CO2 Pressure Research Articles

Interfacial properties of CO2 and liquid sulfur in high-sulfur gas fields: Molecular simulations on carbonate mineral surfaces

As the global energy landscape transforms, the development of high-sulfur natural gas has become increasingly critical. However, sulfur deposition during these gas field developments significantly affects operational efficiency. This study employed molecular dynamics simulation to explore the effectiveness of CO2 in alleviating sulfur deposition on carbonate rock reservoirs. Specifically, it examined the interfacial tension between liquid sulfur and CO2, the wettability of sulfur on carbonate rock mineral surfaces, and the kinetics of CO2 displacing liquid sulfur. Results show that as CO2 pressure increases from 10 MPa to 60 MPa, the interfacial tension between liquid sulfur and CO2 decreases by 84 %, from 35.54 mN/m to 5.53 mN/m. The contact angles of sulfur droplets on calcite and dolomite surfaces stabilize at 41.82° ± 2.10° and 44.33° ± 3.27°, respectively, indicating greater sulfur spread on calcite surfaces. With higher CO2 pressures, sulfur deposition on mineral surfaces and interfacial tension both decrease significantly, while the wetting angle of liquid sulfur increases, particularly on dolomite. At 60 MPa CO2 pressure, the adsorption energy of dolomite for liquid sulfur drops from 364.56 kcal/mol to 25.46 kcal/mol, a 93 % reduction, suggesting CO2′s dual role in displacing sulfur and promoting its desorption from mineral surfaces. Furthermore, the efficiency of sulfur deposition alleviation in carbonate rock slit structures improves and stabilizes at around 40 MPa CO2 pressure. This study presents a potential environmentally friendly approach for efficiently developing high-sulfur gas fields, and its findings provide practical insights for optimizing CO2 injection strategies to mitigate sulfur deposition.

Impact of Alaska atmospheric blocking on the carbon flux in the Northeast Pacific Ocean

The Northeast Pacific Ocean (NEP) is one of the important carbon sinks in the global ocean. The causes of carbon flux changes in this region have been widely studied, but the physical processes associated with large scale climate variability remain controversial primarily due to scarcity of spatially and temporally continuous observations. In this study, we constructed a high-resolution sea surface partial pressure of CO2 (pCO2) from satellite observations for the NEP from 2003 to 2020 using the machine learning based XGBoost model. By analyzing the interannual large-scale high-latitude atmospheric dynamics and ocean physical conditions over the NEP, we find that the CO2 flux density (FCO2) anomalies have a strong correlation with the Alaskan atmospheric blocking events. In the region north of 48°N, anomalous cyclones triggered by atmospheric blocking increased sea surface height (SSH), which reduced the replenishment of dissolved inorganic carbon (DIC) from deep seawater, leading to enhanced carbon uptake. By contrast, in the region south of 48°N, the increase in sea surface temperature (SST) triggered by atmospheric blocking reduced the solubility of CO2 in seawater, resulting in a decrease in regional carbon flux. These results provide new perspectives for better understanding and predicting the effects of high-latitude atmospheric dynamics on regional ocean carbon fluxes.

Visible Light Photoredox‐Catalyzed Three‐Component Reaction of Styrenes with Malonic Esters and CO2

A visible light photoredox‐catalyzed bifunctionalization of styrenes with malonic esters and CO2 to form two C(sp3)–C bonds has been developed. The reaction proceeds at room temperature with 0.1 mol% of the organic photocatalyst (4DPAIPN) and cesium carbonate as a base at a CO2 pressure of 4 atm. This results in the production of 3‐arylpropane‐1,1,3‐tricarboxylic acid esters in yields ranging from 48% to 99%.

Research on the Biogas Production Mechanism of Mudstone in the Qaidam Basin under Different CO2 Pressures.

