%0 Journal Article %1 Mhadeshwar2005 %A Mhadeshwar, A. B. %A Vlachos, D. G. %D 2005 %J Journal of Physical Chemistry B %K ADSORPTION; CATALYSTS; CO DENSITY-FUNCTIONAL H-2 HIGH-TEMPERATURES HYDROGEN MECHANISMS; OXIDATION; PREFERENTIAL RHODIUM SENSITIVITY; SHIFT; STRUCTURE SURFACE-REACTION THEORY; WATER-GAS %N 35 %P 16819-16835 %T Hierarchical multiscale mechanism development for methane partial oxidation and reforming and for thermal decomposition of oxygenates on Rh %U <Go to ISI>://000231687400037 %V 109 %X A thermodynamically consistent C-1 microkinetic model is developed for methane partial oxidation and reforming and for oxygenate (methanol and formaldehyde) decomposition on Rh via a hierarchical multiscale methodology. Sensitivity analysis is employed to identify the important parameters of the semiempirical unity bond index quadratic exponential potential (UBI-QEP) method and these parameters are refined using quantum mechanical density functional theory. With adjustment of only two pre-exponentials in the CH4 oxidation subset, the Q mechanism captures a multitude of catalytic partial oxidation (CPOX) and reforming experimental data as well as thermal decomposition of methanol and formaldehyde. We validate the microkinetic model against high-pressure, spatially resolved CPOX experimental data. Distinct oxidation and reforming zones are predicted to exist, in agreement with experiments, suggesting that hydrogen is produced from reforming of methane by H2O formed in the oxidation zone. CO is produced catalytically by partial oxidation up to moderately high pressures, with water-gas shift taking place in the gas-phase at sufficiently high pressures resulting in reduction of CO selectivity.

@article{Mhadeshwar2005, abstract = {A thermodynamically consistent C-1 microkinetic model is developed for methane partial oxidation and reforming and for oxygenate (methanol and formaldehyde) decomposition on Rh via a hierarchical multiscale methodology. Sensitivity analysis is employed to identify the important parameters of the semiempirical unity bond index quadratic exponential potential (UBI-QEP) method and these parameters are refined using quantum mechanical density functional theory. With adjustment of only two pre-exponentials in the CH4 oxidation subset, the Q mechanism captures a multitude of catalytic partial oxidation (CPOX) and reforming experimental data as well as thermal decomposition of methanol and formaldehyde. We validate the microkinetic model against high-pressure, spatially resolved CPOX experimental data. Distinct oxidation and reforming zones are predicted to exist, in agreement with experiments, suggesting that hydrogen is produced from reforming of methane by H2O formed in the oxidation zone. CO is produced catalytically by partial oxidation up to moderately high pressures, with water-gas shift taking place in the gas-phase at sufficiently high pressures resulting in reduction of CO selectivity.}, added-at = {2007-11-22T09:11:49.000+0100}, author = {Mhadeshwar, A. B. and Vlachos, D. G.}, biburl = {https://www.bibsonomy.org/bibtex/273c8498ba7edc1d7d2a54a6ba94c08dd/tboehme}, endnotereftype = {Journal Article}, interhash = {e9d454b4f60f9b46121193b173edf5f5}, intrahash = {73c8498ba7edc1d7d2a54a6ba94c08dd}, journal = {Journal of Physical Chemistry B}, keywords = {ADSORPTION; CATALYSTS; CO DENSITY-FUNCTIONAL H-2 HIGH-TEMPERATURES HYDROGEN MECHANISMS; OXIDATION; PREFERENTIAL RHODIUM SENSITIVITY; SHIFT; STRUCTURE SURFACE-REACTION THEORY; WATER-GAS}, month = Sep, number = 35, pages = {16819-16835}, shorttitle = {Hierarchical multiscale mechanism development for methane partial oxidation and reforming and for thermal decomposition of oxygenates on Rh}, timestamp = {2007-11-22T09:12:02.000+0100}, title = {Hierarchical multiscale mechanism development for methane partial oxidation and reforming and for thermal decomposition of oxygenates on Rh}, url = {<Go to ISI>://000231687400037 }, volume = 109, year = 2005 }