Density Functional Theory Studies of Dehydrogenation of Methane and Hydrogenation of Benzene over Ni-and Ru-based Bimetallic Catalyst-Medical Journal

The reactions involving breaking and making of a C-H bond on transition metal surfaces is one of the hottest research points in heterogeneous catalysis. The addition of another metal as a promoter can improve the efficiency of this process. In the thesis, first-principle calculations based on density functional theory are used to investigate the reaction mechanism for hydrogenation and dehydrogenation reactions on metal surfaces, where the activation of methane on Ni catalyst and hydrogenation of benzene on Ru catalyst are taken as the research systems. By examining the effect of the metal promoters in the catalysts, the synergetic effects of the bimetallic catalysts as well as the C-H bond breaking and making mechanism are revealed. The main results of the work are summarized as follows:(1) The dry reforming of methane on Ni catalyst is investigated. The adsorption energies of all the reaction intermediates as well as the activation energies for all the elementary reactions that involved in dry reforming of methane on Ni(111), Ni(100) and Ni(211) surfaces are calculated. With the combination of the DFT results and statistic thermodynamic formulism as well as the transition state theory, the reaction constants for all the elementary reactions are estimated. Based on this, a full microkinetic model is constructed, and the surface coverages of the reaction intermediates and the reaction rates for all the elementary reactions are obtained. Thus, the dominant reaction pathway and the rate-determining step are identified.(2) The activation of methane on alloyed Ni/Fe(111) surface is investigated. Two bulk models with different Ni to Fe molar ratios are constructed and XRD simulations are conducted to evaluate their reliability. The calculated results show that, with the increase of the Fe content, the adsorption of the reaction intermediates involved in methane dissociation is strengthened, which facilitates the formation of surface C atoms. The dissolution of C from surface to the bulk of the catalyst particle is found to be thermodynamically favorable, and the diffusion of C through the catalyst particle is hindered as the Fe content increases. With the combination of the kinetic analysis, the effect of the reaction conditions on the C concentration in the catalyst particle is revealed.(3) The synergetic effects of Ni-based bimetallic catalyst are investigated. Several transition metals are introduced into the Ni catalyst, and the surface alloy models are constructed accordingly. The activation of methane is taken as a probe reaction to investigate the synergetic effect. The ensemble effect and the ligand effect of the bimetallic catalyst are discussed, and the electrostatic interaction energy between Ni atom and the second metal atom are estimated. Using the activation energy of the first step in methane dissociation and the C binding energy as descriptors, the optimal catalyst for activation of methane is single out. which gives some insights into rational designing new catalyst.(4) The reaction mechanism for benzene hydrogenation on Ru(0001) surface is investigated. The adsorption energies of all the possible reaction intermediates are calculated, and the most stable adsorption configurations as well as the most stable isomers on Ru(0001) are identified. Based on this, the activation energies for the six elementary reactions in hydrogenation of benzene to cyclohexane are calculated in both low and high H coverages, and the high H coverage is found to be very crucial for the reaction. The-mode adsorption is a key point to produce cyclohexene on Ru catalyst.(5) The effect of the introduction of Zn into Ru catalyst on the selectivity to cyclohexene is investigated. The adsorption energies of the reaction intermediates and the activation energies for the elementary reactions are calculated. With the comparison to the results from the conditions at different H coverages, the effect of Zn on the

selectivity to cyclohexene is revealed. Zn is found to facilitate the desorption and retard the deep hydrogenation of cyclohexene, which leads to the incease of the selectivity to cyclohexene. Reference: Medical information: http://www.nlm.nih.gov/medlineplus/ medical questions answered: http://www.healthqas.org health news: http://www.medicalnewstoday.com