Abstract
We used cyclic voltammetry (CV) to study the electrochemical redox properties of a series of solid-state polyoxometalate composite hybrid materials supported on indium tin oxide-coated glass. The hybrid materials are composed of the organofunctionalized polyoxocationic species, \([{\text{NaV}}^{\text{IV}}_{6} {\text{O}}_{ 6}\){(OCH2CH2)2N(CH2CH2OH)}6]+, in combination with the Keggin-structure polyoxoanions (PW12O40)3−, (SiW12O40)4−, or (SiMo12O40)4−. CV results show that the hybrid materials are electrochemically active, with redox events attributable to their electrochemically active molecular constituents. Strong chemical–environmental effects are also observed.
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References
Ammam M (2013) Polyoxometalates: formation, structures, principal properties, main deposition methods and application in sensing. J Mater Chem A 1:6291–6312. https://doi.org/10.1039/C3TA01663C
Baker LCW, Glick DC (1998) Present general status of understanding of heteropoly electrolytes and a tracing of some major highlights in the history of their elucidation. Chem Rev 98:3–50. https://doi.org/10.1021/cr960392l
Blazevic A, Rompel A (2016) The Anderson–Evans polyoxometalate: from inorganic building blocks via hybrid organic–inorganic structures to tomorrows “Bio-POM”. Coord Chem Rev 307:42–64. https://doi.org/10.1016/j.ccr.2015.07.001
Clemente-Juan JM, Coronado E, Gaita-Arino A (2012) Magnetic polyoxometalates: from molecular magnetism to molecular spintronics and quantum computing. Chem Soc Rev 41:7464–7478. https://doi.org/10.1039/C2CS35205B
Dubal DP, Chodankar NR, Kim DH, Gomez-Romero P (2018) Towards flexible solid-state supercapacitors for smart and wearable electronics. Chem Soc Rev 47:2065–2129. https://doi.org/10.1039/c7cs00505a
Fernandes DM, Freire C (2015) Carbon nanomaterial–phosphomolybdate composites for oxidative electrocatalysis. ChemElectroChem 2:269–279. https://doi.org/10.1002/celc.201402271
Genovese M, Lian K (2015) Polyoxometalate modified inorganic–organic nanocomposite materials for energy storage applications: a review. Curr Opin Solid State Mater Sci 19:126–137. https://doi.org/10.1016/j.cossms.2014.12.002
Herrmann S, Ritchie C, Streb C (2015) Polyoxometalate-conductive polymer composites for energy conversion, energy storage and nanostructured sensors. Dalton Trans 44:7092–7104. https://doi.org/10.1039/C4DT03763D
Ji YC, Huang LJ, Hu J, Streb C, Song YF (2015) Polyoxometalate-functionalized nanocarbon materials for energy conversion, energy storage and sensor systems. Energy Environ Sci 8:776–789. https://doi.org/10.1039/C4EE03749A
Khan MI, Tabussum S, Doedens RJ (2003) A novel cationic heteropolyoxovanadium(IV) cluster functionalized with organic ligands: synthesis and characterization of the fully reduced species [MnIIVIV 6O6{(OCH2CH2)2N(CH2CH2OH)}6]Cl2. Chem Commun. https://doi.org/10.1039/b211195k
Khan MI, Tabussum S, Doedens RJ, Golub VO, O’Connor CJ (2004) Functionalized metal oxide clusters: synthesis, characterization, crystal structures, and magnetic properties of a novel series of fully reduced heteropolyoxovanadium cationic clusters decorated with organic ligands: [MVIV 6O6{(OCH2CH2)2N(CH2CH2OH)}6]X (M=Li, X=Cl·LiCl; M=Na, X=Cl·H2O; M=Mg, X=2Br·H2O; M=Mn, Fe, X=2Cl; M=Co, Ni, X=2Cl·H2O). Inorg Chem 43:5850–5859. https://doi.org/10.1021/ic049417m
Khan MI, Zheng Y, Li H, Swenson L, Basha A, Doedens RJ (2014) Organo-functionalized metal-oxide clusters: synthesis and characterization of the reduced cationic species [NaVIV 6O6{(OCH2CH2)2NH}6]+. Dalton Trans 43:16509–16514. https://doi.org/10.1039/C4DT02174F
