Project description:MgO-based sorbents are a promising option for CO2 capture at intermediate temperatures. MgO-based sorbents are often hybridized with alkali metal salts to promote the CO2 capture performance. However, MgO-based sorbents often suffer a rapid decrement of CO2 capture performance during multicycle carbonation-calcination reactions due to the reduction of active sites. In this study, we attempted to enhance the durability of MgO-based sorbents by modifying their morphology. A tubular-shaped MgO-based sorbent was synthesized using a carbon nanotube template. Various characterization experiments and evaluations were performed with the synthesized MgO-based materials. The MgO sample with modified structure exhibited a specific morphology consisting of elongated plate-like structures separated by empty spaces. This separation is expected to prevent MgO agglomeration and preserve the modified morphology during iterative CO2 capture reactions. The MgO with modified structure achieved higher cycling stability with four times slower performance decay than the control MgO, even though identical chemical compositions were applied.
Project description:The formation of a MgCO3 shell hampers CO2 capture efficiency in MgO. Our previous studies developed MgO/Mg(OH)2 composites to facilitate CO2 diffusion, improving capture efficiency. However, MgCO3 still formed along the interfaces. To tackle this issue, we engineered the MgO/Mg(OH)2 interfaces by incorporating Cl-, SO42-, and PO43- additives. Novel MgO-H2O-MgX (X = Cl-, SO42-, and PO43-) composites were synthesized to explore the role of additives in preventing MgCO3 formation. MgO-Mg(OH)2-MgCl2 nano-composites displayed enhanced CO2 adsorption and stability. This breakthrough paves the way for effective bio-inspired strategies in overcoming CO2 transport barriers in MgO-based adsorbents.
Project description:This work provides insight into the local structure of Na in MgO-based CO2 sorbents that are promoted with NaNO3. To this end, we use X-ray absorption spectroscopy (XAS) at the Na K-edge to interrogate the local structure of Na during the CO2 capture (MgO + CO2 ↔ MgCO3). The analysis of Na K-edge XAS data shows that the local environment of Na is altered upon MgO carbonation when compared to that of NaNO3 in the as-prepared sorbent. We attribute the changes observed in the carbonated sorbent to an alteration in the local structure of Na at the NaNO3/MgCO3 interfaces and/or in the vicinity of [Mg2+···CO32-] ionic pairs that are trapped in the cooled NaNO3 melt. The changes observed are reversible, i.e., the local environment of NaNO3 was restored after a regeneration treatment to decompose MgCO3 to MgO. The ex situ Na K-edge XAS experiments were complemented by ex situ magic-angle spinning 23Na nuclear magnetic resonance (MAS 23Na NMR), Mg K-edge XAS and X-ray powder diffraction (XRD). These additional experiments support our interpretation of the Na K-edge XAS data. Furthermore, we develop in situ Na (and Mg) K-edge XAS experiments during the carbonation of the sorbent (NaNO3 is molten under the conditions of the in situ experiments). These in situ Na K-edge XANES spectra of molten NaNO3 open new opportunities to investigate the atomic scale structure of CO2 sorbents modified with Na-based molten salts by using XAS.
Project description:A silicon-stereogenic aminosilanol was isolated in excellent diastereomeric ratio and the absolute configuration was determined. The silanol is configurative and condensation stable in solution and shows stereoselective transformations with a clean stereospecific pathway in follow-up reactions, which leads to the isolation of a silicon-stereogenic zinc complex and siloxane compounds. Investigations with 18 O-labelled water and mass spectrometry analysis revealed an otherwise hidden exchange of oxygen atoms of silanol and water in solution that proceeds with retention of the configuration at the silicon center. This novel combination of a stereochemical probe and isotopic labeling in a silicon-stereogenic compound opens new analytic possibilities to study stereochemical courses of reactions with the aid of chiral silanols mechanistically.
Project description:MgO is a promising solid oxide-based sorbent to capture anthropogenic CO2 emissions due to its high theoretical gravimetric CO2 uptake and its abundance. When MgO is coated with alkali metal salts such as LiNO3, NaNO3, KNO3, or their mixtures, the kinetics of the CO2 uptake reaction is significantly faster resulting in a 15 times higher CO2 uptake compared to bare MgO. However, the underlying mechanism that leads to this dramatic increase in the carbonation rate is still unclear. This study aims to determine the most favourable location for the nucleation and growth of MgCO3 and more specifically, whether the carbonation occurs preferentially at the buried interface, the triple phase boundary (TPB), and/or inside the molten salt of the NaNO3-MgO system. For this purpose, a model system consisting of a MgO single crystal that is structured by ultra-short pulse laser ablation and coated with NaNO3 as the promoter is used. To identify the location of nucleation and growth of MgCO3, micro X-ray computed tomography, scanning electron microscopy, Raman microspectroscopy and optical profilometry were applied. We found that MgCO3 forms at the NaNO3/MgO interface and not inside the melt. Moreover, there was no preferential nucleation of MgCO3 at the TPB when compared to the buried interface. Furthermore, it is found that there is no observable CO2 diffusion limitation in the nucleation step. However, it was observed that CO2 diffusion limits MgCO3 crystal growth, i.e. the growth rate of MgCO3 is approximately an order of magnitude faster in shallow grooves compared to that in deep grooves.
