Silicon Clathrate-Supported Catalysts with Low Work Functions for Ammonia Synthesis.

Diamond-type silicon has a work function of ≈4.8 eV, and conventional n- or p-type doping modifies the value only between 4.6 and 5.

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

Actinide complexes, which could enable the electrocatalytic HO 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 (ArO)An (marked as [AnL]) with desirable electron transport between metal and ligand arene are investigated for H production. The metal center is changed from Ac to Pu.

CO Cleavage Reaction Driven by Alkylidyne Complexes of Group 6 Metals and Uranium: A Density Functional Theory Study on Energetics, Reaction Mechanism, and Structural/Bonding Properties.

Designing novel catalysts is essential for the efficient conversion of metal alkylidyne into metal oxo ketene complexes in the presence of CO, which to some extent resolves the environmental concerns of the ever-increasing carbon emission. In this regard, a series of metal alkylidyne complexes, []M≡CCH(THF) ([] = {(CH[C(CF)O])N}; M = Cr, Mo, W, and U), have been comprehensively studied by relativistic density functional theory calculations. The calculated thermodynamics and kinetics unravel that the tungsten complex is capable of catalyzing the CO cleavage reaction, agreeing with the experimental findings for its analogue.

Relativistic DFT Probe for Reaction Energies and Electronic/Bonding Properties of Polypyrrolic Hetero-Bimetallic Actinide Complexes: Effects of Uranyl -Oxo Functionalization.

A series of hetero-bimetallic actinide complexes of the Schiff-base polypyrrolic macrocycle (L), featuring cation-cation interactions (CCIs), were systematically investigated using relativistic density functional theory (DFT). The tetrahydrofuran (THF) solvated complex [(THF)(OUOU)(THF)(L)] has high reaction free energy (Δ), and its replacement with electron-donating iodine promotes the reaction thermodynamics to obtain uranyl iodide [(I)(OUOU)(I)(L)] (-). Retaining this coordination geometry, calculations have been extended to other An(IV) (An = Th, Pa, Np, Pu), i.

Main-Group Metals Stabilized Polypyrrolic Uranyl(V) Complexes via Cation-Cation Interaction with the Uranyl -Oxo Atom: A Relativistic Density Functional Theory Study.

To explore the innovative uranyl(V) complexes by deeply understanding their coordination stability, relativistic density functional theory calculations have been performed to investigate the experimentally reported [(py)(RAlOUO)(py)(HL)] [R = Me (), Bu ()] and [{(py)MOUO}(py)(HL)] [M = Li (), Na (), K ()] and their uranyl(VI) counterparts. Structural and topological analyses along with transformation-reaction energies and redox potentials were systematically studied. Geometrical and quantum theory of atoms in molecules analyses implied a linear U-O-M feature in - and a bent one in and .

Actinyl-Modified g-CN as CO Activation Materials for Chemical Conversion and Environmental Remedy via an Artificial Photosynthetic Route.

With the reported CO activation for the oxidation of benzene to phenol (-ENE → -OL) by the graphitic carbon nitride g-CN () via an artificial photosynthetic route as inspiration, -valent actinyls (AnO) (An = U, Np, Pu; m = VI, V; = 2, 1) have been introduced for its further modification. Our calculations indicate thermodynamic spontaneity in the feasibility of g-CN-(AnO) () formation. The magnificent structural and electronic properties of are utilized for CO activation in terms of the rarely studied -ENE → -OL conversion.

Inverse Trans Influence in Low-Valence Actinide-Group 10 Metal Complexes of Phosphinoaryl Oxides: A Theoretical Study via Tuning Metals and Donor Ligands.

The recognition and in-depth understanding of inverse trans influence (ITI) have successfully guided the synthesis of novel actinide complexes and enriched actinide chemistry. Those complexes, however, are mainly limited to the involvement of high-valence actinide and/or metal-ligand multiple bonds. Examples containing both low oxidation state actinide and metal-metal single bond remain rare.