Glucose-derived carbon materials with tailored properties as electrocatalysts for the oxygen reduction reaction.

Nitrogen-doped biomass-derived carbon materials were prepared by hydrothermal carbonization of glucose, and their textural and chemical properties were subsequently tailored to achieve materials with enhanced electrochemical performance towards the oxygen reduction reaction. Carbonization and physical activation were applied to modify the textural properties, while nitrogen functionalities were incorporated via different N-doping methodologies (ball milling and conventional methods) using melamine. A direct relationship between the microporosity of the activated carbons and the limiting current density was found, with the increase of microporosity leading to interesting improvements of the limiting current density. Regardless of the doping method used, similar amounts of nitrogen were incorporated into the carbon structures. However, significant differences were observed in the nitrogen functionalities according to the doping method applied: ball milling appeared to originate preferentially quaternary and oxidized nitrogen groups, while the formation of pyridinic and pyrrolic groups was favoured by conventional doping. The onset potential was improved and the two-electron mechanism of the original activated sample was shifted closer to a four-electron pathway due to the presence of nitrogen. Interestingly, the high pyridinic content related to a high ratio of pyridinic/quaternary nitrogen results in an increase of the onset potential, while a decrease in the quaternary/pyrrolic nitrogen ratio favors an increase in the number of electrons. Accordingly, the electrocatalyst with the highest performance was obtained from the activated sample doped with nitrogen by the conventional method, which combined the most appropriate textural and chemical properties: high microporosity and adequate proportion of the nitrogen functionalities.

Insights into the effect of the catalytic functions on selective production of ethylene glycol from lignocellulosic biomass over carbon supported ruthenium and tungsten catalysts.

The one-pot conversion of cellulose to ethylene glycol (EG) was investigated using a combination of a ruthenium catalyst supported on carbon nanotubes modified with nitric acid (Ru/CNT1) and a tungsten catalyst supported on commercial non-treated carbon nanotubes (W/CNT0). This physical mixture allowed to obtain an EG yield of 41% in just 5 h at 205 °C and 50 bar of H2, which overcame the result obtained using a Ru-W bimetallic catalyst supported on commercial carbon nanotubes (35%) under the same conditions. Tissue paper, a potential waste cellulosic material, and eucalyptus were also tested under the same conditions and EG yields of 34 and 36%, respectively, were attained over the aforementioned catalytic physical mixture. To the best of our knowledge, this work presents for the first time the catalytic conversion of lignocellulosic materials, namely tissue paper and eucalyptus, directly into EG by an environmentally friendly process.

Simultaneous catalytic conversion of cellulose and corncob xylan under temperature programming for enhanced sorbitol and xylitol production.

Sorbitol and xylitol yields can be improved by converting cellulose and xylan simultaneously, due to a synergetic effect between both substrates. Furthermore, both yields can be greatly enhanced by simply adjusting the reaction conditions regarding the optimum for the production of each product, since xylitol (from xylan) and sorbitol (from cellulose) yields are maximized when the reaction is carried out at 170 and 205°C, respectively. Therefore, the combination of a simultaneous conversion of cellulose and xylan with a two-step temperature approach, which consists in the variation of the reaction temperature from 170 to 205°C after 2h, showed to be a good strategy for maximizing the production of sorbitol and xylitol directly from mixture of cellulose and xylan. Using this new and environmentally friendly approach, yields of sorbitol and xylitol of 75 and 77%, respectively, were obtained after 6h of reaction.

Direct catalytic production of sorbitol from waste cellulosic materials.

Cotton wool, cotton textile, tissue paper and printing paper, all potential waste cellulosic materials, were directly converted to sorbitol using a Ru/CNT catalyst in the presence of H2 and using only water as solvent, without any acids. Conversions up to 38% were attained for the raw substrates, with sorbitol yields below 10%. Ball-milling of the materials disrupted their crystallinity, allowing reaching 100% conversion of cotton wool, cotton textile and tissue paper after 4h, with sorbitol yields around 50%. Mix-milling these materials with the catalyst greatly enhanced their conversion rate, and the materials were efficiently converted to sorbitol with a yield around 50% in 2h. However, ball- and mix-milled printing paper presented a conversion of only 50% after 5h, with sorbitol yields of 7%. Amounts of sorbitol of 0.525, 0.511 and 0.559g could be obtained from 1g of cotton wool, cotton textile and tissue paper, respectively.

Ethyl Acetate Abatement on Copper Catalysts Supported on Ceria Doped with Rare Earth Oxides.

Different lanthanide (Ln)-doped cerium oxides (Ce0.5Ln0.5O1.75, where Ln: Gd, La, Pr, Nd, Sm) were loaded with Cu (20 wt. %) and used as catalysts for the oxidation of ethyl acetate (EtOAc), a common volatile organic compound (VOC). For comparison, both Cu-free (Ce-Ln) and supported Cu (Cu/Ce-Ln) samples were characterized by N2 adsorption at -196 °C, scanning/transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and temperature programmed reduction in H2. The following activity sequence, in terms of EtOAc conversion, was found for bare supports: CeO2 ≈ Ce0.5Pr0.5O1.75 > Ce0.5Sm0.5O1.75 > Ce0.5Gd0.5O1.75 > Ce0.5Nd0.5O1.75 > Ce0.5La0.5O1.75. Cu addition improved the catalytic performance, without affecting the activity order. The best catalytic performance was obtained for Cu/CeO2 and Cu/Ce0.5Pr0.5O1.75 samples, both achieving complete EtOAc conversion below ca. 290 °C. A strong correlation was revealed between the catalytic performance and the redox properties of the samples, in terms of reducibility and lattice oxygen availability. Νo particular correlation between the VOC oxidation performance and textural characteristics was found. The obtained results can be explained in terms of a Mars-van Krevelen type redox mechanism involving the participation of weakly bound (easily reduced) lattice oxygen and its consequent replenishment by gas phase oxygen.