HCN Adsorption on the Fe(100), Fe(111) and Fe(110) Surfaces: a Density Functional Theory Study

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Twenty kinds of adsorptions of HCN on the Fe(100), Fe(111) and Fe(110) surfaces at the 1/4 monolayer coverage are found using the density functional theory. For Fe(100), the adsorption energy of the most stable configuration where the HCN locates at the fourfold site with the C-N bonded to four Fe atoms is 1.928 eV. The most favored adsorption structure for HCN on Fe(111) is f-η3(N)-h-η3(C), in which the C-N bond is almost parallel to the surface, and the adsorption energy is 1.347 eV. On Fe(110), the adsorption energy in the most stable configuration in which HCN locates at the two long-bridge sites is 1.777 eV. The adsorption energy of the parallel orientation for HCN is larger than that of the perpendicular configuration. The binding mechanism of HCN on the Fe(100), Fe(111) and Fe(110) surfaces is also analyzed by Mulliken charge population and the density of states in HCN. The result indicates that the configurations in which the adsorbed HCN becomes the non-linear are beneficial to the formation of the addition reaction for hydrogen. The nature that the introduction of Fe into the catalyst could increase the catalytic activity of the bimetallic catalyst in the addition reaction of hydrogen for nitriles is revealed. Twenty kinds of adsorption of HCN on the Fe (100), Fe (111) and Fe (110) surfaces at the 1/4 monolayer coverage are found using the density functional theory. For Fe (100), the adsorption energy of the most stable configuration where the HCN locates at the fourfold site with the CN bonded to four Fe atoms is 1.928 eV. The most favored adsorption structure for HCN on Fe (111) is f-η3 (N) -h-η3 (C), in which the CN bond is almost parallel to the surface, and the adsorption energy is 1.347 eV. On Fe (110), the adsorption energy in the most stable configuration where HCN locates at the two long-bridge sites is 1.777 eV. The binding mechanism of HCN on the Fe (100), Fe (111) and Fe (110) surfaces is also analyzed by Mulliken charge population and the density of states in HCN. The result indicates that the configurations in which the adsorbed HCN becomes the non-linear are beneficial to the formation of the addition reaction for hydrogen. The nature that the introduction of Fe into the catalyst could increase the catalytic activity of the bimetallic catalyst in the addition reaction of hydrogen for nitriles is revealed.
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