多金属氧酸盐及其溶液自聚集行为研究进展

doi:10.11944/j.issn.1000-0518.2018.06.170292

摘要/Abstract

摘要：

多金属氧酸盐(POM)是一类由过渡金属与氧原子桥连而成的阴离子簇合物,由于其特殊的分子结构及优异的物理化学性质,使其在催化、医药、材料科学、表面化学、超分子化学等领域有广泛的应用价值。 POM在稀的水溶液中能够发生自聚集,形成类似两亲分子溶液中的“有序聚集体结构”,赋予其新的结构和性质,以期开发出新型纳米器件及在催化、药物等领域得到应用。本文介绍了POM的主要结构、性质和近年来的应用,阐述了其在溶液中自聚集行为的研究状况和新进展。

关键词: 多金属氧酸盐, 有机/多金属氧酸盐杂化体, 自聚集, 囊泡

Abstract:

Polyoxometalate(POM) is an anion cluster composed of transition metal and oxygen atoms. Due to its special molecular structure and excellent physical and chemical properties, POM has a wide range of applications in catalysis, surface and supramolecular chemistry, as well as biological, pharmaceutical, and material sciences. POM in dilute aqueous solution can occur self-aggregation, forming a “ordered aggregates structure” similar to the structure of amphiphilic molecule in solution, which gives new structure and property for the development of new nano-devices and in the field of catalysis, medicines and other applications. This review briefly introduced the structure, properties and applications of POM, and summarized the research status and new progress of self-aggregation of POM in solution.

Key words: polyoxometalate, organic/polyoxometalate hybrids, self -aggregation, vesicles

党利芳,王蕊欣,谢美娜,焦纬洲. 多金属氧酸盐及其溶液自聚集行为研究进展[J]. 应用化学, 2018, 35(6): 625-644.

DANG Lifang,WANG Ruixin,XIE Meina,JIAO Weizhou. Research Progress of Polyoxometalates and Their Self-aggregation Behaviors in Solution[J]. Chinese Journal of Applied Chemistry, 2018, 35(6): 625-644.

