Research progress in synthesis, functionalization and metal adsorption of silica-based mesoporous materials

doi:10.16085/j.issn.1000-6613.2023-1424

Abstract

Abstract:

Silicon-based mesoporous materials are an emerging class of "milestone" materials with unique structure and properties such as tunable pore size, high specific surface area, ordered pore system and stable backbone for functionalization. So far, the application fields of these materials are still expanding, especially they have significant advantages in the adsorption of pollutants in wastewater and metal separation. Firstly, the research work of silicon-based mesoporous materials was briefly introduced, among which M41S and SBA series were the most widely studied. The preparation factors of silicon-based mesoporous materials, including template agent, silicon source, synthesis conditions and the effects of their interactions were reviewed. Material modification was inevitable. This paper summarized the research work of inorganic, organic and other modifications, and explained the function of functional modification on the structure and properties of materials. Finally, the application of these materials in metal adsorption and their adsorption properties and mechanisms were discussed, and the development direction of the synthesis and application of silicon-based mesoporous materials was prospected, which provided a theoretical basis for the reference in practical engineering.

Key words: silica, mesoporous, synthesis, composites, adsorption

摘要：

硅基介孔材料是一类具有“里程碑式”意义的新兴材料，其具有可调孔径、高比表面积、有序孔体系、易于功能化的稳定骨架等独特的结构和性能。发展至今，这些材料应用领域仍在不断扩展，尤其在吸附废水中的污染物和金属分离方面有着显著的优势。本文首先简要介绍了硅基介孔材料的研究工作，其中M41S和SBA系列介孔材料的研究最为广泛；综述了硅基介孔材料的制备要素，包括模板剂、硅源、合成条件，以及三者之间的相互作用对材料合成的影响；材料改性是研究的热点，对无机、有机和其他改性三个部分的研究工作做了总结，阐述了功能化修饰在材料的结构和性能方面的作用；最后探讨了这些材料在金属吸附方面的应用及其对金属的吸附特性和机理，并展望了硅基介孔材料在合成和应用方面的发展方向，为其在实际中的工程应用提供理论依据。

关键词: 二氧化硅, 介孔, 合成, 复合材料, 吸附

CLC Number:

O643

LIU Li, FENG Bo, WEN Yang, GU Qixiong. Research progress in synthesis, functionalization and metal adsorption of silica-based mesoporous materials[J]. Chemical Industry and Engineering Progress, 2024, 43(9): 5063-5078.

刘丽, 冯博, 文洋, 古启雄. 硅基介孔材料的合成、功能化及对金属的吸附研究进展[J]. 化工进展, 2024, 43(9): 5063-5078.

Figures/Tables 15

References 111

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硅源	硅前体提取方法	硅质量分数/%	介孔材料	参考文献
玉米芯灰	碱提酸沉	50.4	提取SiO₂	[34]
甘蔗渣和叶灰	煅烧和酸浸	88.0~95.0	SiNPs	[35]
麦秆灰	碱回流	99.0	MCM-41	[36]
麦秸灰	碱回流	>90.0	MCM-41	[37]
稻壳灰	碱熔/酸浸	88.5/95.4	KCC-1	[38]
棕榈油燃料灰	碱熔/酸浸	47.7/85.5	SBA-15	[39]
粉煤灰	碱熔	46.2~54.8	MCM-41	[40]
硅灰	—	96.9	SiNPs	[41]
铜矿石尾矿	碱性熔盐	68.2	MCM-41	[42]
金矿尾矿	碱熔	36.4/77.7	MSU-3/SBA-15	[43]
铁矿尾矿	碱熔	71.3	MS	[44]
再生玻璃	碱熔	97.8	MCM-41	[45]
电子垃圾	碱抽提	78.0	MCM-48	[46]
坡缕石	碱煅烧	50.0	MCM-41	[47]
阿尔及利亚膨润土	碱熔	60.5	MCM-41/SBA-15	[48]
高岭土	煅烧和酸浸	95.17	MCM-41	[49]
埃洛石	碱老化	32.3	SBA-15	[50]
硅藻土	碱抽提	92.8	MCM-41	[51]
累托石	碱抽提	40.4	MCM-41	[52]
珍珠岩	酸浸和碱抽提	70.8	MCM-41	[53]

硅源	硅前体提取方法	硅质量分数/%	介孔材料	参考文献
玉米芯灰	碱提酸沉	50.4	提取SiO₂	[34]
甘蔗渣和叶灰	煅烧和酸浸	88.0~95.0	SiNPs	[35]
麦秆灰	碱回流	99.0	MCM-41	[36]
麦秸灰	碱回流	>90.0	MCM-41	[37]
稻壳灰	碱熔/酸浸	88.5/95.4	KCC-1	[38]
棕榈油燃料灰	碱熔/酸浸	47.7/85.5	SBA-15	[39]
粉煤灰	碱熔	46.2~54.8	MCM-41	[40]
硅灰	—	96.9	SiNPs	[41]
铜矿石尾矿	碱性熔盐	68.2	MCM-41	[42]
金矿尾矿	碱熔	36.4/77.7	MSU-3/SBA-15	[43]
铁矿尾矿	碱熔	71.3	MS	[44]
再生玻璃	碱熔	97.8	MCM-41	[45]
电子垃圾	碱抽提	78.0	MCM-48	[46]
坡缕石	碱煅烧	50.0	MCM-41	[47]
阿尔及利亚膨润土	碱熔	60.5	MCM-41/SBA-15	[48]
高岭土	煅烧和酸浸	95.17	MCM-41	[49]
埃洛石	碱老化	32.3	SBA-15	[50]
硅藻土	碱抽提	92.8	MCM-41	[51]
累托石	碱抽提	40.4	MCM-41	[52]
珍珠岩	酸浸和碱抽提	70.8	MCM-41	[53]

