Two unusual 3D honeycomb networks based on Wells–Dawson arsenomolybdates with d¹⁰transition-metal-pyrazole connectors

Abstract

Herein, two Wells -Dawson-type arsenomolybdates, formulated as [Cu(pyr)][AsMoO] (1) and [Ag(pyr)][AsMoO] (2) (pyr = pyrazole), were hydrothermally synthesized and structurally characterized via single-crystal X-ray diffraction, elemental analysis, IR and UV-vis-NIR spectroscopies, XPS, XRD, and TG analysis. The structural analysis indicated that compounds 1 and 2 were isomorphic. They are the first reported 3D honeycomb structures of Wells-Dawson-type arsenomolybdates. The [M(pyr)] (M = Cu and Ag) connected with [AsMoO] polyoxoanions to form the {8·12}{8} topological structure. The contributions of organic ligands, pH value, reaction temperature, and transition-metal (TM) to the construction of 3D networks were elucidated. Furthermore, compounds 1 and 2 exhibited fluorescence properties in the solid state at room temperature, highly efficient catalytic ability for the degradation of five organic dyes (MB, RhB, MO, AP, and CR) under UV irradiation, and obvious electrocatalytic activities for the reduction of HO. The mechanisms of photocatalysis and electrocatalysis have also been discussed in detail.

Arsenomolybdates for Photocatalytic Degradation of Organic Dyes

“…The photocatalytic activity of {pyr}{Hbib} 2 {As III 2 (OH) 2 As V 2 Mo 18 O 62 } was evaluated for the degradation of AP under UV irradiation [51], the degradation rate is 91.02% after UV light irradiation 90 min. In addition, the photocatalytic activity of noncapped 0D analog (H 2 bimyb) 3 [25].…”

“…The arsenomolybdates are essential member of the heteropolymolybdates family [22], because of the redox properties of Mo and As atoms. The discoveries of many excellent articles on arsenomolybdates for ferromagnetic, antitumor activity, electrocatalysis properties, and lithium-ion battery performance have been reported in the last years [23][24][25][26]. However, there is no stress and discuss on the progress of arsenomolybdates for degradation of organic dyes.…”

Self-Assembly of Biarsenate Capped Keggin Arsenomolybdates with Tetravanadium Substitution for Photocatalytic Degradation of Organic Dyes

“…Zhu et al synthesized [{Cu 10 (pz) 11 Cl 4 } {As 2 III As 2 V Mo 6 V Mo 12 VI O 62 }]·H 2 O, which showed efficient antitumor activity . While our group assembled [M­(pyr) 2 ] 6 [As 2 Mo 18 O 62 ] (M = Cu and Ag, pyr = pyrazole) with outstanding photocatalysis and electrocatalysis properties, and [{Cu­(btp) 2 } 3 {As 2 Mo 18 O 62 }] (btp = 1,3-bis­(1,2,4-triazol-1-yl)­propane) with excellent photocatalytic and lithium-ion battery performance. , …”

“…16 Niu's group constructed 17 Recently, Xue addressed an X-shaped [As 6 Fe 7 Mo 22 O 98 ] 25− polyoxoanion, which exhibits overall ferromagnetic interaction. 18 20,21 In recent years, the transition metal substituted Keggin POMs have attracted considerable attention, because they show multifarious structures and special properties. 22−25 Meanwhile, the many capped Keggin POMs have also been prepared, such as 28 The few examples of monoarsenic-capped Keggin derivatives were reported.…”

Hydrophobic POM Electrocatalyst Achieves Low Voltage “Charge” in Zn‐Air Battery Coupled with Bisphenol A Degradation

“…Polyoxometalates (POMs) are distinguished electrocatalysts, which have received great success in PDR [43,44] . But hydrophilic character ruins their ORR activities and prospects in Zn‐air battery.…”