Formation Of Bicarbonate Research Articles

Assessing the impacts of simulated ocean alkalinity enhancement on viability and growth of nearshore species of phytoplankton

Abstract. Over the past 250 years, atmospheric CO2 concentrations have risen steadily from 277 to 405 ppm, driving global climate change. In response, new tools are being developed to remove carbon from the atmosphere using negative emission technologies (NETs), in addition to reducing anthropogenic emissions. One proposed NET is ocean alkalinity enhancement (OAE), in which artificially raising the alkalinity favours formation of bicarbonate from CO2, leading to a decrease in the partial pressure of CO2 in the water. Subsequent invasion of atmospheric CO2 results in net sequestration of atmospheric carbon. The aim of this study was to investigate the impact of simulated OAE, through the alteration of pH, on phytoplankton representative of the spring and fall blooms in nearshore, temperate waters. The potential impacts of OAE were assessed through (1) an analysis of prior studies investigating the effects of elevated pH on phytoplankton growth rates and (2) an experimental assessment of the potential impact of short-term (10 min) and long-term (8 d) elevation of pH on the viability and subsequent growth rates of two representative nearshore species of phytoplankton. Viability was assessed with a modified serial dilution culture–most probable number assay. Chlorophyll a fluorescence was used to test for changes in photosynthetic competence and apparent growth rates. There were no significant impacts on the viability or growth rates of the diatom Thalassiosira pseudonana and the prymnesiophyte Diacronema lutheri (formerly Pavlova lutheri) with short-term (10 min) exposure to elevated pH. However, there was a significant decrease in growth rates with long-term (8 d) exposure to elevated pH. Short-term exposure is anticipated to more closely mirror the natural systems in which land-based OAE will be implemented because of system flushing and dilution. The analysis of prior studies indicates wide variability in the growth response to elevated pH within and between taxonomic groups, with about 50 % of species expected to not be impacted by the pH increase anticipated from unequilibrated mineral-based OAE. To the extent that the growth responses reflect (largely unreported) parallel reductions in dissolved inorganic carbon (DIC) availability, the susceptibility may be reduced for OAE in which CO2 ingassing is not prevented.

CO2 Hydrogenation through Electrochemical Hydrogen Activation in a Gas-Vapor Fed Reactor

An attractive concept in the chemical manufacturing industry is the adoption of a circular carbon economy, which can include continuous capture and conversion of CO2 into industrially relevant chemical feedstocks. This has driven considerable research interest in electrochemical CO2 reduction.1 Despite this popularity, major challenges remain even for the most advanced CO2 reduction reactors, including low conversion rates and energy efficiencies; moreover, in many cases, multiple carbon-containing products are generated, which add to costs for downstream separation.2 By contrast, thermochemical CO2 hydrogenation is well established and typically demonstrates higher energy efficiency and selectivity compared to electrochemical CO2 reduction.3,4 This notable contrast drives our interest in better understanding the physics that governs differences in reactivity between thermocatalytic and electrocatalytic CO2 reduction reactors. To address these questions, we are pursuing a unique approach that involves feeding humidified CO2 and H2, respectively, to the cathode and anode of an electrochemical membrane-electrode assembly (MEA). This presentation will cover initial work we have undertaken to design and validate this reactor for the study CO2 electro-reduction.The overall design of our reactor resembles a hydrogen fuel cell fed with humidified H2 and CO2. Thus, it was initially benchmarked through operation as an electrochemical hydrogen pump, wherein humidified Ar was fed to the cathode and humidified H2 was fed to the anode with Pt/C as the catalyst on each side of the membrane. Under these conditions, a cation exchange membrane (CEM) readily generated current densities in excess of 1 A/cm2 with monotonic decreases in polarization with increased temperature at fixed current. We then undertook analogous hydrogen pumping experiments using anion exchange membranes (AEM) that had been ion-exchanged with hydroxide, carbonate, and bicarbonate anions. We observed net proton transport between the anode and cathode chambers in each case, albeit with higher ionic resistance for AEMs in the bicarbonate form.We then undertook further studies to demonstrate the ability to reduce CO2 using H2 fed to the anode. This operating mode eliminates the need for a liquid anode feed, which dramatically reduces the driving force for CO2 crossover via bicarbonate formation. Moreover, the Pt/C anode catalyst is expected to oxidize hydrogen with minimal polarization, allowing the total cell polarization to be interpreted simply as the cathode potential on the RHE scale. CO2 reduction experiments were carried out using commercial Cu/C catalyst with online gas chromatography and NMR for product analysis of volatile and condensable products, respectively. Operation with a CEM yielded only H2(g) at the cathode, but initial experiments with an AEM in the carbonate/bicarbonate form gave high selectivity to ethanol at 70 oC.

