高性能CeO2/片状CdS复合光电极材料的制备及在光阴极保护中应用

doi:10.15541/jim20190057

无机材料学报 ›› 2019, Vol. 34 ›› Issue (12): 1334-1340.DOI: 10.15541/jim20190057

高性能CeO₂/片状CdS复合光电极材料的制备及在光阴极保护中应用

魏科年^1,²,刘展²,左士祥²,严向玉²,吴凤芹²,李霞章²,姚超^1,²(),刘孝恒¹()

^1. 南京理工大学软化学与功能材料教育部重点实验室, 南京 210094
^2. 常州大学石油化工学院, 江苏省先进催化与绿色制造协同创新中心, 常州 213164

收稿日期:2019-01-28 修回日期:2019-03-07 出版日期:2019-12-20 网络出版日期:2019-05-13
作者简介:WEI Ke-Nian (1978-), male, candidate of PhD. E-mail: kn@cczu.edu.cn

Preparation of CeO₂/Flake-like CdS Composites as High-Performance Photoanodes for Photoelectrochemical Cathodic Protection

WEI Ke-Nian^1,²,LIU Zhan²,ZUO Shi-Xiang²,YAN Xiang-Yu²,WU Feng-Qin²,LI Xia-Zhang²,YAO Chao^1,²(),LIU Xiao-Heng¹()

^1. Key Laboratory for Soft Chemistry and Functional Materials, Ministry of Education, Nanjing University of Science and Technology, Nanjing 210094, China
^2. Advanced Catalysis and Green Manufacturing Collaborative Innovation Center, School of Petrochemical Engineering, Changzhou University, Changzhou 213164, China

Received:2019-01-28 Revised:2019-03-07 Published:2019-12-20 Online:2019-05-13
Supported by:
Foundation item: Fundamental Research Funds for the Central Universities(30916014103);Key R&D Programs of Jiangsu Province(BE2018649);Innovation Team of Six Talent Peaks of Jiangsu Province(XCL-CXTD-029);Key R&D Programs of Changzhou City(CE20185007)

摘要/Abstract

摘要：

通过逐步合成法制备了具有储存电子和物理阻隔功能的CeO₂/CdS纳米复合材料, 并用于光电阴极保护。通过XRD, TEM, UV-Vis和PL等手段对制备的纳米复合材料进行表征。在模拟白光照射下研究不同质量比的CeO₂/CdS复合材料的光电化学性质。在黑暗条件下, 涂有CeO₂/CdS(质量比0.2 : 1)的304不锈钢涂层的电位比 CeO₂/CdS(质量比0.2 : 1)粒子涂层更正。在白光照射下, CeO₂/CdS(质量比0.2 : 1)复合材料的最大光电流密度为 700 μA·cm ^-2, 涂有CeO₂/CdS(质量比0.2 : 1)的304不锈钢涂层的电位为-650 mV(vs. SCE), 明显低于304不锈钢腐蚀电位(-200 mV vs. SCE), 表明片状CdS具有物理阻隔性能及CeO₂/CdS复合材料具有显著的光电化学性能。这主要是由于CeO₂纳米颗粒和CdS纳米片之间形成了异质结, 促进了光致电子和空穴的有效分离, 从而提高了光电转换效率。此外, 由于CeO₂具有储存电子的功能, 在黑暗条件下可以继续释放电子, 能够提供12 h的阴极保护性能。

关键词: CeO₂/CdS复合材料, 异质结构, 物理阻隔, 光电化学阴极保护

Abstract:

CeO₂/CdS nanocomposites with the function of storing electrons and physical barrier were fabricated for photocathodic protection through a stepwise synthetic route. The obtained smples were characterized by XRD, TEM, UV-Vis and PL. The photoelectrochemical properties of CeO₂/CdS with different mass ratios were investigated under white light irradiation. The maximum photocurrent density of CeO₂/CdS (mass ratio 0.2 : 1) is 700 μA·cm ^-2 and the potential of the 304 stainless steel coated with CeO₂/CdS (mass ratio 0.2 : 1) shifts to -650 mV (vs. SCE), which is significantly lower than the corrosion potential (-200 mV vs. SCE). The above results indicate that the CeO₂/CdS composites exhibit remarkable photo cathodic properties which are attributed to the heterostructure of CeO₂ nanoparticles and CdS nanosheets, and the structure facilitates the separation of photo-induced electron and hole. Furthermore, the CeO₂/CdS composites can also provide cathodic protection for 12 h in the dark.

Key words: CeO₂/CdS composite, heterostructure, physical barrier, photoelectrochemical cathodic protection

中图分类号:

TB332

魏科年, 刘展, 左士祥, 严向玉, 吴凤芹, 李霞章, 姚超, 刘孝恒. 高性能CeO₂/片状CdS复合光电极材料的制备及在光阴极保护中应用[J]. 无机材料学报, 2019, 34(12): 1334-1340.

