Single‐point Attack of Two H₂O Molecules towards a Lewis Acid Site on the GaAl₁₂ Clusters for Hydrogen Evolution

Abstract

The hydrogen evolution reaction (HER) of water with metallic aluminum-based materials provides an important way to address the global energy challenge; however, fundamental mechanism and reaction dynamics governing the chemical and electronic properties remain a debated research topic. Here we further study the HER mechanisms for water splitting on typical 13-atoms clusters, Al 12 Ga and Al 13 , by first-principles DFT calculations. We noted that the doping of a Ga atom into the Al 13 cluster could reduce the transition state barrier for H 2 O dissociation on the metal cluster. Furthermore, it is interesting that the second water molecule prefers to adsorb on the same metal site giving rise to both thermodynamically and kinetically favorable reaction pathways. Based on the well-established complementary active sites (CAS) mechanism for metal cluster reactivity, we provide insights into the reaction dynamics of such metal clusters with two water molecules, which also sheds light on the Eley-Rideal and Langmuir-Hinshelwood mechanisms in surface science. Natural bond orbitals (NBO) analysis was conducted to evaluate the donor-acceptor charge-transfer interactions between the cluster and the nucleophilic reagent. These results gain a better understanding of the mechanism for water reacting with aluminum-based materials.[a] Dr.

Cluster−π Interactions Cause Size-Selective Reactivity of Cationic Silver Clusters with Acetylene: The Distinctive Ag7+[C2H2]

“…Quantum theory of atoms in molecules (AIM), electron localization function (ELF) analysis and noncovalent interaction plots based on independent gradient model (IGM), localized molecular orbital energy decomposition analysis (LMO-EDA), and natural bond orbital (NBO) − analysis were conducted to fully demonstrate the bond nature and strength of cluster−π noncovalent interactions in Ag 7 + [C 2 H 2 ] clusters. The NBO patterns are plotted via the software packages of visual molecular dynamics (VMD) , and Multiwfn . The LMO-EDA is calculated at the MP2 level of theory by the GAMESS program. , …”

Unravelling the Weak Interactions in Binary Clusters of Serotonin and Amino Acid Residues

“…The interaction energies are further corrected with basis‐set superposition errors (BSSEs) via the counterpoise procedure. Analyses on the quantum theory of atoms in molecules (AIM) and noncovalent interaction plots based on the independent gradient model (IGM) are carried out using the Multifunctional Wavefunction Analyzer (Multiwfn) software, and visualized by Visual Molecular Dynamics (VMD) package . Also, natural bond orbital (NBO) analysis, molecular electrostatic potential (MEP) analysis, and mutual penetration distance (MPD) analysis are conducted based on the DFT calculations.…”

Reactivity of Cobalt Clusters Con±/0 with Ammonia: Co3+ Cluster Catalysis for NH3 Dehydrogenation

“…In particular, the rate-determining single-step barrier energy (TS 2b ) drops to 1.28 eV, which is surmountable in view of an energy gain of 3.26 eV at the adsorption of two NH 3 molecules, and the final HER step is exothermic (2.42 eV). Previous experimental and theoretical studies on the reactivities of aluminum and aluminum iodide clusters with methanol have revealed that the presence of a first ligand could tune the charge distribution on metal cluster surfaces, thus affecting the reaction of the second molecule. − …”