Sodium phenoxide is considered as one of the potentially promising hydrogen storage materials due to its high hydrogen capacity and enhanced thermodynamic properties. However, efficient catalysts are needed to overcome kinetic barriers of the hydrogenation and dehydrogenation processes. In the present work, an ultrafine amorphous Ru–B alloy catalyst was synthesized by a solid-phase ball milling of RuCl 3 with NaBH 4 and subsequently tested for the hydrogenation of sodium phenoxide in an aqueous solution at room temperature . The conversion of phenoxide is significantly improved by 48.9 % on the Ru 3.9 B alloy catalyst compared with pristine Ru nanoparticles . Kinetic studies revealed that the hydrogenation of sodium phenoxide is of first-order with respect to H 2 pressure and zero-order to the concentration of sodium phenoxide over the Ru 3.9 B catalyst. Characterizations showed that the electronic structure of Ru is well modulated by B, leading to an electron-rich state of Ru. The highly active catalysis may be due to the fine dispersion, amorphous state, and electron-rich state of Ru in the ultrafine alloy.
Green synthesis of poly(isosorbide carbonate) (PIC) with remarkable properties is a huge challenge in industrial applications due to low molecular weight and harsh reaction conditions. We reported a novel pathway to synthesize high molecular weight PIC through melt polymerization of isosorbide (ISB) and dimethyl carbonate (DMC), which are derived from the biomass and CO2, respectively. The effects of metal ion-containing compound catalyst on chemical structures, terminal groups, and molecular weight of PIC in the process of melt polycondensation were studied. Compared with the best reported catalyst lithium acetylacetonate, the weight-average molecular weight (Mw) of PIC was increased by using our preferred catalyst sodium tert-butoxide from 46 500 to 55 100 with the ISB conversion up to 99.0%, and the reaction time was decreased from 12 h to only 2.5 h, as far as we know, which is the highest Mw value and the most efficient catalyst achieved by one-step method. According to the results of the experiment and simulation, we found that high catalytic performance was ascribed to the weak interaction energy of anion–cation of catalyst and the strong proton acceptance ability of the anion of the catalyst. Meanwhile, increasing the interaction energy of anion–cation of the catalyst could inhibit the occurrence of the methylation side reaction and interestingly the activated endohydroxyl groups of ISB were found to be more easily methylated. Finally, based on the captured and detected intermediates of the two-stages of the reaction, a possible mechanim for the synergetic effects of cation–anion through hydrogen bond formation was proposed.
A primary Fourier transform infrared (FTIR) method capable of determining acidity in ester-based oils is described and evaluated. Absolute free fatty acid (%FFA) and acid value (AV) calibrations were devised by spiking oleic acid into a refined, acid-free oil and measuring νCOO– at ∼1569 and νphenolate– at ∼1588 cm–1, respectively, in the second-derivative differential spectra. The FTIR acidity predictions were compared to the AOCS titrimetric method using acid mixtures as well as acid containing used vendor oils of undefined makeup and provenance, using two spectroscopically divergent reference oils as AC0. Relative to the AOCS reference method, the FTIR procedure was found to be both more accurate (±0.107 vs ±0.122) and reproducible (±0.025 vs ± 0.077) in determining %FFA and similar in predicting AV. The FTIRphenolate method overcomes a variety of limitations of earlier FTIR-based methods, being particularly simple and well suited to routine, semiautomated acidity analysis of ester-based oils using a basic FTIR spectrometer.
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