WEI Ke-Nian, LIU Zhan, ZUO Shi-Xiang, YAN Xiang-Yu, WU Feng-Qin, LI Xia-Zhang, YAO Chao, LIU Xiao-Heng. Preparation of CeO₂/Flake-like CdS Composites as High-Performance Photoanodes for Photoelectrochemical Cathodic Protection[J]. Journal of Inorganic Materials, 2019, 34(12): 1334-1340.

图/表 11

Fig. 1 Schematic sketch of the experimental setup for photoelectrochemical cathodic protection investigation

Fig. 2 XRD patterns of (a) CdS, (b) CeO2/CdS (0.1 : 1.0), (c) CeO2/CdS (0.2 : 1.0), (d) CeO2/CdS (0.3 : 1.0) and (e) CeO2

Fig. 3 TEM images of (a) CdS, (b) CeO2, (c) CeO2/CdS (0.1 : 1.0), (d) CeO2/CdS (0.2 : 1.0), and (e) HRTEM image and EDX pattern of CeO2/CdS (0.2 : 1.0)

Fig. 4 UV-Vis diffuse reflection spectra of (a) CdS, (b) CeO2/CdS (0.1 : 1.0), (c) CeO2/CdS (0.2 : 1.0), (d) CeO2/CdS (0.3 : 1.0) and (e) CeO2

Fig. 5 PL spectra of CdS and CeO2/CdS(0.1 : 1.0), CeO2/CdS (0.2 : 1.0) and CeO2/CdS(0.3 : 1.0)

Fig. 6 (a-g) Polarization curves for uncoated 304SS, 304SS coated with CeO2/CdS (0.1 : 1.0), CeO2/CdS (0.2 : 1.0) and CeO2/CdS (0.3 : 1.0) in the white-light illumination and in the dark; (h) polarization curves for CeO2/CdS (0.2 : 1.0) nanoparticles in the dark

Fig. 7 Photocurrent-time curves of (a) CdS, (b) CeO2/CdS (0.1 : 1.0), (c) CeO2/CdS (0.3 : 1.0) and (d) CeO2/CdS (0.2 : 1.0)

Fig. 8 (a) Nyquist plots of pure 304SS, 304SS coupled with CdS and CeO2/CdS(0.1 : 1), CeO2/CdS(0.2 : 1) and CeO2/CdS (0.3 : 1) in the dark and white-light illumination; (b) Schematics of the equivalent circuit obtained by EIS result fitting

Table 1 Fitting results of the Nyquist plots using the equivalent circuits of Fig. 8

Electrode	R_s /Ω	Q_f		R_f/Ω	Q_dl		R_ct/Ω
Electrode	R_s /Ω	Y₀	n	R_f/Ω	Y₀	n	R_ct/Ω
CeO₂/CdS(0.3 : 1.0)^a	5.548	3.32×10^-5	0.914	1.35×10⁶	5.11×10^-5	1.000	3.73×10⁵
CeO₂/CdS(0.2 : 1.0)^a	4.889	2.85×10^-5	0.917	3.35×10⁵	5.02×10^-5	1.000	2.30×10⁵
CeO₂/CdS(0.1 : 1.0)^a	4.615	1.97×10^-5	0.945	1.34×10⁵	5.62×10^-5	0.907	2.15×10⁵
CdS^a	4.041	2.22×10^-4	0.987	1.30×10⁵	2.46×10^-5	0.949	2.40×10⁵
uncoated 304SS	4.413	5.99×10^-5	1.000	4.50×10⁴	6.27×10^-5	0.903	2.70×10⁵
CdS^b	1.968	1.79×10^-4	1.000	8.10×10³	4.12×10^-4	0.843	2.19×10⁴
CeO₂/CdS(0.1 : 1.0)^b	3.928	1.10×10^-3	0.766	1.43×10⁴	5.56×10^-5	0.884	1.58×10⁴
CeO₂/CdS(0.2 : 1.0)^b	13.39	9.21×10^-6	0.859	2.36×10³	1.07×10^-6	0.914	1.15×10³
CeO₂/CdS(0.3 : 1.0)^b	4.021	3.47×10^-3	0.533	3.14×10⁴	8.46×10^-5	0.903	4.35×10³

Fig. 9 OCP variations of 304SS electrodes coupled with the as-obtained samples

Fig. 10 Mechanism of CeO2/CdS composite for 304SS photocathodic protection

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高性能CeO₂/片状CdS复合光电极材料的制备及在光阴极保护中应用

Preparation of CeO₂/Flake-like CdS Composites as High-Performance Photoanodes for Photoelectrochemical Cathodic Protection

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