量子点自修饰TiO2p-n同质结的构建及光催化性能

doi:10.7503/cjcu20200107

摘要/Abstract

摘要：

在n型TiO₂纳米片表面原位沉积p型TiO₂量子点构建了量子点自修饰的TiO₂ p-n同质结(PNT-x), 并利用透射电子显微镜(TEM)、 X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)、 X射线光电子能谱(XPS)、稳态荧光光谱(PL)、拉曼光谱(Raman)、紫外-可见漫反射光谱(UV-Vis DRS)、电化学测试及电化学交流阻抗谱(EIS)对复合物的组成、结构和光催化性能进行了表征和研究. 结果表明, PNT-x具有TiO₂量子点自修饰的结构, 量子点和纳米片中分别含有金属缺陷和氧缺陷, 其含量随组成变化可控, 并使得PNT-x表现出p-n同质结的典型特征, 与n-n Ⅱ型同质结以及块状p-n同质结相比, PNT-x中费米能级相差更大, 界面内电场更强, 具有更高的电荷分离和传递效率. 光照下, 样品的光催化活性顺序为PNT-400>p-25>PNT-600>PNT-200>p-TiO₂>n-TiO₂, 其中PNT-400的光催化产氢速率高达41.7 mmol·g^-1·h^-1, 分别为n-TiO₂纳米片、 Ⅱ型同质结和块状p-n同质结的4.3倍、 3.6倍和2.3倍, 并表现出优异的催化稳定性.

关键词: 二氧化钛, p-n同质结, 缺陷调控, 电荷分离, 光催化产氢

Abstract:

Quantum dots(QDs) self-decorated TiO₂ p-n homojunction(PNT-x) samples were fabricated by in-situ depositing p-type TiO₂ QDs on the surface of n-type TiO₂ nanosheets. The composition and structure of the samples were characterized by transmission electron microscopy(TEM), X-ray diffraction(XRD), Fourier transform infrared spectroscopy(FTIR), X-ray photoelectron spectroscopy(XPS), photoluminescence spectrometry(PL), Raman spectrometry, UV visible diffuse reflectance spectrometry(UV-Vis DRS), photoelectrochemical test and electrochemical impedance spectroscopy(EIS) analyses. The results indicate that PNT-x exhibits TiO₂ QDs self-decorated structure. Meanwhile, there exist metal and oxygen vacancies in QDs and nanosheets, respectively, and the content of vacancies can be modulated by the composition. Therefore, the as-prepared PNT-x show typical characteristics of p-n homojunction, and the difference of Fermi level and internal electrical field is stronger than that in n-n type Ⅱ homojunction and bulk p-n homojunction, thus leading to a significantly high charge separation and transfer efficiency. Under illumination, the order of photocatalytic activity is PNT-400>p-25>PNT-600>PNT-200>p-TiO₂>n-TiO₂, and PNT-400 display the photocatalytic hydrogen evolution rate as high as 41.7 mmol·g^-1·h^-1, which is 4.3, 3.6 and 2.3 times that of n-TiO₂ nanosheets, type Ⅱ homojunction and bulk p-n homojunction, respectively, as well as a good catalytic stability.

Key words: TiO₂, p-n Homojunction, Defect modulation, Charge separation, Photocatalytic H₂ evolution

中图分类号:

O643.3

王非凡, 王松博, 姚柯奕, 张蕾, 杜威, 程鹏高, 张建平, 唐娜. 量子点自修饰TiO₂p-n同质结的构建及光催化性能[J]. 高等学校化学学报, 2020, 41(7): 1615-1624.

WANG Feifan, WANG Songbo, YAO Keyi, ZHANG Lei, DU Wei, CHENG Penggao, ZHANG Jianping, TANG Na. Construction and Photocatalytic Performance of Quantum Dots Self-decorated TiO₂ p-n Homojunction^†[J]. Chemical Journal of Chinese Universities, 2020, 41(7): 1615-1624.

图/表 11

Scheme 1 Fabrication procedures of n-TiO2 and TiO2 p-n homojunctions

Fig.1 XRD patterns(A) and FTIR spectra(B) of n-TiO2(a), GNT-200(b), GNT-400(c), GNT-600(d) and TiGly(e)

Fig.2 XRD patterns(A) and FTIR spectra(B) of n-TiO2(a), PNT-200(b), PNT-400(c), PNT-600(d) and p-TiO2(e)

Fig.3 TEM images of n-TiO2(A), PNT-200(B), PNT-400(D), PNT-600(E) and HRTEM image of PNT-400(C)

Fig.4 TG profile of n-TiO2(a), GNT-200(b), GNT-400(c), GNT-600(d) and TiGly(e)

Fig.5 UV-Vis DRS spectra(A) and XPS valence-band spectra(B) of n-TiO2(a), PNT-200(b), PNT-400(c), PNT-600(d) and p-TiO2(e) Inset in (A): the corresponding plots of transformed Kubelka-Munk function vs. the photoenergy.

Fig.6 Raman spectra(A) and enlarged spectra between 100—220 cm-1(B) of n-TiO2(a), PNT-200(b), PNT-400(c), PNT-600(d) and p-TiO2(e)

Fig.7 Ti2p XPS spectra of p-TiO2(A), n-TiO2(B), PNT-200(C), PNT-400(D), PNT-600(E) and O1s XPS spectra(F) of n-TiO2(a), PNT-200(b), PNT-400(c), PNT-600(d), and p-TiO2(e)

Fig.8 Photocatalytic and photoelectrochemical performance of the as-prepared samples (A) Photodegradation rates of phenol and MO. a. PNT-200, b. PNT-400, c. PNT-600, d. p-TiO2, e. n-TiO2, f. NNT-400, g. BPNT-400, h. P25; (B) time course of photocatalytic H2 evolution; (C) linear sweep voltammetry(LSV) curves; (D) recycling of H2 evolution using PNT-400.

Fig.9 Steady-state photo-luminance spectra(A) and Nyquist plots(B) of n-TiO2(a), PNT-200(b), PNT-400(c), PNT-600(d) and p-TiO2 (e) Inset in (B): enlarged EIS plots of PNT-400.

Scheme 2 Schematic illustration of QDs self-decorated TiO2 p-n homojunction and the facilitated charge transfer and separation across the interface

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量子点自修饰TiO₂p-n同质结的构建及光催化性能

Construction and Photocatalytic Performance of Quantum Dots Self-decorated TiO₂ p-n Homojunction^†

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