Latest progress in covalently modified polyoxometalates-based molecular assemblies and advanced materials

Abstract

Covalently modified polyoxometalates (POMs), which benefit from the synergistic effect between POMs and covalently grafted moieties, have received increasing attention in various fields. Recent studies on the covalently modified POMs mainly focus on the function-directed POMs assemblies. In this review, we summarized the latest progress (2017-2022) of covalently modified POMs from functional perspective, which can be classified as assembly chemistry, photochemistry, electrochemistry, homogeneous/heterogeneous catalysis and biological application.The roles of POMs and covalently grafted moieties in these hybrids, especially the rational design for the specific application were considered and emphasized.

Engineering of PMo12@NiCo-LDH compositevia in situencapsulation-reassembly strategy for highly selective photocatalytic reduction of CO2to CH4

“…[1][2][3] POMs have been applied for the manufacturing of fine chemicals and medicines, and also in energy storage, material chemistry, etc. 1,2,4,5 However, from both fundamental science and application point of view, POMs still face huge challenges such as low BET surface area (<10 m 2 g −1 ), easy loss of activity, and difficult separation and recovery. Under such circumstances, the heterogenization of POMs is considered a feasible approach to overcome the above-mentioned limitations.…”

Latest progress in asymmetrically functionalized Anderson-type polyoxometalates

“…In recent years, due to the rapid development of POM chemistry, remarkable reviews about covalent modification of POMs have been published. 12,18,49–53 However, there are few reports on asymmetrically functionalized Anderson-type polyoxometalates. Here in this review, we concentrate on the synthetic methodologies of asymmetric Anderson POMs and the functionalities of the resulting hybrids.…”

Electrochemically Reconstructed Vanadic Oxide-Doped Cobalt Pyrophosphate as an Electrocatalyst for the Oxygen Evolution Reaction

“…Although the well-known noble-metal-based materials, such as RuO 2 and IrO 2 , have been regarded as the most efficient electrocatalysts for the OER, , the high cost and stability hindered their further application. The transition-metal-based materials due to their low cost, extraordinary redox nature, and abundant active site, not only including iron, cobalt, nickel composite materials , but also metal oxygen cluster hybrids, − as well as metal–organic framework (MOF), have been extensively exploited for the preparation of the electrocatalysts. Among them, cobalt or nickel-based materials were the most promising candidates as alternative electrocatalysts for the OER, relying on their excellent electrocatalytic activities.…”