Effect of hollow structure on the acetone adsorption property of tungsten-substituted MFI zeolite

doi:10.11949/0438-1157.20211439

Abstract

Abstract:

Zeolite adsorbents for the adsorption and removal of volatile organic compounds (VOCs) have attracted considerable attention in recent years. However, the low adsorption capacity, slow adsorption rate, and hydrophilic nature strongly restrict the development of zeolite-type VOCs adsorbents. In this paper, tungsten-substituted MFI zeolites (HWS-1_S and HWS-1_W) with two kinds of hollow structures (fully and multichambered) are prepared by post-treating the siliceous MFI (S-1) and tungsten-substituted MFI (WS-1) through desilication and tungstation, respectively. And the effect of the hollow morphology on VOCs adsorption performance is investigated by using acetone as an adsorbate. The results show that HWS-1_S and HWS-1_W exhibit faster adsorption rates for acetone compared to the parent S-1 and WS-1 benefitted from their highly interconnected hollow structures. HWS-1_S shows a limited adsorption capacity (27.4 mg·g^-1) of acetone than S-1 due to its reduced micropore volume, while HWS-1_W presents an increased adsorption capacity (51.2 mg·g^-1) of acetone compared with WS-1, which could be ascribed to the defect removal by tungstation. Acetone dominatly performs as physical absorption on both HWS-1_S and HWS-1_W based on the fitting results of adsorption kinetics. Moreover, substitution of W atoms within zeolite frameworks can neutralize silanol groups and further enhance the hydrophobicity of zeolite adsorbents, leading an effective resistance of competitive adsorption of water.

Key words: VOCs, acetone, adsorption, tungsten-substituted zeolite, hollow structure, adsorption kinetics

摘要：

吸附容量高、吸附速率快以及憎水性强是分子筛用于挥发性有机物(VOCs)高效吸附的主要性能指标。分别以纯硅(S-1)和W掺杂(WS-1)MFI分子筛为母体，通过一步水热脱硅/补钨后处理制备了具有全空腔(HWS-1_S)和多孔芯(HWS-1_W)的两种中空结构分子筛，并以典型的VOCs气体分子丙酮为探针，系统研究了中空结构形态对于分子筛吸附性能的影响。结果表明：HWS-1_S表面部分开孔，内部全空腔且与外部连通，相比于母体S-1，相对结晶度较低，微孔孔容减少；HWS-1_W表面开孔细微，内部出现不规则的大/中孔结构，相比母体WS-1，相对结晶度提高，微孔孔容增大。干气条件下，HWS-1_S与HWS-1_W相比母体S-1和WS-1对丙酮具有更快的吸附速率；HWS-1_S微孔孔容损失严重，导致吸附容量有限(27.4 mg·g^-1)；HWS-1_W由于重结晶修复了部分结构缺陷，提高了丙酮吸附容量(51.2 mg·g^-1）。通过吸附动力学拟合，HWS-1_S和HWS-1_W符合典型的孔扩散机理，对丙酮主要以物理吸附为主。湿气条件下，W掺杂可有效中和中空分子筛表面硅醇基团，在一定程度上提高了W掺杂中空分子筛抗水汽竞争吸附能力。

关键词: VOCs, 丙酮, 吸附, W掺杂分子筛, 中空结构, 吸附动力学

CLC Number:

TQ 424.25

Xu WANG, Leyao ZHANG, Haoxuan ZHANG, Jiahui YAN, Yushuai WU, Dong WU, Huiyong CHEN, Xiaoxun MA. Effect of hollow structure on the acetone adsorption property of tungsten-substituted MFI zeolite[J]. CIESC Journal, 2022, 73(3): 1194-1206.

王旭, 张乐瑶, 张昊轩, 演嘉辉, 吴玉帅, 吴冬, 陈汇勇, 马晓迅. 中空孔结构对W掺杂MFI分子筛丙酮吸附行为的研究[J]. 化工学报, 2022, 73(3): 1194-1206.

