氨基膦酸酯功能化碳材料对钍的选择性电吸附性能研究
收稿日期: 2024-02-19
网络出版日期: 2024-03-20
基金资助
中国科协青年人才托举工程项目(2022QNRC001);江西省“双千计划”项目(JXSQ2020101005);赣州市“揭榜挂帅”科技项目(赣市科发［2022］57号);赣州市科技计划项目(2022CXRC9671);赣州市“苏区之光”高层次创新团队项目(GZSQZG202301018)
Study on selective electrosorption of thorium by carbon material containing aminophosphonate functional group
Received date: 2024-02-19
Online published: 2024-03-20
针对高纯稀土中微痕量放射性元素钍的分离去除，以氨基化的碳纳米管（CNT-N）为基底，制备了氨基膦酸酯功能化碳电极材料（CNT-P）。采用高分辨场发射扫描电子显微镜（SEM）、比表面分析仪、X射线光电子能谱分析仪（XPS）、热重分析仪（TGA）、傅里叶变换红外光谱仪（FT-IR）和电化学工作站等对CNT-P的形貌、组成和电化学性能进行表征和分析。研究了溶液介质、pH、电压、钍离子的初始浓度（c0）等因素对钍吸附性能的影响。探讨了CNT-P对钍与稀土离子的吸附选择性，考察了CNT-P的再生循环使用性能。结果表明：CNT-P同时包含介孔和大孔结构，其比表面积、孔容和平均孔径分别为111.6 m2/g、0.85 cm3/g和30.13 nm；CNT-P在盐酸溶液中对钍的最大电吸附容量达219 mg/g；电压为3.5 V时，钍与稀土离子的分离系数均大于10；经5次吸附-解吸循环后，CNT-P对钍的吸附容量是初次吸附的87%，并基本保持稳定。该电极材料对于稀土中微痕量钍的高效去除具有良好的应用前景。
权家园 , 付春燕 , 邓必成 , 黄亚斌 , 况王强 , 邝圣庭 , 廖伍平 . 氨基膦酸酯功能化碳材料对钍的选择性电吸附性能研究[J]. 无机盐工业, 2024 , 56(12) : 42 -50 . DOI: 10.19964/j.issn.1006-4990.2024-0084
To separate and remove trace thorium from rare earths，a carbon electrode material（CNT-P） was prepared by modifying aminated carbon nanotubes（CNT-N） with phosphonate.The morphology，composition and electrochemical properties of CNT-P were analyzed by scanning electron microscope（SEM），surface area analyzer，X-ray photoelectron spectroscopy（XPS），thermogravimetric analyzer（TGA），Fourier transform infrared spectrometer（FT-IR） and electrochemical workstation.The effects of solution medium，pH，voltage and the initial thorium concentration on the adsorption of thorium were studied.The adsorption selectivity of CNT-P toward thorium and rare earths was discussed.The regenerative recycling performance of CNT-P was examined.The results indicated that CNT-P was a mesoporous and macroporous structure combined electrode material，with a BET specific surface area of 111.6 m2/g，a pore volume of 0.85 cm3/g and an average pore size of 30.13 nm.The maximum electrosorption capacity of CNT-P towards thorium reached 219 mg/g in hydrochloric acid solution.The separation factors for Th/REs were higher than 10 at voltage of 3.5 V.After 5 cycles of adsorption-desorption，the adsorption capacity of CNT-P toward thorium maintained 87% as compared with its initial adsorption and basically kept stable.Therefore，CNT-P showed a promising application prospect for the efficient removal of micro-trace thorium from rare earth earths.
