溶胶-凝胶法制备介孔硅酸钙调湿材料及其性能研究

doi:10.16552/j.cnki.issn1001-1625.2025.1182

摘要/Abstract

摘要：

为实现环境湿度的高效调控并降低能源消耗，本研究聚焦于具有调节湿度功能的介孔硅酸钙材料的孔结构设计与性能优化。采用溶胶-凝胶法结合真空干燥，以正硅酸乙酯（TEOS）为硅源、四水合硝酸钙（Ca（NO₃）₂·4H₂O）为钙源，系统考察了醇水比（摩尔比，n（C₂H₅OH）/n（H₂O）=1/2~1/6）、钙硅比（摩尔比，n（Ca）/n（Si）=0.9/1~1.5/1）及焙烧温度（100~1 000 ℃）对材料结构与性能的影响。通过FT-IR、XRD、SEM、BET、TG-DTG及24 h吸放湿率测试进行系统表征，揭示了上述参数与材料孔隙结构、物相组成及调湿性能之间的构效关系。结果表明，在醇水比1/4、钙硅比1.4/1、焙烧温度500 ℃的优化条件下，材料呈现3.8~20.8 nm的窄分布介孔结构，并表现出优异的调湿能力（24 h吸湿率为207.36%，24 h放湿率为172.17%）。本研究为开发高性能介孔硅酸钙调湿材料提供了系统的工艺路线与理论基础，对推动建筑节能与绿色调湿材料的发展具有积极意义。

关键词: 介孔, 硅酸钙, 孔径分布, 吸附, 脱附, 24 h吸放湿率

Abstract:

To achieve efficient environmental humidity regulation while reducing energy consumption， this study focused on the pore structure design and performance optimization of mesoporous calcium silicate materials with humidity-regulating capabilities. Employing the sol-gel method combined with vacuum drying， with tetraethyl orthosilicate （TEOS） as the silicon source and calcium nitrate tetrahydrate （Ca（NO₃）₂·4H₂O） as the calcium source， the effects of alcohol-water ratio （molar ratio， n（C₂H₅OH）/n（H₂O）=1/2~1/6）， calcium-silicon ratio （molar ratio， n（Ca）/n（Si）=0.9/1~1.5/1）， and calcination temperature （100~1 000 ℃） on the material structure and properties were systematically investigated. Systematic characterization via FT-IR， XRD， SEM， BET， TG-DTG， and 24 h moisture adsorption/desorption tests revealed structure-property relationships between these parameters and the material’s pore structure， phase composition， and humidity-regulating performance. Results indicate that under optimized conditions of an alcohol-water ratio of 1/4， a calcium-silicon ratio of 1.4/1， and a calcination temperature of 500 ℃， the material exhibits a narrowly distributed mesoporous structure （3.8~20.8 nm） with outstanding humidity-regulating capabilities （24 h moisture absorption rate of 207.36%； 24 h moisture desorption rate of 172.17%）. This study provides a systematic process route and theoretical foundation for developing high-performance mesoporous calcium silicate humidity-regulating materials， holding positive significance for advancing building energy efficiency and green humidity-regulating materials.

Key words: mesoporous, calcium silicate, pore size distribution, adsorption, desorption, 24 h moisture adsorption and desorption rate

中图分类号:

TB34

杨雪, 姜洪义. 溶胶-凝胶法制备介孔硅酸钙调湿材料及其性能研究[J]. 硅酸盐通报, 2026, 45(6): 2160-2170.

YANG Xue, JIANG Hongyi. Sol-Gel Synthesis of Mesoporous Calcium Silicate Humidity-Regulating Material and Its Performance[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(6): 2160-2170.

图/表 21

图1 不同醇水比样品的氮气吸附-脱附曲线

Fig.1 Nitrogen adsorption-desorption isotherms of samples with different alcohol-water ratios

图2 不同醇水比样品的孔径分布曲线

Fig.2 Pore size distribution curves of samples with different alcohol-water ratios

图3 不同醇水比样品的孔容及比表面积曲线

Fig.3 Pore volume and specific surface area curves of samples with different alcohol-water ratios

图4 醇水比为1/4的样品的SEM照片

Fig.4 SEM images of sample with ethanol-water ratio of 1/4

图5 不同醇水比样品的24 h吸放湿率曲线

Fig.5 24 h moisture absorption and desorption rate curves of samples with different alcohol-water ratios

图6 不同钙硅比样品的氮气吸附-脱附曲线

Fig.6 Nitrogen adsorption-desorption isotherms of samples with different calcium-silicon ratios

图7 不同钙硅比样品的孔径分布曲线

Fig.7 Pore size distribution curves of samples with different calcium-silicon ratios