结构	代表性材料	代表性结构
核-壳结构	Fe₃O₄@nSiO₂@mSiO₂球体 Fe₃O₄@mSiO₂球体（单核） Fe₃O₄-x@mSiO₂球体（多核）
嵌式结构	Fe _x O _y -SBA-15米粒状颗粒 Fe _x O _y -MCM-41球状颗粒 Fe₂O₃/FeO _x -SBA-16 Fe₃O₄/Fe₂O₃-mSiO₂球体/纳米棒 Fe₃O₄/FMSMs球体
摇铃式中空结构	Fe₃O₄/Fe₂O₃@mSiO₂椭圆体 Fe₃O₄/Fe₂O₃@mSiO₂椭圆体（双介孔壳） Fe₃O₄/Fe₂O₃@mSiO₂球体（模板法） Fe₃O₄/Fe₂O₃@mSiO₂球体（多壳可调） Fe₃O₄@mSiO₂球体（水热腐蚀法）
mSiO₂封装Fe₃O₄	mSiO₂封装Fe₃O₄	—

结构	代表性材料	代表性结构
核-壳结构	Fe₃O₄@nSiO₂@mSiO₂球体 Fe₃O₄@mSiO₂球体（单核） Fe₃O₄-x@mSiO₂球体（多核）
嵌式结构	Fe _x O _y -SBA-15米粒状颗粒 Fe _x O _y -MCM-41球状颗粒 Fe₂O₃/FeO _x -SBA-16 Fe₃O₄/Fe₂O₃-mSiO₂球体/纳米棒 Fe₃O₄/FMSMs球体
摇铃式中空结构	Fe₃O₄/Fe₂O₃@mSiO₂椭圆体 Fe₃O₄/Fe₂O₃@mSiO₂椭圆体（双介孔壳） Fe₃O₄/Fe₂O₃@mSiO₂球体（模板法） Fe₃O₄/Fe₂O₃@mSiO₂球体（多壳可调） Fe₃O₄@mSiO₂球体（水热腐蚀法）
mSiO₂封装Fe₃O₄	mSiO₂封装Fe₃O₄	—

吸附材料	金属	条件		吸附容量/mg·g^-1	等温模型	动力学模型	参考文献
吸附材料	金属	pH	T/K	吸附容量/mg·g^-1	等温模型	动力学模型	参考文献
Al-MCM-41	Cs(Ⅰ)	7	RT	84.0	Freundlich	—	[96]
MCM-41/NH₂-NTAA-MCM-41	MnO₄(Ⅰ)	3	RT	23.3/164.5	Langmuir	PSO	[97]
MCM-41/NH₂-NTAA-MCM-41	Pb(Ⅱ)	5	RT	37.8/147.5	Langmuir	PSO	[97]
胍-SBA-16	Pb(Ⅱ)	8	303	289.9	Langmuir	PSO	[98]
	Hg(Ⅱ)	5	308	259.9
	Cd(Ⅱ)	5	313	228.8
氨基丙基-SBA-15/ 氨基丙基-PVP-SBA-15	Ni(Ⅱ)	6.66	298	19.2/72.4	Langmuir	PFO	[99]
	Cu(Ⅱ)			27.3/128.2
	Pb(Ⅱ)			65.8/175.4
壳聚糖-MCM-41	Be(Ⅱ)	6	RT	—	Langmuir和Freundlich	PSO	[100]
8-羟基喹啉-MSNs	V(Ⅱ)	4	RT	492.6	Langmuir	—	[101]
聚羧酸气凝胶	Pd(Ⅱ)	2.3	RT	369.0	Sips	—	[102]
二硫代草酰胺-SBA-15	Co(Ⅱ)	10	318	2500.0	Freundlich	PSO	[103]
Sr(Ⅱ)印迹聚合物	Sr(Ⅱ)	6.5	298/308	47.3/89.1	Langmuir	PSO	[90]
壳聚糖-PAA-MCM-41	Hg(Ⅱ)	4	298	164.0	Langmuir	PSO	[51]
硫杂冠醚@SBA-15	Au(Ⅲ)	2	303	129.1	Langmuir	PSO和PFO	[104]
MnFe₂O₄-MCM-41-SH	Sb(Ⅲ)	7	RT	164.8	Langmuir	PSO	[105]
EDTA-MSF	Nd(Ⅲ)	6	298	117.0	Langmuir	PSO	[76]
Dy(Ⅲ)印迹IMS	Dy(Ⅲ)	2	298	22.3	Langmuir	PSO	[106]
硫醇-SBA-15	Pt(Ⅳ)	1~4	RT	222.0	Langmuir	—	[107]
铀酰离子印迹-MS	U(Ⅵ)	5.2	298	80.0	Langmuir	PSO	[92]
氨基丙基-MCM-41	Cr(Ⅵ)	2	298	78.8	Langmuir	—	[95]
氨基丙基-CH₃-MCM-41	Cr(Ⅵ)	2	298	29.2	Langmuir	—	[95]
乙醇胺-KIT-6	Re(Ⅶ)	3	303	111.4	Langmuir	—	[108]