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通过形成碱性碳酸锌,显著增强了 ZnO 上 HO 光催化还原 CO 的性能。

Significant Enhancement of Photocatalytic Reduction of CO with HO over ZnO by the Formation of Basic Zinc Carbonate.

机构信息

Department of Chemical, Biological and Pharmaceutical Engineering, New Jersey Institute of Technology , Newark, New Jersey 07102, United States.

出版信息

Langmuir. 2017 Jul 11;33(27):6667-6676. doi: 10.1021/acs.langmuir.7b00620. Epub 2017 Jun 27.

Abstract

Electron-hole pair separation efficiency and adsorption performance of photocatalysts to CO are the two key factors affecting the performance of photocatalytic CO reduction with HO. Distinct from conventional promoter addition, this study proposed a novel approach to address these two issues by tuning the own surface features of semiconductor photocatalyst. Three ZnO samples with different morphologies, surface area, and defect content were fabricated by varying preparation methods, characterized by XRD, TEM, and room-temperature PL spectra, and tested in photoreduction of CO with HO. The results show that the as-prepared porous ZnO nanosheets exhibit a much higher activity for photoreduction of CO with HO when compared to ZnO nanoparticles and nanorods attributed to the existence of more defect sites, that is, zinc and oxygen vacancies. These defects would lower the combination rate of electron-hole pair as well as promote the formation of basic zinc carbonate by Lewis acid-base interaction, which is the active intermediate species for photoreduction of CO. ZnO nanoparticles and ZnO nanorods with few defects show weak adsorption for CO leading to the inferior photocatalytic activities. This work provides new insight on the CO activation under light irradiation.

摘要

光催化剂中电子-空穴对的分离效率和对 CO 的吸附性能是影响水相光催化 CO 还原性能的两个关键因素。有别于传统的助催化剂添加方式,本研究提出了一种通过调节半导体光催化剂自身表面特性来解决这两个问题的新方法。通过改变制备方法,制备了具有不同形貌、比表面积和缺陷含量的三种 ZnO 样品,通过 XRD、TEM 和室温 PL 光谱进行了表征,并在水相光催化 CO 还原反应中进行了测试。结果表明,与 ZnO 纳米粒子和纳米棒相比,所制备的多孔 ZnO 纳米片在水相光催化 CO 还原反应中表现出更高的活性,这归因于存在更多的缺陷位,即锌和氧空位。这些缺陷会降低电子-空穴对的复合率,并通过路易斯酸碱相互作用促进碱性碳酸锌的形成,这是 CO 光还原的活性中间物种。缺陷较少的 ZnO 纳米粒子和 ZnO 纳米棒对 CO 的吸附较弱,导致其光催化活性较差。这项工作为光照下 CO 的活化提供了新的见解。

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