离子改性的CON材料用于吸附分离NF3

doi:10.16085/j.issn.1000-6613.2022-2371

化工进展 ›› 2023, Vol. 42 ›› Issue (11): 6076-6085.DOI: 10.16085/j.issn.1000-6613.2022-2371

• 资源与环境化工 • 上一篇

离子改性的CON材料用于吸附分离NF₃

伍岳¹(), 李晓宇¹, 陶春珲¹, 张莹², 李印辉¹, 张文祥¹, 杨伯伦¹, 马和平¹()

^1.西安交通大学化学工程与技术学院，陕西西安 710000
^2.西安交通大学化学学院，陕西西安 710000

收稿日期:2022-12-28 修回日期:2023-02-28 出版日期:2023-11-20 发布日期:2023-12-15
通讯作者: 马和平
作者简介:伍岳（1994—），男，博士研究生，研究方向为气体吸附分离。E-mail：wuyue2507@stu.xjtu.edu.cn。
基金资助:
国家自然科学基金(22178280);核数据基础重点实验室项目(JCKY2021201C151);西安交通大学“青年拔尖人才”项目(HG6J001)

Adsorptive separation of NF₃ using ion-modified CON material

WU Yue¹(), LI Xiaoyu¹, TAO Chunhui¹, ZHANG Ying², LI Yinhui¹, ZHANG Wenxiang¹, Yang Bolun¹, MA Heping¹()

^1.School of Chemical Engineering and Technology, Xi’an Jiaotong University, Xi’an 710000, Shaanxi, China
^2.School of Chemistry, Xi’an Jiaotong University, Xi’an 710000, Shaanxi, China

Received:2022-12-28 Revised:2023-02-28 Online:2023-11-20 Published:2023-12-15
Contact: MA Heping

摘要/Abstract

摘要：

从半导体刻蚀废气中吸附分离NF₃具有重要的工业应用价值。通过在多孔有机分子笼（cage-like organic network，CON）中引入碘离子，制得了高NF₃吸附选择性的离子型吸附剂（I-CON）。DFT理论计算表明，碘离子的引入在吸附剂孔道表面形成了离子化的电场环境，使被吸附的NF₃分子发生诱导极化，因此增强了材料对NF₃的吸附能力。单组分气体吸附测试结果表明，相较于CON，I-CON对NF₃的吸附容量从30.49mL/g提高到45.13mL/g，理想吸附溶液理论选择性从10.59~15.49提高到15.01~19.47；在穿透曲线测试中，I-CON也比CON表现出更强的NF₃动态吸附能力。以上结果证实了离子改性能够增强材料对NF₃的吸附分离性能，为分离与回收NF₃提供了技术参考。

关键词: 多孔有机材料, 离子型吸附剂, 吸附分离, 三氟化氮, 含氟电子气体

Abstract:

Adsorptive separation of NF₃ from semiconductor exhaust gases has become an increasingly important topic in industrial applications. By introducing iodine ions into cage-like organic network (CON), quaternized I-CON material was prepared. The DFT calculation revealed that the electric field was formed on the pore surface by introducing iodide ions, which enhanced the inducing force between NF₃ molecule and I-CON framework. Compared with CON, the NF₃ adsorption capacity of I-CON increased from 30.49mL/g to 45.13mL/g and the IAST selectivity increased from 10.59—15.49 to 15.01—19.47 according to the single-component gas adsorption results. Moreover, the dynamic adsorption selectivity of I-CON was also higher than that of CON in the breakthrough tests. Thus, separation ability of CON could be effectively improved by ion modification, showing its potential for the real-world NF₃ capture and enrichment.

Key words: porous organic material, ionic adsorbent, adsorptive separation, nitrogen trifluoride, fluorinated greenhouse gases

中图分类号:

TQ 028.1

伍岳, 李晓宇, 陶春珲, 张莹, 李印辉, 张文祥, 杨伯伦, 马和平. 离子改性的CON材料用于吸附分离NF₃[J]. 化工进展, 2023, 42(11): 6076-6085.

WU Yue, LI Xiaoyu, TAO Chunhui, ZHANG Ying, LI Yinhui, ZHANG Wenxiang, Yang Bolun, MA Heping. Adsorptive separation of NF₃ using ion-modified CON material[J]. Chemical Industry and Engineering Progress, 2023, 42(11): 6076-6085.

图/表 10

图1 通过季铵化制备碘离子修饰的I-CON分子笼示意图

图2 CON、I-CON与N2、NF3的吸附结构、原子电荷、电子密度差的模拟计算结果

图3 CON和I-CON分子笼材料的结构表征

表1 TEM能谱分析I-CON得到的元素质量分数

元素	原子分数/%	质量分数/%
C	78.28	47.04
N	15.03	10.53
I	6.68	42.41

图4 CON和I-CON分子笼的孔道结构表征

图5 CON和I-CON分子笼的吸附分离性能测试

表2 DSLF模型的拟合参数以及决定系数

参数	CON		I-CON
参数	NF₃	N₂	NF₃	N₂
A₁	2.9004	0.14512	1.47377	0.0020
A₂	1.3342	0.32764	0.37852	2.6073
B₁	0.0013	0.03972	0.00698	2.694×10^-6
B₂	0.0174	0.00362	0.07495	0.00131
C₁	1.2060	0.22587	0.80515	7.40315
C₂	0.8493	1.23156	1.08581	1.03448
R²	0.995	0.999	0.999	0.999

图6 CON和I-CON分子笼对气体的等容吸附热

图7 两种材料的穿透曲线测试

图8 通入氦气条件下CON和I-CON材料的脱附曲线

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离子改性的CON材料用于吸附分离NF₃

Adsorptive separation of NF₃ using ion-modified CON material

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