Hydrogenation and hydrodeoxygenation are significant and distinct approaches for the conversion of biomass and biomass-derived oxygenated chemicals into high value-added chemicals and fuels. However, it remains a great challenge to synthesize catalysts that simultaneously possess excellent hydrogenation and hydrodeoxygenation performance. Herein, we report a catalyst made of isolated single-atom Ru supported on mesoporous graphitic carbon nitride (Ru/mpg-CN), fabricated by a wet impregnation method. The as-prepared Ru/mpg-CN catalyst shows excellent hydrogenation and hydrodeoxygenation performance. First-principles calculations reveal that the Ru atom is mobilized, and the active site is induced by adsorption of the reactants. A systematic reaction mechanism is proposed, suggesting that vanillyl alcohol is the deoxygenation prohibited product, while 2-methoxy- p-cresol is the deoxygenation allowed product. Thus, the excellent selectivity for the hydrogenation or hydrodeoxygenation of vanillin at different temperatures results from switching between the two types of products.
A copper-based catalyst, which was
supported by sulfonate group (−SO3H) grafted active
carbon (AC), was prepared and activated simultaneously by liquid phase
chemical reduction method. The modified copper catalyst, Cu/AC–SO3H, displayed an enhanced catalytic performance for selective
hydrogenation of furfural (FAL) to furfuryl alcohol (FOL) in liquid
phase, in which almost 100% FOL yield was obtained at 378 K and 0.4
MPa of hydrogen pressure after 120 min reaction. The effect of −SO3H was evaluated and illustrated by the combination of reaction
performance and physicochemical characterizations, such as X-ray diffraction
(XRD), Fourier transform infrared spectroscopy (FT-IR), and X-ray
photoelectron spectrometer (XPS) measurements. Through grafting sulfonate
group on the support, better dispersion of nanoparticles, higher reduction
degree of Cu, and stronger adsorption of FAL can be attained to contribute
high hydrogenation performance. In addition, the effects of reaction
conditions (such as reaction temperature, H2 pressure,
reaction time, solvent, and catalyst to FAL mass ratio) were evaluated
intensively. Also, the Cu/AC–SO3H catalyst showed
an excellent catalytic performance for transfer hydrogenation of FAL,
in which 2-propanol was utilized as the solvent and hydrogen donor
concurrently. Cycling test proved the prepared catalyst could be recycled
and reused for several times without noticeably reduced catalytic
activity of hydrogenation.
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