Understanding CO2 adsorption mechanisms in porous adsorbents: A solid-state NMR survey

Reaching a historic high of 36.3 gigatonnes in 2021, global CO₂ emissions from fossil fuel combustion continue to increase at an alarming rate. CO₂ removal technologies are part of the solution to tackle this crucial environmental challenge. Thus, the development of porous materials for storage and capture of gas molecules (in particular, carbon capture and storage) has attracted great interest both in academic and industrial communities due to its potential in mitigating atmospheric CO₂ concentrations.Atomic-scale studies in porous materials are essential to stimulate progress in the design of better CO₂-adsorbents by elucidating gas-sorption surface mechanisms.Spectroscopic techniques have the potential to shed light on the structural details of distinct materials' surfaces, including the type of chemical species formed upon CO₂ adsorption. Herein, we review the last 5 years of scientific developments wherein solid-state NMR and computational studies have been explored to investigate at the atomic level the structure and molecular dynamics of CO₂ species formed at porous surfaces.     

Modeling synergistic adsorption of phenol/aniline mixtures in the aqueous phase onto porous polymer adsorbents

The adsorption equilibria of phenol and aniline on nonpolar polymer adsorbents (NDA-100, XAD-4, NDA-16 and NDA-1800) were investigated in single- and binary-solute adsorption systems at 313 K. The results showed that all the adsorption isotherms of phenol and aniline on these adsorbents can be well fitted by Freundlich and Langmuir equations, and the experimental uptake of phenol and aniline in all binary-component systems is obviously higher than predicted by the extended Langmuir model, arising presumably from the synergistic effect caused by the laterally acid-base interaction between the adsorbed phenol and aniline molecules. A new model (MELM) was developed to quantitatively describe the synergistic adsorption behavior of phenol/aniline equimolar mixtures in the binary-solute systems and showed a marked improvement in correlating the binary-solute adsorption of phenol and aniline by comparison with the widely used extended Langmuir model. The newly developed model confirms that the synergistic coefficient of one adsorbate is linearly correlated with the adsorbed amount of the other, and the larger average pore size of adsorbent results in the greater synergistic effect of phenol/aniline equimolar mixtures adsorption.     

Heavy metal ion adsorption onto polypyrrole-impregnated porous carbon

Polypyrrole-impregnated porous carbon was readily synthesized using vapor infiltration polymerization of pyrrole monomers. The results show that the functionalized polymer layer was successfully coated onto the pore surface of carbon without collapse of mesoporous structure. The modified porous carbon exhibited an improved complexation affinity for heavy metal ions such as mercury, lead, and silver ions due to the amine group of polypyrrole. The introduced polypyrrole layer could provide the surface modification to be applied for heavy metal ion adsorbents. Especially, polymer-impregnated porous carbon has an enhanced heavy metal ion uptake, which is 20 times higher than that of adsorbents with amine functional groups. Furthermore, the relationship between the coated polymer amount and surface area was also investigated in regard to adsorption capacity.     

Investigation into the absorptive properties and the secondary porous structure of adsorbents acting as molecular sieves

Summary By starting from data of the literature on the x-ray structure determinations and the composition of the unit celis in crystals of type A zeolites we have calculated limiting values for the amounts and volumes adsorbed by the said zeolites.and these values are in good agreement with the experimental data.     

Polanyi-based models for the adsorption of naphthalene from aqueous solutions onto nonpolar polymeric adsorbents

In this research, naphthalene was adopted as the representative model compound of PAHs, and static adsorption of naphthalene from aqueous solution onto three commercial polymeric adsorbents with different pore structure was investigated. Nonlinear isotherms models, i.e., Freundlich, Langmuir, and Polanyi-Dubinin-Manes (PDM) models were tested to fit experimental data, and the experimental data were found to fit well by the PDM model. Through both isotherm modeling and constructing "characteristic curve," Polanyi theory was useful to describe the adsorption process of naphthalene by polymeric adsorbents, providing evidence that a micropore filling phenomenon was involved during the adsorption process. In addition, a good linear correlation was obtained between the naphthalene adsorption capacities and the micropore volume of adsorbents (Vmicro), whereas no linear relationship was found between the naphthalene adsorption capacities and the specific surface area of adsorbents. Based on the PDM model, the micropore volumes of adsorbents was introduced to normalize the equilibrium adsorbed volume (qv), plots of qv/V(micro) vs adsorption potential density for naphthalene on three different polymeric adsorbents were collapsed to a single correlation curve, which would be of great benefit to predict the adsorption capacity of adsorbent for the purpose of adsorption engineering design.     

Adsorption kinetics of hemoglobin onto silicate adsorbents

A comparative study was performed of the adsorption kinetics of hemoglobin onto four silicate adsorbents that differed in parameters of porous structure: industrial silochrome, and three silicates obtained by template synthesis. The existence of a reversible stage of the process preceding irreversible protein binding was shown by kinetic analysis. Rate constants for the reversible stage of the process and the effective constants of first order rate were calculated. It was concluded that the adsorption rate is the highest on silochrome and the lowest on silicate of MCM-41 type, the pore size of which is comparable to the diameter of a hemoglobin molecule. The constant of the desorption rate for the first reversible stage of the process was shown in the case of mesoporous silicates to be lower by a factor of 3.5–4 than in the case of silochrome.     

