The density functional theory (DFT) of the water-gas shift (WGS) reaction over molybdenum carbide was studied with the aim of understanding the dissociation of H(2)O, the OH group, and CO to determine on what sections of molybdenum carbide CO(2) and H(2) formed and whether they played a role in the reaction. The energy diagram of each elementary step, the reaction of the hydrogen and oxygen atoms with CO, and the transition state for this elementary step were also studied. The IR spectra of the CO adsorption was experimentally analyzed for the identification of several candidates of the CO adsorption modes. The adsorptions of the threefold Mo site (a) with and (b) without the underlying C atom of the second layer have the second and highest adsorption energies of -281.59 and -321.00 kJ/mol, respectively. The IR data showed that the bands at 1626 cm(-1) from the IR experiments are (a) the nearest adsorption of the threefold Mo site with the underlying C atom at the calculated/corrected band of 1621 cm(-1). The calculated/corrected threefold adsorption (b) had the highest adsorption energy but exhibited an IR band at 1147 cm(-1) which was not observed in the experimental data. The C-O bond length increased to 1.49 from 1.36 after the H(2)O adsorption (b), suggesting the dissociation of C-O after the H(2)O coadsorption. The WGS reaction on the beta-Mo(2)C(001) slab carbide was calculated and took place as follows: H(2)O was dissociated into OH and H on the Mo(2)C surface and the OH subsequently dissociated into H and O atoms. CO approached the O atom to form CO(2).
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