CO2 Adsorption Measurements Research Articles

Graphene oxide-containing chitosan@HKUST-1 beads with increased chemical stability for CO2 capture

HKUST-1 MOF was crystallized within chitosan matrix to form xerogel beads using an in-situ growth approach. Under mild conditions, CS@HKUST-1 xerogel beads exhibit high specific surface areas (SBET) up to 923 m2 g−1. By further incorporating graphene oxide (GO) to form ternary CS-GO@HKUST-1 xerogel beads, the HKUST-1 MOF structure remained stable for up to two days in a water solution at room temperature, whereas the MOF powder and CS@HKUST-1 xerogel beads underwent significant framework collapse within a day. CO2 adsorption measurements on these xerogel beads also show promising CO2 uptakes, surpassing 2.5 mmol g−1 at 298 K and 1 bar. Moreover, these composites could be regenerated for more than 10 cycles without any loss of quantity adsorbed.

Light-Driven Reverse Water Gas Shift Reaction with 1000-H Stability on High-Entropy Alloy Catalysts.

Highly stable and active catalysts are of significant importance and a longstanding challenge for a number of industrial chemical transformations. Here, motivated by the principle of the high entropy-stabilized structure, high-entropy alloy-loaded porous TiO2 as an efficient and sintering-resistant catalyst for the light-driven reverse water gas‒shift reaction without external heating is synthesized. The optimized CoNiCuPdRu/TiO2 catalyst exhibits a long-term stability of 1000h (1.23molgmetal -1h-1 CO production rate, >99% high selectivity). In situ characterizations confirm that the slow diffusion effect of high-entropy alloys endows the catalyst with excellent structural stability. The CO adsorption measurements and theoretical calculations consolidate that the hydrogen surface coverage weakens CO adsorption on the catalyst surface. Two major problems of catalyst deactivation - sintering and poisoning, are handled in one case, which synergistically enable unparalleled stability. This work provides new guidance for the rational design of ultradurable harsh-condition operation catalysts for industrial catalysis.

Cu nanoparticles immobilized in mesopores generated in zeolite for high-performing CO2 hydrogenation to methanol

Copper nanoparticles (Cu NPs) are commonly used as catalyst active components in CO2 hydrogenation reactions. However, they often lose their catalytic activity due to sintering in most reaction environments. This study explores a solution for Cu-supported catalysts used for methanol production from CO2 hydrogenation by fixing Cu NPs in the mesopores generated in zeolite. Mesopores were generated in NaY zeolite by partially dealuminating its framework. High-resolution (scanning) transmission electron microscopy (HR(S)TEM) and CO adsorption measurements confirm that the synthesized mesoporous zeolite-supported Cu NPs are highly dispersed and fixed within the mesopores. In comparison with conventional microporous zeolite-supported Cu NPs (2 wt%), Cu NPs (2 wt%, average size of 2.2 nm) in mesoporous zeolite increased methanol production from ∼26 mmolgCu−1h−1 to approximately 56 mmolgCu−1h−1 at 250 °C. By further modifying the mesoporous zeolite with Zr (2 wt%), Cu NPs increased in size, and the methanol production rate increased approximately 2.2 folds to 125 mmolgCu−1h−1 under similar conditions due to zeolite electronic modification and the newly formed Zr-zeolite/Cu interface. However, the addition of Zr significantly increased the Cu NP size and moved part of them out of the mesopores, lowering their stability. In situ DRIFTS experiments reveal CO2 hydrogenation proceeds through the formate route via a direct formation of dominantly carbonate (*CO3), which hydrogenates to formate (*HCOO) and traces of methoxy (*H3CO), and subsequently methanol (CH3OH). This study reports the design of active and stable catalysts for CO2 hydrogenation to methanol by engineering Cu NPs in zeolite pores.