Suitability of rocks, minerals, and cement waste for CO2 removal via enhanced rock weathering

Mineral and rock additions to the environment have been proposed as a pathway to remove atmospheric CO2. This process occurs when hydrated minerals or rocks increase alkalinity, promoting the formation of bicarbonate. In this study, we evaluate the potential of commonly used hydrated rock and mineral powders to enhance alkalinity and react with both atmospheric and concentrated CO2. Silicate minerals and rocks exhibit minimal reactivity with atmospheric CO2 and provide moderate alkalinity enhancement. Volcanic rocks like basalt were shown to release CO2. Ground cement and Mg(OH)2, refined from CO2-free ultramafic rock, significantly increase alkalinity and mineralize both atmospheric and concentrated CO2. However, the effectiveness of cement waste is limit by its variable CaO content and potential heavy metal contributions. Overall, Mg(OH)2, derived from silicates, offers a promising pathway for the removal and storage of CO2.

CO2 Loss into Solution: An Experimental Investigation of CO2 Electrolysis with a Membrane Electrode Assembly Cell.

In pursuit of commercial viability for carbon dioxide (CO2) electrolysis, this study investigates the operational challenges associated with membrane electrode assembly (MEA)-type CO2 electrolyzers, with a focus on CO2 loss into the solution phase through bicarbonate (HCO3 -) and carbonate (CO3 2-) ion formation. Utilizing a silver electrode known for selectively facilitating CO2 to CO conversion, the molar production of CO2, CO, and H2 is measured across a range of current densities from 0 to 600 mA/cm2, while maintaining a constant CO2 inlet flow rate of 58 mL/min. The dynamics of CO2 loss are monitored through measurements of pH changes in the electrolyte and carbon elemental balance analysis. Employing the concept of conservation of elemental carbon, a chemical reaction analysis is conducted, identifying the critical role of the hydroxide (OH-) ion. At lower current densities below 125 mA/cm2, where CO2 reduction predominates, it is observed that CO2 loss is proportional to current density, reaching up to 0.18 mmol/min, and directly correlates with the rate of OH- ion production, indicative of HCO3 -/CO3 2- ion formation. Conversely, at higher current densities above 450 mA/cm2, where hydrogen evolution is the dominant process, CO2 loss is shown to decouple from the OH- ion production rate with a constant limit condition of 0.12 mmol/min, regardless of the current density. This suggests that electrolyte-induced cathode flooding restricts CO2 access to cathode sites. Additionally, pH change in the electrolyte during the electrolysis further infers differing ion populations in the CO2 reduction and hydrogen evolution regimes, and their movement across the membrane. Continued monitoring of the pH change after the cessation of electricity offers insights into the accumulation of HCO3 -/CO3 2- ion at the cathode, influencing salt formation.

Insights into yeast response to chemotherapeutic agent through time series genome-scale metabolic models.

