13X@SiO2: Synthesis and Toluene Adsorption

doi:10.15541/jim20220449

Abstract

Abstract:

In practice, adsorbents such as 13X have strong hydrophilicity due to their low Si/Al ratio, whose competitive adsorption between vapour and volatile organic compounds (VOCs) often impairs the actual removal effect of VOCs on the adsorbents. Here, 13X was modified using CTABr as a templating agent and tetraethoxysilane (TEOS) as a silica source.Based on this modified 13X, a core-shell composites with 13X core and a mesoporous silica shell, named as 13X@SiO₂, was therefore synthesized. Its adsorption performance was tested by using toluene as a probe molecule under different humidity conditions on a penetration experimental device, compared with that of the pristine 13X. The results show that the adsorption capacity of sample 13X@SiO₂-2.6 (2.6 mL TEOS added in the preparation) was about 18% higher than that of 13X original sample under dry conditions. At 30% and 50% relative humidity, the optimum adsorption capacity of 13X@SiO₂ was increased by about 53% and 90%, respectively. In order to test the stability and reusability of the adsorbents, twice regeneration of sample 13X@SiO₂-2.6, treated for 2 h in situ desorption at 350 ℃, were performed, and the result showed that the regenerated sample 13X@SiO₂-2.6 still retained 90% of the original toluene adsorption capacity.

Key words: core-shell structure, composite material, hydrophobic modification, volatile organic compounds, adsorption

CLC Number:

TQ174

MA Xiaosen, ZHANG Lichen, LIU Yanchao, WANG Quanhua, ZHENG Jiajun, LI Ruifeng. 13X@SiO₂: Synthesis and Toluene Adsorption[J]. Journal of Inorganic Materials, 2023, 38(5): 537-543.

Figures/Tables 14

Fig. S1 Diagram of the penetration experimental apparatus

Fig. 1 XRD patterns of the samples of (a) 13X, (b, e) 13X@SiO2-2.2,(c, f) 13X@SiO2-2.6, and (d, g) 13X@SiO2-3.5 (A) Large angle XRD patterns; (B) Small angle XRD patterns

Fig. 2 SEM images of the samples (A) 13X; (B, E, F) 13X@SiO2-2.2; (C) 13X@SiO2-2.6; (D) 13X@SiO2-3.5

Fig. S2 SEM images and the corresponding EDS results of samples (A) 13X; (B) 13X@SiO2-2.2; (C) 13X@SiO2-2.6; (D) 13X@SiO2-3.5

Fig. 3 TEM images of the samples (A, B, E) 13X@SiO2-2.2; (C, D) 13X@SiO2-2.6

Fig. S3 (A) Nitrogen adsorption-desorption isothermal curves and (B) the corresponding pore size distributions decided by a DFT model of samples

Table 1 Textural properties of the samples

Sample	S_BET/(m²·g^-1)	S_ext/(m²·g^-1)	S_mic/(m²·g^-1)	V_mic/(cm³·g^-1)	V_mes/(cm³·g^-1)
13X	314	14	299	0.11	0.02
13X@SiO₂-2.2	324	95	229	0.09	0.07
13X@SiO₂-2.6	337	130	207	0.08	0.09
13X@SiO₂-3.5	444	259	184	0.07	0.18

Fig. S4 FT-IR spectra of the sample (a) 13X; (b) 13X@SiO2-2.2; (C) 13X@SiO2-2.6; (D) 13X@SiO2-3.5

Fig. S5 Images of water droplets on the surfaces of different samples

Fig. 4 Adsorption of toluene on the different adsorbents under dry condition (A) Adsorption breakthrough curves; (B) Saturated adsorption capacity; (C) Comparison of the breakthrough times; (D) Cumulative adsorption capacity of different adsorbents

Fig. S6 (A) Toluene adsorption breakthrough curves and (B) cumulative toluene adsorption capacity of SiO2 under dry condition

