普鲁士蓝/生物炭材料的制备及其氨氮吸附机理

doi:10.15541/jim20220432

无机材料学报 ›› 2023, Vol. 38 ›› Issue (2): 205-212.DOI: 10.15541/jim20220432

普鲁士蓝/生物炭材料的制备及其氨氮吸附机理

于业帆¹(), 徐玲², 倪忠斌¹, 施冬健¹, 陈明清¹()

1.江南大学化学与材料工程学院, 合成与生物胶体教育部重点实验室, 无锡 214122
2.杭州市生态环境局富阳分局, 杭州 311400

收稿日期:2022-07-22 修回日期:2022-10-08 出版日期:2023-02-20 网络出版日期:2022-10-19
通讯作者: 陈明清, 教授. E-mail: mqchen@jiangnan.edu.cn
作者简介:于业帆(1997-), 男, 硕士研究生. E-mail: 6190606052@stu.jiangnan.edu.cn
基金资助:
国家自然科学基金(21571084)

Prussian Blue Modified Biochar: Preparation and Adsorption of Ammonia Nitrogen from Sewage

YU Yefan¹(), XU Ling², NI Zhongbing¹, SHI Dongjian¹, CHEN Mingqing¹()

1. Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, China
2. Fuyang Branch, Hangzhou Municipal Ecology and Environment Bureau, Hangzhou 311400, China

Received:2022-07-22 Revised:2022-10-08 Published:2023-02-20 Online:2022-10-19
Contact: CHEN Mingqing, professor. E-mail: mqchen@jiangnan.edu.cn
About author:YU Yefan (1997-), male, Master candidate. E-mail: 6190606052@stu.jiangnan.edu.cn
Supported by:
National Natural Science Foundation of China(21571084)

摘要/Abstract

摘要：

以氮、磷污染物导致的水体富营养化问题在我国普遍存在。本研究将普鲁士蓝与改性生物炭相结合, 得到普鲁士蓝/生物炭复合材料。通过多种表征手段研究了复合材料的形貌及结构并通过模拟废水测试了其吸附性能。结果表明, 复合材料在pH 8时达到最佳吸附效果, 氨氮去除率在95%以上, 最大吸附量为24.4 mg/g, 比未改性生物碳提高101.3%。对复合材料吸附机理的研究表明, 复合材料通过普鲁士蓝对氨氮的配位作用对多组分污水中氨氮实现了选择性吸附。此外, 复合材料在外加H₂O₂溶液的条件下可形成芬顿氧化体系, 能实现同步催化降解有机污染物和促进氨氮的吸附, 因此有望在多组分富营养化污水治理中投入实际应用。

关键词: 生物炭材料, 普鲁士蓝纳米粒子, 氨氮吸附, 芬顿氧化反应

Abstract:

Eutrophication caused by nitrogen, phosphorus and organic pollutants is a common problem which has attracted much attention in China. Ammonia nitrogen, as a main pollutant, should be removed efficiently to avoid the extension of eutrophication. In this research, Prussian Blue (PB), which can not only capture ammonia nitrogen by vacancy in crystal cell but also degrade organic pollutants by Fenton oxidation, was combined with modified biochar to increase efficiency of ammonia nitrogen removal. Several characterization methods were used to investigate the structure and morphologies of the biochar composite. Adsorption capacity of biochar composite material (BC700-PB) was tested by NH₄Cl solution. The results show that the maximum adsorption capacity to ammonia nitrogen is 24.4 mg/g and the removal efficiency is over 95% within 60 min under the condition of pH 8, which is 101.3% higher than that of the unmodified biochar. The adsorption mechanism of BC700-PB was investigated with Langmuir model and pseudo-second-order kinetic equation which reveal that the adsorption including physical adsorption by biochar and coordination adsorption by PB. Meanwhile, Fenton oxidation process is conducted by PB nanoparticles in the biochar composite material with existence of H₂O₂. The biochar composite material could catalyze H₂O₂ to generate •OH, and achieve degradation of organic pollutants and adsorption of ammonia nitrogen. The PB/biochar composite material can be recycled easily by NaCl solution for several times. In conclusion, the PB/biochar composite is a promising material for eliminating multi-component eutrophication wastewater.

Key words: biochar material, prussian blue nanoparticles, ammonia nitrogen adsorption, Fenton oxidation process

中图分类号:

TQ424

于业帆, 徐玲, 倪忠斌, 施冬健, 陈明清. 普鲁士蓝/生物炭材料的制备及其氨氮吸附机理[J]. 无机材料学报, 2023, 38(2): 205-212.

YU Yefan, XU Ling, NI Zhongbing, SHI Dongjian, CHEN Mingqing. Prussian Blue Modified Biochar: Preparation and Adsorption of Ammonia Nitrogen from Sewage[J]. Journal of Inorganic Materials, 2023, 38(2): 205-212.

