可氧化再生的“核-壳”结构磁性吸附剂Mn0.6Zn0.4Fe2O4@SiO2-CeO2对水中氧氟沙星的吸附机制

徐冬莹; 谢知音; 余静; 刘建英; 徐成华; 邓志勇; 翟婉婷; 郝旗

doi:10.13801/j.cnki.fhclxb.20210722.002

可氧化再生的“核-壳”结构磁性吸附剂Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂对水中氧氟沙星的吸附机制

doi: 10.13801/j.cnki.fhclxb.20210722.002

成都信息工程大学　资源环境学院，成都 610000

基金项目: 成都信息工程大学科研基金资助成果(KYTZ202118)；成都信息工程大学大学生创新创业训练项目(S201910621100)

详细信息

通讯作者:
余静，博士，副教授，硕士生导师，研究方向为水污染控制技术　E-mail：yujing@cuit.edu.cn

中图分类号: X703
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出版历程
- 收稿日期: 2021-05-28
- 修回日期: 2021-06-29
- 录用日期: 2021-07-09
- 网络出版日期: 2021-07-23
- 刊出日期: 2022-06-01

Adsorption mechanism of ofloxacin in water with "core-shell" magnetic adsorbent Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂ capable of oxidation regeneration

College of Resources and Environment, Chengdu University of Information Technology, Chengdu 610000, China

摘要

摘要: 为去除水中难生物降解的氧氟沙星(OFLX)，突破吸附剂固液分离和再生难的瓶颈，采用SiO₂和CeO₂功能化修饰Mn_0.6Zn_0.4Fe₂O₄磁性纳米颗粒，制备得到磁性纳米复合物吸附剂Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂，利用XRD、FTIR、SEM、TEM、和振动样品磁强计等对Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂进行了系统表征。3种动力学模型(拟一级动力学、拟二级动力学和颗粒内扩散模型)、3种等温线模型(Langmuir、Freundlich和D-R模型)和吸附热力学的研究结果表明：该吸附过程的速率由颗粒内扩散和液膜扩散等多种因素共同控制；该吸附过程以物理吸附为主，化学吸附为吸附速率控制步骤；吸附过程可自发进行，为放热和熵减小的过程。FTIR和XRD的表征结果表明，π-π共轭作用、分子间氢键和配位作用等是Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂和OFLX之间的主要相互作用力。经6次吸附-氧化原位再生循环后，Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂对OFLX平衡吸附量为27.00 mg·g⁻¹。研究结果可为难生物降解的OFLX的控制技术研究提供基础理论数据。
- 磁性吸附剂 /
- CeO₂ /
- 氧化再生 /
- 氧氟沙星 /
- 吸附机制 /
- “核-壳”结构
Abstract: In order to remove ofloxacin (OFXL), which is difficult to biodegrade in water, and break through the bottleneck of solid-liquid separation and regeneration of adsorbents, Mn_0.6Zn_0.4Fe₂O₄ magnetic nanoparticles were modified by SiO₂ and CeO₂ to prepare Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂ magnetic nanocompsite adsorbents. The as-prepared Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂ were systematically characterized using XRD, FTIR, SEM, TEM, vibration sample magnetometer. The investigation results of three kinetic models (quasi-first-order kinetics, quasi-second-order kinetics, and intraparticle diffusion models), three isotherm models (Langmuir, Freundlich and D-R models) and adsorption thermodynamics show that the adsorption rate is controlled by multiple factors such as intra-particle diffusion and liquid film diffusion; the adsorption process is dominated by physical adsorption, and the chemical adsorption is the rate-controlling step; the adsorption process is spontaneously and exothermic with entropy increase. The characterization results of FTIR and XRD spectroscopy indicate that the interaction forces between Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂ and OFLX include π-π conjugation, hydrogen bonding and coordination. After six cycles of adsorption-oxidation regeneration in situ, the equilibrium adsorption capacity of Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂ for OFLX is 27.00 mg·g⁻¹. The research results can provide basic theoretical data on the control technology of nonbiodegradable OFLX.
- magnetic adsorbent /
- CeO₂ /
- oxidation regeneration /
- ofloxacin /
- adsorption mechanism /
- "core-shell" structure