Fig. 5 Adsorption of toluene on the different adsorbents under 30% relative humid conditions (A) Adsorption breakthrough curves; (B) Saturated adsorption capacity; (C) Comparison of the breakthrough time; (D) Cumulative adsorption capacities of different adsorbents of toluene

Fig. 6 Adsorption of toluene on the different adsorbents under 50% relative humid conditions (A) Adsorption breakthrough curves; (B) Saturated adsorption capacity; (C) Comparison of the breakthrough time; (D) Cumulative adsorption capacity of different adsorbents of toluene

Fig. S7 (A) Adsorption of toluene on different adsorbents with triple adsorption-desorption cycle. Adsorption penetration curve and (B) saturated adsorption capacity under 50% relative humid conditions

References 30

[1]	KAMAL M S, RAZZAK S A, HOSSAIN M M. Catalytic oxidation of volatile organic compounds (VOCs)-a review. Atmospheric Environment, 2016, 140: 117. DOI URL
[2]	LI W B, WANG J X, GONG H. Catalytic combustion of VOCs on non-noble metal catalysts. Catalysis Today, 2009, 148(1/2): 81. DOI URL
[3]	DENG H, PAN T T, ZHANG Y, et al. Adsorptive removal of toluene and dichloromethane from humid exhaust on MFI, BEA and FAU zeolites: an experimental and theoretical study. Chemical Engineering Journal, 2020, 394: 124986. DOI URL
[4]	ZHANG X D, LV X T, SHI X Y, et al. Enhanced hydrophobic UiO-66 (University of Oslo 66) metal-organic framework with high capacity and selectivity for toluene capture from high humid air. Journal of Colloid and Interface Science, 2018, 539: 152. DOI URL
[5]	BAEK S, KIM J, IHM S. Design of dual functional adsorbent/ catalyst system for the control of VOC’s by using metal-loaded hydrophobic Y-zeolites. Catalysis Today, 2004, 93-95: 575. DOI URL
[6]	BENKHEDDA J, JAUBERT J N, BARTH D, et al. Experimental and modeled results describing the adsorption of toluene onto activated carbon. Journal of Chemical & Engineering Data, 2000, 45(4): 650. DOI URL
[7]	KARKA S, KODUKULA S, NANDURY S V, et al. Polyethylenimine- modified zeolite 13X for CO₂ capture: adsorption and kinetic studies. ACS OMEGA, 2019, 4(15): 16441. DOI URL
[8]	HARLICK P J E, TEZEL F H. An experimental adsorbent screening study for CO₂ removal from N₂. Microporous and Mesoporous Materials, 2004, 76(1/2/3): 71. DOI URL
[9]	SHEN C M, WOREK W M. Cosorption characteristics of solid adsorbents. International Journal of Heat & Mass Transfer, 1994, 37(14): 2123.
[10]	LIU S, PENG Y, CHEN J J, et al. Engineering surface functional groups on mesoporous silica: towards a humidity-resistant hydrophobic adsorbent. Journal of Materials Chemistry A, 2018, 6(28): 13769. DOI URL
[11]	GUILLEMOT M, MIJOIN J, MIGNARD S, et al. Adsorption of tetrachloroethylene (PCE) in gas phase on zeolites of faujasite type: Influence of water vapour and of Si/Al ratio. Microporous and Mesoporous Materials, 2008, 111(1/2/3): 334. DOI URL
[12]	YIN T, MENG X, JIN L P, et al. Prepared hydrophobic Y zeolite for adsorbing toluene in humid environment. Microporous and Mesoporous Materials, 2020, 305: 110327. DOI URL
[13]	JIA L X, SUN X Y, YE X Q, et al. Core-shell composites of USY@mesosilica: synthesis and application in cracking heavy molecules with high liquid yield. Microporous and Mesoporous Materials, 2013, 176: 16-24. DOI URL
[14]	LI R N, XUE T S, LI Z, et al. Hierarchical structure ZSM-5/ SBA-15 composite with improved hydrophobicity for adsorption- desorption behavior of toluene. Chemical Engineering Journal, 2020, 392: 124861. DOI URL
