Template-free Synthesis of Mesoporous Silica with High Specific Surface Area from Natural Halloysite and Its Application in Methylene Blue Adsorption

doi:10.15541/jim20180160

Abstract

Abstract:

Avoiding the use of templates and employing natural minerals as raw materials could promote the cost-efficient preparation of mesoporous materials. This work demonstrated a template-free route to process natural halloysite into mesoporous silica with high specific surface area (SSA) up to 767 m²/g and pore size of about 5 nm. The halloysite was successively calcined, alkali-treated and acid-treated. The transformation of calcined halloysite into crystalline sodium aluminosilicate (zeolite LTA) by longtime alkali-treating, was found to be the key for obtaining high-SSA mesoporous silica in the final acid treatment. The optimized mesoporous silica showed a monolayer adsorption capacity as high as 741 mg/g for methylene blue, suggesting its great potential in adsorption applications.

Key words: halloysite, mesoporous silica, template-free, zeolite, adsorption

CLC Number:

TQ174

CHEN Meng-Qiu, CHEN Yun, SHU Zhu, WANG Yu, WU Hong-Juan, GUO Li-Min. Template-free Synthesis of Mesoporous Silica with High Specific Surface Area from Natural Halloysite and Its Application in Methylene Blue Adsorption[J]. Journal of Inorganic Materials, 2018, 33(12): 1365-1370.

Figures/Tables 11

References 20

[1]	WAN Y, ZHAO D Y.On the controllable soft-templating approach to mesoporous silicates.Chem. Rev., 2007, 107(7): 2821-2860.
[2]	WANG Y, YANG D, LI S,et al. Ru/hierarchical HZSM-5 zeolite as efficient bi-functional adsorbent/catalyst for bulky aromatic VOCs elimination. Microporous Mesoporous Mater., 2018, 258: 17-25.
[3]	REN Y, MA Z, BRUCE P G.Ordered mesoporous metal oxides: synthesis and applications.Chem. Soc. Rev., 2012, 41(14): 4909-4927.
[4]	LI W, ZHAO D Y.An overview of the synthesis of ordered mesoporous materials.Chem. Commun., 2013, 49(10): 943-946.
[5]	YUAN P, TAN D Y, ANNABI-BERGAYA F.Properties and applications of halloysite nanotubes: recent research advances and future prospects. Appl. Clay Sci., 2015, 112-113: 75-93.
[6]	LUN H L, OUYANG J, YANG H M.Enhancing dispersion of halloysite nanotubes via chemical modification. Phys. Chem. Miner., 2014, 41(4): 281-288.
[7]	ABDULLAYEV E, JOSHI A, WEI W,et al. Enlargement of halloysite clay nanotube lumen by selective etching of aluminum oxide. ACS Nano, 2012, 6(8): 7216-7226.
[8]	ZHANG A B, PAN L, ZHANG H Y,et al. Effects of acid treatment on the physico-chemical and pore characteristics of halloysite. Colloid Surf. A-Physicochem. Eng. Asp., 2012, 396: 182-188.
[9]	SHU Z, CHEN Y, ZHOU J, et al. Nanoporous-walled silica and alumina nanotubes derived from halloysite: controllable preparation and their dye adsorption applications. Appl. Clay Sci., 2015, 112-113: 17-24.
[10]	SHU Z, CHEN Y, ZHOU J,et al. Preparation of halloysite-derived mesoporous silica nanotube with enlarged specific surface area for enhanced dye adsorption. Appl. Clay Sci., 2016, 132: 114-121.
[11]	DA SILVA L C C, INFANTE C M C, URIO R D,et al. Adsorption/ desorption of Hg(II) on FDU-1 silica and FDU-1 silica modified with humic acid. Sep. Sci. Technol., 2015, 50(7): 984-992.
[12]	CHANDRASEKAR G, SON W J, AHN W S.Synthesis of mesoporous materials SBA-15 and CMK-3 from fly ash and their application for CO2 adsorption.J. Porous Mat., 2009, 16(5): 545-551.
[13]	LI T T, SHU Z, ZHOU J,et al. Template-free synthesis of kaolin-based mesoporous silica with improved specific surface area by a novel approach. Appl. Clay Sci., 2015, 107: 182-187.
[14]	OUYANG J, ZHOU Z, ZHANG Y,et al. High morphological stability and structural transition of halloysite (Hunan, China) in heat treatment. Appl. Clay Sci., 2014, 101: 16-22.
[15]	JOO Y, SIM J H, JEON Y,et al. Opening and blocking the inner- pores of halloysite. Chem. Commun., 2013, 49(40): 4519-4521.
[16]	HARRIS R G, JOHNSON B B, WELLS J D.Studies on the adsorption of dyes to kaolinite.Clay Clay Min., 2006, 54(4): 435-448.
[17]	BALATHANIGAIMANI M S, SHIM W G, PARK K H,et al. Effects of structural and surface energetic heterogeneity properties of novel corn grain-based activated carbons on dye adsorption. Micropor. Mesopor. Mat., 2009, 118(1/2/3): 232-238.
[18]	HAMEED B H, DIN A T M, AHMAD A L. Adsorption of methylene blue onto bamboo-based activated carbon: kinetics and equilibrium studies.J. Hazard. Mater., 2007, 141(3): 819-825.
[19]	DONG Y L, LU B, ZANG S Y,et al. Removal of methylene blue from coloured effluents by adsorption onto SBA-15. J. Chem. Technol. Biotechnol., 2011, 86(4): 616-619.
[20]	LIU T, LI Y, DU Q,et al. Adsorption of methylene blue from aqueous solution by graphene. Colloid Surf. B-Biointerfaces, 2012, 90: 197-203.

