聚乙烯亚胺改性介孔氧化硅载体孔结构的调控机理

王荣; 杨静; 张涛; 于润升; 董俊才; 张鹏; 曹兴忠; 王宝义; 尹昊

doi:10.7498/aps.72.20230675

摘要

以三嵌段共聚物聚环氧乙烷-聚环氧丙烷-聚环氧乙烷(P123)为模板, 硅酸四乙酯(TEOS, C₈H₂₀O₄Si)为硅源合成了比表面积高达712.5 m²/g, 孔体积为2.44 cm³/g的新型介孔氧化硅载体(MCF). 通过正电子湮没寿命谱(PALS)以及常规表征手段; 例如N₂吸附脱附、透射电子显微镜、热重分析、傅里叶变换红外光谱等系统研究了聚乙烯亚胺(PEI)改性MCF对纳米尺度孔结构的影响. 结果表明, 合成的MCF具有明显的无序介孔结构, 孔与孔之间通过窗口相互连接形成了一个连续的、具有良好热稳定性的多孔通道网络, 同时可以直观看到有机胺PEI已被成功引入到MCF通道中. 为了更全面地评估材料孔径的变化情况, 通过高灵敏度、可探测亚纳米量级的正电子湮没技术研究正电子在PEI负载MCF中的湮没机制, 发现存在τ₃和τ₄两个长寿命分量, 表明样品中存在微孔和介孔. 同时由于PEI分子的引入, 导致τ₃和τ₄呈明显的下降趋势, 之后利用正电子在纯气体中的湮没率公式校正PALS所测得的寿命来计算所得孔尺寸, 发现孔尺寸随着有机分子PEI的填充而逐渐减小, 这将为探究聚乙烯亚胺改性MCF孔结构的调控机理以及有机分子改性介孔分子筛材料体系的孔结构表征提供新的思路.

关键词:

Abstract

A novel mesoporous silica foam (MCF) with a specific surface area of 712.5 m²/g and a pore volume of 2.44 cm³/g is synthesized by using triblock copolymer poly (ethylene oxide, polypropylene oxide and ethylene oxide, P123) as template and TEOS (C₈H₂₀O₄Si) as silicon source. The effect of polyethylenimide (PEI) modified MCF on nanoscale pore structure is studied by positron annihilation lifetime spectroscopy (PALS) and conventional characterization methods, such as N₂ adsorption desorption, transmission electron microscopy, thermogravimetric analysis and Fourier transform infrared spectroscopy. The results show that the synthesized MCF has an obvious disordered mesoporous structure, and a continuous porous network with window connection between the pores is formed. Meanwhile, it can be seen directly that PEI is successfully introduced into MCF pore channels. In order to evaluate the pore size and its distribution more comprehensively, the mechanism of positron annihilation which is highly sensitive to nanometer scale open volumes in PEI loaded MCF is studied. It is found that there are two long life components τ₃ and τ₄, indicating the micropores and mesopores co-existing in the sample. Furthermore, the introduction of PEI molecules results in a significant decrease in τ₃ and τ₄, and the lifetime values are then corrected by using the positron annihilation rate formula in pure gas to calculate the pore size. The results show that the pore size gradually decreases with the filling of the organic molecule PEI. This provides a new insight into the mechanism of regulating the pore structure of MCF by polyethyleneimine modification, as well as the characterization of pore structure in organic-modified mesoporous molecular sieves.

Keywords:

mesoporous silica foam /
positron annihilation lifetime spectroscopy /
nano mesoporous

作者及机构信息

1.
西安科技大学理学院, 西安　710600

2.
西安科技大学材料科学与工程学院, 西安　710600

3.
中国科学院高能物理研究所, 北京　100049

4.
中国科学院大学, 北京　101408

5.
武汉工程大学材料科学与工程学院, 武汉　430073

通信作者: 杨静, yangjing10@xust.edu.cn ; 于润升, yursh@ihep.ac.cn ;

基金项目: 国家自然科学基金(批准号: 12275299, 12075189)、国家重点基础研究发展计划(批准号: 2019YFA0210002)和中国博士后科学基金(批准号: 2018M643813XB)资助的课题.

