电吸附技术及吸附电极材料研究进展

doi:10.11949/0438-1157.20201019

摘要/Abstract

摘要：

电吸附技术得益于环保、清洁、简单和节能的技术优势，在海水脱盐淡化及污染物吸附处理领域具有重要的应用潜力。如何构建高电荷容量的吸附电极是构建高效电吸附装置、提高吸附效率的关键所在。本文从电吸附技术原理出发，介绍了电吸附技术吸附储存离子的双电层理论模型，并对电吸附技术的研究进展进行了总结。随后从吸附电极材料制备角度对碳吸附电极、层状金属氧化物吸附电极、复合型吸附电极分别进行综述，对每一类电极材料特点及不足进行了总结，归纳分析了针对各类材料不足之处的解决方案，并基于高效电吸附技术实际应用目标，对吸附电极材料的设计制备进行了展望。

关键词: 电吸附技术, 双电层, 碳材料吸附电极, 层状金属氧化物电极, 复合型吸附电极

Abstract:

Due to the technical advantages of eco-friendly cleanliness, simplicity and energy saving, electrosorption technology has important application potential in the fields of seawater desalination and pollutant adsorption treatment. The key of high-efficiency electro-sorption and high adsorption capacity for ions is how to construct adsorption electrode with a high charge capacity. In this paper, the theoretical model of double layer for ions adsorption and storage by electro-sorption technology was introduced based on the principle of electro-sorption technology, and the research progress of electro-sorption technology was summarized as well. Next, the carbon adsorption electrode, metal oxide adsorption electrode and composite adsorption electrode were reviewed from the point of materials fabrication, respectively. It summarized the merits and deficiencies of each kind of electrode materials, and the proposed corresponding solutions for the deficiencies from researchers were also analyzed and summarized. With the goal of high-efficient practical application for electro-sorption technology, it also prospected the design and preparation of electrode materials.

Key words: electro-sorption technology, double layer, carbon electrode, layered metal oxide electrode, composite electrode

中图分类号:

TQ 028.8

卞维柏, 潘建明. 电吸附技术及吸附电极材料研究进展[J]. 化工学报, 2021, 72(1): 304-319.

BIAN Weibai, PAN Jianming. Research progress on electro-sorption technology and fabrication of adsorptive electrode materials[J]. CIESC Journal, 2021, 72(1): 304-319.

