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We investigated the adsorption of CO on the flat, stepped, and kinked copper surfaces from density functional theory calculations as well as the temperature programmed desorption and X-ray photoelectron spectroscopy. Several exchange-correlation functionals have been considered to characterize CO adsorption on the copper surfaces. We used the van der Waals density functionals (vdW-DFs), i.e., the original vdW-DF (vdW-DF1), optB86b-vdW, and rev-vdW-DF2, as well as the Perdew-Burke-Ernzerhof (PBE) with dispersion correction (PBE-D2). We have found that vdW-DF1 and rev-vdW-DF2 functionals slightly underestimate the adsorption energy, while PBE-D2 and optB86b-vdW functionals give better agreement with the experimental estimation for CO on Cu(111). The calculated CO adsorption energies on the flat, stepped, and kinked Cu surfaces are 20-27 kJ/mol, which are compatible with the general notion of physisorbed species on solid surfaces. Our results provide a useful insight into appropriate vdW functionals for further investigation of related CO activation on Cu surfaces such as methanol synthesis and higher alcohol production.

We studied the dissociative adsorption of CO2 to CO + O on the Cu(111), Cu(221), Cu(211), and Cu(11 5 9) surfaces by using state-of-the-art density functional theory (DFT) within a generalized gradient approximation (GGA) and van der Waals density functional (vdW-DF) calculations. The activation energy for CO2 dissociation on the flat Cu(111) surface is 1.33 eV. The activation energies on stepped and kinked surfaces are 1.06 eV, 0.67 eV, and 1.02 eV for the Cu(221), Cu(211), and Cu(11 5 9) surfaces, respectively. Even though the activation energy is 0.66 eV lower on the stepped Cu(211) surface than on the flat Cu(111) surface, we conclude that CO2 does not dissociate on "ideal" flat, stepped, or kinked Cu surfaces at low temperature. We attribute the discrepancy between our theoretical results and experimentally observed CO2 dissociation on stepped Cu surfaces below 150 K to other factors such as effects of Cu adatoms, gas phase or condensed CO2 molecules, or interaction with other gas phase molecules.

We performed ab initio molecular dynamics analysis of formate decomposition to CO and H on a Cu(111) surface using van der Waals density functionals. Our analysis shows that the desorbed CO has approximately twice larger bending vibrational energy than the translational, rotational, and stretching vibrational energies. Since formate synthesis, the reverse reaction of formate decomposition, has been suggested experimentally to occur via the Eley-Rideal mechanism, our results indicate that the formate synthesis can be enhanced if the bending vibrational mode of CO is excited rather than the translational and/or stretching vibrational modes. Detailed information on the energy distribution of desorbed CO as a formate decomposition product may provide new insights for improving the catalytic activity of formate synthesis.

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We present a density functional theory study on the adsorption and decomposition mechanisms of monomeric formic acid (HCOOH) on a Cu(111) surface. We used Perdew-Burke-Ernzerhof (PBE) functional, PBE with dispersion correction (PBE-D2), and van der Waals density functionals (vdW-DFs). We found that the adsorption energy of HCOOH by using the PBE functional is smaller than the experimental value, while the PBE-D2 and vdW-DFs give better agreement with experimental results. The activation energies of decomposition calculated by using PBE-D2 and vdW-DFs are lower compared with desorption energies, seemingly in contradiction with experimental findings at room temperature, in which no decomposition of HCOOH on Cu(111) is observed when the surface is exposed to the gas phase HCOOH. We performed the reaction rate analysis based on the first-principles calculations for desorption and decomposition processes to clarify this contradiction. We found that the desorption of monomeric HCOOH is faster than that of its decomposition rate at room temperature because of a much larger pre-exponential factor. Thus, no decomposition of monomeric HCOOH should take place at room temperature. Our analysis revealed the competition between desorption and decomposition processes of HCOOH.

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We have studied the dissociation process of nitric oxide (NO) on Cu(110) and the influence of the hydrogen bond with water by means of density functional theory calculations. We have found that an upright NO adsorbed at a short-bridge site and a side-on NO at a hollow site connecting two short-bridge sites are the two most stable molecularly adsorbed states, and the latter is the precursor for the dissociation process. Various NO dissociation pathways under the influences of the hydrogen bonds with water have been investigated. We have found that hydrogen bonds efficiently reduce the activation energy of NO dissociation by the introductions of a water dimer to O and water dimers to both sides of the side-on NO, respectively. More importantly, the promoting effect of water molecules on NO dissociation is dominant only when one of water molecules in a water dimer forms a hydrogen bond with O of the side-on NO. Our results provide a physical insight into the promoting effect of hydrogen bonds with water, which may be helpful in improving the catalytic activity as well as designing novel catalysts for NO reduction.