ISSN 1008-5548

CN 37-1316/TU

2024年30卷  第3期
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四苯基甲烷球磨法合成多孔碘蒸气吸附材料

Ball⁃milling synthesis of organic porous materials with tetraphenylmethane for iodine vapor adsorption


张承昕1,王余莲1,苏峻樟1,董春阳1,王浩然1,肖坤富1,袁志刚1,苏德生23

(1. 沈阳理工大学 材料科学与工程学院,辽宁 沈阳 110159;2. 辽宁丹炭科技集团有限公司,辽宁 丹东 118100;3. 辽宁省超高功率石墨电极材料专业技术创新中心,辽宁 丹东 118100)


引用格式:

张承昕,王余莲,苏峻樟,等. 四苯基甲烷球磨法合成多孔碘蒸气吸附材料[J]. 中国粉体技术,2024,30(3):158-169.

ZHANG C X, WANG Y L, SU J Z, et al. Ball-milling synthesis of organic porous materials with tetraphenylmethane for iodine vapor adsorption[J]. China Powder Science and Technology,2024,30(3):158−169.

DOI:10.13732/j.issn.1008-5548.2024.03.014

收稿日期:2023-11-22,修回日期:2024-02-22,上线日期:2024-04-18。

基金项目:国家自然科学基金项目,编号:52374271;辽宁省教育厅科学研究青年人才项目,编号: LJKZ0246;辽宁省重点研发计划-应用基础研究项目,编号:2022JH2/101300111;沈阳市科技局项目,编号:22-322-3-03;沈阳市中青年科技创新人才支持计划项 目 ,编 号 :RC220104;辽 宁 省 教 育 厅 重 点 项 目 ,编 号 :LJKMZ20220588;辽 宁 省 大 学 生 创 新 创 业 训 练 项 目 ,编 号 :S202210144002、s202110144057;沈阳理工大学2021年引进高层次人才科研支持经费项目,编号:1010147001011。

第一作者简介:张承昕(1989—),男,讲师,博士,研究方向为有机多孔材料的合成及应用。E-mail: zhcx1989@sylu. edu. cn。

通信作者简介:王余莲(1986—),女,教授,博士,辽宁省“百千万人才工程”人才,硕士生导师,研究方向为功能矿物材料制备及应用。E-mail: ylwang0908@163. com。


摘要:【目的】 避免在核能利用过程中产生的常见放射性污染核素129I和131I等碘蒸气泄漏对环境和生物产生危害,制备并探讨具有丰富孔道的有机多孔聚合物对碘蒸气的吸附性能。【方法】 采用简便快捷的机械合成法,以具有正四面体结构的四苯基甲烷为单体,利用高能行星式球磨机球磨2 h成功制备3种具有较大比表面积和丰富孔道的有机多孔聚合物T-FDA、T-DCM和T-DCE,并利用碘单质在温度为75 ℃的密闭体系内升华模仿放射性碘蒸气分别测试3种多孔材料的碘蒸气吸附性能。【结果】 T-FDA、 T-DCM、 T-DCE的碘蒸气吸附质量分数分别可达461%、486%、444%,达到饱和吸附量的时间分别为5、8、6 h,且多孔材料在循环使用5次后碘吸附性能仅有轻微下降(≤6. 8%)。【结论】 以四苯基甲烷为单体,通过快速球磨法合成的多孔材料具有良好的碘蒸气吸附性能,有望在放射性碘蒸气吸附领域发挥重要作用。

关键词:四苯基甲烷;球磨法;有机多孔材料;碘蒸气吸附

Abstract

Objective Radioactive isotopes of iodine, such as iodine-129 and iodine-131, are prevalent contaminants during nuclear energy utilization. Managing radioactive iodine is a critical concern for researchers and the use of porous materials for iodine vapor adsorption presents a promising solution. However, traditional porous iodine adsorbents, including activated carbon and porous zeolite, exhibit drawbacks such as high density, limited structural versatility, low specific surface area, large pore size, low adsorption capacity, and inadequate cycling performance, significantly impeding their industrial applicability. Given these challenges, it is necessary to develop novel porous materials for efficient iodine vapor adsorption. Porous Organic Polymers (POPs) emerge as a potential solution, characterized by high physical and chemical stability, low density, high porosity, large specific surface area, outstanding adsorption performance, and recyclability, offering a promising prospects in radioactive iodine treatment. Ball mills, as common crushing equipment, find widespread application in industries such as mineral processing, building materials, and chemical industry. Furthermore, researchers use ball mills for chemical synthesis due to their advantages such as brief reaction times, high efficiency, simplicity, and potential for low-cost, straightforward, large-scale industrial production. In this study, tetraphenylmethane, featuring a three-dimensional structure served as the monomer, while a highenergy planetary ball mill functioned as a reactor,enabling swift and efficient construction of three POPs materials. These materials were evaluated for their adsorption performance and recycling ability in a simulated radioactive iodine vapor environment. Our research offers a viable solution for large-scale production of POPs materials and their practical application in iodine vapor adsorption.