Mudstone, a class of sedimentary rocks rich in organic matter, possesses considerable potential for biogas production. Mudstones possess a rich biological origin, which is conducive to refining the mechanisms and enrichment patterns of biogenic gas reservoirs. This has significant theoretical and practical implications for guiding the exploration and development of Quaternary mudstone gas reservoirs. Furthermore, the Qaidam Basin is an excellent place for the geological storage of CO2 due to its rich petroleum reservoir conditions. Experimental research on biogas production under diverse CO2 pressure-mudstone-microorganism-water interactions is conducted to determine the biogas production mechanism of mudstone under different CO2 pressures during sequestration circumstances. According to the results: (1) under supercritical carbon dioxide conditions, there is a slight initial increase in biogas production, followed by a gradual decrease. The periods and peaks of gas production vary among the different reaction groups. As carbon dioxide pressure increases, the gas production cycle lengthens significantly, while the gas yield declines. (2) Siderite and secondary carbonate minerals have increased in the mudstone's mineral fraction both before and after biogas production, while clay mineral groups have decreased. Specifically, there was a notable drop in chlorite and kaolinite. (3) Microorganism species in the system were analyzed, and the results showed that there was a gap in each microorganism's ability to adapt to its surroundings, and the diversity and quantity of bacteria declined with increasing pressure. After carbon dioxide was fluxed, there was a considerable shift in the pattern of biogas generation, which consequently had a major impact on the alterations in mineral fractions.

Respiratory responses and isocapnic buffering phase in child and youth soccer players during an incremental exercise test.

This study investigated the respiratory response and isocapnic buffering (IB) phase during an incremental exercise test to exhaustion in 16 child soccer players (11.9±0.9 years) and 18 youth soccer players (18.2±2.9 years). The IB phase was calculated as the difference in oxygen uptake (VO2) between the respiratory compensation point (RCP) and metabolic threshold (MT) and expressed in either absolute or relative values. The maximal oxygen uptake (VO2max) was higher in youth players than in child players. For youth players, VO2max was measured at 55.9 ± 3.6mLmin-1kg-1 and 74.9 ± 4.8mLmin-1kg-0.75, while for child players, VO2max was 50.8 ± 4.1mLmin-1kg-1 and 67.2 ± 6.1mLmin-1kg-0.75 (p < 0.001). MT and RCP occurred at 69.8 ± 6.7% and 90.9 ± 6.9% of VO2max in child players and at 73.9 ± 5.1% and 91.5 ± 4.5% of VO2max in youth players, respectively. The two groups had no significant difference (p > 0.05). Absolute IB (10.6 ± 2.8 vs 9.7 ± 3.1mLmin-1kg-1), relative IB (23.1 ± 5.7 vs 19.1 ± 6.1), and the ratio of RCP VO2 to MT VO2 (1.3 ± 0.09 vs 1.24 ± 0.09) were similar in child and youth players (p > 0.05). There was no difference in minute ventilation (V̇E, mLmin-1kg-1) and respiratory exchange ratio during exercise between the two groups (p > 0.05). During exercise, respiratory frequency, ventilatory equivalent for carbon dioxide (VE/VCO2) and oxygen (VE/VO2), VE/VCO2 slope, end-tidal O2 pressure were higher in child players than in youth players, while tidal volume (L kg-1), O2 pulse, and end-tidal CO2 pressure were lower (p < 0.05). Despite differences in aerobic capacity and ventilatory response to exercise, child players showed similar IB phase as youth players. Although child players have lower ventilation efficiency than youth players, the higher ventilation response for a given VCO2 may provide an advantage in regulating acid-base balance during intense exercise.

LCxSFC Valve Technologies: Guidelines toward a Successful Online Modulation.