Organism-specific genome-scale metabolic models (GSMMs) can unveil molecular mechanisms within cells and are commonly used in diverse applications, from synthetic biology, biotechnology, and systems biology to metabolic engineering. There are limited studies incorporating time-series transcriptomics in GSMM simulations. Yeast is an easy-to-manipulate model organism for tumor research.Here, a novel approach (TS-GSMM) was proposed to integrate time-series transcriptomics with GSMMs to narrow down the feasible solution space of all possible flux distributions and attain time-series flux samples. The flux samples were clustered using machine learning techniques, and the clusters' functional analysis was performed using reaction set enrichment analysis.A time series transcriptomics response of Yeast cells to a chemotherapeutic reagent-doxorubicin-was mapped onto a Yeast GSMM. Eleven flux clusters were obtained with our approach, and pathway dynamics were displayed. Induction of fluxes related to bicarbonate formation and transport, ergosterol and spermidine transport, and ATP production were captured.Integrating time-series transcriptomics data with GSMMs is a promising approach to reveal pathway dynamics without any kinetic modeling and detects pathways that cannot be identified through transcriptomics-only analysis. The codes are available at https://github.com/karabekmez/TS-GSMM.

Oxygen corrosion of reboiler tube served in production of dilution steam from heat exchanger of petrochemical refinery

This paper reports the oxygen corrosion of heat exchanger tubes serviced in dilute steam generation system. The floating head heat exchanger employed in a petrochemical industry underwent remnant corrosion failures particularly at lower passes of tube bundle. Initially remote field eddy current inspection technique was employed for tube bundle conditional assessment and further, root cause of degradation of tube had been analyzed. Comprehensive experimental techniques including visual examination, tube chemistry analysis, external tube surface morphological analysis, elemental mapping, scanning electron microscopy, light microscopy and x-ray diffraction studies were employed. The tube surface at the degraded position with its cross sectional examination was rigorously evaluated as well. Moreover, actual steam parameters such as pH, conductivity and iron & chloride concentration have been monitored in the petrochemical facility. The detailed analysis concluded that dissolved oxygen in boiler feed water (BFW) was the root cause for corrosion failure. Several other foreign elements were detected and source of each element was discussed in the context of actual heat exchanger operating conditions. Simulated conditions of BFW service have electrochemically been evaluated in two different dissolved oxygen concentrations at 7.5 ppm and 12.7 ppm, respectively. Even small increase of dissolved oxygen in BFW could lead to promotion of oxygen reduction reaction. Theoretically SA179 tubes operated at pH of 9.75 could lead to formation of bicarbonate and it could protect the tube in absence of dissolved oxygen as evaluated by Molecular Dynamics simulation. However, according to obtained results, tube has been degraded due to presence of dissolved oxygen in BFW. Various contributing factors such as external paint/coat removal, absence of de-aerator system in BFW treatment and improper corrosion inhibitor programme were discussed. Several practical countermeasures have been suggested to mitigate oxygen corrosion failure in petrochemical refineries.

Modeling bicarbonate formation in an alkaline solution with multi-level quantum mechanics/molecular dynamics simulations

Understanding carbonate speciation and how it may be modulated is essential for the advancement of carbon dioxide (CO2) capture and storage technologies, which often rely on the transformation of CO2 into carbonate, e.g. via the formation of carbonate minerals. To date, few atomic-level, quantum-mechanics-based simulations have been carried out to characterize how carbonic acid (H2CO3) and bicarbonate ( HCO 3 − ) form in aqueous solution, and how pH affects this process. Recently, Martirez and Carter utilized rare-event sampling density functional theory molecular dynamics simulations in combination with multi-level embedded correlated wavefunction theory, thus accounting for both solvent dynamics and electron correlation accurately, to elucidate the mechanism of H2CO3 formation in neutral solution (J. Am. Chem. Soc., 145, 12561, 2023). Here, we perform a complementary simulation using the same method to map out the energetics of HCO 3 − formation from dissolved CO2 in basic solution. We find that, as in H2CO3 formation, including water dynamics is important to obtain an accurate prediction of the energetics for the aforementioned reaction. Furthermore, only with MD did we identify the correct pathway for the reaction, in which water – not hydroxide – acts as the initial nucleophile and only at the transition state does it lose a proton.

