Efficient Electrochemical Detection of Hydrogen Peroxide Based on Silver-Centered Preyssler-Type Polyoxometalate Hybrids

Abstract

Four polyoxometalate (POM)-based organic–inorganic hybrid compounds, namely, (H2bimb)6H8[((Mn­(H2O)3(μ-bimb))0.5(Mn­(H2O)4)­(Mn­(H2O)5)0.5(AgP5W30O110))2]·29H2O (1), [(Cu­(Hbimb)­(H2O)2(μ-bimb)­Cu­(Hbimb)­(H2O))­(Cu­(H2O)2(μ-bimb)­Cu­(H2O)3)­((Cu­(H2O)2)0.5(μ-bimb)­(Cu­(H2O)3)0.5)­H2(AgP5W30O110)]·12.5H2O (2), (H2bimb)2H­[(Zn­(Hbimb)­(H2O)4(Zn­(Hbimb)­(H2O)2)0.5)2(AgP5W30O110)]·12H2O (3), and (H2bimb)3H2[(Ag­(H2O)2)0.5(Ag­(Hbimb)­Ag­(Hbimb)­(μ-bimb)­Ag)­(Ag­(H2O)2)0.5(AgP5W30O110)]·7H2O (4) (bimb = 1,4-bis­(1H-imidazol-1-yl)­benzene), were hydrothermally synthesized using a silver-centered Preyssler-type POM K14[AgP5W30O110]·18H2O (abbreviated as K-{AgP5W30}) as a precursor. In 1–4, {AgP5W30} clusters integrating the merits of Ag+ and {P5W30} units are modified by different transition metal (TM)-organic fragments to extend the structures into three-dimensional frameworks. As nonenzymatic electrochemical sensor materials, 1–4 show good electrocatalytic activity, high sensitivity, and a low detection limit for detecting hydrogen peroxide (H2O2); 4 possesses the highest sensitivity of 195.47 μA·mM–1·cm–2 for H2O2 detection. Most importantly, the average level of H2O2 detection of these {AgP5W30}-based materials outperforms that of Na-centered Preyssler-type {NaP5W30} and most Keggin-type POM-based materials. The performances of such {AgP5W30} materials mainly stem from the unique advantage of high-negatively charged {AgP5W30} clusters together with the good synergistic effect between {AgP5W30} and TMs. This work expands on the research of high-efficiency POM-based nonenzymatic electrochemical H2O2 sensors using Ag-containing POMs with high negative charges, which is also of great theoretical and practical significance to carry out health monitoring and environmental analysis.

Highly efficient multi-site synergistic catalysis of a polyoxovanadate-based metal–organic framework for benzylic C–H bond oxidation

“…45 The peaks in the range of 700 to 800 cm −1 may be assigned to Cu–O bonds. 46 The apparent absorption bands in the 1200–1600 cm −1 region are ascribed to CN and CC vibrations of the bix ligand. 47 In the Raman spectrum of 1 (Fig.…”

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.…”

Nanostructured Polyoxometalate-Based Heterogeneous Electrode Materials for Electrochemical Sensing of Glucose

“…Polyoxometalates (POMs) are a versatile group of molecular metal oxides formed by early transition metal (TM) centers in high oxidation states (Mo V , Mo VI , W VI , V V , Nb V , and Ta V ) by sharing oxygen atom bridges. , Lacunary POM units can combine with first-row TM cations (Cu, Fe, Mn, Co, Ni, etc.) to form TM-substituted POMs. , POMs are kind of electronic sponges that display efficient, multistep, fast, and reversible multielectron transfer characteristics. − They exhibit many properties in various chemical reactions, such as strong Bro̷nsted acidity, high proton mobility, high solubility in various solvents, and resistance to hydrolysis and oxidative degradation in solutions. − Owing to the above advantages, POM-based materials have attracted extensive interest in the fields of catalysis, materials science, medicine, industry, and others. It should be noted that one of the new orientations in the development of POM-based materials is the use of the electrochemical ability of POMs to construct electrochemical sensors.…”