Aqueous Carbonate Research Articles

Ring Expansion via One-Pot Conversion of Lactone Acetals to Cyclic Enones. Synthesis of (±)-1-epi-Xerantholide.

Baeyer-Villiger oxidation of α-alkoxy ketones 1 provides lactone acetals 2, which react with the lithium salts of dimethyl(alkyl) phosphonates in the presence of LaCl3·2LiCl to provide cyclic enones 3 in good to excellent yields after treatment with dilute aqueous potassium carbonate. Thus, five-, six-, and seven-membered lactones are converted to five-, six-, and seven-membered cyclic enones. The utility of this two-step ring expansion method is demonstrated in the synthesis of (±)-1-epi-xerantholide from 5-methyl-2-cyclohexen-1-one.

Hybrid solvent loop CO2 capture process for zero-emission hydrogen production

Natural gas reforming with CO2 capture is expected to play a crucial role in producing low-carbon hydrogen under the net-zero emission scenario. This work focuses on optimizing the CO2 capture processes for zero-emission hydrogen production, targeting an ultra-high CO2 capture ratio of 99.9 % from the shifted syngas. We present a novel hybrid solvent loop CO2 capture process that enhances capture efficiency by overcoming the inherent trade-off between CO2 absorption kinetics and capacity in conventional processes. This is achieved by utilizing two independent solvent loops, each operating within its optimal performance range. In the lower section of the absorber, a high-capacity solvent, aqueous potassium carbonate, is used to leverage the high CO2 partial pressure. In the upper section, a fast-kinetic solvent, aqueous monoethanolamine, is employed to reduce CO2 concentration to 100 ppm. The conventional process, split-flow process with a multi-pressure stripper, and the hybrid solvent loop process are modeled in Aspen Plus® and compared. Our results demonstrate that the proposed hybrid solvent loop configuration outperforms conventional methods, significantly reducing the CO2 regeneration duty by 25 % and total equivalent work by 16 %. This process enhances the feasibility of low-carbon hydrogen production and supports the goal of achieving net-zero emissions.

Investigating the generation mechanism of nanobubbles and the ion-transport regulation on nanofiltration membranes for efficient salt-salt separation

Nanofoaming-assisted interfacial polymerization (IP) exhibits strong potential to regulate the structure and the separation performance of thin film composite (TFC) membranes. At present, it is recognized that when NaHCO3 is employed as an aqueous foaming agent, the generation of nanobubbles is ascribed to the NaHCO3 acidification and may be enhanced by increasing the NaHCO3 dosage. However, to more accurately measure the generation of nanobubbles, it is necessary to analyze the content and composition of carbonates in the aqueous solution at the initial and final states of interfacial polymerization, which is currently lacking in research. In this work, based on the chemical equilibrium theory, the aqueous carbonate chemistry and the quantity of CO2 released during IP was evaluated through monitoring the pH changes near the interface and calculating the carbonate distribution fraction. Results showed that the pH of the aqueous solution changed from 10.3∼11.4 to 6.0∼6.5 during interfacial polymerization when the NaHCO3 dosage was 0.00∼0.10 wt%. However, this variation in pH was subtle (from ∼9.3 to ∼8.8) when 1.00 wt% NaHCO3 was added, leading to limited transformation of carbonate into H2CO3 and, consequently, less generation of CO2. In the whole dosage range of NaHCO3, 0.10 wt% NaHCO3 contributed to the maximum quantity of CO2 during IP, which was also confirmed by the vesicle-like membrane morphology. The resultant membrane achieved a superior salt-salt separation, with selectivity for Mg2+ and Li+/Na+/K+ enhancements of more than 2 times compared to the membrane without NaHCO3 dosage. This work proposed a new approach to evaluate the inner relationship between NaHCO3 dosage and nanobubble quantity during IP, which provides an ion-transport regulation mechanism of nanofiltration membranes for efficient salt-salt separation.

