Three New Difunctional Electrocatalysts Built from Polyoxometalates and Cu–Tpy Units: Experimental and Theoretical Study

Abstract

Three new organic–inorganic compounds based on polyoxometalates, [(CuCltpy)2(Cu2Cl2(tpy)2)­(α-SiW12O40)]·5H2O (1), [Cu4(tpy)4(H2O)4(α-P2W18O62)]·4H2O (2), and [Cu­(tpy)­(Mo3O10)]·H2O (3) (tpy = 4′-(pyrrol-3-yl)-2,2′:6′,2″-terpyridine), were facilely isolated by hydrothermal technique. X-ray diffraction analysis shows that compound 1 with three-dimensional (3D) supramolecular structure is featured by α-SiW12 clusters, {Cu2Cl2/tpy} dimers, and {CuCl/tpy} monomers. Compound 2 with zero-dimensional (0D) discrete structure is constructed from α-P2W18 clusters and four Cu/tpy units. The one-dimensional (1D) infinite chain of 3 is stemmed from [Mo3O10]2– units and Cu/tpy motifs. Furthermore, we explored the bifunctional electrocatalytic activities of these three compounds for reduction and oxidation. The results show that the [Mo3O10]2–-type hybrid displays better difunctional electrocatalytic activities than heteropolyacids toward both reduction and oxidation. Significantly, the molecular electrostatic potential and the frontier molecular orbital were achieved by density functional theory calculations to analyze the electronic structure of three compounds. The natural bond orbital analysis was also carried out to interpret electron charge distribution.

Experimental and Theoretical Studies on Two Dual-Functional Organic–Inorganic Hybrids Based on [V4O12]4– Clusters

“…Electrocatalysis is one of the important properties owing to the instinctive abilities of transferring and storing electrons. − POM-based compounds are often selected to explore electrocatalytic redox reactions of KBr, H 2 O 2 , dopamine, nitrite (NO 2 – ), AA, and so on. − In this work, the electrocatalytic performances of 1 – 2 -CPEs are studied toward NO 2 – reduction and AA oxidation reaction, respectively.…”

Four New Terpyridine Complexes Based Polyoxometalates with [W10O32]4– Anions as High‐Efficiency Dual‐Site Catalysis for Thioether Oxidation Reaction†

“…[ 29 ] However, there are few reports about using TPY complexes to modify POMs. [ 30 ] Zubieta connected TPY ligands and POMs by the coordination of transition metals, and obtained a series of compounds. [ 31‐32 ] In addition, the most common way to combine TPY and POM anions is through PO 4 3– , tris, metal‐carbon bond or organic π‐bridge, [ 33‐36 ] which exhibit different self‐assembly properties, intermolecular electron transfer, electrochemical activity, and second‐order nonlinear optical response.…”