Experimental and Theoretical Study of Two 3D Difunctional Electrocatalytic Hybrid Vanadate-Containing Metal-Organic Motifs.

Two novel 3D inorganic-organic hybrids based on [VO]/[VO] clusters, [Cu(bbpy)(VO)]·3HO () and [CuAg(pty)(VO)]·HO () (bbpy = 3,5-bis(1-benzimidazole) pyridine, pty = 4'-(4″-pyridyl)-2,2':6',2″-terpyridine), were isolated in the same POV/Cu/N-heterocycle ligand reaction systems. Hybrids and possess novel three-dimensional bimetallic frameworks derived from [VO]/[VO] clusters and Cu-organic complexes. In , bbpy ligands are grafted by Cu to a grid ribbon 2D sheet, which are connected with benzene-like [VO] to yield a 3D framework. In , helical {O-V-O-V-} chains are bridged by Cu(II) ions into a 2D layer including eight-membered rings {VCu} and six-membered rings {VCu}, and the adjoining sheets are joined by Ag-N coordination bonds to form a framework structure. Moreover, hybrid has superior electrocatalytic properties for nitrite reduction and oxidation of ascorbic acid with electrocatalytic efficiencies of 397.2 and 96%, respectively. Hybrid displays coordinated electrocatalytic performance toward oxidation reaction through V and Cu centers. Meanwhile, the corresponding theoretical studies were conducted to evaluate electrocatalytic active sites and charge distribution.