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The selective activation of renewable carboxylic acids could enable the formation of a variety of highly valuable renewable products, including surfactants, valuable dienes, and renewable hydrogen carriers. A kinetic study is performed to enhance understanding of the selective deoxygenation of carboxylic acid on promoted MoO3 at mild temperatures. Although several studies indicate that deoxygenation of oxygenated biomass-derived compounds on MoO3 occurs via a reverse Mars−van Krevelen mechanism, this study suggests that the deoxygenation of pentanoic acid (PA) on an oxygen vacancy can also be explained by a Langmuir−Hinshelwood mechanism. A detailed analysis of the experimental data indicates that the incorporation of Pt on MoO3 shifts the reaction order with respect to hydrogen from 1 to 0.5 at a low partial pressure of PA. We reveal that the rate-determining step (RDS) shifts upon the incorporation of Pt from H2 dissociation to H addition to adsorbed acid molecules. We further illustrate how the RDS can shift as a function of PA coverage. The inhibition effect of PA and its possible causes are discussed for both MoO3 and 0.05 wt % Pt/MoO3 catalysts. Here, we decouple promoter effects from the creation of highly active sites located at the Pt/MoO3 interface. The nature of the active site involved upon Pt incorporation is also studied by separating Pt from MoO3 at a controlled distance using carbon nanotubes as hydrogen bridges, confirming that the kinetically relevant role of Pt is to serve as a promoter of the MoO3. 

Abstract Balancing kinetics, a crucial priority in catalysis, is frequently achieved by sacrificing activity of elementary steps to suppress side reactions and enhance catalyst stability. Dry reforming of methane (DRM), a process operated at high temperature, usually involves fast C-H activation but sluggish carbon removal, resulting in coke deposition and catalyst deactivation. Studies focused solely on catalyst innovation are insufficient in addressing coke formation efficiently. Herein, we develop coke-free catalysts that balance kinetics of elementary steps for overall thermodynamics optimization. Beginning from a highly active cobalt aluminum oxide (CoAl₂O₄) catalyst that is susceptible to severe coke formation, we substitute aluminum (Al) with gallium (Ga), reporting a CoAl_0.5Ga_1.5O₄-R catalyst that performs DRM stably over 1000 hours without observable coke deposition. We find that Ga enhances DRM stability by suppressing C-H activation to balance carbon removal. A series of coke-free DRM catalysts are developed herein by partially substituting Al from CoAl₂O₄with other metals.