Effect of synthesis conditions on the properties of 13X zeolites for CO2 adsorption

ABSTRACT The 13X zeolites were successfully synthesized from sodium silicate and sodium aluminate via hydrothermal treatment, and applied to the adsorption of carbon dioxide (CO2). The properties of the 13X zeolites were characterized and tested by powder X-ray diffraction (XRD), N2-physisorption measurements, CO2-temperature programmed desorption (CO2-TPD) and CO2 adsorption measurements. The results demonstrate that H2O/Na2O, Na2O/SiO2, and SiO2/Al2O3 molar ratios have an important influence on the adsorption performance of CO2 because of their different physicochemical properties. The pure 13X zeolite can be obtained with the optimal H2O/Na2O, Na2O/SiO2 and SiO2/Al2O3 molar ratios of 60, 4 and 3 in the preparation process, respectively. The 13X sample prepared with suitable synthesis conditions possesses the highest crystallinity, the maximum values of specific surface area (720.8 m2/g) and pore volume (0.458 cm3/g) and moderate strength of the interaction between 13X and CO2, thus presenting the highest adsorption capacity of CO2 (118.3 mg/g).

Unique Self-Phosphorylating Polybenzimidazole of the 6F Family for HT-PEM Fuel Cell Application.

High-temperature polymer-electrolyte membrane fuel cells (HT-PEMFCs) are a very important type of fuel cells since they operate at 150-200 °C, making it possible to use hydrogen contaminated with CO. However, the need to improve the stability and other properties of gas-diffusion electrodes still impedes their distribution. Self-supporting anodes based on carbon nanofibers (CNF) are prepared using the electrospinning method from a polyacrylonitrile solution containing zirconium salt, followed by pyrolysis. After the deposition of Pt nanoparticles on the CNF surface, the composite anodes are obtained. A new self-phosphorylating polybenzimidazole of the 6F family is applied to the Pt/CNF surface to improve the triple-phase boundary, gas transport, and proton conductivity of the anode. This polymer coating ensures a continuous interface between the anode and proton-conducting membrane. The polymer is investigated using CO2 adsorption, TGA, DTA, FTIR, GPC, and gas permeability measurements. The anodes are studied using SEM, HAADF STEM, and CV. The operation of the membrane-electrode assembly in the H2/air HT-PEMFC shows that the application of the new PBI of the 6F family with good gas permeability as a coating for the CNF anodes results in an enhancement of HT-PEMFC performance, reaching 500 mW/cm2 at 1.3 A/cm2 (at 180 °C), compared with the previously studied PBI-O-PhT-P polymer.

Co/SiO2 Catalyst for Methoxycarbonylation of Acetylene: On Catalytic Performance and Active Species.

Reppe carbonylation of acetylene is an atom-economic and non-petroleum approach to synthesize acrylic acid and acrylate esters, which are key intermediates in the textile, leather finishing, and polymer industries. In the present work, a noble metal-free Co@SiO2 catalyst was prepared and evaluated in the methoxycarbonylation reaction of acetylene. It was discovered that pretreatment of the catalyst by different reductants (i.e., C2H2, CO, H2, and syngas) greatly improved the catalytic activity, of which Co/SiO2-H2 demonstrated the best performance under conditions of 160 °C, 0.05 MPa C2H2, 4 MPa CO, and 1 h, affording a production rate of 4.38 gMA+MP gcat-1 h-1 for methyl acrylate (MA) and methyl propionate (MP) and 0.91 gDMS gcat-1 h-1 for dimethyl succinate (DMS), respectively. Transmission electron microscopy (TEM), X-ray diffraction (XRD), and diffuse reflectance infrared Fourier transform spectra of CO adsorption (CO-DRIFTS) measurements revealed that an H2 reduction decreased the size of the Co nanoparticles and promoted the formation of hollow architectures, leading to an increase in the metal surface area and CO adsorption on the catalyst. The hot filtration experiment confirmed that Co2(CO)8 was generated in situ during the reaction or at the pre-activation stage, which served as the genuine active species. Our work provides a facile and convenient approach to the in situ synthetization of Co2(CO)8 for a Reppe carbonylation reaction.

Cellulose-Amine Porous Materials: The Effect of Activation Method on Structure, Textural Properties, CO2 Capture, and Recyclability.

