多级多孔硅酸镍微球的合成及其对碱性品红的高效吸附

doi:10.15541/jim20210063

摘要/Abstract

摘要：

层状硅酸镍因其独特的结构, 在电化学和催化等领域展现出良好的应用前景, 其合成与性能研究近年来受到广泛关注。本研究以氯化镍和正硅酸乙酯为原料, 采用水热法合成了硅酸镍微球, 并详细探究了镍硅比和碱源对产物组成、形貌及孔结构的影响。在优化条件下, 产物呈现由纳米片组装的、平均直径约为2.5 μm的微球形貌, 比表面积为119.6 m²·g^-1, 孔容为0.673 cm³·g^-1。Zeta电位分析表明, 该微球在pH=3~10范围内保持表面电负性。将硅酸镍微球用于处理碱性品红溶液, 吸附过程符合准二级动力学模型。在初始浓度为50 mg·L^-1的条件下, 吸附容量可达120.7 mg·g^-1, 脱除率达96.6%, 远优于改性粘土及近年来报道的多种材料。吸附量与平衡浓度的数据表明, 碱性品红在硅酸镍微球上的吸附符合Freundlich吸附模型, 1/n=0.1678, 表明该吸附为多层非均相吸附且吸附作用力强。

关键词: 硅酸镍, 水热合成, 染料去除, 吸附, 碱性品红

Abstract:

Nickel phyllosilicates have shown considerable potential in many fields such as electrochemistry and catalysis owing to their specific structures, attracting a great attention on preparation and properties of them in recent years. In this study, Ni₃Si₂O₅(OH)₄ microspheres were synthesized via a hydrothermal method by using NiCl₂ and tetraethyl orthosilicate (TEOS) as the raw materials. Effects of Ni/Si molar ratio and alkali source on the phase composition, morphology and textural property of the products were investigated. Under optimized conditions, the as-synthesized Ni₃Si₂O₅(OH)₄ microspheres presented a nanosheets-assembled morphology with an average diameter of ca. 2.5 μm, S_BET of 119.6 m²·g^-1, pore volume of 0.673 cm³·g^-1, and Zeta potential measurements showed that they were negatively charged with pH ranging from 3 to 10. When employed as the adsorbents for basic fuchsin (BF), the Ni₃Si₂O₅(OH)₄ microspheres showed an adsorption capacity of 120.7 mg·g^-1 with the removal efficiency up to 96.6% from 50 mg·L^-1 solution, superior to most of the referred adsorbents in literatures, and the adsorption kinetic data can be well interpretated via the pseudo-second-order model. Data of the relationship between equilibrium adsorption capacity and BF concentration were well fitted by Freundlich isotherm model with the 1/n value of 0.1678, indicating that the surface was heterogeneous and the adsorption strength was strong.

Key words: nickel phyllosilicate, hydrothermal synthesis, dye removal, adsorption, basic fuchsin

中图分类号:

TQ174

王婷婷, 史书梅, 柳晨媛, 朱万诚, 张恒. 多级多孔硅酸镍微球的合成及其对碱性品红的高效吸附[J]. 无机材料学报, 2021, 36(12): 1330-1336.

WANG Tingting, SHI Shumei, LIU Chenyuan, ZHU Wancheng, ZHANG Heng. Synthesis of Hierarchical Porous Nickel Phyllosilicate Microspheres as Efficient Adsorbents for Removal of Basic Fuchsin[J]. Journal of Inorganic Materials, 2021, 36(12): 1330-1336.

图/表 13

Fig. 1 Effect of Ni/Si molar ratio on the phase composition of the products hydrothermally synthesized at 210 ℃ for 12 h with different Ni/Si molar ratios (a) 0.5 : 1; (b) 0.75 : 1; (c) 1 : 1; (d) 1.25 : 1; (e) 1.5 : 1

Fig. 2 SEM and TEM images of the Ni3Si2O5(OH)4 microspheres hydrothermally synthesized at 210 ℃ for 12 h with Ni/Si molar ratio of 1 : 1

Fig. 3 N2 adsorption-desorption isotherms of the products hydrothermally synthesized at 210 ℃ for 12 h with different Ni/Si molar ratios (a) 0.5 : 1; (b) 0.75 : 1; (c) 1 : 1; (d) 1.25 : 1; (e) 1.5 : 1

Fig. 4 Pore size distribution derived from desorption (a) and adsorption (b) branch of the isotherm of the products hydrothermally synthesized with different Ni/Si molar ratios (a1, b1) 0.5 : 1; (a2, b2) 0.75 : 1; (a3, b3) 1 : 1; (a4, b4) 1.25 : 1; (a5, b5) 1.5 : 1

Fig. 5 Effect of alkali source on composition and morphology of the products (a1, b) Ammonia, 26.6 mmol; (a2, c) Sodium hydroxide, 26.6 mmol; (a3, d) Urea, 3.33 mmol; (a4, e) Urea, 6.66 mmol; (a5, f) Urea, 20.0 mmol

