A thermodynamic equilibrium analysis of hydrogen and synthesis gas production from steam reforming of acetic acid and acetone blends as bio-oil model compounds

Thermodynamic analysis of steam reforming of blends of two model oxygenates, acetic acid and acetone, representing carboxylic acids and ketones in bio-oil is performed to investigate the effects of their potential interactions on hydrogen yield, synthesis gas composition and progress of reaction network. The results show that both acetic acid and acetone reach complete conversion at all operating conditions. Higher S/C molar ratio results in higher H₂ and CO₂ yields for both acetic acid and acetone. With the increase in pressure, H₂ and CO yields are diminished whereas CH₄ and CO₂ yields are enhanced. H₂ and CO₂ yields increase with the decrease in acetone concentration in the feed blend. CO and CH₄ production are affected adversely for acetic acid rich blends. The maximum H₂ yield values are 75.54%, 78.34%, 80.09%, 81.78% and 84.17% at 700 °C for acetic acid/acetone blends of 0.0/1.0, 0.3/0.7, 0.5/0.5, 0.7/0.3 and 1.0/0.0, respectively.     

Combined biotin,folic acid,and vitamin B12 supplementation given during the transition period to dairy cows: Part II. Effects on energy balance and fatty acid composition of colostrum and milk

Biotin (B₈), folate (B₉), and vitamin B₁₂ (B₁₂) are involved in several metabolic reactions related to energy metabolism. We hypothesized that a low supply of one of these vitamins during the transition period would impair metabolic status. This study was undertaken to assess the interaction between B₈ supplement and a supplementation of B₉ and B₁₂ regarding body weight (BW) change, dry matter intake, energy balance, and fatty acid (FA) compositions of colostrum and milk fat from d ?21 to 21 relative to calving. Thirty-two multiparous Holstein cows housed in tie stalls were randomly assigned, according to their previous 305-d milk yield, to 8 incomplete blocks in 4 treatments: (1) a 2-mL weekly i.m. injection of saline (0.9% NaCl; B₈?/B₉B₁₂?); (2) 20 mg/d of dietary B₈ (unprotected from ruminal degradation) and 2-mL weekly i.m. injection of 0.9% NaCl (B₈+/B₉B₁₂?); (3) 2.6 g/d of dietary B₉ (unprotected) and 2-mL weekly i.m. injection of 10 mg of B₁₂ (B₈?/B₉B₁₂+); (4) 20 mg/d of dietary B₈, 2.6 g/d of dietary B₉, and 2-mL weekly i.m. injection of 10 mg of B₁₂ (B₈+/B₉B₁₂+) in a 2 × 2 factorial arrangement. Colostrum was sampled at first milking. and milk samples were collected weekly on 2 consecutive milkings and analyzed for FA composition. Body condition score and BW were recorded every week throughout the trial. Within the first 21 d of lactation, B₈?/B₉B₁₂+ cows had an increased milk yield by 13.5% [45.5 (standard error, SE: 1.8) kg/d] compared with B₈?/B₉B₁₂? cows [40.1 (SE: 1.9)], whereas B₈ supplement had no effect. Even though body condition score was not affected by treatment, B₈?/B₉B₁₂+ cows had greater BW loss by 24 kg, suggesting higher mobilization of body reserves. Accordingly, milk de novo FA decreased and preformed FA concentration increased in B₈?/B₉B₁₂+ cows compared with B₈?/B₉B₁₂? cows. In addition, cows in the B₈+/B₉B₁₂? group had decreased milk de novo FA and increased preformed FA concentration compared with B₈?/B₉B₁₂? cows. Treatment had no effect on colostrum preformed FA concentration. Supplemental B₈ decreased concentrations of ruminal biohydrogenation intermediates and odd- and branched-chain FA in colostrum and milk fat. Moreover, postpartum dry matter intake for B₈+ cows tended to be lower by 1.6 kg/d. These results could indicate ruminal perturbation caused by the B₈ supplement, which was not protected from rumen degradation. Under the conditions of the current study, in contrast to B₈+/B₉B₁₂? cows, B₈?/B₉B₁₂+ cows produced more milk without increasing dry matter intake, although these cows had greater body fat mobilization in early lactation as suggested by the FA profile and BW loss.     

