|
- 2017
介孔SiO2/膨胀石墨复合材料的直接合成及其对染料的吸附性能
|
Abstract:
采用简单的一步水热合成法,在含有模板剂、铝盐、膨胀石墨和硅源的水溶液中,利用铝盐水解后所产生的弱酸性环境,直接制备出介孔SiO2/膨胀石墨复合材料,考察了铝盐的添加量对所得复合材料结构和性能的影响。采用XRD、N2吸附和SEM对介孔SiO2/膨胀石墨复合材料的结构和形貌进行了表征。以亚甲基蓝为目标污染物分子,系统评价了复合材料的吸附性能。结果表明,合成时铝盐的添加量在很大范围内变化(rAl/Si=0.25~2.0,体系pH值为3.1~2.3)均可获得具有较大比表面积和孔体积的介孔SiO2/膨胀石墨复合材料,且介孔SiO2以多层膜的形式生长在膨胀石墨碳层上;当rAl/Si=0.25、0.5、1.0时,复合材料孔道有序规整;当rAl/Si=1.0、2.0时,复合材料中介孔孔道规整性下降。介孔SiO2/膨胀石墨复合材料吸附亚甲基蓝的饱和吸附量在52~55 mg·g-1左右,吸附行为主要符合Langmuir方程和伪二级动力学模型。 A series of mesoporous SiO2/expanded graphite (EG) composites were directly synthesized via a facile one-step hydrothermal method in aqueous solutions that contain templates,aluminum salts,expanded graphite and siliceous source.The weak acid environment of reaction solutions were self-generated by the aluminum salts.The effects of the added amount of aluminum salt in the reaction system on the structures and properties of the obtained composites were carefully investigated.The structures and morphologies of the composites were characterized by XRD,N2 physisorption and SEM techniques.Methylene blue (MB) was used as a probe pollutant molecule to systematically evaluate the adsorption properties of the composites.The results show that all mesoporous SiO2/expanded graphite composites have large surface areas and high pore volumes,and they can be prepared by using aluminum salts in a wide range of rAl/Si=0.25-2.0(pH=3.1-2.3).It is further observed that multi-layered mesoporous SiO2 membranes are grown onto the carbon flakes of expanded graphite in SiO2/EG composites.Those SiO2/EG composites synthesized with rAl/Si of 0.25,0.5 and 1.0 have well-ordered mesoporous while those synthesized with rAl/Si of 1.5 and 2.0 have less-ordered mesoporous.Mesoporous SiO2/EG composite adsorption capacity in 52-55 mg·g-1,and the adsorption behavior is mainly in accordance with the Langmuir equation and pseudo-second-order kinetic model. 国家自然科学基金(21103119、21407111);江苏省自然科学基金(BK20151198、BK20140280);江苏省高校自然科学研究项目(14KJA430004);江苏省环境功能材料重点实验室项目(SJHG1310)
[1] | ST?BER W, FINK A, BOHN E. Controlled growth of monodisperse silica spheres in the micron size range[J]. Journal of Colloid and Interface Science, 1968, 26(1):62-69. |
[2] | FANG Y, ZHENG G, YANG J, et al. Dual-pore mesoporous carbon@silica composite core-shell nanospheres for multidrug delivery[J]. Angewandte Chemie-International Edition, 2014, 53(21):5366-5370. |
[3] | VALLE-VIGóN P, SEVILLA M, FUERTES A B. Functionalization of mesostructured silica-carbon composites[J]. Materials Chemistry and Physics, 2013, 139(1):281-289. |
[4] | SUN N, DENG C, Li Y, et al. Highly selective enrichment of N-linked glycan by carbon-functionalized ordered graphene/mesoporous silica composites[J]. Analytical Chemistry, 2014, 86(4):2246-2250. |
[5] | DEVAKI N, PETA S, SANDEEP S K, et al. Facile synthesis of a sulfonated carbon-silica-meso composite and mesoporous silica[J]. Chemical Communications, 2011, 47(41):11537-11539. |
[6] | Sayari A, Yang Y. SBA-15 Templated mesoporous carbon:new insights into the SBA-15 pore structure[J]. Chemistry of Materials, 2005, 17(24):6108-6113. |