CO2 capture via physical adsorption on activated porous carbons represents a promising solution towards effective carbon emission mitigation. Additionally, production costs can be further decreased by utilising biomass as the main precursor and applying energy-efficient activation. In this work, we developed novel cellulose-based activated carbons modified with amines (diethylenetriamine (DETA), 1,2-bis(3-aminopropylamino)ethane (BAPE), and melamine (MELA)) with different numbers of nitrogen atoms as in situ N-doping precursors. We investigated the effect of hydrothermal and thermal activation on the development of their physicochemical properties, which significantly influence the resulting CO2 adsorption capacity. This process entailed an initial hydrothermal activation of biomass precursor and amines at 240 °C, resulting in C+DETA, C+BAPE and C+MELA materials. Thermal samples (C+DETA (P), C+BAPE (P), and C+MELA (P)) were synthesised from hydrothermal materials by subsequent KOH chemical activation and pyrolysis in an inert argon atmosphere. Their chemical and structural properties were characterised using elemental analysis (CHN), infrared spectroscopy (IR), scanning electron microscopy (SEM), and thermogravimetric analysis (TG). The calculated specific surface areas (SBET) for thermal products showed higher values (998 m2 g-1 for C+DETA (P), 1076 m2 g-1 for C+BAPE (P), and 1348 m2 g-1 for C+MELA (P)) compared to the hydrothermal products (769 m2 g-1 for C+DETA, 833 m2 g-1 for C+BAPE, and 1079 m2 g-1 for C+MELA). Carbon dioxide adsorption as measured by volumetric and gravimetric methods at 0 and 25 °C, respectively, showed the opposite trend, which can be attributed to the reduced content of primary adsorption sites in the form of amine groups in thermal products. N2 and CO2 adsorption measurements were carried out on hydrothermal (C) and pyrolysed cellulose (C (P)), which showed a several-fold reduction in adsorption properties compared to amine-modified materials. The recyclability of C+MELA, which showed the highest CO2 adsorption capacity (7.34 mmol g-1), was studied using argon purging and thermal regeneration over five adsorption/desorption cycles.

Experimental Measurements and Molecular Simulation of Carbon Dioxide Adsorption on Carbon Surface

Summary Geological sequestration of carbon dioxide (CO2) in depleted gas reservoirs represents a cost-effective solution to mitigate global carbon emissions. The surface chemistry of the reservoir rock, pressure, temperature, and moisture content are critical factors that determine the CO2 adsorption capacity and storage mechanisms. Shale-gas reservoirs are good candidates for this application. However, the interactions between CO2 and organic content still need further investigation. The objectives of this paper are to (i) experimentally evaluate the adsorption isotherm of CO2 on activated carbon, (ii) quantify the nanoscale interfacial interactions between CO2 and the activated carbon surface using Monte Carlo (MC) and molecular dynamic (MD) simulations, (iii) evaluate the modeling reliability using experimental measurements, and (iv) quantify the influence of temperature and geochemistry on the adsorption behavior of CO2 on the surface of activated carbon. These objectives aim at obtaining a better understanding of the behavior of CO2 injection and storage in the kerogen structure of shale-gas formations, where activated carbon is used as a proxy for thermally mature kerogen. We performed experimental measurements, grand canonical Monte Carlo (GCMC) simulations, and MD simulations of CO2 adsorption and diffusion on activated carbon. The experimental work involved measurements of the high-pressure adsorption capacity of activated carbon using pure CO2 gas at a temperature of 300 K. The simulation work started with modeling and validating an activated carbon structure by calibrating the GCMC simulations with experimental CO2 adsorption measurements. Then, we extended the simulation work to quantify the adsorption isotherms at a temperature range of 250–500 K and various surface chemistry conditions. Moreover, CO2 self-diffusion coefficients were quantified at gas pressures of 0.5 MPa, 1 MPa, and 2 MPa using MD simulations. The experimental results showed a typical CO2 excess adsorption trend for the nanoporous structures, with a density of the sorbed gas phase of 504.76 kg/m3. The simulation results were in agreement with experimental adsorption isotherms with a 10.6% average absolute relative difference. The self-diffusion results showed a decrease in gas diffusion with increasing pressure due to the increase in the adsorbed gas amount. Increasing the simulation temperature from 300 K to 400 K led to a decrease in the amount of adsorbed CO2 molecules by about 87% at 2 MPa pressure. Finally, the presence of charged functional groups (e.g., hydroxyl–OH and carboxyl–COOH) led to an increase in the adsorption of CO2 gas to the activated carbon surface. The outcomes of this paper provide new insights about the parameters affecting CO2 adsorption and sequestration in depleted shale-gas reservoirs. This in turn helps in screening the candidate shale-gas reservoirs for carbon capture, sequestration, and storage to maximize the CO2 storage capacity.

