The investigation on cationic exchange capacity of zeolites: the use as selective ion trappers in the electrokinetic soil technique

The cation exchange capacity (CEC) of porous zeolites allows to adsorb in the framework cavities the cations as pollutant heavy metal ions. We investigate the CEC behaviour of different zeolites in different experimental conditions; in solution where the ion's mobility is spontaneous and free and in the electrokinetic system where the ion's mobility is driven by the electric field. The aim of this study is to investigate if the CEC is an useful property to create a special interface region of zeolites, that if placed in the electrokinetic cell, just before the cathode, could allow to capture and concentrate the heavy metallic ions, during their migrating process. The zeolite 13X investigated in the electrokinetic proofs, retains a good high ions adsorption, even if quite smaller than the relevant free solution condition and well acts as confined trap for the heavy metal ions. In fact no trace of metallic deposition are present on the electrode's surface.     

Catalytically active centres of faujasite-type zeolites in H2S + SO2 reaction

The influence of the basicity and acidity of faujasite-type zeolites on their catalytic activity in the H₂S + SO₂ reaction was investigated. The catalytic activity increases with the increase of the number of alumina—oxygen tetrahedra in the zeolite unit cell. Oxygen anions bound to aluminium cations in the zeolite framework play the role of catalytically active basic sites. Brönsted-type acidity retarded the catalyst activity. The poisoning of acid sites with pyridine causes the increase of the activity of zeolites and the blocking of basic centres causes the decrease of the catalytic activity. The influence of the electrostatic potential of the alkaline cations in the zeolite framework on the catalytic activity was observed.     

Synergy-Compensation Effect of Ferroelectric Polarization and Cationic Vacancy Collaboratively Promoting CO2 Photoreduction

Photocatalytic CO₂ reduction is severely limited by the rapid recombination of photo-generated charges and insufficient reactive sites. Creating electric field and defects are effective strategies to inhibit charge recombination and enrich catalytic sites, respectively. Herein, a coupled strategy of ferroelectric poling and cationic vacancy is developed to achieve high-performance CO₂ photoreduction on ferroelectric Bi₂MoO₆, and their interesting synergy-compensation relationship is first disclosed. Corona poling increases the remnant polarization of Bi₂MoO₆ to enhance the intrinsic electric field for promoting charge separation, while it decreases the CO₂ adsorption. The introduced Mo vacancy (V_Mo) facilitates the adsorption and activation of CO₂, and surface charge separation by creating local electric field. Unfortunately, V_Mo largely reduces the remnant polarization intensity. Coupling poling and V_Mo not only integrate their advantages, resulting in an approximately sevenfold increased surface charge transfer efficiency, but also compensate for their shortcomings, for example, V_Mo largely alleviates the negative effects of ferroelectric poling on CO₂ adsorption. In the absence of co-catalyst or sacrificial agent, the poled Bi₂MoO₆ with V_Mo exhibits a superior CO₂-to-CO evolution rate of 19.75 µmol g⁻¹ h⁻¹, ≈8.4 times higher than the Bi₂MoO₆ nanosheets. This work provides new ideas for exploring the role of polarization and defects in photocatalysis.     

2D Transition Metal Carbides (MXenes) for Carbon Capture

Global warming caused by burning of fossil fuels is indisputably one of mankind's greatest challenges in the 21st century. To reduce the ever‐increasing CO₂ emissions released into the atmosphere, dry solid adsorbents with large surface‐to‐volume ratio such as carbonaceous materials, zeolites, and metal–organic frameworks have emerged as promising material candidates for capturing CO₂. However, challenges remain because of limited CO₂/N₂ selectivity and long‐term stability. The effective adsorption of CO₂ gas (≈12 mol kg^?1) on individual sheets of 2D transition metal carbides (referred to as MXenes) is reported here. It is shown that exposure to N₂ gas results in no adsorption, consistent with first‐principles calculations. The adsorption efficiency combined with the CO₂/N₂ selectivity, together with a chemical and thermal stability, identifies the archetype Ti₃C₂ MXene as a new material for carbon capture (CC) applications.     

