Keggin型多酸XW12O40n-(X=P5+, Si4+, B3+, Zn2+)对甲基橙的光催化降解活性

doi:10.7503/cjcu20170592

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (5): 1003.doi: 10.7503/cjcu20170592

Keggin型多酸XW12 $O 40 n -$ (X=P5+, Si4+, B3+, Zn2+)对甲基橙的光催化降解活性

王斌^1,⁴, 乌英嘎¹, 刘哲林², 王晓红¹, 安智华^1,³, 曾俊¹, 杨鹏¹, 刘宗瑞¹

1. 内蒙古民族大学化学化工学院, 通辽028043
2. 长春理工大学化学与环境工程学院, 长春 130022
3. 纽约大学化学系, 纽约 NY 10003
4. 内蒙古自治区纳米碳材料重点实验室, 通辽 028000

收稿日期:2017-08-31 出版日期:2018-04-23 发布日期:2018-04-23
作者简介:
联系人简介: 刘宗瑞, 男, 教授, 主要从事多酸功能材料研究. E-mail: liuzr716@163.com; 王斌, 男, 博士, 讲师, 主要从事多酸基光电功能材料研究. E-mail: jluwangbin09@163.com
基金资助:
国家自然科学基金(批准号: 21401012, 21661026)、内蒙古自治区自然科学基金(批准号: 2015BS0207)和内蒙古自治区纳米碳材料重点实验室开放课题(批准号: MDK2017025)资助.

Photocatalytic Activity of Keggin Type Polyoxometalates XW₁₂ $O 40 n -$ (X=P⁵⁺, Si⁴⁺, B³⁺, Zn²⁺) Toward Degradation of Methyl Orange^†

WANG Bin^1,^4,^*, WU Yingga¹, LIU Zhelin², WANG Xiaohong¹, AN Zhihua^1,³, ZENG Jun¹, YANG Peng¹, LIU Zongrui^1,^*

1. College of Chemistry and Chemical Engineering, Inner Mongolia University for the Nationalities, Tongliao 028043, China
2. School of Chemistry & Environment Engineering, Changchun University of Science and Technology, Changchun 130022, China;
3. Departmennt of Chemistry, New York University, New York NY 10003, USA
4. Inner Mongolia Key Lab of Carbon Nanomaterials, Tongliao 028000, China

Received:2017-08-31 Online:2018-04-23 Published:2018-04-23
Contact: WANG Bin,LIU Zongrui
Supported by:
Supported by the National Natural Science Foundation of China(Nos.21401012, 21661026), the Natural Science Foundation of Inner Mongolia Autonomous Region, China(No.2015BS0207) and the Open Project of the Inner Mongolia Key Lab of Carbon Nanomaterials, China(No.MDK2017025).

摘要/Abstract

摘要：

通过常规水溶液合成法制备了一系列含不同中心杂原子的Keggin型多金属氧酸盐XW₁₂ $O 40 n -$ (简写为XW₁₂, X=P⁵⁺, Si⁴⁺, B³⁺, Zn²⁺), 并利用粉末X射线衍射(PXRD)、红外光谱(FTIR)和拉曼光谱(Raman)对其结构进行表征, 利用紫外-可见光谱(UV-Vis)和循环伏安曲线(CVs)对其光、电活性进行了研究. 以甲基橙为光催化降解底物, 考察了中心杂原子、催化剂用量、底物分子浓度和体系的pH值等对多金属氧酸盐光催化降解甲基橙活性的影响. 结果表明, 含不同中心杂原子的Keggin型多金属氧酸盐对甲基橙的光催化降解活性顺序为ZnW₁₂>PW₁₂>SiW₁₂>BW₁₂.

