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Polyoxometalates (POMs) have been used for spectrophotometric determinations of silicon and phosphorus under acidic conditions, referred to as the molybdenum yellow method and molybdenum blue method, respectively. Many POMs are redox active and exhibit fascinating but complicated voltammetric responses. These compounds can reversibly accommodate and release many electrons without exhibiting structural changes, implying that POMs can function as excellent mediators and can be applied to sensitive determination methods based on catalytic