WO3纳米花的热处理晶格调控及WO3/CdS/α-S异质结的构筑

doi:10.15541/jim20200023

无机材料学报 ›› 2020, Vol. 35 ›› Issue (12): 1349-1356.DOI: 10.15541/jim20200023 CSTR: 32189.14.10.15541/jim20200023

所属专题：能源材料论文精选(四)：光催化与电催化(2020)

WO₃纳米花的热处理晶格调控及WO₃/CdS/α-S异质结的构筑

林海¹(),苏玮韬¹,朱玉¹,彭湃¹,冯苗^1,²(),于岩^1,²()

福州大学 1. 材料科学与工程学院
2. 生态环境材料先进技术福建省高等学校重点实验室, 福州 350108

收稿日期:2020-01-13 修回日期:2020-03-18 出版日期:2020-12-20 网络出版日期:2020-03-20
作者简介:林海(1994–), 男, 硕士研究生. E-mail: linhaifj@outlook.com
基金资助:
福建省自然科学基金(2019J01225);福建省高校杰出青年科研人才培育计划项目(CL2016-20)

Lattice Control of WO₃ Nanoflowers by Heat Treatment and Construction of WO₃/CdS/α-S Heterojuntion

LIN hai¹(),SU Weitao¹,ZHU Yu¹,PENG Pai¹,FENG Miao^1,²(),YU Yan^1,²()

1. College of Materials Science and Engineering, Fuzhou University, Fuzhou 350108, China
2. Key Laboratory of Eco-Materials Advanced Technology, Fuzhou University, Fuzhou 350108, China

Received:2020-01-13 Revised:2020-03-18 Published:2020-12-20 Online:2020-03-20
About author:LIN Hai(1994–), male, Master candidate. E-mail: linhaifj@outlook.com
Supported by:
Natural Science Foundation of Fujian Province(2019J01225);Distinguished Young Scholars of the Higher Education Institutions of Fujian Province, China(CL2016-20)

摘要/Abstract

摘要：

为研究热处理过程与异质结构筑对WO₃的光电化学效应的影响机制, 采用低温溶剂热法制备纳米花状WO₃, 通过热处理精确调控WO₃纳米花的活性晶面、晶粒尺寸及结晶度。进一步借助循环化学浴法, 构筑WO₃/CdS/α-S异质结, 并研究其光电化学性能与浓度效应。结果表明, (200)晶面是WO₃纳米花的主要暴露晶面, 且比例随热处理温度升高而增大。350 ℃热处理的WO₃纳米花表现出最高的光响应电流。通过构筑WO₃/CdS/α-S梯形异质结, 增强材料在可见光区的吸收, 以牺牲少部分载流子的方式提高整体光生载流子的分离效率, 促进WO₃的宏观光电化学效应的提升。

关键词: 氧化钨, 纳米花, 梯形异质结, 光电响应

Abstract:

In order to study the influence mechanism of heat treatment and heterostructures on the photoelectrochemical effect of WO₃, monoclinic WO₃ nanoflowers were synthesized by low-temperature solvothermal method. The active crystal fact, grain size and crystallinity of WO₃ were controlled by heat treatment. Furthermore, WO₃/CdS/α-S heterojunction was obtained by modified chemical bath deposition, and the concentration effect of its photoelectrochemical performance was studied. The results show that the (200) crystal plane with photoelectrochemical activity is the main exposed crystal plane of WO₃, and the proportion of the exposed crystal plane increases with the heat treatment temperature increasing. The WO₃ nanoflower treated at 350 ℃ showed the highest photoresponse current. By constructing WO₃/CdS/α-S heterojunction, the material's absorption in the visible light region is enhanced, and the overall efficiency of photo-generated carrier separation is improved by sacrificing a small amount of carriers, which promotes the macroelectronic chemical effects of WO₃.

Key words: tungsten oxide, nanoflower, step-scheme heterostructure, photocurrent response

中图分类号:

O646

林海, 苏玮韬, 朱玉, 彭湃, 冯苗, 于岩. WO₃纳米花的热处理晶格调控及WO₃/CdS/α-S异质结的构筑[J]. 无机材料学报, 2020, 35(12): 1349-1356.

LIN hai, SU Weitao, ZHU Yu, PENG Pai, FENG Miao, YU Yan. Lattice Control of WO₃ Nanoflowers by Heat Treatment and Construction of WO₃/CdS/α-S Heterojuntion[J]. Journal of Inorganic Materials, 2020, 35(12): 1349-1356.

图/表 15

图1 WO3纳米花前驱体(a)和W-350(b)的SEM照片; 不同温度热处理样品的XRD图谱(c); Rietveld精修的(002)、(020)、(200)晶面衍射峰位(d)、衍射峰积分面积占比(e)和晶粒尺寸(f)与热处理温度的关系曲线

Fig. 1 SEM images of WO3 nanoflower precursor (a) and W-350 (b); XRD patterns of the samples heat-treated at different temperatures (c); (002), (020), and (200) crystal plane diffraction peak positions (d), diffraction peak integrated area ratios (e) and grain sizes (f) obtained by Rietveld refinement varied as functions of heat treatment temperature

图S1 前驱体(a)、W-310(b)、W-330(c)、W-370(d)、W-390(e)、W-410(f)、W-430(g)、W-450(h)的SEM照片

Fig. S1 SEM images of precursor (a), W-310 (b), W-330 (c), W-370 (d), W-390 (e), W-410 (f), W-430 (g), and W-450 (h).

