Unveiling CO adsorption on Cu surfaces: new insights from molecular orbital principles

Published on Oct 17, 2018in Physical Chemistry Chemical Physics3.43
· DOI :10.1039/C8CP04253E
Kareem M. Gameel4
Estimated H-index: 4
(The: American University in Cairo),
Icell M. Sharafeldin5
Estimated H-index: 5
(The: American University in Cairo)
+ 2 AuthorsNageh K. Allam36
Estimated H-index: 36
(The: American University in Cairo)
Sources
Abstract
CO adsorption on Cu(100), (110), and (111) surfaces has been extensively studied using Kohn–Sham density functional theory calculations. A holistic analysis of adsorption energies, charge transfer, and structural changes has been employed to highlight the variations in adsorption mechanisms upon changing the surface type and the adsorption site. Each surface, with its unique arrangement of atoms, resulted in a varying adsorbate behavior, although the same adsorption site is considered. This directly reflects the influence of the atomic arrangement on the substrate–adsorbate interactions. Site-interactions are rigorously investigated using molecular-orbital and charge transfer principles taking into account the fundamental interaction of frontier (5σ and 2π*) orbitals. Considering the effects of the surface atomic arrangement and density of metal interacting orbitals, along with the relative d-5σ and d-2π* energy spacings, the calculated adsorption preference to higher coordination sites is explained, which also revealed valuable interpretations to the well-known DFT CO adsorption puzzle. In addition, we studied the perturbations occurring upon adsorption to the 3σ and 1π orbitals, which hold the internal C–O bond. Studying 3σ and 1π orbital perturbations provided a wealth of theoretical interpretations for the varying behavior of the adsorbate molecule when similar adsorption sites are compared at different facets.
📖 Papers frequently viewed together
2006
1 Citations
15 Citations
4 Citations
References38
Newest
#1Icell M. Sharafeldin (The: American University in Cairo)H-Index: 5
#2Nageh K. Allam (The: American University in Cairo)H-Index: 36
The gas sensing process involves complicated and precise adsorption mechanisms, and the selection of the right material is mainly based on “guess-and-check” procedures, which necessitates the search for a more systematic approach to discover optimum materials with required specifications. Herein, we report the use of ab initio first-principles methods to expedite the process of finding the material with the highest potential compared to in-lab trial and error. We focused on the NO2 adsorption me...
14 CitationsSource
The so-called CO/Pt(111) puzzle, the experimentally demonstrated preference of CO to adsorb on the top site on the Pt(111) surface rather than the 3-fold hollow sites predicted by standard density functional theory (DFT) methods, was alleged to be solved by properly leveling the CO frontier molecular orbitals. However, the subtle energy difference between the top and hollow sites is of the same order of magnitude as the possible contribution of dispersive forces to this interaction. Herein, the ...
17 CitationsSource
#1Helena Muñoz-Galán (University of Barcelona)H-Index: 1
#2Francesc Viñes (University of Barcelona)H-Index: 36
Last. Francesc Illas (University of Barcelona)H-Index: 85
view all 5 authors...
Here we present a density-functional theory (DFT) study on the suitability of modern corrections for the inclusion of dispersion-related terms (DFT-D) in treating the interaction of graphene and metal surfaces, exemplified by the graphene/Ni(111) system. The Perdew–Burke–Ernzerhof exchange–correlation functional is used as basis, on top of which we tested the family of Grimme corrections (D2 and D3, including Becke–Johnson damping and the Andersson approach) as well as different flavors of the a...
13 CitationsSource
#1Patanachai Janthon (University of Barcelona)H-Index: 5
#2Francesc Viñes (University of Barcelona)H-Index: 36
Last. Francesc IllasH-Index: 85
view all 5 authors...
Graphene-metal contacts have emerged as systems of paramount importance in the synthesis of high-quality and large-size patches of graphene and as vital components of nanotechnological devices. Herein, we study the accuracy of several density functional theory methods using van der Waals functionals or dispersive forces corrections when describing the attachment of graphene on Ni(111). Two different experimentally observed chemisorption states, top-fcc and bridge-top, were put under examination,...
43 CitationsSource
#1Laurids Schimka (University of Vienna)H-Index: 6
#2Judith Harl (University of Vienna)H-Index: 12
Last. Georg Kresse (University of Vienna)H-Index: 125
view all 7 authors...
Although density functional theory is widely used in surface science, it has a tendency to predict surfaces to be more stable than they actually are experimentally. Using a many-electron approach such as the random-phase approximation enables accurate surface and adsorption energies for carbon monoxide and benzene on metal surfaces to be determined.
