A new organic-inorganic hybrid consisting of Keggin-type polyoxometalate ([BW12O40]5−) and protonated piperazine, namely [H5O2]2[Hpip]2.5[BW12O40]·4H2O (pip = piperazine, C4H10N2) (1), has been created under reflux state and identified through material identification devices like single-crystal crystallography, FT-IR and 1H-NMR spectroscopies, Powder XRD, TG-DT Analysis, Field Emission SEM, elemental-analysis and cyclic voltammetry. Crystallography investigation exhibits that the main factor in the formation of 1 is the numerous number of hydrogen bonding between organic and inorganic species. The arrangement of Hpip groups creates holes in which the [BW12O40]5− clusters fit into the holes. Furthermore, the electrochemical and photochemical attributes of 1 have been considered, and the outcomes present that 1 owns privileged electrocatalytic activity against the reduction of nitrite ions as well as an appropriate photochemical effect on methylene blue (MB) dye depredation.
A new organic-inorganic hybrid consisting of Keggin-type polyoxometalate ([BW12O40]5-) and protonated piperazine, namely [H5O2]2[Hpip]2.5[BW12O40]·4H2O (pip = piperazine, C4H10N2) (1), has been created under reflux state. The electrochemical and photochemical attributes of 1 have been considered, and the outcomes present that 1 owns privileged electrocatalytic activity against the reduction of nitrite ions as well as an appropriate photochemical effect on methylene blue (MB) dye depredation.
This is a preview of subscription content, log in to check access.
Buy single article
Instant access to the full article PDF.
Price includes VAT for USA
Subscribe to journal
Immediate online access to all issues from 2019. Subscription will auto renew annually.
This is the net price. Taxes to be calculated in checkout.
Han Z, Gao Y, Zhai X, Peng J, Tian A, Zhao Y and Hu C 2008 Self-process-programmed structural diversity in supramolecular assembly based on polyoxometalate anion and halogen-substituted bipyridine cation Cryst. Growth Des. 9 1225
Dolbecq A, Dumas E, Mayer C R and Mialane P 2010 Hybrid organic-inorganic polyoxometalate compounds: from structural diversity to applications Chem. Rev. 110 6009
Misra A, Kozma K, Streb C and Nyman M 2019 Beyond charge balance: counter-cations in polyoxometalate chemistry Angew. Chem. Int. Edit. 59 596
Shakeela K, Silpa G, Rayala S K and Rao G R 2018 Polyoxometalate entrapped caprolactam gels and their cytotoxicity study J. Chem. Sci. 130 107
Amanchi S R, Patel A and Das S K 2014 Polyoxometalate coordinated transition metal complexes as catalysts: Oxidation of styrene to benzaldehyde/benzoic acid J. Chem. Sci. 126 1641
Zonoz F M 2016 Electrochemistry investigation of the monolacunary and their transition metal substituent Keggin-type polyoxometalates Electrocatalysis 7 215
Liu W-J, Dong L-Z, Li R-H, Chen Y-J, Sun S-N, Li S-L and Lan Y-Q 2019 Different protonic species affecting proton conductivity in hollow spherelike polyoxometalates ACS Appl. Mater. Interf. 11 7030
Liu L, Wang B, Lv J H, Yu K, Wang L, Zhang H, Wang S and Zhou B B 2017 One-step synthesis of two Wells–Dawson arsenotungstate hybrids via M–O–M bridges for efficient adsorption and selective separation of organic pollutants CrystEngComm 19 5653
Varghese C, Shunmugasundaram A, Murugesan R and Abalan T J 2002 EPR investigations of electron transfer in one-electron reduced α-1,4K5[PV2W10O40].3H2O J. Chem. Sci. 114 75
Kaczmarek A M 2018 Eu3+/Tb3+ and Dy3+ POM@ MOFs and 2D coordination polymers based on pyridine-2, 6-dicarboxylic acid for ratiometric optical temperature sensing J. Mater. Chem. C 6 5916
Gupta R, Hussain F, Sadakane M, Kato C, Inoue K and Nishihara S 2016 Lanthanoid template isolation of the α-1, 5 Isomer of Dicobalt (II)-substituted Keggin type phosphotungstates: syntheses, characterization, and magnetic properties Inorg. Chem. 55 8292