Mechanism for the hydrolysis resistance of aluminum nitride powder modified by boric acid

Aluminum nitride (AlN) ceramics are becoming cutting-edge materials for electronic information and communication. However, raw AlN hydrolyzed rapidly, and the high storage costs of this material prevent widespread application. In this study, raw AlN was modified by boric acid (H₃BO₃) at 30 °C to enhance hydrolysis resistance. Transmission electron microscope (TEM), X-ray diffraction (XRD), the magic angle spinning nuclear magnetic resonance (²⁷Al-MAS-NMR and ¹¹B-MAS-NMR), and the fourier transform infrared spectrometer (FTIR) were used to characterize the powder before and after treatment, and the mechanism of hydrolysis resistance was determined. Modification with 0.1 M boric acid did not change the crystal phase of the AlN particles. The modified powder did not hydrolyse at 90% humidity and 70° Celsius. In the presence of boric acid, a network structure of B–O–B linkages ([BO_n], n = 3 or 4) formed that was connected to the AlN core via chemical bonds of B–N–Al and B–O–Al. The protective 6 – 10 nm-thick layer that formed on the surface of the AlN crystal, prevented attack by water molecules and hindered the hydrolysis of aluminium nitride. This study provides an alternative means of preparing anti-hydrolysis AlN powders.     

Nitrogen-phosphorus co-functionalized reduced graphene oxide supported NiCoPd-CeOx nanoparticles as a highly efficient and stable catalyst for formic acid dehydrogenation

Formic acid (HCOOH, FA), a common liquid hydrogen storage material, has attracted tremendous research interest. However, the development of efficient, low-cost and high-stable heterogeneous catalyst for selective dehydrogenation of FA remains a major challenge. In this paper, a simple co-reduction method is proposed to synthesize nitrogen-phosphorus co-functionalized rGO (NPG) supported ultrafine NiCoPd-CeO_x nanoparticles (NPs) with a mean size of 1.2 nm. Remarkably, the as-prepared Ni_0.2Co_0.2Pd_0.6-CeO_x/NPG shows outstanding catalytic activity for FA dehydrogenation, affording a high TOF value of 6506.8 mol H₂ mol Pd^?1 h^?1 at 303 K and a low activation energy of 17.7 kJ mol^?1, which is better than most of the reported heterogeneous catalysts, and can be ascribed to the combined effect of well-dispersed ultrafine NiCoPd-CeO_x NPs, modified Pd electronic structure, and abundant active sites. The reaction mechanism of dehydrogenation of FA is also discussed. Furthermore, the optimized Ni_0.2Co_0.2Pd_0.6-CeO_x/NPG shows excellent stability over 10^th run with 100% conversion and 100% H₂ selectivity, which may provide more possibilities for practical application of FA system on fuel cells.     

Phytic acid-assisted fabrication of superhydrophilic Ru 3D electrode for electrocatalytic hydrogenation of p-Nitrophenol

A superhydrophilic Ru-based 3D electrode, denoted as Ru-PA/NF, was fabricated under the assistance of phytic acid (PA) for electrocatalytic hydrogenation of p-Nitrophenol. PA serves as a multifunctional modulator to facilitate the dispersion of active Ru species in porous nickel foam (NF), meanwhile enhance the surface wettability as well as adjust the micromorphology. In alkaline media, the Ru-PA/NF electrode shows the PNP conversion of 94.68% and the PAP selectivity of 99% after 9 h, accompanied by the faraday efficiency (FE) of 73.15%. Over the superhydrophilic Ru-PA/NF the rate constant of PNP conversion into PAP is 2.62-times higher than that over the hydrophobic Ru/NF prepared without the aid of PA, and FE of Ru-PA/NF is 1.28-times higher than Ru/NF. This can be ascribed to intriguing features of Ru-PA/NF involving higher Ru loading, more exposed sites, superior electrolyte wetting along with faster charge transfer rate.     

