工程科学学报.第43卷，第7期：935-945.2021年7月 Chinese Journal of Engineering,Vol.43,No.7:935-945,July 2021 https://doi.org/10.13374/j.issn2095-9389.2020.06.18.002;http://cje.ustb.edu.cn Cu掺杂对硫化镍精矿制备高效异相类Fenton催化剂 Ni,Mg,Cu)FeO4的影响 刘雅贤，陈婷，韩星，张梅，郭敏区 北京科技大学治金与生态工程学院.北京100083 ☒通信作者，E-mail:guomin(@ustb.edu.cn 摘要以硫化镍精矿为原料，采用共沉淀-煅烧法成功制备出Cu掺杂尖晶石铁氧体NiMg,Cu)Fe2O4异相类Fenton催化 剂.利用X射线衍射(XRD)、扫描电子显微镜(SEM)及X射线光电子能谱(XPS)等手段系统研究了Cu参杂量对所制备产物 微观结构、形貌及催化性能的影响：确立了最优催化体系为光助类Fenton催化体系“Ni,Mg,Cu)FezO,催化剂HO2/可见 光”，揭示了Cu掺杂对(Mg,Ni)FO4催化活性的增强机制.结果表明：在选定的实验条件下，制备得到的产物均为纯相立方 尖晶石铁氧体.当Ni与Cu摩尔比为1：1时，合成的Ni,Mg,Cu)FezO4在可见光照180min条件下对质量浓度为10mgL1 的罗丹明B(RhB)溶液的降解率可达94.5%.究其主要原因为：随着Cu掺杂量的增加，占据(Ni,Mg,Cu)F©zO4八面体位的 Fe*和Cu的相对含量增加，即裸露于铁氧体表面的F©*和Cu*数量增多，以及两者的协同作用，加速了羟基自由基(OH反 应的发生，最终使得RhB溶液的降解效率从73.1%提高至94.5%. 关键词硫化镍精矿旷；Cu掺杂量；尖晶石铁氧体(Ni,Mg,Cu)FezO4;异相类Fenton催化剂：煅烧 分类号TF803.21:TB34 Copper doping effect on the preparation of efficient heterogeneous Fenton-like catalyst (Ni,Mg,Cu)Fe2O from nickel sulfide concentrate LIU Ya-xian,CHEN Ting,HAN Xing,ZHANG Mei,GUO Min School of Metallurgical and Ecological Engineering.University of Science and Technology Beijing.Beijing 00083,China Corresponding author,E-mail:guomin@ustb.edu.cn ABSTRACT Organic contaminants such as dyes and antibiotics have become the focus of water treatment research in recent years due to their complex composition,high toxicity,and difficulty in biodegradation.Spinel ferrite heterogeneous Fenton-like catalysts,with a chemical formula of MFe2(MFe2,M is a divalent metallic cation or its combination,and the divalent cation is generally Ni,Zn, Mn,Co,Cu,and Mg,etc.),have attracted much attention because of their excellent structural stability and good magnetic recovery performance.However,the catalytic activity of these catalysts is not ideal and almost all the reported catalysts are synthesized by pure chemical reagents,which restrict their industrial application.Therefore,the preparation of highly efficient heterogeneous Fenton-like catalysts with low cost becomes the key to the treatment of refractory organic wastewater.In this study,copper-doped spinel ferrite (Ni, Mg,Cu)Fe2O was successfully synthesized from nickel sulfide concentrate by a coprecipitation-calcination method.The effect of copper doping concentration on the structure,micro-morphology,and catalytic performance of as-prepared samples was systematically investigated by X-ray diffraction,scanning electron microscopy,and X-ray photoelectron spectroscopy.The optimal catalytic system was established as the photo-assisted Fenton-like catalytic system,"(Ni,Mg,Cu)Fe2O catalyst/H2O/visible light",and the enhance- ment mechanism of copper doping on the catalytic activity of(Mg.Ni)Fe2O was revealed.Results showed that all formed products were 收稿日期：2020-06-18 基金项目：国家自然科学基金资助项目(U1810205)Cu 掺杂对硫化镍精矿制备高效异相类 Fenton 催化剂 (Ni, Mg, Cu)Fe2O4 的影响 刘雅贤，陈 婷，韩 星，张 梅，郭 敏苣 北京科技大学冶金与生态工程学院，北京 100083 苣通信作者，E-mail：guomin@ustb.edu.cn 摘    要    以硫化镍精矿为原料，采用共沉淀–煅烧法成功制备出 Cu 掺杂尖晶石铁氧体 (Ni, Mg, Cu)Fe2O4 异相类 Fenton 催化 剂. 