Reduction behaviour of (AgNa)A and (AgM2+Na)A zeolites

The reduction of silver-exchanged A zeolites proceeds in at least two distinct steps. At lower reduction temperatures up to 500 K about 67% of the silver ions present in the lattice of the unreduced zeolites are reduced and charged silver clusters (Ag₃⁺) are formed. This process is accompanied by a redistribution of the remaining cations resulting in characteristic changes of the adsorption properties. The position of silver ions in (AgNa)A and (AgM²⁺Na)A zeolites does not influence their reduction behaviour in the first reaction step, The further reduction of the Ag₃⁺ clusters at higher temperatures depends on the Ag-exchange and on the kind of M²⁺ ion, It seems that the low temperature reduction proceeds over either Ag₉⁺ or Ag₉²⁺ species depending on the silver content.     

Strain-Engineering of Mesoporous Cs3Bi2Br9/BiVO4 S-Scheme Heterojunction for Efficient CO2 Photoreduction

Slow charge kinetics and unfavorable CO₂ adsorption/activation strongly inhibit CO₂ photoreduction. In this study, a strain-engineered Cs₃Bi₂Br₉/hierarchically porous BiVO₄ (s-CBB/HP-BVO) heterojunction with improved charge separation and tailored CO₂ adsorption/activation capability is developed. Density functional theory calculations suggest that the presence of tensile strain in Cs₃Bi₂Br₉ can significantly downshift the p-band center of the active Bi atoms, which enhances the adsorption/activation of inert CO₂. Meanwhile, in situ irradiation X-ray photoelectron spectroscopy and electron spin resonance confirm that efficient charge transfer occurs in s-CBB/HP-BVO following an S-scheme with built-in electric field acceleration. Therefore, the well-designed s-CBB/HP-BVO heterojunction exhibits a boosted photocatalytic activity, with a total electron consumption rate of 70.63 µmol g⁻¹ h⁻¹, and 79.66% selectivity of CO production. Additionally, in situ diffuse reflectance infrared Fourier transform spectroscopy reveals that CO₂ photoreduction undergoes a formaldehyde-mediated reaction process. This work provides insight into strain engineering to improve the photocatalytic performance of halide perovskite.     

Fixation of krypton in type-A zeolites and its leakage characteristics

Kr was loaded forcibly into ion-exchanged type-A zeolites (Na⁺-, K+-, Rb⁺- and Ca²⁺-A) by applying both high temperature (300°-500°C) and pressure (51–101 MPa) and the leakage behaviour of the fixed Kr has been investigated. The sufficient amount of Kr was successfully encapsulated into the α-cages of Na⁺-, K⁺-, and Rb⁺-A, although they were hydrated to some extent. The temperatures of maximum rate of Kr leakage increased with increase in the ionic radii of exchanged alkali cations, while the amount of Kr fixed in zeolites decreased. The coexistent hydrated water in the Kr-loaded type-A zeolites was found not to influence the leakage of Kr from them. It was concluded that the fixation of Kr into the α-cages of hydrated type-A zeolites is possible when the effective diameter of the 8-membered oxygen rings is reduced to narrower size by the exchangeable cations with larger ionic radii than Rb⁺ and the encapsulated zeolites are stored in water-free atmosphere.     

介孔材料CO2吸附性能的研究进展

介孔材料以其适中的孔径、大的比表面积、较高的热稳定性和水热稳定性,在吸附、催化、分离等方面有着广阔的应用前景。综述了近年来介孔材料在CO2吸附领域的研究进展,重点介绍了介孔材料及改性介孔材料吸收CO2的方法;并指出以新材料特别是介孔材料为主体进行碳捕集是今后的主要研究方向。     

Introduction of Cr(V), Mo(V) and V(IV) ions in cationic positions of high-silica zeolites by a solid-state reaction

