Two three-dimensional polyanionic clusters [M(P₄Mo₆)₂] (M = Co, Zn) exhibiting excellent photocatalytic CO₂ reduction performance

Abstract

Two captivating {P4Mo6}-based compounds, formulated as (H2bbi)2{[Co2(bbi)][Co(H2O)2]2[Co(H5P4Mo6O31)2]}·4H2O (1) and (H2bbi){[Zn(Hbbi)]2[Zn(bbi)][K2Zn(H2O)4][Zn(H4P4Mo6O31)2]} (2) [bbi = 1,1'-(1,4-butanediyl)bis(imidazole)] were successfully synthesized under hydrothermal conditions. Structural analysis demonstrates that compounds 1 and 2 are constructed...

An isolated doughnut-like molybdenum(v) cobalto-phosphate cluster exhibiting excellent photocatalytic performance for carbon dioxide conversion

“…Hence, it is vital to develop reductive CO 2 photocatalysts with high efficiency, high selectivity and low cost for facilitating this reaction process. 12–21…”

“…Hence, it is vital to develop reductive CO 2 photocatalysts with high efficiency, high selectivity and low cost for facilitating this reaction process. [12][13][14][15][16][17][18][19][20][21] Polyoxometalates (POMs), as a kind of inorganic metal oxygen cluster with redox properties and excellent multi-elec-tron transfer ability, have been subject to extensive studies in numerous domains, such as medicine, [22][23][24] optics, [25][26][27] catalysis, [28][29][30][31][32][33][34][35] electrochemistry, [36][37][38][39][40] etc. Among plenty of POMbased clusters, molybdenum(V) cobalto-phosphate clusters have been considered as prospective promising photocatalysts for CO 2 reduction owing to the presence of reduced Mo V and Co II 42 Although some achievements have been made, there are no reports on isolated inorganic wheellike cobalto-phosphate clusters as CO 2 reduction reaction (CO 2 RR) catalysts until now.…”

“…This phenomenon is ascribed to that the photoelectrons on PS were not sufficient to transfer to the catalyst. Notably, the above CO rate is superior to those of most of the reported POM-based heterogeneous catalysts and POM-based composite catalysts 12,14,16,27,39,40,50,51 For practical application, the stability of [Co@{Co 16 Mo 16 }] is further investigated in Fig. 3d.…”

Two 1D Anderson-Type Polyoxometalate-Based Metal–Organic Complexes as Bifunctional Heterogeneous Catalysts for CO2 Photoreduction and Sulfur Oxidation

“…In comparison, when we replaced {Zn-CrMo 6 } with {Co-CrMo 6 } , the amount of CO could reach 77.4 μmol (turnover number (TON) = 23.8) accompanied by the high selectivity (92.6%) of CO over H 2 and CH 4 (Table S1). The reason for different phenomena is probably that cobalt ions can offer more catalytically active sites to drive CO 2 conversion in view of the same combining circumstance of two POM-based MOCs. , …”

Central Metals to Guide the Bandgap of Hourglass-type Polyoxometalate Hybrids as Photocatalyst for the Reduction of Cr(VI)

“…Among the family of POMs, the reduced hourglass-type {M­[P 4 Mo V 6 O 31 ] 2 } n − (abbr. M­{P 4 Mo 6 } 2 ) polyoxoanionic cluster possesses a high negatively charged surface with all Mo atoms in the +5 oxidation state, which endows the assembled M­{P 4 Mo 6 } 2 cluster with a peculiar reversible redox feature and wide visible-light absorption capacity. − Moreover, the electron structure of M­{P 4 Mo 6 } 2 is flexible and tunable, and can be easily manipulated by adjusting the central metal species, providing the possibilities for the exploitation of high-efficient photocatalysts. − At present, hourglass-type M­{P 4 Mo 6 } 2 photocatalysts have been applied in some photocatalytic process, for example, the photocatalytic degradation of organic dyes, photocatalytic reduction of organic compounds (such as p -nitrophenol), photocatalytic conversion of CO 2 to CH 4 , and so on. Our previous work preliminarily explored the photocatalytic performance of M­{P 4 Mo 6 } 2 -based compounds for Cr­(VI) reduction, and found that the crystal stacking arrangement and conjugated organic components have an effect on the photocatalytic Cr­(VI) reduction activity. − Although significant progress has been made so far, the highly efficient M­{P 4 Mo 6 } 2 -based photocatalysts still need to be explored and the structure–performance relationship between hourglass-type POMs and their photocatalytic performance toward Cr­(VI) reduction still needs to be clarified.…”