磷酸钴修饰Cu3V2O8/ZnO光阳极的动力学特性及光电化学水分解研究

doi:10.6023/A23090403

摘要/Abstract

钒酸铜是一种新兴的应用前景广阔的光阳极材料. 本工作首先制备了不同厚度的Cu₃V₂O₈光电极, 通过强度调制光电流谱、电化学阻抗谱等手段深入探究了影响Cu₃V₂O₈光电性能的关键因素在于光生载流子扩散距离短造成的载流子体相复合严重以及缓慢的氧化动力学造成的表面复合严重. 为解决该问题, 本工作提出了将一维ZnO纳米棒阵列作为支撑骨架以及负载CoPi助催化剂的策略. 一维ZnO纳米棒阵列可作为电子快速传输通道促进光生载流子的体相分离, CoPi助催化剂可提高光生载流子表面分离效率提升氧化动力学.

关键词: 钒酸铜, 氧化锌, 光电化学, 动力学, 强度调制光电流谱

Copper vanadate (Cu₃V₂O₈) has emerged as a promising material for photoelectrochemical applications due to its unique electronic and optical properties. In this study, the preparation of Cu₃V₂O₈ photoelectrodes with different thicknesses was reported and the factors that affect their photoelectrochemical performance were investigated. It is found that the primary limitation of Cu₃V₂O₈ as a photoanode material is the short diffusion distance of the photo-generated charge carriers, which leads to severe bulk recombination and limits the photocurrent density and efficiency. To overcome this limitation, a novel strategy of using one-dimensional ZnO nanorod arrays as a support framework and loading CoPi cocatalyst to enhance the photoelectrochemical performance of Cu₃V₂O₈ was proposed. The ZnO nanorod arrays serve as a rapid electron transfer channel to promote the bulk separation of photo-generated charge carriers, while the CoPi cocatalyst improves the surface separation efficiency of photo-generated charge carriers and enhances the oxidation kinetics. The incorporation of ZnO nanorod arrays and CoPi cocatalyst significantly enhances the photocurrent density and efficiency of Cu₃V₂O₈ photoelectrodes, resulting in a more than 2-fold increase in the photocurrent density and a 50% increase in the photoconversion efficiency. To further understand the underlying mechanisms behind the improved photoelectrochemical performance, a comprehensive analysis of the intensity-modulated photocurrent spectroscopy and electrochemical impedance spectroscopy data was performed. The results show that the incorporation of ZnO nanorod arrays and CoPi cocatalyst leads to a significant reduction in the charge transfer resistance and a decrease in the recombination rate of photo-generated charge carriers, which are responsible for the improved photocurrent density and efficiency. Overall, the study demonstrates the potential of using ZnO nanorod arrays and CoPi cocatalyst as a novel strategy to enhance the photoelectrochemical performance of Cu₃V₂O₈ photoelectrodes. The proposed approach provides a new direction for the development of high-performance photoanode materials for solar energy conversion and other photoelectrochemical applications.

Key words: Cu₃V₂O₈, ZnO, photoelectrochemical, kinetics, intensity modulated photocurrent spectroscopy

引用此文

王志强, 苏进展. 磷酸钴修饰Cu₃V₂O₈/ZnO光阳极的动力学特性及光电化学水分解研究[J]. 化学学报, 2024, 82(1): 26-35.

Zhiqiang Wang, Jinzhan Su. Investigation of the Kinetic Properties and Photoelectrochemical Water Splitting of Cu₃V₂O₈/ZnO Photoanode Modified by Cobalt Phosphate[J]. Acta Chimica Sinica, 2024, 82(1): 26-35.

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图/表 8

图1. (a) CVO-3的场发射扫描电子显微镜(SEM)图片. (b) CVO-1, (c) CVO-2, (d) CVO-3, (e) CVO-4和(f) CVO-5的截面SEM图片

Figure 1. (a) SEM image of CVO-3. SEM images of film cross section of (b) CVO-1, (c) CVO-2, (d) CVO-3, (e) CVO-4 and (f) CVO-5

图2. CVO光电极的(a)紫外可见光吸收图谱(插图为不同旋涂次数的CVO光电极光学图片), (b)基于Tauc plot公式的间接带隙计算图, (c)拉曼光谱, (d) Cu 元素的X射线光电子能谱, (e) V元素的X射线光电子能谱和(f) X射线衍射图谱

Figure 2. (a) UV-Vis absorption spectra (The illustration shows the optical image of the CVO photoelectrode with different coating layers), (b) tauc-plot, (c) Raman spectrum, (d) X-ray photoelectron spectrum of Cu 2p, (e) X-ray photoelectron spectrum of V 2p and (f) X-ray diffraction patterns of CVO photoelectrode