Authors and contacts

1.
College of Science, Xi’an University of Science and Technology, Xi’an 710600, China

2.
College of Materials Science and Engineering, Xi’an University of Science and Technology, Xi’an 710600, China

3.
Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China

4.
University of Chinese Academy of Sciences, Beijing 101408, China

5.
School of Materials Science and Engineering, Wuhan Institute of Technology, Wuhan 430073, China

Corresponding author: Yang Jing, yangjing10@xust.edu.cn ; Yu Run-Sheng, yursh@ihep.ac.cn ;

Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 12275299, 12075189), the National Basic Research Program of China (Grant No. 2019YFA0210002), and the China Postdoctoral Science Foundation (Grant No. 2018M643813XB).

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参考文献

[1]	Song C F, Liu Q L, Ji N, Deng S, Zhao J, Li Y, Song Y J, Li H L 2018 Renewable Sustainable Energy Rev. 82 215 Google Scholar
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[19]	Song T, Zhang P, Zhang C, Gong L L, Cao X Z, Wang B Y, Yu R S, Zhou W 2022 Microporous Mesoporous Mater. 334 111761 Google Scholar
[20]	Chen Q j, Fan F C, Long D H, Liu X J, Lian X Y, Qiao W M, Ling L C 2010 Ind. Eng. Chem. Res. 49 11408 Google Scholar
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施引文献

图 1 (a) PEI改性前后MCF的N₂吸附-脱附等温线; (b) 由吸附曲线得到的孔尺寸; (c) 由脱附曲线得到的窗口尺寸; (d) P/P₀ = 0.99时, 采用BET方程和单点吸附法计算比表面积和孔体积

Fig. 1. (a) N₂ adsorption-desorption isotherms of MCF before and after PEI modification; (b) cell size from adsorption curve; (c) window dimensions obtained from desorption curves; (d) specific surface area and pore volume calculated by BET equation and single point adsorption measurement at P/P₀ = 0.99.

下载: 全尺寸图片幻灯片

图 2 TEM图像　(a) MCF; (b) MCF-60

Fig. 2. TEM images: (a) MCF; (b) MCF-60.

下载: 全尺寸图片幻灯片

图 3 (a) 不同样品的TGA曲线; (b) 样品中的实际PEI含量

Fig. 3. (a) TGA curves of different samples; (b) actual PEI content in the studied samples.

下载: 全尺寸图片幻灯片

图 4 经过不同含量 PEI 溶液浸渍后的样品的傅里叶变换红外光谱图

Fig. 4. Fourier transform infrared spectra of samples impregnated with PEI solution of different contents.

下载: 全尺寸图片幻灯片

图 5 不同含量 PEI浸渍前后样品的正电子湮没寿命谱图

Fig. 5. Positron annihilation lifetime spectra of samples with different PEI contents before and after immersion.

下载: 全尺寸图片幻灯片

图 6 (a) 不同样品中o-Ps的寿命; (b) 相对强度对PEI含量的依赖关系; (c) 校正寿命后得到的样品孔尺寸随PEI含量变化示意图

Fig. 6. (a) Lifetime of o-Ps in different samples; (b) dependence of relative intensity on PEI weight content; (c) diagram of sample hole size changing with PEI weight content obtained after life correction.