[7] | PUZIY A M, BARBARA C, PODDUBNAYA O I, et al. Surface heterogeneity of carbon-silica adsorbents studied on the basis of the complex adsorption investigations[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects, 2003, 213(1):45-57. |
[8] | FENG J, YAO Y, HAN L, et al. Silicone surfactant templating for mesoporous silica@carbon complex[J]. Microporous and Mesoporous Materials, 2013, 174:62-66. |
[9] | WU L, WU Y, LIANG X. One-pot synthesis of a novel catalyst with strong acid sites based on carbon/silica composite[J]. Kinetics and Catalysis, 2013, 54(3):378-381. |
[10] | LIU R L. One-pot synthesis of ordered mesoporous carbon-silica nanocomposites templated by mixed amphiphilic block copolymers[J]. Journal of Materials Science, 2009, 44(13):3600-3607. |
[11] | Glover T G, Dunne K I, Davis R J, et al. Carbon-silica composite adsorbent:characterization and adsorption of light gases[J]. Microporous Mesoporous Mater, 2008, 111(1-3):1-11. |
[12] | 陈华军, 王锐, 丁梧秀, 等. 聚乙二醇聚合度对介孔η-Al2O3纤维形貌及吸附能力的影响[J]. 复合材料学报, 2014, 31(3):845-850. CHEN H J, WANG R, DING W X, et al. Effect of polymerization degree of polyethylene glycol on microtopography and adsorbability of mesoporous η-Al2O3 fibers[J]. Acta Materiae Compositae Sinica, 2014, 31(3):845-850(in Chinese). |
[13] | WU Z Y, WANG H J, ZHUANG T T, et al. Multiple functionalization of mesoporous silica in one-pot:direct synthesis of aluminum-containing plugged SBA-15 from aqueous nitrate solutions[J]. Advanced Functional Materials, 2008, 18(1):82-94. |
[14] | WU Z Y, LU Q Y, FU W H, et al. Fabrication of mesoporous Al-SBA-15 as a methylene blue capturer via a spontaneous infiltration route[J]. New Journal of Chemistry, 2015, 39(2), 985-993. |
[15] | JIANG W J, YIN Y, LIU X Q, et al. Fabrication of supported cuprous sites at low temperatures:an efficient, controllable strategy using vapor-induced reduction[J]. Journal of the American Chemical Society, 2013, 135(22):8137-8140. |
[16] | LIU X Y, SUN L B, LU F, et al. Constructing mesoporous solid superbases by a dualcoating strategy[J]. Journal of Materials Chemistry A, 2013, 1(5):1623-1631. |
[17] | POPAT A, HARTONO B S, FRANCES S, et al. Mesoporous silica nanoparticles for bioadsorption, enzyme immobilisation, and delivery carriers[J]. Nanoscale, 2011, 3(7), 2801-2818. |
[18] | ELZBIETA F. Carbon materials for supercapacitor application[J]. Physical Chemistry Chemical Physics, 2007, 9(15):1774-1785. |
[19] | DINCER A R, GüNE? Y KARAKAYA N, GüNE? E. Comparison of activated carbon and bottom ash for removal of reactive dye from aqueous solution[J]. Bioresource Technology, 2007, 98(4):834-839. |
[20] | SANTA C F, JABER M, GUTH J L, et al. Synthesis of texturally biphasic mesoporous carbon-silica composites and carbons[J]. Microporous and Mesoporous Materials, 2013, 173(12):53-63. |
[21] | LIU R L, SHI Y F, WAN Y, et al. Triconstituent co-assembly to ordered mesostructured polymer-silica and carbon-silica nanocomposites and large-pore mesoporous carbons with high surface areas[J]. Journal of the American Chemical Society, 2006, 128(35):11652-11662. |