Gonçalves C E, Laier L O, Cardoso A L and da Silva M J 2012 Bioadditive synthesis from H3PW12O40-catalyzed glycerol esterification with HOAc under mild reaction conditions Fuel Proc. Technol. 102 46
Hou Y, Niu Y, Zhang C, Pang H and Ma H 2017 Two hybrids based on Keggin polyoxometalates and dinuclear copper (II) complexes: syntheses, structures and electrocatalytic properties J. Chem. Sci. 129 1639
Taghavi M, Ehrampoush M H, Ghaneian M T, Tabatabaee M and Fakhri Y 2018 Application of a Keggin-type heteropoly acid on supporting nanoparticles in photocatalytic degradation of organic pollutants in aqueous solutions J. Clean. Prod. 197 1447
Singhal S, Agarwal S and Kumar A 2019 Isomerization of lighter alkanes by heteropoly acids: a review J. Catal. Catal. 2 1
Tan Y-X, Wang F and Zhang J 2018 Design and synthesis of multifunctional metal–organic zeolites Chem. Soc. Rev. 47 2130
Ribeiro S, Duarte B, de Castro B, Granadeiro C and Balula S 2018 Improving the catalytic performance of Keggin [PW12O40]3− for oxidative desulfurization: ionic liquids versus SBA-15 composite Materials 11 1196
Gopinath S, Kumar P V, Kumar P S M, Arafath K Y, Sivanesan S and Baskaralingam P 2018 Cs-tungstosilicic acid/Zr-KIT-6 for esterification of oleic acid and transesterification of non-edible oils for green diesel production Fuel 234 824
Nuryono N, Qomariyah A, Kim W, Otomo R, Rusdiarso B and Kamiya Y 2018 Octyl and propylsulfonic acid co-fixed Fe3O4@SiO2 as a magnetically separable, highly active and reusable solid acid catalyst in water Mol. Catal. 475 110248
Jovanović S, Holclajtner-Antunović I, Uskoković-Marković S, Bajuk-Bogdanović D, Pavlović V, Tošić D, Milenković M and Marković B T 2018 Modification of graphene oxide surfaces with 12-molybdophosphoric acid: Structural and antibacterial study Mater. Chem. Phys. 213 157
Ross N, Nqakala N, Willenberg S, Sifuba S and Iwuoha E 2019 Electrochemical properties of polyoxometalate (H3PMo12O40)-functionalized graphitic carbon nitride (g-C3N4). Electrocatalysis 2019 1
Zonoz F M, Jamshidi A and Tavakoli S 2013 Preparation, characterization and electrochemical investigation of a new inorganic–organic hybrid material based on Keggin-type polyoxometalate and organic imidazole cation Solid State Sci. 17 83
Yin P, Bayaguud A, Cheng P, Haso F, Hu L, Wang J, Vezenov D, Winans R E and Hao J and Li T 2014 Spontaneous stepwise self-assembly of a polyoxometalate–organic hybrid into catalytically active one-dimensional anisotropic structures Chem.-A Eur. J. 20 9589
Bayaguud A, Li J, She S and Wei Y 2017 A simple synthetic route to polyoxovanadate-based organic–inorganic hybrids using EEDQ as an ester coupling agent Dalton Trans. 46 4602
Roy S, Sarkar S, Pan J, Waghmare U V, Dhanya R, Narayana C and Peter S C 2016 Crystal structure and band gap engineering in polyoxometalate-based inorganic–organic hybrids Inorg. Chem. 55 3364
Lan Y-Q, Li S-L, Shao K-Z, Wang X-L and Su Z-M 2008 Construction of different dimensional inorganic–organic hybrid materials based on polyoxometalates and metal–organic units via changing metal ions: from non-covalent interactions to covalent connections Dalton Trans. 3824
Han Z-b, Wang X-l, Wang L, Wang E-b, Luan G-y, Hu N-h and Jia H-q 2003 Synthesis, electrocatalytic properties and crystal structure of a new organic-inorganic hybrid constructed from dodecamolybdophosphoric acid and benzotriazole Chem. Res. Chin. Univ. 19 127
Cai H, Lü J, Yu K, Zhang H, Wang C, Wang L and Zhou B 2015 Organic–inorganic hybrid supramolecular assembly through the highest connectivity of a Wells–Dawson molybdoarsenate Inorg. Chem. Commun. 62 24
Teng C, Xiao H, Cai Q, Tang J, Cai T and Deng Q 2016 Two supramolecular complexes based on polyoxometalates and Co-EDTA units via covalent connection or non-covalent interaction J. Solid State Chem. 243 146
Zhou E-L, Qin C, Wang X-L, Shao K-Z and Su Z-M 2016 Assembly of two novel 3D organic–inorganic hybrids based on Keggin-type polyoxometalates: syntheses, crystal structures and properties CrystEngComm 18 6370
