Brzezińska Magdalena, García-Muñoz Patricia, Ruppert Agnieszka M, Keller Nicolas
Institute of General and Ecological Chemistry, Faculty of Chemistry, Lodz University of Technology, 90-924 Łódź, Poland.
Institut de Chimie et Procédés pour l'Energie, l'Environnement et la Santé, CNRS/University of Strasbourg, 67087 Strasbourg, France.
Materials (Basel). 2018 Nov 13;11(11):2260. doi: 10.3390/ma11112260.
In this work, the solar light-induced redox photoactivity of ZnO semiconductor material was used to prepare CuO-ZnO composite catalysts at room temperature with a control of the chemical state of the copper oxide phase. Cu₂O-ZnO and CuO-ZnO composite catalysts were prepared by using Cu(acac)₂ in tetrahydrofuran-water and Cu(NO₃)₂ in water as metallic precursor, respectively. Prior to the implementation of the photon-assisted synthesis method, the most efficient photoactive ZnO material was selected from among different ZnO materials prepared by the low temperature polyol and precipitation methods with carbonates and carbamates as precipitation agents. The photocatalytic degradation of the 4-chlorophenol compound in water under simulated solar light was taken as a model reaction. The ZnO support materials were characterized by X-ray diffraction (XRD), surface area and porosimetry measurements, thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), and the synthesis method strongly influenced their photoactivity in terms of 4-chlorophenol degradation and of total organic carbon removal. The most photoactive ZnO material was prepared by precipitation with carbonates and calcined at 300 °C, benefitting from a high specific surface area and a small mean crystallite size for achieving a complete 4-chlorophenol mineralization within 70 min of reaction, with minimum Zn released to the solution. Besides thermal catalysis applications, this work has opened a new route for the facile synthesis of Cu₂O-ZnO heterojunction photocatalysts that could take place under solar light of the heterojunction built between the -type semi-conductor Cu₂O with direct visible light band gap and the ZnO semiconductor phase.
在这项工作中,利用ZnO半导体材料的太阳光诱导氧化还原光活性,在室温下制备了CuO-ZnO复合催化剂,并控制了氧化铜相的化学状态。分别以四氢呋喃-水中的Cu(acac)₂和水中的Cu(NO₃)₂作为金属前驱体,制备了Cu₂O-ZnO和CuO-ZnO复合催化剂。在实施光子辅助合成方法之前,从以碳酸盐和氨基甲酸盐为沉淀剂通过低温多元醇法和沉淀法制备的不同ZnO材料中,选择了最有效的光活性ZnO材料。以模拟太阳光下水溶液中4-氯苯酚化合物的光催化降解作为模型反应。通过X射线衍射(XRD)、表面积和孔隙率测量、热重分析(TGA)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)对ZnO载体材料进行了表征,合成方法在4-氯苯酚降解和总有机碳去除方面对其光活性有很大影响。最具光活性的ZnO材料是通过用碳酸盐沉淀并在300℃下煅烧制备的,得益于高比表面积和小平均微晶尺寸,在70分钟的反应时间内实现了4-氯苯酚的完全矿化,且释放到溶液中的锌最少。除了热催化应用外,这项工作为在具有直接可见光带隙的p型半导体Cu₂O与ZnO半导体相之间构建的异质结的太阳光下,简便合成Cu₂O-ZnO异质结光催化剂开辟了一条新途径。