944 工程科学学报，第43卷，第7期 48.0%,Nio2*的相对含量从77.1%降低到67.3%， 体积分数为1.0%和光照强度为180mWcm2的 表明随着Cu掺杂量的增大，Mg2+和Ni2*从八面体 条件下，Mi:cu=1:1铁氧体对l0 mg'L RhB溶 位向四面体位迁移，也就是说C的引入主要占 液的降解效率最佳，达到94.5%. 据了原八面体位的N2和Mg2的位置.具体结果 (3)研究表明，随着Cu掺杂量的增加，铁氧体 如图9所示 中Cuoe2和Feoe的相对含量增多，Mgo2*和Nio2+ 的相对含量减少，占据尖晶石铁氧体八面体位的 100 Undoped Cu+与八面体位的Fe协同作用促进了反应体系 M:=l:0.6 ((Ni,Mg,Cu)Fe2O4催化剂/H2O2/何见光)中·OH的 图8从：o-1:1 快速生成，最终提高了Cu摻杂铁氧体的催化活性. 60 参考文献 [1]Mudd G M.Global trends and environmental issues in nickel mining:Sulfides versus laterites.Ore GeolRev,010,38(1-2):9 [2] ElshkakiA,Reck BK,Graedel TE.Anthropogenic nickel supply, demand,and associated energy and water use.Resour Conserv Recycl,,2017,125:300 Cu Np. Mg [3] Mu W N,Huang Z P,Xin H X,et al.Extraction of copper and Octahedral position of metal ion nickel from low-grade nickel sulfide ore by low-temperature 图9不同Cu掺杂量铁氧体中金属离子八面体位占比图 roasting,selective decomposition and water-leaching process. Fig.9 Percentages of metal ion octahedral positions in ferrites with J0M2019,71(12):4647 different copper doping amounts [4]Zhao K L,Yan W,Wang X H,et al.Effect of a novel phosphate 综合XPS结果及催化体系“(Ni,Mg,Cu)Fe2O4 on the flotation of serpentine-containing copper-nickel sulfide ore 催化剂H2O2/何见光”的反应机理可知：随着Cu掺 Miner Eng,2020,150:106276 杂量的增多，裸露在(Ni,Mg,Cu)FeO4铁氧体表面 [5]Elkacmi R.Bennajah M.Advanced oxidation technologies for the 八面体位的Fe3+和Cu的数量增多，使得类Fenton treatment and detoxification of olive mill wastewater:a general 反应过程中产生OH的反应更易于发生：同时由 review.J Water Reuse Desalin,2019,9(4):463 [6]Tian Q W,Ran M.Fang GG,et al.ZnAl,O/BiPO,composites as 于Cu*/Cu电对的标准电极电位值((Cu*/Cu)= a heterogeneous catalyst for photo-Fenton treatment of textile and 0.166V)小于Fe3t/Fe2*的电极电位值(E(Fe3+Fe2= pulping wastewater.Sep Purif Technol,2020,239:116574 0.770V),说明=Cu2在类Fenton反应过程中生成 [7] Munoz M,de Pedro Z M,Casas J A,et al.Preparation of 的=Cu能够加快=Fe3t向=Fe2+的转化.总之，占据尖 magnetite-based catalysts and their application in heterogeneous 晶石铁氧体八面体位的Cur2+与八面体位的Fe3协 Fenton oxidation-A review.Appl Catal B:Emviron,2015,176- 同作用促进了OH的快速生成，最终提高了尖晶 177:249 石铁氧体的催化活性(RhB溶液的降解效率从 [8]Zan J,Song H,Zuo S Y,et al.MIL-53(Fe)-derived Fe2O:with 73.1%增加到94.5%（图7）). oxygen vacancy as Fenton-like photocatalysts for the elimination of toxic organics in wastewater.J Cleaner Prod,2020,246: 3结论 118971 [9]Wang N,Zhu L H,Wang D L,et al.Sono-assisted preparation of (1)采用共沉淀一煅烧法，通过向经过除铁预 highly-efficient peroxidase-like Fe:O magnetic nanoparticles for 处理的硫化镍精矿浸出液中添加CuC122H2O,制 catalytic removal of organic pollutants with H2O.Ultrason 备得到了纯相尖晶石铁氧体(Ni,Mg,Cu)Fe2O4异相 Sonochem,2010,17(3):526 类Fenton催化剂，不同Cu掺杂量尖品石铁氧体的 [10]Roonasi P,Nezhad A Y.A comparative study of a series of ferrite 化学式分别为Ni.63Mg0.3oCo.o7Fe2O4、Ni0.4sMgo.21 nanoparticles as heterogeneous catalysts for phenol removal at Co.31Fe2O4和Nio.24Mgo.1sCo.61Fe2O4,其粒径约为 neutral pH.Mater Chem Phys,2016,172:143 [11]Wang G,Zhao D Y,Kou F Y,et al.Removal of norfloxacin by 200~300nm surface Fenton system(MnFe2O/H2O2):Kinetics,mechanism and (2)确定了最佳催化体系为“Ni,Mg,Cu)Fe2O/ degradation pathway.Chem Eng J,2018,351:747 HO,/可见光”，阐明了该体系降解RB溶液的反 [12]Zhong Y H,Liang X L,Tan W,et al.A comparative study about 应机理.在25℃、催化剂用量为1.00gL、H202 the effects of isomorphous substitution of transition metals(Ti,Cr,48.0%， NiOct 2+的相对含量从 77.1% 降低到 67.3%， 表明随着 Cu 掺杂量的增大，Mg2+和 Ni2+从八面体 位向四面体位迁移，也就是说 Cu2+的引入主要占 据了原八面体位的 Ni2+和 Mg2+的位置. 