Figures/Tables 12

Fig.1 XRD patterns of S-1, WS-1, HWS-1_S, and HWS-1_W zeolites

Table 1 Metal （W） contents， synthesis yields， crystallinities and textual properties of various zeolite samples

样品	金属含量/ %(质量)	产率/%	相对结晶度/%	比表面积/(m²·g^-1)	外表面积/(m²·g^-1)	S_外表面积/S_比表面积	微孔孔容/(cm³·g^-1)	总孔容/(cm³·g^-1)	V_微孔孔容/V_总孔容
S-1	—	100	100	427	63	0.15	0.17	0.24	0.71
WS-1	0.01	100	100	352	68	0.19	0.10	0.23	0.43
HWS-1_S	0.09	70	78	253	51	0.20	0.08	0.29	0.28
HWS-1_W	0.13	75	106	385	91	0.24	0.12	0.34	0.35

Fig.2 SEM [(a)—(d)] and TEM [(e)—(f)] images of S-1, WS-1, HWS-1_S, and HWS-1_W zeolites

Fig.3 N2 physisorption isotherms (a), and BJH pore size distribution (b) of S-1, WS-1, HWS-1_S and HWS-1_W zeolites

Fig.4 UV-visible spectra of S-1, WS-1, HWS-1_S and HWS-1_W zeolites

Fig.5 UV-Raman spectra of S-1, WS-1, HWS-1_S and HWS-1_W zeolites

Fig.6 Breakthrough curves of acetone adsorption on parent and corresponding hollow zeolites (a), and differences between saturation capacities and breakthrough capacities on parent and corresponding hollow zeolite adsorbents (b)

Table 2 Fitting of breakthrough curves by using Yoon-Nelson model

样品	Yoon-Nelson模型拟合值			实验值
样品	$τ$ /min^①	$k'$ ^②/min^-1	R²	$τ$ /min
S-1	218	0.024	0.995	216
HWS-1_S	106	0.076	0.996	102
WS-1	140	0.036	0.998	141
HWS-1_W*^③	163	0.092	0.999	162
HWS-1_W	196	0.085	0.998	197

Table 2 Fitting of breakthrough curves by using Yoon-Nelson model

样品	Yoon-Nelson模型拟合值			实验值
样品	$τ$ /min^①	$k'$ ^②/min^-1	R²	$τ$ /min
S-1	218	0.024	0.995	216
HWS-1_S	106	0.076	0.996	102
WS-1	140	0.036	0.998	141
HWS-1_W*^③	163	0.092	0.999	162
HWS-1_W	196	0.085	0.998	197

Table 3 Fitting parameters of acetone adsorption kinetics of parent and corresponding hollow zeolite adsorbents

理论模型	参数	S-1	WS-1	HWS-1_S	HWS-1_W
准一级模型	k₁/min^-1	0.006	0.008	0.01	0.003
	q_e/(mg·g^-1)	64.73	45.64	34.91	110.99
	R²	0.983	0.991	0.988	0.992
准二级模型	k₂/min^-1	5.79×10^-5	7.91×10^-5	1.28×10^-4	7.75×10^-6
	q_e/(mg·g^-1)	87.22	68.93	53.63	198.83
	R²	0.968	0.987	0.985	0.992
班厄姆模型	k₃/min^-^z	9.80×10^-4	1.95×10^-3	2.20×10^-3	1.14×10^-3
	q_e/(mg·g^-1)	59.77	38.33	28.26	62.25
	z	1.388	1.371	1.445	1.346
	R²	0.999	0.999	0.998	0.997
表观扩散系数	(D/r₀²) $×$ 10^-4/s^-1	5.10	8.63	12.9	7.56
表观扩散系数	R²	0.993	0.995	0.996	0.988

Table 3 Fitting parameters of acetone adsorption kinetics of parent and corresponding hollow zeolite adsorbents

理论模型	参数	S-1	WS-1	HWS-1_S	HWS-1_W
准一级模型	k₁/min^-1	0.006	0.008	0.01	0.003
	q_e/(mg·g^-1)	64.73	45.64	34.91	110.99
	R²	0.983	0.991	0.988	0.992
准二级模型	k₂/min^-1	5.79×10^-5	7.91×10^-5	1.28×10^-4	7.75×10^-6
	q_e/(mg·g^-1)	87.22	68.93	53.63	198.83
	R²	0.968	0.987	0.985	0.992
班厄姆模型	k₃/min^-^z	9.80×10^-4	1.95×10^-3	2.20×10^-3	1.14×10^-3
	q_e/(mg·g^-1)	59.77	38.33	28.26	62.25
	z	1.388	1.371	1.445	1.346
	R²	0.999	0.999	0.998	0.997
表观扩散系数	(D/r₀²) $×$ 10^-4/s^-1	5.10	8.63	12.9	7.56
表观扩散系数	R²	0.993	0.995	0.996	0.988

