Photochemical and electrochemical hydrogen evolution reactivity of lanthanide-functionalized polyoxotungstates

Abstract

The first example of hydrogen evolution reactivity (HER) of lanthanide-functionalized Keggin-based polyoxotungstates under photochemical and electrochemical conditions is reported. The HER activity under homogeneous, visible light-driven conditions and under heterogeneous, electrochemical conditions depends on the type of lanthanide functionalization, so that a new class of model HER catalysts for systematic reactivity studies is now accessible.

Synthesis of Pyrazolo‐[4́,3́:5,6]pyrido[2,3‐d]pyrimidine‐diones Catalyzed by a Nano‐sized Surface‐Grafted Neodymium Complex of the Tungstosilicate via Multicomponent Reaction

“…The lower charge density on the spherical surface of HPAs is the most main reason that they are commonly employed as acidic catalysts. Due to the interest in POM‐based coordination complexes, in the last years, our research team introduced different lanthanoid coordination complexes into the POMs systems and obtained a series of novel POM‐based lanthanide clusters, which demonstrated unusual topologies and improved properties …”

A survey of interactions in crystal structures of pyrazine-based compounds

“…POMs as anionic clusters have unique properties in various fields, such as biology (Arefian et al, 2017), photophysical systems (Fashapoyeh et al, 2018), magnetism (Clemente-Juan et al, 2012) and catalysis (Liu et al, 2013). Furthermore, their electron-rich surfaces and accessible oxygen groups make them suitable candidates for the construction of two-component (type I) or three-component (type II) hybrids (Mirzaei et al, 2014).…”

Synthesis, Characterization, Electrochemistry, Photoluminescence and Magnetic Properties of a Dinuclear Erbium(III)-Containing Monolacunary Dawson-Type Tungstophosphate: [{Er(H2O)(CH3COO)(P2W17O61)}2]16−

“…Until now, there are only a few reports on the sandwich-type Ln-POM family, where lanthanide metal centers (Ln III nuclearity ≥ 2) are sandwiched between two lacunary POM ligands [ 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 ]. Lanthanide-containing POM assemblies have demonstrated outstanding properties in various fields of research such as molecular magnetism [ 27 ], imaging [ 28 ], photoluminescence [ 29 ], catalysis [ 30 , 31 ] and electrochemistry [ 32 ]. Magnetic POMs have attracted an increasing interest after the discovery of the first POM-based single molecule magnet (SMM) [ErW 10 O 36 ] 9– [ 33 ].…”

“…Some of the important intrinsic properties of POM clusters are their thermal and hydrolytic stability, tunability of acid and redox properties and high solubility in a variety of solvents, which make them promising catalysts for different chemical processes. The Ln-POMs have exhibited noteworthy catalytic performances in various chemical processes [ 30 , 31 , 32 ]. The photochemistry of Ln-POMs is also of great interest; POM ligands usually act as light harvesting antennae in photoluminescent lanthanopolyoxotungstate species, which sensitize Ln III centers (such as Sm III , Eu III , Tb III and Dy III ) by absorbing incident light and then transferring this excitation to Ln III ions through an energy transfer process [ 29 , 35 ].…”