Abstract
•Bimetallic clusters Pd3M2 are computationally probed as catalyst for Li-O2 battery.•The gap at the Fermi energy of the system can be tailored by alloying.•Pd3Pt2 and Pd3Cu2 clusters show promising result.
We performed computational investigation of the adsorption of bimetallic Pd3M2 (where M changes from Ag, Au, Co, Cu, Mn, Ni, Pt, and Ru) cluster on the hydroxylated alumina surface. Previously, it was shown that small silver cluster can control the rate of discharge at the cathode of lithium-oxygen battery. The gap near the fermi energy was shown to control the oxygen reduction, an important reaction for LiO2 formation. Controlling the gap would ultimately control the rate of LiO2 formation. One can vary the size of the cluster to vary the gap, however, this “knob” provides limited variance in the gap. Alloying, in combination with size variation offer a much wider control of the gap, hence the LiO2 formation. Using Density Functional Theory (DFT), we determined the most stable geometry of the bimetallic clusters Pd3M2 and calculated the binding energies of these clusters on the alumina substrate which ranges from 0.2 eV to 0.25 eV depending upon the composition of the alloy-cluster, its orientation and the adsorption site. We also find that Pd atoms bind strongly with the substrate oxygen atoms with an average short bond-length of about 2.2 Å. We explored how the gap at the Fermi level of the system varies as a function of elemental composition and the calculated gap ranges from 0 meV to 90 meV. Charges distribution using Bader analysis was also performed to probe how charges are transferred between the cluster and the substrate. These preliminary results will open the door for more systematic studies of alloy clusters of different size and stoichiometry for Li-O2 battery cathode design.
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