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The excess energy of subsurface hydrogen species may facilitate overcoming reaction barriers and remarkably alters the reaction pathways. We present an in-depth study on the different reactivity of surface and subsurface hydrogen species in syngas methanation on the O/C-covered Pd(10 by using density functional theory calculations and microkinetic simulations. It is shown that the apparent energy barriers to form H2O and CH4 are reduced by 0.87 and 0.61 eV for the case in which the hot subsurface hydrogen species are involved in the w
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