Online two-dimensional liquid chromatography can be used under various separation modes but is sometimes limited in terms of orthogonality, especially for the analysis of neutral compounds. The use of SFC in the second dimension offers a wide choice of mobile and stationary phases, suggesting retention properties complementary to those of the first dimension. Initial works on online LCxSFC coupling published in the literature highlighted the first difficulties of solvent compatibility or potential problems with bubbles created by CO2 in loops. The present work highlights the impact of the interface between the LC and SFC dimensions on the performance of the 2D separation. Six different configurations have been evaluated, differing by the addition of a makeup flow in the first dimension, a division, or a separation of flow paths in the second dimension. Their performances with empty loops eliminated the need for complex trapping columns, regardless of the LC mobile phase nature. Injection in partial fill mode was possible without any problems of CO2 bubble formation, solvent miscibility, pressure, or modulation repeatability in each of the studied configurations. Selected configurations even allowed for the use of a mobile phase split upstream of the valve, so that the online LCxSFC configuration could be as flexible as LCxLC instrumentation in terms of the first dimension flow rate or second dimension injected volume. The obtained results allowed for building guidelines presenting the best interfaces to set up depending on the nature of the mobile phases in both dimensions. Two applications on monomers of lignin and industrial polymers confirmed preliminary results on configuration testing and illustrated that online LCxSFC could now be easily implemented. Precision tests on retention time were conclusive and are promising for the future use of this technique in industrial routines.

Vinyl-containing covalent organic frameworks co-polymerized with imidazolium ionic liquids for the efficient cycloaddition of CO2 with epoxides

The chemical fixation of CO2 into high value-added cyclic carbonates over metal- and cocatalyst-free heterogeneous catalyst has attracted considerable attention and is still a challenge. Rationally integrating multifunctional units into porous materials has been regarded as a promising strategy to enhance catalytic efficiency. In this study, the poly (ionic liquid)-hierarchical covalent organic framework (R-PIL-COF, R refers to CH2NH2/CH2OH/COOH/CH3) hybrids were successfully fabricated via in situ copolymerization of vinyl-containing covalent organic framework and hydrogen bond donors (HBDs)-functionalized imidazolium ionic liquids. Among, CH2NH2-PIL-COF hybrid bearing acidic and basic sites possess moderate CO2 adsorption ability and hierarchical pore structure which promoted the activation of CO2 and epichlorohydrin. Furthermore, the influence on the catalytic activity of various HBD groups and grafting amounts of poly (ionic liquid)s were systematically investigated, and CH2NH2-PIL–COF–45 % exhibited an exceptional catalytic performance under mild conditions (100 °C and 1 MPa CO2 pressure). Additionally, CH2NH2-PIL–COF–45 % had broad substrate tolerance and excellent stability. Finally, a synergistic catalytic mechanism was proposed based on the experimental and characterization results. The strategy of co-polymerizing ionic liquids to COF provides a new way to develop efficient COF-based hybrids by the integration of nucleophilic units into the COF skeleton for CO2 fixation under cocatalyst-free and mild conditions.

Effects of accelerated carbonation on fine incineration bottom ash: CO2 uptake, strength improvement, densification, and heavy metal immobilization

Incinerating municipal solid waste (MSW) can effectively reduce its mass and volume while producing electricity. However, this process generates incineration bottom ash (IBA), which is an aggregate-like waste containing heavy metals. Due to the higher heavy metal contents, fine IBA can be removed from total IBA and treated separately to promote the use of IBA. Furthermore, MSW incineration generates carbon dioxide (CO2), which is another concern. In this context, it is beneficial to use accelerated carbonation to treat fine IBA, because it can not only contribute to carbon capture but also provide carbonated IBA that may be utilized as aggregates in civil engineering. The accelerated carbonation process of fine IBA is affected by many parameters. Therefore, this study investigated the effects of CO2 pressure (PCO2), initial water content (wi), and carbonation time on the properties of carbonated IBA, including CO2 uptake, unconfined compressive strength (UCS), density, and leaching of heavy metals. The evolution of mineralogy and microstructure of carbonated IBA was also analyzed. The results showed that IBA with wi of 15% and PCO2 of 200 kPa could achieve a CO2 uptake of 6% of IBA mass. The carbonation time significantly affected UCS and dry density of carbonated IBA. As the carbonation time increased from 0 h to 120 h, the UCS increased from 67 kPa to 691 kPa while the dry density increased from 1.38 g/cm3 to 1.51 g/cm3. Compared with untreated IBA, the leaching concentrations of Cu, Cr, Zn, and Pb from carbonated IBA were reduced significantly. As the carbonation time increased, the microstructure of carbonated IBA became denser. This densified structure was one of the reasons for the strength improvement and dry density increment of carbonated IBA.

