Page 54 - 精细化工2020年第2期

·256· 精细化工 FINE CHEMICALS 第 37 卷

使 KOH 催化转酯化效率下降，致生物柴油产率偏低。 performance[J]. Journal of Catalysis, 2012, 289(5): 42-52.
[10] Liu D, Lu K, Poon C, et al. Metal organic frameworks as sensory
虽然锆基 MOFs 材料作为催化剂仍有些不足， materials and imaging agents[J]. Inorganic Chemistry, 2014, 53(4):
1916-1924.
但其比表面积大，孔结构有序且可调控，为锆基 [11] Wang J L, Wang C, Lin W. Metal organic frameworks for light
MOFs 材料的催化应用提供了良好的条件，用于制 harvesting and photocatalysis[J]. Acs Catalysis, 2017, 2(2): 2630-
2640.
备生物柴油，进一步拓展了其应用方向。 [12] Nasalevich M A, Veen M V D, Kapteijn F, et al. Metal organic
frameworks as heterogeneous photocatalysts: Advantages and
challenges[J]. Cryst Eng Comm, 2014, 16(23): 4919-4926.
3 结论 [13] Cavka J H, Jakobsen S, Olsbye U, et al. A new zirconium inorganic
building brick forming metal organic frameworks with exceptional
stability[J]. Journal of the American Chemical Society, 2008, 130(42):
（1）XRD 分析表明：UiO-66 的合成中加入适 13850-13851.
量的酸作为调节剂可提高材料的结晶度，当有机酸 [14] Davis M E. Ordered porous materials for emerging applications[J].
Nature, 2002, 417(6891): 813-821.
量增加到 100 eq 时，结晶度降低甚至导致结构坍塌。 [15] Yang Y, Yao H F, Xi F G, et al. Amino-functionalized Zr (Ⅳ) metal-
organic framework as bifunctional acid-base catalyst for Knoevenagel
2 eq 盐酸和 20 eq 乙酸混合调节剂可以显著提高 condensation[J]. Journal of Molecular Catalysis A Chemical, 2014,
UiO-66 的结晶度。 390(8): 198-205.
[16] Zahn G, Zerner P, Lippke J, et al. Insight into the mechanism of
（2）SEM 和 N 2 吸附-脱附分析表明：有机酸调节 modulated syntheses: In situ synchrotron diffraction studies on the
formation of Zr-fumarate MOFs[J]. Cryst Eng Comm, 2014, 16(39):
剂不仅能增大锆基 MOFs 的晶体尺寸和孔径，对于提 9198-9207.
高比表面积也具有一定作用。3 种有机酸调节剂的对 [17] Han Y, Liu M, Li K, et al. Facile synthesis of morphology- and
size-controlled zirconium metal-organic framework UiO-66: the role
比发现，加入 30 eq 的苯甲酸，可获得高分散尺寸为 of hydrofluoric acid in crystallization[J]. Cryst Eng Comm, 2015,
17(33): 6434-6440.
500 nm 左右，比表面积为 814.9 m²/g 的 UiO-66 八面 [18] Ren J, Langmi H W, North B C, et al. Modulated synthesis of
体晶体，相同当量的甲酸可将 UiO-66 的 BET 比表面 zirconium-metal organic framework (Zr-MOF) for hydrogen storage
applications[J]. International Journal of Hydrogen Energy, 2014,
积提高到 1973.8 m²/g。TGA 分析表明：合成的 39(2): 890-895.
[19] Øien S, Wragg D, Reinsch H, et al. Detailed structure analysis of
UiO-66、UiO-66-NO 2 、UiO-66-NH 2 和 UiO-66-OH atomic positions and defects in zirconium metal organic frameworks[J].
分解温度分别为 500、360、270 和 385 ℃，其热稳 Crystal Growth & Design, 2014, 14(11): 5370-5372.
[20] Abid H R, Ang H M, Wang S. Effects of ammonium hydroxide on
定性完全满足催化麻疯树油制备生物柴油的反应温 the structure and gas adsorption of nanosized Zr-MOFs (UiO-66)[J].
Nanoscale, 2012, 4(10): 3089-3094.
度要求。 [21] Schaate A, Roy P, Godt A, et al. Modulated synthesis of zr-based
（3）使用锆基 MOFs 新材料催化麻疯树油两步 metal–organic frameworks: From nano to single crystals[J].
Chemistry - A European Journal, 2011, 17(24): 6643-6651.
法制备生物柴油，有机配体 2-氨基对苯二甲酸合成 [22] Vermoortele F, Vandichel M, van de Voorde B, et al. Electronic effects
of linker substitution on lewis acid catalysis with metal-organic
的 UiO-66-NH 2 催化活性最高，在第一步预酯化中游 frameworks[J]. Angewandte Chemie International Edition, 2012,
51(20): 4887-4890.