[15]	LI R N, CHONG S J, ALTAF N, et al. Synthesis of ZSM-5/siliceous zeolite composites for improvement of hydrophobic adsorption of volatile organic compounds. Frontiers in chemistry, 2019, 7: 505. DOI PMID
[16]	LIU H J, WEI K Y, LONG C. Enhancing adsorption capacities of low-concentration VOCs under humid conditions using NaY@meso-SiO₂ core-shell composite. Chemical Engineering Journal, 2022, 442: 136108. DOI URL
[17]	MIYAMOTO M, ONO S, KUSUKAMI K, et al. High water tolerance of a core-shell-structured Zeolite for CO₂adsorptive separation under wet conditions. ChemSusChem, 2018, 11(11): 1756. DOI URL
[18]	LIU L Y, DU T, FANG X, et al. Preparation of hydrophobic zeolite 13X@SiO₂and their adsorption properties of CO₂and H₂O. Advanced Materials Research, 2014, 1053: 311. DOI URL
[19]	LIU L Y, SINGH R, LI G, et al. Synthesis of hydrophobic zeolite X@SiO₂ core-shell composites. Materials Chemistry and Physics, 2012, 133(2/3): 1144. DOI URL
[20]	LI R N, XUE T S, BINGRE R, et al. Microporous zeolite@vertically aligned Mg-Al layered double hydroxide core@shell structures with improved hydrophobicity and toluene adsorption capacity under wet conditions. ACS Applied Materials & Interfaces, 2018, 10(41): 34834.
[21]	YI H, LI Z Y, REN C Q. Introduction to the standard relative humidity table for saturated salt solutions (international recommendation). The 7th National Conference on Humidity and Moisture and the 5th Conference on Gas-Humidity Sensitivity, Huhehaote, 1998: 70-72.
[22]	LU S, LIU Q, HAN R, et al. Core-shell structured Y zeolite/ hydrophobic organic polymer with improved toluene adsorption capacity under dry and wet conditions. Chemical Engineering Journal, 2021, 409: 128194. DOI URL
[23]	LUO X, GUO J, CHANG P, et al. ZSM-5@MCM-41 composite porous materials with a core-shell structure: Adjustment of mesoporous orientation basing on interfacial electrostatic interactions and their application in selective aromatics transport. Separation and Purification Technology, 2020, 239: 116516. DOI URL
[24]	XIA H J, WANG J, CHEN G, et al. One-pot synthesis of SiO₂@SiO₂ core-shell microspheres with controllable mesopore size as a new stationary phase for fast HPLC separation of alkyl benzenes and β-agonists. Microchimica Acta, 2019, 186(2): 125. DOI
[25]	罗智恒. 疏水性13X沸石的制备及其在H₂O/CO₂吸附分离中的应用研究. 沈阳: 东北大学硕士学位论文, 2017.
[26]	VELLINGIRI K, KUMAR P, DEEP A, et al. Metal-organic frameworks for the adsorption of gaseous toluene under ambient temperature and pressure. Chemical Engineering Journal, 2017, 307: 1116. DOI URL
[27]	KRAUS M, TROMMLER U, HOLZER F, et al. Competing adsorption of toluene and water on various zeolites. Chemical Engineering Journal, 2018, 351: 356. DOI URL
[28]	LEE K M, KIM N S, NUMAN M, et al. Post synthetic modification of zeolite internal surface for sustainable capture of volatile organic compounds under humid conditions. ACS Applied Materials & Interfaces, 2021, 13(45): 53925.
[29]	JACOBS J H, DEERING C E, LESAGE K L, et al. Rapid cycling thermal swing adsorption apparatus: commissioning and data analyses for water adsorption of zeolites 4A and 13X over 2000 cycles. Industrial & Engineering Chemistry Research, 2021, 60(19): 7487. DOI URL
[30]	FISCHER F, LUTZ W, BUHL J C, et al. Insights into the hydrothermal stability of zeolite 13X. Microporous and Mesoporous Materials, 2018, 262: 258

13X@SiO₂: Synthesis and Toluene Adsorption

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