Distribution and control mechanism of pCO2 and water-air CO2 efflux in the Pearl River Estuary.

Estuaries are generally considered to be important sources of atmospheric CO2. However, the differences between estuaries, and inadequate observations of partial pressure of CO2 in estuarine water (pCO2water) hamper global estuarine CO2 budgeting. In this study, the longitudinal distribution of CO2 in the waters of Modaomen (MSE) and Lingdingyang (LSE), two sub-estuaries of the Pearl River Estuary (PRE), and its influencing mechanism are studied. The change in the distribution of pCO2water along the distance from the upstream estuary to the ocean between LSE and MSE was significantly different. pCO2water at the LSE ranges from 238 to 7267 µatm, whereas the MSE ranges from 406 to 3078 µatm. Stronger microbial respiration and relatively long water retention times were the main influences that led to higher pCO2water at LSE than at MSE. Seasonally, the increase of soil CO2 into the water in the upstream basin caused by precipitation is the potential influencing factor that the water pCO2water in the flood season is higher than in the dry season. PRE was a net source of atmospheric CO2 with an average annual water-air flux of 41.2 ± 33.3mmolm-2day-1. Our results suggest that the differences in longitudinal gradients of pCO2water between estuaries in the same region and the effects of different gas transport velocity models on CO2 emission estimates need to be considered in estuarine CO2 emission budgeting.

Dissolved organic matter (DOM) rather than warming and eutrophication directly affects partial pressure of CO2 (pCO2) in mesocosm systems

Environmental warming and eutrophication pose significant challenges to shallow lake systems, where dissolved organic matter (DOM) serves as a diverse and intricate mixture of organic macromolecules, playing a pivotal role in aquatic ecosystems. Despite its complexity, comprehending the interplay between environmental changes and DOM composition alterations and their subsequent impacts on aqueous CO2 partial pressure (pCO2) is essential for a better understanding of carbon cycling. Yet, our current understanding in this realm remains limited. To address this gap, mesocosm systems were established to investigate how elevated water temperature and eutrophication, alongside changes in DOM composition, influence pCO2 dynamics. Results indicate that while temperature and nutrient levels do not directly influence pCO2 fluctuations, they indirectly affect aqueous pCO2 through their modulation of DOM composition. Elevated temperature and nutrient concentrations notably enhance both the production and degradation of indigenous protein-like organic matter and increase the accumulation of humic-like organic compounds, with phosphorus released from sediment playing a particularly significant role. Furthermore, the degradation rate of protein-like organic matter significantly exceeds its accumulation rate. On the other hand, the impact of water eutrophication on DOM composition surpasses that of temporal temperature variations, with a 2∼4 °C temperature rise showing minimal effects on DOM composition. Notably, the degradation of protein-like organic matter markedly increases aqueous pCO2, while the rise in humic-like organic matter in water exerts minimal influence on pCO2 concentrations. A comprehensive understanding of carbon cycling processes under environmental changes will facilitate effective management of lake ecosystems and the advancement of carbon mitigation technologies.

