交错能带结构钕掺杂钒酸铋形貌与光催化性能调控

doi:10.15541/jim20190409

无机材料学报 ›› 2020, Vol. 35 ›› Issue (7): 789-795.DOI: 10.15541/jim20190409 CSTR: 32189.14.10.15541/jim20190409

所属专题：环境材料论文精选(2020)

交错能带结构钕掺杂钒酸铋形貌与光催化性能调控

徐晶威¹,李政²,王泽普¹,于涵¹,何祺¹,付念³,丁帮福¹(),郑树凯¹,闫小兵¹

1. 河北大学电子信息工程学院
2. 河北大学建筑工程学院
3. 河北大学物理科学与技术学院, 保定 071002

收稿日期:2019-08-12 修回日期:2019-12-03 出版日期:2020-07-20 网络出版日期:2019-12-29
作者简介:徐晶威(1995-), 男, 硕士研究生. E-mail: 770283584@qq.com
XU Jingwei (1995-), male, Master candidate. E-mail: 770283584@qq.com
基金资助:
河北大学高层次人才基金(521000981118);河北省高等学校科学技术研究项目(ZD2017008);国家自然科学基金(61674050)

Morphology and Photocatalytic Performance Regulation of Nd³⁺-doped BiVO₄ with Staggered Band Structure

XU Jingwei¹,LI Zheng²,WANG Zepu¹,YU Han¹,HE Qi¹,FU Nian³,DING Bangfu¹(),ZHENG Shukai¹,YAN Xiaobing¹

1. College of Electronic Information Engineering, Hebei University, Baoding 071002, China
2. College of Civil Engineering and Architecture, Hebei University, Baoding 071002, China
3. College of Physics Science and Technology, Hebei University, Baoding 071002, China

Received:2019-08-12 Revised:2019-12-03 Published:2020-07-20 Online:2019-12-29
Supported by:
Talents of High Level Scientific Research Foundation(521000981118);Science and Technology Research Project of Hebei Colleges and Universities(ZD2017008);National Natural Science Foundation of China(61674050)

摘要/Abstract

摘要：

为了研究混合相异质结对光催化的改性机理, 以五水硝酸铋、六水硝酸钕、偏钒酸钠为原料, 浓硝酸、氢氧化钠为调和剂, 水热合成不同浓度钕掺杂钒酸铋样品。X射线衍射和拉曼峰位分析发现, 钒酸铋呈现钕浓度依赖的单斜到四方相转变。采用扫描电子显微镜表征发现, 这种相变给样品形貌带来巨大变化。小于1at%钕掺杂单斜钒酸铋由不规则颗粒堆积而成, 大于7at%钕掺杂四方相由类似球状或凹槽表面果仁状构成, 而中间混合相由微米长方体棒状组成。规则形貌导致所有掺杂样品光催化降解罗丹明B效率高于无掺杂样品。高分辨透射电子显微镜和莫特-肖特基测试发现, 混合相中形成交错能带异质结, 进一步促进光生电-子空穴对分离并抑制其复合, 使得4at%钕掺杂样品具有99.4%降解效率。

关键词: 钒酸铋, 交错能带, 形貌, 光催化降解

Abstract:

To investigate the modification mechanism of mixed heterogeneous on photocatalysis, a series of Nd³⁺-doped BiVO₄ photo-catalysts with different Nd³⁺ contents were synthesized through a facile hydrothermal reaction. The samples exhibit Nd³⁺ content-dependent phase transition from monoclinic to tetragonal phase, as demonstrated by XRD and Raman analyses. SEM images show that the phase transition is accompanied by obvious morphology variation. Less than 1at% Nd³⁺-doped monocline BiVO₄ is composed of irregular particles, while more than 7at% Nd³⁺ doping results in tetragonal phase BiVO₄ of sphere-like or kernel with groove surface. When Nd³⁺content is in the range of 1at%-7at%, the micron cuboid bars appear in the samples. More importantly, monoclinic and tetragonal phase is concomitant in the product and a heterogeneous junction with staggered band structure is formed. The Rhodamine B degradation efficiencies of all Nd³⁺-doped samples are higher than those of undoped samples due to the regular morphology after doping. The formed heterogeneous junction inhibits photo-generated electrons and holes recombination of Nd³⁺-doped BiVO₄, inducing 99.4% catalytic efficiency in 4at% Nd³⁺-doped sample. The novel morphology and the intrinsic mechanism of photocatalysis enhancement upon Nd³⁺-doped BiVO₄ are obtained from the synthesis strategy and the energy band structure.