Spectroscopic investigation of the adsorption mechanisms of polyacrylamide polymers onto iron oxide particles

The mechanisms of high-molecular-weight polyacrylamide nonionic homopolymer and 25 mol% anionic acrylate-substituted copolymer adsorption onto iron oxide particles were investigated via DRIFT and UV-vis spectroscopies at three pH values (6, 8.5, and 11). While electrostatic interactions play an important role in charged polymer adsorption, this information is not spectroscopically available. At pH values above and below pH 8.5 (the isoelectric point for the anionic polymer), bidentate chelation and hydrogen bonding were the main adsorption mechanisms. At the isoelectric point, monodentate chelation was observed to be the main mode of adsorption, along with hydrogen bonding. For the nonionic polymer, in all cases, hydrogen bonding through the carbonyl group was the main mode of adsorption. The adsorption of both polymers conformed well to the Freundlich model, suggesting that the adsorbed polymer amount increases with increasing polymer concentration up to 7500 g/t solid, rather than approaching monolayer coverage. Spectroscopic evidence was found to suggest that hydrolysis of nonionic polyacrylamide occurs at high pH.     

Diffusion into and adsorption of polyethylenimine on porous silica gel

The polyethyleneimine (PEI)–water–silica gel absorption system was used as a model system to investigate the relationship between diffusion into the porous structure, adsorption rate, and molecular weight of the polymer. Three silica gels, Porasil A, B, and and C having a range of characteristic porosity were used as adsorbents. Adsorption of PEI on Porasil C, which has the majority of its pores much larger than the dimensions of the adsorbate molecule, increased initially with increased molecular weight but became nearly constant at higher molecular weight. Little increase in adsorption occurred for this silica gel with increased ionic strength or with increased pH between 9.5 and 10.8. In contrast, adsorption increased sharply with increased ionic strength and for the same pH range on Porasil A. Molecular weight dependence was reversed. Adsorption decreased with increased molecular weight on Porasil A. In this case, the molecular size of PEI investigated was the same as the majority of pore apertures in the adsorbent. Solution environments (i.e., pH and ionic strength) that decrease the size of the PEI molecule and its affinity for the anionic silica gel surface, thus enabling it to more readily diffuse into the smaller porous regions of the adsorbent, are the apparent causes of the very large adsorption increase. Electrostatic repulsion between PEI molecules do not appear greatly to affect adsorption. Similar adsorption behavior has been reported in the literature for the PEI–cellulosic fiber adsorption system. Maximum adsorption on Porasil A occurred at pH 10.8, the same maximum generally reported for adsorption of PEI on cellulosic fibers. In this case, the silica gel (Porasil A) was found to have a pore size distribution and specific surface area of the same magnitude as cellulosic fibers prepared in the expanded state.     

Iodine adsorption on silver-exchanged titania-derived adsorbents

I-129 is a hazardous fission product due to its long half life and ability to bioaccumulate. Silver mordenite has been studied for the removal of I-129 because of its hydrothermal stability arising from a high Si/Al ratio which subsequently limits its silver loading and iodine capacity. Titanosilicate ETS-10 and the sodium nanotitanate ETS-2 were exchanged to over 35 wt % silver and exposed to saturated iodine vapour at 80 °C under dry and humid conditions. The results indicate that the silver on these materials is reactive toward iodine and that the majority of the silver ions are utilized.     

染料在纳米TiO2薄膜表面吸附性能的研究

采用溶胶－凝胶法制备纳米TiO2薄膜，并通过吸附染料形成染料／TiO2复合薄膜。分析了染料与TiO2薄膜的相互关系，利用紫外可见、比表面等技术研究染料在纳米TiO2薄膜表面的吸附性能，并计算出TiO2薄膜对染料的最大吸附率。研究表明，染料溶液浓度、温度以及TiO2薄膜浸泡时间对染料吸附量有着显著的影响，染料的吸附性能直接影响着太阳能电池的光电转换效率。     

Solution thermodynamics of adsorption in microporous adsorbents

From the conception that the adsorption process in microporous solids consists in a volumetric filling of an adsorption space and the formation of a monophasic system (adsorbateadsorbent) as is the case in solutions, and with the use of solution thermodynamics, expressions were obtained for the well-known isosteric heat of adsorption, the enthalpy of adsorption and the differential heat of adsorption, and non-trivial relations were then established between these thermodynamic magnitudes.

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Zusammenfassung Ausgehend von der Konzeption, daß der Adsorptionsprozeß in mikroporösen Festkörpern eine Auffüllung des Adsorptionsraumes und die Bildung eines monophasischen Systems (Adsorbat-Adsorbent) wie im Falle von Lösungen ist, und unter Anwendung der Thermodynamik von Lösungen wurden Ausdrücke für die isosterische Adsorptionswärme, die Adsorptionsenthalpie und die differentielle Adsorptionswärme erhalten. Nicht-triviale Beziehungen zwischen diesen thermodynamischen Größen wurden abgeleitet.

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