Project description:Growing bacteria have a high concentration of ribosomes to ensure sufficient protein synthesis, which is necessary for genome replication and cellular division. To elucidate whether metabolic activity of soil microorganisms is coupled with growth, we investigated the relationship between rRNA and DNA synthesis in a soil bacterial community using quantitative stable isotope probing (qSIP) with H218O. Most soil bacterial taxa were metabolically active and grew, and there was no significant difference between the isotopic composition of DNA and RNA extracted from soil incubated with H218O. The positive correlation between 18O content of DNA and rRNA of taxa, with a slope statistically indistinguishable from 1 (slope = 0.96; 95% confidence interval [CI], 0.90 to 1.02), indicated that few taxa made new rRNA without synthesizing new DNA. There was no correlation between rRNA-to-DNA ratios obtained from sequencing libraries and the atom percent excess (APE) 18O values of DNA or rRNA, suggesting that the ratio of rRNA to DNA is a poor indicator of microbial growth or rRNA synthesis. Our results support the notion that metabolic activity is strongly coupled to cellular division and suggest that nondividing taxa do not dominate soil metabolic activity.IMPORTANCE Using quantitative stable isotope probing of microbial RNA and DNA with H218O, we show that most soil taxa are metabolically active and grow because their nucleic acids are significantly labeled with 18O. A majority of the populations that make new rRNA also grow, which argues against the common paradigm that most soil taxa are dormant. Additionally, our results indicate that relative sequence abundance-based RNA-to-DNA ratios, which are frequently used for identifying active microbial populations in the environment, underestimate the number of metabolically active taxa within soil microbial communities.
Project description:In this study, magnesium oxide (MgO)-modified carbon adsorbents were fabricated using a nitrogen-enriched carbon precursor by microwave-assisted irradiation for CO2 capture. The X-ray diffraction (XRD) patterns showed the characteristic diffraction peaks of MgO at 43° and 62.5°, and no impurities were apparent. By changing the microwave reaction time, the spherical structure of the parent material was transformed to a hybrid structure with MgO crystalline particles in a carbon matrix. The morphology evolution and properties of the prepared materials were also investigated using transmission electron microscopy and N2 adsorption, respectively. On optimising the conditions, the prepared sample attained a high CO2 uptake of 1.22 mmol/g (5.3 wt.%) under flue gas conditions (15% CO2 in N2). It was found that MgO affected the CO2 capture behaviour by enhancing the fundamental characteristics of the carbon surfaces.
Project description:Monitoring changes in stable oxygen isotope ratios in molecular oxygen allows for studying many fundamental processes in bio(geo)chemistry and environmental sciences. While the measurement of [Formula: see text]O/[Formula: see text]O ratios of [Formula: see text] in gaseous samples can be carried out conveniently and from extracting moderately small aqueous samples for analyses by continuous-flow isotope ratio mass spectrometry (CF-IRMS), oxygen isotope signatures, [Formula: see text]O, could be overestimated by more than 6[Formula: see text] because of interferences from argon in air. Here, we systematically evaluated the extent of such Ar interferences on [Formula: see text]O/[Formula: see text]O ratios of [Formula: see text] for measurements by gas chromatography/IRMS and GasBench/IRMS and propose simple instrumental modifications for improved Ar and [Formula: see text] separation as well as post-measurement correction procedures for obtaining accurate [Formula: see text]O. We subsequently evaluated the consequences of Ar interferences for the quantification of O isotope fractionation in terms of isotope enrichment factors, [Formula: see text], and [Formula: see text]O kinetic isotope effects ([Formula: see text]O KIEs) in samples where [Formula: see text] is consumed and Ar:[Formula: see text] ratios increase steadily and substantially over the course of a reaction. We show that the extent of O isotope fractionation is overestimated only slightly and that this effect is typically smaller than uncertainties originating from the precision of [Formula: see text]O measurements and experimental variability. Ar interferences can become more relevant and bias [Formula: see text] values by more than [Formula: see text] in aqueous samples where fractional [Formula: see text] conversion exceeds 90%. Practically, however, such samples would typically contain less than 25 [Formula: see text]M of [Formula: see text] at ambient temperature, an amount that is close to the method detection limit of [Formula: see text]O/[Formula: see text]O ratio measurement by CF-IRMS.
Project description:A metal-free and selective method to form [18F]aryl-CF2H through nucleophilic radiofluorination of benzyl (pseudo)halides and oxidative C-H activation of benzylic C-H bonds has been developed. The method is operationally simple and tolerates a variety of electron-neutral/deficient arenes and heteroarenes.
Project description:We discovered that CO2 electroreduction strongly favors the conversion of the dominant isotope of carbon (12C) and discriminates against the less abundant, stable carbon 13C isotope. Both absorption of CO2 in the alkaline electrolyte and CO2 electrochemical reduction favor the lighter isotopologue. As a result, the stream of unreacted CO2 leaving the electrolyzer has an increased 13C content, and the depletion of 13C in the product is several times greater than that of photosynthesis. Using a natural abundance feed, we demonstrate enriching of the 13C fraction to ∼1.3% (i.e., +18%) in a single-pass reactor and propose a scalable and economically attractive process to yield isotopes of a commercial purity. Our finding opens pathways to both cheaper and less energy-intensive production of stable isotopes (13C, 15N) essential to the healthcare and chemistry research, and to an economically viable, disruptive application of electrolysis technologies developed in the context of sustainability transition.