水热法制备介孔氧化铝的形貌演化研究

doi:10.15541/jim20140104

摘要/Abstract

摘要：

以硫酸铝铵、尿素为原料, PEG2000作为分散剂, 通过水热法合成了三种形貌的勃姆石(AlOOH)。实验结果显示, 调节水热温度可以制备出AlOOH微球、微纤维和3D分级结构的AlOOH。经SEM分析可知, 在煅烧过程中, AlOOH分解转化为γ-Al₂O₃, 该过程为拓扑过程, 即形貌未发生变化。TEM结果显示, 介孔均匀地分布在AlOOH内。基于此, 我们提出了温度-形貌生长机制。此外, 还研究了γ-Al₂O₃的光致发光性能, 以325 nm为激发光谱时, 其发生光谱的波长在380~500 nm, 光谱中心在409和467 nm处。

关键词: 勃姆石, &amp, #x003b3, -Al2O3, 拓扑, 介孔, 光致发光

Abstract:

Boehmite with varied morphologies was successfully synthesized from aluminum ammonium sulfate hydrate and urea, as well as poly-glycol-2000 by hydrothermal method. The experimental results show that boehmite microspheres, microfibers and 3D hierarchical structured AlOOH can be fabricated only by adjusting hydrothermal temperature. SEM images indicate that boehmite decomposes into γ-Al₂O₃ phase after heat-treatment through a topotactical process. TEM studies present that the mesopores are formed in γ-Al₂O₃ particles. Based on these investigations, a temperature-dependent morphology formation mechanism is proposed. Besides, the as-synthesized alumina excited at 325 nm shows emission in the range of 380 nm to 500 nm, centered at 409 nm and 467 nm.

Key words: boehmite, &amp, #x003b3, -Al2O3, topotactical, mesoporous, photoluminescence

中图分类号:

TQ174

李艳辉, 彭诚, 赵威, 白明敏, 饶平根. 水热法制备介孔氧化铝的形貌演化研究[J]. 无机材料学报, 2014, 29(10): 1115-1120.

LI Yan-Hui, PENG Cheng, ZHAO Wei, BAI Ming-Min, RAO Ping-Gen. Morphology Evolution in Hydrothermal Synthesis of Mesoporous Alumina[J]. Journal of Inorganic Materials, 2014, 29(10): 1115-1120.

图/表 7

Fig. 1 XRD patterns of AlOOH (A), together with their respective (B) wide- and (C) small-angle XRD patterns of γ-Al2O3 powder calcined at 800℃ for 2 h (a) Pre90; (b) Pre120; (c) Pre150

Fig. 2 SEM images of AlOOH (A-B)Pre90;(C-D)Pre120;(E-F)Pre150

Fig. 3 SEM images of γ-Al2O3 obtained from different hydrothermal products calcined at 800℃ for 2 h (A-B) Alu90; (C-D) Alu120; (E-F) Alu150

Fig. 4 TEM image and a typical SAED pattern (inset) of γ-Al2O3 (A-B) Alu90; (C-D) Alu120; (E-F) Alu150

Fig. 5 Barrett-Joyner-Halenda (BJH) pore-size distribution (A-C) and N2 adsorption and desorption isotherm (D-F) of γ-Al2O3 from different hydrothermal products (A, D) Alu90; (B, E) Alu120; (C, F) Alu150

Fig. 6 Schematic diagram of the formation of AlOOH precursor with various morphologies

Fig. 7 Room temperature PL spectra of the as-prepared γ-Al2O3 (a) Alu90; (b) Alu120; (c) Alu150

