Staged biomass pyrolysis or condensation of the pyrolysis vapor generates less complex and concentrated liquid product streams, which provide a very promising route to produce value-added chemicals. Acetol is one of the major light oxygenates in fractionated bio-oil. Here we report an efficient one-pot conversion of acetol to lactic acid, a key platform chemical and an important monomer of biodegradable polymer, in aqueous phase over a bifunctional dealuminated Sn-Beta supported gold catalyst. Under relatively mild conditions (393 K, 1.9 MPa N2 + 0.1 MPa O2), 93.4% acetol conversion and 73.2% selectivity toward lactic acid were achieved. On the basis of measured rate constants, the reaction pathway likely proceeds via kinetically relevant oxidation of acetol to form pyruvaldehyde, followed by hydration and 1,2-hydride shift (internal Meerwein–Ponndorf–Verley reduction and Oppenauer oxidation) on Sn-Lewis sites to produce lactic acid.
Electronic cigarette usage has spiked in popularity over recent years. The enhanced prevalence has consequently resulted in new health concerns associated with the use of these devices. Degradation of the liquids used in vaping have been identified as a concern due to the presence of toxic compounds such as aldehydes in the aerosols. Typically, such thermochemical conversions are reported to occur between 300 and 400 °C. Herein, the low-temperature thermal degradation of propylene glycol and glycerol constituents of e-cigarette vapors are explored for the first time by natural abundance 13C NMR and 1H NMR, enabling in situ detection of intact molecules from decomposition. The results demonstrate that the degradation of electronic nicotine delivery system (ENDS) liquids is strongly reliant upon the oxygen availability, both in the presence and absence of a material surface. When oxygen is available, propylene glycol and glycerol readily decompose at temperatures between 133 and 175 °C over an extended time period. Among the generated chemical species, formic and acrylic acids are observed which can negatively affect the kidneys and lungs of those who inhale the toxin during ENDS vapor inhalation. Further, the formation of hemi- and formal acetals is noted from both glycerol and propylene glycol, signifying the generation of both formaldehyde and acetaldehyde, highly toxic compounds, which, as a biocide, can lead to numerous health ailments. The results also reveal a retardation in decomposition rate when material surfaces are prevalent with no directly observed unique surface spectator or intermediate species as well as potentially slower conversions in mixtures of the two components. The generation of toxic species in ENDS liquids at low temperatures highlights the dangers of low-temperature ENDS use.
Herein, a detailed analysis was carried out using high-field (19.9 T) 27Al magic-angle spinning (MAS) nuclear magnetic resonance (NMR) on three specially prepared aluminum oxide samples where the γ-, δ-, and θ-Al2O3 phases are dominantly expressed through careful control of the synthesis conditions. Specifically, two-dimensional (2D) multiquantum (MQ) MAS 27Al was used to obtain high spectral resolution, which provided a guide for analyzing quantitative 1D 27Al NMR spectra. Six aluminum sites were resolved in the 2D MQ MAS NMR spectra, and seven aluminum sites were required to fit the 1D spectra. A set of octahedral and tetrahedral peaks with well-defined quadrupolar line shapes was observed in the θ-phase dominant sample and was unambiguously assigned to the θ-Al2O3 phase. The distinct line shapes related to the θ-Al2O3 phase provided an opportunity for effectively deconvoluting the more complex spectrum obtained from the δ-Al2O3 dominant sample, allowing the peaks/quadrupolar parameters related to the δ-Al2O3 phase to be extracted. The results show that the δ-Al2O3 phase contains three distinct AlO sites and three distinct AlT sites. This detailed Al site structural information offers a powerful way of analyzing the most complex γ-Al2O3 spectrum. It is found that the γ-Al2O3 phase consists of Al sites with local structures similar to those found in the δ-Al2O3 and θ-Al2O3 phases albeit with less ordering. Spin–lattice relaxation time measurement further confirms the disordering of the lattice. Collectively, this study uniquely assigns 27Al features in transition aluminas, offering a simplified method to quantify complex mixtures of aluminum sites in transition alumina samples.
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