采用硬模板法与溶胶-凝胶法相结合的工艺,以自制的聚苯乙烯(PS)为模板,十六烷基三甲基溴化铵 (CTAB)为阳性表面活性剂,正硅酸四乙酯(TEOS)为硅源制备SiO2空心微球。重点研究升温速率及CTAB、TEOS、氨水用量等工艺参数对SiO2空心微球形貌的影响规律。采用XRD、TEM、SEM、TG、FTIR对微球的物相、微观形貌及介孔结构等进行表征。结果表明：SiO2空心微球粒径为2~5 μm、壁厚为117 nm;SiO2空心微球壁会随着升温速率的增加而出现破损现象;随CTAB用量增加,纳米球数量增加且粒径减小;随TEOS用量增加,球壁变厚直至形成纳米球;氨水小于4 mL时,二氧化硅空心微球不能成形,氨水大于4 mL时,二氧化硅空心微球表面粗糙,有实心颗粒;当升温速率为0.5 ℃/min、CTAB用量为0.05 g、TEOS用量为0.3 mL、氨水用量为4 mL时,且经过抽滤清洗的SiO2空心微球的形貌最佳。
The hollow SiO2 microspheres were prepared through the hard template method and sol-gel method by using self-made polystyrene (PS) as template, cetyltrimethyl ammonium bromide (CTAB) as cationic surfactant and Tetraethyl orthosilicate (TEOS) as silica source. Effects of heating rate, content of CTAB, TEOS and ammonia on the morphology of hollow SiO2 microspheres were discussed. The phase, morphology and mesoporous structure of hollow SiO2 microspheres were characterized by XRD, TEM, SEM, TG and FTIR, which shows the successful preparation of hollow silica sphere. The particle sizes of hollow SiO2 microspheres are 2-5 μm and the thickness is 117 nm. The hollow SiO2 microsphere wall damage with the increase of heating rate. With increasing CTAB content, the number of nanospheres increase and the particle sizes of nanospheres decrease. With increasing TEOS content, the thicknesses of spheres increase until nanospheres are formed. When ammonia is less than 4 mL, hollow SiO2 microsphere cannot be formed. When ammonia is greater than 4 mL, hollow SiO2 microsphere have rough surface with solid particles. The optimized conditions are determined as follows: the heating rate is 0.5 ℃/min, the amount of CTAB is 0.05 g, the amount of TEOS is 0.3 mL, the amount of ammonia is 4 mL and then hollow SiO2 microspheres are treated through filtering and cleaning.
[1] LI Y, SHI J.Hollow-structured mesoporous materials: chemical synthesis, functionalization and applications[J]. Advanced Materials, 2014, 26(20): 3176-3205.
[2] SHARMA J, POLIZOS G.Hollow silica particles: recent progress and future perspectives[J]. Nanomaterials, 2020, 10(8): 1599.
[3] WEI X, ZHAO C, MA J, et al.Ultra-low dielectric closed porous materials via incorporating surface-functionalized hollow silica microspheres: preparation, interface property and low dielectric performance[J]. RSC Advances, 2016, 6(3): 1870-1876.
[4] XIE Q, LU H, WANG X, et al.Functionalized hollow mesoporous silica for detection of staphylococcus aureus and sterilization[J]. Journal of Environmental Chemical Engineering, 2021, 9(5): 105892.
[5] RAJPUT S M, GANGELE K, POLURI K M, et al.Drug induced catanionic vesicles assisted fabrication of hollow silica nano-spheres as the new age chemo-drug carrier[J]. Colloid and Interface Science Communications, 2021, 44: 100466.
[6] 李爱坤, 李丽娅, 吴隆文, 等. 溶胶凝胶法制备SiO2包覆Fe85Si9.6Al5.4软磁复合粉末[J]. 中国有色金属学报, 2013, 23(4): 1065-1072.
LI Aikun, LI Liya, WU Longwen, et al.Preparation of Fe85Si9.6Al5.4 soft magnetic composite powder with silica insulation coating by sol-gel method[J]. Transactions of Nonferrous Metals Society of China, 2013, 23(4): 1065-1072.
[7] ZHAO N, MAO A, SHAO Z, et al.Anisotropic porous ceramic material with hierarchical architecture for thermal insulation[J]. Bioinspiration and Biomimetics, 2022, 17: 015002.
[8] 刘纯, 殷恒波, 石莉萍, 等. 纳米SiO2空心微球对重金属离子的吸附特性[J]. 中国有色金属学报, 2013, 23(6): 1661-1665.