444 CitationsSource
#1Predrag Lazić (Forschungszentrum Jülich)H-Index: 27
#2Mojtaba Alaei (IUT: Isfahan University of Technology)H-Index: 7
Last. Stefan Blügel (Forschungszentrum Jülich)H-Index: 85
view all 6 authors...
We study the chemisorption of CO molecule into sites of different coordination on (111) surfaces of late 4dand 5dtransition metals. In an attempt to solve the well-known CO adsorption puzzle, i.e., discrepancies of adsorption site preferences with experiment which appear in the standard density functional theory calculations, we have applied the relatively new van der Waals-density functional of nonlocal correlation. In all considered cases this reduces or completely solves the site prefer...
96 CitationsSource
A study of the adsorption of CO on late 4d and 5d transition metal (111) surfaces (Ru, Rh, Pd, Ag, Os, Ir and Pt) considering atop and hollow site adsorption is presented. The applied functionals include the gradient-corrected Perdew–Burke–Ernzerhof (PBE) and Becke–Lee–Yang–Parr (BLYP) functionals, and the corresponding hybrid Hartree–Fock density functionals HSE and B3LYP. We find that PBE-based hybrid functionals (specifically HSE) yield, with the exception of Pt, the correct site order on all...
263 CitationsSource
#1Alessandro Stroppa (University of Vienna)H-Index: 36
#2Konstantinos Termentzidis (University of Vienna)H-Index: 20
Last. Jiirgen Hafner (University of Vienna)H-Index: 12
view all 5 authors...
We present a detailed study of the adsorption of CO on Cu, Rh, and Pt (111) surfaces in top and hollow sites. The study has been performed using the local density approximation, the gradient corrected functional PBE, and the hybrid Hartree-Fock density functionals PBE0 and HSE03 within the framework of generalized Kohn-Sham density functional theory using a plane-wave basis set. As expected, the local density approximation and generalized gradient approximation functionals show a tendency to fav...
150 CitationsSource
#1Qing-Miao Hu (MPG: Max Planck Society)H-Index: 25
#2Karsten Reuter (MPG: Max Planck Society)H-Index: 71
Last. Matthias Scheffler (MPG: Max Planck Society)H-Index: 142
view all 3 authors...
It is shown that the errors of present-day exchange-correlation (XC) functionals are rather short ranged. For extended systems, the correction can therefore be evaluated by analyzing properly chosen clusters and employing highest-quality quantum chemistry methods. The XC correction rapidly approaches a universal dependence with cluster size. The method is applicable to bulk systems as well as to defects in the bulk and at surfaces. It is demonstrated here for CO adsorption at transition-metal su...
130 CitationsSource
#1Sara E. Mason (UPenn: University of Pennsylvania)H-Index: 13
#2Ilya GrinbergH-Index: 38
Last. Andrew M. RappeH-Index: 83
view all 3 authors...
We use density functional theory (DFT) with the generalized gradient approximation (GGA) and our first-principles extrapolation method for accurate chemisorption energies (Mason et al. Phys. Rev. B 2004, 69, 161401R) to calculate the chemisorption energy for CO on a variety of transition metal surfaces for various adsorbate densities and patterns. We identify adsorbate through-space repulsion, bonding competition, and substrate-mediated electron delocalization as key factors determining the pref...
27 CitationsSource
Cited By12
Newest
#1Ahmed H. Biby (The: American University in Cairo)H-Index: 3
#2Sarah A. Tolba (The: American University in Cairo)H-Index: 5
Last. Nageh K. Allam (The: American University in Cairo)H-Index: 36
view all 3 authors...
Abstract The development of efficient photoelectrodes via defect engineering of wide-band gap metal oxides has been the prime focus for many years. Specifically, the effect of carbon defects in wide-band gap metal oxides on their performance in photoelectrochemical (PEC) applications raised numerous controversies and still elusive. Herein, the effect of various carbon defects in m-ZrO2 was investigated using the density functional theory to probe the thermodynamic, electronic, and optical proper...
1 CitationsSource
#1Nicolas Néel (Technische Universität Ilmenau)H-Index: 22
#2Jörg Kröger (Technische Universität Ilmenau)H-Index: 34
The control and observation of reactants forming a chemical bond at the single-molecule level is a longstanding challenge in quantum physics and chemistry. Using a single CO molecule adsorbed at the apex of an atomic force microscope tip together with a Cu(111) surface, the molecular bending is induced by torques due to van der Waals attraction and Pauli repulsion. As a result, the vertical force exhibits a characteristic dip-hump evolution with the molecule-surface separation, which depends sen...
