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Despite their high tunability and versatility, the use of Keggin polyoxometalates (POMs) as deoxydehydration (DODH) catalysts has never been fully exploited. To date, only one study reported a single catalytic test using H3PMo12O40 (HPMo12), as part of a broader screening of various Mo-based catalysts1. In this contribution, we report for the very first time the promising catalytic performances in DODH of 1,2-hexanediol (chosen as model substrate) of tetrabutylammonium phosphododecamolybdate (TBAPMo12) (100 % conversion, 52 % selectivity). This Keggin salt was easily obtained by ion metathesis and precipitation of the commercially available HPMo12 with TBABr. Additionally, we show that it is possible to boost the catalytic performances of (TBA)3PW12O40 (TBAPW12), which in its pristine form is not as performant (45 % conversion, 23 % selectivity) as its Mo counterpart. To do so, the monolacunary form of PW12 was synthesized ((TBA)4H3PW11O39 = TBAHPW11) and then metalated with a Re precursor, yielding a very active (100 % conversion, 73 % selectivity) (TBA)4PW11ReVO40 (TBAPW11Re) mixed-metal compound. TBAPW11Re was fully characterized by PXRD, IR, 31P NMR, ICP-AES, UV–vis and elemental analysis and its catalytic nature was investigated together with TBAPMo12. Cold filtration tests and recycling experiments revealed that it is their partial dissolution that leads to DODH-active species. IR and 31P NMR data indicated that these active species are the dissolved PMo12 and PW11Re POMs themselves and not monometallic species.
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Magerat, A., Hermans, S., & Gaigneaux, E. (2025). A novel versatile platform as efficient deoxydehydration (DODH) catalysts: Keggin polyoxometalates. Applied Catalysis B: Environmental, 375, 125432. https://doi.org/10.1016/j.apcatb.2025.125432 (Original work published 2025)