Interaction of carbon dioxide with Ni(110): A combined experimental and theoretical study

Abstract

We present a combined experimental and theoretical study of the CO(2) interaction with the Ni(110) surface. Photoelectron spectroscopy, temperature-programmed desorption, and high-resolution electron energy loss spectroscopy measurements are performed at different coverages and for increasing surface temperature after adsorption at 90 K with the aim to study the competing processes of CO(2) dissociation and desorption. Simulations are performed within the framework of density functional theory using ab initio pseudopotentials, focusing on selected chemisorption geometries, determining the energetics and the structural and vibrational properties. Both experimental and theoretical vibrational frequencies yield consistent indications about two inequivalent adsorption sites that can be simultaneously populated at low temperature: short-bridge site with the molecular plane perpendicular to the surface and hollow site with the molecular plane inclined with respect to the surface. In both sites, the molecule has pure carbon or mixed oxygen-carbon coordination with the metal and is negatively charged and bent. Predicted energy barriers for adsorption and diffusion on the surface suggest a preferential adsorption path through the short-bridge site to the hollow site, which is compatible with the experimental findings. Theoretical results qualitatively support literature data concerning the increase of the work function upon chemisorption

CO2 dissociation on Ni(211)

“…Both 10 and 11 have very close E ads (À3.03 and À3.07 eV, respectively), while 9 is much higher in energy (À2.51 eV). There are three co-adsorption modes (12)(13)(14) for HCOO dissociation from 9 to 11, respectively, and 14 has the largest co-E ads of 14 (À2.98 eV) from free CO 2 molecule, while 12 is the lowest (À2.34 eV).…”

“…Recently, Wang et al [11] calculated CO 2 adsorption and activation on Ni(1 1 1), (1 0 0) and (1 1 0), and found that CO 2 adsorption is more favored on (1 1 0). The interaction of CO 2 with Ni(1 1 0) [12,13] and Co(1 1 1) [14] also is investigated in detail, and the most stable adsorbed structure is asymmetric with carbon close to the surface and oxygen pointing upward.…”

First-principles calculations on the role of Ni-doping in Cu clusters: From geometric and electronic structures to chemical activities towards CO2

“…For instance, a recent theoretical calculation predicts that the degree of activation of CO 2 adsorbed on Cu(hkl) surfaces is in the order of Cu(110) > Cu(100) > Cu(111) [8], with an CO 2 adsorption energy of 0.335, 0.229 and 0.200 eV, respectively. It is claimed that Ni(110) [7] is the only transition metal surface of low Miller indices to bind CO 2 chemically (0.32 eV) under ultra high vacuum without the co-adsorption of alkali metals as electron donors [4]. Interestingly, recent experiments [9][10][11] show that Ni/Cu alloy system can be 60 times more active for CO 2 activation than pure Cu.…”

“…The above-mentioned synthesis reaction is performed at industrial scales on transition metal (TM)-based catalysts, such as Cu [2] and Ni [3]. However, recent studies show that except for alkali-metal promoted surfaces [4] and a few late TM elements, such as Fe [5], Co [6], Ni [3,7] and Cu [2,8], CO 2 adsorbs rather weakly on metal surfaces and is poorly activated. The degree of CO 2 activation is also sensitive to the surface structure.…”

A multi-technique study of CO2 adsorption on Fe3O4 magnetite

“…These positions are similar to those reported on Ni(110) surface, where the CO 2 is physisorbed in a linear configuration. 38 C 1s spectra of 0.18 × 10 14 CO 2 /cm 2 (see Fig. S5 of the supplementary material), which corresponds to saturation of the defect peaks plus 1% of the monolayer coverage, reveal a single peak at 291.3 eV, identical to that of the physisorbed monolayer.…”