Novel tri-solvent amines absorption for flue gas CO2 capture: Efficient absorption and regeneration with low energy consumption

Blended amine scrubbing is considered as a promising alternative to the monoamine scrubbing process due to the potential for enhanced CO2 capture efficiency and reduced energy consumption. However, striking a balance between absorption rate and regeneration energy consumption in blended amine systems by establishing suitable interactions between activated amines and proton-acceptor amines remains a significant challenge. In this study, a novel blended amine system, involving tertiary amine diethanolamine (DEEA) as the main agent and several monoamines as promoters, was first proposed to achieve highly effective CO2 capture. The designed tri-solvent amine system of DEEA combined with piperazine (PZ) and 4-amino-1-methylpiperidine (PD) (denoted as DEEA + PZ + PD) exhibited exceptional CO2 loading (0.988 mol CO2/mol amine), superior cyclic capacity (0.788 mol CO2/mol amine), and reduced regeneration heat duty (2.14 GJ/t), surpassing monoethanolamine (MEA) by 79.6 %, 277 %, and decreasing by 43.7 %, respectively. Furthermore, the performance improvement mechanism of DEEA + PZ + PD was systematically elucidated, showcasing the swift CO2 absorption facilitated by PD or PZ in the initial reaction phase, and the subsequent formation of bicarbonate from PDCOO− and DEEA in the later stage, enhancing CO2 absorption capacity. The predominant reaction products, bicarbonate and unstable carbamate (PZ(COO−)2, PDCOO−), contribute to the high regeneration efficiency and minimal energy consumption during regeneration for DEEA + PZ + PD. Consequently, this facilely prepared tri-solvent amine system, characterized by high capture efficiency and low energy consumption, holds promise for achieving carbon–neutral operations in coal-fired power plants.

Effect of the presence of trace sulfur dioxide on piperazine-based amine absorbents for carbon dioxide capture

The effect of the presence of trace SO2 in industrial flue gas on the amine-scrubbing-based absorption process for CO2 capture has been a matter of concern. This study aimed to investigate the effect of trace SO2 on the CO2 capture process using piperazine-based amine absorbents, focusing on SO2 resistance capability, SO2/CO2 absorption selectivity, and cyclic stability. The presence of trace SO2 not only restrains CO2 absorption, but also promotes the formation of carbamate within the piperazine-based amine absorbents. Remarkably, the incorporation of aminoethyl group in piperazine-based amine absorbents can enhance the SO2 resistance capability by promoting the formation of carbamate, while piperazine-based amine absorbents with hydroxyethyl group can promote the formation of bicarbonate to reduce the SO2 resistance capability. The work offers valuable insights into the efficient application of novel amine absorbents for CO2 capture from practical industrial flue gas.

Water effect on CO2 absorption mechanism and phase change behavior in [N1111][Gly]/EtOH anhydrous biphasic absorbent: In density functional theory and molecular dynamics view

Ionic liquids-based anhydrous biphasic absorbents have the potential to lower the energy consumption for CO2 capture. Recent experimental studies have revealed that the presence of water in [N1111][Gly]/EtOH system leads to generation of a new CO2-product – bicarbonate and affects the phase change behavior. However, the reaction pathway for bicarbonate formation remains unclear. In this work, the reaction pathways were investigated in depth through quantum chemical calculations employing density functional theory, with reaction rate constants determined via transition state theory. Among the three possible reaction pathways, the base-catalyzed CO2 hydration reaction prevailed, i.e. a one-step reaction involving [Gly]-, H2O, and CO2. An H atom in H2O was transferred to [Gly]-’s amino group, forming protonated [Gly]-, and hydroxide combined with CO2 to generate bicarbonate. Additionally, molecular dynamics simulations were conducted to understand the phase change behaviors with varying water content. When water content exceeded 5 wt%, an increased water content led to reduced hydrogen bonding among products and enhanced hydrogen bonding of products-solvent with the solvent, diminishing product self-aggregation. No phase change behavior were observed at water contents up to 80 wt%. This study could well explain the experimental phenomena of water effect on CO2 absorption in [N1111][Gly]/EtOH, providing theoretical references for application of ILs-based anhydrous biphasic absorbent.

