RESUMO
Selective transformation of levulinic acid (LA) to γ-valerolactone (GVL) using novel heterogeneous catalysts is one of the promising strategies for viable biomass processing. In this framework, we developed a continuous flow process for the selective hydrogenation of LA to GVL using several nanostructured Ni/SiO2 catalysts. The structural, textural, acidic, and redox properties of Ni/SiO2 catalysts, tuned by selectively varying the Ni amount from 5 to 40 wt %, were critically investigated using numerous materials characterization techniques. Electron microscopy images showed the formation of uniformly dispersed Ni nanoparticles on the SiO2 support, up to 30% Ni loading (average particle size is 9.2 nm), followed by a drastic increase in the particles size (21.3 nm) for 40% Ni-loaded catalyst. The fine dispersion of Ni particles has elicited a synergistic metal-support interaction, especially in 30% Ni/SiO2 catalyst, resulting in enhanced acidic and redox properties. Among the various catalysts tested, the 30% Ni/SiO2 catalyst showed the best performance with a remarkable 98% selectivity of GVL at complete conversion of LA for 2 h reaction time. Interestingly, this catalyst showed a steady selectivity to GVL (>97%), with a 54.5% conversion of LA during 20 h time-on-stream. The best performance of 30% Ni/SiO2 catalyst was attributed to well-balanced catalytic properties, such as ample amounts of strong acidic sites and abundant active metal sites. The obtained results show a great potential of applying earth-abundant nickel/silica catalysts for upgrading biomass platform molecules into value-added chemicals and high-energy-density fuels.
RESUMO
We have synthesized CuO nanostructures with flake, dandelion-microsphere, and short-ribbon shapes using solution-phase methods and have evaluated their structure-performance relationship in the heterogeneous catalysis of liquid-phase oxidative coupling reactions. The formation of nanostructures and the morphological evolution were confirmed by transmission electron microscopy, scanning electron microscopy, X-ray diffraction analysis, X-ray photoelectron spectroscopy, Raman spectroscopy, energy-dispersive X-ray spectroscopy, elemental mapping analysis, and Fourier transform infrared spectroscopy. CuO nanostructures with different morphologies were tested for the catalytic oxidative coupling of aromatic amines to imines under solvent-free conditions. We found that the flake-shaped CuO nanostructures exhibited superior catalytic efficiency compared to that of the dandelion- and short-ribbon-shaped CuO nanostructures. We also performed extensive density functional theory (DFT) calculations to gain atomic-level insight into the intriguing reactivity trends observed for the different CuO nanostructures. Our DFT calculations provided for the first time a detailed and comprehensive view of the oxidative coupling reaction of benzylamine over CuO, which yields N-benzylidene-1-phenylmethanamine as the major product. CuO(111) is identified as the reactive surface; the specific arrangement of coordinatively unsaturated Cu and O sites on the most stable CuO(111) surface allows N-H and C-H bond-activation reactions to proceed with low-energy barriers. The high catalytic activity of the flake-shaped CuO nanostructure can be attributed to the greatest exposure of the active CuO(111) facets. Our finding sheds light on the prospective utility of inexpensive CuO nanostructured catalysts with different morphologies in performing solvent-free oxidative coupling of aromatic amines to obtain biologically and pharmaceutically important imine derivatives with high selectivity.