Methods In this study, we successfully synthesized three distinct porous organic polymers (POPs), namely T-FDA, T-DCM,and T-DCE, utilizing a rapid and efficient ball milling approach, resulting in materials characterized by high specific surface area and abundant pore structure. The synthesis process involved employing tetraphenylmethane as a three-dimensional structure monomer, along with either anhydrous ferric chloride or anhydrous aluminum trichloride as catalysts, and three different crosslinking agents (dimethoxymethane, dichloromethane, and1,2-dichloroethane) to generate the aforementioned POPs materials. The synthesis procedure commenced by introducing the requisite reagents into a 250 mL zirconia grinding jar containing 50 zirconia spheres (Diameter:10 mm), followed by purging the jar with argon atmosphere before sealing it. Subsequently, the planetary high-energy ball mill was set to a revolution speed and rotation speed of 400 r/min, and the milling process was terminated after 2 hours of operation at room temperature. Subsequently, the iodine vapor adsorption capacity of the porous materials was evaluated. Specifically,0. 2 g of POPs powders were accurately weighed and placed into a pre-weighed small sample bottle.Additionally,2 g of iodine was introduced into another sample bottle. These two bottles were then positioned within a glass container to create a sealed system. This closed system was subsequently transferred into an oven set at 75 ℃, thereby exposing the powder to a saturated iodine vapor environment. At predetermined time intervals (1,2,3,4,5,6,8,12,16,20, and 24 hours), the sealed container was removed from the oven and rapidly cooled, following which the mass of the sample bottle was accurately determined.

Results and Discussion The resulting porous materials T-FDA, T-DCM, and T-DCE exhibit high specific surface area (398,516, and 753 m²/g respectively), abundant pore channels, and excellent structural stability. These materials are characterized by a significant presence of micropores (<2 nm) and even ultra-micropores (<0. 7 nm), alongside a certain proportion of mesopores. The interconnected nature of these pores confers unique advantages to the materials, particularly in the realm of adsorption, notably in the adsorption and separation of gas substances such as radioactive iodine vapor. Based on experimental findings, the iodine adsorption capacity of T-FDA, T-DCM, and T-DCE can reach up to 461%,486%, and 444% respectively.These materials achieve adsorption saturation at the 5th,8th, and 6th hour respectively. Furthermore, to assess the materials' cycling performance, iodine vapor adsorption recycling experiments were conducted five times for each of T-FDA,T-DCM, and T-DCE. The results indicate that the iodine vapor adsorption efficiency of T-FDA only slightly decreases after five cycles of use,with the iodine vapor adsorption amount reducing from 461% initially to 454% after the fifth cycling, representing a decrease of only 1. 5%. For T-DCM, its iodine vapor adsorption capacity decreases from 486% for the first time to 473% for the fifth time,corresponding to a reduction of 2. 7%. Similarly, the iodine vapor adsorption of T-DCE decreases from 444% for the first time to 414% for the fifth time, with a reduction of 6. 8%. Notably, the iodine adsorption performance of the three porous materials only slightly decreases after five cycles of use.

Conclusion In this study, utilizing the ball-milling method, three porous materials(T-FDA, T-DCM, and T-DCE) were synthesized within a remarkably short period of 2 hours. Subsequently, structural analyses and evaluated the iodine vapor adsorption performance of these materials were conducted. Our findings revealed that T-FDA, T-DCM, and T-DCE exhibited specific surface areas of 398,516, and 753 m²/g, respectively. These materials showcased abundant micropores, continuous multi-level pore distribution, and a relatively stable structure. To assess their practical utility, we applied these porous materials to iodine vapor adsorption in a closed system operating at 75 ℃, simulating the vapor evaporation environment of radioactive iodine with standard iodine elements. The experimental outcomes demonstrated impressive iodine adsorption mass fractions of 461%,486%, and 444% for    T-FDA, T-DCM, and T-DCE, respectively. Remarkably, these materials exhibited reusability for up to 5cycles with only a marginal decrease in performance (≤6. 8%). Our results underscore the exceptional iodine vapor adsorption performance of the porous materials synthesized via fast ball milling, suggesting their potential significance in the context of radioactive iodine adsorption. Moreover, the ball milling synthetic method offers advantages including short reaction time, high efficiency, low energy consumption, and avoidance of extensive energy and organic solvent usage, thereby harboring considerable potential for large-scale industrial production.