Adsorptive removal of carbon dioxide gas by TEA-activated biochar prepared using different biomass precursor

The presence of carbon dioxide (CO2) pollutant in the atmosphere has resulted in catastrophic damage to environmental sustainability. Adsorbents such as activated carbon (AC), zeolite, and silica have been studied for the adsorption of CO2, and AC has gained much research traction as AC offers high surface area, high porosity, high removal capacity and fast kinetic in removing pollutants. Biomass wastes are abundant, cheap, and high in carbon content, making them ideal for AC production. Sugarcane bagasse (SB), coconut shell (CS), and empty palm oil fruit bunch (FB) biomass wastes were used to make AC adsorbent in this study. The wastes were converted into carbon through a carbonisation process, followed by chemical activation using triethanolamine (TEA). The physicochemical characteristics of the AC adsorbents were characterised for their surface morphologies, elemental composition, surface area and porosity, and measurement of their effectiveness towards removing CO2 gas. The result of characterisation analysis shows AC from SB and CS have excellent pore formation compared to AC from FB on their surfaces. The elemental composition shows AC-CS have the highest surface area of 684.82 m2/g with the highest elemental carbon content of 90.00% among the AC adsorbents. The CO2 adsorption measurement shows AC-CS had the highest adsorption capacity of 2.5595 mmol/g, followed by AC-SB (Q = 1.9193 mmol/g) and AC-FB (Q = 1.5745 mmol/g). The high adsorption capacity and excellent physicochemical characteristics of AC-CS indicate promising capabilities of the AC adsorbent for further utilisation in the industrial application of CO2 removal.

CO2-Induced Gate-Opening Adsorption on a Chabazite/Phillipsite Composite Zeolite Transformed from a Faujasite Zeolite Using Organic Structure-Directing Agent-Free Steam-Assisted Conversion.

Organic structure-directing agent-free steam-assisted conversion and Cs+ ion exchange were used to transform the faujasite (FAU)-type zeolite to the Cs+-type chabazite/phillipsite (CHA/PHI) composite zeolite. Compared with the pure PHI-type zeolite, the Cs+-type CHA/PHI zeolite showed gate-opening CO2 adsorption behavior and good thermal stability. In situ powder X-ray diffraction (PXRD) of the CO2 adsorption was measured to elucidate the mechanism for the gate-opening adsorption on the CHA/PHI zeolite. The Na+-type CHA/PHI zeolite did not show such adsorption behavior, and the PXRD pattern of the Na+-type CHA/PHI zeolite did not change with increasing CO2 partial pressure, which suggests that this unique adsorption behavior was caused by the PHI framework transition or Cs+ ions moving in both the CHA and PHI frameworks. Furthermore, in situ Fourier-transform infrared spectra of CO2 adsorption and CO2 breakthrough measurement on the Cs+-type CHA/PHI zeolite suggest that the CHA and PHI frameworks in the CHA/PHI zeolite shared eight-membered-ring windows and that CO2 molecules could easily diffuse from a CHA cage to a PHI framework. The ideal adsorbed solution theory was used to calculate the CO2/N2 separation selectivity for the Cs+-type CHA/PHI zeolite. At 298 and 318 K, the Cs+-type CHA/PHI composite zeolite showed a high CO2/N2 separation coefficient of >10,000 compared with other zeolites with high CO2 adsorption capacity. Furthermore, the CO2 working capacity was calculated for the Cs+-type CHA/PHI zeolite in both the pressure- and temperature-swing processes, and the results showed that the CHA/PHI composite zeolite could selectively separate CO2 from the CO2/N2 gas mixtures released from power generation plants operating using these processes.

