电化学阳极氧化法制备类纳米管结构WO<sub>3</sub>光阳极用于光电催化全分解水

引用本文: 李凌凤, 赵小龙, 潘东来, 李贵生. 电化学阳极氧化法制备类纳米管结构WO₃光阳极用于光电催化全分解水[J]. 催化学报, 2017, 38(12): 2132-2140. doi: 10.1016/S1872-2067(17)62948-6 shu

Citation: Lingfeng Li, Xiaolong Zhao, Donglai Pan, Guisheng Li. Nanotube array-like WO₃/W photoanode fabricated by electrochemical anodization for photoelectrocatalytic overall water splitting[J]. Chinese Journal of Catalysis, 2017, 38(12): 2132-2140. doi: 10.1016/S1872-2067(17)62948-6 shu

电化学阳极氧化法制备类纳米管结构WO₃光阳极用于光电催化全分解水

上海师范大学, 生命与环境科学学院, 资源化学教育部重点实验室, 上海市稀土功能材料重点实验室, 上海 200234
基金项目:
国家自然科学基金（21207090，21477079，21261140333）；PCSIRT （IRT1269）；上海师范大学基金（DXL122，S30406）.

摘要: 近年来，随着能源和环境问题日益凸显，新型可再生能源的开发利用意义重大.其中开发高效的光阳极材料用于光电催化全分解水引起了广泛的研究兴趣.纳米WO₃由于其禁带宽度适中，被证明是一种效果良好的光催化分解水产氧的催化剂，但无法直接用于催化析氢.若将其作为光阳极材料，在施加较低偏压下可用于高效光电催化全分解水.纳米WO₃电极的众多制备方法中，电化学氧化法因其方法简单，高效，制备成本低而具有重要的应用价值.然而，通常情况下电化学氧化法得到的纳米WO₃薄膜多为无规则形貌或多孔膜.本文发展了一种简单的阳极氧化法，通过优化调变其制备过程中的氧化时间，氧化电压，电解质离子浓度以及焙烧温度，确定了最佳制备条件（1 h，40 V，0.15 mol/L NH₄F，400 ℃）时样品的光电催化全分解水活性最高，其光电催化析氢和析氧的速率分别达到了3.93和1.96 μmol/cm²/h，且量子效率达5.23%的，此NAs-WO₃/W薄膜的光电催化活性和稳定性远超商业WO₃/W薄膜.
场发射扫描电镜结果显示，所制样品是一种新型的形貌规整的类纳米管阵列状WO₃薄膜.并进一步通过X射线衍射（XRD）、高分辨透射电子显微镜（HRTEM）、X射线光电子能谱（XPS）、紫外可见光谱、光电转换效率、光电流测试、和交流阻抗等手段研究了其晶体结构、表面化学组成、光学及光电化学性质.同时通过实验与计算获得了NAs-WO₃/W薄膜在420 nm单色光照下的表面空穴分离率，并与商业WO₃制备得到的WO₃/W薄膜进行了相关对比.XRD，HRTEM和XPS结果表明，所制NAs-WO₃/W薄膜是由暴露（020）和（202）晶面的单斜晶相WO₃构成.交流阻抗测试表明，NAs-WO₃/W的交流阻抗值要远小于商业WO₃/W，说明其光生载流子分离效果要比商业化的WO₃/W高；且NAs-WO₃/W薄膜的表面空穴分离率是商业WO₃/W薄膜的三倍.由此可见NAs-WO₃/W具有优异的光电催化性能（高光电转换效率和空穴分离效率），能有效应用于可见光全分解水反应，这主要归因于其类纳米管阵列的特殊一维结构、高结晶度的单斜态WO₃及WO₃与金属W片之间的强相互作用.本文为高效光电转换材料的制备提供了新的技术与途径.

关键词:

English

Nanotube array-like WO₃/W photoanode fabricated by electrochemical anodization for photoelectrocatalytic overall water splitting

Key Laboratory of Resource Chemistry of Ministry of Education, Shanghai Key Laboratory of Rare Earth Functional Materials, College of Life and Environmental Science, Shanghai Normal University, Shanghai 200234, China
Received Date: 09 October 2017
Revised Date: 27 October 2017
Fund Project:
This work was supported by the National Natural Science Foundation of China (21207090, 21477079, 21261140333), PCSIRT (IRT1269), and a scheme administrated by Shanghai Normal University (DXL122, and S30406).

Abstract: Photoactive WO₃ is attractive as a photocatalyst for green energy evolution through water splitting. In the present work, an electrochemical anodic oxidation method was used to fabricate a photo-responsive nanotube array-like WO₃/W (NA-WO₃/W) photoanode from W foil as a precursor. Compared with a reference commercial WO₃/W electrode, the NA-WO₃/W photoanode exhibited enhanced and stable photoelectrocatalytic (PEC) activity for visible-light-driven water splitting with a typical H₂/O₂ stoichiometric ratio of 2:1 and quantum efficiency of approximately 5.23% under visible-light irradiation from a light-emitting diode (λ=420 nm, 15 mW/cm²). The greatly enhanced PEC performance of the NA-WO₃/Wphotoanode was attributed to its fast electron-hole separation rate, which resulted from the one-dimensional nanotube array-like structure, high crystallinity of monoclinic WO₃, and strong interaction between WO₃ and W foil. This work paves the way to a facile route to prepare highly active photoelectrodes for solar light transfer to chemical energy.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

电化学阳极氧化法制备类纳米管结构WO₃光阳极用于光电催化全分解水

English

Nanotube array-like WO₃/W photoanode fabricated by electrochemical anodization for photoelectrocatalytic overall water splitting

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电化学阳极氧化法制备类纳米管结构WO3光阳极用于光电催化全分解水

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