Phase transformation and catalytic performance of metal-doped MgFe2O4 prepared from saprolite laterite
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摘要: 采用酸浸-水熱-煅燒法從腐泥土型紅土鎳礦中制備磁性多金屬共摻雜型MgFe2O4異相類芬頓(Fenton)催化劑.利用X射線衍射(XRD)、傅立葉紅外光譜(FTIR)、掃描電子顯微鏡(SEM)和比表面積及孔徑分布測定(BET-BJH)等手段, 考察了煅燒溫度對所制備產物結構、形貌和比表面積及孔徑分布的影響, 并研究了所制備產物作為異相Fenton催化劑降解羅丹明B (RhB)溶液的催化活性.結果表明, 水熱合成產物為層狀雙(多)金屬氫氧化物和尖晶石型MgFe2O4復合物.通過300℃的煅燒, 層狀雙(多)金屬氫氧化物就能分解并生成MgFe2O4; 隨著煅燒溫度的提高, 產物結晶度增加、粒徑尺寸變大, 形貌逐漸生長為近球型顆粒且分散度漸漸提高, 同時介孔數量減少、比表面積減小.經過500℃煅燒的試樣H-C500顯示出優異的催化降解活性.在體系反應溫度為45℃、pH值為6.44、催化劑用量為0.625 g·L-1且H2O2體積分數為1.0%的條件下, 經過300 min, 10 mg·L-1的羅丹明B溶液降解率可達到97.8%, 同時總有機碳(TOC)去除率達到77.8%.重復使用3次后, 催化劑仍能保持較高活性, 降解率和TOC去除率減少量分別少于3.0%和5.0%.
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關鍵詞:
- 腐泥土型紅土鎳礦 /
- 酸浸 /
- 水熱 /
- 煅燒 /
- 共摻雜MgFe2O4 /
- 異相類Fenton催化劑
Abstract: Heterogeneous Fenton-like method has attracted considerable attention because of its potential effectiveness in mineralization of organic contaminants in a wide range of reaction medium pH. Spinel ferrites MFe2O4 (M=Fe, Zn, Cu, Ni, Mn, Co) as heterogeneous Fenton-like catalysts have been studied extensively due to their good catalytic activity, prominent physical and chemical stability, and excellent magnetic properties, which allow their easy separation from the reaction medium by magnetic field for further circular utilization. Considering the group of ferrites, limited research focused on the utilization of MgFe2O4 as heterogeneous Fenton catalytic agent, whereas most of the catalysts are synthesized by pure chemical reagents. In this study, magnetic multi-metal co-doped MgFe2O4 heterogeneous Fenton-like catalyst was synthesized from saprolite laterite by acid leaching-hydrothermal calcination method. The effect of calcination temperature on the phase, morphology, specific surface area, and pore size distribution of samples were characterized by X-ray diffraction, scanning electron microscopy, Fourier-transform infrared, Brunauer-Emmett-Teller/Barrett-Joyner-Halenda analysis. The catalytic activity of the as-prepared products as heterogeneous Fenton catalysts for the degradation of Rhodamine B (RhB) solution was also investigated. The results show that the layered double (multi) hydroxides coupled with a portion of magnesium ferrite are synthesized by hydrothermal method, and the cubic crystal MgFe2O4 is obtained by decomposition of the layered double (multi) hydroxides after calcination above 300℃. With the increase in calcining temperature, the crystallinity of the products increases, and the particle size becomes larger. The morphology gradually grows to near spheroidal particles, and the dispersion degree gradually increases. Meanwhile, the pore size becomes larger, and the specific surface area is reduced. Calcination of sample H-C500 exhibits the best catalytic activity for the degradation of RhB after 500℃, achieving 97.8% degradation efficiency of 10 mg·L-1 RhB after 300 min at the reaction conditions of 45℃, pH 6.44, 0.625 g·L-1 catalyst dosage, and 1.0% (volume fraction) H2O2. The total organic carbon (TOC) removal could reach 77.8%. The reused catalyst can still maintain high activity, and after three consecutive degradation cycles, the reduction of degradation efficiency and TOC removal efficiency are less than 3.0% and 5.0%, respectively. -
圖 1 水熱及不同溫度煅燒產物的X射線衍射圖譜
Figure 1. XRD patterns of as-prepared products through hydrothermal method and calcinated at different temperatures
圖 4 產物場發射掃描電鏡圖片((c), (d)插圖為粒徑分布). (a) P; (b) H; (c) H-C500; (d) H-C1000
Figure 4. FESEM micrographs of products (Inset: particle-size distribution): (a) P; (b) H; (c) H-C500; (d) H-C1000
圖 5 產物H、H-C500和H-C1000的孔結構特征. (a) 吸附-脫附等溫曲線; (b) BJH孔徑分布曲線
Figure 5. Pore structure characteristics of products H, H-C500 and H-C1000: (a) adsorption-desorption isotherm curves; (b) BJH pore-size distribution curves
圖 6 產物H-C500的X射線光電子能譜圖. (a) 全譜圖; (b) Fe 2p高分辨譜圖; (c) Al 2p高分辨譜圖; (d) Mg 2p高分辨譜圖; (e) Ni 2p高分辨譜圖
Figure 6. XPS spectrum of product H-C500: (a) the whole XPS spectrum; (b) Fe 2p high resolution spectrum; (c) Al 2p high resolution spectrum; (d) Mg 2p high resolution spectrum; (e) Ni 2p high resolution spectrum
圖 8 最優條件下捕獲·OH自由基產生2-羥基對苯二甲酸熒光光譜圖(a)和相應的·OH自由基濃度(b)
Figure 8. Fluorescence spectra of 2-hydroxy terephthalic acid produced by trapping ·OH radicals under the optimal condition (a) and corresponding ·OH radical concentrations (b)
圖 9 產物H-C500的磁滯回線圖(a)及其循環利用降解RhB實驗圖(b)
Figure 9. Hysteresis loops of product H-C500 (a) and its recycling study of the degradation of RhB (b)
圖 10 H-C500及其循環使用三次后試樣的X射線衍射圖譜
Figure 10. XRD patterns of samples H-C500 and used H-C500 after three successive recycles
表 1 X射線熒光光譜分析測定紅土鎳礦化學成分(質量分數)
Table 1. Chemical compositions of saprolite laterite analyzed by XRF ?
% Ni Co Mn Mg Fe Cr Al Ti Ca Si Zn 2.60 0.06 0.42 9.68 19.17 0.64 2.63 0.05 0.18 21.36 0.02 
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表 2 ICP-OES測定紅土鎳礦浸出液中主要金屬元素含量及浸出率
Table 2. Chemical analysis and leaching efficiency of leaching solution by ICP-OES
元素 質量濃度/(g·L-1) 浸出率/% Ni 1.79 86.25 Co 0.05 95.83 Mn 0.31 93.15 Mg 6.47 83.54 Fe 13.49 87.98 Al 0.82 38.74
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表 3 原子吸收光譜測定最優條件下不同反應時間溶液中Fe離子濃度
Table 3. Change of leaching concentration for iron ions with reaction 11:02:58
反應時間/min 質量濃度/(mg·L-1) 60 ＜0.1 120 ＜0.1 180 ＜0.1 240 ＜0.1 300 ＜0.1
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