Behaviors of hydrate cap formation via CO2-H2O collaborative injection:Applying to secure marine carbon storage

Leakage prevention of carbon dioxide (CO2) determines the safety of carbon marine geological storage. Hydrate caps have been proven to be one of the most effective structures for preventing CO2 leakage, which has attracted worldwide attention. However, the structure and formation behavior of hydrate caps during CO2 storage process are still unclear. In this study, a strategy of CO2-H2O co-injection was proposed to simulate the actual flow process and accelerate the hydrate cap formation rate. A series of CO2-H2O flow rates (0.25–10 mL/min) were employed. The results show that there will be four stages for the dynamic formation process of hydrate cap: fluid migration and diffusion, local hydrate formation, local area plugging, and hydrate cap formation. What's more, the water-gas flow ratio is inversely proportional to hydrate cap formation rate and positively proportional to the carbon storage efficiency. Meanwhile, the huge sealed capacity of hydrate cap was also proved in this work. The sequestration pressure of CO2 under hydrate cap exceeds 12 MPa, and the maximum carbon storage efficiency increases from 53.12% to 93.30%. Moreover, the macrostructure of hydrate cap consists of two layers with a certain hydrate saturation: the zero-permeability layer and the low-permeability layer. The zero-permeability layer determined the sealed capacity of hydrate cap. These findings may provide a theoretical foundation for the prevention of CO2 leakage in actual project of carbon marine geological storage.

Metabolic processes drive spatio-temporal variations of carbon sink/source in a karst river

Riverine carbon dioxide (CO2) exchange is a crucial component of the global carbon cycle. However, the changes in the CO2 sink/source in karst rivers caused by differences in lithological features and climate, hindered the resolution of the spatio-temporal heterogeneity of global inland water carbon emissions. Here, we use hydrochemical data and CO2 gas isotopic data to reveal the spatio-temporal variations of CO2 sink/source in karst rivers and their controlling mechanisms. Fifty-two monitoring transects were set up in the subtropical Lijiang River in southwest China in June and December 2019. Our results indicated that the CO2 flux across the water-air interface (FCO2) in the Lijiang River basin ranged from −43.77 to 519.67 mmol/(m2·d). In June, the Lijiang River acted as an atmospheric carbon source due to higher water temperatures (Twater). However, driven by hydrodynamic conditions and the metabolism of aquatic photosynthesis, the river shifts from being an atmospheric carbon source in June to an atmospheric carbon sink in December. The stable isotopes of CO2 (δ13C-CO2) show significant differences in the spatio-temporal variations of CO2 sink/source. In December, the transects of the Lijiang River basin with a negative CO2 flux are significantly negatively correlated with dissolved oxygen (DO) and chlorophyll-a (Chl-a) concentration (p < 0.05). This confirms that the enhancement of aquatic photosynthesis efficiency increased water DO concentrations, which resulted in the positive movement of water δ13C-CO2 and a decrease in the partial pressure of CO2 (pCO2) and FCO2. Comparative analysis with global river FCO2 indicates that under the combined driving forces of metabolic processes of aquatic photosynthetic organisms and hydrodynamic conditions, rivers tend to act more frequently as CO2 sinks, particularly in subtropical and temperate rivers. In conclusion, this study represents a new example focusing on CO2 dynamics to address the spatio-temporal heterogeneity of carbon emissions in inland waters on a global scale.

Tertiary amine based-biphasic solvent using ionic liquids as an activator to advance the energy-efficient CO2 capture