N-doped sponge-like biochar: A promising CO2 sorbent for CO₂/CH₄ and CO2/N₂ gas separation

Sponge-like biochar sorbents were prepared from the dissolution of chitosan followed by freeze-drying methodology and pyrolysis at three different temperatures (400, 600, and 800 °C) to produce sustainable N-enriched carbon materials with enhanced CO2 uptake from CO2/CH4 and CO2/N2 gas mixtures. The pyrolysis process was reproduced by operando TGA-IR to study the gas evolved from the pyrolysis process. It was found that the pyrolysis temperature highly influences the textural properties of the chitosan sponge-like biochar materials, impacting mainly the amount and type of the N-species on the sample but also at the microporosity. XPS revealed the transformation of the amino groups from chitosan into pyridinic-N, pyrrolic-N, graphitic center-N, and graphitic valley-N or pyridine-N oxide species during the pyrolysis process. Increasing the pyrolysis temperature enhanced the quantity of the latter two N-type species. All sponge-like biochars adsorbed higher amounts of CO2 compared with CH4 and N2 gases, with maximum CO2 uptake (∼1.6 mmol⋅g−1) at 100 kPa and 25 °C for the sample pyrolyzed at 600 °C (named CTO_P600). Biochar produced at 800 °C showed no longer adsorption capacity for CH4 and N2, having the highest selectivity value for CO2/N2 separation under continuous flux conditions among all prepared biochar sorbents. Isobaric CO2 adsorption measurements on the CTO_P600 sorbent revealed that physisorption phenomena predominantly governed the CO2 adsorption process, which was confirmed by its consistent adsorption capacity after 10 consecutive adsorption–desorption cycles. Moreover, the biochar exhibited tolerance to water vapor adsorption, indicating its suitability to work under moisture-rich conditions.

Insights into the Oxidative Degradation Mechanism of Solid Amine Sorbents for CO2 Capture from Air: Roles of Atmospheric Water

AbstractDirect air capture (DAC) processes for extraction of CO2 from ambient air are unique among chemical processes in that they operate outdoors with minimal feed pretreatments. Here, the impact of humidity on the oxidative degradation of a prototypical solid supported amine sorbent, poly(ethylenimine) (PEI) supported on Al2O3, is explored in detail. By combining CO2 adsorption measurements, oxidative degradation rates, elemental analyses, solid‐state NMR and in situ IR spectroscopic analysis in conjunction with 18O labeling of water, a comprehensive picture of sorbent oxidation is achieved under accelerated conditions. We demonstrated that the presence of water vapor can play an important role in accelerating the degradation reactions. From the study we inferred the identity and kinetics of formation of the major oxidative products, and the role(s) of humidity. Our data are consistent with a radical mediated autooxidative degradation mechanism.

Insights into the Oxidative Degradation Mechanism of Solid Amine Sorbents for CO2 Capture from Air: Roles of Atmospheric Water.

Direct air capture (DAC) processes for extraction of CO2 from ambient air are unique among chemical processes in that they operate outdoors conditions with minimal feed pretreatments. Here, the impact of humidity on the oxidative degradation of a prototypical solid supported amine sorbent, poly(ethylenimine) (PEI) supported on Al2O3, is explored in detail. By combining CO2 adsorption measurements, oxidative degradation rates, elemental analyses, solid-state NMR and in situ IR spectroscopic analysis in conjunction with 18O labeling of water, a comprehensive picture of sorbent oxidation is achieved under accelerated conditions. We demonstrated that the presence of water vapor can play an important role in accelerating the degradation reactions. From the study we inferred the identity and kinetics of formation of the major oxidative products, and the role(s) of humidity. Our data are consistent with a radical mediated autooxidative degradation mechanism.

Hydrogen, carbon dioxide, and methane adsorption potential on Jordanian organic-rich source rocks: Implications for underground H2 storage and retrieval

Hydrogen (H2) storage in geological formations offers a potential large-scale solution suitable for an industrial-scale hydrogen economy. However, the presence of organic residuals can significantly influence the H2 storage efficiency, as well as cushion gas performance, such as CO2 and CH4, injected to maintain healthy reservoir pressure. Thus, the H2 storage efficiency and cushion gas selectivity were thoroughly investigated in this work based on H2, CO2, and CH4 adsorption measurements using, for the first time, actual organic-rich carbonate-rich Jordanian source rock samples (TOC = 13 % to 18 %), measured at 60 °C temperature and a wide range of pressure (0.1 – 10.0 MPa). Initially, the samples were characterized using various analytical methods. Results demonstrated that H2 adsorption capacities reached up to 0.47 mol/kg at 9.0 MPa. The measured adsorption of CO2 was four times higher than H2. An increase in TOC significantly decreased H2 adsorption compared to CO2 and CH4. Additionally, CO2 demonstrated preferential behavior as a cushion gas compared to CH4, attributed mainly to the calcite content and presence of carboxyl and sulfonyl groups. This study provides fundamental data for understanding H2 potential storage issues in an organic-rich rock formation and thus aids in the industrial implementation of an H2 supply chain.

