The experimentally validated computational models developed herein, for the first time, show that Mn-promotion does not enhance the activity of the surface Na2WO4 catalytic active sites for CH4 heterolytic dissociation during OCM. Contrary to previous understanding, it is demonstrated that Mn-promotion poisons the surface WO4 catalytic active sites resulting in surface WO5 sites with retarded kinetics for C-H scission. On the other hand, dimeric Mn2O5 surface sites, identified and studied via ab initio molecular dynamics and thermodynamics, were found to be more efficient in activating CH4 than the poisoned surface WO5 sites or the original WO4 sites. However, the surface reaction intermediates formed from CH4 activation over the Mn2O5 surface sites are more stable than those formed over the Na2WO4 surface sites. The higher stability of the surface intermediates makes their desorption unfavorable, increasing the likelihood of over-oxidation to CO x , in agreement with the experimental findings in the literature on Mn-promoted catalysts. Consequently, the Mn-promoter does not appear to have an essential positive role in synergistically tuning the structure of the Na2WO4 surface sites towards CH4 activation but can yield MnO x surface sites that activate CH4 faster than Na2WO4 surface sites, but unselectively.
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