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图 1 Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂的XRD图谱 (a)、SEM图像 (b)、HRTEM图像 (c)、SAED图像 (d)

Figure 1. XRD pattern (a), SEM image (b), HRTEM image (c) and SAED image (d) of Mn_0.6Zn_0.4Fe₂O₄ @SiO₂-CeO₂

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图 2 Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂的XPS图谱 (a) 和FTIR图谱 (b)

Figure 2. XPS (a) and FTIR (b) spectra of Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂

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图 3 Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂的磁化曲线 (a) 和磁分离效果图 (b)

Figure 3. Magnetic hysteresis curve (a) and magnetic separation effect picture (b) of Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂

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图 4 Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂吸附氧氟沙星(OFLX)的拟一级、拟二级动力学模型((a)~(c))和颗粒内扩散模型(d)的拟合曲线

Figure 4. Fitting curves of the quasi-first-order, quasi-second-order kinetic models ((a)-(c)) and intragranular diffusion model (d) for adsorption of ofloxacin (OFXL) on Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂

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图 5 Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂在298 K (a)、308 K (b) 和318 K (c) 条件下吸附OFLX的吸附等温线模型拟合曲线

Figure 5. Fitting curves of adsorption isotherms models of OFLX by Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂ at 298 K (a), 308 K (b) and 318 K (c)

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图 6 Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂的吸附-氧化原位再生循环

Figure 6. Cycle of adsorption-regeneration in situ by advanced oxidation processes of Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂

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图 7 OFLX分子结构图及OFLX和Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂的FTIR图谱

Figure 7. OFLX molecular structure diagram and FTIR spectra of OFLX and Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂

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图 8 OFLX和Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂吸附OFLX前后的XPS图谱

Figure 8. XPS spectra of OFLX and Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂ before and after adsorption of OFLX

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表 1 Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂吸附OFLX的吸附动力学拟合结果

Table 1. Fitting results of adsorption kinetics of OFLX by Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂

Temperature/K	q_e,exp/ (mg·g⁻¹)	Quasi-first-order kinetic model			Quasi-second-order kinetic model
Temperature/K	q_e,exp/ (mg·g⁻¹)	q_e,cal/(mg·g⁻¹)	K₁/min⁻¹	R²	q_e,cal/(mg·g⁻¹)	K₂/min⁻¹	R²
298	25.17	23.54	−0.2419	0.9691	24.74	0.01784	0.9943
308	23.72	22.24	−0.2638	0.9712	23.29	0.02166	0.9946
318	26.49	25.15	−0.2702	0.9792	26.26	0.02039	0.9976
Notes: q_e,exp—Experimental amount of OFLX removed per unit mass of adsorbent; K₁, K₂—Quasi-first-order kinetic constant and quasi-second-order kinetic constant; q_e,cal—Calculation amount of OFLX removed per unit mass of adsorbent.

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表 2 Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂吸附OFLX的吸附等温线模型的拟合结果

Table 2. Fitting results of adsorption isotherms models of OFLX by Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂

Temperature/K	Langmuir			Freundlich
Temperature/K	q_m/(mg·g⁻¹)	b/(L·mg⁻¹)	R²	K_f/(mg·g⁻¹)	n/(mg·g⁻¹)	R²
298	33.98	0.7189	0.9651	16.81	4.430	0.9899
308	35.47	0.3340	0.9944	13.72	3.650	0.9941
318	46.01	0.3322	0.9961	16.51	3.226	0.9735
Notes: q_m—Langmuir adsorption maximum; b—Langmuir coefficient of distribution of the adsorption; K_f—Freundlich coefficient of distribution of the adsorption; n—Freundlich isotherm constant.