Source
The water-gas shift (WGS) reaction is a key step in hydrogen production, particularly to meet the high-purity H2 requirement of PEM fuel cells. The catalysts currently employed in large-scale WGS plants require a two-step process to overcome thermodynamic and kinetic limitations. Ni-Cu/CeO2 solids are promising catalysts for the one-step process required for small-scale applications, as the addition of Cu hinders undesired methanation reactions occurring on Ni/CeO2. In this work, we performed ca...
Source
#1Dhanshree Pandey (HBNI: Homi Bhabha National Institute)H-Index: 4
#2C. Kamal (HBNI: Homi Bhabha National Institute)H-Index: 13
Last. Aparna Chakrabarti (HBNI: Homi Bhabha National Institute)H-Index: 21
view all 4 authors...
Abstract Using van der Waals dispersion corrected density functional theory, we study the adsorption of three environmentally important gases, namely, H2, CO and NO on the pristine Aluminene as well as transition metal (TM) atom substituted Aluminene surface. Interestingly, we observe enhanced adsorption of all the gases for the TM-substituted Aluminene, when compared to the pristine case. It has been found that the Kubas interaction plays an important role in stabilizing the H2 adsorption on TM...
3 CitationsSource
#1Damian GizińskiH-Index: 1
#2Anna BrudziszH-Index: 1
Last. Tomasz CzujkoH-Index: 26
view all 6 authors...
3 CitationsSource
#1S. Amaya-Roncancio (CONICET: National Scientific and Technical Research Council)H-Index: 6
#2L. Reinaudi (CONICET: National Scientific and Technical Research Council)H-Index: 1
Last. M. Cecilia Gimenez (National University of Cordoba)H-Index: 5
view all 3 authors...
Abstract Adsorption and dissociation of carbon monoxide on metal clusters M13 (M = Ag, Co, Cu, Fe, Ni and Ru), has been studied. Structure stabilities of metal clusters, adsorption sites, adsorption energies and the activation energies for the dissociation of CO were determined using density functional theory. Cohesive and binding energies of metal atoms in M13 clusters of studied metals were calculated, showing the different strength interaction of metal atoms in each particle. Three active ads...
1 CitationsSource
#1Rong Wang (Harbin University of Science and Technology)
#2Beien Zhu (CAS: Chinese Academy of Sciences)H-Index: 14
Last. Yi Gao (CAS: Chinese Academy of Sciences)H-Index: 50
view all 4 authors...
CO2 reduction has attracted extensive attentions for its wide applications in chemical engineering and green chemistry. As one of major commercial catalysts, Cu have been widely studied considering its low price and high catalytic efficiency. However, previous studies were mostly focused on the Cu(111) surface, while other surfaces were rarely studied. In this work, we employed the density functional theory calculations to fully investigate the adsorption of all intermediates and products of CO2...
Source
#1Heyuan Huang (TJU: Tianjin University)H-Index: 3
#2Yingzhe Yu (TJU: Tianjin University)H-Index: 13
Last. Minhua Zhang (TJU: Tianjin University)H-Index: 20
view all 3 authors...
Periodic density function theory (DFT) and kinetic Monte Carlo (kMC) method are carried out to investigate CO dissociation process on the Mn-doped Fe(100) surface. The energetics information of relevant atomistic processes and adsorption features of relevant species are obtained from DFT calculations. Subsequently, kMC simulations are performed with DFT results employed as database. Simulations show that the energy barriers for CHO and COH formations are 0.09 eV and 0.35 eV larger than that for ...
2 CitationsSource
#1Selin Demir (Bursa Technical University)H-Index: 1
#2Mehmet Ferdi Fellah (Bursa Technical University)H-Index: 12
Abstract In this study, Density Functional Theory calculations have been utilized for the platinum doped (4,0) single walled carbon nanotube (SWCNT) in order to investigate the use of the CO gas sensor at room temperature. Hybrid B3LYP method with 6-31G (d,p) basis set for C, O and H atoms and LanL2DZ basis set for Pt atom have been used in calculations. The structural and electronic properties have been detailed. The charge distributions obtained for structures showed that charge transfer was o...
8 CitationsSource
#1Basant A. Ali (The: American University in Cairo)H-Index: 9
#2Nageh K. Allam (The: American University in Cairo)H-Index: 36
Our life is turning into an electronic world where we need our devices charged all the time. Although batteries have been doing the job so far, we need devices that charge way faster with longer cycling stability. The answer could be supercapacitors; however, electrode materials that maintain both high energy density and high power density are yet to be discovered. Currently, researchers base their work on guess and check methods to modify electrode materials with limited organized work that tar...
15 CitationsSource