	Si/Al^a	SiO₂	Al₂O₃	Fe₂O₃	MgO	CaO	Na₂O	K₂O	Others	LOI^b
Halloysite	1.03	45.2	37.2	0.305	0.008	0.738	0.022	0.057	1.35	15.1
Calcined halloysite	1.03	52.8	43.5	0.356	0.009	0.862	0.026	0.067	1.58	0.8

	Si/Al^a	SiO₂	Al₂O₃	Fe₂O₃	MgO	CaO	Na₂O	K₂O	Others	LOI^b
Halloysite	1.03	45.2	37.2	0.305	0.008	0.738	0.022	0.057	1.35	15.1
Calcined halloysite	1.03	52.8	43.5	0.356	0.009	0.862	0.026	0.067	1.58	0.8

	Si	Al	Na	O
NaOH-0.5h	18.39	16.79	1.93	62.91
NaOH-1h	20.92	15.16	6.50	57.41
NaOH-2h	20.06	15.25	7.94	56.71
NaOH-4h	19.23	15.08	9.76	55.88
NaOH-6h	20.34	13.70	9.85	56.05
NaOH-0.5h-HCl	32.37	0.81	0.39	66.43
NaOH-1h-HCl	32.43	0.83	0.43	66.31
NaOH-2h-HCl	32.71	0.67	0.14	66.49
NaOH-4h-HCl	32.37	0.90	0.42	66.31
NaOH-6h-HCl	32.61	0.59	0.48	66.33

	Si	Al	Na	O
NaOH-0.5h	18.39	16.79	1.93	62.91
NaOH-1h	20.92	15.16	6.50	57.41
NaOH-2h	20.06	15.25	7.94	56.71
NaOH-4h	19.23	15.08	9.76	55.88
NaOH-6h	20.34	13.70	9.85	56.05
NaOH-0.5h-HCl	32.37	0.81	0.39	66.43
NaOH-1h-HCl	32.43	0.83	0.43	66.31
NaOH-2h-HCl	32.71	0.67	0.14	66.49
NaOH-4h-HCl	32.37	0.90	0.42	66.31
NaOH-6h-HCl	32.61	0.59	0.48	66.33

Samples	SSA/(m²·g^-1)	S_micro/(m²·g^-1)	S_external/(m²·g^-1)	V_t/(cm³·g^-1)	V_micro/(cm³·g^-1)	V_meso/(cm³·g^-1)
NaOH-0.5h-HCl	547	17.2	530	0.762	0.002	0.760
NaOH-1h-HCl	573	33.8	539	0.826	0.007	0.819
NaOH-2h-HCl	709	12.7	696	0.725	0	0.725
NaOH-4h-HCl	749	13.4	736	0.703	0	0.703
NaOH-6h-HCl	767	8.64	759	0.669	0	0.669