生物炭载硫化铁对2,4-二氯苯氧乙酸的催化氧化降解
Oxidative degradation of 2,4-dichlorophenoxyacetic acid catalyzed by the biochar supported iron sulfide
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摘要: 以木质生物炭为载体制备了负载型硫化铁(FeSx/BC),采用扫描电镜/能量色散X射线光谱(SEM/EDX)、X射线粉末衍射(XRD)和X射线光电子能谱(XPS)对其结构进行了表征分析.然后将其用于催化除草剂2,4-二氯苯氧乙酸(2,4-D)的类Fenton氧化降解,并与市售硫化亚铁(c-FeS)进行对比.结果表明,生物炭可以提高硫化铁分散性,炭载催化剂中的Fe主要以Fe3S4形式存在.与c-FeS相比,采用FeSx/BC催化降解2,4-D的反应速率常数(kobs)提高了约20倍.降解反应速率随催化剂、H2O2用量增加而提高,但是随初始pH(2.0-9.0)上升而下降.机理研究表明,生物炭作为电子穿梭体有助于提高·OH的生成量,促进2,4-D降解中间产物转化、并使脱氯反应更完全.Abstract: The supported iron sulfide (FeSx/BC) was prepared by loading on a wood biochar, and then characterized by SEM/EDX, XRD and XPS. It was used for catalyzing the Fenton-like oxidation of herbicide 2,4-dichlorophenoxyacetic acid (2,4-D), and compared with the commercial ferrous sulfide (c-FeS). The results indicated that the biochar improved the dispersion of iron sulfide, which existed mainly in the form of Fe3S4. The reaction rate constant (kobs) for 2,4-D degradation catalyzed by FeSx/BC was nearly 20 times that using the c-FeS. The degradation reaction was accelerated by increasing the dosages of catalyst and H2O2, while the reaction rate dropped with the rising initial pH (2.0-9.0). The mechanism studies showed that the biochar acting as the electron shuttle enhanced the production of·OH, which in turn promoted the transformation of degradation intermediates and facilitated the more complete dechlorination of 2,4-D.
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Key words:
- biochar /
- iron mineral /
- Fenton reaction /
- herbicide /
- dechlorination
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[1] 孙红文, 吕俊岗, 翟洪艳, 等. Fenton法与光Fenton法降解2,4-D的研究[J]. 环境化学,2005,24(4):365-369. SUN H W, LÜ J G, ZHAI H Y, et al. Study on degradation of 2,4-D by Fenton and photo-Fenton reaction[J]. Environmental Chemistry, 2005, 24(4):365-369(in Chinese).
[2] HE J, YANG X, MEN B, et al. Interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials:A review[J]. Journal of Environmental Science, 2016, 39:97-109. [3] 冯勇, 吴德礼, 马鲁铭. 铁氧化物催化类Fenton反应[J]. 化学进展, 2013, 25(7):1219-1228. FENG Y, WU D L, MA M L. Iron oxide catalyzed Fenton-like reaction[J]. Progress in Chemistry, 2013, 25(7):1219-1228(in Chinese).
[4] 冯勇, 吴德礼, 马鲁铭. 黄铁矿催化类Fenton反应处理阳离子红X-GRL废水[J]. 中国环境科学, 2012, 32(6):1011-1017. FENG Y, WU D L, MA M L. Treatment of Cationic Red X-GRL wastewater by pyrite catalyzed Fenton-like reaction[J]. China Environmental Science, 2012, 32(6):1011-1017(in Chinese).
[5] CHEN H, ZHANG Z, FENG M, et al. Degradation of 2,4-dichlorophenoxyacetic acid in water by persulfate activated with FeS (mackinawite)[J]. Chemical Engineering Journal, 2017, 313:498-507. [6] ZHAO L, CHEN Y, LIU Y, et al. Enhanced degradation of chloramphenicol at alkaline conditions by S(-Ⅱ) assisted heterogeneous Fenton-like reactions using pyrite[J]. Chemosphere, 2017, 188:557-566. [7] 陈再明, 陈宝梁, 周丹丹. 水稻秸秆生物碳的结构特征及其对有机污染物的吸附性能[J]. 环境科学学报, 2013, 33(1):9-19. CHEN Z M, CHEN B L, ZHOU D D. Composition and sorption properties of rice-straw derived biochars[J]. Acta Scientiae Circumstantiae, 2013, 33(1):9-19(in Chinese).
[8] 王菲, 孙红文. 生物炭对极性与非极性有机污染物的吸附机理[J]. 环境化学, 2016, 35(6):1134-1141. WANG F, SUN H W. Sorption mechanisms of polar and apolar organic contaminants onto biochars[J]. 2016, 35(6):1134-1141(in Chinese).