图/表 10

参考文献 87

1	Rosegrant M W, Cline S A. Global food security: challenges and policies[J]. Science, 2003, 302(5652): 1917-1919.
2	McGinnis R L, Elimelech M. Global challenges in energy and water supply: the promise of engineered osmosis[J]. Environ. Sci. Technol., 2008, 42(23): 8625-8629.
3	Lu X L, Castrillón S R V, Shaffer D L, et al. In situ surface chemical modification of thin-film composite forward osmosis membranes for enhanced organic fouling resistance[J]. Environ. Sci. Technol., 2013, 47(21): 12219-12228.
4	Hichour M, Persin F, Sandeaux J, et al. Fluoride removal from waters by donnan dialysis[J]. Sep. Purif. Technol., 1999, 18(1): 1-11.
5	Saha S. Treatment of aqueous effluent for fluoride removal[J]. Water Res., 1993, 27(8): 1347-1350.
6	Porada S, Zhao R, Wal A V D, et al. Review on the science and technology of water desalination by capacitive deionization[J]. Prog. Mater. Sci., 2013, 58(8): 1388-1442.
7	Kim C, Lee J, Kim S, et al. TiO₂ sol-gel spray method for carbon electrode fabrication to enhance desalination efficiency of capacitive deionization[J]. Desalination, 2014, 342: 70-74.
8	Lee J, Kim S, Yoon J. Rocking chair desalination battery based on prussian blue electrodes[J]. ACS Omega, 2017, 2(4): 1653-1659.
9	Liu Y, Xu X T, Wang M, et al. Metal-organic framework-derived porous carbon polyhedra for highly efficient capacitive deionization[J]. Chem. Commun., 2015, 51: 12020-12023.
10	LiuY, Lu T, Sun Z, et al. Ultra-thin carbon nanofiber networks derived from bacterial cellulose for capacitive deionization[J]. J. Mater. Chem. A., 2015, 3: 8693-8700.
11	Zhao C X, Zhang L F, Ge R S, et al. Treatment of low-level Cu(Ⅱ) wastewater and regeneration through a novel capacitive deionization-electrodeionization(CDI-EDI) technology[J]. Chemosphere, 2019, 217: 763-772.
12	Pierre A C, Pajonk G M. Chemistry of aerogels and their applications[J]. Chem. Rev., 2002, 102(11): 4243- 4266.
13	Wang G, Qian B Q, Dong Q, et al. Highly mesoporous activated carbon electrode for capacitive deionization[J]. Sep. Purif. Technol., 2013, 103: 216-221.
14	Zou L D, Li L X, Song H H, et al. Using mesoporous carbon electrodes for brackish water desalination[J]. Water Res., 2008, 42(8/9): 2340-2348.
15	Choi J H. Fabrication of a carbon electrode using activated carbon powder and application to the capacitive deionization process[J]. Sep. Purif. Technol., 2010, 70(3): 362-366.
16	Chen Z, Song C, Sun X, et al. Kinetic and isotherm studies on the electrosorption of NaCl from aqueous solutions by activated carbon electrodes[J]. Desalination, 2011, 267(2/3): 239-243.
17	Liu X, Zhou A, Pan T, et al. Ultrahigh-rate-capability of a layered double hydroxide supercapacitor based on a self-generated electrolyte reservoir[J]. J. Mater. Chem. A., 2016, 4: 8421-8427.
18	Cai J, Zhang Y, Pan B, et al. Efficient defluoridation of water using reusable nanocrystalline layered double hydroxides impregnated polystyrene anion exchanger[J]. Water Res., 2016, 102: 109-116.
19	Zou Y, Wang X, Wu F, et al. Controllable synthesis of Ca-Mg-Al layered double hydroxides and calcined layered double oxides for the efficient removal of U(Ⅵ) from wastewater solutions[J]. ACS Sustain. Chem. Eng., 2017, 5(1): 1173-1185.
20	Wan D, Liu H, Zhao X, et al. Role of the Mg/Al atomic ratio in hydrotalcite-supported Pd/Sn catalysts for nitrate adsorption and hydrogenation reduction[J]. J. Colloid Interf. Sci., 2009, 332(1): 151-157.
21	Yue C J, Xu Q N, Ping G L, et al. Ionic [Ru] complex with recyclability by electro-adsorption for efficient catalytic transfer hydrogenation of aryl ketones[J]. Pol. J. Chem.Technol., 2007, 19(4): 75-79.
22	Kang J, Kim T Y, Kyusik J, et al. Comparison of salt adsorption capacity and energy consumption between constant current and constant voltage operation in capacitive deionization[J]. Desalination, 2014, 352: 52-57.
23	Eran A, Malachi N, Yaniv B, et al. Limitations of charge efficiency in capacitive deionization processes (Ⅲ): the behavior of surface oxidized activated carbon electrodes[J]. Electrochim. Acta., 2010, 56(1): 441-447.
24	Oki T K, Kanae S J. Global hydrological cycles and world water resources[J]. Science, 2006, 313(5790): 1068-1072.
25	Tang W, Kovalsky P, Cao B, et al. Investigation of fluoride removal from low-salinity groundwater by single-pass constant-voltage capacitive deionization[J]. Water Res., 2016, 99: 112-121.
26	Wang S, Wang G, Wu T, et al. Membrane-free hybrid capacitive deionization system based on redox reaction for high-efficiency NaCl removal[J]. Environ. Sci. Technol., 2019, 53(11): 6292-6301.
27	Xu D, Tong Y, Yan T, et al. N, P-codoped meso-/microporous carbon derived from biomass materials via a dual-activation strategy as high-performance electrodes for deionization capacitors[J]. ACS Sustain. Chem. Eng., 2017, 5(7): 5810-5819.
28	Li Y, Hussain I, Qi J, et al. N-doped hierarchical porous carbon derived from hyper cross-linked diblock copolymer for capacitive deionization[J]. Sep. Purif. Technol., 2016, 165: 190-198.
29	Xie J, Xue Y, He M, et al. Organic-inorganic hybrid binder enhances capacitive deionization performance of activated-carbon electrode[J]. Carbon, 2017, 123: 574-582.