参考文献 33

[1]	UDDIN A, TSUDA H, WU S, et al. Catalytic decomposition of biomass tars with iron oxide catalysts. Fuel, 2008, 87(4): 451-459.
[2]	ZHU Z, LIU H, SUN H, et al. Surfactant assisted hydrothermal and thermal decomposition synthesis of alumina microfibers with mesoporous structure. Chem. Eng. J., 2009, 155(3): 925-930.
[3]	PHAM A L T, LEE C, DOYLE F M, et al. A silica-supported iron oxide catalyst capable of activating hydrogen peroxide at neutral pH values. Environ. Sci. Technol., 2009, 43(23): 8930-8935.
[4]	REDDY C, CAO S A W, TAN O, et al. Preparation and Characterization of Iron Oxide-zirconia Nano Powder for Its Use as an Ethanol Sensor Material. Ceramics Transactions: Wiley- Ame-rican Ceramic Society, 2012: 67.
[5]	BISWAL R C. Pure and Pt-loaded gamma iron oxide as sensor for detection of sub ppm level of acetone. Sens Actuators B, 2011, 157(1): 183-188.
[6]	GUARDIA P, LABARTA A, BATLLE X. Tuning the size, the shape, and the magnetic properties of iron oxide nanoparticles. J. Phys. Chem. C, 2010, 115(2): 390-396.
[7]	LAURENT S, FORGE D, PORT M, et al. Magnetic iron oxide nanoparticles: synthesis, stabilization, vectorization, physicoch-emical characterizations, and biological applications. Chem. Rev., 2008, 108(6): 2064.
[8]	BREZESINSKI T, WANG J, TOLBERT SH, et al. Ordered mesoporous α-MoO3 with iso-oriented nanocrystalline walls for thin-film pseudocapacitors. Nat. Mater., 2010, 9(2): 146-151.
[9]	VIVERO-ESCOTO J L, SLOWING I I, TREWYN B G, et al. Mesoporous silica nanoparticles for intracellular controlled drug delivery. Small, 2010, 6(18): 1952-1967.
[10]	CHEN D, HUANG F, CHENG Y B, et al. Mesoporous anatase TiO2 beads with high surface areas and controllable pore sizes: a superior candidate for high-performance dye-sensitized solar cells. Adv. Mater., 2009, 21(21): 2206-2210.
[11]	ROSSINYOL E, ARBIOL J, PEIRÓ F, et al. Nanostructured metal oxides synthesized by hard template method for gas sensing applications. Sens. Actuators B, 2005, 109(1): 57-63.
[12]	ZHU Z, LIU H, SUN H, et al. PEG-directed hydrothermal synthesis of multilayered alumina microfibers with mesoporous structures. Microporous Mesoporous Mater., 2009, 123(1/2/3): 39-44.
[13]	PELLEGRINO T, MANNA L, KUDERA S, et al. Hydrophobic nanocrystals coated with an amphiphilic polymer shell: a general route to water soluble nanocrystals. Nano Lett., 2004, 4(4): 703-707.
[14]	TORCHILIN V P, SHTILMAN M I, TRUBETSKOY V S, et al. Amphiphilic vinyl polymers effectively prolong liposome circulation time in vivo. Biochimica et Biophysica Acta (BBA)- Biomembranes, 1994, 1195(1): 181-184.
[15]	DENGLER E C, LIU J, KERWIN A, et al. Mesoporous silica-supported lipid bilayers (protocells) for DNA cargo delivery to the spinal cord. J. Controlled Release, 2013, 168(2): 209-224.
[16]	MELLAERTS R, FAYAD E J, VAN DEN MOOTER G, et al. In Situ FT-IR investigation of etravirine speciation in pores of SBA-15 ordered mesoporous silica material upon contact with water. Mol. Pharmaceutics, 2013, 10: 567-573.
[17]	CHEON J Y, AHN C, YOU D J, et al. Ordered mesoporous carbon-carbon nanotube nanocomposites as highly conductive and durable cathode catalyst supports for polymer electrolyte fuel cells. J. Mater. Chem., 2013, 1(4): 1270-1283.
[18]	FANG Y, LV Y, CHE R, et al. Two-dimensional mesoporous carbon nanosheets and their derived graphene nanosheets: synthesis and efficient lithium ion storage. J. Am. Chem. Soc., 2013, 135(4): 1524-1530.
[19]	CAI W, YU J, ANAND C, et al. Facile synthesis of ordered mesoporous alumina and alumina-supported metal oxides with tailored adsorption and framework properties. Chem. Mater., 2011, 23(5): 1147-1157.
[20]	CHEN C, AHN W S. CO2 capture using mesoporous alumina prepared by a Sol-Gel process. Chem. Eng. J., 2011, 166(2): 646-651.
[21]	XU J, WANG A, WANG X, et al. Synthesis, characterization, and catalytic application of highly ordered mesoporous alumina-carbon nanocomposites. Nano Research, 2011, 4(1): 50-60.
[22]	HOUNSLOW M, MUMTAZ H, COLLIER A, et al. A micro-mechanical model for the rate of aggregation during precipitation from solution. Chem. Eng. Sci., 2001, 56(7): 2543-2552.
[23]	CLARIDGE J B, YORK A P, BRUNGS A J, et al. Study of the temperature-programmed reaction synthesis of early transition metal carbide and nitride catalyst materials from oxide precursors. Chem. Mater., 2000, 12(1): 132-142.
[24]	ZHAO Z, ZHANG W, REN P, et al. Insights into the topotactic conversion process from layered silicate RUB-36 to FER-type zeolite by layer reassembly. Chem. Mater., 2013, 25(6): 840-847.
[25]	CUDENNEC Y, LECERF A. The transformation of Cu (OH)2 into CuO, revisited. Solid State Sciences, 2003, 5(11): 1471-1474.
[26]	GOULD W, COOK F, WEBSTER G. Factors affecting urea hydrolysis in several Alberta soils. Plant Soil, 1973, 38(2): 393-401.
[27]	LIAO H D, ZHANG W P, SUN X M, et al. Preparation and thermodynamic study of self-dispersal nano-AlOOH. Key Eng. Mater., 2012, 512:100-105.
[28]	BURTON W K, CABRERA N, FRANK F. The growth of crystals and the equilibrium structure of their surfaces. Philos. Trans. R. Soc. A, 1951, 243(866): 299-358.
[29]	PENN R L, BANFIELD J F. Morphology development and crystal growth in nanocrystalline aggregates under hydrothermal conditions: Insights from titania. Geochim Cosmochim Acta, 1999, 63(10): 1549-1557.
[30]	NAGAHAMA K, OUCHI T, OHYA Y. Temperature‐induced hydrogels through self-Assembly of cholesterol-substituted star PEG-b-PLLA copolymers: an injectable scaffold for tissue engineering. Adv. Funct. Mater., 2008, 18(8): 1220-1231.
[31]	ZHI H, LÜ C, ZHANG Q, et al. A new PEG-1000-based dicationic ionic liquid exhibiting temperature-dependent phase behavior with toluene and its application in one-pot synthesis of benzopyrans. Chem. Commun., 2009, 20: 2878-2880.
[32]	LI Y, PENG C, LI L, et al. Self-assembled 3D Hierarchically structured γ-alumina by hydrothermal method. J. Am. Ceram. Soc., 2014, 97(1): 35-39.
[33]	YU Z Q, CHANG D, LI C, et al. Blue photoluminescent properties of pure nanostructured γ-Al2O3. J. Mater. Res., 2001, 16(7): 1890-1893.