The newly developed tertiary amine-based biphasic solvents have low reaction heat, and good desorption performance, but no CO2 reactivity under low CO2 pressure. A novel tertiary amine-based biphasic solvent (DMEA/[DETAH]Lys/n-BuOH/H2O, abbreviated as D-DL-B-H) using ionic liquids (ILs) as the activator was proposed. With the assistance of [DETAH]Lys, the CO2-rich phase exhibited enhanced CO2 loading (from 3.69 to 4.09 mol/L) and CO2 distribution (from 88.5 % to 96.8 %). In addition, at 5 kPa, D-DL-B-H achieved an absorption capacity up to 1.58 mol/L, which was 79 times that of the DMEA/n-BuOH/H2O, suggesting the D-DL-B-H had good CO2 capture property at low CO2 pressure. At 393.15 K, the desorption efficiency of D-DL-B-H was as high as 80.9 %. In addition, the Qreg of D-DL-B-H was reduced to 1.78 GJ/t CO2, accounting for 44.61 % of the 30 wt% MEA. At 323.15 K, the viscosity of the CO2-rich phase was only 4.63 mPa·s, and the corrosion rate was 46.88 % of 30 wt% MEA. The reaction mechanism obtained from 13C NMR and DFT analysis indicated that [DETAH]Lys was more inclined to react with CO2 than DMEA. The main reason for the occurrence of phase splitting was the formation of hydrogen bonds between the CO2 product and the water.

Enhanced prediction of corrosion rates of pipeline steels using simulated annealing-optimized ANFIS models

Accurate prediction of corrosion rates is crucial for preventing infrastructure failures, reducing maintenance costs, and ensuring operational safety. Traditional models often struggle to account for the complex, non-linear interactions between environmental factors and material properties. This study presents a novel approach integrating Simulated Annealing (SA) with an Adaptive Network-based Fuzzy Inference System (ANFIS) to improve corrosion rate predictions for pipeline steels. The SA-ANFIS model features six input neurons representing temperature, H₂S pressure, CO₂ pressure, salinity, moisture content, and material type. These factors influence corrosion rates, represented by a single output neuron. The SA algorithm optimizes the ANFIS model's parameters, enhancing its ability to handle non-linear relationships. Historical corrosion data for P110SS, L80, and 2205 Duplex steel were used, incorporating environmental variables such as temperature, pH, and gas pressures. The SA-ANFIS model achieved superior accuracy, with a maximum error of 2.8424 % and an average error of 1.2536 %, outperforming the GA-ANFIS model and conventional ANFIS and SVR models. The SA-ANFIS model offers a robust, optimized tool for predicting corrosion in petroleum pipelines, significantly improving prediction accuracy under harsh conditions.

A Greener Way of Making Cellulose Clothing

Cotton is the world's most demanding non-food crop. Cotton grows in arid countries such as India and China. However, its production consumes an enormous 250 billion tons of water annually, amplifying water scarcity. Cellulose, found in plants like wood, bamboo, and mosses, offers a sustainable alternative for textiles. Traditionally, cellulose is processed into textiles using the viscose method, which involves carbon disulfide. This process releases hydrogen sulfide, harmful to aquatic life and human health, and carbon disulfide, a hazardous pollutant affecting the reproductive system and vision. Many research groups have proposed an alternative method, which involves dissolving cellulose in dimethyl sulfoxide (DMSO) and Diazabicyclo[5.4.0]undec-7-ene (DBU) under 1 atm of CO2. DBU, with a pKaH ~ 12, deprotonates cellulose’s hydroxyl groups forming a DMSO-soluble cellulose carbonate complex that can be spun into filaments. However, DBU is costly, hazardous, and prone to hydrolysis, leading to byproducts. The objective of the research was to find a more environmentally friendly, less toxic, and cost-effective base for cellulose dissolution. Two tertiary amines, triethylamine (pKaH~9) and tripropylamine (pKaH~10.7), were tested. Due to its low basicity triethylamine failed to dissolve cellulose even under high CO2 pressure (up to 50 bar), resulting in a cloudy solution. Tripropylamine is insoluble in DMSO, therefore resulting in a phase separation of a tripropylamine layer and cellulose/DMSO layer. Additionally, 2,2,6,6-tetramethyl-piperidine was also tested at high CO2 pressure (up to 50 bar), but a biphasic solution was formed at 10 bar . This indicates that the protonated form of the base does not dissolve in DMSO. Ultimately, no alternative base was found to be sufficiently basic to deprotonate the hydroxyl groups on cellulose and promote dissolution, even at high pressure.