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表 3 Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂的D-R等温吸附模型的拟合结果

Table 3. Fitting results of D-R isotherm adsorption model of Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂

Temperature/K	q_m/(mg·g⁻¹)	k/10⁻⁷(mol²·kJ⁻²)	E/(kJ·mol⁻¹)	R²
298	41.89	0.462	3.29	0.8089
308	62.43	0.102	7.00	0.9280
318	87.18	1.050	2.18	0.9973
Notes: q_m—D-R adsorption maximum; k—Adsorption energy constant; E—Free energy of adsorption.

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表 4 Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂吸附OFLX的热力学参数

Table 4. Thermodynamic parameters of adsorption of OFLX by Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂

Temperature/K	lnK_d	ΔG^Θ/(kJ·mol⁻¹)	ΔH^Θ/(kJ·mol⁻¹)	ΔS^Θ/(J·mol⁻¹·K⁻¹)
298	4.817	−11.93	−43.8	−107.83
308	3.675	−9.41
318	3.411	−9.02
Notes: K_d—Adsorption thermodynamic equilibrium constant; ΔG^Θ—Gibbs free energy variation of the adsorption process; ΔH^Θ—Enthalpy change of the adsorption process; ΔS^Θ—Entropy change of theadsorption process.

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表 5 不同吸附材料对OFLX吸附性能比较

Table 5. Comparison of the adsorption performance of OFLX by different adsorption materials

Adsorption material	BET/(m²·g⁻¹)	Balance time/min	q_e/(mg·g⁻¹)	Reference
Magnetic biochar	254	1440	22.00	[32]
Zrconium-based MOFs	519	120	35.46	[33]
Shell polysacchar/biochar composites	141	1300	6.64	[34]
MCM41	1026	120	39.20	[35]
Mn_0.6Zn_0.4Fe₂O₄@SiO₂-CeO₂	169	120	30.38	This report
Notes: BET—Specific surface area; MOFs—Metal organic framework; MCM41—Ordered mesoporous molecular sieve.

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参考文献(41)