Indole-3-Carbinol Upconversion with Copper Oxide Nanoparticles Supported Graphitic Carbon Nitride: A Sustainable Approach

Electro-organic chemistry offers a sustainable and efficient approach to organic synthesis by utilizing electrochemical processes. This field has gained significant attention due to its potential for minimizing waste, reducing energy consumption, and enabling selective transformations. Herein, we report the development of a graphitic carbon nitride-coated carbon fiber electrode modified with electropolymerized amino-2-thiazole and electrodeposited Cu2O nanoparticles from copper nitrate trihydrate for the oxidation of Indole-3-carbinol (IC). Scanning electron microscopy, X-ray diffraction analysis, and X-ray photoelectron spectroscopy studies were carried out to characterize the developed electrode. Cyclic voltammetry, electrochemical impedance spectroscopy, and bulk electrolysis techniques were employed for the electrochemical studies. The enhanced electrochemical activity of the Cu2O-pAT-GCN-TCFP electrode compared to the individual GCN and polymer electrode was studied using electrochemical characterization, which revealed a 3-fold increase in the current response for Cu2O-pAT-GCN-TCFP (0.0011 A) compared to the bare electrode. The reaction was carried out using an aqueous carbonate buffer solution as an electrolyte via bulk electrolysis at a set potential of 0.82 V. The product obtained was isolated by column chromatography to obtain a yield of 74% and characterized by proton nuclear magnetic resonance (1H NMR) spectroscopy. Additionally, the Cu2O-pAT-GCN-TCFP electrode was studied for its stability, reproducibility, and selectivity.

Water Transport Management in a Bipolar Membrane for CO2 Electrolysis Application

Bipolar membranes (BPMs) offer significant potential for electrochemical technologies, especially in CO2 electrolysis. Their unique ability to create pH gradients provides optimum chemical microenvironments at the cathode and anode for efficient, cheap and sustainable CO2 electrolysis. However, state-of-the-art BPMs are limited in their performance due to phenomena such as membrane degradation and membrane dehydration leading to low ionic conductivity, and hence their complete potential for various electrochemical technologies is yet to be realized. Previous studies have identified water transport as one of the main factors limiting the performance of BPM. A multi-physics model of BPM can serve as a useful tool to gain a comprehensive understanding of different performance limiting factors and thereafter propose solutions to overcome these limitations. The goal of the present study is to provide model based design guidelines for a BPM that facilitates efficient water transport, making it a suitable candidate for integration into a zero-gap CO2 reduction electrolyzer operating at industrial-grade performance levels.We have built a 1-D continuum model of a BPM kept in an aqueous (bi)carbonate electrolyte solution, incorporating physical phenomena such as water-dependent transport of ions and neutral species, field-enhanced homogeneous reactions (water-dissociation and acid-base reactions) along with CO2 phase transfer reaction at the BPM-aqueous electrolyte interfaces. The continuum model employs Poisson-Nernst-Planck equations to resolve local chemical species concentration. The effect of the electric field on the equilibrium dissociation constants of various charge-generating homogenous reactions is incorporated. This becomes important especially at interfaces within the domain where a sharp increase in electric field is observed. Unlike previous modeling studies, we also incorporate mass-conservation equation for water transport to resolve local water concentration inside the BPM. Local water concentration influences the transport of species in the BPM through their water-dependent activity and diffusivity. The electric potential distribution is resolved by incorporating water-dependent local permittivity of the BPM.Our model investigates both the reverse and forward bias operational modes of the BPM. In alignment with the experimental observation, in the reverse bias regime, the model identifies a distinct initial phase where current density is limited, with the majority of the current carried by protons and hydroxide ions at low overpotentials. As the potential increases, there's a rapid increase in current density, indicating a breakdown regime caused by an electric field-enhanced water dissociation reaction at the BPM interface. At even higher potentials, the polarization curve enters a third phase where the current density saturates characterized by water transport limitation. This aspect of the BPM polarization curve is uniquely captured by our model. Conversely, in the forward bias mode, as expected we do not observe any limitations due to mass transport, since water is generated at the bipolar junction. Here, the model forecasts a saturation of CO2 in the electrolyte, leading to gas bubbles forming at the BPM interface. To address the issue of water transport limitation, we conduct various parametric studies focusing on different membrane characteristics, such as individual layer thicknesses and their ion exchange capacities. The outcomes of these analyses provide crucial guidelines for optimizing these parameters and enhancing water management in BPM-based systems.

Photoinduced Carbon Dioxide Release via a Metastable Photoacid in a Nonaqueous Environment.