30	Bian Y H, Yang X F, Liang P, et al. Enhanced desalination performance of membrane capacitive deionization cells by packing the flow chamber with granular activated carbon[J]. Water Res., 2015, 85: 371-376.
31	Stern A. On the counter-transference in psychoanalysis[J]. Psychoanalytic Review, 1924, 11(2): 166-174.
32	吴旭冉, 贾志军, 马洪运, 等. 电化学基础(Ⅲ)——双电层模型及其发展[J]. 储能科学与技术, 2013, 2(2): 152-156.
	Wu X R, Jia Z J, Ma H Y, et al. Fundamentals of electrochemistry(Ⅲ): Electrical double layer model and its development[J]. Energy Storage Science and Technology, 2013, 2(2): 152-156.
33	Grahame D C. The electrical double layer and the theory of electrocapillarity[J]. Chem. Rev., 1947, 41(3): 441-501.
34	Zhang C, He D, Ma J, et al. Faradaic reactions in capacitive deionization(CDI)-problems and possibilities: a review[J]. Water Res., 2018, 128: 314-330.
35	Gao X, Omosebi A, Landon J, et al. Surface charge enhanced carbon electrodes for stable and efficient capacitive deionization using inverted dsorption-desorption behavior[J]. Energy Environ. Sci., 2015, 8(3): 897-909.
36	Yang J, Zou L D, Choudhury N R. Ion-selective carbon nanotube electrodes in capacitive deionisation[J]. Electrochim. Acta., 2013, 91: 11-19.
37	Zhao Y J, Wang Y, Wang R G, et al. Performance comparison and energy consumption analysis of capacitive deionization and membrane capacitive deionization processes [J]. Desalination, 2013, 324: 127-133.
38	Dutta S, Huang S Y, Chen C, et al. Cellulose framework directed construction of hierarchically porous carbons offering high-performance capacitive deionization of brackish water[J]. ACS Sustain. Chem. Eng., 2016, 4(4): 1885-1893.
39	Linneen N, Delnick F, Islam S Z, et al. Application of the macrohomogeneous line model for the characterization of carbon aerogel elec-trodes in capacitive deionization[J]. Electrochim. Acta., 2019, 301: 1-7.
40	Chang L, Hang Y. 3D Channel-structured graphene as efficient electrodes for capacitive deionization[J]. J. Colloid Interf. Sci., 2018, 538: 420-425.
41	Lee B, Park N, Kang K S, et al. Enhanced capacitive deionization by dispersion of CNTs in activated carbon electrode[J]. ACS Sustain. Chem. Eng., 2018, 6(2): 1572-1579.
42	Wang H T, Na C Z. Binder-free carbon nanotube electrode for electrochemical removal of chromium[J]. ACS Appl. Mater. Interf., 2014, 6(2): 20309-20316.
43	Liu P, Yan T, Shi L, et al. Graphene-based materials for capacitive deionization[J]. J. Mater. Chem. A, 2017, 5: 13907-13943.
44	Almarzooqi F A, Alghaferi A A, Saadat I, et al. Application of capacitive deionisation in water desalination: a review[J]. Desalination, 2014, 342: 3-15.
45	Landon J, Gao X, Kulengowski B, et al. Impact of pore size characteristics on the electrosorption capacity of carbon xerogel electrodes for capacitive deionization[J]. J. Electrochem. Soc., 2012, 159(11): 1861-1866.
46	Wang G, Qian B Q, Dong Q, et al. Highly mesoporous activated carbon electrode for capacitive deionization[J]. Sep. Purif. Technol., 2013, 103: 216-221.
47	Li H, Gao Y, Pan L, et al. Electrosorptive desalination by carbon nanotubes and nanofibres electrodes and ion-exchange membranes[J]. Water Res., 2008, 42(20): 4923-4928.
48	Wang L, Wang M, Huang Z H, et al. Capacitive deionization of NaCl solutions using carbon nanotube sponge electrodes[J]. J. Mater. Chem., 2011, 21: 18295-18299.
49	Zhao R, Biesheuvel P M, Miedema H, et al. Charge efficiency: a functional tool to probe the double-layer structure inside of porous electrodes and application in the modeling of capacitive deionization[J]. J. Phys. Chem. Lett., 2010, 1(1): 205-210.
50	Huang Z H, Wang M, Wang L, et al. Relation between the charge efficiency of activated carbon fiber and its desalination performance[J]. Langmuir, 2012, 28: 5079- 5084.
51	Farmer J C, Fix D V, Mack G V, et al. Capacitive deionization of NaCI and NaNO₃ solutions with carbon aerogel electrodes[J]. J. Electrochem. Soc., 1996, 143: 159-169.
52	Jia F, Sun K, Yang B, et al. Defect-rich molybdenum disulfide as electrode for enhanced capacitive deionization from water[J]. Desalination, 2018, 446: 21-30.
53	Biesheuvel P M, Suss M E, Hamelers H V M, et al. Theory of water desalination by porous electrodes with immobile chemical charge[J]. Colloid. Interfac. Sci., 2015, 9: 1-5.
54	Wu T T, Wang G, Zhan F, et al. Surface-treated carbon electrodes with modified potential of zero charge for capacitive deionization[J]. Water Res., 2016, 93: 30-37.
55	Liu P Y, Wang H, Yan T T, et al. Grafting sulfonic and amine functional groups on 3D graphene for improved capacitive deionization[J]. J. Mater. Chem. A., 2016, 4: 5303-5313.
56	Zhang J, Yan T, Fang J, et al. Enhanced capacitive deionization of saline water using N-doped rod-like porous carbon derived from dual-ligand metal-organic frame-works[J]. Environ. Sci.: Nano, 2020, 7(3): 926-937.
57	Gao T, Li H, Zhou F, et al. Mesoporous carbon derived from ZIF-8 for high efficient electrosorption[J]. Desalination, 2019, 451: 133-138.
58	Wang H, Wei D, Gang H, et al. Hierarchical porous carbon from the synergistic "Pore-on-Pore"strategy for efficient capacitive deionization[J]. ACS Sustainable Chem. Eng., 2020, 8(2): 1129-1136.
59	Chen Y, Li Z, Zhu Y, et al. Atomic Fe dispersed on N-doped carbon hollow nanospheres for high-efficiency electrocatalytic oxygen reduction[J]. Adv. Mater. 2019, 31(8): 1806312.
