Unusual electrochemical reduction of copper(II) to copper(I) in polyoxotungstates |
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| Institution: | 1. Hip Preservation Center, Sports Medicine, Orthopedics Department, University of Colorado, Aurora, Colorado, U.S.A.;2. University of Colorado School of Medicine, Aurora, Colorado, U.S.A.;1. Institute of Chemistry, Jan Kochanowski University, 15G Świętokrzyska Str., 25-406 Kielce, Poland;2. Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Okólna 2, 50-950 Wrocław, Poland;3. Faculty of Chemistry, Wrocław University of Technology, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland;4. Institute of Physical and Theoretical Chemistry, Wroclaw University of Technology, Wyb. Wyspiańskiego 27, 50-370 Wrocław, Poland;1. Henan Key Laboratory of Polyoxometalate Chemistry, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan, 475004, China;2. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, PR China;1. Shenzhen Key Laboratory of Polymer Science and Technology, Guangdong Research Center for Interfacial Engineering of Functional Materials, College of Materials Science and Engineering, Shenzhen University, 1066 Xueyuan Avenue, Shenzhen 518055, Guangdong Province, PR China;2. Key Laboratory of Optoelectronic Devices and Systems of Ministry of Education and Guangdong Province, College of Optoelectronic Engineering, Shenzhen University, Shenzhen 518060, PR China;1. State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metals Chemistry and Resources Utilization of Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, China;2. State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China |
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| Abstract: | The electrochemical behaviour of the copper-substituted Keggin-type and sandwich-type polyoxotungstate anions of the compounds α-(C4H9)4N]4HPW11CuIIO39] and α-B-(C4H9)4N]7H3CuII4(H2O)2(PW9O34)2] was studied by cyclic voltammetry in acetonitrile. In both cases two copper 1-electron reduction waves were detected in the cathodic scan. The first one was due to the reduction of one CuII to CuI in the polyoxoanion and the second one to the consecutive reduction of the preformed CuI to Cu0, with the consequent deposition/adsorption of the ejected metal atom at the glassy carbon electrode surface. In the anodic scan, Cu0 was re-oxidised with regeneration of the initial copper(II) complexes, via a CuI intermediate. The observed two-step reduction of copper(II) to copper(0) and the formation of intermediate species containing copper(I) is here reported for the first time for copper substituted polyoxotungstates. The co-ordination of the acetonitrile molecules to the copper ions must play a role in the formation of the copper(I) species, which are not detected in aqueous solution. |
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