Capturing carbon dioxide (CO2) from the atmosphere is a scientific and technological challenge. CO2 can be captured by forming carbamate bonds with amines, most notably monoethanolamine (MEA). Regenerating MEA by releasing captured CO2 requires that the carbamate solution be heated. Recently, photoacids were used to induce a pH change to release CO2 from aqueous carbonate solutions. We report a merocyanine photoacid that releases CO2 from nonaqueous carbamate solutions of MEA, which has a CO2 loading capacity that is higher than that of water. On the basis of the absorption spectra of the photoacid in the presence of acids and CO2, we show that the photoacid cycle and the CO2 capture of MEA are two separate equilibria coupled to each other via protons. We demonstrate that irradiating the sample with 405 nm light induces the release of CO2, which we detect using an in-line mass spectrometer. This work highlights an alternative path for optimizing a photoinduced CO2 capture and release system.

Thermodynamic Predictions of Hydrogen Generation during the Serpentinization of Harzburgite with Seawater-derived Brines

Salty aqueous solutions (brines) occur on Earth and may be prevalent elsewhere. Serpentinization represents a family of geochemical reactions where the hydration of olivine-rich rocks can release aqueous hydrogen, H2(aq), as a byproduct, and hydrogen is a known basal electron donor for terrestrial biology. While the effects of lithological differences on serpentinization products have been thoroughly investigated, effects focusing on compositional differences of the reacting fluid have received less attention. In this contribution, we investigate how the chemistry of seawater-derived brines affects the generation of biologically available hydrogen resulting from the serpentinization of harzburgite. We numerically investigate the serpentinization of ultramafic rocks at equilibrium with an array of brines at different water activities (a proxy for salt concentration in aqueous fluids and a determinant for habitability) derived from seawater evaporation. Because the existing supersaturation of aqueous calcium carbonate, a contributor to dissolved inorganic carbon (DIC) in natural seawater, cannot be captured in equilibrium calculations, we bookend our calculations by enabling and suppressing carbonate minerals when simulating serpentinization. We find that the extent of DIC supersaturation can provide an important control of hydrogen availability. Increased DIC becomes a major sink for hydrogen by producing formate and associated complexes when the reacting fluids are acidic enough to allow for CO2. Indeed, H2(aq) reduces CO2(aq) to formate, leading to a hydrogen deficit. These conclusions provide additional insights into the habitability of brine systems, given their potential for serpentinization across diverse planetary bodies such as on Mars and ocean worlds.

Crosslinked hydrogel-derived carbons activated by trace amounts of aqueous potassium carbonate for carbon dioxide adsorption

A new method for green synthesis of activated carbon using chitosan-based hydrogel precursors is reported. Chitosan-based hydrogel materials are designed to absorb trace amounts of non-toxic and non-corrosive activating agent K2CO3 from dilute aqueous solution. The K2CO3 impregnated hydrogels are further freeze-dried and converted to activated carbons with tuneable pore structure by a single-step pyrolysis. Activated carbon with highest pore volume of 0.76 cm3/g and surface area of 2026 m2/g is obtained by using K2CO3 as low as 0.23 g per gram of chitosan hydrogel. It can adsorb maximum CO2 of 4.2 mmol/g at 25 °C and 1 bar. This study demonstrates that biopolymer hydrogels impregnated with trace amounts of K2CO3 are excellent precursor materials to design high surface area carbons for CO2 capture.

Chemical Textures on Rare Earth Carbonates: An Experimental Approach to Mimic the Formation of Bastnäsite.

The interaction between multi-component rare earth element (REE) aqueous solutions and carbonate grains (dolomite, aragonite, and calcite) are studied at hydrothermal conditions (21-210°C). The effect of ionic radii of five REEs (La, Ce, Pr, Nd, Dy) on solid formation are analyzed using two solution types: equal REE concentrations and concentrations normalized to Post Archean Australian Shale Standard (PAAS). The interaction replaces the host Ca-Mg carbonate grains with a series of REE minerals (lanthanite → kozoite → bastnäsite → cerianite). At 165°C, equal concentration solutions promote kozoite crystallization, maintaining similar REE ratios in solids and solution. PAAS solutions result in zoned REE-bearing crystals with heterogeneous elemental distributions and discreet REE phases (e.g., cerianite). Chemical signatures indicate metastable REE-bearing phases transforming into more stable polymorphs, along with symplectite textures formed by adjacent phase reactions. Overall, experiments highlight the dependence of polymorph selection, crystallization pathway, mineral formation kinetics, and chemical texture on REE concentrations, ionic radii, temperature, time, and host grain solubility.

