Carbidic Mo is the sole kinetically-relevant active site for catalytic methane dehydroaromatization on Mo/H-ZSM-5

Systematic variation of Mo/Al = {0.10, 0.25, 0.35} in Mo/H-ZSM-5 catalysts effects similar to 20x change of Mo-to-H+ ratio during methane dehydroaromatization (DHA) reactions at steady state and on deactivating catalysts. Mo and Bronsted-acid site count, respectively enumerated by ethane hydrogenolysis probe reaction and dimethyl ether chemical titration, evolve disparately during DHA catalysis, indicating the two sites reduce in number by distinct mechanisms. The deactivation of Mo/H-ZSM-5 catalytic activity is uniquely attributed to the loss of active, or accessible, Mo sites, evinced by (i) the non-selective nature of deactivation (i.e. that deactivation occurs without modification of residual active sites), (ii) invariance in product distribution from Mo/H+ = 0.10-2.1, and (iii) linear correspondence between Mo-catalyzed ethane hydrogenolysis rate and active site count during DHA on deactivating samples. DHA forward rate - the intrinsic kinetic descriptor of catalyst activity - normalizes by Mo content at steady state and on deactivating catalysts with Mo/Al = 0.10-0.35 for Mo-based contact times in the range tau(Mo) = 0.79-44 mol(Mo) s mol(c)(1), unequivocally establishing Mo aggregates as the sole kinetically-relevant active site on Mo/H-ZSM-5. Bronsted-acid site content over a similar to 40x range in tau(H+) = 1.4-54 mol(H+) s mol(c)(1) has no discernable correlation with or effect on DHA rate, methane conversion, or product distribution - demonstrating H+ does not catalyze any rate- or selectivity-determining steps in the benzene formation pathway and suggesting that the benefits of zeolitic acid sites are only to disperse Mo during catalyst synthesis and, conceivably, to catalyze equilibrated reaction steps. (C) 2020 Elsevier Inc. All rights reserved.