Copper doping effect on the preparation of efficient heterogeneous Fenton-like catalyst (Ni, Mg, Cu)Fe2O4 from nickel sulfide concentrate
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摘要: 以硫化鎳精礦為原料，采用共沉淀–煅燒法成功制備出Cu摻雜尖晶石鐵氧體(Ni, Mg, Cu)Fe2O4異相類Fenton催化劑。利用X射線衍射(XRD)、掃描電子顯微鏡(SEM)及X射線光電子能譜(XPS)等手段系統研究了Cu摻雜量對所制備產物微觀結構、形貌及催化性能的影響；確立了最優催化體系為光助類Fenton催化體系“(Ni, Mg, Cu)Fe2O4催化劑/H2O2/可見光”，揭示了Cu摻雜對(Mg, Ni)Fe2O4催化活性的增強機制。結果表明：在選定的實驗條件下，制備得到的產物均為純相立方尖晶石鐵氧體。當Ni與Cu摩爾比為1∶1時，合成的(Ni, Mg, Cu)Fe2O4在可見光照180 min條件下對質量濃度為10 mg?L?1的羅丹明B(RhB)溶液的降解率可達94.5%。究其主要原因為：隨著Cu摻雜量的增加，占據(Ni, Mg, Cu)Fe2O4八面體位的Fe3+和Cu2+的相對含量增加，即裸露于鐵氧體表面的Fe3+和Cu2+數量增多，以及兩者的協同作用，加速了羥基自由基(·OH)反應的發生，最終使得RhB溶液的降解效率從73.1%提高至94.5%。
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關鍵詞:
- 硫化鎳精礦 /
- Cu摻雜量 /
- 尖晶石鐵氧體(Ni，Mg，Cu)Fe2O4 /
- 異相類Fenton催化劑 /
- 煅燒
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 enhancement mechanism of copper doping on the catalytic activity of (Mg, Ni)Fe2O4 was revealed. Results showed that all formed products were pure spinel ferrites under the selected synthesis conditions. With 1∶1 molar ratio of Ni to Cu, the formed (Ni, Mg, Cu)Fe2O4 catalyst achieved 94.5% degradation efficiency for 10-mg?L?1 RhB solution under visible light irradiation for 180 min. This observed behavior may be ascribed mainly to the increased relative contents of Fe3+ and Cu2+ ions at octahedral site. Hydroxyl radical (·OH) reaction accelerated due to increased amount of Fe3+ and Cu2+ exposed on the surface and enhanced synergetic effect between Fe3+ and Cu2+. This improved the degradation efficiency of RhB solution from 73.1% to 94.5%. -
圖 2 樣品的XRD圖譜。（a）不同Cu摻雜量合成的樣品的XRD圖譜；（b）(311)晶面最強峰對應2θ角度偏移的放大圖
Figure 2. XRD patterns of samples: (a) XRD patterns of Cu-doped samples; (b) enlarged views of 2θ angle shift corresponding to the strongest peaks of the (311) crystal planes
S1—undoped Cu sample; S2—MNi∶Cu=1∶0.6 sample; S3— MNi∶Cu=1∶1 sample
圖 3 不同Cu摻雜量合成樣品的SEM圖及粒徑統計分布圖。（a）和（d）未摻雜Cu的樣品；（b）和（e）MNi∶Cu=1∶0.6的樣品；（c）和（f）MNi∶Cu=1∶1的樣品
Figure 3. SEM images and particle size distributions of Cu-doped samples: (a) and (d) undoped Cu sample; (b) and (e) MNi∶Cu=1∶0.6 sample; (c) and (f) MNi∶Cu=1∶1 sample
圖 4 樣品的XPS圖譜。（a）不同Cu摻雜量鐵氧體的XPS全譜圖；（b）Fe 2p的高分辨圖譜；（c）Mg 2p的高分辨圖譜；（d）Ni 2p的高分辨圖譜；（e）Cu 2p的高分辨圖譜
Figure 4. XPS spectra of samples: (a) full XPS spectra of copper-doped ferrites; (b) Fe 2p high resolution spectra; (c) Mg 2p high resolution spectra; (d) Ni 2p high resolution spectra; (e) Cu 2p high resolution spectra