CO2 absorption using aqueous potassium carbonate (K2CO3) promoted by piperazine (PZ) in packed column reactor

Carbon dioxide (CO2) is the main contributor in gases that can reduce the heating value and the greenhouse effect on the atmosphere. Several CO2 absorption technologies can be used to reduce CO2 content. Chemical absorption have selectivity and a high absorption rate. This research will study the effect of the addition piperazine (PZ) into 30wt % potassium carbonate (K2CO3) at 30 °C, 40 °C and 50 °C, PZ (1, 3 and 5) % and absorbent flow rate (1, 1.5 and 2) L min−1. The research was conducted in packed column made of stainless steel with height 150 cm and a diameter 9.6 cm filled with packing-type raschig rings made of ceramic arranged randomly to expand the contact between gas and absorbent during CO2 absorption. The process is carried in counter-current, gas streamed at constant flow rate 50 L min−1 from the bottom and absorbent with composition K2CO3, PZ and distilled water streamed from top of column. CO2 loading and CO2 removal in the sample were determined by acid-base titration. The results showed 5% PZ CO2 loading 0.0664 mole CO2/mole K2CO3 and CO2 removal 92.7575% at operating conditions 50 °C and absorbent flow rate 2 L min−1. The addition 5% PZ can increase CO2 removal 16.9525%.

Dynamic Inhibition of Calcite Dissolution in Flowing Acidic Pb2+ Solutions.

Reactions of mineral surfaces with dissolved metal ions at far-from-equilibrium conditions can deviate significantly from those in near-equilibrium systems due to steep concentration gradients, ion-surface interactions, and reactant transport effects that can lead to emergent behavior. We explored the effect of dissolved Pb2+ on the dissolution rate and topographic evolution of calcite (104) surfaces under far-from-equilibrium acidic conditions (pH 3.7) in a confined single-pass laminar-flow geometry. Operando measurements by digital holographic microscopy were conducted over a range of Pb2+ concentrations ([Pb2+] = 0 to 5 × 10-2 M) and flow velocities (v = 1.67-53.3 mm s-1). Calcite (104) surface dissolution rates decreased with increasing [Pb2+]. The inhibition of dissolution and the emergence of unique topographic features, including micropyramids, variable etch pit shapes, and larger scale topographic patterns, became increasingly apparent at [Pb2+] ≥ 5 × 10-3 M. A better understanding of such dynamic reactivity could be crucial for constructing accurate models of geochemical transport in aqueous carbonate systems.

Phenolate-thiazole based reversible “turn-on” chemosensor for the selective detection of carbonate anion: X-ray crystallography, DFT/TDFT, and cell study

A new phenolate-thiazole derivative (L) has been synthesized and structurally characterized.The chemo-sensing activity of L is detected by the naked eye for the aqueous carbonate anion in the pH range of 4 to 8. The selective ‘turn-on’ fluorescence occurs through the formation of a stable intermediate L∙CO32–(1) following the PET mechanism. The limit of detection (LOD) is found 0.18 µM based on the absorbance-based assay.The quinonoid form of bromophenol unit binds strongly with CO32– through thiazole nitrogen and hydrazinic nitrogen. Further, the selective holding of CO32– anion over other planar tetranuclear anions (e.g., SO32–, NO3–) happens with several intra and intermolecular hydrogen bonds as envisaged by the DFT/TDFT study. The formation mechanism of L∙CO32– is proposed based on experimental and theoretical studies. The biological experiments (MTT and cell imaging)reveal the non-cytotoxicity nature of L and the biocompatible uptake of L mostly in the cytoplasm at physiological pH.

