Polyoxometalate Functionalized Cyclic Trinuclear Copper Compounds for Bifunctional Electrochemical Detection and Photocatalytic Reduction of Cr(VI)

Abstract

The design and intentional construction of crystalline materials containing two clusters with redox properties in one framework still remains challenging. Linking oxidative polyoxometalate (POM) clusters and a reductive cyclic trinuclear copper complex (Cu-CTC) to prepare stable catalysts is rarely reported. Herein, we successfully obtained two new polyoxometalate-based metal–organic compounds (POMOCs) [Cu^II₃(PyCA)₃(μ₃-OH)(β-Mo₈O₂₆)_0.5(H₂O)₂]·5H₂O (1), [Cu^II₃(PyCA)₃(μ₃-OH)]₂(Cu^IIW₁₂O₄₀)[Cu^II(H₂O)₆] (2) (PyCA = 1H-pyrazole-4-carbaldehyde) by enabling precursors of Cu-CTC and POM cocrystallization in one pot via hydrothermal method. The [β-Mo₈O₂₆]^4– cluster in compound 1 combined with Cu-CTC units to form a 1D structure, and the [CuW₁₂O₄₀]^6– unit in compound 2 linked two Cu-CTC units to form a sandwich-like 0D structure. Also, Cu-CTC Cu^I₃(PyCA)₃·H₂O (Cu3) was synthesized for performance comparison. A series of characterizations indicate that compound 1 is more conducive to electron transfer than compound 2. In addition, compounds 1 and 2 can act as bifunctional catalysts for the electrochemical detection and photocatalytic reduction of Cr(VI). Particularly, the photoreduction rates of Cr(VI) by compounds 1 and 2 are 96.7% and 96.3% for only 10 and 14 min under visible light, respectively, and it is better than that of Cu3 and most other reported photocatalysts. Furthermore, the active sites and mechanisms for electrochemical detection and photocatalytic reduction of Cr(VI) were discussed.