Abstract
Pt/Al2O3 catalysts with different Pt particle sizes and after phosphorous deposition were studied for liquid phase catalysed furfural hydrogenation. The activity and selectivity were related to various physico-chemical properties studied by scanning transmission electron microscopy, N2 physisorption, 31P nuclear magnetic resonance, diffuse reflectance Fourier transform infrared spectroscopy and attenuated total reflectance infrared spectroscopy. The results indicate that the large particles obtained upon calcination of 1 wt% Pt/Al2O3 at 600 °C exhibited higher turnover frequency per surface Pt; nonetheless, the overall activity decreased due to the loss of surface Pt upon sintering. While in certain cases phosphorous can act as promoter, the addition of this element to Pt/Al2O3 resulted in catalyst poisoning, which was ascribed to Pt encapsulation/blockage effects related to formation of AlPO4. Finally, gradual deactivation of Pt/Al2O3 was observed over five consecutive catalytic cycles which was caused by Pt sintering (from 0.6 to 2.0 nm) as well as by irreversible adsorption of organic reaction intermediates.Graphic
Highlights
Alternative energy sources, such as biomass-based compounds, are attracting significant attention to meet the rising demand for fine chemicals while minimising the harm to the environment [1, 2]
To evaluate the effects of particle size and addition of phosphorous (P) on furfural hydrogenation, the samples studied consisted of: (1) pristine Pt/Al2O3 (Al2O3–Pt) prepared by impregnation and followed by calcination at 500 °C, (2) a catalyst obtained after a second calcination of the pristine sample at 500 °C (Al2O3–Pt-500); (3) a catalyst obtained after a second calcination of the pristine sample at 600 °C (Al2O3–Pt-600) and (4) a catalyst obtained after addition of 2 wt% P to the pristine sample followed by calcination at 500 °C (Al2O3–Pt-2P)
Evaluation of samples prepared with different thermal treatments showed that a relation exists between Pt particle size and catalyst performance
Summary
Alternative energy sources, such as biomass-based compounds, are attracting significant attention to meet the rising demand for fine chemicals while minimising the harm to the environment [1, 2]. The major challenge of furfural hydrogenation is the control of the hydrogenation of C=C or C=O bonds over secondary reaction pathways—e.g. ether by-product formation—using a highly selective catalyst [1, 4]. Studies on different catalyst formulations suggest that activity towards furfural hydrogenation can be affected by noble metal particle size. The selectivity to various products has been reported to be particle size dependent in Pd-based catalysts [4, 6]. The modification of metal-supported catalysts by strongly adsorbed organic compounds such as phosphorous (P) can affect their activity and selectivity [22,23,24]. The addition of P to transition metal catalysts has been reported to increase activation energies for C=C and C=O bonds in hydrodeoxygenation (HDO) reactions, e.g. dehydrogenation of isobutane [25]. The durability of Pt/Al2O3 was investigated over five consecutive furfural hydrogenation cycles and the causes of catalyst deterioration were identified
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