利用Ni(OH)x助催化剂修饰提高g-C3N4纳米片/WO3纳米棒Z型纳米体系的可见光产氢活性的研究

引用本文: 何科林, 谢君, 罗杏宜, 温九青, 马松, 李鑫, 方岳平, 张向超. 利用Ni(OH)_x助催化剂修饰提高g-C₃N₄纳米片/WO₃纳米棒Z型纳米体系的可见光产氢活性的研究[J]. 催化学报, 2017, 38(2): 240-252. doi: 10.1016/S1872-2067(17)62759-1 shu

Citation: Kelin He, Jun Xie, Xingyi Luo, Jiuqing Wen, Song Ma, Xin Li, Yueping Fang, Xiangchao Zhang. Enhanced visible light photocatalytic H₂ production over Z-scheme g-C₃N₄ nansheets/WO₃ nanorods nanocomposites loaded with Ni(OH)_x cocatalysts[J]. Chinese Journal of Catalysis, 2017, 38(2): 240-252. doi: 10.1016/S1872-2067(17)62759-1 shu

利用Ni(OH)_x助催化剂修饰提高g-C₃N₄纳米片/WO₃纳米棒Z型纳米体系的可见光产氢活性的研究

a 华南农业大学材料与能源学院, 广东广州 510642;
b 华南农业大学林学与风景园林学院, 广东广州 510642;
c 华南农业大学新能源与新材料研究所, 农业部能源植物资源与利用重点实验室, 广东省高校生物质能源重点实验室, 广东广州 510642;
d 长沙学院环境光催化应用技术省重点实验室, 湖南长沙市 410022
基金项目:
国家自然科学基金（51672089）；广州市产学研协同创新重大专项（201508020098）；材料复合新技术国家重点实验室（武汉理工大学）开放基金（2015-KF-7）；环境与能源光催化湖南省高等学校“2011协同创新中心”（长沙学院环境光催化应用技术省重点实验室）开放课题（CCSU-XT-04）.

摘要: 光催化技术是目前解决能源和环境问题最具前景的手段之一，因此寻找高效光催化剂已成为光催化技术的研究热点.而在众多半导体催化剂中，廉价、环保且性能稳定的g-C₃N₄光催化剂在太阳光开发利用方面尤其引人关注.然而，由于g-C₃N₄的比表面小，活性位点少，以及光生电子/空穴对易复合等不足，严重导致其较低的光催化量子效率.因此，构造Z型体系和负载助催化剂等策略被广泛应用于提高g-C₃N₄光催化效率.在过去几年中，TiO₂，Bi₂WO₆，WO₃，Bi₂MoO₆，Ag₃PO₄和ZnO已经被成功证实可以与g-C₃N₄耦合而构造Z型光催化剂体系.其中，WO₃/g-C₃N₄光催化剂体系，具有可见光活性的WO₃导带中的光生电子和g-C₃N₄价带中的光生空穴容易实现Z型复合，从而保留了WO₃的强氧化能力和g-C₃N₄的高还原能力，最终大幅度提高了整个体系的光催化活性.在g-C₃N₄的各种产氢助催化剂中，由于常用的Pt，Ag和Au等贵金属的高成本和低储量等问题严重限制了它们的实际应用，所以近年来各种非贵金属助催化剂（包括纳米碳，Ni，NiS，Ni（OH）₂，WS₂和MoS₂等）得到了广泛的关注.我们采取廉价且丰富的Ni（OH）_x助催化剂修饰g-C₃N₄/WO₃耦合形成的Z型体系，开发出廉价高效的WO₃/g-C₃N₄/Ni（OH）_x三元产氢光催化体系.在该三元体系中，Ni（OH）_x和WO₃分别用于促进g-C₃N₄导带上光生电子和价带的光生空穴的分离及利用，从而使得高能的g-C₃N₄的光生电子在Ni（OH）_x富集并应用于光催化产氢，而高能的WO₃的光生空穴被应用于氧化牺牲剂三乙醇胺，最终实现了整个体系的高效光催化产氢活性及稳定性.
我们通过直接焙烧钨酸铵和硫脲制备出WO₃纳米棒/g-C₃N₄，并采用原位光沉积方法将Ni（OH）_x纳米颗粒负载到WO₃/g-C₃N₄上.随后，我们采取X射线衍射（XRD）、高分辨透射电子显微镜（HRTEM）、X射线光电子能谱分析（XPS）和比表面和孔径分布等表征手段来研究光催化剂的结构与形貌；采取紫外-可见漫反射表征方法来研究其光学性能；采取荧光光谱，阻抗和瞬态光电流曲线等表征手段来测试光催化剂的电荷分离性能；采取极化曲线和电子自旋共振谱等表征手段来证明光催化机理；采取光催化分解水产氢的性能测试来研究光催化剂的光催化活性与稳定性.XRD，HRTEM和XPS表征结果，表明WO₃为有缺陷的正交晶系的晶体，直径为20-40纳米棒且均匀嵌入在g-C₃N₄纳米片上；Ni（OH）_x为Ni（OH）₂与Ni的混合物，其Ni（OH）₂与Ni的摩尔比为97.4：2.6，Ni（OH）_x粒径为20-50 nm且均匀分散在g-C₃N₄纳米片上，WO₃/g-C₃N₄/Ni（OH）_x催化剂界面之间结合牢固，其中WO₃和Ni（OH）_x均匀分布在g-C₃N₄上.紫外-可见漫反射表征结果表明，随着缺陷WO₃的负载量增加，复合体系的吸收边与g-C₃N₄相比产生明显的红移，而加入Ni（OH）_x助催化剂使得催化剂体系的颜色由黄变黑，明显地增加了可见光的吸收.荧光光谱，阻抗和瞬态光电流曲线结果表明，WO₃和Ni（OH）_x的加入能有效地促进光生电子/空穴的分离.极化曲线结果表明，掺入WO₃和Ni（OH）_x能降低g-C₃N₄的析氢过电位，从而提高光催化剂表面的产氢动力学.·O₂^-和·OH电子自旋共振谱表明成功形成了WO₃/g-C₃N₄耦合Z型体系.光催化分解水产氢的性能测试表明，20% WO₃/g-C₃N₄/4.8% Ni（OH）_x产氢效率最高（576 μmol/（g·h）），分别是g-C₃N₄/4.8% Ni（OH）_x，20% WO₃/g-C₃N₄和纯g-C₃N₄的5.7，10.8和230倍.上述结果充分证明，Ni（OH）_x助催化剂修饰和g-C₃N₄/WO₃ Z型异质结产生了极好的协同效应，最终实现了三元体系的极高的光催化产氢活性.

