低温分相法制备高比表面积微/介孔SiOC陶瓷

doi:10.15541/jim20180375

摘要/Abstract

摘要：

以含氢聚硅氧烷(PHMS)、四甲基四乙烯基环四硅氧烷(D₄^vi)和铂络合物为原料, 采用热交联合成交联体, 通过水蒸汽辅助热解促进前驱体低温分相及后续HF对SiOC陶瓷侵蚀基础上, 获得高比表面积微/介孔SiOC陶瓷。采用XRD、FT-IR、SEM和BET等测试技术对试样的物相组成、化学键、微观结构、比表面积和孔径分布等进行了表征。实验结果表明, 水蒸气能够促进前驱体低温分相, 使SiOC陶瓷中生成Si-O-Si键、SiO₂纳米畴和SiO₂纳米晶, 这些可以作为造孔剂而被HF侵蚀, 从而提高了SiOC陶瓷的比表面积。在热解温度1300℃条件下, 微/介孔SiOC陶瓷具有最大比表面积1845.5 m²/g, 孔径分布2.0~10 nm。

关键词: 微/介孔SiOC陶瓷, 低温分相, 物相组成, 微观结构, 侵蚀

Abstract:

Micro/meso-porous SiOC ceramics with high surface area and narrow pore size distribution were prepared by the low temperature phase separation method (namely water vapor assisted pyrolysis) followed by etching in hydrofluoric acid (HF) solution. The cross-linked body was made from hydrogen-containing polysiloxane (PHMS), tetramethyl-tetravinylcycletetrasiloxane (D₄^vi) and Pt-complex by thermal cross-linking. Phase compositions, chemical bonds, microstructures, and specific surface area of the prepared SiOC ceramic were investigated by XRD, FT-IR, SEM, and BET, etc. Water vapor can promote the precursor to produce Si-O-Si bonds, SiO₂-rich clusters, and SiO₂ nanocrystals in SiOC ceramics. All of these species act as pore-forming substrate and can be etched away by HF. Water vapor injection and pyrolysis temperature have important effects on phase compositions, microstructures and specific surface area of SiOC porous ceramics, which have a maximum specific surface area of 1845.5 m²/g and pore size distribution of 2.0-10 nm at pyrolysis temperature of 1300℃.

Key words: micro/meso-porous SiOC, low temperature phase separation, phase composition, microstructure, etching

中图分类号:

TQ174

李家科, 韩效奇, 刘欣, 王艳香, 郭平春, 杨志胜. 低温分相法制备高比表面积微/介孔SiOC陶瓷[J]. 无机材料学报, 2018, 33(12): 1360-1364.

LI Jia-Ke, HAN Xiao-Qi, LIU Xin, WANG Yan-Xiang, GUO Ping-Chun, YANG Zhi-Sheng. Preparation of High Specific Surface Area Micro/Meso-porous SiOC Ceramics by the Low Temperature Phase Separation Method[J]. Journal of Inorganic Materials, 2018, 33(12): 1360-1364.

图/表 7

Fig. 1 XRD patterns of SiOC ceramics pyrolyzed in Ar +H2O at different temperatures(a) Before etching; (b) After etching

Fig. 2 XRD patterns of SiOC ceramics pyrolyzed in Ar at different temperatures(a) Before etching; (b) After etching

Fig. 3 FT-IR spectra of SiOC ceramics pyrolyzed in Ar+ H2O and Ar at 1300℃ before and after etching

Fig. 4 SEM cross section images of SiOC pyrolyzed at 1300℃ in Ar+H2O before (a) and after (b) etching, in Ar before (c) and after (d) etching

Fig. 5 N2 adsorption (solid symbols) and desorption (open symbols) isotherms for the samples obtained from SiOC ceramics pyrolyzed in (a) Ar +H2O and (b) Ar at 1300℃ after etching

Fig. 6 Cumulative specific surface area (S), interval specific surface area (dS) and pore size distribution (PSD) for SiOC ceramics pyrolyzed in Ar +H2O (a) and in Ar (b) at 1300℃ after etching

