Preparation of 2-hydroxy-1-naphthalene Functionalized SBA-15 Adsorbent for the Adsorption of Chromium(III) Ions from Aqueous Solution

doi:10.15541/jim20210109

Abstract

Abstract:

SBA-15 mesoporous material functionalized with 2-hydroxy-1-naphthaldehyde denoted as Q-SBA-15 was synthesized by using Schiff’s base reaction to remove Cr(III) ions from aqueous solution. A series of characterizations were performed to analyze the morphology, pore structure, element distribution and chemical properties of Q-SBA-15. The results showed that BET surface area and pore size of SBA-15 decreased after modified with 2-hydroxy- 1-naphthaldehyde, but the surface morphology and crystal structure of SBA-15 did not change significantly. To investigate the adsorption properties of Q-SBA-15 toward Cr(III) ions, effects of solution pH and ionic strength were studied. Moreover, adsorption kinetics, adsorption isotherm models, adsorption thermodynamics, and regeneration performance of Q-SBA-15 were analyzed. Adsorption process toward Cr(III) ions onto Q-SBA-15 was well followed by pseudo-second order kinetic model and Langmuir isotherm model. The maximum adsorption capacity of Q-SBA-15 was 102.3 mg/g toward Cr(III) ions under the conditions of 40 ℃ and pH 6. The Cr(III) adsorption onto Q-SBA-15 was found to be spontaneous and endothermic process. The adsorption process mainly based on the coordination chelation of Cr(III) ions with the functionalized groups on Q-SBA-15. Furthermore, Q-SBA-15 exhibited good reusability. Therefore, Q-SBA-15 can be used as a promising adsorbent for removal of Cr(III) ions from aqueous solution.

Key words: SBA-15, functionalization, adsorption, Cr(III)

CLC Number:

O647

GUO Yu, JIANG Xiaoqing, WU Hongmei, XIAO Yu, WU Dafu, LIU Xin. Preparation of 2-hydroxy-1-naphthalene Functionalized SBA-15 Adsorbent for the Adsorption of Chromium(III) Ions from Aqueous Solution[J]. Journal of Inorganic Materials, 2021, 36(11): 1163-1170.

Figures/Tables 17

Fig. 1 Schematic diagram of the synthetic process for Q-SBA-15

Fig. 2 (a, b) SEM images, (c, d) EDX elemental analyses, (e) XRD patterns and (f) TG curves of (a, c) SBA-15 and (b, d) Q-SBA-15 samples

Fig. 3 (a) N2 adsorption-desorption isotherms, (b) pore size distributions of SBA-15 and Q-SBA-15, (c, d) TEM images of Q-SBA-15

Table 1 Textural properties of the synthesized samples

Sample	S_BET/(cm²·g^-1)	Pore size/nm
SBA-15	757	9.6
Q-SBA-15	283	6.7

Fig. 4 (a) FT-IR spectra of Q-SBA-15 and SBA-15, and (b) XPS survey spectrum of Q-SBA-15

Fig. 5 Effect of solution pH on the adsorption of Cr(III) with Q-SBA-15

Fig. 6 Effects of ionic strength on Cr(III) adsorption

Fig. 7 Linearized fitting curves of (a) Langmuir model and (b) Freundlich model for adsorption of Cr(III) on Q-SBA-15

Table 2 Different model parameters for adsorption of Cr(III) by Q-SBA-15 at different temperatures

Temperature /℃	Langmuir			Freundlich
Temperature /℃	q_m/(g·mg^-1)	K_L	R²	K_F	n	R²
30	106.84	0.09	0.988	24.59	3.12	0.836
40	108.23	0.25	0.997	48.39	5.47	0.913
50	112.74	0.41	0.997	42.72	4.27	0.697

Fig. 8 XPS spectra of Q-SBA-15 (a) Overview spectra of Q-SBA-15 before and after Cr(III) adsorption; (b) Cr2p spectrum of Q-SBA-15 after Cr(III) adsorption; C1s spectra of (c) Q-SBA-15 (before adsorption) and (d) Q-SBA-15 (after adsorption); N1s spectra of (e) Q-SBA-15 (before adsorption) and (f) Q-SBA-15 (after adsorption)