图3. CVO光阳极的(a)光电流密度结果谱图, (b)应用偏压转换效率谱图, (c)莫特肖特基测试谱图, (d)瞬态光电流密度结果谱图, (e)电化学阻抗谱-奈奎斯特图, (f)电化学阻抗谱-伯德图, (h)表面注入效率, (i)体相分离效率和(j)强度调制光电流谱

Figure 3. (a) Photocurrent density spectrum, (b) applied bias photon-to-current efficiency spectrum, (c) Mott-Schottky plots, (d) transient photocurrent density curves, (e) electrochemical impedance spectra-Nyquist plot, (f) electrochemical impedance spectra-Bode-phase plot, (h) surface injection efficiency curves, (i) bulk phase separation efficiency curves and (j) intensity modulated photocurrent spectroscopy of CVO photoanode

样品	D_n/(cm²•s^-1)	τ_d/ms	k_tr	k_rec	η_tr/%	L_D/nm
CVO-1	1.20×10^-4	0.40	3.65	1.36	72.86	141.36
CVO-2	7.60×10^-5	0.63	3.73	2.58	59.05	112.28
CVO-3	7.60×10^-5	0.63	4.06	2.53	61.59	112.28
CVO-4	6.04×10^-5	0.80	2.96	3.35	46.85	100.08
CVO-5	6.04×10^-5	0.80	2.24	2.78	44.62	100.08

表1. 光电极电荷传输和复合动力学参数

Table 1. Charge transfer and recombination kinetic parameters of photoelectrode

图4. (a) ZnO, (b) CVO/ZnO和(c) CoPi/CVO/ZnO的场发射扫描电子显微镜图片. (d) ZnO, (e) CVO/ZnO和(f) CoPi/CVO/ZnO的截面SEM图片

Figure 4. SEM images of (a) ZnO, (b) CVO/ZnO and (c) CoPi/CVO/ZnO. SEM images of film cross section of (d) ZnO, (e) CVO/ZnO and (f) CoPi/ CVO/ZnO

图5. CoPi/CVO/ZnO复合光电极的(a) X射线衍射图谱, (b)拉曼光谱, (c) X射线光电子能谱全谱图, (d) Zn元素X射线光电子能谱, (e) O元素X射线光电子能谱和(f) 紫外可见光吸收谱(插图为CoPi/CVO/ZnO复合光电极光学图片)

Figure 5. (a) X-ray diffraction patterns, (b) Raman spectra, (c) XPS wide survey spectra, (d) X-ray photoelectron spectrum of Zn element, (e) X-ray photoelectron spectrum of O element and (f) UV-Vis absorption spectra (the illustration shows the optical image of the CoPi/CVO/ZnO composite photoelectrodes)

图6. CoPi/CVO/ZnO复合光电极的(a)光电流密度结果谱图, (b)应用偏压转换效率谱图, (c)莫特肖特基测试谱图, (d)电化学阻抗谱-奈奎斯特图, (e)瞬态光电流密度结果谱图, (f)表面注入效率, (h)体相分离效率, (i)强度调制光电流谱和(j)光照下CoPi/CVO/ZnO复合光电极导带价带能级和电荷转移机理示意图

Figure 6. (a) Photocurrent density spectrum, (b) applied bias photon-to-current efficiency spectrum, (c) Mott-Schottky plots, (d) electrochemical impedance spectra-Nyquist plot, (e) transient photocurrent density curves, (f) surface injection efficiency curves, (h) bulk phase separation efficiency curves, (i) intensity modulated photocurrent spectra, and (j) the VB and CB energy levels and the mechanism of charge transfer in CoPi/CVO/ZnO composite photoelectrode

样品	D_n/(cm²•s^-1)	τ_d/ms	k_tr	k_rec	η_tr/%
CVO-3	7.60×10^-5	0.63	4.06	2.53	61.59
ZnO	1.67×10^-4	0.29	3.61	1.40	72.23
CVO/ZnO	9.06×10^-5	0.53	3.73	2.15	63.41
CoPi/CVO/ZnO	1.14×10^-4	0.42	5.72	0.84	87.22

表2. 光电极电荷传输和复合动力学参数

Table 2. Charge transfer and recombination kinetic parameters of photoelectrode

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磷酸钴修饰Cu₃V₂O₈/ZnO光阳极的动力学特性及光电化学水分解研究

Investigation of the Kinetic Properties and Photoelectrochemical Water Splitting of Cu₃V₂O₈/ZnO Photoanode Modified by Cobalt Phosphate

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