Fig.7 Fitting of acetone adsorption kinetics on S-1 (a), WS-1 (b), HWS-1_S (c), and HWS-1_W (d) zeolite adsorbents

Fig.8 W-M model curves (a) and fitting of apparent diffusion coefficients (b) of parent and hollow zeolites adsorbents

Table 4 Acetone adsorption breakthrough times and saturation adsorption capacities of parent and corresponding hollow zeolite adsorbents at RH = 0 and RH = 10%

样品	穿透时间 $t$ /min^①		饱和吸附量 $Q e$ /(mg·g^-1)		(Q_wet/Q_dry)/%
样品	RH=0	RH=10%	RH=0	RH=10%	(Q_wet/Q_dry)/%
S-1	120	96	59.2	49.7	83.9
HWS-1_S	48	36	27.4	21.5	78.5
WS-1	80	60	36.8	32.1	87.2
HWS-1_W*^②	135	100	42.3	36.4	86.0
HWS-1_W	160	120	51.2	40.4	78.9
HWS-1_W_R^③	156	110	50.1	38.8	77.4

Table 4 Acetone adsorption breakthrough times and saturation adsorption capacities of parent and corresponding hollow zeolite adsorbents at RH = 0 and RH = 10%

样品	穿透时间 $t$ /min^①		饱和吸附量 $Q e$ /(mg·g^-1)		(Q_wet/Q_dry)/%
样品	RH=0	RH=10%	RH=0	RH=10%	(Q_wet/Q_dry)/%
S-1	120	96	59.2	49.7	83.9
HWS-1_S	48	36	27.4	21.5	78.5
WS-1	80	60	36.8	32.1	87.2
HWS-1_W*^②	135	100	42.3	36.4	86.0
HWS-1_W	160	120	51.2	40.4	78.9
HWS-1_W_R^③	156	110	50.1	38.8	77.4

