Multilevel quantum mechanical calculations show the role of promoter molecules in the dehydration of methanol to dimethyl ether in H-ZSM-5.

Methyl carboxylate esters promote the formation of dimethyl ether (DME) from the dehydration of methanol in H-ZSM-5 zeolite. We employ a multilevel quantum method to explore the possible associative and dissociative mechanisms in the presence, and absence, of six methyl ester promoters. This hybrid method combines density functional theory, with dispersion corrections (DFT-D3), for the full periodic system, with second-order Møller-Plesset perturbation theory (MP2) for small clusters representing the reaction site, and coupled cluster with single, double, and perturbative triple substitution (CCSD(T)) for the reacting molecules. The calculated adsorption enthalpy of methanol, and reaction enthalpies of the dehydration of methanol to DME within H-ZSM-5, agree with experiment to within chemical accuracy (∼4 kJ mol-1). For the promoters, a reaction pathway via an associative mechanism gives lower overall reaction enthalpies and barriers compared to the reaction with methanol only. Each stage of this mechanism is explored and related to experimental data. We provide evidence that suggests the promoter's adsorption to the Brønsted acid site is the most important factor dictating its efficiency.

Small Cobalt Nanoparticles Favor Reverse Water-Gas Shift Reaction Over Methanation Under CO2 Hydrogenation Conditions.

Cobalt-based catalysts are well-known to convert syngas into a variety of Fischer-Tropsch (FTS) products depending on the various reaction parameters, in particular particle size. In contrast, the reactivity of these particles has been much less investigated in the context of CO2 hydrogenation. In that context, Surface organometallic chemistry (SOMC) was employed to synthesize highly dispersed cobalt nanoparticles (Co-NPs) with particle sizes ranging from 1.6 to 3.0 nm. These SOMC-derived Co-NPs display significantly different catalytic performances under CO2 hydrogenation conditions: while the smallest cobalt nanoparticles (1.6 nm) catalyze mainly the reverse water-gas shift (rWGS) reaction, the larger nanoparticles (2.1-3.0 nm) favor the expected methanation activity. Operando X-ray absorption spectroscopy shows that the smaller cobalt particles are fully oxidized under CO2 hydrogenation conditions, while the larger ones remain mostly metallic, paralleling the observed difference of catalytic performances. This fundamental shift of selectivity, away from methanation to reverse water-gas shift for the smaller nanoparticles is noteworthy and correlates with the formation of CoO under CO2 hydrogenation conditions.