We have found that the utilization of carbon nanotubes as support for ruthenium nanoparticles increases hydrogenation activity over 40 times in terms of turnover frequency (TOF) when compared to activated carbon in the transformation of hydroxymethylfurfural to dimethylfuran. Catalysts based on carbon nanotubes produced 83.5% yield of dimethylfuran (TOF 819.7 h −1 ) in under 1 h at 150 °C and less than 20 bar hydrogen pressure, whereas the activated carbon catalyst required more than 3 h to give an 80% yield of dimethylfuran (TOF 36 h −1 ). The superior accessibility of pores in carbon nanotubes, plus an electronic promotional effect in the carbon nanotubes, appear to be responsible for the superior activity of the catalysts supported on carbon nanotubes. The catalysts were synthesized by impregnation and characterized by X-ray diffraction, X-ray photoelectron spectroscopy, nitrogen physisorption, temperature-programmed reduction, electron microscopy and pulse CO chemisorption to propose the structure−activity relationships. This work highlights the importance of the support in hydrogenating reactions with ruthenium and the potential applicability of carbon nanotubes as supports for the hydrogenation of other bioderivatives.
Recent developments in the transformation of biobased 5-hydroxymethylfurfural (HMF) into a potential liquid fuel, 2,5-dimethylfuran (DMF), are summarised. This review focuses briefly on the history of HMF conversion to DMF in terms of the feedstock used and emphasises the ideal requirements in terms of the catalytic properties needed in HMF transformation into DMF. The recent state of the art and works on HMF transformation into DMF are discussed in comparison to noble metals and non-noble metals as well as bimetallic catalysts. The effect of the support used and the reaction conditions are also discussed. The recommendations for future work and challenges faced are specified.
The aim of this work was to improve the processability of triglycidyl-p-aminophenol (TGPAP) epoxy resin. To achieve this improvement, a diluent, the diglycidyl ether of bisphenol F (DGEBF or BPF), was added to TGPAP, and the blended epoxy was then cured with 4, 4′-diaminodiphenyl sulfones (DDS). A response surface methodology (RSM) was used, with the target response being to achieve a blended resin with a high glass transition temperature (Tg) and maximum pot life (or processing window, PW). Characterization through dynamic mechanical thermal analysis (DMTA) and using a rheometer indicated that the optimum formulation was obtained at 55.6 wt.% of BPF and a stoichiometric ratio of 0.60. Both values were predicted to give Tg at 180 °C and a processing window of up to 136.1 min. The predicted values were verified, with the obtained Tg and processing window (PW) being 181.2 ± 0.8 °C and 140 min, respectively, which is close to the values predicted using the RSM.
N-heterocyclic carbenes (NHCs) are common ancillary ligands in organometallic compounds that are used to alter the electronic and steric properties of a metal centre. To date, various NHCs have been synthesised with different electronic properties, which can be done by modifying the backbone or changing the nitrogen substituents group. This study describes a systematic modification of NHCs by the inclusion of fluorine substituents and examines the use of selenium-NHC compounds to measure the π-accepting ability of these fluorinated NHC ligands. Evaluation of the 77Se NMR chemical shifts of the selenium adducts reveals that fluorinated NHCs have higher chemical shifts than the non-fluorinated counterparts, IMes and IPh. Higher 77Se NMR chemical shifts values indicate a stronger π-accepting ability of the NHC ligands. The findings of this study suggest that the presence of fluorine atoms has increased the π-accepting ability of the corresponding NHC ligands. This work supports the advantage of the 77Se NMR chemical shifts of selenium-NHC compounds for assessing the influence of fluorine substituents on NHC ligands.
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