Highly Efficient Catalysts for CO2 Fixation using Guanidinium‐Functionalized Zr‐MOFs

AbstractAn effective approach for tuning CO2 adsorption, activation and transformations of various epoxides in CO2 fixation reactions is introducing functional groups into the pores of metal‐organic frameworks (MOFs) through ligand modification. Herein, a novel ionic ligand, 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene‐biphenyl‐4,4′‐dicarboxylic acid (H2BPDC−[TBD]+Br−), was synthesized to construct derivatives of the cationic guanidinium‐containing Zr‐MOF (UiO67‐[TBD]+Br−) with free bromide ions, as multifunctional heterogeneous catalysts. The materials were characterized comprehensively by multiple techniques such as PXRD, FTIR, TGA, SEM, EDS, 1H NMR, 13C NMR, mass spectrometry (MS), elemental analysis, as well as N2 and CO2 adsorption measurements. The synthesized UiO67‐[TBD]+Br− exhibits an efficient heterogeneous catalytic performance in the CO2 fixation reaction with epoxides, with high yield and selectivity, under mild conditions (0.1 MPa CO2, 80 °C, without co‐catalyst and solvent). In addition, these catalysts display good thermal stability, recyclability and could be reused at least five times without a significant decrease in their catalytic performance.

Engineering vacancy and hydrophobicity of spherical coral-like CuO catalyst for effective electrochemical CO2 reduction to ethylene

Electrochemical carbon dioxide reduction (ECR) to ethylene by using renewable energy is a viable way to tackle the global climate change, and beneficial to facilitate closing the carbon cycle. Herein, a sulfur-doped spherical coral-like CuO (S-CuO) catalyst was facile synthesized, which is enabling efficient conversion CO2-to-C2H4. The obtained 5% S-CuO can reach the Faradaic efficiency (C2H4) of 48.4% with a current density of 15 mA cm−2 at -1.3 V vs. RHE, which maintained stability over 20 h in 0.1 M KHCO3 electrolyte. XPS, SEM, TEM, and XRD were applied in the characterization of the materials. EPR, CO2 adsorption measurements and density functional theory calculations results indicate that the incorporation of S can promote CO2 adsorption, activation and the formation of *COOH intermediate, which is boosting CO2 conversion enabling the high selectivity to C2H4. Compared to unmodified CuO, electrocatalytic studies show that the greatly increased C2H4 activity on S-CuO is because of the fast electron transfer. Meanwhile, the contact angle measurement reveals the excellent selectivity is derived from the suppression of the hydrogen evolution reaction after the S doping.

Occurrence of moisture in deep gas-bearing shale matrix and its impacts on methane adsorption/desorption capability under favorable reservoir conditions.

To comprehend impacts of moisture on exploring and producing shale gas, the rules of pseudo-in situ moisture occurrence in deep shales were revealed through low-pressure N2 adsorption and desorption, and CO2 adsorption measurements. The influences of pseudo-in situ moisture on CH4 adsorption/desorption in the shales were explored at 353.15 K and pressures up to 30 MPa by using the volumetric method. Results showed that the pseudo-in situ moisture content of the shales ranges between 0.57% and 0.94%, which positively correlates with clay mineral content but negatively correlates with organic matter and quartz. The clay minerals contribute more to moisture occurrence mainly via adsorption effect. The pores with the diameters of 1.10-4.10 nm of the shales serve as dominant space for accommodating moisture. Moreover, the pseudo-in situ moisture reduces saturated adsorption capacity and isosteric adsorption heat of CH4 on the shales, suggesting the weakened adsorption affinity toward CH4-shale system. Typically, the minor pseudo-in situ moisture could significantly weaken CH4 adsorption capability of the shales with low clay mineral content through blocking pore throats of organic matter-hosted pores. However, the abundant pseudo-in situ moisture only slightly reduces CH4 adsorption capability of the shales with high clay mineral content due to continuous distribution of organic matter-hosted pores. The aforementioned different roles are dominated by the difference in occurrence characteristics of organic matter-hosted pores and clay mineral-hosted pores between the shales with low clay mineral content and the shales with high clay mineral content. Furthermore, the pseudo-in situ moisture strengthens CH4 adsorption/desorption hysteresis on the shales associated with moisture uptake-induced clay mineral swelling, thereby raising difficulty for CH4 desorption from the shales.