下载: 全尺寸图片幻灯片

[1]	Song C F, Liu Q L, Ji N, Deng S, Zhao J, Li Y, Song Y J, Li H L 2018 Renewable Sustainable Energy Rev. 82 215 Google Scholar
[2]	Xu X C, Song C S, Andresen J M, Miller B G, Scaroni A W 2002 Energy Fuels 16 1463 Google Scholar
[3]	Ma X L, Wang X X, Song C S 2009 J. Am. Chem. Soc. 131 5777 Google Scholar
[4]	Zhao D Y, Feng J L, Huo Q S, Melosh N, Fredrickson G H, Chmelka B F, Stucky G D 1998 Science 279 548 Google Scholar
[5]	Xiong H F, Zhang Y H, Wang S G, Liew K Y, Li J L 2008 J. Phys. Chem. A 112 9706 Google Scholar
[6]	Liu H, Wang G X, Liu J, Qiao S Z, Ahn H 2011 J. Mater. Chem. A 21 3046 Google Scholar
[7]	Zhang Z Y, Zuo F, Feng P Y 2010 J. Mater. Chem. A 20 2206 Google Scholar
[8]	Lu B W, Kawamoto K 2013 J. Environ. Chem. Eng. 1 300 Google Scholar
[9]	Belmabkhout Y, Serna-Guerrero R, Sayari A 2010 Ind. Eng. Chem. Res. 49 359 Google Scholar
[10]	Kim S, Ida J, Guliants V V, Lin Y S 2005 J. Phys. Chem. B 109 6287 Google Scholar
[11]	Wang L, Ma L, Wang A, Liu Q, Zhang T 2007 Chin. J. Catal. 28 805 Google Scholar
[12]	Zheng F, Tran D N, Busche B J, Fryxell G E, Addleman R S, Zemanian T S, Aardahl C L 2005 Ind. Eng. Chem. Res 44 3099 Google Scholar
[13]	Zelenak V, Halamova D, Gaberova L, Bloch E, Llewellyn P 2008 Microporous Mesoporous Mater. 116 358 Google Scholar
[14]	Mosquera M J, Pozo J, Esquivias L, Rivas T, Silva B 2002 J. Non-Cryst. Solids 311 185 Google Scholar
[15]	Brandt W, Paulin R 1968 Phys. Rev. Lett. 21 193
[16]	Zaleski R 2015 Nukleonika 60 795 Google Scholar
[17]	Schmidt-Winkel P, Lukens W W, Yang P, Margolese D I, Lettow J S, Ying J Y, Stucky G D 2000 Chem. Mater. 12 686 Google Scholar
[18]	Schmidt-Winkel P, Lukens W W, Zhao D, Yang P, Chmelka B F, Stucky G D 1999 J. Am. Chem. Soc. 121 254 Google Scholar
[19]	Song T, Zhang P, Zhang C, Gong L L, Cao X Z, Wang B Y, Yu R S, Zhou W 2022 Microporous Mesoporous Mater. 334 111761 Google Scholar
[20]	Chen Q j, Fan F C, Long D H, Liu X J, Lian X Y, Qiao W M, Ling L C 2010 Ind. Eng. Chem. Res. 49 11408 Google Scholar
[21]	Ouyang J, Zheng C H, Gu W, Zhang Y, Yang H M, Suib S L 2018 Chem. Eng. J. 337 342 Google Scholar
[22]	Klinthong W, Huang C H, Tan C S 2016 Ind. Eng. Chem. Res. 55 6481 Google Scholar
[23]	Ghoul M, Bacquet M, Crini G, Morcellet M 2003 J. Appl. Polym. Sci. 90 799 Google Scholar
[24]	Saito H, Hyodo T 2003 Phys. Rev. Lett. 90 193401 Google Scholar
[25]	Wiertel M, Surowiec Z, Budzyński M, Gac W 2013 Nukleonika 58 245
[26]	尹昊, 宋通, 彭雄刚, 张鹏, 于润升, 陈喆, 曹兴忠, 王宝义 2023 物理学报 72 114101 Google Scholar Yin H, Song T, Peng X G, Zhang P, Yu R S, Chen Z, Cao X Z, Wang B Y 2023 Acta Phys. Sin. 72 114101 Google Scholar
[27]	Dull T L, Frieze W E, Gidley D W, Sun J N, Yee A F 2001 J. Phys. Chem. B 105 4657 Google Scholar

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聚乙烯亚胺改性介孔氧化硅载体孔结构的调控机理