Keywords:tetraphenylmethane; ball-milling method; porous organic polymer; iodine vapor adsorption


参考文献(References)

[1]AHAD J, AHMAD M, FAROOQ A, et al. Removal of iodine by dry adsorbents in filtered containment venting system after10 years of Fukushima accident[J]. Environmental Science and Pollution Research,2023,30(30):74628-74670.

[2]GENG T, ZHANG H C, LIU M, et al. Preparation of biimidazole-based porous organic polymers for ultrahigh iodine catureand formation of liquid complexes with iodide/polyiodide ions[J]. Journal of Materials Chemistry A,2020,8(5):2820-2826.

[3]SHETTY D, RAYA J, HAN D S, et al. Lithiated polycalix[4]arenes for efficient adsorption of iodine from solution andvapor phases[J]. Chemistry of Materials,2017,29(21):8968-8972.

[4]HO K, PARK D, PARK M K, et al. Adsorption mechanism of methyl iodide by triethylenediamine and quinuclidineimpregnated activated carbons at extremely low pressures[J]. Chemical Engineering Journal,2020,396 125215.

[5]HUVE J, RYZHIKOV A,NOUALI H, et al. Porous sorbents for the capture of radioactive iodine compounds: a review[J].RSC Advances,2018,8(51):29248-29273.

[6]ZHAO Q,LIAO C,CHEN G,et al. In situ confined synthesis of a copper-encapsulated silicalite-1 zeolite for highly efficient iodine capture[J]. Inorganic Chemistry,2022,61(49):20133-20143.

[7]XIONG S, TANG X, PAN C, et al. Carbazole-bearing porous organic polymers with a mulberry-like morphology for efficient iodine capture[J]. ACS Applied Materials & Interfaces,2019,11(30):27335-27342.

[8]HAO Q, TAO Y, DING X, et al. Porous organic polymers: a progress report in China[J]. Science China Chemistry,2023,66(3):620-682.

[9]ZHAI L, HAN D, DONG J, et al. Constructing stable and porous covalent organic frameworks for efficient iodine vapor capture[J]. Macromolecular Rapid Communications,2021,42(13):2100032.

[10]CHANG J, LI H, ZHAO J, et al. Tetrathiafulvalene-based covalent organic frameworks for ultrahigh iodine capture[J].Chemical Science,2021,12(24):8452-8457.

[11]宋玲,黄清,蒋选峰. 三嗪基有机多孔材料的制备及碘吸附性能研究[J]. 化学工程,2022,50(8):20-25.SONG L, HUANG Q, JIANG X F. Preparation of triazine-based organic porous materials and iodine adsorption properties[J]. Chemical Engineering (China),2022,50(8):20-25.

[12]ZOU J, WEN D,ZHAOY. Flexible three-dimensional diacetylene functionalized covalent organicframeworks for efficient iodine capture[J]. Dalton Transactions,2023,52(3):731-736.

[13]LIU N, MA H, SUN R, et al. Porous triptycene network based on Tröger’s base for CO2 capture and iodine enrichment[J]. ACS Applied Materials & Interfaces,2023,15(25):30402-30408.

[14]HASSAN A,DAS N. Chemically stable and heteroatom containing porous organic polymers for efficient iodine vapor capture and its storage[J]. ACS Applied Polymer Materials,2023,5(7):5349-5359.

[15]李滢,康晓明,陈曦,等. 再生微粉颗粒级配对水泥凝胶体微观结构及强度的影响[J]. 中国粉体技术,2022,28(3):107-115.

LI Y, KANG X M, CHEN X, et al. Effect of particle size distribution of recycled concrete powders on microstructure and strength of cement gel [J]. China Powder Science and Technology,2023,28(3):107-115.

[16]于颖,曹丙强 . 无铅双钙钛矿纳米粉体 Cs2AgBiBr6的球磨法制备工艺与性能[J]. 中国粉体技术,2023,29(6):91-100.

