Bifunctional Platinum‐Incorporated Polyoxoniobate Derived Catalyst for N‐formylation of Piperidine Using CO2

Abstract Alkaline salt of platinum‐incorporated heteropolyoxoniobate [Pt(Nb 6 O 19 ) 2 ] 12− ( Pt(Nb6)2 ) was fabricated and applied for N ‐formylation of various amines including piperidine under CO 2 and H 2 atmosphere. Pt(Nb6)2 achieved the selective formation of 1‐formylpiperidine, whereas the absence of Pt species, H 2 , and CO 2 resulted in a trace amount of the product. The structural characterization revealed that the sandwich‐type structure of Pt(Nb6)2 was transformed into Pt nanoparticles incorporated with polyoxoniobates ([Nb 6 O 19 ] 8− ) on the NbO x bulk matrix (NbPOM‐PtNPs/NbO x ) under reaction conditions. The N ‐formylation of amines in the presence of CO 2 and H 2 proceeded by the bifunctional NbPOM‐PtNPs/NbO x where the basic sites of [Nb 6 O 19 ] 8− and the redox property of Pt promoted the generation of formamides.