Fig. 9 Regeneration property of Q-SBA-15

Fig. S1 (a) Effect of contacting time on the adsorption capacity of Cr(III) by Q-SBA-15 and (b) EDX analyses of Q-SBA-15 after adsorption of Cr(III)

Fig. S2 Fitting curves for adsorption of Cr(III) by (a) pseudo-first-order model and (b) pseudo-first-order model

Table S1 Kinetic parameters for Cr(III) adsorption onto Q-SBA-15

Sample	q_e,exp/(mg·g^-1)	Pseudo first-order model			Pseudo second-order model
Sample	q_e,exp/(mg·g^-1)	K₁/ min^-1	q_e,_cal/(mg·g^-1)	R²	K₂/(g·mg^-1·min^-1)	q_e,_cal/(mg·g^-1)	R²
Q-SBA-15	102.3	0.0647	61.75	0.857	4.26×10^-4	119.19	0.979

Table S2 Comparison of Cr(III) adsorption performance with different materials selected from literature

Adsorbent	q_m/(mg·g^-1)	References
Biomass-based hydrogel	41.7	[1]
m-MCM-41-NH₂	36.92	[2]
Graphene oxide	13.3	[3]
Thiol-functionalized MCM-41	15.34	[4]
TS-SBA-15	95.68	[5]
NH₂-SBA-15	24.88	[6]
Q-SBA-15	102.3	This work

Fig. S3 Plots of lnKc versus 1/T for the adsorption of Cr(III) by Q-SBA-15

Table S3 Thermodynamic parameters of Cr(III) adsorption on Q-SBA-15

Sample	Tempera- ture/K	K_c	ΔG/ (kJ·mol^-1)	ΔS/ (kJ·mol·K^-1)	ΔH/ (kJ·mol^-1)
Q-SBA-15	293	1.846	-4.386	0.128	33.118
	303	2.095	-5.666
	313	2.650	-6.946
	318	2.780	-7.586
	323	3.088	-8.226