图8 不同钙硅比样品的孔容及比表面积曲线

Fig.8 Pore volume and specific surface area curves of samples with different calcium-silicon ratios

图9 钙硅比为0/1、1.0/1、1.4/1的样品的FT-IR谱

Fig.9 FT-IR spectra of samples with calcium-silicon ratios of 0/1， 1.0/1， and 1.4/1

图10 不同钙硅比样品的24 h吸放湿率曲线

Fig.10 24 h moisture absorption and desorption rate curves of samples with different calcium-silicon ratios

图11 焙烧温度为100~500 ℃时样品的氮气吸附-脱附曲线

Fig.11 Nitrogen adsorption-desorption isotherms of samples calcined at temperatures ranging from 100 ℃ to 500 ℃

图12 焙烧温度为500~1 000 ℃时样品的氮气吸附-脱附曲线

Fig.12 Nitrogen adsorption-desorption isotherms of samples calcined at temperatures ranging from 500 ℃ to 1 000 ℃

图13 不同焙烧温度样品的孔径分布曲线

Fig.13 Pore size distribution curves of samples at different calcination temperatures

图14 不同焙烧温度样品的孔容及比表面积曲线

Fig.14 Pore volume and specific surface area curves of samples at different calcination temperatures

图15 不同焙烧温度样品的SEM照片

Fig.15 SEM images of samples at different calcination temperatures

图16 经过60 ℃真空干燥4 h的凝胶样品的TG-DTG曲线

Fig.16 TG-DTG curves of gel samples dried under vacuum at 60 ℃ for 4 h

图17 干燥后凝胶和焙烧温度为100、400、500 ℃的样品的FT-IR谱

Fig.17 FT-IR spectra of dried gel and samples calcined at 100， 400， and 500 ℃

图18 焙烧温度为500、600、700、1 000 ℃的样品的FT-IR谱

Fig.18 FT-IR spectra of samples calcined at 500， 600， 700， and 1 000 ℃

图19 焙烧温度为100~500 ℃的样品的XRD谱

Fig.19 XRD patterns of samples calcined at temperatures ranging from 100 ℃ to 500 ℃

图20 焙烧温度为600~1 000 ℃的样品的XRD谱

Fig.20 XRD patterns of samples calcined at temperatures ranging from 600 ℃ to 1 000 ℃

图21 不同焙烧温度样品的24 h吸、放湿率曲线

Fig.21 24 h moisture absorption and desorption rate curves of samples at different calcination temperatures

