Unraveling the Role of Orbital Interaction in the Electrochemical HER of the Trimetallic AgAuCu Nanobowl Catalyst

Abstract

Unraveling the origins of the electrocatalytic activity of composite nanomaterials is crucial but inherently challenging. Here, we present a comprehensive investigation of the influence of different orbitals’ interaction in the AuAgCu nanobowl model electrocatalyst during the hydrogen evolution reaction (HER). According to our theoretical study, AgAuCu exhibits a lower energy barrier than AgAu and AgCu bimetallic systems for the HER, suggesting that the trimetallic AgAuCu system interacts optimally with H*, resulting in the most efficient HER catalyst. As we delve deeper into the HER activity of AgAuCu, it was observed that the presence of Cu allows Au to adsorb the H* intermediate through the hybridization of s orbitals of hydrogen and s, d x 2 –y 2, and d z 2 orbitals of Au. Such orbital interaction was not present in the cases of AgAu and AgCu bimetallic systems, and as a result, these bimetallic systems exhibit lower HER activities.

Directed Dual Charge Pumping Tunes the d‐Orbital Configuration of Pt Cluster Boosting Hydrogen Evolution Kinetic

“…[ 66–68 ] This optimization is beneficial for weakening the bonding between the reaction intermediate and the active site, thereby facilitating an efficient HER. [ 69,70 ] The conclusions drawn from these theoretical simulations confirm that the charge rearrangement around Pt active sites induced by EMSI and the ligand effect optimizes the H + adsorption and desorption behavior, resulting in improved HER kinetics.…”

Deciphering orbital hybridization in heterogeneous catalysis

“…43 Similar s-p orbital interactions for HER to favorable H desorption could also be found in MoS 2 systems with the non-metal S as the active sites and other related systems with s orbital electrons such as Au. 44,45 These above-mentioned active catalytic sites are mainly unique main group elements. The interactions could be apparently altered once changing catalytic sites from the main group elements to most of the TMs with localized sharp d orbital beneath Fermi level.…”

Manipulating the Spatial Position of Ru Confined in the Co Crystal Lattice Encapsulated in the Metal–Organic Framework Matrix To Boost Hydrogen Evolution Reaction

“…Zeolitic imidazolate frameworks (ZIFs) are a type of metal–organic framework (MOF) consisting of organic ligands linked by coordination bonds and metal ions/clusters. − With regular morphology and ordered porous channel structure, ZIFs are widely used as a versatile template to prepare electrocatalysts with tunable structures and composition. − At present, a variety of synthetic strategies of MOF-derived electrocatalysts have been developed, e.g., defect engineering, , microstructure modulation, and heteroatom doping, which might enhance the catalytic HER activity by exposing additional catalytic active sites and optimizing the electronic structure of catalytic materials. For instance, bimetallic active site electrocatalysts have a “ligand” effect due to the charge transfer between atoms of two different groups, which makes the electrocatalytic performance superior to that of single-site electrocatalysts. − More importantly, MOF is a well-defined platform to regulate the specific spatial loading position, which is crucial for an electrocatalyst to maximize the active metal sites with suitable local coordination environment, , optimize the mass and charge transportation process and simultaneously protect the metal sites from corrosion with electrolyte, , thus enhancing the catalytic durability during practical electrochemical reaction.…”