[22] | GlOVER T G, LEVAN M D. Carbon-silica composite adsorbent:Sensitivity to synthesis conditions[J]. Microporous and Mesoporous Materials, 2009, 118(1-3):21-27. |
[23] | QIN H, HU Z, WANG F, et al. Facile preparation of ordered mesoporous silica-carbon composite nanoparticles for glycan enrichment[J]. Chemical Communications, 2013, 49(45):5162-5164. |
[24] | Wang Z M, Wang W D, Coombs Neil, et al. Graphene oxide-periodic mesoporous silica sandwich nanocomposites with vertically oriented channels[J]. ACS Nano, 2010, 4(12):7437-7450. |
[25] | SOBOLKINA A, MECHTCHERINE V, BELLMANN C, et al. Surface properties of CNTs and their interaction with silica[J]. Journal of Colloid & Interface Science, 2014, 413(1):43-53. |
[26] | GUO J X, SAHA P, LIANG J F, et al. Multi-walled carbon nanotubes coated by multi-layer silica for improving thermal conductivity of polymer composites[J]. Journal of Thermal Analysis and Calorimetry, 2013, 113(2):467-474. |
[27] | LIU C, CHEN Z, CHENG X, et al. Preparation and structure analysis of expanded graphite-based composites made by phosphoric acid activation[J]. Journal of Porous Materials, 2010, 17(4), 425-428. |
[28] | 陈君良, 姚屠鹏, 朱宏亮. 巯基功能化纳米Fe3O4-高分子磁性复合材料的合成及其对水中亚甲基蓝的吸附作用[J]. 复合材料学报, 2014, 31(2):323-330. CHEN J L, YAO T P, ZHU H L. Preparation of thiol-functionalized nano-Fe3O4-polymer magnetic composite and its adsorption properties on methylene blue in water[J]. Acta Materiae Compositae Sinica, 2014, 31(2):323-330(in chinese). |
[29] | 张晓涛, 王喜明. 木质纤维素/纳米蒙脱土复合材料对废水中Cu(Ⅱ)的吸附及解吸[J]. 复合材料学报, 2015, 32(2):385-394. ZHANG X T, WANG X M. Adsorption and desorption of Cu(Ⅱ) in wastewater by lignocellulose/nano-montmorillonite composites[J]. Acta Materiae Compositae Sinica, 2015, 32(2):385-394(in chinese). |
[30] | LUEKING A D, LING P, NARAYANAN D L, et al. Effect of expanded graphite lattice in exfoliated graphite nanofibers on hydrogen storage[J]. The Journal of Physical Chemistry B, 2005, 109(26):12710-12717. |
[31] | WANG S, XU S, LIU C, et al. Characterization and adsorption behaviors of a novel synthesized mesoporous silica coated carbon composite[J]. Chinese Journal of Chemical Engineering, 2016, 24(1):190-195. |
[32] | WANG Z, STEIN A. Morphology control of carbon, silica, and carbon/silica nanocomposites:from 3D ordered macro-/mesoporous monoliths to shaped mesoporous particles[J]. Chemistry of Materials, 2007, 20(3):1029-1040. |
[33] | PARK H B, LEE Y M. Fabrication and characterization of nanoporous carbon/silica membranes[J]. Advanced Materials, 2005, 17(4):477-483. |
[34] | WANG Z M, WANG W, COOMBS N, et al. Graphene oxide periodic mesoporous silica sandwich nanocomposites with vertically oriented channels[J]. ACS Nano 2010, 4(12), 7437-7450. |
[35] | WEI H, LV Y, HAN L, et al. Facile synthesis of transparent mesostructured composites and corresponding crack-free mesoporous carbon/Silica monoliths[J]. Chemistry of Materials, 2011, 23(9):2353-2360. |