Calcinatión of H-mordenite or H-ZSM—5 with some compounds of Cr(III), Cr(VI), Mo(V) and V(V) is accompanied by the migration of metal ions into zeolite channels. The ions, which migrate from the outer surface of zeolite crystals, are coordinated in the cationic positions of the zeolites. Most of the migrated ions are located in H-ZSM—5 channels as isolated cations (Cr(V), Mo(V), V(IV)) accessible to gas phase molecules. The accessibility of the cations is confirmed by the strong influence of O₂ adsorption on hyperfine structure (h.f.s.) of e.s.r. spectra for Cr(V), Mo(V) and V(IV). The possibility of cation introduction in high-silica zeolites by a solid-state reaction is determined by the presence of acid sites which may be considered as powerful ‘traps’ for migrating ions. The solid-state interaction at temperatures up to 820°C does not permit the exchange of Na⁺ cations for polyvalent cations.     

Amine-impregnated MCM-41 in post-combustion CO2 capture: Synthesis,characterization, isotherm modelling

In this study, a composite mesoporous silica material MCM-41 (Mobil composite matter) is impregnated with monoethanolamine (MEA) as primary linear amine, benzylamine (BZA) as primary cyclic amine and N-(2-aminoethyl) ethanolamine (AEEA) as secondary diamine and the effects of amine loading, amine type, CO₂ partial pressure and adsorption temperatures on the CO₂ adsorption are investigated. The CO₂ adsorption performances of MCM-41 and amine impregnated MCM-41 samples are studied up to 1 bar of CO₂ partial pressure and the temperature range of 25–60 °C. The amine loadings (% impregnation) are optimized for maximum CO₂ uptake. The materials are characterised using N₂ adsorption/desorption isotherm, Fourier Transform Infrared (FT-IR) Spectroscopy, Thermogravimetric (TGA) and Elemental (CHNS) analysis. The materials have shown good structural and thermal stability. The MCM-41-40%AEEA, MCM-41-40%BZA and MCM-41-50%MEA samples are exhibited the CO₂ adsorption capacity of 2.34 mmol/g (102.98 mg/g), 0.908 mmol/g (39.96 mg/g) and 1.47 mmol/g (64.69 mg/g) respectively. The CO₂ uptake of MCM-41-40%AEEA is 3.5 times higher than that of in MCM-41 (0.68 mmol/g) and it is also the highest reported value as di-amine impregnated MCM-41. The results indicated that the adsorption capacities of the materials (MCM-41 and MCM-41-40%AEEA) are decreased with an increase of adsorption temperature in the range of 25–60 °C. The Freundlich, Langmuir, Sips and Toth isotherm models are used to correlate and predict experimental CO₂ adsorption data. The Sips and Toth isotherm models are found to be better fitted with the experimental data. The isosteric heat of adsorption of MCM-41 and MCM-41-40%AEEA samples are also calculated from Van’t Hoff plot using iSorbHP-win instrumental analysis software in the experimental temperature range.     

Enhancing Electrochemical CO2 Reduction on Perovskite Oxide for Solid Oxide Electrolysis Cells through In Situ A-Site Deficiencies and Surface Carbonate Deposition Induced by Lithium Cation Doping and Exsolution

Solid oxide electrolysis cells (SOECs) hold enormous potential for efficient conversion of CO₂ to CO at low cost and high reaction kinetics. The identification of active cathodes is highly desirable to promote the SOEC's performance. This study explores a lithium-doped perovskite La_0.6-xLi_xSr_0.4Co_0.7Mn_0.3O_3-δ (x = 0, 0.025 0.05, and 0.10) material with in situ generated A-site deficiency and surface carbonate as SOEC cathodes  for CO₂ reduction. The experimental results indicate that the SOEC with the La_0.55Li_0.05Sr_0.4Co_0.7Mn_0.3O_3-δ cathode exhibits a current density of 0.991 A cm⁻² at 1.5 V/800 °C, which is an improvement of ≈30% over the pristine sample. Furthermore, SOECs based on the proposed cathode demonstrate excellent stability over 300 h for pure CO₂ electrolysis. The addition of lithium with high basicity, low valance, and small radius, coupled with A-site deficiency, promotes the formation of oxygen vacancy and modifies the electronic structure of active sites, thus enhancing CO₂ adsorption, dissociation process, and CO desorption steps as corroborated by the experimental analysis and the density functional theory calculation. It is further confirmed that Li-ion migration to the cathode surface forms carbonate and consequently provides the perovskite cathode with an impressive anti-carbon deposition capability, as well as electrolysis activity.     

