一种新型膦酸锆孔材料的合成及其对金属离子的吸附性质

doi:10.15541/jim20160183

摘要/Abstract

摘要：

骨架含强配位基的有机无机杂化多级孔材料合成是目前吸附研究的一个重要领域。以bis (hexamethylene) triamino-N, N-bisacetyl-phosphonic acid和ZrOCl₂·8H₂O为原料、应用水热合成技术合成了一种新型膦酸锆多级孔材料ZrPTA, 并通过FT-IR、TGA、XRD、XPS、SEM以及元素分析等手段对制备产物进行了表征。研究结果表明, ZrPTA具有棒状微形貌, 其内部存在大量直径为1.38 nm和1.93 nm的微孔以及直径为2.99 nm的介孔, 其表面积为112.2 m²/g。ZrPTA对水溶液中Pb²⁺、Cu²⁺和Cd²⁺三种金属离子具有良好的吸附作用, 最大吸附量分别为742.7、689.8和627.0 mg/g, 远远高于文献报道值。这一性质使ZrPTA具有潜在的废水处理功效, 显示出诱人的应用前景。

关键词: 膦酸锆, 孔材料, 水热合成, 内表面, 吸附

Abstract:

Synthesis of organic-inorganic hybrid hierarchical porous materials with strong ligand in framework is an important field of current research in adsorption. A new kind of inorganic/organic hierarchical zirconium phosphonate material (ZrPTA) with porous structure was prepared from bis(hexamethylene)triamino-N, N-bisacetyl- phosphonic acid and ZrOCl₂·8H₂O in water solution by using hydrothermal synthesis technology. The samples were characterized by FT-IR spectroscope, TGA, XRD, XPS, SEM and element analysis. The results show that the material possesses a rod-like morphology, and the rods contain micropores of 1.38 nm and 1.93 nm in diameter, mesopores of 2.99 nm in diameter, and a surface area of ~112.2 m²/g. The as-prepared ZrPTA is more efficient in removing Pb²⁺, Cu²⁺ and Cd²⁺ from wastewater. Its maximum adsorption capacities for Pb²⁺, Cu²⁺ and Cd²⁺ are 742.7, 689.8 and 627.0 mg/g, respectively, which is much higher than the maximum adsorption capacities of the adsorbents reported. The perfect properties make the material good prospects in application as an adsorbent in wastewater processing.

Key words: zirconium phosphonate, porous materials, hydrothermal synthesis, interfaces, adsorption

中图分类号:

TQ174

Abubaker Abutartour, Lotfia El Majdoub, 史亚赛, 李妮丽, 徐庆红. 一种新型膦酸锆孔材料的合成及其对金属离子的吸附性质[J]. 无机材料学报, 2017, 32(3): 305-312.

ABUBAKER Abutartour, LOTFIA El-Majdoub, SHI Ya-Sai, LI Ni-Li, XU Qing-Hong. A New Porous Zirconium Phosphonate Hybride Material and Its Adsorption Properties[J]. Journal of Inorganic Materials, 2017, 32(3): 305-312.

图/表 13

图1 Bis(hexamethylene)triamino-N-N-bisacetyl-phosphorus分子结构

Fig. 1 Structures of bis(hexamethylene)triamino-N-N-bisac- etylphosphorus oxychloride

图2 (A)双(六甲撑)三胺(a)、bis(hexamethylene)triamino-N-N-bisacetylphosphorus oxychloride(b)及ZrPTA(c)的红外光谱图; (B) ZrPTA经过不同pH盐酸溶液浸泡1h后样品的红外光谱(a: pH=5.0; b: pH=6.0; c: 未浸泡)

Fig. 2 (A) FT-IR spectra of bis(hexamethylene)triamine (a), bis(hexamethylene)triamino-N-N-bisacetyl-phosphorus oxychloride (b) and ZrPTA (c); (B) FT-IR spectra of ZrPTA immersed in HCl solutions with different pH (a: pH=5.0; b: pH=6.0; c: unimmersed)

图3 ZrPTA (A)及经过不同pH盐酸溶液处理后的ZrPTA(B)的XRD图谱

Fig. 3 PXRD patterns of ZrPTA (A) and ZrPTA delt in HCl solutions with different pH (B)

图4 ZrPTA的氮气吸脱附曲线(a)及孔分布曲线(b)

Fig. 4 N2 adsorption-desorption isotherms curve (a) and pore width distribution (b) of ZrPTA

