CO Desorption from Oxygen Species on Carbonaceous Surface: 1. Effects of the Local Structure of the Active Site and the Surface Coverage
نویسندگان
چکیده
A systematic theoretical study using the density functional theory is performed to provide molecular-level understanding on the desorption of carbon monoxide from surface oxygen complexes that are formed in the gasification and combustion of coal. Particularly, a CO molecule release from carbonyl oxygen complexes in the presence of different oxygen environments was analyzed. Molecular carbonyl models of different sizes in the zigzag, armchair, and tip shapes of the active sites were selected. It was found that the shape of the local active site has a strong effect on the CO desorption energy, and they are correlated with the broaden feature of the CO molecule desorption in the temperature-programmed desorption (TPD) experiments of oxidized carbonaceous material. The calculated desorption activation energy range is in good agreement with experimental data. Molecular size convergence analyses on the carbonyl models suggest that the smallest graphene molecular system for accurate desorption structure on char is a three-ring molecule. The activation energy and normal-mode analyses for selected carbonyl complexes suggest that carbonyl surface oxygen complexes are stable structures and that they can be considered as labile surface oxygen complexes. The CO molecule desorption energy is affected by the influence of different neighboring surface oxygen groups on the carbon surface as well as the aromatic character of the molecular models. The desorption energy analysis suggests that the CO molecule can be adsorbed on clean carbonized surface to form stable structures. The preadsorbed oxygen group decreases the CO adsorption sticking probability on oxidized materials, but it remains an energetically favorable process.
منابع مشابه
Kinetic study of CO desorption from cathodic electrochemically treated carbon paper supported Pt electrodes
Platinum particles were grown directly by an electrodeposition process on electrochemically treated carbon paper (CP) for kinetic study of carbon monoxide (CO) desorption. The treatment on CP was performed by applying −2 V for cathodic oxidation over 5 min. Treated CP was characterized by FTIR to investigate the oxygen groups on its surface. CO surface coverage at each temperature was determine...
متن کاملCoadsorption of Dioxygen and Carbon Monoxide on a Mg(100) Surface
The activation of carbon monoxide by oxygen on Mg(100) surface has been investigated by X-ray photoelectron spectroscopy (XPS). Carbon monoxide is only weakly adsorbed (dispersion-type forces) on a magnesium surface. The XPS result has shown that the dissociation of carbon monoxide leading to the formation of a metastable surface carbonate species occurs through the participation of an oxyg...
متن کاملCO Adsorption on the V (100) Surface: A Density Functional Study
Adsorption of CO molecule on the Vanadium surface has been studied by using of the DFT method with LANL2DZ,6-31G* and 6-31G** basis sets by GGA approximation of theory. Using periodic first principles simulations we investigate the interaction of oxygen molecule with regular V (100) surface. The limitation of this approach is the use of thin metallic slabs with a limited range for their coverag...
متن کاملInvestingation and Chemisorption study of Oxygen Atoms and Cr (100) surface by DFT calculation
This study concerns about quantum chemical modeling behavior of 02 on Cr (100)surface by using density functional theory (DFT) by LANL2DZ and 6 — 31G* basissets, we presented the results of our first principles electronic structure calculationson the 02 molecules and their interface with Cr (100) surface. The chromium metalhas the body-centered cubic structure, and chromium cluster has five Cr ...
متن کاملThe effect of surface chemical functional groups on the adsorption and desorption of a polar molecule, acetone, from a model carbonaceous surface, graphite
The role of surface chemical heterogeneity in adsorption on a model carbonaceous surface (highly oriented pyrolitic graphite, HOPG) was investigated by temperature programmed desorption of acetone, a representative polar volatile organic compound. It was observed that oxygen-containing functional groups exist on air cleaved HOPG. The presence of surface functional groups reduces the binding ene...
متن کامل