References 39

[1]	ALAGU K, VENU H, JAYARAMAN J, et al. Novel water hyacinth biodiesel as a potential alternative fuel for existing unmodified diesel engine: performance, combustion and emission characteristics. Energy, 2004, 179:295-305. DOI URL
[2]	EBO D A, NANNE D V, BIRITWUM N K. Assessment of heavy metal pollution in the main Pra River and its tributaries in the Pra Basin of Ghana. Environmental Nanotechnology Monitoring & Management, 2018, 10:264-271.
[3]	HASHEM M A, ISLAM A, MOHSIN S, et al. Green environment suffers by discharging of high-chromium-containing wastewater from the tanneries at Hazaribagh. Bangladesh. Sustainable Water Resources Management, 2015, 1(4):343-347. DOI URL
[4]	EL-SHAHAWI M S, HASSAN S M, OTHMAN A M, et al. Retention profile and subsequent chemical speciation of chromium(III) and (VI) in industrial wastewater samples employing some onium cations loaded polyurethane foams. Microchemical Journal, 2008, 89(1):13-19. DOI URL
[5]	BULUT V N, OZDES D, BEKIRCAN O, et al. Carrier element- free coprecipitation (CEFC) method for the separation, preconcentration and speciation of chromium using an isatin derivative. Analytica Chimica Acta, 2009, 632(1):35-41. DOI URL
[6]	MAO C P, SONG Y X, CHEN L X, et al. Human health risks of heavy metals in paddy rice based on transfer characteristics of heavy metals from soil to rice. Catena, 2019, 175:339-348. DOI URL
[7]	LIU X L, PANG H W, LIU X W, et al. Orderly porous covalent organic frameworks-based materials: superior adsorbents for pollutants removal from aqueous solutions. The Innovation, 2021, 2(1):100076. DOI URL
[8]	WANG X X, LI X, WANG J Q, et al. Recent advances in carbon nitride-based nanomaterials for the removal of heavy metal ions from aqueous solution. Journal of Inorganic Materials, 2020, 35:260-270.
[9]	GAO X P, GUO C, ZHAO Z, et al. Adsorption of heavy metal ions by sodium alginate based adsorbent-a review and new perspectives. International Journal of Biological Macromolecules, 2020, 164(1):4423-4434. DOI URL
[10]	CHIRANGANO M, TONNI A K, AHMAD B A. Comparative biosorption of chromium(VI) using chemically modified date pits (CM-DP) and olive stone (CM-OS): kinetics, isotherms and influence of co-existing ions. Chemical Engineering Research and Design, 2020, 156:251-262. DOI URL
[11]	GODIYA C B, CHENG X, LI D, et al. Carboxymethyl cellulose/polyacrylamide composite hydrogel for cascaded treatment/reuse of heavy metal ions in wastewater. Journal of Hazardous Materials, 2018, 364(1):28-38. DOI URL
[12]	GIL C, MARIA L, FERRI A, et al. Distribution of chromium species in a Cr-polluted soil: presence of Cr(III) in glomalin related protein fraction. Science of the Total Environment, 2014, 493:828-833. DOI URL
[13]	ATIKAH M N, PEI S G, MOHD S A, et al. Adsorptive nanocomposite membranes for heavy metal remediation: recent progresses and challenges. Chemosphere, 2019, 232:96-112. DOI URL
[14]	RUIHUA M, BIN L, XI C, et al. Adsorption of Cu(II)and Co(II) from aqueous solution using lignosulfonate/chitosan adsorbent. International Journal of Biological Macromolecules, 2020, 163(1):120-127. DOI URL
[15]	BERA A, TRIVEDI J S, KUMAR S B, et al. Anti-organic fouling and anti-biofouling poly(piperazineamide) thin film nanocomposite membranes for low pressure removal of heavy metal ions. Journal of Hazardous Materials, 2018, 343:86-97. DOI URL
[16]	WU H M, XIAO Y, GUO Y, et al. Functionalization of SBA-15 mesoporous materials with 2-acetylthiophene for adsorption of Cr(III) ion. Microporous and Mesoporous Materials, 2020, 292:109754. DOI URL
[17]	CAROLIN C F, KUMAR P S, SARAVANAN A, et al. Efficient techniques for the removal of toxic heavy metals from aquatic environment: a review. Journal of Environmental Chemical Engineering, 2017, 5(3):2782-2799. DOI URL
[18]	SURENDRAN P, ANEESH M, ANANDHU M, et al. Chelation dependent selective adsorption of metal ions by Schiff base modified SBA-15 from aqueous solutions. Journal of Environmental Chemical Engineering, 2020, 8(5):104248. DOI URL
[19]	BETIHA M A, MOUSTAFA Y M, EL-SHAHAT M F, et al. Polyvinylpyrrolidone-aminopropyl-SBA-15 Schiff-base hybrid for efficient removal of divalent heavy metal cations from wastewater. Journal of Hazardous Materials, 2020, 397:112675.