Key words： carbon electrode; thorium; rare earths; electrosorption; separation
| [1] | LU Youcai， ZHANG Zhifeng， LI Yanling，et al.Extraction and recovery of cerium（Ⅳ） and thorium（Ⅳ） from sulphate medium by an α-aminophosphonate extractant［J］.Journal of Rare Earths，2017，35（1）：34-40. |
| [2] | LANKAPATI H M， DANKHARA P M， LATHIYA D R，et al.Removal of lanthanum，cerium and thorium metal ions from aqueous solution using ZrT hybrid ion exchanger［J］.Sustainable Energy Technologies and Assessments，2021，47：101415. |
| [3] | DEB A K S， MOHANTY B N， ILAIYARAJA P，et al.Adsorptive removal of thorium from aqueous solution using diglycolamide functionalized multi-walled carbon nanotubes［J］.Journal of Radioanalytical and Nuclear Chemistry，2013，295（2）：1161-1169. |
| [4] | PERREAULT F， FONSECA DE FARIA A， ELIMELECH M.Environmental applications of graphene-based nanomaterials［J］.Chemical Society Reviews，2015，44（16）：5861-5896. |
| [5] | CHAI Shuqian， XI Jiarui， CHEN Ling，et al.Selective ion removal by capacitive deionization（CDI）-based technologies［J］.Processes，2022，10（6）：1075. |
| [6] | XU Youze， ZHONG Zhenyu， ZENG Xianhui，et al.Novel materials for heavy metal removal in capacitive deionization［J］.Applied Sciences，2023，13（9）：5635. |
| [7] | 周剑.电容去离子电极材料的构筑及其富集铀酰性能研究［D］.合肥：中国科学技术大学，2021. |
| ZHOU Jian.Construction of capacitive deionized electrode materials and their enrichment of uranyl［D］.Hefei：University of Science and Technology of China，2021. | |
| [8] | BAO Shenxu， XIN Chunfu， ZHANG Yimin，et al.Application of capacitive deionization in water treatment and energy recovery：A review［J］.Energies，2023，16（3）：1136. |
| [9] | PORADA S， ZHAO R， VAN DER WAL A，et al.Review on the science and technology of water desalination by capacitive deionization［J］.Progress in Materials Science，2013，58（8）：1388-1442. |
| [10] | LI Dawei， PANG Yanan， MENG Nan，et al.Use of steam to prepare super active carbon with large pore volume for efficient capacitive deionization［J］.Diamond and Related Materials，2023，139：110338. |
| [11] | PAN Haojie， YANG Jianmao， WANG Shiping，et al.Facile fabrication of porous carbon nanofibers by electrospun PAN/dimethyl sulfone for capacitive deionization［J］.Journal of Materials Chemistry A，2015，3（26）：13827-13834. |
| [12] | YU Fei， ZHANG Xiaochen， YANG Zhengqu，et al.Carbon aerogel electrode for excellent dephosphorization via flow capacitive deionization［J］.Desalination，2022，528：115614. |
| [13] | QASEMNAZHAND M， KHOEINI F， MARSUSI F.Predicting the new carbon nanocages，fullerynes：A DFT study［J］.Scientific Reports，2021，11（1）：2511. |
| [14] | JHA N， RAMESH P， BEKYAROVA E，et al.High energy density supercapacitor based on a hybrid carbon nanotube-reduced graphite oxide architecture［J］.Advanced Energy Materials，2012，2（4）：438-444. |
| [15] | 周琰，胡丽娟，岑美香，等.茶渣衍生多级孔炭的电化学和吸附性能研究［J］.稀有金属，2022，46（10）：1340-1351. |
| ZHOU Yan， HU Lijuan， CEN Meixiang，et al.Electrochemicaland adsorption performance of tea waste derived carbon with hierarchical pores［J］.Chinese Journal of Rare Metals，2022，46（10）：1340-1351. | |
| [16] | PENG Mengke， WANG Li， LI Longbin，et al.Molecular crowding agents engineered to make bioinspired electrolytes for high-voltage aqueous supercapacitors［J］.eScience，2021，1（1）：83-90. |
| [17] | BALES C， KINSELA A S， MILLER C，et al.Removal of trace uranium from groundwaters using membrane capacitive deionization desalination for potable supply in remote communities：Bench，pilot，and field scale investigations［J］.Environmental Science & Technology，2023，57（30）：11345-11355. |
| [18] | 陈乡，原渊，李宏星，等.用膜电容去离子法净化碱法地浸含铀地下水试验研究［J］.中国资源综合利用，2019，37（5）：11-16. |
| CHEN Xiang， YUAN Yuan， LI Hongxing，et al.Experimental study on purification of uranium-bearing groundwater by membrane capacitance deionization［J］.China Resources Comprehensive Utilization，2019，37（5）：11-16. | |
| [19] | AZIMAN E S， ISMAIL A F.Rapid selective removal of thorium via electrosorption towards efficiently managing rare-earth extraction residue［J］.Journal of Environmental Chemical Engineering，2021，9（4）：105478. |
| [20] | AZIMAN E S， ISMAIL A F， MUTTALIB N A，et al.Investigation of thorium separation from rare-earth extraction residue via electrosorption with carbon based electrode toward reducing waste volume［J］.Nuclear Engineering and Technology，2021，53（9）：2926-2936. |
| [21] | YUSSUF N M， ISMAIL A F， AZIMAN E S，et al.Innovative g-C3N4/AX composite electrode for effective thorium elimination from aqueous solutions［J］.Separation and Purification Technology，2024，330：125205. |
