A new class of green solvents, known as ionic liquids (ILs), has recently been the subject of intensive research on the extractive desulfurization of fuel oils because of the limitation of the traditional hydrodesulfurization method in catalytically removing thiophenic sulfur compounds. In this work, four thiazolium-based ILs, that is, 3-butyl-4-methylthiazolium dicyanamide ([BMTH][DCA]), 3-butyl-4-methylthiazolium thiocyanate ([BMTH][SCN]), 3-butyl-4-methylthiazolium hexafluorophosphate ([BMTH][PF 6 ]), and 3-butyl-4-methylthiazolium tetrafluoroborate ([BMTH][BF 4 ]), are synthesized. The extractive capability of these ILs in removing thiophene (TS) and dibenzothiophene (DBT) from model fuel oils is investigated. [BMTH][DCA] and [BMTH][SCN] present better extractive desulfurization capability than [BMTH][BF 4 ] and [BMTH][PF 6 ], which may be ascribed to the additional pÀp interaction between -CN (in [BMTH][DCA] and [BMTH][SCN]) and thiophenic ring (in TS and DBT); DBT in diesel fuel is more efficiently extracted than TS in gasoline. [BMTH][DCA] offers the best desulfurization results, where 64% and 45% sulfur removal are obtained for DBT and TS, respectively, at IL:oil mass ratio of 1:1, 25 C, 20 min. [BMTH] [DCA] is thus selected to systematically investigate the effects of temperature, IL:oil mass ratio, initial sulfur content, multiple-extraction, and IL regeneration on desulfurization. The mutual solubility of [BMTH][DCA] with fuel oil is also determined. It is observed that the desulfurization capability is not too sensitive to temperature and initial sulfur content, which is desired in industrial application; the sulfur contents in gasoline and diesel fuel are reduced from 558 ppm to 20 ppm (after 5 cycles) and from 547 ppm to 8 ppm (after 4 cycles), respectively. This work may show a new option for deep desulfurization of fuel oils.
Developing efficient, inexpensive, and durable electrocatalysts for the oxygen reduction reaction (ORR) is important for the large‐scale commercialization of fuel cells and metal–air batteries. Herein, a hierarchically porous bimetallic Fe/Co single‐atom‐coordinated N‐doped carbon (Fe/Co‐Nx‐C) electrocatalyst for ORR is synthesized from Fe/Co‐coordinated polyporphyrin using silica template‐assisted and silica‐protection synthetic strategies. In the synthesis, first silica nanoparticles‐embedded, silica‐protected Fe/Co‐polyporphyrin is prepared. It is then pyrolyzed and treated with acidic solution. The resulting Fe/Co‐Nx‐C material has a large specific surface area, large electrochemically active surface area, good conductivity, and catalytically active Fe/Co‐Nx sites. The material exhibits a very good electrocatalytic activity for the ORR in alkaline media, with a half‐wave potential of 0.86 V versus reversible hydrogen electrode, which is better than that of Pt/C (20 wt%). Furthermore, it shows an outstanding operational stability and durability during the reaction. A zinc–air battery (ZAB) assembled using Fe/Co‐Nx‐C as an air‐cathode electrocatalyst gives a high peak power density (152.0 mW cm−2) and shows a good recovery property. Furthermore, the performance of the battery is better than a corresponding ZAB containing Pt/C as an electrocatalyst. The work also demonstrates a synthetic route to a highly active, stable, and scalable single‐atom electrocatalyst for ORR in ZABs.
Platinum (Pt)-based catalysts are widely used for the oxygen reduction reaction (ORR) in many energy conversion and storage devices, such as fuel cells and metal–air batteries. However, Pt is among the least earth abundant and most expensive elements; as a result, these energy devices are currently difficult to scale up. This has motivated researchers to try to develop sustainable and alternative catalysts that can replace Pt as well as other noble metal-based catalysts. Herein, novel Co nanocrystals-loaded, Zn, N, and S codoped carbon materials, dubbed (Co, Zn)/NSC, which have hollow spherical structures and which can serve as efficient ORR catalysts, are developed via a facile synthetic method involving microemulsion and pyrolysis. The key in the synthesis of these nonprecious metal-containing heteroatom-doped nanostructured carbon catalysts is the preparation of nanosized, mixed metal–organic frameworks (MOFs) in solution using microemulsion, and the exploitation of their morphology to produce hollow spherical structures via pyrolysis. Elemental mapping shows the presence of Co, Zn, N, and S atoms throughout the structures of the materials. The material obtained at pyrolysis temperature of 800 °C, denoted (Co, Zn)/NSC-800, exhibits excellent electrocatalytic activity for ORR in alkaline and acidic media, with onset potentials of 1.000 and 0.802 V vs RHE, respectively. In addition, the catalyst is stable and tolerates the methanol crossover reaction in both cases. Thus, this material has the potential to replace Pt catalysts in fuel cells. Moreover, the synthetic approach used to make it can be extended to produce other robust, nonprecious transition metal-based catalysts for ORR.
To evaluate the administration of Bifidobacterium animalis subsp. lactis, BB-12® (BB-12) on infant colic in breastfed infants, a double-blind, placebo-controlled randomised study was conducted in Chengdu, China from April 2016 to October 2017 with 192 full-term infants less than 3 months of age and meeting the ROME III criteria for infant colic. After a 1-week run-in the infants were randomly assigned to receive daily BB-12 (1×109 cfu/day) or placebo for 3 weeks. Crying/fussing time were recorded using a 24 h structured diary. The primary endpoint was the proportion of infants achieving a reduction in crying and fussing time of ≥50% from baseline. Parent’s/caregiver’s health related quality of life was measured using a modified PedsQL™ 2.0 Family Impact Module and immunological biomarkers were evaluated from faecal samples at baseline and after the 21-day intervention. The percentage of infants achieving a reduction in the daily crying/fussing time ≥50% after the 21-day intervention was significantly higher in the infants supplemented with BB-12 (P<0.001). The mean number of crying episodes was significantly reduced in the BB-12 group compared to the placebo group (10.0±3.0 to 5.0±1.87 vs 10.5±2.6 to 7.5±2.8, respectively) (P<0.001) and the mean daily sleep duration was markedly increased from baseline to end of intervention in the BB-12 group compared to the infants in the placebo group (60.7±104.0 vs 31.9±102.7 min/day, respectively) (P<0.001). The faecal levels of human beta defensin 2, cathelicidin, slgA, calprotectin and butyrate were statistically higher in the BB-12 group compared to the placebo group after the 21-day intervention. At the end of the intervention the parent’s/caregiver’s physical, emotional and social functioning scores were significantly higher for the BB-12 group compared to the placebo group (all P<0.05). Supplementation of BB-12 is effective in reducing crying and fussing in infants diagnosed with infant colic.
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