参考文献

[1]	Moll H E,Dolbecq A,Mbomekalle I M,et al. Tuning the Photochromic Properties of Molybdenum Bisphosphonate Polyoxometalates[J]. Inorg Chem,2012,51(4):2291-2302.
[2]	WANG Miao.Synthesis and Properties of Polyoxometalate-Based Photochromic Materials[D]. Beijing:Beijing University of Chemical Technology,2012(in Chinese). 王淼. 多酸基光致变色材料的合成与性能研究[D]. 北京:北京化工大学,2012.
[3]	CHEN Wei.Hierarchical Assembly and Performance Research of Polyoxometalates FuncyIional Matericals Induced by Covalent Modification[D]. Beijing:Beijing University of Chemical Technology,2014(in Chinese). 陈伟. 共价诱导的多酸分子有序组装及性能研究[D]. 北京:北京化工大学,2014.
[4]	XU Lin,WANG Enbo.Assembly Syntheses of New Functional Molecule-Based Materials Using Polyoxometalates as Building Blocks[J]. Chinese J Inorg Chem,2000,16(2):218-228(in Chinese). 许林,王恩波. 多金属氧酸盐作为构筑块自组装合成新型功能性分子材料[J]. 无机化学学报,2000,16(2):218-228.
[5]	Fatemeh F,Bamoharram,Ali Ahmadpour,Majid M Heravi,et al. Recent Advances in Application of Polyoxometalates for the Synthesis of Nanoparticles[J]. Synth React Inorg Met-Org Nano-Met Chem,2012,42(2):209-230.
[6]	KONG Yumei,PENG Jun,XUE Bo,et al. Preparation and Antibacterial Activity of Amino Acid Polyoxometalate Self-Assembled Multilayer Films[J]. Chem J Chinese Univ,2006,27(5):801-804(in Chinese). 孔育梅,彭军,薛博,等. 氨基酸多金属氧酸盐纳米粒子复合膜的制备及抗菌活性[J]. 高等学校化学学报,2006,27(5):801-804.
[7]	Yin P,Li D,Liu T B.Solution Behaviors and Self-assembly of Polyoxometalates as Models of Macroions and Amphiphilic Polyoxometalate-Organic Hybrids as Novel Surfactants[J]. Chem Soc Rev,2012,41(22):7368-7383.
[8]	Müller A,Beckmann E,B gge H,et al. Inorganic Chemistry Goes Protein Size:A Mo368 Nano-Hedgehog Initiating Nanochemistry by Symmetry Breaking[J]. Angew Chem Int Ed,2002,41(7):1162-1167.
[9]	Cronin L,Beugholt C,Krickemeyer E,et al. “Molecular Symmetry Breakers” Generating Metal-Oxide-Based Nanoobject Fragments as Synthons for Complex Structures:[[Mo(128)Eu(4)O(388)H(10)(H(2)O)(81)](2)](20-), A Giant-Cluster Dimer[J]. Angew Chem,2002,41(15):2805-2808.
[10]	Krebs B,Paulat-B schen I. The Structure of the Potassium Isopolymolybdate K8[Mo36O12(H2O)16]·nH2O(n=36.40)[J]. Acta Cryst,2001,38(38):1710-1718.
[11]	Tytko K H,Sch nfeld D C B,Buss B,et al. A Macroisopolyanion of Molybdenum:Mo360[J]. Angew Chem Int Ed,1973,12(4):330-332.
[12]	Müller A,Shah S Q N,Bögge H,et al. Molecular Growth From a Mo176 to a Mo248 Cluster[J]. Nature,1999,397(6714):48-50.
[13]	Stracke J J,Finke R G.Water Oxidation Catalysis Beginning with Co4(H2O)2$(PW_{9}O_{34})^{10-}_{2}$ When Driven by the Chemical Oxidant Ruthenium(III)tris(2,2'-bipyridine):Stoichiometry, Kinetic, and Mechanistic Studies en Route to Identifying the True Catalyst[J]. ACS Catal,2013,4(1):79-89.
[14]	Yu L,Ding Y,Zheng M.Polyoxometalate-Based Manganese Clusters as Catalysts for Efficient Photocatalytic and Electrochemical Water Oxidation[J]. Appl Catal B,2017,(209):45-52.
[15]	Hill C L,Gueletii I V,Song J,et al. Photocatalytic Polyoxometalate Compositions of Tungstovanadates and Uses as Water Oxidation Catalysts:US,14/387745[P]. 2017.
