Moreno-Castilla Carlos, López-Ramón María Victoria, Fontecha-Cámara María Ángeles, Álvarez Miguel A, Mateus Lucía
Department of Inorganic Chemistry, Faculty of Science, University of Granada, 18071 Granada, Spain.
Department of Inorganic and Organic Chemistry, Faculty of Experimental Science, University of Jaen, 23071 Jaen, Spain.
Nanomaterials (Basel). 2019 Jun 20;9(6):901. doi: 10.3390/nano9060901.
Copper ferrites containing Cu ions can be highly active heterogeneous Fenton catalysts due to synergic effects between Fe and Cu ions. Therefore, a method of copper ferrite nanosphere (CFNS) synthesis was selected that also permits the formation of cuprite, obtaining a CFNS composite that was subsequently calcined up to 400 °C. Composites were tested as Fenton catalysts in the mineralization of phenol (PHE), -nitrophenol (PNP) and -aminophenol (PAP). Catalysts were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and magnetic measurements. Degradation of all phenols was practically complete at 95% total organic carbon (TOC) removal. Catalytic activity increased in the order PHE < PNP < PAP and decreased when the calcination temperature was raised; this order depended on the electronic effects of the substituents of phenols. The as-prepared CFNS showed the highest catalytic activity due to the presence of cubic copper ferrite and cuprite. The Cu surface concentration decreased after calcination at 200 °C, diminishing the catalytic activity. Cuprite alone showed a lower activity than the CFNS composite and the homogeneous Fenton reaction had almost no influence on its overall activity. CFNS activity decreased with its reutilization due to the disappearance of the cuprite phase. Degradation pathways are proposed for the phenols.
由于铁离子和铜离子之间的协同效应,含铜离子的铁酸铜可以成为高活性的非均相芬顿催化剂。因此,选择了一种合成铁酸铜纳米球(CFNS)的方法,该方法还能形成赤铜矿,从而获得一种CFNS复合材料,随后将其煅烧至400°C。对该复合材料作为芬顿催化剂用于苯酚(PHE)、对硝基苯酚(PNP)和对氨基酚(PAP)的矿化反应进行了测试。通过透射电子显微镜(TEM)、扫描电子显微镜(SEM)、X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)、X射线光电子能谱(XPS)和磁性测量对催化剂进行了表征。在总有机碳(TOC)去除率达到95%时,所有酚类的降解几乎完全。催化活性按PHE < PNP < PAP的顺序增加,且在煅烧温度升高时降低;该顺序取决于酚类取代基的电子效应。由于存在立方铁酸铜和赤铜矿,所制备的CFNS表现出最高的催化活性。在200°C煅烧后,铜表面浓度降低,催化活性减弱。单独的赤铜矿表现出比CFNS复合材料更低的活性,并且均相芬顿反应对其整体活性几乎没有影响。由于赤铜矿相的消失,CFNS的活性随着其重复使用而降低。文中还提出了酚类的降解途径。