非通孔多孔氧化铝基底上原位生成Pd纳米材料的制备及应用

doi:10.11944/j.issn.1000-0518.2017.06.160329

摘要/Abstract

摘要：

以非双通的多孔氧化铝(AAO)(Al基底为支撑体)为模板,基底Al作为还原剂,在AAO孔道内原位合成了Pd单质(Pd/AAO)。本文详细研究了AAO阻挡层的去除以及Pd/AAO的酸腐蚀处理后的情况。采用扫描电子显微镜观察了不同条件下形成的形貌,提出了一个近似合理的生成Pd单质的机理。评价了其对苯硼酸和对溴苯甲醛Suzuki反应的活性。摩尔分数0.06%Pd催化剂在温和的实验条件下可以高效催化Suzuki反应,产率达到99.8%。 Pd/AAO固体片状结构在液相反应中直接从溶液中取出即可进行下一次反应,易于分离和回收,可使用性强。此研究为有机反应异相催化剂的设计提供了一个有效的思路,在实际应用中具有一定的指导意义。

关键词: 多孔氧化铝, 阻挡层, Pd, Suzuki反应

Abstract:

Using non-through-hole anodic aluminum oxide(AAO) as templates, with Al substrate as support body, Pd nanomaterials were prepared in situ in the channels of AAO with Al substrate as reducing agent. The removal of barrier layer and acid corrosion post-treatment of synthesized Pd/AAO were studied. The Pd morphologies under different situations were observed by scanning electronic microscopy. A plausible mechanism of Pd formation was proposed. The catalytic activity for Suzuki reaction of 4-bromobenzene carboxylic acid and phenylboronic acid was investigated with Pd/AAO as heterogeneous catalysts. It is found that Pd/AAO catalysts exhibit excellent catalytic activity, and the yield is up to 99.8% with 0.06% molar fraction of Pd. The catalysts with sheet structure are easily separated for recovery by just taking out of the solution and can be reused in the next time. This research gives a practical method for the design of heterogeneous catalysts in organic reactions.

Key words: porous alumina, barrier layer, Pd, Suzuki reaction

陈梓庭, 梁营. 非通孔多孔氧化铝基底上原位生成Pd纳米材料的制备及应用[J]. 应用化学, 2017, 34(6): 705-711.

CHEN Ziting, LIANG Ying. Preparation and Application of Pd Nanomaterials Grown in situ on Non-Through-Hole Porous Alumina[J]. Chinese Journal of Applied Chemistry, 2017, 34(6): 705-711.

