Theoretical Investigation of Catalytic Water Splitting by the Arene-Anchored Actinide Complexes

Abstract

Actinide complexes, which could enable the electrocatalytic H2O reduction, are not well documented because of the fact that actinide-containing catalysts are precluded by extremely stable actinyl species. Herein, by using relativistic density functional theory calculations, the arene-anchored trivalent actinide complexes (Me,MeArO)3 ArAn (marked as [AnL]) with desirable electron transport between metal and ligand arene are investigated for H2 production. The metal center is changed from Ac to Pu. Electron-spin density calculations reveal a two-electron oxidative process (involving high-valent intermediates) for complexes [AnL] (An = P–Pu) along the catalytic pathway. The electrons are provided by both the actinide metal and the arene ring of ligand. This is comparable to the previously reported uranium catalyst (Ad,MeArO)3 mesU (Ad = adamantine and mes = mesitylene). From the thermodynamic and kinetic perspectives, [PaL] offers appreciably lower reaction energies for the overall catalytic cycle than other actinide complexes. Thus, the protactinium complex tends to be the most reactive for H2O reduction to produce H2 and has the advantage of its experimental accessibility.

Weak Bimetal Coupling-Assisted MN4 Catalyst for Enhanced Carbon Dioxide Reduction Reaction

“…The type of chemical bond can be identified based on the QTAIM values. It can be observed that the energy density H ( r ) of the M o –O bond in U i Mo o – O CO is negative, and ρ( r ) > 0, ∇ 2 ρ( r ) > 0, suggesting a dative bond. ,, It is evident that U i Mo o – O CO exhibits larger absolute values than ones of U i Nd o – O CO and U i U o – O CO. This discrepancy suggests a stronger interaction of the Mo o –O bond, that is, Mo o has a stronger ability to adsorb CO 2 .…”

Unraveling complexation and enantioseparation of a new chiral‐at‐uranium complex to chiral pesticides R/S‐malaoxons

“…However, conducting experiments is bound to be difficult and contingent, so the use of computational methods can provide the theoretical basis and alternative solutions for experimental studies and avoid many risks. 3 The design and applications of uranyl complexes have been quite extensive, such as studies employing uranyl complexes for the separation of lanthanides and actinides, [4][5][6][7][8][9] the separation of chiral enantiomers, [10][11][12][13][14][15][16] and the removal and extraction of radionuclides. [17][18][19][20] Among them, the separation of chiral enantiomers using uranyl-containing receptors is a promising and valuable study.…”