Kuzman, Dino; Damjanović, Vladimir; Toplak, Juraj; Medak, Glorija; Halasz, Ivan; Hrenar, Tomica; Cindrić, Marina; Vrdoljak, Višnja (2026) Synthesis, structural characterization and properties of a series of heteropolyoxomolybdates: [AlMo6(OH)6O18]3−, [GeMo12O40]4−, [GeMo6O22(Hmal)3]7−, [SiMo12O40]4−, and [TeMo6O24]6−. Dalton Transactions, 55 (8). pp. 3442-3453. ISSN 1477-9226
![[img]](https://fulir.irb.hr/style/images/fileicons/application_pdf.png) |
PDF
- Published Version
- article
Available under License Creative Commons Attribution Non-commercial. Download (3MB) |
Abstract
Eight heteropolyoxomolybdates were synthesized and characterized, comprising three Anderson-type compounds [Co(ox)(NH3)4]3[AlMo6(OH)6O18]7H2O (1), [Co(ox)(NH3)4]6[TeMo6O24]16H2O (2), and Na2[Co(ox)(en)2]4[TeMo6O24]16H2O (3), four Keggin-type compounds [Co(ox)(NH3)4]4[GeMo12O40]6H2O (4), [Co(ox)(NH3)4]4[SiMo12O40]6H2O (5), [Co(ox)(en)2]4[GeMo12O40]12H2O (6), and [Co(ox)(en)2]4[SiMo12O40]12H2O (7), as well as one coordination polymer Na4[Co(ox)(NH3)4]3[GeMo6O22(Hmal)3]7.75H2O (8) featuring an extensive three-dimensional coordination framework. Additionally, two reaction intermediates, [{Co(ox)(NH3)4}2Na2(H2O)6{H4Mo8O28}]4H2O (1a) and [Co(ox)(NH3)4]2[Al(mal)2(H2O)2]Hmal2H2O (1b), were also isolated. Compounds [Co(NH3)6][Al(mal)2(H2O)2](NO3)2H2O (9) and [Co(en)3]2[Mo8O26(H2O)2]Cl26H2O (10) were the only products obtained from reactions involving Al3+ as the heteroatom and complex cations [Co(NH3)6]3+ or [Co(en)3]3+. All compounds were prepared by hydrothermal synthesis and the mechanochemical method followed by vapour-assisted ageing. The reactions between sodium molybdate and [Co(ox)(NH3)4]NO3H2O in the presence of AlCl3 or GeO2 and malonic acid were monitored in situ by Raman spectroscopy. The initial transformation involves a remarkably fast reaction between sodium molybdate and malonic acid, generating new species that subsequently reacted with other mixture components. The photocatalytic activities of compounds 1, 2, 4 and 5 in the degradation of the safranin T dye under visible light irradiation, both with and without hydrogen peroxide, were also examined. Compounds 4 and 5 exhibit the highest activities. To investigate the mechanisms driving the crystallization process, we monitored the transformation kinetics of amorphous intermediates into the final crystalline products within an aqueous slurry at room temperature. We employed ex situ powder X-ray diffraction (PXRD), a technique allowing real-time observation of structural changes as they occur. The resulting PXRD data, which generated complex, multi-dimensional datasets (data tensors), were analyzed using the 2nd-order tensor decomposition method, principal component analysis (PCA).
| Item Type: | Article | ||||||||
|---|---|---|---|---|---|---|---|---|---|
| Uncontrolled Keywords: | heteropolyoxomolybdates; Keggin; Anderson; catalysis; principal component analysis; Raman spectroscopy | ||||||||
| Subjects: | NATURAL SCIENCES > Chemistry | ||||||||
| Divisions: | Division of Materials Chemistry Division of Physical Chemistry |
||||||||
| Projects: |
|
||||||||
| Depositing User: | Ana Zečević | ||||||||
| Date Deposited: | 20 May 2026 11:44 | ||||||||
| URI: | https://fulir.irb.hr:/id/eprint/11987 | ||||||||
| DOI: | 10.1039/d5dt03064a |
Actions (login required)
 |
View Item |
Altmetric
Altmetric