Fig. 6 Schematic illustration for the formation of Ni3Si2O5(OH)4 microspheres

Fig. 7 Molecular structure of BF (a), Zeta potential of Ni3Si2O5(OH)4 microspheres (Ni/Si molar ratio of 1 : 1) (b), variation of the adsorption rate and capacity with adsorption time at different pH (Ni/Si molar ratio of 1 : 1) (c), and effect of Ni/Si molar ratio on the adsorption performance (d)

Fig. S1 Linear regression with pseudo-first-order (PFO) (a) and pseudo-second-order (PSO) (b) kinetic models

Fig. S2 Adsorption isotherms of BF on the Ni3Si2O5(OH)4 microspheres fitted with the Langmuir (a) and Freundlich (b) isotherm models

Table S1 Textural properties of the products

Ni/Si molar ratio	S_BET /(m²·g^-1)	Pore volume /(cm³·g^-1)	Average pore diameter/nm
0.5 : 1	139.4	0.884	6.00
0.75 : 1	128.2	0.511	5.58
1 : 1	119.6	0.673	5.90
1.25 : 1	101.1	0.426	5.86
1.5 : 1	95.5	0.564	8.68

Table S2 Adsorption kinetic model parameters for the adsorption of BF on the Ni3Si2O5(OH)4 microspheres

q_e,exp/(mg·g^-1)	Pseudo-first-order kinetic model			Pseudo-second-order kinetic model
q_e,exp/(mg·g^-1)	q_e,calc1/(mg·g^-1)	k₁/min^-1	R²	q_e,calc2/(mg·g^-1)	k₂/(mg·g^-1·min^-1)	R²
120.7	55.2	0.0483	0.8526	118.5	0.0051	0.9979

Table S3 Comparison of the adsorption capacities for BF on various adsorbents

Adsorbents	Initial concentration of BF solution/(mg·L^-1)	Adsorption equilibrium time/min	Maximum adsorption capacity /(mg·g^-1)	Ref.
Alkali-activated diatomite	15	30	4.85	[1]
(Acrylamide-co-sodium methacrylate )-graft-chitosan gel	125	180	6.1	[2]
β-cyclodextrin-carboxymethyl cellulose-graphene oxide composite	100	150	6.5	[3]
Hydroxy-aluminum pillared bentonite	100	10-15	6.6	[4]
Iron-manganese oxide coated kaolinite	40	50	8.16	[5]
Copper vinylphosphonate	30	150	19.29	[6]
Fe-ZSM-5	20	240	25.8	[7]
β-cyclodextrin-styrene-based polymer	50	180	29.6	[8]
CoFe₂O₄-HA-ECH	33.8	30	31.3	[9]
Magnetic chitosan/graphene oxide	50	70	32.8	[10]
Activated carbon/ferrospinel composite	100	60	49.9	[11]
Al-MCM-41	60	240	54	[12]
Ba(B₂Si₂O₈) microspheres	30	240	58.0	[13]
NiFe₂O₄/polythiophene nanocomposite	50	30	76	[14]
Ni₃Si₂O₅(OH)₄	50	180	120.7	This work

Table S4 Corresponding fitting parameters originated from the non-linear regression by using Langmuir and Freundlich isotherm models

Langmuir isotherm model			Freundlich isotherm model
q_m/(mg·g^-1)	b/(L·mg^-1)	R²	k_f	1/n	R²
176.7	4.7474	0.7920	104.9	0.1678	0.9919