关键词:

English

Enhanced visible light photocatalytic H₂ production over Z-scheme g-C₃N₄ nansheets/WO₃ nanorods nanocomposites loaded with Ni(OH)_x cocatalysts

a College of Materials and Energy, Guangzhou 510642, Guangdong, China;
b College of Forestry and Landscape Architecture, South China Agricultural University, Guangzhou 510642, Guangdong, China;
c Key Laboratory of Energy Plants Resource and Utilization, Ministry of Agriculture, Key Laboratory of Biomass Energy of Guangdong Regular Higher Education Institutions, Institute of New Energy and New Materials, South China Agricultural University, Guangzhou 510642, Guangdong, China;
d Hunan Key Laboratory of Applied Environmental Photocatalysis, Changsha University, Changsha 410022, Hunan, China
Received Date: 30 October 2016
Revised Date: 20 November 2016
Available Online: 02 March 2017
Fund Project:
This work was supported by the National Natural Science Foundation of China (51672089), the Industry and Research Collaborative Innovation Major Projects of Guangzhou (201508020098), the State Key Laboratory of Advanced Technology for Material Synthesis and Processing (Wuhan University of Technology) (2015-KF-7) and the Hunan Key Laboratory of Applied Environmental Photocatalysis (Changsha University) (CCSU-XT-04).

Abstract: Novel WO₃/g-C₃N₄/Ni(OH)_x hybrids have been successfully synthesized by a two-step strategy of high temperature calcination and in situ photodeposition. Their photocatalytic performance was investigated using TEOA as a hole scavenger under visible light irradiation. The loading of WO₃ and Ni(OH)_x cocatalysts boosted the photocatalytic H₂ evolution efficiency of g-C₃N₄. WO₃/g-C₃N₄/Ni(OH)_x with 20 wt% defective WO₃ and 4.8 wt%Ni(OH)_x showed the highest hydrogen production rate of 576 μmol/(g·h), which was 5.7, 10.8 and 230 times higher than those of g-C₃N₄/4.8 wt%Ni(OH)_x, 20 wt%WO₃/C₃N₄ and g-C₃N₄ photocatalysts, respectively. The remarkably enhanced H₂ evolution performance was ascribed to the combination effects of the Z-scheme heterojunction (WO₃/g-C₃N₄) and loaded cocatalysts (Ni(OH)_x), which effectively inhibited the recombination of the photoexcited electron-hole pairs of g-C₃N₄ and improved both H₂ evolution and TEOA oxidation kinetics. The electron spin resonance spectra of ^·O_2^- and ·OH radicals provided evidence for the Z-scheme charge separation mechanism. The loading of easily available Ni(OH)_x cocatalysts on the Z-scheme WO₃/g-C₃N₄ nanocomposites provided insights into constructing a robust multi-ple-heterojunction material for photocatalytic applications.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

利用Ni(OH)_x助催化剂修饰提高g-C₃N₄纳米片/WO₃纳米棒Z型纳米体系的可见光产氢活性的研究

English

Enhanced visible light photocatalytic H₂ production over Z-scheme g-C₃N₄ nansheets/WO₃ nanorods nanocomposites loaded with Ni(OH)_x cocatalysts

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