新型光催化剂钨酸锌的制备及性能改性研究进展

doi:10.11896/cldb.18040056

材料导报

2019, Vol. 33

Issue (9): 1541-1549 https://doi.org/10.11896/cldb.18040056

金属与金属基复合材料

新型光催化剂钨酸锌的制备及性能改性研究进展

侯珊, 刘向春

西安科技大学材料科学与工程学院,西安 710054

Preparation and Properties Modification of Novel Photocatalyst Zinc Tungstate: a Review

HOU Shan, LIU Xiangchun

College of Materials Science and Engineering, Xi’an University of Science and Technology, Xi’an 710054

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摘要当今世界,全球能源危机和环境污染问题日趋紧迫,严重危害人类健康并制约着人类社会发展。为了人类可持续发展,迫切需要开发和应用清洁无污染的新能源来解决环境问题。近年来,光催化氧化技术因其室温深度反应以及可直接利用太阳能作为光源来驱动反应等特点,成为一种高效、理想的环境污染治理技术,引起了各国研究者的密切关注,开发和应用高效的光催化剂已成为环境领域的研究热点。
过去几十年,二氧化钛(TiO₂)因无毒、廉价易得、稳定性好等特点,成为研究最广的半导体光催化剂。然而,较窄的光频率响应范围、低的太阳能利用率等缺点限制了其实用化进程。为此,研究人员采用各种不同的制备方法,研究开发了大量具有不同结构的非TiO₂基光催化材料,包括简单氧化物、复合金属氧化物、钙钛矿型复合氧化物等。其中,钨酸锌(ZnWO₄)是一种具有宽禁带、高激发能、高紫外光响应、高催化活性等独特物理化学特性的重要新型非TiO₂基半导体光催化剂,被认为是最有潜力的金属钨酸盐光催化剂之一,其纳米粉体的制备合成及性能研究可为可见光催化降解有机污染物开辟一条新的路径,具有极其重要的研究价值,也是近些年来新型光催化剂研究的焦点。
ZnWO₄半导体光催化剂的晶体形貌、尺寸、组成、掺杂物等对其光催化活性具有重要影响。目前,研究者们已通过固相反应法、水热法、溶剂热法、溶胶-凝胶法、化学沉淀法、微乳液法、模板法等不同的制备方法合成了具有不同形貌、尺寸和结晶度的ZnWO₄纳米光催化剂,探讨了制备工艺、晶体特性(形貌、尺寸、组成、结晶程度等)、光催化性能之间的关系。但这些方法合成的ZnWO₄光响应区域仍然较窄,只能吸收太阳光谱中具有较高能量的紫外光,其光量子产率仍然较低。为了进一步提高ZnWO₄的光响应范围,科学家们采用掺杂改性和材料复合等多种活性改进方法来提高其光电转换效率、拓宽光波吸收范围,使其具有良好的可见光响应,优化了其光催化性能。
因此,加深制备工艺和性能改性方法对ZnWO₄晶体形貌、尺寸、组成等特性影响以及这些特性对光催化活性影响的理解,对进一步推进钨酸盐光催化材料的研究和应用具有重要的科学意义和实用价值。基于此,本文在分析ZnWO₄晶体结构特点的基础上,主要从制备方法、掺杂改性和材料复合这三个方面综述了近年来ZnWO₄光催化剂的研究进展,探讨了其结构、形貌、性能之间的相互关系,并进一步指出了ZnWO₄光催化剂的发展前景及提高其光催化性能的主要措施。