S1—undoped Cu sample; S2—MNi∶Cu=1∶0.6 sample; S3—MNi∶Cu = 1∶1 sample
圖 5 降解曲線及熒光光譜圖。（a）不同催化反應體系中RhB溶液的降解曲線；（b）Ni0.63Mg0.30Cu0.07Fe2O4/H2O2/可見光催化體系捕獲·OH產生2-羥基對苯二甲酸熒光光譜圖
Figure 5. Degradation curves and fluorescence spectra: (a) the degradation curves of RhB solutions in different catalytic reaction systems; (b) fluorescence spectra of 2-hydroxyterephthalic acid produced by the catalytic system of Ni0.63Mg0.30Cu0.07Fe2O4/H2O2/vis capturing ·OH radicals
圖 6 Cu摻雜量不同的催化劑降解RhB溶液的吸光度曲線。（a）未摻雜；（b）MNi∶Cu=1∶0.6；（c）MNi∶Cu=1∶1
Figure 6. Absorbance curves of RhB solution degraded by catalysts with different Cu doping: (a) undoped; (b) MNi∶Cu = 1∶0.6; (c) MNi∶Cu = 1∶1
圖 7 降解曲線和動力學曲線。（a）不同Cu摻雜量的催化劑降解RhB溶液的曲線；（b）不同Cu摻雜量的催化劑降解RhB溶液的動力學特征曲線
Figure 7. Degradation curves and kinetic curves: (a) RhB degradation by samples with different Cu doping amounts; (b) kinetic characteristics curves of RhB degradation by samples with different Cu doping amounts
圖 8 催化體系“(Ni,Mg,Cu)Fe2O4催化劑/H2O2/可見光”的反應機理圖
Figure 8. Reaction mechanism diagram of catalytic system “(Ni,Mg,Cu)Fe2O4 catalyst/H2O2/visible light”
圖 9 不同Cu摻雜量鐵氧體中金屬離子八面體位占比圖
Figure 9. Percentages of metal ion octahedral positions in ferrites with different copper doping amounts
表 1 X射線熒光光譜分析測定硫化鎳精礦主要化學成分
Table 1. Chemical compositions of nickel sulfide concentrate analyzed by XRF
% Components Fe S Si Ni Mg Cu Al Ca Co Mass fraction 14.06 12.12 7.88 6.28 6.25 1.37 1.14 1.09 0.16 Components K Ti Na Cr Zn Mn Pb Cl O and others Mass fraction 0.11 0.08 0.10 0.07 0.08 0.04 0.03 0.02 49.12 
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表 2 ICP-AES測定硫化鎳精礦浸出液中主要金屬元素含量
Table 2. Main metal elements in the leaching solution of nickel sulfide concentrate by ICP-AES analysis
Concentration Fe Ni Mg Cu Co Al Ca Ti K Cr Zn Mn Mass concentration/(g?L?1) 40.84 3.305 0.965 0.698 0.023 0.210 0.275 0.005 0.016 0.009 0.009 0.007 Molar concentration/(mol?L?1) 0.729 0.056 0.040 0.011 0.001 0.008 0.007 <0.001 <0.001 <0.001 <0.001 <0.001
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表 3 不同Cu含量(Ni,Mg,Cu)Fe2O4的化學式和晶胞參數的計算結果
Table 3. Chemical formula and unit cell parameters of (Ni,Mg,Cu)Fe2O4 with different Cu contents
MNi∶Cu (molar ratio) Chemical formula a/nm Undoped Ni0.63Mg0.30Cu0.07Fe2O4 0.4285 1∶0.6 Ni0.48Mg0.21Cu0.31Fe2O4 0.4287 1∶1 Ni0.24Mg0.15Cu0.61Fe2O4 0.4289
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