[16]	Wang J M,Yan L,Li G X,et al. Mono-Substituted Keggin-Polyoxometalate Complexes as Effective and Recyclable Catalyst for the Oxidation of Alcohols with Hydrogen Peroxide in Biphasic System[J]. Tetrahedron Lett,2005,46(41):7023-7027.
[17]	Zhang H,Zhang X,Ding Y,et al. Hydroxylation of Phenol Catalyzed by Copper Keggin-Type Heteropoly Compounds with Hydrogen Peroxide[J]. New J Chem,2002,26(4):376-377.
[18]	Jing L,Shi J,Zhang F M,et al. Polyoxometalate-Based Amphiphilic Catalysts for Selective Oxidation of Benzyl Alcohol with Hydrogen Peroxide under Organic Solvent-Free Conditions[J]. Ind Eng Chem Res,2013,52(30):10095-10104.
[19]	Sun Z X,Fang S N,Li F Y,et al. Enhanced Photovoltaic Performance of Copper Phthalocyanine by Incorporation of Polyoxometalate[J]. J Photochem Photobiol A,2013,252(48):25-30.
[20]	Wang T Q,Sun Z X,Li F Y,et al. Nanostructured Polyoxometalate-Modified SnO2, Photoanode with Improved Photoelectrochemical Performance[J]. Electrochem Commun,2014,47(10):45-48.
[21]	Carriazo D,Addamo M,Marcì G,et al. Tungstophosphoric Acid Supported on Polycrystalline TiO2, for the Photodegradation of 4-Nitrophenol in Aqueous Solution and Propan-2-ol in Vapour Phase[J]. Appl Catal A,2009,356(2):172-179.
[22]	Yanagida S,Nakajima A,Sasaki T,et al. Preparation and Photocatalytic Activity of Keggin-Ion Tungstate and TiO2, Hybrid Layer-by-Layer Film Composites[J]. Appl Catal A,2009,366(1):148-153.
[23]	WEI Jun,LI Zhikui.Synthesis and Photocatalysis Properties of POM/TiO2 Composite Catalyst[J]. J Macromol Sci,2012,28(1):84-88(in Chinese). 魏君,李志奎. 多酸/二氧化钛复合光催化剂的制备及光催化苯胺的研究[J]. 分子科学学报,2012,28(1):84-88.
[24]	Yin Q,Tan J M,Besson C,et al. A Fast Soluble Carbon-Free Molecular Water Oxidation Catalyst Based on Abundant Metals[J]. Science,2010,328(5976):342-345.
[25]	Song F,Ding Y,Ma B,et al. K7[CoⅢCoⅡ(H2O)W11O39]:A Molecular Mixed-Valence Keggin Polyoxometalate Catalyst of High Stability and Efficiency for Visible Light-Driven Water Oxidation[J]. Energy Environ Sci,2013,6(4):1170-1184.
[26]	SONG Fangyuan,DING Yong,ZHAO Chongchao.Progress in Polyoxometalates-Catalyzed Water Oxidation[J]. Acta Chim Sin,2014,72(2):133-144(in Chinese). 宋芳源,丁勇,赵崇超. 多金属氧酸盐催化的水氧化研究进展[J]. 化学学报,2014,72(2):133-144.
[27]	Ogata A,Yanagie H,Ishikawa E,et al. Antitumour Effect of Polyoxomolybdates: Induction of Apoptotic Cell Death and Autophagy in Vitro and in Vivo Models[J]. Br J Cancer,2007,98(2):399-409.
[28]	Yanagie H,Ogata A,Mitsui S,et al. Anticancer Activity of Polyoxomolybdate[J]. Biomed Pharmacother,2006,60(7):349.
[29]	Prudent R,Moucadel V,Laudet B,et al. Identification of Polyoxometalates as Nanomolar Noncompetitive Inhibitors of Protein Kinase CK2[J]. Chem Biol,2008,15(7):683-692.
[30]	Matteis L D,Mitchell S G,Fuente J M D L. Supramolecular Antimicrobial Capsules Assembled from Polyoxometalates and Chitosan[J]. J Mater Chem B,2014,2(41):7114-7117.
[31]	Nomiya K,Torii H,Hasegawa T,et al. Insulin Mimetic Effect of a Ttungstate Cluster. Effect of Oral Administration of Homo-Polyoxotungstates and Vanadium-Substituted Polyoxotung-States on Blood Glucose Level of STZ Mice[J]. J Inorg Biochem,2001,86(4):657-667.