图/表 9

图1 BC700 (a)和BC700-PB (b)的SEM照片, BC700 (c)和BC700-PB (d)的TEM照片

Fig. 1 SEM images of BC700 (a) and BC700-PB (b), and TEM images of BC700 (c) and BC700-PB (d)

图2 BC700和BC700-PB的氮气吸脱附曲线(a)和孔径分布图(b)

Fig. 2 N2 adsorption-desorption curves (a) and pore size distributions (b) of BC700 and BC700-PB

图3 BC700-PB和BC700的XRD图谱(a)和红外光谱图(b)

Fig. 3 XRD patterns (a) and FT-IR spectra (b) of BC700-PB and BC700

图4 BC700和BC700-PB的XPS全谱(a), BC700(b, d)和BC700-PB (c, e)的C1s(b, c)与O1(d, e)与BC700-PB的N1s(f)XPS谱图

Fig. 4 Full XPS spectra (a) of BC700 and BC700-PB, core-level XPS spectra of the elemental C1s (b, c) and O1s (d, e) of BC700 (b, d) and BC700-PB (c, e), and N1s (f) of BC700-PB Colorful figures are available on website

图5 BC700和BC700-PB添加量对吸附氨氮效果的影响(a)(pH 8, C0=50 mg/L, t=60 min), 和体系pH(b)(dosage=5 g/L, C0=50 mg/L, t=60 min)、在不同共存离子(50 mg/L)中污染物初始浓度(c)(dosage=5 g/L, pH 8, t=60 min)以及反应时间(d)(dosage=5 g/L, pH 8, C0=50 mg/L)对BC700-PB吸附氨氮效果的影响

Fig. 5 Effect of dosage on the removal of NH3-N by of BC700 and BC700-PB (pH 8, C0=50 mg/L, t=60 min) (a), effects of pH (dosage=5 g/L, C0=50 mg/L, t=60 min) (b), initial concentration and coexisting ions (C0=50 mg/L, dosage=5 g/L, pH 8, t=60 min) (c), and reaction time(dosage=5 g/L, pH 8, C0=50 mg/L) (d) on the removal of NH3-N by BC700-PB

图6 BC700-PB对氨氮的吸附和催化示意图

Fig. 6 Schematic diagram of adsorption and catalysis removal of ammonia nitrogen by BC700-PB

图7 BC700-PB对氨氮的吸附热力学的Langmuir模型(a)和Freundlich模型(b)拟合; BC700-PB对氨氮的吸附动力学的拟一级动力学模型(c)和拟二级动力学模型(d)拟合

Fig. 7 Langmuir (a) and Freundlich models (b) of NH3-N on BC700-PB, and pseudo-first-order kinetic (c) and pseudo-second-order kinetic (d) models of NH3-N on BC700-PB

图8 BC700-PB的循环吸附性能(pH 8, dosage=5 g/L, C0= 50 mg/L)

Fig. 8 Recycling removal property of BC700-PB (pH 8, dosage=5 g/L, C0=50 mg/L)

图9 不同吸附剂、添加剂对氨氮和HA双组分污水的吸附效果的影响(pH 2, dosage=5 g/L, C0=50 mg/L) (a)和BC700-PB体系中添加了DMPO的EPR谱图(b)

Fig. 9 Effects of adsorbents and additive on the removal efficiency for mixed solution of NH3-N and HA(pH 2, dosage=5 g/L, C0=50 mg/L) (a), and EPR spectra of DMPO-OH (b) adducts in the systems of BC700-PB

