“…Moreover, ceria has served as an efficient catalyst for water gas shift reaction − among other catalytic applications due to the outstanding oxygen storage capacity as well as the ease in oxygen vacancies generation and reparation. To date, several examples exist of discrete Ce IV /M oxo compounds, clusters, and polyoxometalates, which have been predominantly investigated for magnetic studies but few for catalysis. − Meanwhile, ceria-supported vanadium catalysts have demonstrated high potential in oxidative catalysis, like oxidative dehydrogenation, , cyclohexene epoxidation, and methanol oxidation. , Therefore, developing and interrogating heterometallic CeV-oxo clusters for catalysis poses a great interest to both the catalytic and bimetallic Ce/V cluster field. Recently, a V polyoxovanadate, ( n -Bu 4 N) 2 [(Ce III (dmso) 3 ) 2 V IV V V 11 O 33 Cl] with Ce III dopants, and a cluster, Ce 4 V 4 O 13 , were synthesized; these clusters were utilized for indigo degradation and thioanisole oxidation, respectively. , However, the aforementioned clusters resembled vanadium doped with cerium rather than bulk ceria, and these materials also formed extended crystals with no internal porosity, limiting reactivity as a heterogeneous catalyst.…”