| [22] | ZHU Zhaowu， PRANOLO Y， CHENG Chuyong.Separation of uranium and thorium from rare earths for rare earth production：A review［J］.Minerals Engineering，2015，77：185-196. |
| [23] | HU Youcai， DING Jianhua， REN Guangyuan，et al.Highly efficient extraction of thorium from aqueous solution by 2-carboxyethylphosphonic acid-functionalized chitosan xerogel［J］.Separation and Purification Technology，2022，303：122188. |
| [24] | 苏杰，况王强，邝圣庭，等.Cextrant 230对氟碳铈矿盐酸优浸液中钍和铁的选择性去除［J］.中国稀土学报，2023，41（1）：178-186. |
| SU Jie， KUANG Wangqiang， KUANG Shengting，et al.Selective removal of thorium and iron from selective hydrochloric acid leach solution of bastnaesite by solvent extraction using cextrant 230［J］.Journal of the Chinese Society of Rare Earths，2023，41（1）：178-186. | |
| [25] | KUANG Shengting， ZHANG Zhifeng， LI Yanling，et al.Selective extraction and separation of Ce（Ⅳ） from thorium and trivalent rare earths in sulfate medium by an α-aminophosphonate extractant［J］.Hydrometallurgy，2017，167：107-114. |
| [26] | WEI Haiqin， LI Yanling， ZHANG Zhifeng，et al.Selective extraction and separation of Ce（Ⅳ） and Th（Ⅳ） from RE（Ⅲ） in sulfate medium using di（2-ethylhexyl）-N-heptylaminomethylp-hosphonate［J］.Solvent Extraction and Ion Exchange，2017，35（2）：117-129. |
| [27] | YANG Bin， ZHANG Xuyi， TAN Sen，et al.Ultra-selective removal of thorium from rare earths by aminophosphonic acid-modified porous silica［J］.Separation and Purification Technology，2024，341：126952. |
| [28] | 李艳玲，邝圣庭，廖伍平.Cextrant 230/二异辛基琥珀酸酯磺酸钠/正庚烷反相微乳液萃取钍［J］.应用化学，2022，39（12）：1927-1936. |
| LI Yanling， KUANG Shengting， LIAO Wuping.Extraction of thorium（Ⅳ） using cextrant 230/anionic surfactant sodium bis（2-ethylhexyl）sulfosuccinate/n-heptane microemulsion［J］.Chinese Journal of Applied Chemistry，2022，39（12）：1927-1936. | |
| [29] | YANG Xiaojing， ZHANG Zhifeng， KUANG Shengting，et al.Removal of thorium and uranium from leach solutions of ion-adsorption rare earth ores by solvent extraction with Cextrant 230［J］.Hydrometallurgy，2020，194：105343. |
| [30] | WANG Hui， KUANG Shengting， LIAO Wuping.Synergistic extraction and separation of thorium from rare earths in chloride media using mixture of Cextrant 230 and Cyanex 923［J］.Journal of Rare Earths，2024，42（4）：759-767. |
| [31] | TOMELLINI S， SMITH G， WOODRUFF H，et al.On-line infrared（IR） spectral interpretation of organic compounds using A Fourier transform（FT） sized minicomputer［C］//1981 Intl Conf on Fourier Transform Infrared Spectroscopy.Columbia.SPIE，1981. |
| [32] | DAVIS M E.Ordered porous materials for emerging applicatio- ns［J］.Nature，2002，417（6891）：813-821. |
| [33] | FOROUTAN R， PEIGHAMBARDOUST S J， ESVANDI Z，et al.Evaluation of two cationic dyes removal from aqueous environments using CNT/MgO/CuFe2O4 magnetic composite powder：A comparative study［J］.Journal of Environmental Chemical Engineering，2021，9（2）：104752. |
| [34] | CHERKASOV R A， GARIFZYANOV A R， LEONT’EV S V，et al.Extraction of scandium ions by new aminophosphinyl extractants［J］.Russian Journal of General Chemistry，2009，79（12）：2599-2605. |
| [35] | LIU Danyang， HUANG Kuan， XIE Leijie，et al.Relation between operating parameters and desalination performance of capacitive deionization with activated carbon electrodes［J］.Environmental Science：Water Research & Technology，2015，1（4）：516-522. |
| [36] | LI Haibo， ZOU Linda， PAN Likun，et al.Using graphene nano-flakes as electrodes to remove ferric ions by capacitive deionization［J］.Separation and Purification Technology，2010，75（1）：8-14. |
| [37] | CHEN Qile， KONG Xian， LI Jipeng，et al.Electrokinetic desalination using honeycomb carbon nanotubes（HC-CNTs）：A conceptual study by molecular simulation［J］.Physical Chemistry Chemical Physics，2014，16（35）：18941-18948. |
| [38] | YILMAZ C E， ASLANI M A A， ASLANI C K.Adsorption of Th（Ⅳ） on the modified multi-walled carbon nanotubes using central composite design［J］.Radiochimica Acta，2019，107（5）：377-386. |
| [39] | BAJPAI M， KATOCH S S， CHATURVEDI N K.Comparative study on decentralized treatment technologies for sewage and graywater reuse：A review［J］.Water Science and Technology，2019，80（11）：2091-2106. |
| [40] | LIU Yong， GAO Xin， ZHANG Lu，et al.Mn2O3 nanoflower decorated electrospun carbon nanofibers for efficient hybrid capacitive deionization［J］.Desalination，2020，494：114665. |
/
| 〈 |
|
〉 |