Exothermic, sluggish biphasic extraction of uranyl through polygonal bipyramidal chloroacetamide complexes in ionic liquid

An exothermic, spontaneous, highly efficient, sluggish biphasic extractive mass transfer of uranyl ion have been reported from aqueous acidic solution using chloroacetamide ligands into highly viscous ionic liquid involving UO2(NO3)(Chloroacetamide)2+ species predominantly following diffusion controlled ‘cation exchange’ mechanism. The O-donor of chloroacetamide monodentate ligand and O-donor of the bidentate NO3− were coordinated to the UO22+ ion. The average U−OUO2 bond distance is found to be the shortest (1.788 Å), followed by U−Ochloroacetamide (2.439 Å and 2.446 Å for L1 and L2) and U–ONO3 (2.511 Å). The donation of electron density from the O-donors to the central U atom was evidenced by lowering of positive charge (∼0.28) on U atom from [UO2(H2O)5]2+ to UO2(NO3)(Chloroacetamide)2+ complexes. In these uranyl complexes, the contributions from the electrostatic and orbital interaction were found to be ∼73.7–75.2 % and 22.4–23.9 %, respectively of the total contribution, which was estimated as −518.9 and −582.2 kcal mol−1. The ionic liquid based solvent systems exhibited moderate radiolytic stability and good back extract ability using aqueous carbonate complex. The regeneration ability has been clearly demonstrated for five consecutive cycles consisting of one extraction and three back extraction cycles without much compromise on the performance (reduction in DU values were within 5–10 %).

Water-Degradable Oxygen-Rich Polymers with AB/ABB Units from Fast and Selective Copolymerization.

Researchers have been chasing plastics that can automatically and fully degrade into valuable products under natural conditions. Here, we develop a series of water-degradable polymers from the first reported fast and selective cationic copolymerization of formaldehyde (B) with cyclic anhydrides (A). In addition to readily accessible monomers, the method is performed at industrially relevant temperatures (~100 °C), takes tens or even minutes, and uses common acid as the catalyst. Interestingly, such polymers possess tunable AB/ABB-type repeating units, which are considered to be thermodynamic and kinetic products, respectively, resulting in low carbon content ([O] : [C] up to 1 : 1). Notably, the polymers can completely degrade to valuable diacids within 150 days in water at ambient temperature owing to the incorporation of carboxyl terminals and acid-responsive acetal units. By washing with aqueous sodium carbonate, the polymers are relatively stable over several months.

Water‐Degradable Oxygen‐Rich Polymers with AB/ABB Units from Fast and Selective Copolymerization

AbstractResearchers have been chasing plastics that can automatically and fully degrade into valuable products under natural conditions. Here, we develop a series of water‐degradable polymers from the first reported fast and selective cationic copolymerization of formaldehyde (B) with cyclic anhydrides (A). In addition to readily accessible monomers, the method is performed at industrially relevant temperatures (~100 °C), takes tens or even minutes, and uses common acid as the catalyst. Interestingly, such polymers possess tunable AB/ABB‐type repeating units, which are considered to be thermodynamic and kinetic products, respectively, resulting in low carbon content ([O] : [C] up to 1 : 1). Notably, the polymers can completely degrade to valuable diacids within 150 days in water at ambient temperature owing to the incorporation of carboxyl terminals and acid‐responsive acetal units. By washing with aqueous sodium carbonate, the polymers are relatively stable over several months.

New model for aspartic acid species in aqueous calcium carbonate growth environments: challenges and perspectives.

The lack of experimental data on the dynamics of aspartic acid species in water for its range of protonation states and the details of their atomic-level interaction with aqueous calcium carbonate species is a driver for accurate force field development. A classical model that is consistent with the few pieces of experimental data available and with first principles calculations has been developed. The complex dynamics of the aspartate anions relevant to biomineralization and calcium carbonate crystal growth has been explored in water, providing a quantitative description of solvation structure and free energies, including conformational free energy profiles and pairing free energies. The model has been used to probe the structure and dynamics of aqueous calcium aspartate homo- and hetero-chiral clusters, confirming their unlikelihood due to weak and water-mediated interactions. This supports the hypothesis that the formation of such clusters, observed while growing vaterite in the presence of acidic chiral amino acids, is favoured by the presence of the crystal surface.

Concentration dependence of resistance components in solutions containing dissolved Fe2+/Fe3.