Efficient CO2 adsorption on porous carbon with nitrogen functionalities based on polybenzoxazine: High-pressure adsorption characteristics

Ordered-interconnected porous carbon with nitrogen functionalities is a potential adsorbent for CO2 capture since it could adsorb CO2 gas through both physical and chemical mechanisms. Herein, we reported the preparation of ordered-interconnected porous carbons having nitrogen functionalities based on polybenzoxazine using a silica templating method. The CO2 adsorption measurement was performed at 30 °C and the pressure was varied from 1 to 40 bar. The results showed that the specific surface area (SSA) and pore volume showed a correlation trend indicating the increase with increasing silica templates up to 40 % and the carbon samples contained nitrogen functionalities on the surface (pyrrolic and pyridonic nitrogen, pyridinic nitrogen, and oxidized nitrogen). After CO2 activation, the nitrogen functionalities are still present on the surface of the porous carbon and the sample based on 40 wt% of silica (AC40%Si-800) exhibited the greatest SSA (1,391 m2/g) with extremely large pore volume (3.77 cm3/g). This led to the largest amount of CO2 uptake (25.07 mmol/g at 40 bar) recorded to date. For the first time, the computational study revealed that only pyridinic nitrogen (N-6) is capable of chemically adsorbing CO2 molecules via Lewis acid-base interaction, which synergistically enhanced the adsorption capability.

Interfacial Unit-Dependent Catalytic Activity for CO Oxidation over Cerium Oxysulfate Cluster Assemblies.

Atomically precise cerium oxo clusters offer a platform to investigate structure-property relationships that are much more complex in the ill-defined bulk material cerium dioxide. We investigated the activity of the MCe70 torus family (M = Cd, Ce, Co, Cu, Fe, Ni, and Zn), a family of discrete oxysulfate-based Ce70 rings linked by monomeric cation units, for CO oxidation. CuCe70 emerged as the best performing MCe70 catalyst among those tested, prompting our exploration of the role of the interfacial unit on catalytic activity. Temperature-programmed reduction (TPR) studies of the catalysts indicated a lower temperature reduction in CuCe70 as compared to CeCe70. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) indicated that CuCe70 exhibited a faster formation of Ce3+ and contained CO bridging sites absent in CeCe70. Isothermal CO adsorption measurements demonstrated a greater uptake of CO by CuCe70 as compared to CeCe70. The calculated energies for the formation of a single oxygen defect in the structure significantly decreased with the presence of Cu at the linkage site as opposed to Ce. This study revealed that atomic-level changes in the interfacial unit can change the reducibility, CO binding/uptake, and oxygen vacancy defect formation energetics in the MCe70 family to thus tune their catalytic activity.

The Kinetics of Formation of Microporous Polytriazine in Diphenyl Sulfone.

This study highlights the value of nonisothermal kinetic methods in selecting temperature conditions for the isothermal preparation of microporous polymeric materials. A dicyanate ester is synthesized and the kinetics of its polymerization in diphenyl sulfone are studied by calorimetry under nonisothermal conditions. The kinetics are analyzed by a model-based approach, using the Kamal model, as well as by a model-free approach, using an advanced isoconversional method. Both approaches correctly predict the time to completion of polymerization at a given temperature. The material prepared independently at the predicted temperature is characterized by electron microscopy and CO2 adsorption measurements and is confirmed to possess a microporous structure with a multimodal distribution of micropores with two major maxima at ~0.5 and 0.8 nm.