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	侯珊
	刘向春

关键词: 钨酸锌半导体光催化纳米材料掺杂改性

Abstract: Nowadays, the global energy crisis and environmental pollution are becoming more and more serious, which greatly endangers human health and restricts the development of society. Aiming at the sustainable development of human beings, it is urgent to solve environmental problems by developing and applying new clean energy with less pollution. In recent years, photocatalytic oxidation technology has become an efficient and ideal environmental pollution control technology and aroused numerous interests at home and abroad, due to its capacity of deep reaction at room temperature and utilizing solar energy as light source to directly driven reaction. Accordingly, the development and application of highly efficient photocatalysts has become a research hot spot in the field of the environment.
In the past decades, titanium dioxide (TiO₂) has been a widely studied semiconductor photocatalyst, thanks to its nontoxicity, low cost, and favorable stability. Nevertheless, its narrow optical frequency response range and low solar energy utilization rate constitute the bottlenecks for its practical application. Therefore, great efforts have been put into the development of non-TiO₂ photocatalytic materials with different structures by various preparation approaches. These photocatalytic materials include simple oxide, composite metal oxide, perovskite-type composite oxide and series compound. Among of them, zinc tungstate (ZnWO₄) is a novel non-TiO₂ semiconductor photocatalyst with great significance, which features unique physicochemical properties of wide band gap, high excitation energy, strong ultraviolet light response, and satisfactory catalytic activity. Hence, ZnWO₄ has been considered as one of the most promising metal tungstate photocatalysts. The synthesis and properties study of ZnWO₄ nano-powders pave the way for a novel approach for photocatalytic degradation of organic pollutants, exhibiting extremely important research value and is also the focus of new photocatalyst research in recent years.
Generally, the photocatalytic activity of ZnWO₄ semiconductor photocatalyst are greatly affected by the crystal morphology, size, composition, and the dopant. Currently, ZnWO₄ nano-photocatalysts with various morphologies, sizes and crystallinities have been synthesized by diverse preparation methods, including solid phase reaction, hydrothermal method, solvothermal method, sol-gel method, chemical precipitation method, micro-emulsion method, and template method. The relationships among preparation process, crystal characteristics (namely crystal morphology, size, composition, and the degree of crystallization), and photocatalytic properties have been studied. However, the photoresponse range of ZnWO₄ synthesized by these methods is still narrow, and only the ultraviolet with high energy can be absorbed in the entire solar spectrum, resulting in a low optical quantum yield. For the sake of further broadening the photo response range of ZnWO₄, therefore, a variety of improvement approaches of photocatalytic activity, including doping modification and material compounding, have been employed to broaden the photo response range of ZnWO₄, realize its strong visible light responsivity, and further enhance the photocatalytic properties of ZnWO₄.
Consequently, it is of great scientific significance and practical value in promoting the research and application of tungstate photocatalytic materials to dig out the impact of preparation processes and properties modification approaches on the crystal morphology, size and composition of ZnWO₄, and the effect of these characteristics on the photocatalytic activity. Based on the analysis of the ZnWO₄ crystal structure characteristics, the research progress of ZnWO₄ photocatalyst in recent years is summarized from the aspects of preparation method, doping modification and material compounding, and the interrelations among structure, morphology and properties are discussed as well. Meanwhile, the future development prospects of ZnWO₄ photocatalyst is pointed out, and the main measures for optimizing the photocatalytic properties of ZnWO₄ are proposed.

Key words: zinc tungstate semiconductor photocatalysis nanomaterial doping modification

发布日期: 2019-05-10

ZTFLH:

TM281

基金资助: 凝固技术国家重点实验室开放课题(SKLSP201624);国家自然科学基金(51602252);国家重点基础研发项目子课题(2017YFC0703204)

通讯作者: liuxc@126.com

作者简介: 侯珊,硕士研究生。2015年本科毕业于陕西理工大学,获工学学士学位。现为西安科技大学材料科学与工程学院硕士研究生,在刘向春教授的指导下进行科学研究,主要研究方向为光催化应用方面新型功能纳米半导体材料的设计合成。刘向春,教授、硕士研究生导师、博士。于1998年获中国地质大学学士学位,并分别在2005年和2007年获西北工业大学硕士和博士学位。现为西安科技大学材料科学与工程学院教授、材料学学科带头人,并担任多个国际期刊和中文核心期刊审稿专家以及西安市科技计划项目评审专家,主要从事光催化应用方面新型功能纳米结构材料的设计合成。

引用本文:

侯珊, 刘向春. 新型光催化剂钨酸锌的制备及性能改性研究进展[J]. 材料导报, 2019, 33(9): 1541-1549.
HOU Shan, LIU Xiangchun. Preparation and Properties Modification of Novel Photocatalyst Zinc Tungstate: a Review. Materials Reports, 2019, 33(9): 1541-1549.

链接本文:

http://www.mater-rep.com/CN/10.11896/cldb.18040056 或 http://www.mater-rep.com/CN/Y2019/V33/I9/1541

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