Truly combining the advantages of polymeric and zeolite membranes for gas separations.

Mixed-matrix membranes (MMMs) have been investigated to render energy-intensive separations more efficiently by combining the selectivity and permeability performance, robustness, and nonaging properties of the filler with the easy processing, handling, and scaling up of the polymer. However, truly combining all in one single material has proven very challenging. In this work, we filled a commercial polyimide with ultrahigh loadings of a high-aspect ratio, CO2-philic Na-SSZ-39 zeolite with a three-dimensional channel system that precisely separates gas molecules. By carefully designing both zeolite and MMM synthesis, we created a gas-percolation highway across a flexible and aging-resistant (more than 1 year) membrane. The combination of a CO2-CH4 mixed-gas selectivity of ~423 and a CO2 permeability of ~8300 Barrer outperformed all existing polymer-based membranes and even most zeolite-only membranes.

Tuning Functionalized Ionic Liquids for CO2 Capture.

The increasing concentration of CO2 in the atmosphere is related to global climate change. Carbon capture, utilization, and storage (CCUS) is an important technology to reduce CO2 emissions and to deal with global climate change. The development of new materials and technologies for efficient CO2 capture has received increasing attention among global researchers. Ionic liquids (ILs), especially functionalized ILs, with such unique properties as almost no vapor pressure, thermal- and chemical-stability, non-flammability, and tunable properties, have been used in CCUS with great interest. This paper focuses on the development of functionalized ILs for CO2 capture in the past decade (2012~2022). Functionalized ILs, or task-specific ILs, are ILs with active sites on cations or/and anions. The main contents include three parts: cation-functionalized ILs, anion-functionalized ILs, and cation-anion dual-functionalized ILs for CO2 capture. In addition, classification, structures, and synthesis of functionalized ILs are also summarized. Finally, future directions, concerns, and prospects for functionalized ILs in CCUS are discussed. This review is beneficial for researchers to obtain an overall understanding of CO2-philic ILs. This work will open a door to develop novel IL-based solvents and materials for the capture and separation of other gases, such as SO2, H2S, NOx, NH3, and so on.

Covalent Organic Frameworks with Ionic Liquid-Moieties (ILCOFs): Structures, Synthesis, and CO2 Conversion.

CO2, an acidic gas, is usually emitted from the combustion of fossil fuels and leads to the formation of acid rain and greenhouse effects. CO2 can be used to produce kinds of value-added chemicals from a viewpoint based on carbon capture, utilization, and storage (CCUS). With the combination of unique structures and properties of ionic liquids (ILs) and covalent organic frameworks (COFs), covalent organic frameworks with ionic liquid-moieties (ILCOFs) have been developed as a kind of novel and efficient sorbent, catalyst, and electrolyte since 2016. In this critical review, we first focus on the structures and synthesis of different kinds of ILCOFs materials, including ILCOFs with IL moieties located on the main linkers, on the nodes, and on the side chains. We then discuss the ILCOFs for CO2 capture and conversion, including the reduction and cycloaddition of CO2. Finally, future directions and prospects for ILCOFs are outlined. This review is beneficial for academic researchers in obtaining an overall understanding of ILCOFs and their application of CO2 conversion. This work will open a door to develop novel ILCOFs materials for the capture, separation, and utilization of other typical acid, basic, or neutral gases such as SO2, H2S, NOx, NH3, and so on.

A Cooperative OSDA Blueprint for Highly Siliceous Faujasite Zeolite Catalysts with Enhanced Acidity Accessibility.

A cooperative OSDA strategy is demonstrated, leading to novel high-silica FAU zeolites with a large potential for disruptive acid catalysis. In bottom-up synthesis, the symbiosis of choline ion (Ch+ ) and 15-crown-5 (CE) was evidenced, in a form of full occupation of the sodalite (sod) cages with the trans Ch+ conformer, induced by the CE presence. CE itself occupied the supercages along with additional gauche Ch+ , but in synthesis without CE, no trans was found. The cooperation, and thus the fraction of trans Ch+ , was closely related to the Si/Al ratio, a key measure for FAU stability and acidity. As such, a bottom-up handle for lowering the Al-content of FAU and tuning its acid site distribution is shown. A mechanistic study demonstrated that forming sod cages with trans Ch+ is key to the nucleation of high-silica FAU zeolites. The materials showed superior performances to commercial FAU zeolites and those synthesized without cooperation, in the catalytic degradation of polyethylene.