Experimental and modelling studies of carbon dioxide adsorption by porous biomass derived activated carbon

The goal of the study was to produce a low-cost activated carbon from agricultural residues via single stage carbon dioxide (CO₂) activation and to investigate its applicability in capturing CO₂ flue gas. The performance of the activated carbon was characterized in terms of the chemical composition, surface morphology as well as textural characteristics. The adsorption capacity was investigated at three temperatures of 25, 50 and 100 °C for different types of adsorbate, such as purified carbon dioxide and binary mixture of carbon dioxide and nitrogen. The purified CO₂ adsorption study showed that the greatest adsorption capacity of the optimized activated carbon of 1.79 mmol g^?1 was obtained at the lowest operating temperature. In addition, the adsorption study proved that the adsorption capacity for binary mixtures was lower due to the reduction in partial pressure. The experimental values of the purified CO₂ adsorption were modelled by the Lagergren pseudo-first-order model, pseudo-second-order model, and intra-particle diffusion model. Based on the analysis, it inferred that the adsorption of CO₂ followed the pseudo-second-order model with regression coefficient value higher than 0.995. In addition, the adsorption study was governed by both film diffusion and intra-particle diffusion. The activation energy that was lesser than 25 kJ mol^?1 implied that physical adsorption (physisorption) occurred.     

Bimetallic Metal‐Organic Frameworks: Probing the Lewis Acid Site for CO2 Conversion

A highly porous metal‐organic framework (MOF) incorporating two kinds of second building units (SBUs), i.e., dimeric paddlewheel (Zn₂(COO)₄) and tetrameric (Zn₄(O)(CO₂)₆), is successfully assembled by the reaction of a tricarboxylate ligand with Zn^II ion. Subsequently, single‐crystal‐to‐single‐crystal metal cation exchange using the constructed MOF is investigated, and the results show that Cu^II and Co^II ions can selectively be introduced into the MOF without compromising the crystallinity of the pristine framework. This metal cation‐exchangeable MOF provides a useful platform for studying the metal effect on both gas adsorption and catalytic activity of the resulted MOFs. While the gas adsorption experiments reveal that Cu^II and Co^II exchanged samples exhibit comparable CO₂ adsorption capability to the pristine Zn^II‐based MOF under the same conditions, catalytic investigations for the cycloaddition reaction of CO₂ with epoxides into related carbonates demonstrate that Zn^II‐based MOF affords the highest catalytic activity as compared with Cu^II and Co^II exchanged ones. Molecular dynamic simulations are carried out to further confirm the catalytic performance of these constructed MOFs on chemical fixation of CO₂ to carbonates. This research sheds light on how metal exchange can influence intrinsic properties of MOFs.     

Effect of Synthesis Parameters on the Formation of Zeolitic Imidazolate Framework 8 (ZIF-8) Nanoparticles for CO2 Adsorption

