How electron-deficient Cp ligand facilitates Rh-catalyzed annulations with alkynes

The mechanism and origin of CpX ligand effects on Rh-catalyzed annulations with alkynes were investigated by using DFT calculations and the approach of energy decomposition analysis (EDA). The results reveal...

First-Principles Study of Pt-Based Bifunctional Oxygen Evolution & Reduction Electrocatalyst: Interplay of Strain and Ligand Effects

We examined the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) of Pt-based Pt3M/Pt nanoalloy catalysts (where M represents a 3d transition metal) for bifunctional electrocatalysts using spin-polarized density functional theory calculations. First, the stability of the Pt3M/Pt catalyst was investigated by calculating the bulk formation energy and surface separation energy. Using the calculated adsorption energies for the OER/ORR intermediates in the modeled catalysts, we predicted the OER/ORR overpotentials and potential limiting steps for each catalyst. The origins of the enhanced catalytic reactivity in Pt3M/Pt catalysts caused by strain and ligand effects are explained separately. In addition, compared to Pt(111), the OER and ORR activities in a Pt3Ni/Ptskin catalyst with a Pt skin layer were increased by 13.7% and 18.4%, respectively, due to the strain and ligand effects. It was confirmed that compressive strain and ligand effects are key factors in improving the catalytic performance of OER/ORR bifunctional catalysts.

Ligand Effects on Intramolecular Configuration, Intermolecular Packing, and Optical Properties of Metal Nanoclusters

Surface modification has served as an efficient approach to dictate nanocluster structures and properties. In this work, based on an Ag22 nanocluster template, the effects of surface modification on intracluster constructions and intercluster packing modes, as well as the properties of nanoclusters or cluster-based crystallographic assemblies have been investigated. On the molecular level, the Ag22 nanocluster with larger surface steric hindrance was inclined to absorb more small-steric chlorine but less bulky thiol ligands on its surface. On the supramolecular level, the regulation of intramolecular and intermolecular interactions in nanocluster crystallographic assemblies rendered them CIEE (crystallization-induced emission enhancement)-active or -inactive nanomaterials. This study has some innovation in the molecular and intramolecular tailoring of metal nanoclusters, which is significant for the preparation of new cluster-based nanomaterials with customized structures and enhanced performances.