[32]	Boden G,Chen X,Ruiz J,et al. Turco:Effects of Vanadyl Sulfate on Carbohydrate and Lipid Metabolism in Patients with Non-Insulin-Dependent Diabetes Mellitus[J]. Metabolism,1996,45(9):1130-1135.
[33]	Liu S,Kurth D G,Volkmer D.Polyoxometalates as pH-Sensitive Probes in Self-Assembled Multilayers[J]. Chem Commun,2002,9(9):976.
[34]	Long D L,Burkholder E,Cronin L. Polyoxometalate Clusters, Nanostructures and Materials:From Self Assembly to Designer Materials and Devices[J]. Chem Soc Rev,2007,38(15):105-121.
[35]	Zhang T,Liu S,Kurth D G,et al. Organized Nanostructured Complexes of Polyoxometalates and Surfactants that Exhibit Photoluminescence and Electrochromism[J]. Adv Funct Mater,2010,19(4):642-652.
[36]	Poulos A S,Constantin D,Davidson P,et al. Photochromic Hybrid Organic-Inorganic Liquid-Crystalline Materials Built from Nonionic Surfactants and Polyoxometalates:Elaboration and Structural Study[J]. Langmuir,2008,24(12):6285-6291.
[37]	Dolbecq A,Dumas E,Mayer C R,et al. Hybrid Organic-Inorganic Polyoxometalate Compounds:From Structural Diversity to Applications[J]. Chem Rev,2010,41(52):6009-6048.
[38]	Lehn J M. Supramolecular Chemistry:From Molecular Information Toward Self-Organization and Complex Matter[J]. Rep Prog Phys,2004,67(3):249-265(17).
[39]	JIA Xiangfeng,FAN Dawei,TANG Peiqin,et al. “Second Organized Structures” of Nanoscale Inorganic Polyoxomolybdate Compounds[J]. Acta Phys-Chim Sin,2006,22(10):1300-1304(in Chinese). 贾祥凤,范大伟,唐培芹,等. 纳米级无机聚钼酸盐“二级有序聚集体”[J]. 物理化学学报,2006,22(10):1300-1304.
[40]	Scheele C W,Hermstädt S F. Carl Wilhelm Scheele.Sämmtliche Physische und Chemische Werke[M]. Mayer and Müller,1793.
[41]	Berzelius J J. Beitrag zur näheren Kenntniss des Molybdäns[J]. Ann Phys-Berlin,1826,82(4):369-392.
[42]	Zhang J,Song Y F,Cronin L,et al. Reverse-Vesicle Formation of Organic-Inorganic Polyoxometalate-Containing Hybrid Surfactants with Tunable Sizes[J]. Chemistry,2010,16(37):11320-11324.
[43]	Zhang J,Song Y F,Cronin L,et al. Self-Assembly of Organic-Inorganic Hybrid Amphiphilic Surfactants with Large Polyoxometalates as Polar Head Groups[J]. J Am Chem Soc,2008,130(130):14408-14409.
[44]	Pradeep C P,Misdrahi M F,Li F Y,et al. Synthesis of Modular-Inorganic-Organic-Onorganic Polyoxometalates and Their Assembly into Vesicles[J]. Angew Chem Int Ed,2009,48:8309-8313.
[45]	Liu T B.Hydrophilic Macroionic Solutions:What Happens When Soluble Ions Reach the Size of Nanometer Scale?[J]. Langmuir,2009,26(12):9202-9213.
[46]	Liu T B,Diemann E,Li H,et al. Self-Assembly in Aqueous Solution of Wheel-Shaped Mo154 Oxide Clusters into Vesicles[J]. Nature,2003,426(6962):59-62.
[47]	Müller A,Das S K,Fedin V P,et al. Rapid and Simple Isolation of the Crystalline Molybdenum-Blue Compounds with Discrete and Linked Nanosized Ring-Shaped Anions:Na15$[Mo^{Ⅵ}_{126} Mo^{Ⅴ}_{28} O_{462} H_{14} (H_{2}O)_{70}] _{0.5} [Mo^{Ⅵ}_{124} Mo^{Ⅴ}_{28} O_{457} H_{14}(H_{2}O)_{68}] _{0.5} · $ ca.400H2O and Na22$[Mo^{Ⅵ}_{118} Mo^{Ⅴ}_{28} O_{442} H_{14} (H_{2}O)_{58}]$ ca.250H2O[J]. Z Anorg Allg Chem,1999,625(7):1187-1192.
[48]	Sogami I,Ise N.On the Electrostatic Interaction in Macroionic Solutions[J]. J Chem Phys,1984,81(12):6320-6332.
