TiO2改性石墨烯电极电吸附去除污水中NH4+

doi:10.11949/0438-1157.20200092

摘要/Abstract

摘要：

通过水热法制备得到TiO₂改性石墨烯复合材料（RGO/TiO₂），考察了其形貌结构和电化学性能。将其组装成电极，对比未改性石墨烯（RGO）电极和RGO/TiO₂电极的电吸附NH₄⁺性能。重点考察外加电压、循环流速、初始浓度等工艺参数对RGO/TiO₂电极电吸附NH₄⁺的影响，并对其电吸附NH₄⁺特性和对模拟实际含NH₄⁺废水深度脱NH₄⁺效果进行研究。结果表明：RGO/TiO₂复合材料具有三维孔洞结构，比表面积为382.08 m²·g^-1，比电容量在扫速为0.01 V·s^-1时达到325.80 F·g^-1，优于RGO材料。RGO/TiO₂电极的初次电吸附量较RGO电极提升了28.3%，循环再生吸附10次后，RGO/TiO₂电极的NH₄⁺吸附量仅降低了5.87%，循环再生吸附性能优于RGO电极。外加电压2.0 V、循环流速35 ml·min^-1和NH₄⁺初始浓度1.0 mmol·L^-1为RGO/TiO₂电极的最佳NH₄⁺电吸附条件。RGO和RGO/TiO₂电极电吸附NH₄⁺过程符合准一级动力学模型和Freundlich等温吸附模型，电吸附NH₄⁺为非均匀表面的多层吸附行为，以物理吸附为主。RGO/TiO₂电极4级串联时对模拟实际含NH₄⁺炼油净化水的去除率达到86.84%。

关键词: 石墨烯, TiO₂, 复合材料, 电吸附, NH₄⁺

Abstract:

In this study, the TiO₂ modified graphene composite material (RGO/ TiO₂) was prepared by hydrothermal method, and its morphological structure and electrochemical properties were investigated. Then RGO/TiO₂ material was assembled into electrode, and NH₄⁺ ions electrosorption efficiencies of unmodified graphene (RGO) electrode and the RGO/TiO₂ electrode were compared. The effects of applied voltage, circulating velocity and initial concentration on NH₄⁺ ions electrosorption by RGO/TiO₂ electrode were investigated. The characteristics of NH₄⁺ ions electrosorption and the effect of advanced NH₄⁺ ions removal from simulated actual wastewater containing NH₄⁺ ions were also studied. The results showed that the RGO/TiO₂ composite material had a three-dimensional pore structure with specific surface area of 382.08 m²·g^-1 and specific capacitance of 325.80 F·g^-1 at a scan rate of 0.01 V·s^-1, which were better than those of the RGO material. The initial adsorption capacity of RGO/TiO₂ electrode was 28.3% higher than that of RGO electrode. After 10 cycles of regeneration adsorption, the adsorption capacity of NH₄⁺ ions of RGO/TiO₂ electrode only decreased 5.87%, and its cyclic regeneration adsorption property was better than that of RGO electrode. In addition, the applied voltage 2.0 V, circulating velocity 35 ml·min^-1 and initial concentration 1.0 mmol·L^-1 were the optimal NH₄⁺ ions electrosorption conditions for RGO/TiO₂ electrode. The electrosorption process of NH₄⁺ ions by RGO and RGO/TiO₂ electrodes was in accordance with the quasi-first-order kinetic model and the Freundlich isothermal adsorption model. The electrosorption of NH₄⁺ions was a multi-layer adsorption behavior on heterogeneous surface and physical adsorption was the dominant. When the RGO/TiO₂ electrode was connected in 4-stage series, the removal efficiency of simulated actual NH₄⁺refining purified water reached 86.84%.

Key words: graphene, TiO₂, composites, electrosorption, NH₄⁺

中图分类号:

X 703.1

皋海岭,徐斌,高月香,朱月明,张松贺,张毅敏. TiO₂改性石墨烯电极电吸附去除污水中NH₄⁺[J]. 化工学报, 2020, 71(11): 5309-5319.

Hailing GAO,Bin XU,Yuexiang GAO,Yueming ZHU,Songhe ZHANG,Yimin ZHANG. Removal of ammonium ions in wastewater by electrosorption with TiO₂ modified graphene electrode[J]. CIESC Journal, 2020, 71(11): 5309-5319.