Hypoxic burden and sleep hypoventilation in obese patients

IntroductionNovel biomarkers of hypoxic load have emerged, as sleep apnea-specific hypoxic burden which provides more precise assessment of intermittent hypoxemia severity. Our main objective was to assess the potential benefit of hypoxic burden to identify obesity-related sleep hypoventilation. We hypothesized that hypoxic burden may help diagnose obesity-related sleep hypoventilation better than usual sleep respiratory measures (i.e., apnea-hypopnea index (AHI), mean SpO2, time with SpO2 < 90 %). MethodsThis retrospective study was conducted from June 2022 to October 2023 at the University Hospital of Rouen, France. All consecutive obese patients (BMI ≥30 kg/m2), adults, with no other respiratory or neurological diseases who underwent a polysomnography or polygraphy with concomitant capnography were included. Sleep hypoventilation was defined according to American Academy of Sleep Medicine criteria based on transcutaneous CO2 monitoring (PtcCO2). Diagnostic performance of sleep-related respiratory measures i.e., sleep apnea-specific hypoxic burden, apnea-hypopnea index (AHI), mean SpO2, time with SpO2 < 90 % was evaluated using Receiver Operating Characteristic (ROC) curves. Correlations between sleep-related respiratory measures were assessed by a Spearman correlation matrix. ResultsAmong 107 obese patients with analyzed capnography, 37 (35 %) had sleep hypoventilation. Patients were 53 ± 14 years old, mean BMI = 38 ± 6 kg/m2, mean AHI = 26.5 ± 25/h, mean hypoxic burden = 67 ± 109 %min/h, mean SpO2 = 91.5 ± 3 %, mean time with SpO2<90 % = 19.4 ± 28 %, mean PtcCO2 = 6.2 ± 0.7 kPa. A low positive correlation was found between hypoxic burden and mean PtcCO2 (r = 0.4, p < 0.001). Multivariate logistic regression model explaining sleep hypoventilation was insufficient with area under ROC curve of hypoxic burden estimated at 0.74 (95 % CI 0.65 to 0.84). ConclusionHypoxic burden has low correlation with transcutaneous CO2 pressure and a low ability to diagnose obesity-related sleep hypoventilation.

Ambient-pressure alkoxycarbonylation for sustainable synthesis of ester

Alkoxycarbonylation reactions are common in the chemical industry, yet process sustainability is limited by the inefficient utilization of CO. In this study, we address this issue and demonstrate that significant improvements can be achieved by adopting a heterogeneously catalyzed process, using a Ru/NbOx catalyst. The Ru/NbOx catalyst enables the direct synthesis of methyl propionate, a key industrial commodity, with over 98% selectivity from CO, ethylene and methanol, without any ligands or acid/base promoters. Under ambient CO pressure, a high CO utilization efficiency (336 mmolestermolCO−1h−1) is achieved. Mechanistic investigations reveal that CO undergoes a methoxycarbonyl (COOCH3) intermediate pathway, attacking the terminal carbon atom of alkene and yielding linear esters. The origins of prevailing linear regioselectivity in esters are revealed. The infrared spectroscopic feature of the key COOCH3 species is observed at 1750 cm−1 (C=O vibration) both experimentally and computationally. The broad substrate applicability of Ru/NbOx catalyst for ester production is demonstrated. This process offers a sustainable and efficient approach with high CO utilization and atom economy for the synthesis of esters.