关键词: 多金属氧酸盐, 光催化活性, 降解, 有机染料

Abstract:

A series of Keggin type polyoxometalates with different central heteroatoms was prepared by the conventional aqueous synthesis method and characterized by powder X-Ray diffraction(PXRD), infrared spectroscopy(FTIR) and Raman spectroscopy(Raman). The optical and electrical activities of the polyoxometalates were studied by UV-Vis spectroscopy and cyclic voltammetry(CV). The influenece of central heteroatoms, catalyst dosage, substrate concentration and pH values on photocatalytic activity of the polyoxometalates toward methyl orange were investigated. The photodegradation activity of different Keggin type polyoxometalates toward methyl orange is in the order of ZnW₁₂>PW₁₂>SiW₁₂>BW₁₂.

Key words: Polyoxometalate, Photocatalytic activity, Dagradation, Organic dye

中图分类号:

O644
O611.3

TrendMD:

王斌, 乌英嘎, 刘哲林, 王晓红, 安智华, 曾俊, 杨鹏, 刘宗瑞. Keggin型多酸XW12 $O 40 n -$ (X=P5+, Si4+, B3+, Zn2+)对甲基橙的光催化降解活性. 高等学校化学学报, 2018, 39(5): 1003.

WANG Bin,WU Yingga,LIU Zhelin,WANG Xiaohong,AN Zhihua,ZENG Jun,YANG Peng,LIU Zongrui. Photocatalytic Activity of Keggin Type Polyoxometalates XW₁₂ $O 40 n -$ (X=P⁵⁺, Si⁴⁺, B³⁺, Zn²⁺) Toward Degradation of Methyl Orange^†. Chem. J. Chinese Universities, 2018, 39(5): 1003.

图/表 11

Fig.1 Ball-stick(A) and polyhedral(B) structures of Keggin type heteropolyanions XW12O40n-(X=P5+, Si4+, B3+, Zn2+)

Fig.2 Powder XRD patterns of different Keggin type polyoxometalates Note:a. ZnW12; b. BW12; c. SiW12; d. PW12.

Table 1 Infrared vibrational peaks of XW12O40n- (X=P5+, Si4+, B3+, Zn2+)(cm-1)

Compound	$υ X — O a$	$υ W — O d$	$υ W — O c — W$	$υ W — O b — W$
PW₁₂	1082	980	889	792
SiW₁₂	1019	979	925, 879	783
BW₁₂	1004	958	911	807
ZnW₁₂	432	935	877, 833	783, 703

Table 1 Infrared vibrational peaks of XW12O40n- (X=P5+, Si4+, B3+, Zn2+)(cm-1)

Compound	$υ X — O a$	$υ W — O d$	$υ W — O c — W$	$υ W — O b — W$
PW₁₂	1082	980	889	792
SiW₁₂	1019	979	925, 879	783
BW₁₂	1004	958	911	807
ZnW₁₂	432	935	877, 833	783, 703

Fig.3 Raman spectra of different Keggin type polyoxometalates Note:a. ZnW12; b. BW12; c. SiW12; d. PW12.

Fig.4 UV-Vis absorption spectra of different Keggin type polyoxometalates Note: a. ZnW12; b. BW12; c. SiW12; d. PW12.

Fig.5 Cyclic voltammetry of Keggin type polyoxometalates Note:a. PW12; b. SiW12; c. BW12; d. ZnW12.

Fig.6 Degradation rate of methyl orange(A) and degradation ratio vs. irradiation time(B) using XW12O40n-(X=Zn2+, B3+, Si4+, P5+) as photocatalysts

Fig.7 Degradation rate of methyl orange with different ZnW12 catalyst concentrations

Fig.8 Degradation rate of methyl orange with different concentrations using ZnW12 as photocatalyst

Fig.9 Degradation rate of methyl orange in 0.5 mol/L H2SO4/Na2SO4 buffer solution with different pH value

Fig.10 Repeatability of photocatalytic degradation of methyl orange by ZnW12 Note:a. No. 1; b. No. 2; c. No. 3.

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Keggin型多酸XW12 $O 40 n -$ (X=P5+, Si4+, B3+, Zn2+)对甲基橙的光催化降解活性

Photocatalytic Activity of Keggin Type Polyoxometalates XW₁₂ $O 40 n -$ (X=P⁵⁺, Si⁴⁺, B³⁺, Zn²⁺) Toward Degradation of Methyl Orange^†

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