图5 ZrPTA可能的孔结构示意图

Fig. 5 Possible porous structure in ZrPTA

图6 ZrPTA的透射电镜(a)及扫描电镜(b)照片

Fig. 6 TEM (a) and SEM (b) images of ZrPTA

图7 ZrPTA的差热-热失重分析曲线

Fig. 7 TG-DTA curves of ZrPTA

图8 ZrPTA在pH=4.0的酸性环境中对不同浓度金属离子的吸附随时间变化关系曲线

Fig. 8 Change of adsorptions of ZrPTA to metal ions with different concentrations with time ^(adsorbent dosage=1.0 g/L, temperature is (25±2)℃, pH=4.0)^(a) 900 mg/L; (b) 800 mg/L; (c) 700 mg/L; (d) 600 mg/L; (e) 500 mg/L

表1 吸附剂ZrPTA对三种金属离子在不同起始浓度条件下的吸附量(mg/g)及吸附百分率

Table 1 Adsorption date (mg/g) and adsorption percents (%) (in the bracket) of the adsorbent to three metal ions at different origin concentrations

	500/(mg·L^-1)	600/(mg·L^-1)	700/(mg·L^-1)	800/(mg·L^-1)	900/(mg·L^-1)
Pb²⁺	459.21 (91.84)	541.25 (90.20)	586.33 (83.76)	670.15 (83.76)	742.96 (82.55)
Cd²⁺	422.98 (84.59)	516.33 (86.05)	611.97 (87.42)	676.21 (84.52)	627.04 (69.67)
Cu²⁺	452.15 (90.43)	534.87 (89.14)	619.43 (88.48)	671.04 (83.88)	689.81 (76.64)

表2 ZrPTA对Pb2+、Cu2+及Cd2+的最大吸附量与来自不同文献吸附剂最大吸附量的比较

Table 2 Comparison of qe of ZrPTA for Pb2+, Cu2+ and Cd2+ with those of different types of adsorbents in references

Adsorbents	Magnetic chelating resin	Zwitterionic hybrid polymers	ZrPTA	Polycarboxy-lated starch	Ion-imprinted fiber	ZrPTA	Porous bioadsorbent	Activated carbon	ZrPTA
		to Pb²⁺			to Cu²⁺			to Cd²⁺
q_e /(mg·g^-1)	571.8	380.2	742.7	128.3	120.0	689.8	278.6	157.4	627.0
Temperature	45℃	45℃	25℃	40℃	30℃	25℃	25℃	25℃	25℃
pH	6.0	5.0	4.0	7.0	6.0	4.0	5.0	5.0	4.0
Ref	[20]			[21]			[22]

图9 ZrPTA(a)、ZrPTA/Pb2+(b)、ZrPTA/Cd2+(c)及ZrPTA/Cu2+ (d)中N1s X光电子能谱图

Fig. 9 XPS spectra of N1s in ZrPTA (a), ZrPTA/Pb2+ (b), ZrPTA/Cd2+ (c) and ZrPTA/Cu2+ (d)

图10 在固定浓度(c0 = 900mg/L), ZrPTA对Pb2+、Cu2+和Cd2+的平衡吸附量随温度(从30℃到80℃)的变化关系曲线

Fig. 10 Relations between the equilibrium adsorption amounts at a given concentration (c0 = 900mg/L) and temperature (from 30℃ to 80℃) of ZrPTA to Pb2+, Cu2+ and Cd2+

图11 室温条件下, ZrPTA 对Pb2+、 Cu2+和 Cd2+的平衡吸附量随溶液酸碱度的变化关系曲线

Fig. 11 Equilibrium adsorption amounts of ZrPTA to Pb2+, Cu2+ and Cd2+ in different pH solution at room temperature