Unidirectional ice-templating for aerogel adsorbents: Excellent pore structure and high CO2 capture performance for direct air capture

The ultralow atmospheric partial pressure of CO2 (∼40 Pa) presents a significant challenge for direct air capture (DAC). In this study, high-performance porous aerogel adsorbents are prepared using the unidirectional freezing–ice-templating method. The dispersion of the mixed solution is effectively improved by particle size modulation, and functionalized materials with abundant gas channels are constructed by the rapid cooling of liquid N2. The adsorbents feature a cross-structure comprising monolayer active components and nanoscale layered carriers. The unique micro/mesoporous composite structure of the adsorbents facilitates gas-phase transport. When the functional group efficiency is increased by 5.8 times, the prepared adsorbents demonstrate excellent CO2 capture capacity (1.17 mmol/g and 148 mol/m3) and a low adsorption half-time (1.28 min). The unique cross-structure of the adsorbents renders them hydrophobic; thus, they show higher adsorption capacity at high humidity than other moisture swing adsorbents. At the molecular scale, quantum chemical calculations show that appropriate coordination between the active components and carriers enhance the water vapor hindering ability of the adsorbents. The developed aerogel adsorbents significantly expand the application scenarios for moisture swing adsorbents and enhance the efficiency of DAC.

Carbonation mechanism and cementation properties of recycled cement paste based on CO2 injection time and pressure

Current applications of recycled cement paste (RCP) carbonation mainly focus on using carbonized particles as filler materials or enhancing the adhesion of hardened cement paste to aggregates. However, there is limited research on the carbon dioxide (CO2) sequestration effectiveness and strength improvement mechanisms of carbonized waste recycled concrete powder as a cementitious material. This study investigates the carbonation mechanism and cementation properties of RCP under various carbonation conditions. The phase composition and microstructural evolution of RCP are systematically analyzed through detailed characterization tests, exploring the impact of carbonation time and CO2 pressure on the mechanical properties of the RCP samples. These findings demonstrate that prolonged carbonation enhances the formation of calcium carbonate (CaCO3) and crystalline silica (SiO2), which in turn improves particle bonding and reduces porosity. Higher CO2 pressure results in increased carbonation products and tighter interparticle binding. Advanced nuclear magnetic resonance (NMR) analyses indicate that carbonation facilitates the transition of Al from six- to four-coordinated states and the polymerization of SiO4 tetrahedra, leading to enhanced structural cohesion. This study demonstrates the potential of carbonation in reshaping the cementitious properties of RCP, highlighting its environmental and economic benefits for recycling construction waste.

Cenozoic Carbon Dioxide: The 66 Ma Solution

The trend in partial pressure of atmospheric CO2, P(CO2), across the 66 MYr of the Cenozoic requires elucidation and explanation. The Null Hypothesis sets sea surface temperature (SST) as the baseline driver for Cenozoic P(CO2). The crystallization and cooling of flood basalt magmas is proposed to have heated the ocean, producing the Paleocene–Eocene Thermal Maximum (PETM). Heat of fusion and heat capacity were used to calculate flood basalt magmatic Joule heating of the ocean. Each 1 million km3 of oceanic flood basaltic magma liberates ~5.4 × 1024 J, able to heat the global ocean by ~0.97 °C. Henry’s Law for CO2 plus seawater (HS) was calculated using δ18O proxy-estimated Cenozoic SSTs. HS closely parallels Cenozoic SST and predicts the gas solute partition across the sea surface. The fractional change of Henry’s Law constants, Hn−HiHn−H0 is proportional to ΔP(CO2)i, and Hn−HiHn−H0×∆P(CO2)+P(CO2)min, where ΔP(CO2) = P(CO2)max − P(CO2)min, closely reconstructs the proxy estimate of Cenozoic P(CO2) and is most consistent with a 35 °C PETM ocean. Disparities are assigned to carbonate drawdown and organic carbon sedimentation. The Null Hypothesis recovers the glacial/interglacial P(CO2) over the VOSTOK 420 ka ice core record, including the rise to the Holocene. The success of the Null Hypothesis implies that P(CO2) has been a molecular spectator of the Cenozoic climate. A generalizing conclusion is that the notion of atmospheric CO2 as the predominant driver of Cenozoic global surface temperature should be set aside.