Zeolitic imidazole frameworks-8 (ZIF-8) is a subclass of metal-organic frameworks (MOFs) with the transition metal cations (Zn²⁺) linked by imidazolate anions forming tetrahedral frameworks in zeolite-like topologies. This article reports on the synthesis of ZIF-8 nanoparticles by varying the synthesis parameters at room temperature. The crystallization duration, molar ratios, and pH of the mixture solution were varied in order to study the effects of these parameters on the formation of ZIF-8 nanoparticles. The structural and morphology transformation of the resultant particles were characterized using x-ray diffraction, field emission scanning electron microscopy, and Brunauer–Emmett–Teller (BET) surface analysis. The CO₂ adsorption characteristics of ZIF-8 nanoparticles were tested using CO₂ physisorption analysis. Mature structural evolution was observed for ZIF-8 synthesized at 60 and 1440 min, but insufficient crystallization was found for ZIF-8 synthesized at 5 min. Meanwhile, ZIF-8 nanoparticles synthesized under lower amount of methanol resulted in larger particle size and higher crystallinity. Poorly intergrown ZIF-8 nanoparticles were observed for samples synthesized using a mixture solution with pH 8.2. Although different particle sizes and relative crystallinities were obtained for the ZIF-8 samples, synthesis using different molar ratios of the mixture solution, insignificant variations of BET surface areas, and CO₂ adsorption capacities were found.     

Sorption of carbon dioxide in cation exchanged Y type zeolites: Sorption isotherms and state of sorbed molecule

The sorption of carbon dioxide in a series of Y type zeolites exchanged with La³⁺, Ca²⁺, NH₄⁺ and mixtures of these cations, is studied in the range 273–423 K. The results are discussed in terms of cation specificity and contribution of quadrupole moment to the sorption energetics. Equilibrium sorption capacity followed the sequence Na-Y > La(32)-Y > … > La(92)-Y for La³⁺ exchanged zeolites and Na-Y > Ca(85)-Y > … H(85)-Y > La(60)H(25)-Y > La(60) Ca(25)-Y for other zeolites. At comparatively lower pressures and higher temperatures Ca(85)-Y was found to have highest sorption capacity, indicating predominently the effect of cationic charge over that of cation density on the CO₂ sorption at low coverage. The decrease in sorption capacity CO₂ was 70% as compared to only 10% in case of nitrogen sorption from NaY to La(92)-Y.The sorption data yielded linear Dubinin plots, however, the saturation capacities obtained from these plots, were found to be higher as compared to those obtained experimentally. Both the Koble—Corrigan and Sips equation gave linear plots up to a pressure of 300 Torr. The number of active centres for CO₂ sorption, estimated from Koble-Corrigan exponent ‘n’ decreased with the increase in temperature and the degree of exchange.The sorption data fitted the statistical isotherm models derived from Langmuir and Volmer equation for ideal systems. The linear plots of ln K_L and In K_v against coverage were obtained in case of NaY and H(85)-Y indicating the applicability of both the localized and mobile sorption without interaction. In case of Ca(85)-Y and La³⁺ exchanged zeolites both the ln K_L and In K_v did not yield linear plots against coverage indicating neither localized nor mobile model with or without molecule—molecule interaction, could represent the sorption data.     

Preparation and CO_2 adsorption properties of porous carbon by hydrothermal carbonization of tree leaves

Porous carbon materials were prepared by hydrothermal carbonization(HTC) and KOH activation of camphor leaves and camellia leaves. The morphology, pore structure, chemical properties and CO_2 capture ability of the porous carbon prepared from the two leaves were compared. The effect of HTC temperature on the structure and CO_2 adsorption properties was especially investigated. It was found that HTC temperature had a major effect on the structure of the product and the ability to capture CO_2. The porous carbon materials prepared from camellia leaves at the HTC temperature of 240℃ had the highest proportion of microporous structure, the largest specific surface area(up to 1823.77 m~2/g) and the maximum CO_2 adsorption capacity of 8.30 mmol/g at 25℃ under 0.4 MPa. For all prepared porous carbons, simulation results of isothermal adsorption model showed that Langmuir isotherm model described the adsorption equilibrium data better than Freundlich isotherm model. For porous carbons prepared from camphor leaves, pseudo-first order kinetic model was well fitted with the experimental data. However,for porous carbons prepared from camellia leaves, both pseudo-first and pseudo-second order kinetics model adsorption behaviors were present. The porous carbon materials prepared from tree leaves provided a feasible option for CO_2 capture with low cost, environmental friendship and high capture capability.     

