2-吡啶甲醛功能化SBA-15介孔材料的制备及其对Cr(Ⅲ)离子的吸附

doi:10.16085/j.issn.1000-6613.2021-1827

摘要/Abstract

摘要：

通过席夫碱反应将2-吡啶甲醛成功嫁接到氨基化的SBA-15介孔分子筛上，本文获得了一种新型功能化SBA-15吸附剂（N-SBA-15）。采用傅里叶变换红外光谱、X射线衍射、元素分析、扫描电子显微镜、透射电子显微镜、X射线光电子能谱、热重分析和氮气吸附-脱附等手段对N-SBA-15的表面官能团、形貌、孔道结构和表面化学性质进行了详细的表征分析。利用N-SBA-15对水溶液中的Cr(Ⅲ)进行了吸附实验，其最大吸附容量为84.3mg/g。动力学分析和等温吸附研究结果表明，N-SBA-15对Cr(Ⅲ)的吸附过程符合准二级动力学模型和Langmuir模型。吸附热力学分析表明，该吸附过程是自发的吸热过程（?G<0、?S>0、?H>0）。吸附机理分析表明该吸附过程主要是由N-SBA-15表面有机官能团与Cr(Ⅲ)的配位作用实现的。而且，N-SBA-15吸附剂经过5次吸附-脱附测试，仍然对Cr(Ⅲ)具有较高的吸附容量。

关键词: SBA-15, 2-吡啶甲醛, 席夫碱, 吸附, Cr (Ⅲ)

Abstract:

A novel functionalized SBA-15 material (N-SBA-15) was synthesized via Schiff's base reaction of 2-pyridinecarboxaldehyde with amino modified SBA-15 mesoporous material for adsorption of Cr(Ⅲ) ions from aqueous solution. The organic functional groups, morphology, pore structure and chemical property of N-SBA-15 were determined by FTIR, XRD, EDX, SEM, TEM, XPS, TGA and N₂ adsorption-desorption. Moreover, the adsorption performance of N-SBA-15 adsorbent on Cr(Ⅲ) ions in aqueous solution was investigated. The adsorption capacity of 84.3mg/g toward Cr(Ⅲ) ions was obtained. The kinetics analysis and adsorption isotherms revealed that the adsorption process of Cr(Ⅲ) ions by N-SBA-15 was consistent with pseudo-second-order kinetic model and Langmuir isotherm model. The thermodynamic parameters showed that Cr(Ⅲ) adsorption onto N-SBA-15 was spontaneous, endothermic and entropy-increasing process (?G<0, ?S>0, ?H>0). The adsorption mechanism analysis indicated that Cr(Ⅲ) adsorption onto N-SBA-15 was mainly based on the chemical combination of N atoms on the organic functional groups of N-SBA-15 through coordination bond. Furthermore, N-SBA-15 still kept high adsorption capacity after five adsorption–desorption cycles.

Key words: SBA-15, 2-pyridinecarboxaldehyde, Schiff's base, adsorption, Cr(Ⅲ)

中图分类号:

O647

姜晓庆, 郭宇, 吴红梅. 2-吡啶甲醛功能化SBA-15介孔材料的制备及其对Cr(Ⅲ)离子的吸附[J]. 化工进展, 2022, 41(7): 3915-3924.

JIANG Xiaoqing, GUO Yu, WU Hongmei. Synthesis of 2-pyridinecarboxaldehyde functionalized SBA-15 mesoporous material for the adsorption of Cr(Ⅲ) ions from aqueous solution[J]. Chemical Industry and Engineering Progress, 2022, 41(7): 3915-3924.