LIU Chun, YIN Hengbo, SHI Liping, et al.Adsorbability characteristic of hollow SiO2 nanospheres for heavy metal ions[J]. Transactions of Nonferrous Metals Society of China, 2013, 23(6): 1661-1665.
[9] WANG H, TANG Q, CHEN Z, et al.Recent advances on silica- based nanostructures in photocatalysis[J]. Science China- Materials, 2020, 63(11): 2189-2205.
[10] ZOU H, SHANG K.Synthetic strategies for hollow particles with open holes on their surfaces[J]. Materials Chemistry Frontiers, 2021, 5(10): 3765-3787.
[11] LI C, ZHAO X, CHENG M, et al.Application of hollow mesoporous organosilica nanoparticles as pH and redox double stimuli-responsive nanocontainer in the controlled release of corrosion inhibitor molecules[J]. Progress in Organic Coatings, 2021, 159: 106437.
[12] VELAZQUEZ-PALENZUELA A, WANG H, YANG N, et al.Preparation of TiO2-based hollow microspheres by spray drying and their use as novel active pigments for photocatalytic coatings[J]. Progress in Organic Coatings, 2021, 160: 106518.
[13] 蔡佳文, 李跃, 吴春春, 等. 缓蚀剂负载中空SiO2微球的制备及性能[J]. 硅酸盐学报, 2020, 48(4): 584-591.
CAI Jiawen, LI Yue, WU Chunchun, et al.Preparation and properties of hollow SiO2 microspheres supported by corrosion inhibitors[J]. Journal of the Chinese Ceramic Society, 2020, 48(4): 584-591.
[14] WU C, LU Z, LI Z, et al.Assembly of colloidal nanoparticles into hollow superstructures by controlling phase separation in emulsion droplets[J]. Small Structures, 2021, 2(6): 2100005.
[15] NEMOTO T, SAKAI T, OKADA T.Unimodal sized silica nanocapsules produced through water-in-oil emulsions prepared by sequential irradiation of kilo-and submega-hertz ultrasounds[J]. Rsc Advances, 2021, 11(37): 22921-22928.
[16] 张硕. 利用纳米碳酸钙为模板制备二氧化硅空心微球[J]. 材料导报, 2020, 34(S2): 1091-1094.
ZHANG Shuo.Preparation of hollow silica microspheres using nano calcium[J]. Materials Review, 2020, 34(S2): 1091-1094.
[17] 段国伟, 谢李昭, 赵驰, 等. 聚合物模板微球表面电性对中空二氧化硅微球形貌的影响[J]. 高分子学报, 2017(5): 785-792.
DUAN Guowei, XIE Lizhao, ZHAO Chi, et al.Effect of surface electrical properties of polymer template microspheres on morphology of hollow silicon dioxide microspheres[J]. Acta Polymerica Sinica, 2017(5): 785-792.
[18] DEEPIKA D, JAGADEESHBABU P E.Synthesis of silica hollow core shell nanoparticles by sacrificial nitrated polystyrene template approach for targeted drug delivery application[J]. Materials Today: Proceedings, 2021, 45: 740-744.
[19] ZHOU X, CHENG X, FENG W, et al.Synthesis of hollow mesoporous silica nanoparticles with tunable shell thickness and pore size using amphiphilic block copolymers as core templates[J]. Dalton Transactions, 2014, 43(31): 11834-11842.
[20] 李殷杰, 王骥, 潘超逸, 等. 两步法和双模板法制备中空二氧化硅微球的比较[J]. 应用化工, 2020, 49(12): 3064-3068, 3073.
LI Yinjie, WANG Ji, PAN Chaoyi, et al.Comparison of preparation of hollow silica microspheres by two-step method and double template method[J]. Applied Chemical Industry, 2020, 49(12): 3064-3068, 3073.
[21] 聂志欣, 蒋平平, 赵汇行, 等. 中空介孔二氧化硅负载磷钨酸催化剂的制备及其在生物柴油合成中的应用[J]. 中国油脂, 2021, 46(7): 48-56.
NIE Zhixin, JIANG Pingping, ZHAO Huixing, et al.Preparation of mesoporous silica supported phosphotungstic acid catalyst and its application in biodiesel synthesis[J]. China Oils and Fats, 201, 46(7): 48-56.
[22] 陆仕稳. 以聚苯乙烯微球为模板制备中空介孔二氧化硅微球[D]. 哈尔滨: 哈尔滨工业大学, 2012.
LU Shiwen.Preparation of hollow mesoporous silica microspheres based on the polystyrene templates[D]. Harbin: Harbin Institute of Technology, 2012.
