Computational Screening of Near-Surface Alloys for CO₂ Electroreduction

Abstract

Electrochemical conversion of carbon dioxide (CO 2 ) into chemical feedstocks provides an attractive solution to our pressing energy and environment problems. Here, we report that transition metal near-surface alloys (NSAs) are promising catalysts for CO 2 electroreduction. Based on first-principles calculations on 190 candidates, we propose a number of NSAs which show promise of highly active and selective catalysts for formic acid, carbon monoxide, methanol, and ethylene production, while simultaneously suppress competing hydrogen evolution reaction (HER). We predict that Pd/W, Au/Hf, and Au/Zr NSAs are more active than most known electrodes for formic acid formation with overpotentials significantly lower than that of HER. Ag/Hf and Ag/Zr are revealed as superior catalysts for the production of carbon monoxide with overpotentials of 0.77 V lower than that on pure Ag electrode. We find that methanol and ethylene can be produced on Ag/Ta and Ag/Nb NSAs whose overpotentials are ∼15% lower than that on Cu (211) surface. On the other hand, their overpotentials for HER are six times more negative than that on Cu (211). The work demonstrates the great potential of transition metal catalysts by modulating their near surface properties.

DFT Comparison the Performance of Pd10Sn5 and Pd10Ag5 Electrocatalyst for Reduction of CO2

“…The subsequent step of producing adsorbed CO is faster than the free energy of HCOOH. It shows that the stability of CO is greater than HCOOH, this is consistent with the conclusion that the adsorption of CO* is relatively strong on Cu, Pd and Pt 40 …”

Influence of Van der Waals Interactions on the Solvation Energies of Adsorbates at Pt‐Based Electrocatalysts

“…Therefore, here we study the role of vdW interactions on the solvation energy of hydroxyl (*OH) adsorbed on near‐surface alloys (NSAs) of Pt and late transition metals. Those versatile alloys are salient model catalysts for a variety of electrocatalytic reactions . We observe that: (i) the predictions of *OH solvation at Pt NSAs are comparable for PBE and PW91 (group 1); (ii) The predictions of *OH solvation at Pt NSAs are comparable among RPBE, vdW functionals and GGAs with dispersion corrections (group 2); and (iii) The *OH solvation energies decrease on average by ∼0.14 eV from functionals in group 2 with respect to those in group 1.…”

Electrochemical CO2 Reduction to C1 Products on Single Nickel/Cobalt/Iron‐Doped Graphitic Carbon Nitride: A DFT Study

“…All elementary steps with their free‐energy changes are presented in Table S4 (in the Supporting Information). The free energies of the initial protonation steps for CRR (*CO 2 +H + +e − →*COOH or *CO 2 +H + +e − →*OCHO) and HER (proton–electron pair, H + +e − ) can be calculated to discern the selectivity for CRR and HER . Figure shows the selectivity for CRR versus HER on Ni‐C 3 N 4 , Co‐C 3 N 4 , and Fe‐C 3 N 4 , in which the part below the dashed line are CRR‐selective catalysts.…”