Cho, Jinwon Lee, Sangheon Han, Jonghee Yoon, Sung Pil Nam, Suk Woo Choi, Sun Hee Lee, Kwan-Young Ham, Hyung Chul 2024-01-20T08:34:16Z 2024-01-20T08:34:16Z 2021-09-02 2014-10-02 1932-7447 https://pubs.kist.re.kr/handle/201004/126256 The critical role of the AgPd ligand effect (which is tuned by changing the number of Pd atomic layers) in determining the dehydrogenation and dehydration of HCOOH on the bimetallic Pd/Ag catalysts was elucidated by using the spin-polarized density functional theory (DFT) calculations. Our calculations suggest that the selectivity to H-2 production from HCOOH on the bimetallic Pd/Ag catalysts strongly depends on the Pd atomic layer thickness at near surface. In particular, the thinnest Pd monolayer in the Pd/Ag system is responsible for enhancing the selectivity of HCOOH decomposition toward H2 production by reducing the surface binding strength of specific intermediates such as HCOO and HCO. The dominant AgPd ligand effect by the substantial charge donation to the Pd surface from the subsurface Ag [which significantly reduce the density of state (particularly, d(z2-r2) orbital) near the Fermi level] proves to be a key factor for the selective hydrogen production from HCOOH decomposition, whereas the expansive (tensile) strain imposed by the underlying Ag substrate plays a minor role. This work hints on the importance of properly engineering the surface activity of the AgPd coreshell catalysts by the interplay between ligand and strain effects. English American Chemical Society OXIDATION PD PLATINUM SURFACE ADSORPTION GENERATION ELECTRODES METHANOL STRAIN HCOOH Importance of Ligand Effect in Selective Hydrogen Formation via Formic Acid Decomposition on the Bimetallic Pd/Ag Catalyst from First-Principles Article 10.1021/jp5050817 1 The Journal of Physical Chemistry C, v.118, no.39, pp.22553 - 22560 The Journal of Physical Chemistry C 118 39 22553 22560 scie scopus 000342652000018 2-s2.0-84907766294 Chemistry, Physical Nanoscience & Nanotechnology Materials Science, Multidisciplinary Chemistry Science & Technology - Other Topics Materials Science Article OXIDATION PD PLATINUM SURFACE ADSORPTION GENERATION ELECTRODES METHANOL STRAIN HCOOH Formic acid Pd/Ag alloy DFT