Electrolyte solutions containing Fe2+/Fe3+ are suitable for liquid thermoelectric conversion devices (LTEs), because they are inexpensive materials and exhibit a high electrochemical Seebeck coefficient α. Here, we investigated the concentration (c) dependence of resistance components, i.e., solvent (Rs), charge-transfer (Rct), and diffusion (Rdif) resistances, of dissolved-Fe2+/Fe3+-containing aqueous, methanol (MeOH), acetone, and propylene carbonate (PC) solutions. We found that the c dependence of Rs and Rdif are well reproduced by empirical formulas, and , where η(c) is viscosity at c. We further found that the magnitudes of Cs and Cdif are nearly independent of solvent, suggesting that η is one of the significant solution parameters that determine Rs and Rdif.

Carbon nanotube heterogenization improves cobalt pyridyldiimine complex CO2 reduction activity in aqueous carbonate buffer.

We present two novel cobalt pyridyldiimine complexes functionalized with pyrene. Initially modest in homogeneous acetonitrile solution, their electrocatalytic CO2 reduction performance significantly improves upon immobilization on MWCNTs in an aqueous carbonate buffer. The complexes exhibit outstanding stability, with CO selectivity exceeding 97%, and TON and TOF values reaching up to 104 and above 1.2 s-1, respectively.

The influence of a permanent magnetic field on the crystallization of calcium carbonate from carbonate aqueous solutions

The effect of a permanent magnetic field on the crystallization of calcium carbonate from carbonate aqueous solutions was studied. Based on the equations for the first- and second-order dissociation constants of carbonic acid, the stability constants of NaCO3- and NaHCO30 complexes, the mass balance and electroneutrality equations, the values of the system components and the ratio between the components of the carbonate subsystem were determined, and it was established that the main species in experimental conditions are СО32-, NaСО3- and HСО3- and the main components of the carbonate subsystem are СО32- (86.7%) and HСО3- (13.19%). Studies have shown that with a significant excess of CO32- over HCO3- ions in the solution at temperatures of 18-20˚C, calcite and vaterite are most likely formed. During the crystallization of calcium carbonate from an aqueous carbonate solution in a magnetic field of 125-250 mT, the size of the crystallites increases significantly compared to the absence of a magnetic field.

Metabolic flux analysis of coenzyme Q10 synthesized by Rhodobacter sphaeroides under the influence of different pH regulators

Coenzyme Q10 (CoQ10) is crucial for human beings, especially in the fields of biology and medicine. The aim of this experiment was to investigate the conditions for increasing CoQ10 production. At present, microbial fermentation is the main production method of CoQ10, and the production process of microbial CoQ10 metabolism control fermentation is very critical. Metabolic flux is one of the most important determinants of cell physiology in metabolic engineering. Metabolic flux analysis (MFA) is used to estimate the intracellular flux in metabolic networks. In this experiment, Rhodobacter sphaeroides was used as the research object to analyze the effects of aqueous ammonia (NH3·H2O) and calcium carbonate (CaCO3) on the metabolic flux of CoQ10. When CaCO3 was used to adjust the pH, the yield of CoQ10 was 274.43 mg·L−1 (8.71 mg·g−1 DCW), which was higher than that of NH3·H2O adjustment. The results indicated that when CaCO3 was used to adjust pH, more glucose-6-phosphate (G6P) entered the pentose phosphate (HMP) pathway and produced more NADPH, which enhanced the synthesis of CoQ10. At the chorismic acid node, more metabolic fluxes were involved in the synthesis of p-hydroxybenzoic acid (pHBA; the synthetic precursor of CoQ10), enhancing the anabolic flow of CoQ10. In addition, Ca2+ produced by the reaction of CaCO3 with organic acids promotes the synthesis of CoQ10. In summary, the use of CaCO3 adjustment is more favorable for the synthesis of CoQ10 by R. sphaeroides than NH3·H2O adjustment. The migration of metabolic flux caused by the perturbation of culture conditions was analyzed to compare the changes in the distribution of intracellular metabolic fluxes for the synthesis of CoQ10. Thus, the main nodes of the metabolic network were identified as G6P and chorismic acid. This provides a theoretical basis for the modification of genes related to the CoQ10 synthesis pathway.