参考文献 25

[1]	LIN S, SHEN S L, ZHOU A, et al. Assessment and management of lake eutrophication: a case study in Lake Erhai, China. Science of The Total Environment, 2020, 751(1): 141618. DOI URL
[2]	SHENG K, ZHANG P, OU S J, et al. Spatiotemporal nutrient patterns, composition, and implications for eutrophication mitigation in the Pearl River Estuary, China. Estuarine, Coastal and Shelf Science, 2022, 266(5): 107749. DOI URL
[3]	HUANG W, ZHANG Y, LI D. Adsorptive removal of phosphate from water using mesoporous materials: a review. Journal of Environmental Management, 2017, 193(15): 470. DOI PMID
[4]	ZHANG M, SONG G, GELARDI D L, et al. Evaluating biochar and its modifications for the removal of ammonium, nitrate, and phosphate in water. Water Research, 2020, 186(1): 116303. DOI URL
[5]	LU Y, CAI Y, ZHANG S, et al. Application of biochar-based photocatalysts for adsorption-(photo)degradation/reduction of environmental contaminants: mechanism, challenges and perspective. Biochar, 2022, 4: 45. DOI URL
[6]	QIU M, LIU L, LING Q, et al. Biochar for the removal of contaminants from soil and water: a review. Biochar, 2022, 4: 19. DOI URL
[7]	LIANG L, XI F, TAN W, et al. Review of organic and inorganic pollutants removal by biochar and biochar-based composites. Biochar, 2021, 3(1): 255. DOI URL
[8]	GONG Y P, NI Z Y, XIONG Z Z, et al. Phosphate and ammonium adsorption of the modified biochar based on Phragmites australis after phytoremediation. Environmental Science & Pollution Research, 2017, 24(9): 8326.
[9]	YI A, MP A, MVSA B, et al. A SAXS study of the pore structure evolution in biochar during gasification in H₂O, CO₂ and H₂O/CO₂. Fuel, 2021, 292: 120384. DOI URL
[10]	XIAO Y, WU Z J, CUI M, et al. Co-modification of biochar and bentonite for adsorption and stabilization of Pb²⁺ ions. Journal of Inorganic Materials, 2021, 36(10): 1083. DOI
[11]	ANDREAS L. Prussian blue, an inorganic evergreen. Journal of Chemical Education, 1981, 58(12): 1013. DOI URL
[12]	LIN H, FANG Q, WANG W, et al. Prussian blue/PVDF catalytic membrane with exceptional and stable Fenton oxidation performance for organic pollutants removal. Applied Catalysis B: Environmental. 2020, 273(15): 119047. DOI URL
[13]	TAKAHASHI A, TANAKA H, PARAJULI D, et al. Historical pigment exhibiting ammonia gas capture beyond standard adsorbents with adsorption sites of two kinds. Journal of the American Chemical Society, 2016, 138(20): 6376. DOI PMID
[14]	TAKAHASHI A, MINAMI K, NODA K, et al. Trace ammonia removal from air by selective adsorbents reusable with water. ACS Applied Materials and Interfaces, 2020, 12(13): 15115. DOI URL
[15]	WAN S, QIU L, TANG G, et al. Ultrafast sequestration of cadmium and lead from water by manganese oxide supported on a macro-mesoporous biochar. Chemical Engineering Journal, 2020, 387(1): 124095. DOI URL
[16]	HUFF M D, LEE J W. Biochar-surface oxygenation with hydrogen peroxide. Journal of Environmental Management, 2016, 165(1): 17. DOI PMID
[17]	ZHAO G, FENG J J, ZHANG Q L, et al. Synthesis and characterization of Prussian blue modified magnetite nanoparticles and its application to the electrocatalytic reduction of H₂O₂. Journal of Materials Chemistry, 2005, 17(12): 3154. DOI URL
[18]	FENG S S, CAO X, ZHENG W, et al. In-situ formed Prussian blue nanoparticles supported by porous biochar as highly efficient removal of cesium ions. Journal of Environmental Chemical Engineering, 2022, 10(3): 107972. DOI URL
[19]	AI J, LU C, BERG F, et al. Biochar catalyzed dichlorination-which biochar properties matter. Journal of Hazardous Materials, 2021, 406(15): 124724. DOI URL
[20]	CHEN L, CHEN X L, ZHOU C H, et al. Environmental-friendly montmorillonite-biochar composites: facile production and tunable adsorption-release of ammonium and phosphate. Journal of Cleaner Production, 2017, 156(10): 648. DOI URL
[21]	SIZMUR T, FRESNO T, AKGUL G, et al. Biochar modification to enhance sorption of inorganics from water. Bioresource Technology, 2017, 246: 34. DOI PMID
[22]	CUI X, HAO H, HE Z, et al. Pyrolysis of wetland biomass waste: potential for carbon sequestration and water remediation. Journal of Environmental Management, 2016, 173(15): 95. DOI PMID
[23]	YIN L A, NT A, TKL A, et al. Microwave assisted hydrothermal preparation of rice straw hydrochars for adsorption of organics and heavy metals. Bioresource Technology, 2019, 273: 136. DOI PMID
[24]	LI L, LAI C, HUANG F, et al. Degradation of naphthalene with magnetic bio-char activate hydrogen peroxide: synergism of bio-char and Fe-Mn binary oxides. Water Research, 2019, 160(1): 238. DOI PMID
[25]	SUN Y M, ZHOU P, ZHANG P, et al. New insight into carbon materials enhanced Fenton oxidation: a strategy for green iron(III)/ iron(II) cycles. Chemical Engineering Journal, 2022, 450(15): 138423. DOI URL

普鲁士蓝/生物炭材料的制备及其氨氮吸附机理

Prussian Blue Modified Biochar: Preparation and Adsorption of Ammonia Nitrogen from Sewage

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