图/表 17

图1 电吸附测试装置

Fig.1 Electrosorption test device

图2 CDI单元模块

Fig.2 CDI unit module

图3 RGO和RGO/TiO2的SEM、EDS和TEM图

Fig.3 SEM, EDS and TEM images of RGO and RGO/TiO2

图4 RGO和RGO/TiO2的N2吸脱附曲线

Fig.4 Nitrogen adsorption-desorption isotherms of RGO and RGO/TiO2

图5 RGO和RGO/TiO2的XRD谱图

Fig.5 XRD patterns of RGO and RGO/TiO2

图6 RGO和RGO/TiO2的XPS全谱图(a)，RGO/TiO2的Ti 2p高分辨谱图(b)

Fig.6 XPS survey of RGO and RGO/TiO2 (a), high resolution Ti 2p spectra of RGO/TiO2 (b)

图7 RGO和RGO/TiO2在不同扫描速率下的CV曲线

Fig.7 The CV curves of RGO and RGO/TiO2 at different scan rates

图8 RGO和RGO/TiO2在1 A·g-1电流密度下的恒电流充放电曲线

Fig.8 Galvanostatic charge-discharge curves of RGO and RGO/TiO2 at a current density of 1 A·g-1

图9 RGO和RGO/TiO2 电极的循环再生吸附性能

Fig.9 Regenerated electrosorptive capacities of RGO and RGO/TiO2 electrodes

图10 外加电压对RGO/TiO2电极电吸附NH4+的去除率和吸附量的影响

Fig.10 Effect of applied voltage on removal efficiency and electrosorption capacity of NH4+ by RGO/TiO2 electrode

图11 循环流速对RGO/TiO2电极去除NH4+的去除率和吸附量的影响 (a)；不同循环流速下RGO/TiO2电极电吸附NH4+的浓度变化 (b)

Fig.11 Effect of circulating velocity on removal efficiency and electrosorption capacity of NH4+ by RGO/TiO2 electrode (a); Electrosorption concentration changes of NH4+ by RGO/TiO2 electrode under different circulating velocities (b)

图12 初始浓度对RGO/TiO2 电极电吸附NH4+的去除率和吸附量的影响

Fig.12 Effect of initial concentration on removal efficiency and electrosorption capacity of NH4+ by RGO/TiO2 electrode

表1 RGO和RGO/TiO2电极电吸附NH4+的Freundlich模型拟合结果

Table 1 Fitting results of Freundlich models for NH4+ removal by RGO and RGO/TiO2 electrodes

样品	K_F	1/n	R²
RGO	7.545	0.436	0.995
RGO/TiO₂	9.914	0.332	0.998

图13 RGO (a)和RGO/TiO2 (b)电极的Freundlich模型线性拟合

Fig.13 Linear fitting of Freundlich model for RGO (a) and RGO/TiO2 (b) electrodes

表2 RGO和RGO/TiO2电极电吸附NH4+准一级动力学模型拟合结果

Table 2 Fitting results of quasi-first-order kinetic model for NH4+ removal by RGO and RGO/TiO2 electrodes

电压/V	RGO			RGO/TiO₂
电压/V	K₁	q_e/ (mg·g^-1)	R²	K₁	q_e/ (mg·g^-1)	R²
1.4	0.249	3.70	0.999	0.138	4.62	0.998
1.6	0.160	4.67	0.998	0.107	5.21	0.991
1.8	0.174	5.00	0.995	0.101	5.56	0.994
2.0	0.107	6.51	0.993	0.053	8.61	0.996

图14 RGO (a)和RGO/TiO2 (b)电极的准一级动力学模型拟合

Fig.14 Fitting of the quasi-first-order kinetic model for RGO (a) and RGO/TiO2 (b) electrodes

图15 RGO/TiO2电极电吸附模拟实际含NH4+炼油净化水的处理效果

Fig.15 Effect of electrosorption treatment of simulated actual NH4+ refining purified water by RGO/TiO2 electrode