离脂肪酸的转化率为 50.7%，第二步酯化油经过转 [23] Morris W, Doonan C J, Yaghi O M. Postsynthetic modification of a
酯化得到的生物柴油产率为 51.6%，脂肪酸甲酯含 metal-organic framework for stabilization of a hemiaminal and
ammonia uptake[J]. Inorganic Chemistry, 2011, 50(15): 6853-6855.
量达 99%以上。 [24] Piscopo C G, Polyzoidis A, Schwarzer M, et al. Stability of UiO-66
under acidic treatment: Opportunities and limitations for post-
参考文献： synthetic modifications[J]. Microporous & Mesoporous Materials,
2015, 208: 30-35.
[1] Yaghi O M, O'Keeffe M, Ockwig N W, et al. Reticular synthesis and [25] Valenzano L, Civalleri B, Chavan S, et al. Disclosing the complex
the design of new materials[J]. Nature, 2003, 423(6941): 705-714. structure of UiO-66 metal organic framework: Synergic combination
[2] Rowsell J L C, Yaghi O M. Metal organic frameworks: A new class of experiment and theory[J]. Chemistry of Materials, 2011, 23(7):
of porous materials[J]. Microporous & Mesoporous Materials, 2004, 1700-1718.
73(1): 3-14. [26] Tsuruoka T, Furukawa S, Takashima Y, et al. Nanoporous nanorods
[3] Chen B, Xiang S, Qian G. Metal-organic frameworks with functional fabricated by coordination modulation and oriented attachment
pores for recognition of small molecules[J]. Accounts of Chemical growth[J]. Angewandte Chemie, 2009, 48(26): 4739-4743.
Research, 2010, 43(8): 1115-1124. [27] Ma Shun (马顺), Wang Yong (汪勇), Tang Shuze (唐书泽). Study on
[4] Seoane B, Castellanos S, Dikhtiarenko A, et al. Multi-scale crystal preparation of biodiesel from high acid value water by two-step
engineering of metal organic frameworks[J]. Coordination Chemistry method[J]. Journal of the Chinese Cereals and Oils Association (中国
Reviews, 2016, 307(8): 147-187. 粮油学报), 2011, 26(6): 40-44.
[5] Li J R, Kuppler R J, Zhou H C. ChemInform abstract: Selective gas [28] Gao Xiaolong (高晓龙), Tan Chuanbo (谭传波), Wu Suxi (吴苏喜).
adsorption and separation in metal organic frameworks[J]. Chemical Study on the preparation of biodiesel from waste white earth oil by
Society Reviews, 2009, 38(5): 1477-1504. two-step method[J]. China Oils and Fats (中国油脂), 2014, 39(10):
[6] Jia Junhua, Lin Xiang, Claire Wilson, et al. Twelve-connected porous 59-62.
metal-organic frameworks with high H 2 adsorption[J]. Chemical [29] Cirujano F G, Corma A, Xamena F X L I. Zirconium-containing
Communications, 2007, 8(8): 840-842. metal organic frameworks as solid acid catalysts for the esterification
[7] Trens P, Belarbi H, Shepherd C, et al. Adsorption and separation of of free fatty acids: Synthesis of biodiesel and other compounds of
xylene isomers vapors onto the chromium terephthalate-based porous interest[J]. Catalysis Today, 2015, 257: 213-220.
material MIL-101(Cr): An experimental and computational study[J]. [30] Zuo Tongmei (左同梅), Li Weimin (李为民), Zhao Qiang (赵强),
Microporous & Mesoporous Materials, 2014, 183(1): 17-22. et al. Synthesis of biodiesel through catalyzed by a novel
[8] Cora A, Garcia H, Xamena F X L I. ChemInform abstract: Engineering transesterification alkaline ioIlic liquid[J]. Journal of Fuel Chemistry
metal organic frameworks for heterogeneous catalysis[J]. Chemical and Technology (燃料化学学报), 2014, 42(2): 200-206.
Reviews, 2010, 41(46): 4606-4655. [31] Wu Qin (吴芹), Chen He (陈和), Han Minghan (韩明汉), et al.
[9] Ramos-Fernandez E V, Pieters C, Linden B V D, et al. Highly Preparation of biodiesel by transesterification of cottonseed oil
dispersed platinum in metal organic framework NH 2-MIL-101(Al) catalyzed by B acid ionic liquid[J]. Petrochemical Technology (石油
containing phosphotungstic acid-characterization and catalytic 化工), 2006, 35(6): 583-586.