60	Li Y J, Liu Y, Wang M, et al. Phosphorus-doped 3D carbon nanofiber aerogels derived from bacterial-cellulose for highly-efficient capacitive deionization[J]. Carbon, 2018, 130: 377-383.
61	Liu Y, Chen T Q, Lu T, et al. Nitrogen-doped porous carbon spheres for highly efficient capacitive deionization[J]. Electrochim. Acta, 2015, 158: 403-409.
62	Liu X J, Liu H, Mi M J, et al. Nitrogen-doped hierarchical porous carbon aerogel for high-performance capacitive deionization[J]. Sep. Purif. Technol., 2019, 224: 44-50.
63	Wang G, Deng J, Yan, T, et al. Turning on electrocatalytic oxygen reduction by creating robust Fe-N_x species in hollow carbon frameworks viain-situ growth of Fe doped ZIFs on g-C₃N₄ [J]. Nanoscale, 2020, 12(9): 5601-5611.
64	Peng Y, Lu B, Chen S. Carbon-supported single atom catalysts for electrochemical energy conversion and storage[J]. Adv. Mater., 2018, 30(48): 1801995.
65	Wang G Z, Yan T T, Zhang J P, et al. Trace-Fe-enhanced capacitive deionization of saline water by boosting electron transfer of electro-adsorption sites[J]. Environ. Sci. Technol., 2020, 54(13): 8411-8419.
66	Zou Y, Wang X, Wu F, et al. Controllable synthesis of Ca-Mg-Al layered double hydroxides and calcined layered double oxides for the efficient removal of U(VI) from wastewater solutions[J]. ACS Sustain. Chem. Eng., 2017, 5: 1173-1185.
67	Lei C, Zhu X, Zhu B, et al. Superb adsorption capacity of hierarchical calcined Ni/Mg/Al layered double hydroxides for Congo red and Cr(VI) ions[J]. J. Hazard. Mater., 2017, 321: 801-811.
68	Li C M, Wei M, Evans D G, et al. Layered double hydroxide-based nanomaterials as highly efficient catalysts and adsorbents[J]. Small, 2014, 10: 4469-4486.
69	Yuan C, Li J, Hou L, et al. Ultrathin mesoporous NiCo₂O₄ nanosheets supported on Ni foam as advanced electrodes for super-capacitors[J]. Adv. Funct. Mater., 2012, 22: 4592-4597.
70	Xi W, Li H B. The pseudo-capacitive deionization behaviour of CuAl-mixed metal oxides[J]. Environ. Sci.: Water Res. Technol., 2020, 6: 296-302.
71	Bai Z Y, Hu C Z, Liu H J, et al. Selective adsorption of fluoride from drinking water using NiAl-layered metal oxide film electrode[J]. J. Colloid Interf. Sci., 2019, 539: 146-151.
72	Lei X D, Wang B, Liu J F, et al. Three-dimensional NiAl-mixed metal oxide film: preparation and capacitive deionization performances[J]. RSC Adv., 2014, 4: 41642-41648.
73	Hu C Z, Wang T, Dong J J, et al. Capacitive deionization from reconstruction of NiCoAl-mixed metal oxide film electrode based on the"memory effect"[J]. Appl. Surf. Sci., 2018, 459: 767-773.
74	KimY J, Choi J H. Selective removal of nitrate ion using a novel composite carbon electrode in capacitive deionization[J]. Water Res., 2012, 46(18): 6033-6039.
75	Yang J, Zou L D, Song H H, et al. Development of novel MnO₂/nanoporous carbon composite electrodes in capacitive deionization technology[J]. Desalination, 2011, 276(1/2/3): 199-206.
76	Zhang D S, Wen X R, Shi L Y, et al. Enhanced capacitive deionization of graphene/mesoporous carbon composites[J]. Nanoscale, 2012, 4: 5440-5446.
77	Min X B, Zhu M F, He Y J, et al. Selective removal of Clˉ and Fˉ from complex solution via electrochemistry deionization with bismuth/reduced graphene oxide composite electrode[J]. Chemosphere, 2020, 251: 126319.
78	Liu C, Hsu P C, Xie J, et al. A half-wave rectified alternating current electrochemical method for uranium extraction from seawater[J]. Nat. Energy, 2017, 2: 17007.
79	Wang Y, Qu J H, Wu R C, et al. The electrocatalytic reduction of nitrate in water on Pd/Sn-modified activated carbon fiber electrode[J]. Water Res., 2006, 40(6): 1224-1232.
80	Yin H J, Zhao S L, Wan J W, et al. Three-dimensional graphene/metal oxide nanoparticle hybrids for high-performance capacitive deionization of saline water[J]. Adv. Mater., 2013, 25: 6270-6276.
81	Hu C Z, Dong J J, Wang T, et al. Nitrate electro-sorption/reduction in capacitive deionization using a novel Pd/NiAl-layered metal oxide film electrode[J]. Chem. Eng. J., 2018, 335: 475-482.
82	Bai Z Y, Dong J J, Liu G, et al. Denitrification enhancement by electro-sorption/reduction using a layered metal oxide electrode loaded with Pd-Cu nanoparticles[J]. Electrochem. Commun., 2020, 110: 106607.
83	Lyu H X, Hu K, Fan J S, et al. 3D hierarchical layered double hydroxide/carbon spheres composite with hollow structure for high adsorption of dye[J]. Appl. Surf. Sci., 2020, 500: 144037.
84	Hong S P, Yoon H S, Lee J H, et al. Selective phosphate removal using layered double hydroxide/reduced graphene oxide(LDH/rGO) composite electrode in capacitive deionization[J]. J. Colloid Interf. Sci., 2020, 564: 1-7.
85	Wang J, Gao F F, Du X, et al. A high-performance electroactive PPy/rGO/NiCo-LDH hybrid film for removal of dilute dodecyl sulfonate ions[J]. Electrochim. Acta., 2020, 331: 135288.
86	Yang J, Zou L D, Song H H. Preparing MnO₂/PSS/CNTs composite electrodes by layer-by-layer deposition of MnO₂ in the membrane capacitive deionisation[J]. Desalination, 2012, 286: 108-114.
87	Zhang Y J, Xue J Q, Li F, et al. Preparation of polypyrrole/chitosan/carbon nanotube composite nano-electrode and application to capacitive deionization process for removing Cu²⁺[J]. Chem. Eng. Process., 2019, 139: 121-129.