CO2 capture performance of a 1-dimethylamino-2-propanol/N-(2-hydroxyethyl) ethylenediamine biphasic solvent

Biphasic solvents are widely used for CO2 capture owing to their low regeneration heats; however, they typically suffer from poor regeneration performance and excessive energy consumption. In this study, a mixture of 1-dimethylamino-2-propanol (1DMA2P) and N-(2-hydroxyethyl) ethylenediamine (AEEA) was proposed for CO2 capture. By optimizing the 1DMA2P and AEEA concentrations, this biphasic solvent achieved superior phase separation and excellent absorption and regeneration performance. The proportion of CO2-rich phase was 66.67 %, with a CO2-rich phase loading of up to 5.07 mol/L. The desorption rate was improved by 106.7 % compared to that of conventional 5 mol/L monoethanolamine, and the regeneration efficiency up to 71.8 % in 60 min. Initially, CO2 reacted with AEEA at a faster rate to form a carbamate product. Subsequently, 1DMA2P acted as a proton acceptor, facilitating the formation of bicarbonates and carbonates. Nuclear magnetic resonance analysis indicated that the reaction products (AEEACOO-, AEEAH+, and HCO3–/CO32–) migrated to one phase, whereas 1DMA2P and any unreacted AEEA migrated to the other phase. Additionally, the disparity in polarity between the reactants and reaction products constituted the primary determinant for the phase transition. Notably, the regeneration heat of the 1DMA2P/AEEA biphasic solvent (1.83 GJ/t CO2) was approximately 54.1 % lower than that of conventional 5 mol/L monoethanolamine. Owing to its superior absorption properties, excellent regeneration performance, and low regeneration heat, the 1DMA2P/AEEA biphasic solvent is a promising candidate for practical CO2 capture systems.

Evaluation of the effect of water on CO2 absorption in AMP and DMSO systems

Non-aqueous precipitating amine systems for carbon capture allows for CO2 desorption at lower temperatures than conventional aqueous amine systems and can potentially reduce the energy requirement for regeneration. In this work, the influence of water accumulation that may arise from humid gases entering the absorption column was investigated for absorption systems containing 2-amino-2-methyl-1-propanol (AMP) and dimethyl sulfoxide (DMSO). The physical solubility of CO2 decreased with increasing water concentration, as expected from the lower solubility of CO2 in water than in DMSO. The CO2 loading capacity was increased with the addition of water, resulting from formation of bicarbonate with water present in the system. Low lean loadings of 0.1 mol CO2/mol AMP and precipitation was observed in 23 wt% AMP/DMSO with 9 wt% added water, suggesting that some water accumulation might be tolerable while still maintaining the desired properties of the absorption system. NMR was used to study the CO2 reaction products at 30–88 °C. The results suggested that 88 °C can be used for regeneration of the system even with water accumulated in the system. At 80 °C formation of the tentatively assigned species 4,4-dimethyl-1,3-oxazolidin-2-one was observed, indicating that thermal degradation of AMP may occur above this temperature.