[1]	LIANG R, LUO S, JING F, et al. A simple strategy for fabrication of Pd@MIL-100(Fe) nanocomposite as a visible-light-driven photocatalyst for the treatment of pharmaceuticals and personal care products (PPCPs)[J]. Applied Catalysis B: Environmental,2015,176:240-248.
[2]	PERES M S, MANIERO M G, GUIMARAES J R. Photocatalytic degradation of ofloxacin and evaluation of the residual antimicrobial activity[J]. Photochemical & Photobiological Sciences,2015,14(3):556-562.
[3]	SHE P F, LUO Z, CHEN L H, et al. Efficacy of levofloxacin against biofilms of Pseudomonas aeruginosa isolated from patients with respiratory tract infections in vitro[J]. MicrobiologyOpen,2019,8(5):e00720. doi: 10.1002/mbo3.720
[4]	ASHTON D, HILTON M, THOMAS K V. Investigating the environmental transport of human pharmaceuticals to streams in the United Kingdom[J]. Science of the total environment,2004,333(1-3):167-184. doi: 10.1016/j.scitotenv.2004.04.062
[5]	YU R B, WU Z C. High adsorption for ofloxacin and reusability by the use of ZIF-8 for wastewater treatment[J]. Microporous and Mesoporous Materials,2020,308:110494. doi: 10.1016/j.micromeso.2020.110494
[6]	SHOKOOHI R, GHOBADI N, GODINI K, et al. Antibiotic detection in a hospital wastewater and comparison of their removal rate by activated sludge and earthworm-based vermifilteration: Environmental risk assessment[J]. Process Safety and Environmental Protection,2020,134:169-177. doi: 10.1016/j.psep.2019.10.020
[7]	DING J Q, HE Y, WANG P C, et al. Performances of simultaneous removal of trace-level ofloxacin and sulfamethazine by different ozonation-based treatments[J]. Journal of Cleaner Production,2020,277:124120.
[8]	CHEN D N, XIE Z J, ZENG Y Q, et al. Accelerated photocatalytic degradation of quinolone antibiotics over Z-scheme MoO₃/g-C₃N₄ heterostructure by peroxydisulfate under visible light irradiation: Mechanism, kinetic and products[J]. Journal of the Taiwan Institute of Chemical Engineers,2019,104:250-259. doi: 10.1016/j.jtice.2019.08.007
[9]	NASUHOGLU D, RODAYAN A, BERK D, et al. Removal of the antibiotic levofloxacin (LEVO) in water by ozonation and TiO₂ photocatalysis[J]. Chemical Engineering Journal,2012,189:41-48.
[10]	FENG C S, CHEN C, ZHU Y, et al. Degradation of ofloxacin using peroxymonosulfate activated by nitrogen-rich graphitized carbon microspheres: Structure and performance controllable study[J]. Journal of Environmental Sciences,2021,99:10-20. doi: 10.1016/j.jes.2020.06.003
[11]	MA P L, LIU Q J, LIU P L, et al. Green synthesis of Fe/Cu oxides composite particles stabilized by pine needle extract and investigation of their adsorption activity for norfloxacin and ofloxacin[J]. Journal of Dispersion Science and Technology,2020,217:1-18.
[12]	孙宏伟, 陈建峰. 我国化工过程强化技术理论与应用研究进展[J]. 化工进展, 2011, 30(1):1-15. SUN H W, CHEN J F. Advances in fundamental study and application of chemical process intensification technology in China[J]. Chemical Industry and Engineering Progress,2011,30(1):1-15(in Chinese).
[13]	ZHENG C F, ZHENG H L, WANG Y J, et al. Modified magnetic chitosan microparticles as novel superior adsorbents with huge “force field” for capturing food dyes[J]. Jour-nal of hazardous materials,2019,367:492-503. doi: 10.1016/j.jhazmat.2018.12.120
[14]	YUAN Y, WU Y, WANG H, et al. Simultaneous enrichment and determination of cadmium and mercury ions using magnetic PAMAM dendrimers as the adsorbents for magnetic solid phase extraction coupled with high performance liquid chromatography[J]. Journal of hazardous materials,2020,386:121658. doi: 10.1016/j.jhazmat.2019.121658
