席夫碱钴改性CoCr-LDHs材料光催化降解亚甲基蓝研究

doi:10.15541/jim20180558

摘要/Abstract

摘要：

采用共沉淀法合成席夫碱钴(SBCo)插层钴铬水滑石(CoCr-LDHs)材料。通过X射线粉末衍射(XRD)、紫外-可见漫反射光谱(UV-Vis DRS)、扫描电子显微镜(SEM)、透射电子显微镜(TEM-EDX)、X射线光电子能谱(XPS)、比表面积(BET)分析表征CoCr-LDHs以及CoCr/SBCo-LDHs材料的结构和性质。以H₂O₂作光催化助剂, 考察了不同插层量、催化剂用量以及亚甲基蓝溶液的初始浓度对光催化活性的影响, 并探究了光催化降解过程的动力学和主要的活性基团。实验结果表明: H₂O₂有助于提高水滑石材料的光催化性能, 以氙灯模拟太阳光, 20 mg CoCr/SBCo_0.5-LDHs和H₂O₂的协同作用对初始浓度为25 mg/L的亚甲基蓝降解率高达99%。亚甲基蓝的光降解过程符合准一级动力学模型, 且起主要作用的活性基团为h ⁺和·OH。

关键词: 席夫碱钴, 钴铬水滑石, 光催化, H₂O₂助剂, 亚甲基蓝, 动力学

Abstract:

A series new material of cobalt (Ⅱ) with Schiff-base intercalated cobalt-chromium layered double hydroxides (CoCr/SBCo-LDHs) were successfully prepared via coprecipitation. Their structure and property of the CoCr-LDHs and CoCr/SBCo-LDHs materials were thoroughly characterized by X-ray powder diffraction (XRD), UV-Vis DRS, scanning electron microscope (SEM), transmission electrons microscope (TEM) and energy dispersive X-ray spectroscope (EDX), X-ray photoelectron spectroscope, and specific surface area analyzer. Using H₂O₂ as photocatalytic additive, the effects of different intercalation amount, catalyst dosage and initial concentration of methylene blue (MB) solution on photocatalytic activity were investigated, and the kinetics and main active groups of photocatalytic degradation process were explored. Experimental results show that H₂O₂ can improve the photocatalytic performance of hydrotalcite materials. Under the condition of the Xenon lamp simulated sunlight and MB initial concentration of 25 mg/L, the photocatalytic degradation rate of MB by 20 mg CoCr/SBCo_0.5-LDHs and H₂O₂ was 99%. The photodegradation process of MB conforms to the quasi-first-order kinetic model, and the active groups playing major role are h ⁺ and ·OH.

Key words: Schiff base cobalt, CoCr-LDHs, photocatalysis, hydrogen peroxide additive, methylene blue, dynamics

中图分类号:

0643

张晓锋,张冠华,孟跃,薛继龙,夏盛杰,倪哲明. 席夫碱钴改性CoCr-LDHs材料光催化降解亚甲基蓝研究[J]. 无机材料学报, 2019, 34(9): 974-982.

ZHANG Xiao-Feng,ZHANG Guan-Hua,MENG Yue,XUE Ji-Long,XIA Sheng-Jie,NI Zhe-Ming. Photocatalytic Degradation of Methylene Blue by Schiff-base Cobalt Modified CoCr Layered Double Hydroxides[J]. Journal of Inorganic Materials, 2019, 34(9): 974-982.

图/表 14

图1 席夫碱钴配合物合成路线图

Fig. 1 Diagram of preparative route of SBCo

图2 样品的XRD(A)、UV-Vis漫反射光谱图(B)以及(ahv)2 vs hv图谱(C)

Fig. 2 XRD patterns (A) and UV-Vis diffuse reflectance spectra (B) and plots of (ahv)2 vs hv (C) for the samples

图3 席夫碱Co(a)及CoCr/SBCo-LDHs(b)材料的结构示意图

Fig. 3 Molecular structure of Salen-Co(II) (a) and CoCr/SBCo-LDHs (b)

图4 CoCr-LDHs和CoCr/SBCo0.5-LDHs的SEM、TEM照片及EDX谱图

Fig. 4 SEM and TEM images of CoCr-LDHs and CoCr/ SBCo0.5-LDHs, and EDX analysis of CoCr/SBCo0.5-LDHs SEM images of CoCr-LDHs(A) and CoCr/SBCo0.5-LDHs (B); TEM images of CoCr/SBCo0.5-LDHs (C) and EDX analysis of designated area (D)

图5 CoCr-LDHs(A, B)和CoCr/SBCo-LDHs(C~E)材料的XPS分析结果

Fig. 5 XPS analysis for CoCr-LDHs (A, B) and CoCr/SBCo0.5-LDHs (C-E)

图6 CoCr-LDHs (A)和CoCr/SBCo-LDHs (B)的低温氮气吸附脱附等温线和孔径分布(插图)

Fig. 6 N2 adsorption-desorption isotherms and pore size distribution curves (insets) for CoCr-LDHs (A) and CoCr/SBCo-LDHs (B)

表1 CoCr-LDHs和CoCr/SBCo0.5-LDHs的结构性能参数

Table 1 Textural properties for CoCr-LDHs and CoCr/SBCo0.5-LDHs

Sample	Surface area/(m²?g^-1)	Pore volume/(cm³?g^-1)	Average pore size/nm	Peak of pore size distribution/nm
CoCr-LDHs	96.4	0.537	22.5	20, 65
CoCr/SBCo_0.5-LDHs	107.8	0.526	19.2	18, 30, 60

表2 催化剂和H2O2分别对MB的降解率

Table 2 Degradation rate of methylene blue by catalyst and H2O2

Catalyst	CoCr-LDHs	CoCr/SBCo_0.25-LDHs	CoCr/SBCo_0.5-LDHs	CoCr/SBCo_0.75-LDHs	H₂O₂
Degradation/%	7	9	10	10	13

图7 席夫碱钴插层量对光催化MB的影响

Fig. 7 Influence of intercalated schiff-base cobalt dosage intercalation on photocatalytic MB a: No catalyst and H2O2; b: CoCr-LDHs; c: CoCr/SBCo0.25-LDHs; d: CoCr/SBCo0.5-LDHs; e: CoCr/SBCo0.75-LDHs

图8 催化剂用量对光催化MB的影响

Fig. 8 Influence of catalyst amounts on photocatalytic MB

图9 MB的浓度对光催化性能的影响

Fig. 9 Effect of MB concentration on photocatalytic performance

图10 不同材料光降解MB的准一级动力学

Fig. 10 Pseudo-first-order kinetics of photodegradation of MB by different materials

表3 不同材料光降解MB的准一级动力学参数

Table 3 Pseudo-first-order kinetic parameters for MB photodegradation by different materials

LDHs	K/h^-1	R²	t_1/2/h
CoCr-LDHs	0.0095	0.9536	72.9628
CoCr/SBCo_0.25-LDHs	0.0564	0.9689	12.2898
CoCr/SBCo_0.5-LDHs	0.8869	0.9984	0.7815
CoCr/SBCo_0.75-LDHs	0.1241	0.9961	5.5854

图11 活性基团淬灭实验

Fig. 11 Quenching experimental of reactive group

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