Kozhevnikov IV (2002) Catalysis by polyoxometalates, catalysts for fine chemical synthesis 2. Wiley, West Sussex
Kozhevnikov IV, Matveev KI (1982) Heteropolyacids in catalysis. Russ Chem Rev 51:1075–1088. https://doi.org/10.1070/RC1982v051n11ABEH002941
Launay JP, Massart R, Souchay P (1974) Gradual reduction of molybdosilicates and related compounds. J Less Common Met 36:139–150. https://doi.org/10.1016/0022-5088(74)90093-9
Li QY, Zhang L, Dai JL, Tang H, Li Q, Xue HG, Pang H (2018) Polyoxometalate-based materials for advanced electrochemical energy conversion and storage. Chem Eng J 351:441–461. https://doi.org/10.1016/j.cej.2018.06.074
Ma YQ, Liu XP, Li JP, Wang R, Yu MQ (2017) Transition metal salts of H4PMo11VO40 for efficient H2S removal in the liquid redox process. Chem Pap 71:647–652. https://doi.org/10.1007/s11696-016-0064-9
Maeda K, Himeno S, Osakai T, Saito A, Hori T (1994) A voltammetric study of Keggin-type heteropolymolybdate anions. J Electroanal Chem 364:149–154. https://doi.org/10.1016/0022-0728(93)02936-C
Moffat JB (2001) Metal-oxygen clusters. Kluwer Academic, New York. https://doi.org/10.1021/ja015374m
Papaconstantinou E, Hisia A (2003) Photochemistry and photocatalysis by polyoxometalates. In: Borrás-Almenar JJ, Coronado E, Müller A, Pope MT (eds) Polyoxometalate molecular science, NATO science series, vol 98. Kluwer Academic Publishers, Dordrecht, pp 381–416. https://doi.org/10.1007/978-94-010-0091-8
Pope MT (1983) Heteropoly and isopoly oxometalates. Springer, West Berlin. https://doi.org/10.1002/ange.19840960939
Sadakane M, Steckhan E (1998) Electrochemical properties of polyoxometalates as electrocatalysts. Chem Rev 98:219–238. https://doi.org/10.1021/cr960403a
Smith DP, Pope MT (1973) Heteropoly 12-metallophosphates containing tungsten and vanadium. Preparation, voltammetry, and properties of mono-, di-, tetra-, and hexavanado complexes. Inorg Chem 12:331–336. https://doi.org/10.1021/ic50120a018
Swenson L, Orozco JC, Kaduk JA, Khan MI (2016) Electrostatic self-assembly of composite materials containing Keggin structure polyoxoanions and functionalized Anderson structure polyoxometallic cations. Inorganica Chim Acta 444:43–50. https://doi.org/10.1016/j.ica.2016.01.026
Tanaka N, Unoura K, Itabashi E (1982) Voltammetric and spectroelectrochemical studies of dodecamolybdophosphoric acid in aqueous and eater-dioxane solutions at a gold- minigrid optically transparent thin-layer electrode. Inorg Chem 21:1662–1666. https://doi.org/10.1021/ic00134a077
Yamase T (1998) Photo- and electrochromism of polyoxometalates and related materials. Chem Rev 98:307–326. https://doi.org/10.1021/cr9604043
Yang H, Song T, Liu L, Devadoss A, Xia F, Han H, Park H, Sigmund W, Kwon K, Paik U (2013) Polyaniline/polyoxometalate hybrid nanofibers as cathode for lithium ion batteries with improved lithium storage capacity. J Phys Chem C 117:17376–17381. https://doi.org/10.1021/jp401989j
Zhang GF, Wang R, Yu FL, Zhao HX (2009) Clean fuel-oriented investigation of thiophene oxidation by hydrogen peroxide using polyoxometalate as catalyst. Chem Pap 63:617–619. https://doi.org/10.2478/s11696-009-0063
Zheng S-T, Yang G-Y (2012) Recent advances in paramagnetic-TM-substituted polyoxometalates (TM=Mn, Fe Co, Ni, Cu). Chem Soc Rev 41:7623–7646. https://doi.org/10.1039/C2CS35133A
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Swenson, L., Khan, M.I. Electrochemical properties of polyoxometalate composite materials containing multiple redox centers. Chem. Pap. 73, 2611–2617 (2019). https://doi.org/10.1007/s11696-019-00815-9
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DOI: https://doi.org/10.1007/s11696-019-00815-9