[15]	ROTO R, YUSRAN Y, KUNCAKA A. Magnetic adsorbent of Fe₃O₄@SiO₂ core-shell nanoparticles modified with thiol group for chloroauric ion adsorption[J]. Applied Surface Science,2016,377:30-36. doi: 10.1016/j.apsusc.2016.03.099
[16]	BANIAMERIAN H, TEIMOORI M, SABERI M. Fe₂O₃/TiO₂/Activated carbon nanocomposite with synergistic effect of adsorption and photocatalysis[J]. Chemical Engineering & Technology,2021,44(1):130-139.
[17]	WANG R, YU J, HAO Q. Activated carbon/Mn_0.6Zn_0.4Fe₂O₄ composites: Facile synthesis, magnetic performance and their potential application for the removal of methylene blue from water[J]. Chemical Engineering Research and Design,2018,132:215-225. doi: 10.1016/j.cherd.2018.01.027
[18]	姜德彬, 余静, 叶芝祥, 等. 磁性纳米复合物对水中亚甲基蓝的吸附及其机理[J]. 中国环境科学, 2016, 36(6):1763-1772. doi: 10.3969/j.issn.1000-6923.2016.06.025 JIANG D B, YU J, YE Z X, et al. Adsorption and mechanism of methylene blue from water by magnetic nanocomposites[J]. China Environmental Science,2016,36(6):1763-1772(in Chinese). doi: 10.3969/j.issn.1000-6923.2016.06.025
[19]	LV Z J, ZHONG Q, OU M. Utilizing peroxide as precursor for the synthesis of CeO₂/ZnO composite oxide with enhanced photocatalytic activity[J]. Applied Surface Science,2016,376:91-96. doi: 10.1016/j.apsusc.2016.01.280
[20]	李小军, 李绪翠. 紫外分光光度法测定氧氟沙星片的含量[J]. 药品评价, 2005, 04(2):63-64. LI X J, LI X C. Content determination of ofloxacin in tablets by UV-spectrohotometry[J]. Drug evaluation,2005,04(2):63-64(in Chinese).
[21]	JIN B F, WEI Y C, ZHAO Z, et al. Three-dimensionally ordered macroporous CeO₂/Al₂O₃-supported Au nanoparticle catalysts: Effects of CeO₂ nanolayers on catalytic activity in soot oxidation[J]. Chinese Journal of Catalysis,2017,38(9):1629-1641. doi: 10.1016/S1872-2067(17)62798-0
[22]	HAN Z T, SANI B, MROZIK W, et al. Magnetite impregnation effects on the sorbent properties of activated carbons and biochars[J]. Water research,2015,70:394-403. doi: 10.1016/j.watres.2014.12.016
[23]	奚丽荷, 江海军, 朱忠其, 等. CeO₂掺杂TiO₂光催化剂的性能研究[J]. 功能材料, 2007, 7:1146-1148. doi: 10.3321/j.issn:1001-9731.2007.07.029 XI L H, JIANG H J, ZHU Z Q, et al. Study on properties of CeO₂-doped TiO₂[J]. Journal of Functional Materials,2007,7:1146-1148(in Chinese). doi: 10.3321/j.issn:1001-9731.2007.07.029
[24]	BOKARE A, CHOI W. Review of iron-free Fenton-like systems for activating H₂O₂ in advanced oxidation processes[J]. Journal of hazardous materials,2014,275:121-135. doi: 10.1016/j.jhazmat.2014.04.054
[25]	WU Y, LUO H, WANG H. Adsorption properties of modified sawdust for conge red removal from wastewater[J]. Huanjing Kexue Xuebao/Acta Scientiae Circumstantiae,2014,34(7):1680-1688.
[26]	马锋锋, 赵保卫, 刁静茹. 小麦秸秆生物炭对水中Cd²⁺的吸附特性研究[J]. 中国环境科学, 2017, 37(2):551-559. MA F F, ZHAO B W, DIAO J R. Adsorptive characteristics of cadmium onto biochar produced from pyrolysis of wheat straw in aqueous solution[J]. China Environmental Science,2017,37(2):551-559(in Chinese).
[27]	苏龙, 张海波, 程红艳, 等. 木耳菌糠生物炭对阳离子染料的吸附性能研究[J]. 中国环境科学, 2021, 41(2):693-703. doi: 10.3969/j.issn.1000-6923.2021.02.023 SU L, ZHANG H B, CHENG H Y, et al. Study on adsorption properties of biochar derived from spent Auricularia auricula substrate for cationic dyes[J]. China Environmental Science,2021,41(2):693-703(in Chinese). doi: 10.3969/j.issn.1000-6923.2021.02.023
[28]	ZULFIKAR M A, AFRITA S, WAHYUNINGRUM D, et al. Preparation of Fe₃O₄-chitosan hybrid nano-particles used for humic acid adsorption[J]. Environmental Nanotechnology, Monitoring & Management,2016,6:64-75.