Key words: BiVO₄, staggered energy band, morphology, photocatalytic degradation

中图分类号:

O643

徐晶威,李政,王泽普,于涵,何祺,付念,丁帮福,郑树凯,闫小兵. 交错能带结构钕掺杂钒酸铋形貌与光催化性能调控[J]. 无机材料学报, 2020, 35(7): 789-795.

XU Jingwei,LI Zheng,WANG Zepu,YU Han,HE Qi,FU Nian,DING Bangfu,ZHENG Shukai,YAN Xiaobing. Morphology and Photocatalytic Performance Regulation of Nd³⁺-doped BiVO₄ with Staggered Band Structure[J]. Journal of Inorganic Materials, 2020, 35(7): 789-795.

图/表 10

表1 制备不同浓度钕掺杂样品所需三种原料质量

Table 1 Usage of three raw materials for the synthesis of Nd3+-doped samples with different contents of Nd3+

Raw material	Nd(NO₃)₃?6H₂O/g	Bi(NO₃)₃?5H₂O/g	NaVO₃/g
Pure	0	4.8507	1.2193
1at%	0.0438	4.8022	1.2193
2at%	0.0867	4.7537	1.2193
4at%	0.1753	4.6567	1.2193
7at%	0.3068	4.5111	1.2193
9at%	0.3945	4.4141	1.2193
15at%	0.6575	4.1230	1.2193
30at%	1.3150	3.3954	1.2193
50at%	2.1917	2.4253	1.2193
70at%	3.0684	1.4552	1.2193
100at%	4.3835	0	1.2193

图1 不同浓度钕掺杂样品的XRD图谱(a, b); 以及优化后单斜(c)和四方相(d)的超晶胞结构

Fig. 1 XRD patterns of Nd3+-doped BiVO4 with different contents of Nd3+and monoclinic and tetragonal standard patterns (a, b), supercell configurations of optimized monoclinic (c) and tetragonal (d)

表2 纯相和4at%钕掺杂样品的XPS分析结果

Table 2 XPS results of pure and 4at% Nd3+-doped samples

Element	Pure		Nd³⁺-doped
Element	Peak	Percentage	Peak	Percentage
Nd3d	-	0	993.64	0.48
Bi4f	158.74	11.63	158.99	13.68
O1s	529.53	50.77	529.72	57.37
V2p	516.43	9.33	516.55	10.3

图2 纯相(a)、4at%(b)、9at%(c)钕掺杂钒酸铋拉曼光谱

Fig. 2 Raman spectra of pure phase (a), 4at% (b), and 9at% (c) Nd3+-doped BiVO4

图3 4at%钕掺杂样品不同放大倍率的TEM照片(a, b), 插图为I和II区域傅里叶变换衍射斑点

Fig. 3 TEM images of 4at% Nd3+-doped BiVO4 with different magnifications (a,b), where the inset in (b) represented the Fourier transform diffraction spots of I and II regions

图4 纯相(a)、4at% (b)、9at% (c)、50at% (d)和100at% (e)钕掺杂钒酸铋的SEM照片

Fig. 4 SEM images of pure (a), 4at% (b), 9at% (c), 50at% (d), and 100at% (e) Nd3+-doped BiVO4

图5 自制光催化降解实验装置(a)和样品光催化降解罗丹明B的效率曲线(b)

Fig. 5 Schematic of self-made photocatalytic degradation experimental device (a) and photocatalytic degradation curves of Rhodamine B over the prepared samples (b)

图6 三个样品的漫反射光谱图(a)以及用KM公式拟合得到的带隙(b)

Fig. 6 Diffuse reflectance spectra of three samples (a) and band gap obtained by fitting KM formula (b)

图7 莫特肖特基曲线导出的平带电压(a)以及异质结能带结构图(b)

Fig. 7 Flat band voltage derived from Motto-Schotty curve (a) and energy band structure of heterojunction (b)

图8 三个典型样品的粒径分布(a)、光致发光(b)、阻抗谱(c)和光电流(d)

Fig. 8 Pore distribution (a), photoluminescence (b), impedance spectra (c), and photocurrent (d) of three typical samples

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交错能带结构钕掺杂钒酸铋形貌与光催化性能调控

Morphology and Photocatalytic Performance Regulation of Nd³⁺-doped BiVO₄ with Staggered Band Structure

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交错能带结构钕掺杂钒酸铋形貌与光催化性能调控

Morphology and Photocatalytic Performance Regulation of Nd3+-doped BiVO4 with Staggered Band Structure

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Morphology and Photocatalytic Performance Regulation of Nd³⁺-doped BiVO₄ with Staggered Band Structure