[20]	XIAO Y, GUO Y, WU H M, et al. Adsorption of chromium(III) ions with amino functionalized mesoporous silica adsorbent. Chemical Industry and Engineering Progress, 2020, 30(9):263-272.
[21]	CE L, WANG B D, HAN Y F, et al. Adsorption of lead ion on amino-functionalized fly-ash-based SBA-15 mesoporous molecular sieves prepared via two-step hydrothermal method. Microporous and Mesoporous Materials, 2017, 252:105-115. DOI URL
[22]	MOHAMMAD M S, ALI S R, MEHDI A, et al. Functionalization of SBA-15 by dithiooxamide towards removal of Co(II) ions from real samples: isotherm, thermodynamic and kinetic studies. Advanced Powder Technology, 2019, 30(9):1823-1834. DOI URL
[23]	ANBARASU G, MALATHY M, KARTHIKEYAN P, et al. Silica functionalized Cu(II) acetylacetonate Schiff base complex: an efficient catalyst for the oxidative condensation reaction of benzyl alcohol with amines. Journal of Solid State Chemistry, 2017, 253:305-312. DOI URL
[24]	HUANG S J, MA C Z, LIAO Y Z, et al. Superb adsorption capacity and mechanism of poly(1-amino-5-chloroanthraquinone) nanofibrils for lead and trivalent chromium ions. Reactive and Functional Polymers, 2016, 106:76-85. DOI URL
[25]	NICALAS F, FRANCISCO J, PEREZ A, et al. Chromium(VI) removal from water by means of adsorption-reduction at the surface of amino-functionalized MCM-41 sorbents. Microporous and Mesoporous Materials, 2017, 239:138-146. DOI URL
[26]	KRISHNA S K, YADAV D, SHARMA S K, et al. Cu(II) Schiff base complex grafted guar gum: catalyst for benzophenone derivatives synthesis. Applied Catalysis A: General, 2020, 601:117529. DOI URL
[27]	HEMANDEZ-MORALES V, NAVA R, ACOSTA-SILVA Y J, et al. Adsorption of lead(II) on SBA-15 mesoporous molecular sieve functionalized with -NH₂ groups. Microporous and Mesoporous Materials, 2012, 160:133-142. DOI URL
[28]	FELLENZ N, PEREZ-ALONSO F J, MARTIN P P, et al. Chromium(VI) removal from water by means of adsorption- reduction at the surface of amino-functionalized MCM-41 sorbents. Microporous and Mesoporous Materials, 2017, 239:138-146. DOI URL
[29]	CHEN F Y, HONG M Z, YOU W J, et al. Simultaneous efficient adsorption of Pb²⁺ and MnO₄^- ions by MCM-41 functionalized with amine and nitrilotriacetic acid anhydride. Applied Surface Science, 2015, 357:856-865. DOI URL
[30]	LIU S, CUI H Z, LI Y L, et al. Bis-pyrazolyl functionalized mesoporous SBA-15 for the extraction of Cr(III) and detection of Cr(VI) in artificial jewelry samples. Microchemical Journal, 2017, 131:130-136. DOI URL
[31]	KUMAR P A, RAY M, CHAKRABORTY S. Adsorption behaviour of trivalent chromium on amine-based polymer aniline formaldehyde condensate. Chemical Engineering Journal, 2009, 149(1/2/3):340-347. DOI URL
[32]	WAN L, TONG S T. Adsorption of Cr³⁺ from aqueous solution on mesoporous activated carbon. Environmental Protection of Chemical industry, 2012, 32(1):75-80.
[33]	ZHANG X P. Modification of UIO-66-NH₂ by 3, 4-dihydroxy benzaldehyde and its adsorption properties for U(VI). Rubber and Plastic Technology and Equipment, 2021, 47(2):43-50.
[34]	YI C L, YE X, LI T L, et al. Study the adsorption characteristics of biomanganese oxide to four heavy metals. Industrial Safety and Environmental Protection, 2021, 47(3):94-98.
[35]	CHENG FU-QIANG, JI TIAN-TIAN, XUE MIN, et al. Preparation of thiohydroxy-functionalized mesoporous materials and its adsorption to Cr⁶⁺. Journal of Inorganic Materials, 2020, 35(2):194-198.
[36]	ZHU MING-YU, FAN DE-ZE, LIU BEI, et al. C@K₂Ti₆O₁₃ hierarchical nano materials: effective adsorption removel of Cr(VI). Journal of Inorganic Materials, 2020, 35(3):310-314.
[37]	PONCE-LIRA B, OTAZO-SÁNCHEZ E M, REGUERA E, et al. Lead removal from aqueous solution by basaltic scoria: adsorption equilibrium and kinetics. International Journal of Environmental Science and Technology, 2017, 14:1181-1196.
[38]	SONG X T, NIU Y Z, ZHANG P P, et al. Removal of Co(II) from fuel ethanol by silica-gel supported PAMAM dendrimers: combined experimental and theoretical study. Fuel, 2017, 199(1):91-101.
[39]	BHAUMIK M, MAITY A, SRINIVASU V V, et al. Enhanced removal of Cr(VI) from aqueous solution using polypyrrole/Fe₃O₄ magnetic nanocomposite. Journal of Hazardous Materials, 2011, 190(1/2/3):381-390.