[49]	Kepler G M,Fraden S.Attractive Potential Between Confined Colloids at Low Ionic Strength[J]. Phys Rev Lett,1994,73(2):356.
[50]	Crocker J C,Grier D G.When Like Charges Attract:The Effects of Geometrical Confinement on Long-Range Colloidal Interactions[J]. Phys Rev Lett,1996,77(9):1897-1900.
[51]	Ito K,Nakamura H,Yoshida H,et al. On the Dynamic Character of “Ordered” Structure in Polymer Latex Suspensions[J]. J Am Chem Soc,2002,110(21):6955-6963.
[52]	Chen B L,Jiang H J,Zhu Y,et al. Monitoring the Growth of Polyoxomolybdate Nanoparticles in Suspension by Flow Field-Flow Fractionation[J]. J Am Chem Soc,2005,127(12):4166-4167.
[53]	Zhu Y,Cammersgoodwin A,Zhao B,et al. Kinetic Precipitation of Solution-Phase Polyoxomolybdate Followed by Transmission Electron microscopy:A Window to Solution-Phase Nanostructure[J]. Chemistry,2004,10(10):2421-2427.
[54]	M L K,Anish Bhatt,Liu G,et al. A Complete Macroion- “Blackberry” Assembly-Macroion Transition with Continuously Adjustable Assembly Sizes in {Mo132} Water/Acetone Systems[J]. J Am Chem Soc,2007,129(20):6453-6460.
[55]	Liu T B.An Unusually Slow Self-Asembly of Inorganic Ions in Dilute Aqueous Solution[J]. J Am Chem Soc,2003,125(2):312-313.
[56]	Liu G,Liu T B.Strong Attraction Among the Fully Hydrophilic {Mo72Fe30} Macroanions[J]. J Am Chem Soc,2005,127(19):6942-6943.
[57]	Liu G,Liu T B.Thermodynamic Properties of the Unique Self-Assembly of {Mo72Fe30} Inorganic Macro-Ions in Salt-Free and Salt-Containing Aqueous Solutions[J]. Langmuir,2005,21(7):2713-2720.
[58]	Pigga J M,Kistler M L,Shew C Y,et al. Counterion Distribution Aaround Hydrophilic Mmolecular Macroanions:The Source of the Attractive Force in Self-Assembly[J]. Angew Chem Int Ed,2009,48(35):6538-6542.
[59]	Kistler M L,Liu T B,Gouzerh P,et al. Molybdenum-Oxide Based Unique Polyprotic Nanoacids Showing Different Deprotonations and Related Assembly Processes in Solution[J]. Dalton T,2009,26(26):5094-5100.
[60]	Liu G,Liu T B,Mal S S,et al. Wheel-Shaped Polyoxotungstate [Cu20Cl(OH)24(H2O)12(P8W48O184)]25- Macroanions Form Supramolecular “Blackberry” Structure in Aqueous Solution[J]. J Am Chem Soc,2006,128(31):10103-10110.
[61]	Mishra P P,Jing J,Francesconi L C,et al. Self-Assembly of Yttrium-Containing Lacunary Polyoxotungstate Macroanions in Solution with Controllable Supramolecular Structure Size by pH or Solvent Content[J]. Langmuir,2008,24(17):9308-9313.
[62]	Li H L,Qi W,Li W,et al. A Highly Transparent and Luminescent Hybrid Based on the Copolymerization of Surfactant-Encapsulated Polyoxometalate and Methyl Methacrylate[J]. Adv Mater,2010,17(22):2688-2692.
[63]	Sun H,Li H L,Bu W F,et al. Self-Organized Microporous Structures Based on Surfactant-Encapsulated Polyoxometalate Complexes[J]. J Phys Chem B,2006,110(49):24847-24854.
[64]	Zhang J,Song Y F,Cronin L,et al. Self-Assembly of Organic-Inorganic Hybrid Amphiphilic Surfactants with Large Polyoxometalates as Polar Head Groups[J]. J Am Chem Soc,2008,130(44):14408-14409.
[65]	Yan Y,Li B,Li W,et al. Controllable Vesicular Structure and Reversal of a Surfactant-Encapsulated Polyoxometalate Complex[J]. Soft Matter,2009,5(20):4047-4053.