Effects of Ru particle size over TiO2 on the catalytic performance of CO2 hydrogenation

The influence of metal particle size over heterogeneous catalysts on the catalytic performance has always been an interesting subject due to its significance from both fundamental and practical perspectives. In this work, we regulated the synthesis of TiO2 by the hydrolysis of different titanium precursors, and as-prepared TiO2 supports were employed to load Ru with impregnation method. Interestingly, we synthesized three Ru-TiO2 catalysts with different Ru particle sizes of 1.1, 2.9 and 5.2 nm. The Ru-TiO2 catalysts were next tested for CO2 hydrogenation reaction, the results show that the medium Ru particles on TiO2 exhibited the best CO2 methanation activity. Based on the characterizations, we observed that the medium Ru particles exhibited the best redox properties compared with small and large Ru particles, which was beneficial to the H2 dissociation; in addition, the medium Ru particles exhibited a moderate ability to activate CO2, resulting in the most favorable formation and decomposition of bidentate bicarbonate. Consequently, the Ru-TiO2 catalyst with medium Ru particles showed the highest activity for CO2 methanation. This study provides a new method to prepare Ru-TiO2 catalysts with different Ru sizes and also presents an understanding of Ru particle size effects on CO2 hydrogenation.

Mechanistic insights into the role of zinc oxide, zirconia and ceria supports in Cu-based catalysts for CO[formula omitted] hydrogenation to methanol

Copper-based catalysts enable the hydrogenation of CO2 to methanol (MeOH). Selective MeOH synthesis requires the interaction of copper with a metal oxide support to facilitate CO2 adsorption and hydrogenation. Here, we systematically appraise the role of ZnO, ZrO2 and CeO2 in Cu-based catalysts for low-pressure (1 bar) MeOH synthesis. During temperature-programmed desorption (TPD) of CO2, the bare ZnO, ZrO2, and CeO2 exhibited desorption events at both low (70–100 °C) and high (400–700 °C) temperatures, also observed when combining each support with copper. Investigations in a packed bed reactor showed suppressed CO by-production over Cu-ZrO2, leading to a 1.5-fold improvement as compared to Cu-ZnO. Upon Cu-CeO2, CO2 was prone to undergo reduction to CO and desorb, resulting in a MeOH yield 9 times lower than over Cu-ZrO2. Experiments aiming at intermittent operation with successive start-ups and shut-downs showed that the performance of Cu-ZrO2 catalyst remained stable, whilst Cu-ZnO deteriorated monotonically, ascribed to sintering driven by OH and H2O species. In situ infrared spectroscopy demonstrated that methanol synthesis over Cu-ZnO progresses via a single pathway with formate species, whilst parallel formate and bicarbonate pathways were demonstrated over Cu-ZrO2. Unlike Cu-ZnO, the formation of bicarbonate over Cu-ZrO2 allows surface OH species to participate in MeOH synthesis, which we link to the superior performance and stability of Cu-ZrO2.

Mg-incorporated sorbent for efficient removal of trace CO from H2 gas

Removal of trace CO impurities is an essential step in the utilization of Hydrogen as a clean energy source. While various solutions are currently employed to address this challenge, there is an urgent need to improve their efficiency. Here, we show that a bead-structured Mg, Cu, and Ce-based sorbent, Mg13CuCeOx, demonstrates superior removal capacity of trace CO from H2 with high stability. The incorporation of Mg boosts sorption performance by enhancing the porous structure and Cu+ surface area. Remarkably, compared to existing pelletized sorbents, Mg13CuCeOx exhibits 15.5 to 50 times greater equilibrium capacity under pressures below 10 Pa CO and 31 times longer breakthrough time in removing 50 ppm CO in H2. Energy-efficient oxidative regeneration using air at 120 °C allows its stable sorption performance over 20 cycles. Through in-situ DRIFTS analysis, we elucidate the reaction mechanism that Mg augments the surface OH groups, promoting the formation of bicarbonate and formate species. This study highlights the potential of MgCuCeOx sorbents in advancing the hydrogen economy by effectively removing trace CO from H2.