参考文献 22

[1]	EMAMIPOUR H, JOHNSEN D L, ROOD M J, et al.Novel activated carbon fiber cloth filter with functionalized silica nanoparticles for adsorption of toxic industrial chemicals.Adsorption, 2015, 21(4): 265-272.
[2]	KRASUCKA P, GOWOREK J, KIERYS A.Synthesis of the mesostructured polymer- silica composite and silicon dioxide through polymer swelling in silica precursor.Adsorption, 2016, 22(4): 663-671.
[3]	KRUSZKA B, WIŚNIEWSKI M, TERZYK A P. Phenol adsorption on different nano-sized carbon materials: first comparative study.Adsorption, 2016, 22(4): 437-444.
[4]	WU SHENG-JU, LI FENG-TING, XU RAN, et al.Synthesis of thiol-functionalized MCM-41 mesoporous silicas and its application in Cu(II), Pb(II), Ag(I) and Cr(VI) removal.Journal of Nanoparticle Research, 2010, 12(6): 2111-2124.
[5]	MERCIER L, PINNAVAIA T J.Heavy metal ion adsorbents formed by the grafting of thiol functionality to mesoporous silica molecular sieves: factors affecting Hg2+ uptake.Environmental Science & Technology, 1998, 32(18): 2749-2754.
[6]	BROWN J, MERCIER L, PINNAVAIA T J.Selective adsorption of Hg2+ by thiol-functionalized nanoporous silica.Chemical Communication, 1999, 69-70.
[7]	YUAN Z Y, REN T Z, SU B L.Hierarchically mesostructured titania materials with an unusual interior macroporous structure. Advanced Materials, 2003, 15(17): 1462-1465.
[8]	YUAN Z Y, REN T Z, AZIOUNE A, et al.Facile and generalized preparation of hierarchically mesoporous-macroporous binary metal oxide materials.Chemistry of Materials, 2006, 18(7): 1753-1767.
[9]	ABUTARTOUR A, JIA Y J, LOTﬁA E M, et al. A new hierarchical porous zirconium phosphate membrane and its adsorption properties.Microporous and Mesoporous Materials, 2014, 196: 1-7.
[10]	ZHANG X J, MA T Y, YUAN Z Y.Synthesis of hierarchically meso-/macroporous titanium tetraphosphonate materials with large adsorption capacity of heavy metal ions.Chemistry Letter, 2008, 37(7): 746-747.
[11]	CLEARFIELD A, STYNES J A.The preparation of crystalline zirconium phosphate and some observations on its ion exchange behaviour.Journal of Inorganic Nuclear Chemistry, 1964, 26(1): 117-129.
[12]	CLEARFIELD A, BLESSING R H.New crystalline phases of zirconium phosphate possessing ion-exchange properties.Journal of Inorganic Nuclear Chemistry, 1968, 30(8): 2249-2258.
[13]	ALBERTI G, COSTANTINO U, ALLULLI S, et al.Crystalline Zr(RPO3)2 and Zr(ROPO3)2 compounds (R=organic radical): a new class of materials having layered structure of the zirconium phosphate type.Journal of Inorganic Nuclear Chemistry, 1978, 40(6): 1113-1117.
[14]	CLEARFIELD A.Group IV phosphates as catalysts and catalyst supports.Journal of Molecular Catalysis, 1984, 27(1/2): 251-262.
[15]	ALBERTI G.Syntheses, crystalline structure, and ion-exchange properties of insoluble acid salts of tetravalent metals and their salt forms.Accounts of Chemical Research, 1978, 11(4): 163-170.
[16]	BELLEZZA F, CIPICIANI A, COSTANTINO U, et al.Adsorption of myoglobin onto porous zirconium phosphate and zirconium benzenephosphonate obtained with template synthesis. Langmuir, 2006, 22(11): 5064-5069.
[17]	HOGARTH W H J, DINIZ D C J C, DRENNAN J, et al. Proton conductivity of mesoporous Sol-Gel zirconium phosphates for fuel cell applications.Journal of Materials Chemistry, 2005, 15: 754-758.
[18]	KAPOOR M P, INAGAKI S, YOSHIDA H.Novel zirconium-titanium phosphates mesoporous materials for hydrogen production by photoinduced water splitting.Journal of Physical Chemistry B, 2005, 109(19): 9231-9238.
[19]	CRISAFULLY R, MILHOME M A, CAVALCANTE R M, et al.Removal of Some polycyclic aromatic hydrocarbons from petrochemical wastewater using low-cost adsorbents of natural origin.Bioresource Technology, 2008, 99(10): 4515-4519.
[20]	REN T Z, YUAN Z Y, SU B L.Surfactant-assisted preparation of hollow microspheres of mesoporous TiO2.Chemical Physics Letter, 2003, 374(1/2): 170-175.
[21]	GUERRERO G, MUTIN P, VIOUX A.Anchoring of phosphonate and phosphinate coupling molecules on titania particles. Chemistry of Materials, 2001, 13(11): 4367-4373.
[22]	JAIMEZ E, HIX G B, SLADE R C A. Phosphate-phosphonate of titanium (iv) prepared from phosphonomethyliminodiacetic acid: characterisation, n-alkylamine intercalation and proton conductivity.Solid State Ionics, 1997, 97(1-4): 195-201.