References 44

1	He C, Cheng J, Zhang X, et al. Recent advances in the catalytic oxidation of volatile organic compounds: a review based on pollutant sorts and sources[J]. Chemical Reviews, 2019, 119(7): 4471-4568.
2	Maudhuit A, Raillard C, Héquet V, et al. Adsorption phenomena in photocatalytic reactions: the case of toluene, acetone and heptane[J]. Chemical Engineering Journal, 2011, 170(2/3): 464-470.
3	孙静, 董一霖, 李法齐, 等. Co₃O₄改性USY分子筛吸附和催化氧化甲苯特性研究[J]. 化工学报, 2021, 72(6): 3306-3315.
	Sun J, Dong Y L, Li F Q, et al. Study on adsorption and catalytic oxidation characteristics of toluene on Co₃O₄ modified USY molecular sieve[J]. CIESC Journal, 2021, 72(6): 3306-3315.
4	高君安, 王伟, 张傑, 等. 用于高湿度废气中甲苯吸附净化的疏水型ZSM-5分子筛的合成及其吸附性能研究[J]. 化工学报, 2020, 71(1): 337-343.
	Gao J A, Wang W, Zhang J, et al. Study on synthesis and adsorption performance of hydrophobic ZSM-5 zeolites for removal of toluene in high-humidity exhaust gas[J]. CIESC Journal, 2020, 71(1): 337-343.
5	Sui H, Liu J J, He L, et al. Adsorption and desorption of binary mixture of acetone and ethyl acetate on silica gel[J]. Chemical Engineering Science, 2019, 197: 185-194.
6	Baek S W, Kim J R, Ihm S K. Design of dual functional adsorbent/catalyst system for the control of VOC’s by using metal-loaded hydrophobic Y-zeolites[J]. Catalysis Today, 2004, 93/94/95: 575-581.
7	Ouzzine M, Romero-Anaya A J, Lillo-Ródenas M A, et al. Spherical activated carbons for the adsorption of a real multicomponent VOC mixture[J]. Carbon, 2019, 148: 214-223.
8	Yang C T, Miao G, Pi Y H, et al. Abatement of various types of VOCs by adsorption/catalytic oxidation: a review[J]. Chemical Engineering Journal, 2019, 370: 1128-1153.
9	Zhang X Y, Gao B, Creamer A E, et al. Adsorption of VOCs onto engineered carbon materials: a review[J]. Journal of Hazardous Materials, 2017, 338: 102-123.
10	Zhang L, Peng Y X, Zhang J, et al. Adsorptive and catalytic properties in the removal of volatile organic compounds over zeolite-based materials[J]. Chinese Journal of Catalysis, 2016, 37(6): 800-809.
11	Shah I K, Pre P, Alappat B J. Effect of thermal regeneration of spent activated carbon on volatile organic compound adsorption performances[J]. Journal of the Taiwan Institute of Chemical Engineers, 2014, 45(4): 1733-1738.
12	Veerapandian S K P, de Geyter N, Giraudon J M, et al. The use of zeolites for VOCs abatement by combining non-thermal plasma, adsorption, and/or catalysis: a review[J]. Catalysts, 2019, 9(1): 98.
13	Song W, Justice R E, Jones C A, et al. Size-dependent properties of nanocrystalline silicalite synthesized with systematically varied crystal sizes[J]. Langmuir, 2004, 20(11): 4696-4702.
14	Li X Q, Zhang L, Yang Z Q, et al. Adsorption materials for volatile organic compounds (VOCs) and the key factors for VOCs adsorption process: a review[J]. Separation and Purification Technology, 2020, 235: 116213.
15	Lou F J, Zhang G H, Ren L M, et al. Impacts of nano-scale pore structure and organic amine assembly in porous silica on the kinetics of CO₂ adsorptive separation[J]. Nano Research, 2021, 14(9): 3294-3302.
16	Chen L H, Sun M H, Wang Z, et al. Hierarchically structured zeolites: from design to application[J]. Chemical Reviews, 2020, 120(20): 11194-11294.
17	Li Y, Li L, Yu J H. Applications of zeolites in sustainable chemistry[J]. Chem, 2017, 3(6): 928-949.
18	Feng A H, Yu Y, Mi L, et al. Structural, textural and toluene adsorption properties of NH₄HF₂ and alkali modified USY zeolite[J]. Microporous and Mesoporous Materials, 2019, 290: 109646.
19	Feng A H, Mi L, Yu Y, et al. Development of intracrystalline mesoporosity in NH₄HF₂-etched NaY zeolites by surfactant-templating and its effect on toluene adsorption[J]. Chemical Engineering Journal, 2020, 390: 124529.
20	Cosseron A F, Daou T J, Tzanis L, et al. Adsorption of volatile organic compounds in pure silica CHA, BEA, MFI and STT-type zeolites[J]. Microporous and Mesoporous Materials, 2013, 173: 147-154.
21	Zhu L L, Shen D K, Luo K H. A critical review on VOCs adsorption by different porous materials: species, mechanisms and modification methods[J]. Journal of Hazardous Materials, 2020, 389: 122102.
22	Dai C Y, Zhang A F, Li L L, et al. Synthesis of hollow nanocubes and macroporous monoliths of silicalite-1 by alkaline treatment[J]. Chemistry of Materials, 2013, 25(21): 4197-4205.