Speciation and gas-liquid equilibrium study of CO2 absorption in aqueous MEA-DEEA blends

The blending of primary amines, with fast reaction kinetic, together with tertiary amines, with a large loading capacity, is an increasingly popular approach to develop high-performance CO2 capture sorbents with low energy requirements for regeneration. In this study, we investigated the CO2 absorption performance of several aqueous solutions obtained by mixing ethanolamine (MEA) and diethylethanolamine (DEEA) and compared them with that of individual MEA and DEEA. CO2 loadings at equilibrium were measured experimentally under a wide range of operating conditions, at temperatures between 298 and 323 K, CO2 partial pressures in the range 5–60 kPa, and different amine mixing ratios. In addition, 13C NMR spectroscopy was employed to elucidate the reaction mechanisms and identify the species formed during CO2 capture. The results of the study reveal the intricate interplay of MEA and DEEA in CO2 capture, where MEA carbamate formation predominates in the early stages, gradually shifting to bicarbonate formation as the amine concentration decreases. Moreover, excess properties, which reflect non-ideal behaviors in amine blends, were introduced as a key parameter in the study. An excess property model, based on excess CO2 loading, was developed to accurately predict the CO2 equilibrium solubility without constant experimental measurement. As a result, good agreement was found between the experimental data and those calculated with the model (excess CO2 loading) under the same operating conditions, with a average relative deviation of 1.1%.

Zwitterionic "Solutions" for Reversible CO2 Capture.

The zwitterions resulting from the covalent attachment of 3- or 4-hydroxy benzene to the 1,3-dimethylimidazolium cation represent basic compounds (pKa of 8.68 and 8.99 in aqueous solutions, respectively) that chemisorb in aqueous solutions 0.58 mol/mol of carbon dioxide at 1.3 bar (absolute) and 40 °C. Equimolar amounts of chemisorbed CO2 in these solutions are obtained at 10 bar and 40 °C. Chemisorption takes place through the formation of bicarbonate in the aqueous solution using imidazolium-containing phenolate. CO2 is liberated by simple pressure relief and heating, regenerating the base. The enthalpy of absorption was estimated to be -38 kJ/mol, which is about 30 % lower than the enthalpy of industrially employed aqueous solutions of MDEA (estimated at -53 kJ/mol using the same experimental apparatus). The physisorption of CO2 becomes relevant at higher pressures (>10 bar) in these aqueous solutions. Combined physio- and chemisorption of up to 1.3 mol/mol at 40 bar and 40 °C can be attained with these aqueous zwitterionic solutions that are thermally stable and can be recycled at least 20 times.

CO2 Capture and Release in Amine Solutions: To What Extent Can Molecular Simulations Help Understand the Trends?

Absorption in amine solutions is a well-established advanced technology for CO2 capture. However, the fundamental aspects of the chemical reactions occurring in solution still appear to be unclear. Our previous investigation of aqueous monoethanolamine (MEA) and 2-amino-2-methyl-1,3-propanediol (AMPD), based on ab initio molecular dynamics simulations aided with metadynamics, provided new insights into the reaction mechanisms leading to CO2 capture and release with carbamate formation and dissociation. In particular, the role of water-strongly underestimated in previous computational studies-was established as essential in determining the development of all relevant reactions. In this article, we apply the same simulation protocol to other relevant primary amines, namely, a sterically hindered amine (2-amino-2-methyl-1-propanol (AMP)) and an aromatic amine (benzylamine (BZA)). We also discuss the case of CO2 capture with the formation of bicarbonate. New information is thus obtained that extends our understanding. However, quantitative predictions obtained using molecular simulations suffer from several methodological problems, and comparison among different chemical species is especially demanding. We clarify these problems further with a discussion of previous attempts to explain the different behaviors of AMP and MEA using other types of models and computations.