参考文献 22

[1]	NIU R P， CHEN X Y， LIU H. Analysis of the impact of a fresh air system on the indoor environment in office buildings［J］. Sustainable Cities and Society， 2022， 83： 103934. DOI URL
[2]	LIU C， ZHANG Y L， SUN L M， et al. Influence of indoor air temperature and relative humidity on learning performance of undergraduates［J］. Case Studies in Thermal Engineering， 2021， 28： 101458. DOI URL
[3]	MELIA R J W， DU VE FLOREY C， MORRIS R W， et al. Childhood respiratory illness and the home environemt II. association between respiratory illness and nitrogen dioxide， temperature and relative humidity［J］. International Journal of Epidemiology， 1982， 11（2）： 164-169. DOI URL
[4]	TU Y D， WANG R Z， GE T S， et al. Comfortable， high-efficiency heat pump with desiccant-coated， water-sorbing heat exchangers［J］. Scientific Reports， 2017， 7： 40437. DOI
[5]	BRAMBILLA A， SANGIORGIO A. Mould growth in energy efficient buildings： causes， health implications and strategies to mitigate the risk［J］. Renewable and Sustainable Energy Reviews， 2020， 132： 110093. DOI URL
[6]	TANAKA， MIYANO S. The variance of humidity in room according to wall materials［A］. Research Report of Architectural Institute of Japan， 1949： 21-25.
[7]	彭小芹，何丽娟，刘艳萌. 水热法制备水化硅酸钙纳米粉体［J］. 重庆大学学报（自然科学版）， 2005， 28（5）： 59-62.
	PENG X Q， HE L J， LIU Y M. Hydrated calcium silicate with nm-order size manufactured by using dynamic autoclaved technology［J］. Journal of Chongqing University （Natural Science Edition）， 2005， 28（5）： 59-62 （in Chinese）.
[8]	潘雅婷. 超级活性炭、介孔硅酸钙、二氧化硅气凝胶及氧化石墨烯作为阿维菌素缓释载体的制备与研究［D］. 南昌：华东交通大学， 2021.
	PAN Y T. Preparation and study of super activated carbon， mesoporous calcium silicate， silica aerogel， and graphene oxide as sustained-release carriers for avermectin［D］. Nanchang： East China Jiaotong University， 2021 （in Chinese）.
[9]	MIAO J J， ZHU W H， YUE L， et al. Reutilizing paper mill sludge as humidity regulating material by hydrothermal solidifying［J］. Waste and Biomass Valorization， 2022， 13（8）： 3585-3595. DOI
[10]	韦祖宇. 介孔硅酸钙和介孔硅酸镁粉体的制备及其性能研究［D］. 北京：北京化工大学， 2025.
	WEI Z Y. Preparation and performance study of mesoporous calcium silicate and mesoporous magnesium silicate powders［D］. Beijing： Beijing University of Chemical Technology， 2025 （in Chinese）.
[11]	CHIKAO A， TAKASHI M， YUKIHISA M， et al. 水蒸気吸着法による多孔質体の細孔分布測定［J］. 粉体工学会誌， 1983， 20（3）： 115-121.
	CHIKAO A， TAKASHI M， YUKIHISA M， et al. Measurement of pore distribution in porous materials using the water vapor adsorption method［J］. Journal of the Society of Powder Technology， 1983， 20（3）： 115-121 （in Japanese）. DOI URL
[12]	中华人民共和国国家质量监督检验检疫总局，中国国家标准化管理委员会. 建筑材料及制品的湿热性能吸湿性能的测定：［S］. 北京：中国标准出版社， 2006.
	General Administration of Quality Supervision， Inspection and Quarantine of the People’s Republic of China， AdministrationStandardization. Hygrothermal performance of building materials and products—determination of hygroscopic sorption properties：［S］. Beijing： Standards Press of China， 2006 （in Chinese）.
[13]	中华人民共和国国家质量监督检验检疫总局，中国国家标准化管理委员会. 建筑材料及制品的湿热性能含湿率的测定烘干法：［S］. 北京：中国标准出版社， 2006.
	General Administration of Quality Supervision， Inspection and Quarantine of the People’s Republic of China， AdministrationStandardization. Hygrothermal performance of building materials and produts—determinaton of moisture content by drying at elevated temperature：［S］. Beijing： Standards Press of China， 2006 （in Chinese）.
[14]	张锐，秦丹丹，王海龙，等. 溶胶凝胶法制备SiO₂工艺［J］. 郑州大学学报（工学版）， 2006， 27（3）： 119-122.
	ZHANG R， QIN D D， WANG H L， et al. Preparation of SiO₂ sol-gel［J］. Journal of Zhengzhou University （Engineering Science）， 2006， 27（3）： 119-122 （in Chinese）.
[15]	LEE B S， LIN H P， CHAN J C， et al. A novel sol-gel-derived calcium silicate cement with short setting time for application in endodontic repair of perforations［J］. International Journal of Nanomedicine， 2018， 13： 261-271. DOI URL
[16]	HOU D S， LU Z Y， ZHAO T J， et al. Reactive molecular simulation on the ordered crystal and disordered glass of the calcium silicate hydrate gel［J］. Ceramics International， 2016， 42（3）： 4333-4346. DOI URL
[17]	夏淑婷. 连续流动合成多孔硅酸钙镁及其生物活性研究［D］. 杭州：浙江工业大学， 2020.
	XIA S T. Study on continuous flow synthesis of porous calcium-magnesium silicate and its biological activity［D］. Hangzhou： Zhejiang University of Technology， 2020 （in Chinese）.
[18]	JAWAD AHMED M， SCHOLLBACH K， VAN DER LAAN S， et al. A quantitative analysis of dicalcium silicate synthesized via different sol-gel methods［J］. Materials & Design， 2022， 213： 110329.
[19]	MEISZTERICS A， SINKÓ K. Sol-gel derived calcium silicate ceramics［J］. Colloids and Surfaces A： Physicochemical and Engineering Aspects， 2008， 319（1/2/3）： 143-148.
[20]	ZHANG M L， CHANG J. Surfactant-assisted sonochemical synthesis of hollow calcium silicate hydrate （CSH） microspheres for drug delivery［J］. Ultrasonics Sonochemistry， 2010， 17（5）： 789-792. DOI URL
[21]	胡锦轩，李德梁，金依濛，等. 复合改性纤维基调湿材料吸放湿性能研究［J］. 新型建筑材料， 2024， 51（8）： 13-17.
	HU J X， LI D L， JIN Y M， et al. Study on the moisture absorption and desorption properties of composite modified fiber-based humidity-controlling material［J］. New Building Materials， 2024， 51（8）： 13-17 （in Chinese）.
[22]	YIN J H， LI W Y， WANG J， et al. Irreversible microstructural changes of calcium silicate hydrate during the first drying-resaturation cycle［J］. Cement and Concrete Research， 2023， 163： 107032. DOI URL