23	Medeiros-Costa I C, Dib E, Nesterenko N, et al. Silanol defect engineering and healing in zeolites: opportunities to fine-tune their properties and performances[J]. Chemical Society Reviews, 2021, 50(19): 11156-11179.
24	Grand J, Talapaneni S N, Vicente A, et al. One-pot synthesis of silanol-free nanosized MFI zeolite[J]. Nature Materials, 2017, 16(10): 1010-1015.
25	Grand J, Talapaneni S N, Aleksandrov H A, et al. Hydrophobic tungsten-containing MFI-type zeolite films for exhaust gas detection[J]. ACS Applied Materials & Interfaces, 2019, 11(13): 12914-12919.
26	Dubray F, Moldovan S, Kouvatas C, et al. Direct evidence for single molybdenum atoms incorporated in the framework of MFI zeolite nanocrystals[J]. Journal of the American Chemical Society, 2019, 141(22): 8689-8693.
27	Guo Y, Quan X, Lu N, et al. High photocatalytic capability of self-assembled nanoporous WO₃ with preferential orientation of (002) planes[J]. Environmental Science & Technology, 2007, 41(12): 4422-4427.
28	Zhang H Y, Yang X T, Song X J, et al. Hydrothermal synthesis of tungsten-tin bimetallic MFI type zeolites and their catalytic properties for cyclohexene epoxidation[J]. Microporous and Mesoporous Materials, 2020, 303: 110277.
29	Wang X, You Q, Wu Y S, et al. Tungsten-substituted Silicalite-1 with an interconnected hollow structure for catalytic epoxidation of cyclohexene[J]. Microporous and Mesoporous Materials, 2021, 317: 111028.
30	Dai C Y, Zhang S H, Zhang A F, et al. Hollow zeolite encapsulated Ni–Pt bimetals for sintering and coking resistant dry reforming of methane[J]. Journal of Materials Chemistry A, 2015, 3(32): 16461-16468.
31	Wang Y S, Jia H, Fang X, et al. CO₂ and water vapor adsorption properties of framework hybrid W-ZSM-5/silicalite-1 prepared from RHA[J]. RSC Advances, 2020, 10(41): 24642-24652.
32	Wu H Y, Zhang X L, Yang C Y, et al. Alkali-hydrothermal synthesis and characterization of W-MCM-41 mesoporous materials with various Si/W molar ratios[J]. Applied Surface Science, 2013, 270: 590-595.
33	Watmanee S, Suriye K, Praserthdam P, et al. Formation of isolated tungstate sites on hierarchical structured SiO₂- and HY zeolite-supported WO _x catalysts for propene metathesis[J]. Journal of Catalysis, 2019, 376: 150-160.
34	Hu Q, Li J J, Hao Z P, et al. Dynamic adsorption of volatile organic compounds on organofunctionalized SBA-15 materials[J]. Chemical Engineering Journal, 2009, 149(1/2/3): 281-288.
35	Li X F, Wang J, Guo Y Y, et al. Adsorption and desorption characteristics of hydrophobic hierarchical zeolites for the removal of volatile organic compounds[J]. Chemical Engineering Journal, 2021, 411: 128558.
36	Chandak M V, Lin Y S. Hydrophobic zeolites as adsorbents for removal of volatile organic compounds from air[J]. Environmental Technology, 1998, 19(9): 941-948.
37	Mi Z R, Li J, Lu T T, et al. Reducing the dosage of the organic structure-directing agent in the crystallization of pure silica zeolite MFI (silicalite-1) for volatile organic compounds (VOCs) adsorption[J]. Inorganic Chemistry Frontiers, 2021, 8(13): 3354-3362.
38	Guo M, Liu Q, Lu S, et al. Synthesis of silanol-rich MCM-48 with mixed surfactants and their application in acetone adsorption: equilibrium, kinetic, and thermodynamic studies[J]. Langmuir, 2020, 36(39): 11528-11537.
39	Fang H J, Zheng A M, Chu Y Y, et al. ¹³C chemical shift of adsorbed acetone for measuring the acid strength of solid acids: a theoretical calculation study[J]. The Journal of Physical Chemistry C, 2010, 114(29): 12711-12718.
40	Huang S S, Deng W, Zhang L, et al. Adsorptive properties in toluene removal over hierarchical zeolites[J]. Microporous and Mesoporous Materials, 2020, 302: 110204.
41	Zhou J, Fan W, Wang Y D, et al. The essential mass transfer step in hierarchical/nano zeolite: surface diffusion[J]. National Science Review, 2020, 7(11): 1630-1632.
42	Zhu Z G, Xu H, Jiang J G, et al. Hydrophobic nanosized all-silica beta zeolite: efficient synthesis and adsorption application[J]. ACS Applied Materials & Interfaces, 2017, 9(32): 27273-27283.
43	Bal'Zhinimaev B S, Paukshtis E A, Toktarev A V, et al. Effect of water on toluene adsorption over high silica zeolites[J]. Microporous and Mesoporous Materials, 2019, 277: 70-77.
44	Iyoki K, Kikumasa K, Onishi T, et al. Extremely stable zeolites developed via designed liquid-mediated treatment[J]. Journal of the American Chemical Society, 2020, 142(8): 3931-3938.