参考文献 28

1	Güerena D, Lahman J, Hanley K, et al. Nitrogen dynamics following field application of biochar in a temperate North American maize-based production system[J]. Plant and Soil, 2013, 365(1/2): 239-254.
2	Buss S R, Herbert A W, Morgan P, et al. A review of ammonium attenuation in soil and groundwater[J]. Quarterly Journal of Engineering Geology and Hydrogeology, 2004, 37(4): 347-359.
3	Bouwer H. Agricultural contamination: problems and solutions[J]. Water Environment and Technology, 1989, 1(2): 292-297.
4	El-Deen A G, Choi J H, Kim C S, et al. TiO₂ nanorod-intercalated reduced graphene oxide as high performance electrode material for membrane capacitive deionization[J]. Desalination, 2015, 361(1): 53-64.
5	刘琳, 李莹, 鄂涛, 等. 球状纳米二氧化钛/石墨烯复合材料的合成及导电性能[J]. 材料工程, 2019, 47(8): 97-102.
	Liu L, Li Y, E T, et al. Synthesis and electrical conductivity of spherical nano-TiO₂/graphene composites[J]. Journal of Materials Engineering, 2019, 47(8): 97-102.
6	Hu X B, Yu Y, Hou W M, et al. Effects of particle size and ph value on the hydrophilicity of graphene oxide[J]. Applied Surface Science, 2013, 273(19): 118-121.
7	施周, 杨文浩, 杨灵芳, 等. 等离子改性CNT/TiO₂电极吸附去除水中苯酚的研究[J]. 中国环境科学, 2015, 35(9): 2664-2669.
	Shi Z, Yang W H, Yang L F, et al. Electrosorption of phenol in aqueous solution using a plasma-activated CNT/TiO₂ electrode[J]. China Environment Science, 2015, 35(9): 2664-2669.
8	李海红, 杨洁, 郭雅妮, 等. Al₂O₃/ACF复合电极材料的制备及性能表征[J]. 化工学报, 2015, 66(11): 4703-4709.
	Li H H, Yang J, Guo Y N, et al. Preparation and properties characterization of Al₂O₃/ACF composite electrode materials[J]. CIESC Journal, 2015, 66(11): 4703-4709.
9	Fan C S, Tseng S C, Li K C, et al. Electro-removal of arsenic(Ⅲ) and arsenic(Ⅴ) from aqueous solutions by capacitive deionization[J]. Journal of Hazardous Materials, 2016, 312(15): 208-215.
10	胡瑞兵. 介孔RGO/TiO₂复合材料的制备及其对盐酸四环素光催化活性研究[D]. 兰州: 兰州理工大学, 2018.
	Hu R B. Preparation and photocatalytic activity for tetracycline hydrochloride of mesoporous RGO/TiO₂ composite[D]. Lanzhou: Lanzhou University of Technology, 2018.
11	Zhou Y H, Liu C J, Li Y, et al. Platinum nanoparticles supported on noncovalent functionalized graphene as cathode catalysts for aluminum-air batteries[J]. Advanced Materilas Research, 2013, 800(1): 526-530.
12	王瑶, 吉庆华, 李永峰, 等. 石墨烯凝胶电极的制备及电吸附Pb^{2 +}的性能[J]. 环境科学, 2017, 38(9): 3747-3754.
	Wang Y, Ji Q H, Li Y F, et al. Preparation and Pb²⁺ electrosorption characteristics of graphere hydrogels electrode[J]. Environmental Science, 2017, 38(9): 3747-3754.
13	Wang D, Zhou Z H, Yang H, et al. Preparation of TiO₂ loaded with crystalline nano-Ag by a one-step low-temperature hydrothermal method[J]. Journal of Materials Chemistry, 2012, 22(32): 16306-16311.
14	Chen Q, Zhou M, Zhang Z M, et al. Preparation of TiO₂ nanotubes/reduced graphene oxide binary nanocomposites enhanced photocatalytic properties[J]. Journal of Materials Science Materials in Electronics, 2017, 28(13): 9416-9422.
15	Liu L, Luo C, Xiong J, et al. Reduced graphene oxide (rGO) decorated TiO₂, microspheres for visible-light photocatalytic reduction of Cr(Ⅵ)[J]. Journal of Alloys and Compounds, 2016, 690(8): 771-776.