YU Y, CAO B Q. Preparation process and property of lead-free double perovskite nano-powder Cs2AgBiBr6by ball milling[J].China Powder Science and Technology,2023,29(6):91-100.

[17]ZHAN Z, YU J, LI S, et al. Ultrathin hollow Co/N/C spheres from hyper-crosslinked polymers by a new universal strategy with boosted ORR efficiency[J]. Small,2023,19(16):2207646.

[18]WANG S L, ZHANG C X, SHU Y, et al. Layered microporous polymers by solvent knitting method[J]. Science Advances,2017,3(3):e1602610.

[19]ZHANG C X, WANG S L, ZHAN Z, et al. Synthesis of MWCNT-based hyper-cross-linked polymers with thicknesstunable organic porous layers[J]. ACS Macro Letters,2019,8(4):403-408.

[20]陈潇禄,袁珍闫,仲迎春,等 . 机械球磨制备三苯胺基 PAF-106s及 C2烃吸附性质[J]. 高等学校化学学报,2022,43(3):20210771.

CHEN X L,YUAN Z Y,ZHONG Y C,et al. Preparation of triphenylamine based PAF-106s via mechanical ball milling and C2 hydrocarbons adsorption property[J]. Chemical Journal of Chinese Universities,2022,43(3):20210771.

[21]OUYANG H, SONG K, DU J, et al. Creating chemisorption sites for enhanced CO2 chemical conversion activity through amine modification of metalloporphyrin-based hypercrosslinked polymers[J]. Chemical Engineering Journal,2022,431:134326.

[22]ERRAHALI M, GATTI G, TEI L, et al. Microporous hyper-cross-linked aromatic polymers designed for methane and carbon dioxide adsorption[J]. The Journal of Physical Chemistry C,2014,118(49):28699-28710.

[23]SUN H, LA P, ZHU Z, et al. Capture and reversible storage of volatile iodine by porous carbon with high capacity[J]. Journal of Materials Science,2015,50(22):7326-7332. 

[24]HE X, ZHANG SY, TANG X, et al. Exploration of 1D channels in stable and high-surface-area covalent triazine polymers for effective iodine removal[J]. Chemical Engineering Journal,2019,371:314-318. 

[25]SHAO L, SANG Y, LIU N, et al. One-step synthesis of N-containing hyper-cross-linked polymers by two crosslinking strategies and their CO2 adsorption and iodine vapor capture[J]. Separation and Purification Technology,2021,262:118352. 

[26]CHEN R, HU T, ZHANG W, et al. Synthesis of nitrogen-containing covalent organic framework with reversible iodine capture capability[J]. Microporous and Mesoporous Materials,2021,312:110739. 

[27]WANG J, WANG L, WANG Y, et al. Covalently connected core–shell NH2-UiO-66@Br-COFs hybrid materials for CO2capture and I2 vapor adsorption[J]. Chemical Engineering Journal,2022,438:135555. 

[28]HE D, JIANG L, YUAN K, et al. Synthesis and study of low-cost nitrogen-rich porous organic polyaminals for efficient adsorption of iodine and organic dye[J]. Chemical Engineering Journal,2022,446:137119. 

[29]LIU C, JIN Y, YU Z, et al. Transformation of porous organic cages and covalent organic frameworks with efficient iodine vapor capture performance[J]. Journal of the American Chemical Society,2022,144(27):12390-12399. 

[30]万欢爱, 邵礼书, 刘娜, 等 . 氮修饰木质素基超交联聚合物的制备及其放射性碘捕获[J]. 化工进展, 2022, 41(10):5599-5611. 

WAN H A, SHAO L S, LIU N, et al. Preparation of nitrogen modified lignin-based hyper-cross-linked polymers and their radioactive iodine capture[J]. Chemical Industry and Engineering Progress,2022,41(10):5599-5611. 

[31]RUIDAS S, CHOWDHURY A, GHOSH A, et al. Covalent organic framework as a metal-free photocatalyst for dye degradation and radioactive iodine adsorption[J]. Langmuir,2023,39(11):4071-4081. 

[32]QIU N, WANG H, TANG R, et al. Synthesis of phenothiazine-based porous organic polymer and its application to iodine adsorption[J]. Microporous and Mesoporous Materials,2024,363:112833. 

[33]ZHANG J, PU N, LI M, et al. High-efficient Ag(I) ion binding, Ag(0) nanoparticle loading, and iodine trapping in ultrastable benzimidazole-linked polymers[J]. Separation and Purification Technology,2024,328:125052.