具体结果 如图 9 所示. 100 80 60 40 20 0 Fe3+ Cu2+ Ni2+ Mg2+ Percentage of metal ion octahedral site/ % Octahedral position of metal ion Undoped MNi∶Cu=1∶0.6 MNi∶Cu=1∶1 图 9 不同 Cu 掺杂量铁氧体中金属离子八面体位占比图 Fig.9 Percentages of metal ion octahedral positions in ferrites with different copper doping amounts 综合 XPS 结果及催化体系“(Ni,Mg,Cu)Fe2O4 催化剂/H2O2 /可见光”的反应机理可知：随着 Cu 掺 杂量的增多，裸露在 (Ni,Mg,Cu)Fe2O4 铁氧体表面 八面体位的 Fe3+和 Cu2+的数量增多，使得类 Fenton 反应过程中产生·OH 的反应更易于发生；同时由 于 Cu2+/Cu+电对的标准电极电位值（E ϴ (Cu2+/Cu+ )= 0.166 V）小于 Fe3+/Fe2+的电极电位值（E ϴ (Fe3+/Fe2+)= 0.770 V），说明≡Cu2+在类 Fenton 反应过程中生成 的≡Cu+能够加快≡Fe3+向≡Fe2+的转化. 总之，占据尖 晶石铁氧体八面体位的 Cu2+与八面体位的 Fe3+协 同作用促进了·OH 的快速生成，最终提高了尖晶 石铁氧体的催化活性 （ RhB 溶液的降解效率 从 73.1% 增加到 94.5%（图 7））. 3    结论 （1）采用共沉淀−煅烧法，通过向经过除铁预 处理的硫化镍精矿浸出液中添加 CuCl2 ·2H2O，制 备得到了纯相尖晶石铁氧体 (Ni,Mg,Cu)Fe2O4 异相 类 Fenton 催化剂. 不同 Cu 掺杂量尖晶石铁氧体的 化学式分别为 Ni0.63Mg0.30Cu0.07Fe2O4、Ni0.48Mg0.21 Cu0.31Fe2O4 和 Ni0.24Mg0.15Cu0.61Fe2O4，其粒径约为 200～300 nm. （2）确定了最佳催化体系为“(Ni,Mg,Cu)Fe2O4 / H2O2 /可见光”，阐明了该体系降解 RhB 溶液的反 应机理. 在 25 ºC、催化剂用量为 1.00 g·L−1、H2O2 体积分数为 1.0 % 和光照强度为 180 mW·cm−2 的 条件下 ， MNi∶Cu=1∶1 铁氧体对 10 mg·L−1 RhB 溶 液的降解效率最佳，达到 94.5%. （3）研究表明，随着 Cu 掺杂量的增加，铁氧体 中 CuOct 2+和 FeOct 3+的相对含量增多，MgOct 2+和 NiOct 2+ 的相对含量减少，占据尖晶石铁氧体八面体位的 Cu2+与八面体位的 Fe3+协同作用促进了反应体系 （ (Ni,Mg,Cu)Fe2O4 催化剂/H2O2 /可见光）中·OH 的 快速生成，最终提高了 Cu 掺杂铁氧体的催化活性. 参    考    文    献 Mudd G M. Global trends and environmental issues in nickel mining: Sulfides versus laterites. Ore Geol Rev, 2010, 38（1-2）: 9 [1] Elshkaki A, Reck B K, Graedel T E. Anthropogenic nickel supply, demand, and associated energy and water use. Resour Conserv Recycl, 2017, 125: 300 [2] Mu W N, Huang Z P, Xin H X, et al. Extraction of copper and nickel from low-grade nickel sulfide ore by low-temperature roasting, selective decomposition and water-leaching process. JOM, 2019, 71（12）: 4647 [3] Zhao K L, Yan W, Wang X H, et al. Effect of a novel phosphate on the flotation of serpentine-containing copper-nickel sulfide ore. Miner Eng, 2020, 150: 106276 [4] Elkacmi R, Bennajah M. Advanced oxidation technologies for the treatment and detoxification of olive mill wastewater: a general review. J Water Reuse Desalin, 2019, 9（4）: 463 [5] Tian Q W, Ran M, Fang G G, et al. ZnAl2O4 /BiPO4 composites as a heterogeneous catalyst for photo-Fenton treatment of textile and pulping wastewater. Sep Purif Technol, 2020, 239: 116574 [6] Munoz M, de Pedro Z M, Casas J A, et al. Preparation of magnetite-based catalysts and their application in heterogeneous Fenton oxidation – A review. Appl Catal B: Environ, 2015, 176- 177: 249 [7] Zan J, Song H, Zuo S Y, et al. MIL-53(Fe)-derived Fe2O3 with oxygen vacancy as Fenton-like photocatalysts for the elimination of toxic organics in wastewater. J Cleaner Prod, 2020, 246: 118971 [8] Wang N, Zhu L H, Wang D L, et al. Sono-assisted preparation of highly-efficient peroxidase-like Fe3O4 magnetic nanoparticles for catalytic removal of organic pollutants with H2O2 . Ultrason Sonochem, 2010, 17（3）: 526 [9] Roonasi P, Nezhad A Y. A comparative study of a series of ferrite nanoparticles as heterogeneous catalysts for phenol removal at neutral pH. Mater Chem Phys, 2016, 172: 143 [10] Wang G, Zhao D Y, Kou F Y, et al. Removal of norfloxacin by surface Fenton system (MnFe2O4 /H2O2 ): Kinetics, mechanism and degradation pathway. Chem Eng J, 2018, 351: 747 [11] Zhong Y H, Liang X L, Tan W, et al. A comparative study about the effects of isomorphous substitution of transition metals (Ti, Cr, [12] · 944 · 工程科学学报，第 43 卷，第 7 期