[1]	Bingchun SHENG, Jianguo YU, Sen LIN. Study on lithium resource separation from underground brine with high concentration of sodium by aluminum-based lithium adsorbent [J]. CIESC Journal, 2023, 74(8): 3375-3385.
[2]	Ruihang ZHANG, Pan CAO, Feng YANG, Kun LI, Peng XIAO, Chun DENG, Bei LIU, Changyu SUN, Guangjin CHEN. Analysis of key parameters affecting product purity of natural gas ethane recovery process via ZIF-8 nanofluid [J]. CIESC Journal, 2023, 74(8): 3386-3393.
[3]	Yan GAO, Peng WU, Chao SHANG, Zejun HU, Xiaodong CHEN. Preparation of magnetic agarose microspheres based on a two-fluid nozzle and their protein adsorption properties [J]. CIESC Journal, 2023, 74(8): 3457-3471.
[4]	Ji CHEN, Ze HONG, Zhao LEI, Qiang LING, Zhigang ZHAO, Chenhui PENG, Ping CUI. Study on coke dissolution loss reaction and its mechanism based on molecular dynamics simulations [J]. CIESC Journal, 2023, 74(7): 2935-2946.
[5]	Jie WANG, Xiaolin QIU, Ye ZHAO, Xinyang LIU, Zhongqiang HAN, Yong XU, Wenhan JIANG. Preparation and properties of polyelectrolyte electrostatic deposition modified PHBV antioxidant films [J]. CIESC Journal, 2023, 74(7): 3068-3078.
[6]	Shaoyun CHEN, Dong XU, Long CHEN, Yu ZHANG, Yuanfang ZHANG, Qingliang YOU, Chenglong HU, Jian CHEN. Preparation and adsorption properties of monolayer polyaniline microsphere arrays [J]. CIESC Journal, 2023, 74(5): 2228-2238.
[7]	Caihong LIN, Li WANG, Yu WU, Peng LIU, Jiangfeng YANG, Jinping LI. Effect of alkali cations in zeolites on adsorption and separation of CO₂/N₂O [J]. CIESC Journal, 2023, 74(5): 2013-2021.
[8]	Chenxin LI, Yanqiu PAN, Liu HE, Yabin NIU, Lu YU. Carbon membrane model based on carbon microcrystal structure and its gas separation simulation [J]. CIESC Journal, 2023, 74(5): 2057-2066.
[9]	Yu PAN, Zihang WANG, Jiayun WANG, Ruzhu WANG, Hua ZHANG. Heat and moisture performance study of Cur-LiCl coated heat exchanger [J]. CIESC Journal, 2023, 74(3): 1352-1359.
[10]	Xuanjun WU, Chao WANG, Zijian CAO, Weiquan CAI. Deep learning model of fixed bed adsorption breakthrough curve hybrid-driven by data and physical information [J]. CIESC Journal, 2023, 74(3): 1145-1160.
[11]	Xiaowan PENG, Xiaonan GUO, Chun DENG, Bei LIU, Changyu SUN, Guangjin CHEN. Modeling and simulation of CH₄/N₂ separation process with two absorption-adsorption columns using ZIF-8 slurry [J]. CIESC Journal, 2023, 74(2): 784-795.
[12]	Jinlin MENG, Yu WANG, Qunfeng ZHANG, Guanghua YE, Xinggui ZHOU. Pore network model of low-temperature nitrogen adsorption-desorption in mesoporous materials [J]. CIESC Journal, 2023, 74(2): 893-903.
[13]	Wan XU, Zhenbin CHEN, Huijuan ZHANG, Fangfang NIU, Ting HUO, Xingsheng LIU. Study on synthesis, adsorption and desorption performance of linear temperature-sensitive segment polymer regulated intelligent $R e O 4 -$ ion-imprinted polymer [J]. CIESC Journal, 2023, 74(2): 941-952.
[14]	Jiahao JIANG, Xiaole HUANG, Jiyun REN, Zhengrong ZHU, Lei DENG, Defu CHE. Qualitative and quantitative study on Pb²⁺ adsorption by biochar in solution [J]. CIESC Journal, 2023, 74(2): 830-842.
[15]	Yingxi DANG, Peng TAN, Xiaoqin LIU, Linbing SUN. Temperature swing for CO₂ capture driven by radiative cooling and solar heating [J]. CIESC Journal, 2023, 74(1): 469-478.