利用 X 射线衍射 (XRD)、扫描电子显微镜 (SEM) 及 X 射线光电子能谱 (XPS) 等手段系统研究了 Cu 掺杂量对所制备产物 微观结构、形貌及催化性能的影响；确立了最优催化体系为光助类 Fenton 催化体系“(Ni, Mg, Cu)Fe2O4 催化剂/H2O2 /可见 光”，揭示了 Cu 掺杂对 (Mg, Ni)Fe2O4 催化活性的增强机制. 结果表明：在选定的实验条件下，制备得到的产物均为纯相立方 尖晶石铁氧体. 当 Ni 与 Cu 摩尔比为 1∶1 时，合成的 (Ni, Mg, Cu)Fe2O4 在可见光照 180 min 条件下对质量浓度为 10 mg∙L−1 的罗丹明 B(RhB) 溶液的降解率可达 94.5%. 究其主要原因为：随着 Cu 掺杂量的增加，占据 (Ni, Mg, Cu)Fe2O4 八面体位的 Fe3+和 Cu2+的相对含量增加，即裸露于铁氧体表面的 Fe3+和 Cu2+数量增多，以及两者的协同作用，加速了羟基自由基 (·OH) 反 应的发生，最终使得 RhB 溶液的降解效率从 73.1% 提高至 94.5%. 关键词    硫化镍精矿；Cu 掺杂量；尖晶石铁氧体 (Ni，Mg，Cu)Fe2O4；异相类 Fenton 催化剂；煅烧 分类号    TF803.21；TB34 Copper doping effect on the preparation of efficient heterogeneous Fenton-like catalyst (Ni, Mg, Cu)Fe2O4 from nickel sulfide concentrate LIU Ya-xian，CHEN Ting，HAN Xing，ZHANG Mei，GUO Min苣 School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083, China 苣 Corresponding author, E-mail: guomin@ustb.edu.cn ABSTRACT    Organic contaminants such as dyes and antibiotics have become the focus of water treatment research in recent years due to their complex composition, high toxicity, and difficulty in biodegradation. Spinel ferrite heterogeneous Fenton-like catalysts, with a chemical formula of MFe2O4 (MFe2O4 , M is a divalent metallic cation or its combination, and the divalent cation is generally Ni, Zn, Mn, Co, Cu, and Mg, etc.), have attracted much attention because of their excellent structural stability and good magnetic recovery performance. However, the catalytic activity of these catalysts is not ideal and almost all the reported catalysts are synthesized by pure chemical reagents, which restrict their industrial application. Therefore, the preparation of highly efficient heterogeneous Fenton-like catalysts with low cost becomes the key to the treatment of refractory organic wastewater. In this study, copper-doped spinel ferrite (Ni, Mg, Cu)Fe2O4 was successfully synthesized from nickel sulfide concentrate by a coprecipitation –calcination method. The effect of copper doping concentration on the structure, micro-morphology, and catalytic performance of as-prepared samples was systematically investigated by X-ray diffraction, scanning electron microscopy, and X-ray photoelectron spectroscopy. The optimal catalytic system was established as the photo-assisted Fenton-like catalytic system, “(Ni, Mg, Cu)Fe2O4 catalyst/H2O2 /visible light”, and the enhance￾ment mechanism of copper doping on the catalytic activity of (Mg, Ni)Fe2O4 was revealed. Results showed that all formed products were 收稿日期: 2020−06−18 基金项目: 国家自然科学基金资助项目（U1810205） 工程科学学报，第 43 卷，第 7 期：935−945，2021 年 7 月 Chinese Journal of Engineering, Vol. 43, No. 7: 935−945, July 2021 https://doi.org/10.13374/j.issn2095-9389.2020.06.18.002; http://cje.ustb.edu.cn