Getting insight into the CO tolerance over Co-modified MnSm/Ti catalyst for NH3-SCR of NOx at low temperature: Experiments and DFT studies

The existence of carbon monoxide (CO) in industrial boilers flue gas can suppress the performance of the selective catalytic reduction with NH3 (NH3-SCR) for NOx removal at low temperatures over the Mn-based catalyst, and the related mechanism is needed to be revealed for improving the NH3-SCR performance. In this work, the effects of CO on the NH3-SCR performance over MnSm/Ti catalyst were studied, and the CO tolerance of the catalyst with cobalt (Co) modification at low temperatures was evaluated. The DFT calculations were performed to reveal the mechanism for the modification of Co over the MnSm/Ti catalyst. The NOx conversion for MnSm/Ti catalyst decreased by 15.2%-21.4% at 150–300 ℃ due to the presence of CO in the NH3-SCR reaction atmosphere. After introducing Co into MnSm/Ti catalyst, the NOx conversion for MnSmCo/Ti catalyst only decreased by 8.9%-13.8% at 150–300 ℃ with the presence of CO. It was evidenced that the CO tolerance of the MnSm/Ti catalyst was enhanced with the Co modification. The characterizations of catalysts revealed that the adsorptions of NH3 and NO over the MnSm/Ti catalyst were inhibited by the presence of CO in the mixed atmosphere. Furthermore, the presence of CO in the flue gas resulted in the formation of carbonates, bicarbonates, and bridging formate on the surface of the MnSm/Ti catalysts, which would cause a decrease in the content of Mn4+ and Oα on the surface of the catalyst surface. Introducing Co into MnSm/Ti catalyst could enhance the adsorption of NH3 by forming more Lewis acid sites over the MnSmCo/Ti catalyst. The contents of Mn4+ and Oα over MnSmCo/Ti catalyst were increased via the strong electronic interaction between Co ions and Mn ions. DFT calculations proved that the adsorption of CO over the catalyst was suppressed by the modification of Co with the change of the adsorption energy of CO from −167.25 kJ/mol to −53.82 kJ/mol. Additionally, the Co modification facilitated the decomposition of the carbonate formed over the catalyst with the energy barrier of related reactions decreasing from 214.67 kJ/mol to 24.45 kJ/mol, thus improving the CO tolerance of the catalyst.

Longitudinal assessment of mitochondrial dysfunction in acute traumatic brain injury using hyperpolarized [1-13 C]pyruvate.

[13 C]Bicarbonate formation from hyperpolarized [1-13 C]pyruvate via pyruvate dehydrogenase, a key regulatory enzyme, represents the cerebral oxidation of pyruvate and the integrity of mitochondrial function. The present study is to characterize the chronology of cerebral mitochondrial metabolism during secondary injury associated with acute traumatic brain injury (TBI) by longitudinally monitoring [13 C]bicarbonate production from hyperpolarized [1-13 C]pyruvate in rodents. Male Wistar rats were randomly assigned to undergo a controlled-cortical impact (CCI, n = 31) or sham surgery (n = 22). Seventeen of the CCI and 9 of the sham rats longitudinally underwent a 1 H/13 C-integrated MR protocol that includes a bolus injection of hyperpolarized [1-13 C]pyruvate at 0 (2 h), 1, 2, 5, and 10 days post-surgery. Separate CCI and sham rats were used for histological validation and enzyme assays. In addition to elevated lactate, we observed significantly reduced bicarbonate production in the injured site. Unlike the immediate appearance of hyperintensity on T2 -weighted MRI, the contrast of bicarbonate signals between the injured region and the contralateral brain peaked at 24 h post-injury, then fully recovered to the normal level at day 10. A subset of TBI rats demonstrated markedly increased bicarbonate in normal-appearing contralateral brain regions post-injury. This study demonstrates that aberrant mitochondrial metabolism occurring in acute TBI can be monitored by detecting [13 C]bicarbonate production from hyperpolarized [1-13 C]pyruvate, suggesting that [13 C]bicarbonate is a sensitive in-vivo biomarker of the secondary injury processes.