图/表 17

参考文献 40

1	SELVARAJ R, SANTHANAM M, SELVAMANI V, et al. A membrane electroflotation process for recovery of recyclable chromium(Ⅲ) from tannery spent liquor effluent[J]. Journal of Hazardous Materials, 2018, 346: 133-139.
2	CHOW Y N, LEE L K, ZAKARIA N A, et al. Phytotoxic effects of trivalent chromium-enriched water irrigation in Vigna unguiculata seedling[J]. Journal of Cleaner Production, 2018, 202: 101-108.
3	LIU W, YU Y X. Removal of recalcitrant trivalent chromium complexes from industrial wastewater under strict discharge standards[J]. Environmental Technology & Innovation, 2021, 23: 101644.
4	LIU G J, CUI C C, JIANG L, et al. Visible light-induced hydrogels towards reversible adsorption and desorption based on trivalent chromium in aqueous solution[J]. Reactive and Functional Polymers, 2021, 163: 104886.
5	LYU T, MA R G, KE K, et al. Synthesis of gallic acid functionalized magnetic hydrogel beads for enhanced synergistic reduction and adsorption of aqueous chromium[J]. Chemical Engineering Journal, 2021, 408: 127327.
6	KYZIOŁ-KOMOSIŃSKA J, AUGUSTYNOWICZ J, LASEK W, et al. Callitriche cophocarpa biomass as a potential low-cost biosorbent for trivalent chromium[J]. Journal of Environmental Management, 2018, 214: 295-304.
7	LATIF A, SHENG D, SUN K, et al. Remediation of heavy metals polluted environment using Fe-based nanoparticles: mechanisms, influencing factors, and environmental implications[J]. Environmental Pollution, 2020, 264:114728.
8	RAMALINGAM B, VENKATACHALAM S S, KIRAN M S, et al. Rationally designed shewanella oneidensis biofilm toilored graphene-magnetite hybrid nanobiocomposite as reusable living functional nanomaterial for effective removal of trivalent chromium[J]. Environmental Pollution, 2021, 278: 116847.
9	LI M J, MA C X, YIN X X, et al. Investigating trivalent chromium biosorption-driven extracellular polymeric substances changes of Synechocystis sp. PCC 7806 by parallel factor analysis (PARAFAC) analysis[J]. Bioresource Technology Reports, 2019, 7: 100249.
10	EL-SHAHAWI M S, HASSAN S 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[J]. Microchemical Journal, 2008, 89(1): 13-19.
11	JIANG D M, YANG Y H, HUANG C T, et al. Removal of the heavy metal ion nickel (Ⅱ) via an adsorption method using flower globular magnesium hydroxide[J]. Journal of Hazardous Materials, 2019, 373: 131-140.
12	张振国, 张铭栋, 顾平, 等. 沸石材料吸附水中放射性锶和铯的研究进展[J]. 化工进展, 2019, 38(4): 1984-1995.
	ZHANG Zhenguo, ZHANG Mingdong, GU Ping, et al. Progress in adsorption of radioactive strontium and cesium from aqueous solution on zeolite materials[J]. Chemical Industry and Engineering Progress, 2019, 38(4): 1984-1995.
13	DU X, ZHANG Q, QIAO W L, et al. Controlled self-assembly of oligomers-grafted fibrous polyaniline/single zirconium phosphate nanosheet hybrids with potential-responsive ion exchange properties[J]. Chemical Engineering Journal, 2016, 302: 516-525.
14	MARCINIAK M, GOSCIANSKA J, FRANKOWSKI M, et al. Optimal synthesis of oxidized mesoporous carbons for the adsorption of heavy metal ions[J]. Journal of Molecular Liquids, 2019, 276: 630-637.
15	WU H M, XIAO Y, GUO Y, et al. Functionalization of SBA-15 mesoporous materials with 2-acetylthiophene for adsorption of Cr(Ⅲ) ions[J]. Microporous and Mesoporous Materials, 2020, 292: 109754.
16	RADI S, TIGHADOUINI S, MASSAOUDI M EL, et al. Thermodynamics and kinetics of heavy metals adsorption on silica particles chemically modified by conjugated β-ketoenol furan[J]. Journal of Chemical & Engineering Data, 2015, 60(10): 2915-2925.
17	ORTIZ-BUSTOS J, MARTÍN A, MORALES V, et al. Surface-functionalization of mesoporous SBA-15 silica materials for controlled release of methylprednisolone sodium hemisuccinate: influence of functionality type and strategies of incorporation[J]. Microporous and Mesoporous Materials, 2017, 240: 236-245.
18	О DUDARKO, KOBYLINSKA N, MISHRA B, et al. Facile strategies for synthesis of functionalized mesoporous silicas for the removal of rare-earth elements and heavy metals from aqueous systems[J]. Microporous and Mesoporous Materials, 2021, 315: 110919.
19	LI S L, LI S Q, WEN N, et al. Highly effective removal of lead and cadmium ions from wastewater by bifunctional magnetic mesoporous silica[J]. Separation and Purification Technology, 2021, 265: 118341.
20	DINDAR M H, YAFTIAN M R, ROSTAMNIA S. Potential of functionalized SBA-15 mesoporous materials for decontamination of water solutions from Cr(Ⅵ), As(Ⅴ) and Hg(Ⅱ) ions[J]. Journal of Environmental Chemical Engineering, 2015, 3(2): 986-995.
