Reaction kinetics were studied to quantify the effects of polar aprotic organic solvents on the acid-catalyzed conversion of xylose into furfural. A solvent of particular importance is g-valerolactone (GVL), which leads to significant increases in reaction rates compared to water in addition to increased product selectivity. GVL has similar effects on the kinetics for the dehydration of 1,2-propanediol to propanal and for the hydrolysis of cellobiose to glucose. Based on results obtained for homogeneous Brønsted acid catalysts that span a range of pK a values, we suggest that an aprotic organic solvent affects the reaction kinetics by changing the stabilization of the acidic proton relative to the protonated transition state. This same behavior is displayed by strong solid Brønsted acid catalysts, such as H-mordenite and H-beta.
Well-defined
Cu catalysts containing different amounts of zirconia
were synthesized by controlled surface reactions (CSRs) and atomic
layer deposition methods and studied for the selective conversion
of ethanol to ethyl acetate and for methanol synthesis. Selective
deposition of ZrO2 on undercoordinated Cu sites or near
Cu nanoparticles via the CSR method was evidenced by UV–vis
absorption spectroscopy, scanning transmission electron microscopy,
and inductively coupled plasma absorption emission spectroscopy. The
concentrations of Cu and Cu-ZrO2 interfacial sites were
quantified using a combination of subambient CO Fourier transform
infrared spectroscopy and reactive N2O chemisorption measurements.
The oxidation states of the Cu and
ZrO2 species for these catalysts were determined using
X-ray absorption near edge structure measurements, showing that these
species were present primarily as Cu0 and Zr4+, respectively. It was found that the formation of Cu-ZrO2 interfacial sites increased the turnover frequency by an order of
magnitude in both the conversion of ethanol to ethyl acetate and the
synthesis of methanol from CO2 and H2.
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