Atomically Dispersed Electron Traps in Cu Doped BiOBr Boosting CO2 Reduction to Methanol by Pure H2O

Overall photocatalytic conversion of CO₂ and pure H₂O driven by solar irradiation into methanol provides a sustainable approach for extraterrestrial synthesis. However, few photocatalysts exhibit efficient production of CH₃OH. Here, BiOBr nanosheets supporting atomic Cu catalysts for CO₂ reduction are reported. The investigation of charge dynamics demonstrates a strong built-in electric field established by isolated Cu sites as electron traps to facilitate charge transfer and stabilize charge carriers. As result, the catalysts exhibit a substantially high catalytic performance with methanol productivity of 627.66 µmol g_catal⁻¹ h⁻¹ and selectivity of ≈90% with an apparent quantum efficiency of 12.23%. Mechanism studies reveal that the high selectivity of methanol can be ascribed to energy-favorable hydrogenation of *CO intermediate giving rise to *CHO. The unfavorable adsorption on Cu₁@BiOBr prevents methanol from being oxidized by photogenerated holes. This work highlights the great potential of single-atom photocatalysts in chemical transformation and energy storage reactions.     

Carbon dioxide adsorption using amine-functionalized mesocellular siliceous foams

Mesocellular siliceous foams (MCFs) with and without remaining template were prepared and modified by polyethylenimine (PEI) or mixed amines [Diethylenetriamine and PEI or 3-aminopropyltrimethoxysilane (APTMS) and PEI]. These samples were evaluated for their adsorption capacities for CO₂ at different temperatures. With the increase of PEI loading, the optimal adsorption temperature shifts to higher temperature for samples prepared in our study. The remaining template in MCF materials plays an important role in promoting CO₂ adsorption capacity, which could be 3.24 mmol/g when the amount of PEI loading is 70 % at 85 °C. Meanwhile, the remaining template contributes greatly to the dispersion of PEI, resulting in higher adsorption capacity at low temperature. The effect of the amount of remaining template was studied, and it was found that CO₂ adsorption capacity decreases with increasing template. The CO₂ adsorption capacities for mixed-amine-modified MCFs are higher than those of the samples modified by PEI only, which was ascribed to the better dispersion of PEI. MCF modified with the mixing of APTMS and PEI exhibited highest adsorption capacity of 2.67 mmol/g at 50 °C. These findings reveal that pore structure, PEI loading, PEI dispersion, and remaining template work together to influence the CO₂ adsorption performance.     

Metal–Organic‐Framework‐Based Catalysts for Photoreduction of CO2

Photoreduction of CO₂ into reusable carbon forms is considered as a promising approach to address the crisis of energy from fossil fuels and reduce excessive CO₂ emission. Recently, metal–organic frameworks (MOFs) have attracted much attention as CO₂ photoreduction‐related catalysts, owing to their unique electronic band structures, excellent CO₂ adsorption capacities, and tailorable light‐absorption abilities. Recent advances on the design, synthesis, and CO₂ reduction applications of MOF‐based photocatalysts are discussed here, beginning with the introduction of the characteristics of high‐efficiency photocatalysts and structural advantages of MOFs. The roles of MOFs in CO₂ photoreduction systems as photocatalysts, photocatalytic hosts, and cocatalysts are analyzed. Detailed discussions focus on two constituents of pure MOFs (metal clusters such as Ti–O, Zr–O, and Fe–O clusters and functional organic linkers such as amino‐modified, photosensitizer‐functionalized, and electron‐rich conjugated linkers) and three types of MOF‐based composites (metal–MOF, semiconductor–MOF, and photosensitizer–MOF composites). The constituents, CO₂ adsorption capacities, absorption edges, and photocatalytic activities of these photocatalysts are highlighted to provide fundamental guidance to rational design of efficient MOF‐based photocatalyst materials for CO₂ reduction. A perspective of future research directions, critical challenges to be met, and potential solutions in this research field concludes the discussion.