[9] ZHU X, LI C, LI J, et al. Thermal treatment of biochar in the air/nitrogen atmosphere for developed mesoporosity and enhanced adsorption to tetracycline[J]. Bioresource Technology, 2018, 263:475-482. [10] KAPPLER A, WUESTNER M L, RUECKER A, et al. Biochar as an electron shuttle between bacteria and Fe (Ⅲ) minerals[J]. Environmental Science & Technology Letter, 2014, 1:339-344. [11] FANG G, GAO J, LIU C, et al. Key role of persistent free radicals in hydrogen peroxide activation by biochar:Implications to organic contaminant degradation[J]. Environmental Science & Technology, 2014, 48:1902-1910. [12] ZHANG Y, XU X, CAO L, et al. Characterization and quantification of electron donating capacity and its structure dependence in biochar derived from three waste biomasses[J]. Chemosphere, 2018, 211:1073-1081. [13] YAN J, HAN L, GAO W, et al. Biochar supported nanoscale zerovalent iron composite used as persulfate activator for removing trichloroethylene[J]. Bioresource Technology, 2015, 175:269-274. [14] OUYANG D, YAN J, QIAN L, et al. Degradation of 1, 4-dioxane by biochar supported nano magnetite particles activating persulfate[J]. Chemosphere, 2017, 184:609-617. [15] 于晓丹, 林鑫辰, 冯威, 等. Fe3O4/TiO2@生物碳骨架复合材料的一步法制备及UV-Fenton催化性能[J]. 高等学校化学学报, 2018,39:154-160. YU X D, LIN X C, FENG W, et al. One-step preparation and UV-Fenton properties of Fe3 [16] 周奥, 曹新强, 顾彦, 等. 以生物炭为内核的BC@BiOBr催化剂的制备及可见光光催化性能[J]. 环境化学, 2019,38(2):235-242. ZHOU A, CAO X Q, GU Y, et al. Preparation of BC@BiOBr catalyst with biochar as core and its visible light photocatalytic performance[J]. Environmental Chemistry, 2019, 38(2):235-242(in Chinese).
[17] CHEN H, ZHANG Z, YANG Z, et al. Heterogeneous Fenton-like catalytic degradation of 2,4-dichlorophenoxyacetic acid in water with FeS[J]. Chemical Engineering Journal, 2015, 273:481-489. [18] TONG M, YUAN S, MA S, et al. Production of abundant hydroxyl radicals from oxygenation of subsurface sediments[J]. Environmental Science & Technology, 2016, 50(1):214-221. [19] CHOE Y J, BYUN J Y, KIM S H, et al. Fe3S4/Fe7S8-promoted degradation of phenol via heterogeneous, catalytic H2O2 scission mediated by S-modified surface Fe2+ species[J]. Applied Catalysis B:Environmental, 2018, 233:272-280. [20] LÜ Y, LI J, LI Y, et al. The roles of pyrite for enhancing reductive removal of nitrobenzene by zero-valent iron[J]. Applied Catalysis B:Environmental, 2019, 242:9-18. [21] FANG G, ZHU C, DIONYSIOU D D, et al. Mechanism of hydroxyl radical generation from biochar suspensions:Implications to diethyl phthalate degradation[J]. Bioresource Technology, 2015, 176:210-217. [22] QIN Y, ZHANG L, AN T. Hydrothermal carbon-mediated Fenton-like reaction mechanism in the degradation of alachlor:Direct electron transfer from hydrothermal carbon to Fe (Ⅲ)[J]. ACS Applied Material and Interface, 2017, 9:17115-17124. [23] ZHANG Y, ZHANG K, DAI C, et al. An enhanced Fenton reaction catalyzed by natural heterogeneous pyrite for nitrobenzene degradation in an aqueous solution[J]. Chemical Engineering Journal, 2014, 244:438-445. [24] LEE H, PARK S H, PARK Y K, et al. Photocatalytic reactions of 2, 4-dichlorophenoxyacetic acid using a microwave-assisted photocatalysis system[J]. Chemical Engineering Journal, 2015, 278:259-264. [25] AZIZ K H H, MIESSNER H, MUELLER S, et al. Comparative study on 2, 4-dichlorophenoxyacetic acid and 2, 4-dichlorophenol removal from aqueous solutions via ozonation, photocatalysis and non-thermal plasma using a planar falling film reactor[J]. Journal of Hazardous Materials, 2018, 343:107-115. [26] 黄锦铌, 李任超, 金晓英, 等. 有机膨润土负载纳米铁类Fenton法去除水中2,4-二氯酚[J]. 福建师大学报(自然科学版),2015,(3):59 -64. HUANG J N, LI R C, JIN X Y, et al. Fenton-like oxidation of 2,4-DCP in aqueous solution using organobentonite loaded nZVI[J]. Journal of Fujian Normal University (Natural Science Edition), 2015, (3):59-64(in Chinese).
[27] LI R, GAO Y, JIN X, et al. Fenton-like oxidation of 2, 4-DCP in aqueous solution using iron-based nanoparticles as the heterogeneous catalyst[J]. Journal of Colloids and Interface Science, 2015, 438:87-93. [28] ZHU X, LI J, XIE B, et al. Accelerating effects of biochar for pyrite-catalyzed Fenton-like oxidation of herbicide 2,4-D[J]. Chemical Engineering Journal, 2019, DOI:10.1016/j.cej.2019.123605.
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