21	肖昱, 郭宇, 吴红梅, 等. 氨基功能化介孔硅吸附剂的制备及其对铬(Ⅲ)的吸附行为[J]. 化工进展, 2020, 39(1): 257-266.
	XIAO Yu, GUO Yu, WU Hongmei, et al. Adsorption of chromium(Ⅲ) ions with amino functionalized mesoporous silica adsorbent[J]. Chemical Industry and Engineering Progress, 2020, 39(1): 257-266.
22	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[J]. Microchemical Journal, 2017, 131: 130-136.
23	CORREIA L M M, SOLIMAN M M A, GRANADEIRO C M, et al. Vanadium C-scorpionate supported on mesoporous aptes-functionalized SBA-15 as catalyst for the peroxidative oxidation of benzyl alcohol[J]. Microporous and Mesoporous Materials, 2021, 320: 111111.
24	RIBEIRO S O, GRANADEIRO C M, ALMEIDA P L, et al. Effective zinc-substituted keggin composite to catalyze the removal of sulfur from real diesels under a solvent-free system[J]. Industrial & Engineering Chemistry Research, 2019, 58(40): 18540-18549.
25	ZHOU Y, BAO R L, YUE B, et al. Synthesis, characterization and catalytic application of SBA-15 immobilized rare earth metal sandwiched polyoxometalates[J]. Journal of Molecular Catalysis A: Chemical, 2007, 270(1/2): 50-55.
26	HAO S Y, ZHONG Y J, PEPE F, et al. Adsorption of Pb²⁺ and Cu²⁺ on anionic surfactant-templated amino-functionalized mesoporous silicas[J]. Chemical Engineering Journal, 2012, 189/190: 160-167.
27	GOLLAKOTA A R K, MUNAGAPATI V S, SHADANGI K P, et al. Encapsulating toxic Rhodamine 6G dye, and Cr(Ⅵ) metal ions from liquid phase using AlPO₄-5 molecular sieves. Preparation, characterization, and adsorption parameters[J]. Journal of Molecular Liquids, 2021, 336: 116549.
28	HERNÁNDEZ-MORALES V, NAVA R, ACOSTA-SILVA Y J, et al. Adsorption of lead (Ⅱ) on SBA-15 mesoporous molecular sieve functionalized with-NH₂ groups[J]. Microporous and Mesoporous Materials, 2012, 160: 133-142.
29	LIU C, JIN R N, OUYANG X K, et al. Adsorption behavior of carboxylated cellulose nanocrystal-polyethyleneimine composite for removal of Cr(Ⅵ) ions[J]. Applied Surface Science, 2017, 408: 77-87.
30	SALMANI M H, EHRAMPOUSH M H, ESLAMI H, et al. Synthesis, characterization and application of mesoporous silica in removal of cobalt ions from contaminated water[J]. Groundwater for Sustainable Development, 2020, 11: 100425.
31	MAHMOUDI F, AMINI M M, SILLANPÄÄ M. Hydrothermal synthesis of novel MIL-100(Fe)@SBA-15 composite material with high adsorption efficiency towards dye pollutants for wastewater remediation[J]. Journal of the Taiwan Institute of Chemical Engineers, 2020, 116: 303-313.
32	SHARMA R, KUMAR D. Adsorption of Cr(Ⅲ) and Cu(Ⅱ) on hydrothermally synthesized graphene oxide-calcium-zinc nanocomposite[J]. Journal of Chemical & Engineering Data, 2018, 63(12): 4560-4572.
33	张永德, 黄松涛, 罗学刚, 等. 膨化稻壳对铀及伴生重金属离子的吸附机理[J]. 化工进展, 2016, 35(9): 2707-2714.
	ZHANG Yongde, HUANG Songtao, LUO Xuegang, et al. Adsorption characteristics and mechanism of U(Ⅵ) and associated heavy metals on expanded rice husk[J]. Chemical Industry and Engineering Progress, 2016, 35(9): 2707-2714.
34	王重庆, 王晖, 江小燕, 等. 生物炭吸附重金属离子的研究进展[J]. 化工进展, 2019, 38(1): 692-706.
	WANG Chongqing, WANG Hui, JIANG Xiaoyan, et al. Research advances on adsorption of heavy metals by biochar[J]. Chemical Industry and Engineering Progress, 2019, 38(1): 692-706.
35	DENG S B, TING Y P. Polyethylenimine-modified fungal biomass as a high-capacity biosorbent for Cr(Ⅵ) anions: sorption capacity and uptake mechanisms[J]. Environmental Science & Technology, 2005, 39(21): 8490-8496.
36	LEI Z M, AN Q D, FAN Y, et al. Monolithic magnetic carbonaceous beads for efficient Cr(Ⅵ) removal from water[J]. New Journal of Chemistry, 2016, 40(2): 1195-1204.
37	PARAB H, JOSHI S, SHENOY N, et al. Determination of kinetic and equilibrium parameters of the batch adsorption of Co(Ⅱ), Cr(Ⅲ) and Ni(Ⅱ) onto coir pith[J]. Process Biochemistry, 2006, 41(3): 609-615.
38	QIU Y, ZHANG Q, GAO B, et al. Removal mechanisms of Cr(Ⅵ) and Cr(Ⅲ) by biochar supported nanosized zero-valent iron: synergy of adsorption, reduction and transformation[J]. Environmental Pollution, 2020, 265: 115018.
39	ARIM A L, QUINA M J, GANDO-FERREIRA L M. Uptake of trivalent chromium from aqueous solutions by xanthate pine bark: characterization, batch and column studies[J]. Process Safety and Environmental Protection, 2019, 121:374-386.
40	WANG J H, MAO M, ATIF S, et al. Adsorption behavior and mechanism of aqueous Cr(Ⅲ) and Cr(Ⅲ)-EDTA chelates on DTPA-chitosan modified Fe₃O₄@SiO₂ [J]. Reactive and Functional Polymers, 2020, 156: 104720.

