Polyoxometalates-Functionalized Electrodes for (Photo)Electrocatalytic Applications: Recent Advances and Prospects

Abstract

This review is intended to provide an up-to-date and comprehensive description of recent advances since the mid-2010s in the elaboration and the involvement of polyoxometalates (POMs)-functionalized (photo)­electrodes in (photo)­electrocatalytic reactions. Focus has been essentially placed not only on reactions of high interest, such as hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and CO2 reduction reaction (CDRR) but also on other more “confidential” reactions (e.g., reduction of oxyanionic species and ascorbic acid oxidation). It is now well-known that POMs represent one class of fascinating compounds largely explored in inorganic chemistry, highlighted by the large number of complexes with structural, redox, and functional diversities which make them particularly attractive as efficient electrocatalysts for a wide range of significant multiredox reactions. The transposition of homogeneous electrocatalysis to (photo)­electrode-supported electrocatalysis using POMs and its derivatives undoubtedly constitutes a really promising avenue toward the development of modern electrochemical devices, which could be of high interest for applications in chemical sensing, biosensing, electroanalysis, and solar-driven fuel cells.

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

“…The electronic structure of polyoxoanions together with low-energy protonation makes such objects very attractive for PCET reactions. The most important catalytic process in this field is water oxidation [ 31 , 32 ]. Such POM catalysts as [{Ru IV 4 (OH) 2 (H 2 O) 4 }(γ-SiW 10 O 34 ) 2 ] 10− [ 33 , 34 , 35 ] and [Co II 4 (H 2 O) 2 (B-α-PW 9 O 34 ) 2 ] 10− have become classics [ 36 , 37 ].…”

Reducing Systematic Uncertainty in Computed Redox Potentials for Aqueous Transition-Metal-Substituted Polyoxotungstates

“…8 Conventionally, hexacoordinate transition-metals are introduced so the sixth coordination site are occupied by solvent ligands from the local environ-ment�see Figure 1. These structures have attracted significant interest as single atom catalysts 9 in fields including water oxidation, 10,11 carbon dioxide reduction, 12,13 and nitrogen activation (Scheme 1). 14 Early computational work on POMs have primarily focused on charged molecules using implicit solvation models.…”

CsPbBr3/Polyoxometalate Composites for Selective Photocatalytic Oxidation of Benzyl Alcohol

“…Polyoxometalates (POMs) are metal oxide anionic clusters generally composed of redox metal centers (Mo, W, V, Nb, and Ta) with d 0 electronic configurations. 12 The heteroatom, type of transition metals, and the addenda atom of POM could influence the redox potential to a certain extent, 13−15 which significantly affects the photogenerated electron-transfer efficiency and the photocatalytic efficiency. Additionally, due to their distinctive redox behavior acting as the shuttle of electrons and protons while keeping their structure intact, POM-based composite catalysts can enhance the catalytic activity and selectivity, including water splitting, 16−18 CO 2 reduction, 19−21 and organic transformation.…”

“…Polyoxometalates (POMs) are metal oxide anionic clusters generally composed of redox metal centers (Mo, W, V, Nb, and Ta) with d 0 electronic configurations . The heteroatom, type of transition metals, and the addenda atom of POM could influence the redox potential to a certain extent, − which significantly affects the photogenerated electron-transfer efficiency and the photocatalytic efficiency.…”