A new Keggin-based organic-inorganic nanohybrid in the role of a dual-purpose catalyst


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.

Graphic abstract

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, access via your institution.

Scheme 1
Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7


  1. 1.

    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

    Article  Google Scholar 

  2. 2.

    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

    CAS  Google Scholar 

  3. 3.

    Misra A, Kozma K, Streb C and Nyman M 2019 Beyond charge balance: counter-cations in polyoxometalate chemistry Angew. Chem. Int. Edit. 59 596

    Article  Google Scholar 

  4. 4.

    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

    Article  Google Scholar 

  5. 5.

    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

    CAS  Article  Google Scholar 

  6. 6.

    Zonoz F M 2016 Electrochemistry investigation of the monolacunary and their transition metal substituent Keggin-type polyoxometalates Electrocatalysis 7 215

    CAS  Google Scholar 

  7. 7.

    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

    CAS  Article  Google Scholar 

  8. 8.

    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

  9. 9.

    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

    CAS  Article  Google Scholar 

  10. 10.

    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

    CAS  Article  Google Scholar 

  11. 11.

    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

    CAS  Google Scholar 

  12. 12.

    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

    Article  Google Scholar 

  13. 13.

    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

    CAS  Article  Google Scholar 

  14. 14.

    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

    CAS  Article  Google Scholar 

  15. 15.

    Singhal S, Agarwal S and Kumar A 2019 Isomerization of lighter alkanes by heteropoly acids: a review J. Catal. Catal. 2 1

    Google Scholar 

  16. 16.

    Tan Y-X, Wang F and Zhang J 2018 Design and synthesis of multifunctional metal–organic zeolites Chem. Soc. Rev. 47 2130

    CAS  Article  Google Scholar 

  17. 17.

    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

    Article  Google Scholar 

  18. 18.

    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

  19. 19.

    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

    Google Scholar 

  20. 20.

    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

    Google Scholar 

  21. 21.

    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

    Google Scholar 

  22. 22.

    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

  23. 23.

    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

  24. 24.

    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

  25. 25.

    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

    CAS  Google Scholar 

  26. 26.

    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

  27. 27.

    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

    CAS  Google Scholar 

  28. 28.

    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

    CAS  Google Scholar 

  29. 29.

    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

    CAS  Article  Google Scholar 

  30. 30.

    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

  31. 31.

    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

    CAS  Google Scholar 

  32. 32.

    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

  33. 33.

    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

    CAS  Google Scholar 

  34. 34.

    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

    CAS  Google Scholar 

  35. 35.

    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

  36. 36.

    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

  37. 37.


  38. 38.


  39. 39.

    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

    CAS  Google Scholar 

  40. 40.

    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

  41. 41.

    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

    CAS  Article  Google Scholar 

  42. 42.

    Sanchez C, Livage J, Launay J and Fournier M 1983 Electron delocalization in mixed-valence tungsten polyanions J. Am. Chem. Soc. 105 6817

    CAS  Article  Google Scholar 

  43. 43.

    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

    Google Scholar 

  44. 44.

    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

    CAS  Article  Google Scholar 

  45. 45.

    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

    CAS  Article  Google Scholar 

  46. 46.

    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

    CAS  Article  Google Scholar 

  47. 47.

    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

    CAS  Article  Google Scholar 

  48. 48.

    Ghanbari F and Moradi M 2017 Application of peroxymonosulfate and its activation methods for degradation of environmental organic pollutants Chem. Eng. J. 310 41

    CAS  Google Scholar 

  49. 49.

    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

    CAS  Article  Google Scholar 

Download references


The author thanks the Research Council of Hakim Sabzevari University and Tsinghua University for partial support of this work.

Author information



Corresponding authors


Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (PDF 942 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

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

Download citation


  • nanohybrid
  • Keggin
  • crystallography
  • electrocatalyst
  • photocatalyst