Rational Synthesis of Chabazite (CHA) Zeolites with Controlled Si/Al Ratio and Their CO2 /CH4 /N2 Adsorptive Separation Performances.

Separation of CO2 from CH4 and N2 is of great significance from the perspectives of energy production and environment protection. In this work, we report the rational synthesis of chabazite (CHA) zeolites with controlled Si/Al ratio by using N,N,N-trimethyl-1-adamantammonium hydroxide (TMAdaOH) as an organic structure-directing agent, wherein the dependence of TMAdaOH consumption on the initial Si/Al ratio was investigated systematically. More TMAdaOH is required to direct the crystallization of CHA with higher Si/Al ratio. Once the product Si/Al ratio is larger than 24, the amount of TMAdaOH consumption remains nearly constant. CHA zeolites with different Si/Al ratios and charge-compensating cations were then applied for the separation of CO2 /CH4 /N2 mixtures. The equilibrium selectivities predicted by ideal adsorbed solution theory (IAST) and ideal selectivities calculated from the ratio of Henry's constants for both CO2 /CH4 and CO2 /N2 decrease with the zeolite Si/Al ratio increasing, whereas the percentage regenerability of CO2 presents the opposite trend. Therefore, there is a trade-off between adsorption selectivity and regenerability for the adsorbents. There is a weaker interaction between CO2 molecules and the H-type zeolites than that on the Na-type ones, thus a higher regenerability can be achieved. This study indicates that it is possible to design CHA zeolites with different physicochemical properties to meet various adsorptive separation requirements.

Organic-Free, ZnO-Assisted Synthesis of Zeolite FAU with Tunable SiO2 /Al2 O3 Molar Ratio.

Zeolite FAU with tunable SiO2 /Al2 O3 molar ratio has been successfully synthesized in the absence of organic structure-directing agents (OSDA). Specifically, the addition of zinc species contributes to the feasible and effective adjustment of the framework SiO2 /Al2 O3 molar ratio between about 4 and 6 depending on the amount of zinc species added in the batch composition. In contrast, a typical OSDA such as tetramethylammonium hydroxide (TMAOH) has a limited effect on the SiO2 /Al2 O3 molar ratio of the zeolite. The role of zinc species is essential for the crystallization of zeolite FAU with a higher SiO2 /Al2 O3 molar ratio under the particular synthesis conditions. It is speculated that zinc species may suppress the incorporation of aluminum into the aluminosilicate framework, which is due to the Coulombic repulsive interaction. A higher SiO2 /Al2 O3 molar ratio is also found to be accompanied by a lower CO2 adsorption heat for CO2 /CH4 separation.

Enhanced Trace Carbon Dioxide Capture on Heteroatom-Substituted RHO Zeolites under Humid Conditions.

Boron and copper heteroatoms were successfully incorporated into the frameworks of high-silica RHO zeolite by adopting a bulky alkali-metal-crown ether (AMCE) complex as the template. These heteroatom-doped zeolites show both larger micropore surface areas and volumes than those of their aluminosilicate analogue. Proton-type RHO zeolites were then applied for the separation of CO2 /CH4 /N2 mixtures, as these zeolites have weaker electric fields and, thus, lower heats of adsorption. The adsorption results showed that a balance between working capacity and adsorption heat could be achieved for these heteroatom-doped zeolites. Ideal adsorbed solution theory predictions indicate that these zeolites should have high selectivities even for remarkably dilute sources of CO2 . Finally, the heteroatom-substituted zeolites, especially the boron-substituted one, could be thermally regenerated rapidly at 150 °C after full hydration and maintained high regenerability for up to 30 cycles; therefore, they are potential candidates for trace CO2 removal under humid conditions.

Targeted Synthesis of Ultrastable High-Silica RHO Zeolite Through Alkali Metal-Crown Ether Interaction.

High-silica RHO zeolite was directly synthesized using an alkali metal-crown ether (AMCE) complex as organic structure-directing agent (OSDA). Derived from the UV-vis spectra and zeolite patterns, the crown ether-cesium cation interaction was found to have crucial effect on the enhancement of silica content within the zeolite framework. The synthesized RHO zeolites possess up to four times larger silica/alumina ratio (SAR) values than that in their conventional form, which gives them extraordinarily rigid frameworks even after hydrothermal aging under 800 °C. Compared to commercial zeolites, copper-exchanged high-silica RHO zeolites demonstrate considerably high reaction activity in NOX removal, making them promising candidates for diesel exhaust treatment.