Wang Q-Q, Wang D-X, Wu Y-L, Zhang Q-P and Xiong H-Y 2018 Synthesis and properties of a new organic-inorganic hybrid compound based on α-Keggin polyoxometalate:[Cu(Dione)2(H2O)]2(SiW2O) J. Chem. Soc. Pak. 40 123
Xu L-J, Zhou W-Z, Zhang L-Y, Li B, Zang H-Y, Wang Y-H and Li Y-G 2015 Organic–inorganic hybrid assemblies based on Ti-substituted polyoxometalates for photocatalytic dye degradation CrystEngComm 17 3708
Zhao H-Y, Yang B-F and Yang G-Y 2017 Two new 2D organic–inorganic hybrids assembled by lanthanide-substituted polyoxotungstate dimers and copper–complex linkers Inorg. Chem. Commun. 84 212
Jamshidi A, Zonoz F M, Wei Y and Maleki B 2018 An organic-inorganic nano-hybrid material containing a mixed-addenda Keggin-type polyoxometalate, piperazine: Synthesis, characterization, its electrochemical investigation Inorg. Chim. Acta 477 233
Jiao Y-Q, Qin C, Zang H-Y, Chen W-C, Wang C-G, Zheng T-T, Shao K-Z and Su Z-M 2015 Assembly of organic–inorganic hybrid materials constructed from polyoxometalate and metal–1, 2, 4-triazole units: synthesis, structures, magnetic, electrochemical and photocatalytic properties CrystEngComm 17 2176
Wood E 1987 Data for biochemical research by RMC Dawson, DC Elliott, WH Elliott and KM Jones, pp 580. Oxford Science Publications, OUP, Oxford, 1986.£ 35/$59. ISBN 0-19-855358-7 Biochem. Edu. 15 97
Mao R, Zhan F, Bu N, Cao Y, Hu P, Gong G and Zhen Q 2016 Room-temperature mechanochemical preparation and electrochemistry properties of polyoxometalate-based inorganic-organic hybrid Mater. Lett. 173 111
Zak A K, Majid W A, Abrishami M E and Yousefi R 2011 X-ray analysis of ZnO nanoparticles by Williamson–Hall and size–strain plot methods Solid State Sci. 13 251
Javadi F and Tayebee R 2016 Preparation and characterization of ZnO/nanoclinoptilolite as a new nanocomposite and studying its catalytic performance in the synthesis of 2-aminothiophenes via Gewald reaction Micropor. Mesopor. Mater. 231 100
Sanchez C, Livage J, Launay J and Fournier M 1983 Electron delocalization in mixed-valence tungsten polyanions J. Am. Chem. Soc. 105 6817
Téazéa A, Hervéa G, Finke R G and Lyon D K 2007 α-, β-, and γ-dodecatungstosilicic acids: isomers and related lacunary compounds Inorg. Synth. 27 85
Wang Q, Khungwa J, Li L, Liu Y, Wang X and Wang S 2018 Fabrication of polyoxometalate/GO/PDDA hybrid nanocomposite modified electrode and electrocatalysis for nitrite ion, ascorbic acid and dopamine J. Electroanal. Chem. 824 91
Li X, Wang Y, Zhou K, Wang Y, Han T and Sha J 2018 Isomeric organic ligand dominating polyoxometalate-based hybrid compounds: synthesis and as electrocatalysts and pH-sensitive probes J. Coord. Chem. 71 468
Chen S, Xiang Y, Banks M K, Xu W, Peng C and Wu R 2019 Polyoxometalate-coupled graphene nanohybrid via gemini surfactants and its electrocatalytic property for nitrite Appl. Surf. Sci. 466 110
Jamshidi A and Zonoz F M 2017 Synthesis, characterization, electrochemical behavior and electrocatalytical properties towards nitrate and iodate by alcohol solvated Keggin-type polyoxometalate: The effects of weak intermolecular interactions and solvent on electrocatalytical activity J. Mol. Liq. 242 993
Ghanbari F and Moradi M 2017 Application of peroxymonosulfate and its activation methods for degradation of environmental organic pollutants Chem. Eng. J. 310 41
Tong L, Wang Z, Xia C, Yang Y, Yuan S, Sun D and Xin X 2017 Self-assembly of peptide-polyoxometalate hybrid sub-micrometer spheres for photocatalytic degradation of Methylene Blue J. Phys. Chem. B 121 10566
The author thanks the Research Council of Hakim Sabzevari University and Tsinghua University for partial support of this work.
Electronic supplementary material
Below is the link to the electronic supplementary material.
About this article
Cite this article
JAMSHIDI, A., MOHAMMADI ZONOZ, F. & WEI, Y. A new Keggin-based organic-inorganic nanohybrid in the role of a dual-purpose catalyst. J Chem Sci 132, 37 (2020). https://doi.org/10.1007/s12039-020-1739-x