[29]	PATHAK P D, MANDAVGANE S A. Preparation and characterization of raw and carbon from banana peel by microwave activation: application in citric acid adsorption[J]. Journal of Environmental Chemical Engineering,2015,3(4):2435-2447. doi: 10.1016/j.jece.2015.08.023
[30]	SHEN S B, PAN T L, LIU X Q, et al. Adsorption of Rh (III) complexes from chloride solutions obtained by leaching chlorinated spent automotive catalysts on ion-exchange resin Diaion WA21J[J]. Journal of Hazardous Materials,2010,179(1-3):104-112. doi: 10.1016/j.jhazmat.2010.02.064
[31]	REZA R, AHMARUZZAMAN M, SIL A, et al. Comparative adsorption behavior of ibuprofen and clofibric acid onto microwave assisted activated bamboo waste[J]. Industrial & Engineering Chemistry Research,2014,53(22):9331-9339.
[32]	赵华轩, 郎印海. 磁性生物炭对水中CIP和OFL的吸附行为和机制[J]. 环境科学, 2018, 39(8):3729-3735. ZHAO H X, LANG Y H. Behaviors and mechanisms of CIP and OFL adsorption by magnetic biochar[J]. Environmental Science,2018,39(8):3729-3735(in Chinese).
[33]	崔颖, 孙国峰, 任苏瑜, 等. 锆基MOF材料用于水中抗生素的吸附研究[J]. 环境科学与技术, 2019, 42(3):103-108. CUI Y, SUN G F, REN S Y, et al. Zrconium-based MOFs for antibiotics adsorption in water[J]. Environmental Science & Technology,2019,42(3):103-108(in Chinese).
[34]	ZHU C, LANG Y, LIU B, et al. Ofloxacin adsorption on chitosan/biochar composite: Kinetics, isotherms, and effects of solution chemistry[J]. Polycyclic Aromatic Compounds,2018:1-11.
[35]	李鹤然, 宋立娜, 胡贝贝, 等. 介孔硅材料MCM41对盐酸左氧氟沙星的吸附行为[J]. 沈阳药科大学学报, 2017, 34(4):285-289+296. LI H R, SONG L N, HU B B, et al. Experimental and kinetic studies on levofloxacin hydrochloride adsorption by MCM41[J]. Journal of Shenyang Pharmaceutical University,2017,34(4):285-289+296(in Chinese).
[36]	王新欣, 孟昭福, 刘欣, 等. BS-18两性修饰膨润土对四环素和诺氟沙星复合污染的吸附[J]. 环境科学, 2020, 3:1-11. WANG X X, MENG Z F, LIU X, et al. Adsorption of BS-18 amphoterically modified bentonite to tetracycline and norfloxacin combined pollutants[J]. Environmental Science,2020,3:1-11(in Chinese).
[37]	鲁浩, 杜姣姣, 肖剑, 等. 霍州和兴和褐煤的热溶解聚及其有机氧的赋存形态[J]. 燃料化学学报, 2018, 46(8):897-904. doi: 10.3969/j.issn.0253-2409.2018.08.001 LU H, DU J J, XIAO J, et al. Thermal dissolution of Huozhou and Xinghe lignites and the occurrence forms of organic oxygen in them[J]. Journal of Fuel Chemistry and Technology,2018,46(8):897-904(in Chinese). doi: 10.3969/j.issn.0253-2409.2018.08.001
[38]	李忠, 文春梅, 郑华艳, 等. 载体表面性质对Cu₂O/AC催化剂结构和活性的影响[J]. 高等学校化学学报, 2010, 31(1):145-152. LI Z, WEN C M, ZHENG H Y, et al. Effects of the active carbon surface properties on the structure and catalytic activity of Cu₂O/AC catalyst[J]. Chemical Journal of Chinese Universities,2010,31(1):145-152(in Chinese).
[39]	CHIANG Y C, LEE C Y, LEE H C. Surface chemistry of polyacrylonitrile-and rayon-based activated carbon fibers after post-heat treatment[J]. Materials Chemistry and Physics,2007,101(1):199-210. doi: 10.1016/j.matchemphys.2006.03.007
[40]	WANG T Q, JIANG Z F, AN T C, et al. Enhanced visible-light-driven photocatalytic bacterial inactivation by ultrathin carbon-coated magnetic cobalt ferrite nanoparticles[J]. Environmental science & technology,2018,52(8):4774-4784.
[41]	胡强, 熊志波, 白鹏, 等. 铈钛掺杂促进铁氧化物低温SCR脱硝性能的机理[J]. 中国环境科学, 2016, 36(8):2304-2310. doi: 10.3969/j.issn.1000-6923.2016.08.009 HU Q, XIONG Z B, BAI P, et al. Promotional mechanism of cerium oxide and titanium oxide doping on the low-temperature NH₃-SCR activity of iron oxide[J]. China Environmental Science,2016,36(8):2304-2310(in Chinese). doi: 10.3969/j.issn.1000-6923.2016.08.009