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材料研究学报  2016, Vol. 30 Issue (4): 285-291    DOI: 10.11901/1005.3093.2015.542
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钴掺杂羟基锆柱撑钛酸盐材料的制备与光催化性能
何丽雯1,2, 孙东亚1,2, 廉冀琼2, 林碧洲1()
1. 华侨大学材料科学与工程学院 厦门 361021
2. 厦门理工学院材料科学与工程学院 厦门 361024
Preparation and Photocatalytic Property of Co-Doped Hydroxyl-Zr Pillared Titanate
HE Liwen1,2, SUN Dongya1,2, LIAN Jiqiong2, LIN Bizhou1,**()
1. College of Materials Science & Engineering, Huaqiao University, Xiamen 361021, China
2. College of Materials Science & Engineering, Xiamen University of Technology, Xiamen 361024, China
引用本文:

何丽雯, 孙东亚, 廉冀琼, 林碧洲. 钴掺杂羟基锆柱撑钛酸盐材料的制备与光催化性能[J]. 材料研究学报, 2016, 30(4): 285-291.
Liwen HE, Dongya SUN, Jiqiong LIAN, Bizhou LIN. Preparation and Photocatalytic Property of Co-Doped Hydroxyl-Zr Pillared Titanate[J]. Chinese Journal of Materials Research, 2016, 30(4): 285-291.

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摘要: 

采用剥离-重堆积的方法将聚合羟基锆离子和Co2+混合溶液嵌入到钛酸盐板层间, 制得了钴掺杂锆柱撑材料(CZPT), 考察了Co对锆柱撑复合材料(简写为ZPT)的形成及其催化活性的影响。利用X-射线衍射(XRD)、扫描/透射电子显微镜(SEM/HR-TEM)、紫外-可见吸收光谱(UV-Vis)和N2吸附等方法对复合材料进行了表征。结果表明, 掺入质量分数为5%(1∶20)的Co可以使ZPT样品的介孔和比表面积明显增大。同时, 可以抑制体系光生电子与空穴的复合, 吸收光波长有明显的红移。CZPT系列柱撑材料在紫外和可见光辐照下催化降解罗丹明(RhB)的脱色率明显高于ZPT。其中, 复合材料CZPT-5的催化活性最好, 表明材料的光催化活性还与掺杂后柱撑材料中含Co客体与主体间的电子耦合作用有关。

关键词 复合材料钛酸盐纳米片层钴掺杂柱撑材料羟基锆离子光催化    
Abstract

Mesoporous nanocomposite of Co-doped hydroxyl-Zr -pillared titanate (CZPT) was prepared via an exfoliation-restacking route, and the pre-exfoliated layered titanate was reassembled in an aqueous solution containing hydroxyl-Zr oligocations and Co ions. The influence of the doping Co cations on the preparation and catalytic activity of Zr-pillared titanate (abbreviated as ZPT) composites was investigated. The prepared CZPT was characterized by powder X-ray diffraction, scanning electron microscope, transmission electron microscopy, UV-Vis spectra and porosity measurements. XRD and N2 absorption results suggested that the ZPT doped with 5% Co (mass fraction) had bigger pore diameter and specific area. The presence of 5% Co could effectively suppress the annihilation of the photogenerated hole-electron pairs, and correspondingly the absorption wavelength exhibits obviously red-shift. The degradation of rhodamine B (RhB) under ultraviolet and visible radiation shows that the as-prepared nanocomposite exhibits higher photocatalytic activities than that of layered titanate alone. The enhanced photocatalytic activity of the as-prepared nanocomposite CZPT-5 for the degradation of RhB under visible irradiation may be attributed to the coupling interaction between cations of the host and the Co containing guest.

Key wordscomposite    titanate nanosheets    Co-doped    pillared materials    hydroxyl-Zr oligocations    photocatalytic
收稿日期: 2015-09-24     
ZTFLH:  O611.5  
基金资助:国家自然科学基金50872037和福建省中青年教师教育科研项目JB14077资助项目
作者简介: 本文联系人: 林碧洲, 教授
图1  剥离-重堆积法制备钛酸盐复合材料流程图
图2  钛酸铯、氢化钛酸盐和柱撑材料的XRD谱
Sample Surface area/m2g-1 Pore volume
/mLg -1
Average
pore size
/nm
SBET
CsxTi2-x/4x/4O4 ~1
CZPT-20 121 0.35 3.71
CZPT-10 122 0.36 3.66
CZPT-5 145 0.40 3.61
ZPT-5 108 0.34 3.81
表1  样品的N2等温吸附-脱附曲线测量所得的数据
Sample Composition
Co Zr Ti O
CZPT-20 0.05 16.27 19.02 64.66
CZPT-10 0.12 15.04 17.92 66.93
CZPT-5 0.14 14.45 16.99 68.43
表2  柱撑材料的元素组成
图3  柱撑材料的N2等温吸脱附曲线
图4  柱撑材料CZPT-5的SEM (a)和HRTEM (b)像
图5  样品的UV-Vis漫散射吸收光谱(a)和相应的(F(R)hv)0.5-hv关系曲线(b)
图6  样品光催化降解罗丹明B的降解率
Sample 1st 2nd 3rd
ZPT-5 52.13 46.18 39.96
CZPT-20 79.91 61.25 49.68
CZPT-10 87.14 58.59 41.01
CZPT-5 91.71 55.32 39.23
表3  柱撑材料的重复催化实验
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