参考文献

[1]	Masuda H,Fukud K. Ordered Metal Nanohole Arrays Made by a Two-step Replication of Honeycomb Structures of Anodic Alumina[J]. Science,1995,268(5216):1466-1468.
[2]	Yang Y,Gao Q M. Influence of Sulfosalicylic Acid in the Electrolyte on the Optical Properties of Porous Anodic Alumina Membranes[J]. Phys Lett,2004,333(3/4):328-333.
[3]	Liu L C,Yoo S H. Electrochemical Growth of Silver Nanobelts in Cylindrical Aluminum Nanochannels[J]. Cryst Growth Des,2011,11(9):3731-3734.
[4]	Wei W,Miao T,Aziz A,et al. Three-Dimensional Ni/TiO2 Nanowire Network for High Areal Capacity Lithium Ion Microbattery Applications[J]. Nano Lett,2012,12(2):655-660.
[5]	Wu G S,Zhang L,Cheng B C,et al. Synthesis of Eu2O3 Nanotubes Arrays Through a Facile Sol-Gel Template Approach[J]. J Am Chem Soc,2004,126(19):5976-5977.
[6]	Laksbmi B B,Dorhout P K,Martin C R. Sol-Gel Template Synthesis of Semiconductor Nanostructures[J]. Chem Mater,1997,9(3):857-861.
[7]	Ergen O,Ruebusch D J,Fang H,et al. Shape-Controlled Synthesis of Single-Crystalline Nanopillar Arrays by Template-assisted Vapor-Liquid-Solid Process[J]. J Am Chem Soc,2010,132(132):13972-13974.
[8]	Yang F,Li Y F,Liu T,et al. Plasma Synthesis of Pd Nanoparticles Decorated-Carbon Nanotubes and Its Application in Suzuki Reaction[J]. Chem Eng J,2013,226((24):52-58.
[9]	Tan L K,Chong M A S,Gao H. Free-Standing Porous Anodic Alumina Templates for Atomic Layer Deposition of Highly Ordered TiO2 Nanotube Arrays on Various Substrates[J]. J Phys Chem C,2008,112(1):69-73.
[10]	Cheng D F,Yagihashi M,Hozumi A. Lamination of Alumina Membranes to Polymer Surfaces:Thick, Hard, Transparent, Crack-free Alumina Films on Polymers with Excellent Adhesion[J]. Appl Mater Interfaces,2011,3(7):2224-2227.
[11]	Liang Y,Wang X D,Liu N,et al. A Facile Method to Synthesise Unique Si Nanostructure Materials by Non-Through-Hole Anodic Alumina Templating[J]. Surf Interface Anal,2013,45(6):1067-1070.
[12]	Cui J,Zhang M,Zhan Y. Synthesis and Characterization Amino-salicylaldimine Palladium-based Complexes and Their Suzuki Coupling Reaction Study[J]. Inorg Chem Commun,2009,12(9):839-841.
[13]	Liu F S,Huang Y T,Lu C,et al. Efficient Salicylaldimine Ligands for a Palladium-catalyzed Suzuki-Miyaura Cross-Coupling Reactions[J]. Appl Organomet Chem,2012,26(8):425-429.
[14]	Brayton D F,Larkin T M,Vicic D A. Synthesis of a Bi(phenoxyketimine) Palladium(Ⅱ) Complex and Its Activity in the Suzuki-Miyaura Reaction[J]. J Organomet Chem,2009,694(18):3008-3011.
[15]	Siamaki A R,Lin Y,Woodberry K,et al. Palladium Nanoparticles Supported on Carbon Nanotubes from Solventless Preparations:Versatile Catalysts for Ligand-free Suzuki Cross Coupling Reactions[J]. J Mater Chem A,2013,1(41):12909-12918.
[16]	Navidi M,Rezadi N,Movassagh B. Palladium(Ⅱ) Schiff Base Complex Supported on Multi-walled Carbon Nanotubes:A Heterogeneous and Reusable Catalyst in the Suzukie Miyaura and Copper-free Sonogashira Hagihara Reactions[J]. J Organometal Chem,2013,743(3):63-69.
[17]	FENG Cuilan,LIU Jianping,GUI Jianzhou,et al. Application of Magnetic Nanoparticles Supported Pd Catalysts in C—C Bond Formation Reactions[J]. Chinese J Appl Chem,2015,32(1):19-26(in Chinese). 冯翠兰,刘建平,桂建舟,等. 磁性纳米粒子负载钯催化剂在C—C键偶联反应中的应用[J]. 应用化学,2015,32(1):19-26.
[18]	Karakhanov E,Maximova,Kardasheva Y,et al. Pd Nanoparticles in Dendrimers Immobilized on Silica-Polyamine Composites as Catalysts for Selective Hydrogenation[J]. ACS Appl Mater Interfaces,2014,6(11):8807-8816.
[19]	Li R,Zhang P,Huang Y M,et al. Facile Approach to Prepare Pd Nanoarray Catalysts within Porous Alumina Templates on Macroscopic Scales[J]. ACS Appl Mater Interfaces,2013,5(23):12695-12700.
[20]	Chee C C,Houy Q,Wamg H,et al. Facile Deposition of Pd Nanoparticles on Carbon Nanotube Microparticles and Their Catalytic Activity for Suzuki Coupling Reactions[J]. J Phys Chem C,2008,112(22):8172-8176.
[21]	XU Guorong,REN Fenglian,SI Shihui,et al. Study on Removal of the Barrier Between Al Substrate and Porous Anodic Alumina by Electrochemical Approach[J]. Acta Phys Chim Sin,2006,22(3):341-344(in Chinese). 徐国荣,任凤莲,司士辉,等. 多孔阳极氧化铝模板电化学法去阻挡层的研究[J]. 物理化学学报,2006,22(3):341-344.
[22]	Tang K J,Yu J H,Zhao Y Y,et al. Fabrication of Super-hydrophobic and Super-oleophilic Boehmite Membranes from Anodic Oxide Film via a Two-phase Thermal Approach[J]. J Mater Chem,2006,16(18):1741-1745.
[23]	Naghipour A,Fakhri A. Heterogeneous Fe3O4@chitosan-Schiff Base Pd Nanocatalyst:Fabrication Characterization and Application as Highly Efficient and Magnetically Recoverable Catalyst for Suzuki-Miyaura and Heck-Mizoroki C—C Coupling Reactions[J]. Catal Commun,2016,73:39-45.
[24]	Veisi H,Khazaei A,Safaei M,et al. Synthesis of Biguanide-functionalized Single-walled Carbon Nanotubes(SWCNTs) Hybrid Materials to Immobilized Palladium as New Recyclable Heterogeneous Nanocatalyst for Suzuki-Miyaura Coupling Reaction[J]. J Mol Catal A:Chem,2014,382(4):106-113.