16	张朕. 膜电容去离子技术去除废水中无机态氮的研究[D]. 天津: 天津科技大学, 2017.
	Zhang Z. Study on the removal of inorganic nitrogen from wastewater by membrane capacitive deionization[D]. Tianjin: Tianjin University of Science and Technology, 2017.
17	金肇岩, 胡筱敏, 孙通, 等. 脉冲电吸附技术深度脱氮及分子动力学模拟[J]. 中国环境科学, 2019, 39(7): 2871-2879.
	Jin Z Y, Hu X M, Sun T, et al. Capacitive deionization using a pulse power supply for depth denitrogenation and molecular dynamics simulation[J]. China Environment Science, 2019, 39(7): 2871-2879.
18	徐乐乐. 多孔炭材料的制备及其电容法脱盐性能研究[D]. 北京: 北京化工大学, 2015.
	Xu L L. Study on preparation and capacitive desalination performance of porous carbon materials[D]. Beijing: Beijing University of Chemical Technology, 2015.
19	施周, 靳兆祺, 邓林, 等. CNT/PANI电极吸附去除水中Cu²⁺的研究[J]. 中国环境科学, 2016, 36(12): 3650-3656.
	Shi Z, Jin Z Q, Deng L, et al. Electrosorption of Cu²⁺ in aqueous solution using CNT/PANI electrodes[J]. China Environmental Science, 2016, 36(12): 3650-3656.
20	周贵忠, 王兆丰, 王绚, 等. 石墨-活性炭纤维复合电极电吸附处理含盐废水的研究[J]. 环境科学, 2014, 35(5): 1832-1837.
	Zhou G Z, Wang Z F, Wang X, et al. Research on treatment of high salt wastewater by the graphite and activated carbon fiber composite electrodes[J]. Environmental Science, 2014, 35(5): 1832-1837.
21	赵研. 强化电容去离子脱盐的实验与机理研究[D]. 沈阳: 东北大学, 2015.
	Zhao Y. Performance and mechanism of improvement to desalination with capacitive deionization[D]. Shenyang: Northeastern University, 2015.
22	Wimalasiri Y, Mossad M, Zou L. Thermodynamics and kinetics of adsorption of ammonium ions by graphene laminate electrodes in capacitive deionization[J]. Desalination, 2015, 357(11): 178-188.
23	石胜启, 王越, 徐世昌, 等. 石墨带电极电容性脱盐试验研究[J]. 水处理技术, 2013, 39(1): 29-32.
	Shi S Q, Wang Y, Xu S C, et al. Experimental study on capacitive deionization of graphite ribbon electrode[J]. Technology of Water Treatment, 2013, 39(1): 29-32.
24	Liu P Y, Wang H, Yan T T, et al. Grafting sulfonic and amine functional groups on 3D graphene for improved capacitive deionization[J]. Journal of Materials Chemistry A, 2016, 4(14): 5303-5313.
25	Liu J, Li W Y, Liu Y G, et al. Titanium(Ⅳ) hydrate based on chitosan template for defluoridation from aqueous solution[J]. Applied Surface Science, 2014, 293(12): 46-54.
26	Chao Y H, Zhu W S, Wu X Y, et al. Application of graphene-like layered molybdenum disulfide and its excellent adsorption behavior for doxycycline antibiotic[J]. Chemical Engineering Journal, 2014, 243(12): 60-67.
27	孟晗. 氧化石墨烯复合材料的制备及其对铅离子的吸附性能研究[D]. 南京: 南京理工大学, 2017.
	Meng H. Study on the preparation of graphere oxide composite and adsorption performances for Pb(Ⅱ) ions[D]. Nanjing: Nanjing University of Science and Technology, 2017.
28	刘方园, 胡承志, 李永峰, 等. MnO₂/CFP复合电极的制备及电吸附Pb^{2 +}特性的研究[J]. 环境科学, 2015, 36(2): 552-558.
	Liu F Y, Hu C Z, Li Y F, et al. Preparation and Pb²⁺ electrosorption characteristics of MnO₂ /CFP composite electrode[J]. Environmental Science, 2015, 36(2): 552-558.

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TiO₂改性石墨烯电极电吸附去除污水中NH₄⁺

Removal of ammonium ions in wastewater by electrosorption with TiO₂ modified graphene electrode

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