We report a novel catalytic conversion of biomass-derived furans and alcohols to aromatics over zeolite catalysts. Aromatics are formed via Diels-Alder cycloaddition with ethylene, which is produced in situ from ethanol dehydration. The use of liquid ethanol instead of gaseous ethylene, as the source of dienophile in this one-pot synthesis, makes the aromatics production much simpler and renewable, circumventing the use of ethylene at high pressure. More importantly, both our experiments and theoretical studies demonstrate that the use of ethanol instead of ethylene, results in significantly higher rates and higher selectivity to aromatics, due to lower activation barriers over the solid acid sites. Synchrotron-diffraction experiments and proton-affinity calculations clearly suggest that a preferred protonation of ethanol over the furan is a key step facilitating the Diels-Alder and dehydration reactions in the acid sites of the zeolite.
Industrial olefin metathesis catalysts generally suffer from low reaction rates and require harsh reaction conditions for moderate activities. This is due to their inability to prevent metathesis active sites (MASs) from aggregation and their intrinsic poor adsorption and activation of olefin molecules. Here, isolated tungstate species as single molecular MASs are immobilized inside zeolite pores by Brønsted acid sites (BASs) on the inner surface. It is demonstrated that unoccupied BASs in atomic proximity to MASs enhance olefin adsorption and facilitate the formation of metallocycle intermediates in a stereospecific manner. Thus, effective cooperative catalysis takes place over the BAS-MAS pair inside the zeolite cavity. In consequence, for the cross-metathesis of ethene and trans-2-butene to propene, under mild reaction conditions, the propene production rate over WO /USY is ca. 7300 times that over the industrial WO/SiO-based catalyst. A propene yield up to 79% (80% selectivity) without observable deactivation was obtained over WO /USY for a wide range of reaction conditions.
As one of the alternative metals to platinum, which supports a wide range of applications in chemistry and catalysis in industry, palladium increasingly receives attention because of its similar physicochemical properties. However, Pd is generally less expensive than Pt and has a richer natural reserve. Herein, some recently developed techniques for the preparation and characterization of Pd‐based bimetallic catalysts are reviewed. The impact on catalytic reactions of interest, including hydrogenation, dehydrogenation, hydrogenolysis, reforming, the oxygen reduction reaction, and hydrodesulfurization are also discussed. It is shown that the catalytic performance of Pd‐based bimetallic catalysts is strongly dependent on the geometric and electronic states of Pd, which can be significantly affected by blended foreign element(s). Rationalization of the structure–activity relationship can provide useful guidelines to the fine tuning of these important catalytic reactions.
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