Stability,reactivity and decomposition kinetics of surface passivated α-AlH3 crystals

As a novel high energy fuel, aluminum hydride (AlH₃) has great potential in the field of solid propellants because of its high hydrogen capacity, which can significantly improve the specific impulse of solid propellants. In order to improve the stability of α-AlH₃, hydrochloric acid has been used to stabilize AlH₃ and the stabilization mechanism has been investigated. Various characterization techniques including scanning electron microscopy, X-ray electron spectrometer, X-ray diffraction, thermal analysis, and vacuum stability test have been employed to investigate the morphology, crystal structure, thermal stability, and decomposition kinetics of raw and passivated α-AlH₃. The results showed that the honeycomb-like structures could be formed on the surface of α-AlH₃ after passivation. First of all, the initial decomposition temperatures of the passivated samples were slightly increased. In particular, for the optimized sample with 105 min passivation time (AlH₃-105min), the initial decomposition temperature (173.4 °C) is increased by 5.6 °C. Moreover, the total decomposition time (1652 min) is improved by about 50% than that of the raw sample (1098 min). Besides, the decomposition activation energies (E_a) of passivated samples are much higher than that of the raw sample (84.8 kJ mol^?1), in which the optimized sample (AlH₃-105min) reaches 107.1 kJ. mol^?1. The decomposition kinetics model may change from 3-D nucleation and nucleus growth model to 2-D nucleation and nucleus growth model. It demonstrates the passivated samples have a lower decomposition rate and higher thermal stability. The stabilization mechanism is as follows: removing the impurities on the surface and accelerating the hydrolysis reaction of AlH₃ to generate complete and dense oxide layers.     

Adaptive response and tolerance to weak acids in Saccharomyces cerevisiae boulardii: a metabolomics approach

Weak acids inhibit the growth of probiotics, such as Saccharomyces boulardii. We explored the tolerance of S. boulardii to different weak acids. S. boulardii had better fermentation ability under lactic acid conditions compared with acetic and butyric acid conditions; however, the budding of S. boulardii was significantly stronger than that of Saccharomyces cerevisiae under acetic acid conditions. Although the surface structure of S. boulardii was destroyed, it produced more daughter cells. S. boulardii metabolites were also significantly different from S. cerevisiae under acidic stress. The growth of S. boulardii under weak acid conditions differed significantly from that of S. cerevisiae. S. boulardii-mediated fingerprints under weak acid conditions were identified as latent biomarkers, related to fructose and mannose metabolism, tricarboxylic acid cycle, and the glycolysis pathway. Identified biomarkers will aid in the genetic engineering of S. boulardii and other Saccharomyces strains for improved acid resistance and biomass yield.     

Changes in polyphenol fractions and bacterial composition after in vitrofermentation of apple peel polyphenol by gut microbiota

The changes in polyphenol fractions after in vitro fermentation of apple peel polyphenol (APP) by gut microbiota as well as the effects of APP on the growth, pH value, short-chain fatty acids (SCFAs) production and intestinal flora composition of gut microbiota fermentation were firstly explored in this study. The relative abundance of Lactobacillus in the APP group was 49.55% with an increment of 49.40% compared with the blank group, while that of Bifidobacterium was 13.32%. Moreover, the flora produced 37.093 ± 0.478 mM of SCFAs including acetic acid, propionic acid, butyric acid and valeric acid during the process of fermentation, thus reduced the environmental pH value. In addition, polyphenol fractions in APP were altered by gut microbiota fermentation to some extent, for example, glycosides were hydrolysed to aglycones. These findings suggested APP as a potential prebiotic agent to alleviate the disorder of intestinal flora.     

Acid–base transport model depicting the dynamic pH response of interfacial reactions

Acid–base transport is integral to many important interfacial reactions in various fields of chemistry, but its theoretical foundation is lacked. Herein, a common acid–base transport model is established owing to the success in deriving buffer transport equations. This model is applicable to most buffer systems by flexibly integrating the transport equations in terms of buffer components, and is verified through the model relationships of buffer transport limiting current by using hydrogen evolution reaction experiments. Based on model calculations, two diagram approaches are proposed to depict the dynamic pH response and aid buffer operation optimizations. The model and methods allow us to quantify the rate-limiting effect of acid–base transport on interfacial reactions and to precisely control the effect through medium regulations. Furthermore, the model has laid the foundation of dynamic pH effect on species transformation and process mechanism, which can be of wide interest in the chemistry encompassing interfacial reactions.