样品	比表面积/cm³·g^-1	孔径/nm	孔容/cm³·g^-1
SBA-15	757.40	9.60	1.04
NH₂-SBA-15	462.92	8.12	0.91
N-SBA-15	335.04	7.67	0.54

样品	比表面积/cm³·g^-1	孔径/nm	孔容/cm³·g^-1
SBA-15	757.40	9.60	1.04
NH₂-SBA-15	462.92	8.12	0.91
N-SBA-15	335.04	7.67	0.54

温度/℃	Langmuir模型			Freundlich模型
温度/℃	q_m/g·mg^-1	K_L/L·mg^-1	R²	K_F/mg·g^-1	n	R²
30	88.34	0.105	0.968	20.60	2.96	0.935
40	91.66	0.269	0.996	31.84	3.51	0.950
50	91.74	0.859	0.999	45.24	4.65	0.775

温度/℃	Langmuir模型			Freundlich模型
温度/℃	q_m/g·mg^-1	K_L/L·mg^-1	R²	K_F/mg·g^-1	n	R²
30	88.34	0.105	0.968	20.60	2.96	0.935
40	91.66	0.269	0.996	31.84	3.51	0.950
50	91.74	0.859	0.999	45.24	4.65	0.775

温度 /℃	q_e（实验） /mg·g^-1	准一级动力学模型			准二级动力学模型
温度 /℃	q_e（实验） /mg·g^-1	K₁/g·mg^-1·min^-1	q_e（计算）/mg·g^-1	R²	K₂/g·mg^-1·min^-1	q_e（计算）/mg·g^-1	R²
30	84.3	0.0162	56.07	0.983	4.36×10^-4	74.96	0.972
40		0.0156	60.42	0.944	4.32×10^-4	79.74	0.966
50		0.0145	64.89	0.969	4.02×10^-4	87.03	0.973