[1]	王祺, 房阔, 贺聪慧, 王凯军. 流动电极电容去离子技术综述：研究进展与未来挑战[J]. 化工学报, 2022, 73(3): 975-989.
[2]	鲁浩天, 陈怡沁, 周静红, 隋志军, 周兴贵. 电化学双电层电容器动态模拟：离子尺寸及扩散系数的优化[J]. 化工学报, 2019, 70(10): 4021-4031.
[3]	张兴磊, 王文, 华黎, 衡建坡. 恒流充放电过程中双电层电容器温度特性[J]. 化工学报, 2016, 67(4): 1207-1214.
[4]	叶遥立, 郭剑, 潘彬, 成少安. 阳极双电层电容对微生物燃料电池性能的影响[J]. 化工学报, 2015, 66(2): 773-778.
[5]	钟溢健, 张济辞, 吴子焱, 尤世界, 王秀蘅, 任南琪. 新型准对称无机膜的正渗透去除Cd²⁺的效能[J]. 化工学报, 2015, 66(1): 386-392.
[6]	杨大勇, 刘莹. 粗糙表面微通道电渗流的数值模拟 [J]. 化工学报, 2008, 59(10): 2577-2581.
[7]	赵亮;刘林华 . 闭口微通道电渗流微混合的数值模拟 [J]. CIESC Journal, 2007, 58(12): 3019-3023.
[8]	李生娟;王树林;徐波;陈新龙 . 双电层电容器活性炭电极的优化 [J]. CIESC Journal, 2006, 57(7): 1617-1621.
[9]	陈福明. 一种去除水中离子的新方法——充电富集法初探 [J]. CIESC Journal, 1999, 50(1): 114-117.