良好的稳定性, 循环使用5次, 甲基橙(MO)的降解率为88%。复合材料光催化降解甲基橙反应遵循一级反应动力学。

关键词: 水热法, 共沉淀法, Bi2MoO6/Ni-Fe LDH复合材料, 光催化

Abstract:

Bi₂MoO₆/Ni-Fe LDH composites were prepared by hydrothermal method and co-precipitation. The morphology and structure of the sample were characterized by XRD, FT-IR, SEM, TEM, XPS and N₂-physisorption. Photocatalytic degradation activity and mechanism of the samples were investigated by the photocatalytic degradation of methyl orange (MO), methylene blue, butyl rhodamine B and phenol under visible light irradiation. The results showed that BET specific surface area of the composites increased with the LDH content increase. Photocatalytic degradation activity of MO under visible irradiation exhibited significant enhancement. After visible light irradiation for 60 min, the Bi₂MoO₆/Ni-Fe LDH composites with LDH content of 4.5wt% showed the highest degradation rate of 91%, higher than that of Bi₂MoO₆and Ni-Fe LDH by 52% and 16%, respectively. And the composites photocatalytic degradation followed first-order reaction kinetics. The composites decolorizing rate still remained 88% after 5 times recycle, showing high catalytic stability.

Key words: hydrothermal method, co-precipitation, Bi2MoO6/Ni-Fe LDH composites, photocatalyst

中图分类号:

O643

曲婷, 黄强, 赵振波. Bi₂MoO₆/Ni-Fe LDH复合材料的制备及可见光催化性能[J]. 无机材料学报, 2015, 30(8): 825-832.

QU Ting, HUANG Qiang, ZHAO Zhen-Bo. Preparation and Visible Light Responsive Photocatalytic Activity of Bi₂MoO₆/Ni-Fe LDH Composites[J]. Journal of Inorganic Materials, 2015, 30(8): 825-832.

图/表 13

图1 Bi2MoO6, Ni-Fe LDH和他们的复合物M1、M2、M3的XRD图谱

Fig. 1 XRD patterns of Bi2MoO6, Ni-Fe LDH and their composites M1, M2 and M3 at Ni-Fe LDH contents of 2%, 4.5% and 15%, respectively

图2 Bi2MoO6、Ni-Fe LDH和他们的复合物M1、M1、M3的FT-IR图谱

Fig. 2 FT-IR spectra of Bi2MoO6 and Ni-Fe LDH and their composites M1, M2 and M3 at Ni-Fe LDH contents of 2%, 4.5% and 15%, respectively

图3 Bi2MoO6(a,b)和Bi2MoO6/Ni-Fe LDH(c,d)复合材料在低倍(a,c)和高倍(b,d)下的SEM照片

Fig. 3 SEM images of Bi2MoO6 (a,b) and Bi2MoO6/Ni-Fe LDH(c,d)) at low (a,c) and high (b,d) magnifications

图4 Bi2MoO6 (a,b)和Bi2MoO6/Ni-Fe LDH复合材料(c,d)在低倍(a,c)和高倍(b,d)下的TEM照片

Fig. 4 TEM images of Bi2MoO6 (a,b) and Bi2MoO6/Ni-Fe LDH(c,d) at low (a,c) and high (b,d) magnifications

图5 Bi2MoO6,Ni-Fe LDH和他们的复合物M1~M3的N2吸附-脱附等温线(a)及孔径分布(b)

Fig. 5 N2 adsorption-desorption isotherms (a) and pore size distributions (b) of Bi2MoO6 and Ni-Fe LDH and their composites M1-M3 samples with different Ni-Fe LDH contents (2%; 4.5%; 15%)

表1 Bi2MoO6、Ni-Fe LDH和复合材料M1~M3的比表面积、孔体积和孔径

Table1 BET surface area, pore volume and pore size of Bi2MoO6, Ni-Fe LDH and their composites M1-M3

Catalyst	Bi₂MoO₆	Ni-Fe LDH	M1	M2	M3
BET surface area /(m²·g^-1)	20.07	80.25	26.64	43.81	58.41
V_pore/(m²·g^-1)	0.153	0.376	0.146	0.210	0.248
d_pore/nm	30.14	16.14	20.26	17.47	15.18

图6 Bi2MoO6和Bi2MoO6/Ni-Fe LDH的XPS图谱

Fig. 6 XPS spectra of Bi2MoO6 and Bi2MoO6/Ni-Fe LDH

图7 不同催化剂光催化MO(a)、MB(b)、Bu-RhB(c)和苯酚(d)降解曲线

Fig. 7 Photocatalytic degradation of MO (a), MB (b), Bu-RhB (c), and phenol (d) by various photocatalysts

图8 可见光下M2重复使用1~5次的光催化降解曲线

Fig. 8 Degradation curves of M2 with Ni-Fe LDH 4.5% for reusing 1 to 5 times

图9 Bi2MoO6/Ni-Fe LDH复合材料光催化降解MO溶液动力学曲线

Fig. 9 Kinetic curves of Bi2MoO6/Ni-Fe LDH composites for photocatalytic degradation of MO

表2 Bi2MoO6/Ni-Fe LDH复合材料光催化降解甲基橙溶液动力学参数

Table 2 Kinetic parameter of Bi2MoO6/Ni-Fe LDH composites for photocatalytic degradation of MO

C₀/(mg·L^-1)	First-order reaction kinetics equation	R
10	ln(c₀/c)=0.03765t-0.0223	0.9965
12	ln(c₀/c)= 0.02122t-0.04275	0.9971
14	ln(c₀/c)= 0.0166t-0.03749	0.9958
16	ln(c₀/c)= 0.01578t-0.01939	0.9962

图10 外加不同清除剂(20 mmol/L的 t-BuOH、0.2 mmol/L的草酸钠、10 mmol/L的K2Cr2O7和0.1 mmol/L 的BQ)时, Bi2MoO6/Ni-Fe LDH复合材料光催化降解MO曲线

Fig. 10 Photocatalytic degradation efficiency for MO by the catalyst Bi2MoO6/Ni-Fe LDH composite after addition of different scavengers (20 mmol/L t-BuOH, 0.2 mmol/L sodium oxalate, 10 mmol/L K2Cr2O7 and 0.1 mmol/L BQ)

图11 可见光下Bi2MoO6/Ni-Fe LDH复合材料降解MO的示意图

Fig. 11 Schematic illustrati on showing MO degradation over Bi2MoO6/Ni-Fe LDH composite under visible light irradiation

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Bi₂MoO₆/Ni-Fe LDH复合材料的制备及可见光催化性能

Preparation and Visible Light Responsive Photocatalytic Activity of Bi₂MoO₆/Ni-Fe LDH Composites

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