Reversible redox activity of {Mo72Fe30} nano-polyoxometalate cluster in three crystalline forms

Selective Oxidation of 2-Chloroethyl Ethyl Sulfide in Aqueous Media Catalyzed by {Mo72M30} Nano-polyoxometalate Clusters Differentiating the Catalytic Activity of Nodal Metals

“…The oxidation peaks of all three catalysts shifted negatively after the addition of H 2 O 2 , but returned to their original position after the continued addition of substrate CEES (Figure b–d). Although the degree of the oxidation potential of the catalyst shifted from positive to negative after the addition of H 2 O 2 has no obvious regularity, the negative shift is consistent with what has already been reported . As compared to the pristine catalyst, the negative shift in the oxidation peak potential of the oxidation products of the catalyst after the addition of H 2 O 2 indicates that the reduced cluster species node metals in the system are more likely to be reoxidized after adding H 2 O 2 , and the resulting oxidation products are the driving force for the subsequent selective oxidation of CEES into CEESO.…”

“…Although the degree of the oxidation potential of the catalyst shifted from positive to negative after the addition of H 2 O 2 has no obvious regularity, the negative shift is consistent with what has already been reported. 49 As compared to the pristine catalyst, the negative shift in the oxidation peak potential of the oxidation products of the catalyst after the addition of H 2 O 2 indicates that the reduced cluster species node metals in the system are more likely to be reoxidized after adding H 2 O 2 , and the resulting oxidation products are the driving force for the subsequent selective oxidation of CEES into CEESO. In addition, Figure 7 shows the XPS spectra of Mo 3d and V 2p in the catalyst {Mo 72 V 30 } before the addition of H 2 O 2 , after the addition of H 2 O 2 , and after the addition of H 2 O 2 and CEES.…”

Unravelling the Bi‐Functional Electrocatalytic Properties of {Mo72Fe30} Polyoxometalate Nanostructures for Overall Water Splitting Using Scanning Electrochemical Microscope and Electrochemical Gating Methods

“…[ 27 ] In these, Keplerate‐type polyoxometalate {Mo 72 Fe 30 } clusters possess distinct properties such as visible‐light‐driven photocatalyst, an anode for Li‐ion batteries, the catalyst for organic synthesis, reversible redox mediators for the synthesis of metal nanoparticles, targeted drug delivery agent, and hybrid materials, proton conductivity, electrocatalyst for HER, and excellent guest/host chemistry. [ 27 , 31 , 32 , 33 , 34 , 35 ] To date, the electrocatalytic properties of {Mo 72 Fe 30 } POM for overall water splitting are not yet studied; however, it is expected that they can possess excellent electrocatalytic activity that is due to the presence of Mo and Fe atoms in their highest oxidation state. [ 36 , 37 ] In this work, we have demonstrated the better electrochemical catalytic properties of {Mo 72 Fe 30 } POM as a universal catalyst for HER and OER applications using standard electrochemical studies.…”

A redox-active inorganic crown ether based on a polyoxometalate capsule

“…According to these observations, we have chosen a charge-neutral POM capsule firstly reported by Müller and co-workers [α-PMo VI 12 O 40 ] 3− ⊂[Mo VI 72 Fe III 30 O 252 (H 2 O) 102 (CH 3 CO 2 ) 15 ] 3+ ·60H 2 O [ I ] (Fig. 1), 30,31 which consists of 20 crown-ether-like pores {Mo VI 3 Fe III 3 O 6 } with alternately-arranged corner-sharing [Mo VI O 6 ] and [Fe III O 6 ] units and an encapsulated [α-PMo VI 12 O 40 ] 3− . Müller and co-workers have reported the molecular structures of a large variety of POM capsules, and some capsules can incorporate cations and organic molecules through the crown-ether-like pores, while its redox property is unexplored.…”