参考文献 24

[1]	RICHARD-PLOUET M, VILMINOT S, GUILLOT M. Synthetic transition metal phyllosilicates and organic-inorganic related phases. New Journal of Chemistry, 2004, 28(9): 1073-1082. DOI URL
[2]	MUNIRASU S, AGGARWAL R, BASKARAN D. Highly efficient recyclable hydrated-clay supported catalytic system for atom transfer radical polymerization. Chemical Communications, 2009(30): 4518-4520.
[3]	SOETAREDJO F E, AYUCITRA A, ISMADJI S, et al. KOH/ bentonite catalysts for transesterification of palm oil to biodiesel. Applied Clay Science, 2011, 53(2): 341-346. DOI URL
[4]	BIAN Z, KAWI S. Preparation, characterization and catalytic application of phyllosilicate: a review. Catalysis Today, 2020, 339: 3-23. DOI URL
[5]	HERNEY-RAMIREZ J, VICENTE MA, MADEIRA LM. Heterogeneous photo-Fenton oxidation with pillared clay-based catalysts for wastewater treatment: a review. Applied Catalysis B: Environmental, 2010, 98(1): 10-26. DOI URL
[6]	KUMAR DUTTA D, JYOTI BORAH B, POLLOV SARMAH P. Recent advances in metal nanoparticles stabilization into nanopores of montmorillonite and their catalytic applications for fine chemicals synthesis. Catalysis Reviews, 2015, 57(3): 257-305. DOI URL
[7]	JIANG B, LI L, BIAN Z, et al. Hydrogen generation from chemical looping reforming of glycerol by Ce-doped nickel phyllosilicate nanotube oxygen carriers. Fuel, 2018, 222: 185-192. DOI URL
[8]	GHIAT I, BOUDJEMAA A, SAADI A, et al. Efficient hydrogen generation over a novel Ni phyllosilicate photocatalyst. Journal of Photochemistry and Photobiology A: Chemistry, 2019, 382: 111952. DOI URL
[9]	LU Y, GUO D, ZHAO Y, et al. Confined high dispersion of Ni nanoparticles derived from nickel phyllosilicate structure in silicalite-2 shell for dry reforming of methane with enhanced performance. Microporous and Mesoporous Materials, 2021, 313: 110842. DOI URL
[10]	KIM B, KIM JS, KIM H, et al. Amorphous multinary phyllosilicate catalysts for electrochemical water oxidation. Journal of Materials Chemistry A, 2019, 7(31): 18380-18387. DOI URL
[11]	DI W, CHENG J, TIAN S, et al. Synthesis and characterization of supported copper phyllosilicate catalysts for acetic ester hydrogennation to ethanol. Applied Catalysis A: General, 2016, 510: 244-259. DOI URL
[12]	BIAN Z, ZHONG W, YU Y, et al. Cu/SiO₂ derived from copper phyllosilicate for low-temperature water-gas shift reaction: role of Cu⁺ sites. International Journal of Hydrogen Energy, 2020, 45(51): 27078-27088. DOI URL
[13]	LEE Y C, KIM E J, YANG J W, et al. Removal of malachite green by adsorption and precipitation using aminopropyl functionalized magnesium phyllosilicate. Journal of Hazardous Materials, 2011, 192(1): 62-70.
[14]	SIVAIAH M V, PETIT S, BEAUFORT M F, et al. Nickel based catalysts derived from hydrothermally synthesized 1 : 1 and 2 : 1 phyllosilicates as precursors for carbon dioxide reforming of methane. Microporous and Mesoporous Materials, 2011, 140(1/2/3): 69-80. DOI URL
[15]	MCDONALD A, SCOTT B, VILLEMURE G. Hydrothermal preparation of nanotubular particles of a 1 : 1 nickel phyllosilicate. Microporous and Mesoporous Materials, 2009, 120(3): 263-266. DOI URL
[16]	YANG Y, LIANG Q, LI J, et al. Ni₃Si₂O₅(OH)₄ multi-walled nanotubes with tunable magnetic properties and their application as anode materials for lithium batteries. Nano Research, 2011, 4(9): 882-890. DOI URL
[17]	WHITE R D, BAVYKIN D V, WALSH F C. Morphological control of synthetic Ni₃Si₂O₅(OH)₄ nanotubes in an alkaline hydrothermal environment. Journal of Materials Chemistry A, 2013, 1(3): 548-556. DOI URL
[18]	GUO Z, DU F, LI G, et al. Controlled synthesis of mesoporous SiO₂/Ni₃Si₂O₅(OH)₄ core-shell microspheres with tunable chamber structures via a self-template method. Chemical Communications, 2008(25): 2911-2913.
[19]	CHEN D, GUO Z, SUN T, et al. Controlled synthesis and catalytic properties of mesoporous nickel-silica core-shell microspheres with tunable chamber structures. Materials Research Bulletin, 2012, 47(9): 2344-2348. DOI URL
[20]	WANG T, LIU C, MA X, et al. Synthesis of Ni₃Si₄O₁₀(OH)₂ porous microspheres as support of Pd catalyst for hydrogenation reaction. Nanomaterials, 2019, 9(7): 998. DOI URL
[21]	GROEN J C, PEFFER L A A, PÉREZ-RAMÍREZ J. Pore size determination in modified micro- and mesoporous materials. Pitfalls and limitations in gas adsorption data analysis. Microporous and Mesoporous Materials, 2003, 60(1/2/3): 1-17. DOI URL
[22]	DONG F, XIONG T, WANG R, et al. Growth mechanism and photocatalytic activity of self-organized N-doped (BiO)₂CO₃ hierarchical nanosheet microspheres from bismuth citrate and urea. Dalton Transactions, 2014, 43(18): 6631-6642. DOI URL
[23]	LI J, XU L, SUN P, et al. Novel application of red mud: facile hydrothermal-thermal conversion synthesis of hierarchical porous AlOOH and Al₂O₃ microspheres as adsorbents for dye removal. Chemical Engineering Journal, 2017, 321: 622-634. DOI URL
[24]	MCKAY G, BLAIR H S, GARDNER J R. Adsorption of dyes on chitin. I. Equilibrium studies. Journal of Applied Polymer Science, 1982, 27(8): 3043-3057. DOI URL