CO2 hydrogenation to formic acid on Pd–Cu nanoclusters: a DFT study

Abstract

Carbon dioxide (CO₂) hydrogenation to formic acid is a promising method for the conversion of CO₂ to useful organic products. The interaction of CO₂ with hydrogen (H₂) on Pd_mCu_n (m + n = 4, 8 and 13) clusters to form formic acid (HCOOH) has been explored using density functional theoretical (DFT) calculations. Pd₂Cu₂, Pd₄Cu₄ and 13-atom Pd₁₂Cu clusters are found to be the most stable among all of the Pd_mCu_n (m + n = 4, 8 and 13) clusters with binding energies of −1.75, −2.16 and −2.40 eV per atom, respectively. CO₂ molecules get adsorbed on the Pd₂Cu₂, Pd₄Cu₄ and Pd₁₂Cu clusters in an inverted V-shaped way with adsorption energies of −0.91, −0.96 and −0.44 eV, respectively. The hydrogenation of CO₂ to form formate goes through a unidentate structure that rapidly transforms into the bidentate structure. To determine the transition state structures and minimum energy paths (MEPs) for CO₂ hydrogenation to formic acid, the climbing image nudge elastic band (CI-NEB) method has been adopted. The activation barriers for the formation of formic acid from formate on Pd₂Cu₂ and Pd₄Cu₄ are calculated to be 0.79 and 0.68 eV, respectively whereas that on the Pd₁₂Cu cluster is 1.77 eV. The enthalpy for the overall process of CO₂ hydrogenation to formic acid on the Pd₂Cu₂, Pd₄Cu₄ and Pd₁₂Cu clusters are found to be 0.83, 0.48 and 0.63 eV, respectively. Analysis of the density of states (DOS) spectra show that the 4d orbital of Pd, the 3d orbital of Cu, and the 2p orbitals of C and O atoms are involved in the bonding between CO₂ molecules and the Pd₂Cu₂ clusters. The CO₂ adsorption on the Pd_mCu_n (m + n = 4 and 8) clusters has also been explained in terms of the charge density distribution analysis.