[66]	Li H L,Yang Y,Wang Y Z,et al. Self-Assembly and Ion-Trapping Properties of Inorganic Nanocapsule-Surfactant Hybrid Spheres[J]. Soft Matter,2011,7(6):2668-2673.
[67]	Li D,Song J,Yin P C,et al. Inorganic-Organic Hybrid Vesicles with Counterion- and pH-Controlled Fluorescent Properties[J]. J Am Chem Soc,2011,133(35):14010-14016.
[68]	Kistler M L,Patel K G,Liu T B.Accurately Tuning the Charge on Giant Polyoxometalate Type Keplerates Through Stoichiometric Interaction with Cationic Surfactants[J]. Langmuir,2009,25(13):7328-7334.
[69]	Liu T B.Surfactant-Induced Trans-Interface Transportation and Complex Formation of Giant Polyoxomolybdate-Based Clusters[J]. J Clust Sci,2003,14(3):215-226.
[70]	Akutagawa T,Jin R,Tunashima R,et al. Nanoscale Assemblies of Gigantic Molecular {Mo154-rings}:(dimethyldioctadecylammonium)20[Mo154O462H8(H2O)70][J]. Langmuir,2008,24(1):231-238.
[71]	Parratt L G.Surface Studies of Solids by Total Reflection of X-Rays[J]. Phys Rev,1954,95(2):359-369.
[72]	Pradeep C P,Misdrahi M F,Li F Y,et al. Synthesis of Modular “Inorganic-Organic-Inorganic” Polyoxometalates and Their Assembly into Vesicles[J]. Angew Chem Int Ed,2009,48(44):8309-8313.
[73]	Zhu Y,Yin P C,Xiao F P,et al. Bottom-Up Construction of POM-Based Macrostructures:Coordination Assembled Paddle-Wheel Macroclusters and their Vesicle-Like Supramolecular Aggregation in Solution[J]. J Am Chem Soc,2013,135(45):17155-17160.
[74]	Noguchi T,Chikara C,Kuroiwa K,et al. Controlled Morphology and Photoreduction Characteristics of Polyoxometalate(POM)/Lipid Complexes and the Effect of Hydrogen Bonding at Mmolecular Interfaces[J]. Chem Commun,2011,47(22):6455.
[75]	Nisar A,Zhuang J,Wang X.Cluster-Based Self-Assembly:Reversible Formation of Polyoxometalate Nanocones and Nanotubes[J]. Chem Mater,2009,21(16):4746.
[76]	Nisar A,Lu Y,Wang X.Assembling Polyoxometalate Clusters into Advanced Nanoarchitectures[J]. Chem Mater,2010,22(11):3511-3518.
[77]	Bu W F,Li H L,Sun H,et al. Polyoxometalate-Based Vesicle and Its Honeycomb Architectures on Solid Surfaces[J]. J Am Chem Soc,2005,127(22):8016-8017.
[78]	Zhang T,Brown J,Oakley R J,et al. Towards Functional Nanostructures:Ionic Self-Assembly of Polyoxometalates and Surfactants[J]. Curr Opin Colloid Interface Sci,2009,14(2):62-70.
[79]	Jia X F,Fan D W,Tang P Q,et al. Hybrid Inorganic/Organic Quasi-Single Crystals of Wheel-Shaped {Mo154} Macro-Anions and Cationic-Surfactants[J]. J Clust Sci,2006,17(3):467-478.
[80]	Haso F,Wang R,Yin P,et al. Supramolecular Assemblies of Polyoxometalate-Tethered Diblock Copolymers with Tunable Sizes in N-Methyl-2-pyrrolidone/Toluene Mixed Solvents[J]. Eur J Inorg Chem,2015,2014(27):4589-4592.
[81]	Haso F,Wang R,He J,et al. Solution Behaviour of a Polymer with Polyoxometalate Inorganic Molecular Clusters on Its Main Chain[J]. New J Chem,2016,40(2):910-913.
[82]	Zhang B,Pradeep C P,Cronin L,et al. Self-Assembly of Triangular Polyoxometalate-Organic Hybrid Macroions in Mixed Solvents[J]. Chem Commun,2015,51(41):8630-8633.
[83]	Tan C X. Self-Assembly, Aggregates Morphology and Ionic Liquid Crystal of Polyoxometalate-Based Hybrid Molecule: From Vesicles to Layered Structure[J]. J Mol Struct,2017:34-39.