图S2 W-310 (a)、W-330 (b)、W-350 (c)、W-370 (d)、W-390 (e)、W-410 (f)、W-430 (g)、W-450 (h)的XRD数据Rietveld精修结果

Fig. S2 Rietveld refinement results of XRD data from W-310 (a), W-330 (b), W-350 (c), W-370 (d), W-390 (e), W-410 (f), W-430 (g), W-450 (h)

表1 不同温度热处理样品的XRD数据Rietveld精修结果

Table 1 Rietveld refinement results of XRD data of the samples heat-treated at different temperatures

Sample	(002) 2θ/(°)	(020) 2θ/(°)	(200) 2θ/(°)	(002) Peak area ratio/%	(020) Peak area ratio/%	(200) Peak area ratio/%	R/%^a	E/%^b
W-310	23.302	23.805	23.989	31.60736	31.93592	36.45672	7.96	7.22
W-330	23.191	23.744	24.063	28.51362	31.21225	40.27413	8.45	9.08
W-350	23.152	23.724	24.110	25.48277	33.41551	41.10171	8.71	8.87
W-370	23.136	23.698	24.171	24.13370	35.22923	40.63707	7.77	8.89
W-390	23.128	23.685	24.217	20.52815	33.02325	46.4486	8.74	8.72
W-410	23.113	23.643	24.203	31.60641	29.83773	38.55586	9.62	11.08
W-430	23.126	23.668	24.268	30.26410	31.89507	37.84083	8.92	8.88
W-450	23.066	23.604	24.202	28.08145	34.16319	37.75536	8.84	9.0

图2 不同温度热处理样品的Raman谱图(a)和UV-Vis-IR吸收光谱图(b)

Fig. 2 Raman spectra (a) and UV-Vis-IR absorption spectra (b) of the samples heat-treated at different temperatures

图S3 W-310 (a)、W-330 (b)、W-350 (c)、W-370 (d)、W-390 (e)、W-410 (f)、W-430 (g)、W-450 (h)的Tauc曲线及根据吸收边截线交点得出的样品带隙Eg

Fig. S3 Tauc plots of W-310 (a), W-330 (b), W-350 (c), W-370 (d), W-390 (e), W-410 (f), W-430 (g), W-450 (h) and the band gaps Eg obtained from the intersection of the absorption edge intercept line

图S4 WO3前驱体与代表性的热处理样品(a), 350 ℃以上热处理样品(b)的Raman谱图

Fig. S4 Raman spectra of WO3 precursor and representative heat-treated samples (a) and the WO3 sample heat-treated above 350 ℃ (b)

图S5 WO3前驱体与热处理样品的FT-IR光谱图

Fig. S5 FT-IR spectra of WO3 precursor and heat-treated samples

图3 不同温度热处理样品的光电流响应曲线(a)、光电流峰值(b)和IPCE谱图(c); W-350的Mott-Schottky曲线(d)

Fig. 3 Photocurrent response curves (a), photocurrent response peak values (b) and IPCE plots (c) of the samples heat-treated at different temperatures; Mott-Schottky curve of W-350 (d) Colourful version is available on offical website

图4 W-350-30C的SEM照片(a); W-350和W-350-30C的XRD图谱(b); W-350(c)和W-350-30C(d)的TEM照片

Fig. 4 SEM image of W-350-30C (a); XRD patterns of W-350 and W-350-30C(b); TEM images of W-350-30C (c) and W-350-30C (d)

图S6 W-350-10C (a)、W-350-20C (b)、W-350-30C (c)、W-350-40C (d)的EDX图谱

Fig. S6 EDX results of W-350-10C (a), W-350-20C (b), W-350-30C (c), and W-350-40C (d)

图5 W-350-30C的XPS全谱(a)、W4f (b)、O1s (c)、Cd3d(d)、S2p(e)的XPS高分辨谱; 不同CdS/α-S表面修饰浓度的γ-WO3纳米花的UV-Vis-IR吸收光谱图(f)和样品照片(g)

Fig. 5 XPS spectrum of sample W-350-30C (a); XPS high-resolution spectra of W4f (b), O1s (c), Cd3d (d) and S2p (e) for sample W- 350-30C; UV-Vis-IR absorption spectra (f) and photos (g) of γ-WO3 nanoflowers with different amounts of CdS/α-S modified on the surface Colourful version is available on offical website

图6 不同CdS/α-S异质结浓度的γ-WO3纳米花的光电流响应曲线(a)、光电流峰值(b)和IPCE测试结果(c); W-350和W-350-30C的EIS曲线(d)

Fig. 6 Photocurrent response curves(a), photocurrent response peak values(b), and IPCE plots(c) of γ-WO3 nanoflowers modified with different amounts of CdS/α-S on the surface; EIS plots of W-350 and W-350-30C(d) Colourful version is available on offical website

图7 CdS/α-S表面修饰γ-WO3纳米花的光生载流子转移机理图

Fig. 7 Schematic diagram of charge carriers transfer in γ-WO3 nanoflowers with CdS/α-S modified on the surface

图S7 亚甲基蓝溶液经W-350避光吸附与不同时间紫外光照射后的UV-Vis光谱图(a); 亚甲基蓝降解率随时间的变化曲线(b)

Fig. S7 UV-Vis spectra of methylene blue solution after absorbed by W-350 in the dark and UV irradiation for different time (a); Variation of methylene blue degradation rate with different time (b)

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WO₃纳米花的热处理晶格调控及WO₃/CdS/α-S异质结的构筑

Lattice Control of WO₃ Nanoflowers by Heat Treatment and Construction of WO₃/CdS/α-S Heterojuntion

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