Polyoxometalate‐Based Metal Organic Frameworks: Recent Advances and Challenges

Abstract

This work is dedicated to exploring efficient and stable POM@MOF catalysts, and a major breakthrough has been achieved mainly by constructing unique structures and doping heteroatomic strategies to enhance electrolytic HER performance, thus improve the efficiency of hydrogen production. However, as this research is concerned with the electrolysis of fresh water, this hydrogen production technology consumes a large amount of fresh water resources, which severely restricts the industrialization of electrolytic water for hydrogen production. Therefore, future work should explore hydrogen precipitation catalysts applied to electrolysis of seawater or wastewater from the perspective of environmental protection and resource conservation.Besides, based on the exposed metal active sites of POMs are proven to be the key hub of catalysis, researchers should therefore combine density flooding theory calculations to deduce the relationship between the charge density distribution on the catalyst active sites and the d-band center displacement, and preferably select the most favorable structure for the adsorption of reaction intermediates, and based on which the structure of POM@MOF-based catalysts should be skillfully designed.

Proton Affinity in the Chemistry of Beta-Octamolybdate: HPLC-ICP-AES, NMR and Structural Studies

“…In the chemistry of group 6 polyoxometalates, the polyoxomolybdates are significantly more labile than the polyoxotungstates, thus making researchers favor the latter in their studies of POM chemistry. However, several studies of polyoxomolybdates’ reactivity [ 39 ] and catalytic performance (electron transfer reactions) appeared [ 40 , 41 , 42 , 43 , 44 , 45 ]. One of the central complexes in this chemistry is (Bu 4 N) 4 [β-Mo 8 O 26 ] ( Scheme 1 ), which is a standard precursor of all reactions in organic media, leading to a huge number of materials with different properties [ 46 , 47 , 48 , 49 ].…”

State-of-the-art advances in the syntheses, structures, and applications of polyoxometalate-based metal–organic frameworks

“…2). [40][41][42][43][44][45][46][47] These organic ligands can be subdivided into rigid, semi-rigid and flexible ligands. The long and flexible organic ligands tend to generate interpenetrating and porous structures of PMOFs.…”

“…Synthetic chemistry of PMOFs has undergone a great deal of developments in the past several years, a large number of PMOFs with excellent physical and chemical properties have been discovered. 40,48,49…”

In-depth analysis on photocatalysts related research trends about polyoxometalate-based materials: A bibliometric study

“…[63] Thirdly, loading POMs on appropriate carriers such as MOFs and TiO2 can overcome the problem that POMs are highly soluble in water. [64][65] In 2021, Jiao et al prepared two cases of POM@MOFs, Ni3PW10@NU-1000 and Ni3P2W16@NU-1000. They were used as a photocatalyst to drive the hydrogen evolution reaction.…”