Table 1 BET results of SiOC ceramics after etching with different pyrolysis temperatures in Ar and Ar+H2O

Temperature/℃	Specific surface area/ (m²·g^-1)		Average pore size/nm		Pore volume/(cm³·g^-1))
Temperature/℃	Ar	Ar +H₂O	Ar	Ar +H₂O	Ar	Ar +H₂O
900	-	58.6	-	2.05	-	0.105
1100	-	435.23	-	2.16	-	0.142
1200	53.65	654.16	1.43	2.23	0.015	0.202
1300	635.13	1845.50	2.25	2.83	0.282	0.788
1400	632.24	1817.20	2.18	2.75	0.286	0.764
1500	633.52	1805.60	2.15	2.77	0.288	0.756

参考文献 14

[1]	IONESCU E, KLEEBE H J, RIEDEL R.Silicon-containing polymer- derived ceramic nanocomposites (PDC-NCs): preparative approaches and properties.Chem. Soc. Rev., 2012, 41(15): 5032-5052.
[2]	FENG Y, LAI S Y, YANG L,et al. Polymer-derived porous Bi2WO6/SiC (O) ceramic nanocomposites with high photodegradation efficiency towards Rhodamine B. Ceram. Int., 2018, 44(7): 8562-8569.
[3]	COLOMBO P.Conventional and novel processing methods for cellular ceramics.Philos. Trans., 2006, 364(1838): 109-124.
[4]	YAN X J, SAHIMI M, TSOTSIS T T.Fabrication of high-surface area nanoporous SiOC ceramics using preceramic polymer precursors and a sacrificial template: precursor effects.Micropor. Mesopor. Mat., 2017, 241: 338-345.
[5]	VAKIFAHMETOGLU C, COLOMBO P.A direct method for the fabrication of macro-porous SiOC ceramics from preceramic polymers.Adv. Eng. Mater., 2008, 10(3): 256-259.
[6]	DIBANDJO P, DIRE S, BABONNEAU F,et al. Influence of the polymer architecture on the high temperature behavior of SiCO glasses: a comparison between linear- and cyclic-derived precursors. J. Non-Cryst. Solids, 2010, 356(3): 132-140.
[7]	FORTUNIAK W, POSPIECH P, MIZERSKA U,et al. Generation of meso- and microporous structures by pyrolysis of polysiloxane microspheres and by HF etching of SiOC microspheres. Ceram. Int., 2018, 44(1): 374-383.
[8]	VAKIFAHMETOGLU C, PRESSER V, YEON S H,et al. Enhanced hydrogen and methane gas storage of silicon oxycarbide derived carbon. Micropor. Mesopor. Mat., 2011, 144(1): 105-112.
[9]	SORARU G D, PENA-ALONSO R, LEONI M.C-rich micro/ mesoporous Si(B)OC:in situ diffraction analysis of the HF etching process. Micropor. Mesopor. Mat., 2013, 172: 125-130.
[10]	XU T H, MA Q S, CHEN Z H.High-temperature behavior of silicon oxycarbide glasses in air environment.Ceram. Int., 2011, 37(7): 2555-2559.
[11]	SAHA A, RAJ R.Crystallization maps for SiCO amorphous ceramics.J. Am. Ceram. Soc., 2007, 90(2): 578-583.
[12]	LI J K, LU K, LIN T S,et al. Preparation of micro-/meso porous SiOC bulk ceramics. J. Am. Ceram. Soc., 2015, 98(6): 1753-1761.
[13]	WU J Q, LI Y M, CHEN L M,et al. Simple fabrication of micro/ nano-porous SiOC foam from polysiloxane. J. Mater. Chem., 2012, 22(14): 6542-6545.
[14]	LIANG T, LI Y L, SU D,et al. Silicon oxycarbide ceramics with reduced carbon by pyrolysis of polysiloxanes in water vapor. J. Eur. Ceram. Soc., 2010, 30(12): 2677-2682.

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