Tuning the Surface Polarity of Microporous Organic Polymers for CO2 Capture

CO₂ capture is very important to reduce the CO₂ concentration in atmosphere. Herein, we report the preparation of microporous polymers with tunable surface polarity for CO₂ capture. Porous polymers functionalized with ‐NH₂, ‐SO₃H, and ‐SO₃Li have been successfully prepared by using a post‐synthesis modification of microporous polymers (P‐PhPh₃ prepared with 1,3,5‐triphenylbenzene as the monomer and AlCl₃ as the catalyst) by chemical transformations, such as nitration–reduction, sulfonation, and cationic exchange. The CO₂ adsorption selectivity (CO₂/N₂ and CO₂/H₂) and isosteric heats of the microporous polymers increase markedly after modification, P‐PhPh₃‐NH₂ and P‐PhPh₃‐SO₃Li afford higher CO₂ uptake capacity than P‐PhPh₃ at pressures of less than 0.15 bar due to the enhanced interaction between CO₂ and the ‐NH₂ and ‐SO₃Li functional groups. Moreover, functionalized porous polymers could be stably used for CO₂ capture. Surface modification is an efficient approach to tune the CO₂ capture properties of porous polymers.     

Advances in Porous Organic Polymers for Efficient Water Capture

Desiccant driven dehumidification for maintaining the proper humidity levels and atmospheric water capture with minimum energy penalty are important aspects in heat pumps, refrigeration, gas and liquid purifications, gas sensing, and clean water production for improved human health and comfort. Water adsorption by using nanoporous materials has emerged as a viable alternative to energy-intensive industrial processes, thus understanding the significance of their porosity, high surface areas, vast pore volumes, chemical and structural features relative to the water adsorption is quite important. In this review article, important features of nanoporous materials are presented, including zeolites, porous carbons, as well as crystalline and amorphous porous organic polymers (POPs) to define the interactions between the water molecules and the polar/non-polar functional groups on the surface of these nanoporous materials. In particular, focus is placed on the recent developments in POPs in the context of water capture as a result of their remarkable stability towards water and wide range of available synthetic routes and building blocks for their synthesis. We also highlighted recent approaches to increase the water sorption capacity of POPs by modifying their structure, morphology, porosity, and chemical functionality while emphasizing their promising future in this emerging area.     

Amorphous Porous Organic Polymers Based on Schiff‐Base Chemistry for Highly Efficient Iodine Capture

Porous organic polymers (POPs) have been considered as prominent adsorbents for volatile iodine. So far, both crystalline and amorphous POPs have accomplished excellent iodine capture capability. Considering the difficulty and challenges in preparing perfect crystalline POPs, more explorations into developing versatile amorphous POPs are needed. Herein, amorphous POPs based on the Schiff‐base reaction were designed and synthesized for volatile iodine removal. Four amorphous POPs products named as NDB‐H , NDB‐S , ADB‐HS , and ADB‐S obtained under different solvothermal conditions were investigated in terms of their morphologies, porosity, and their iodine enrichment performance in detail. It is noteworthy that excellent efficiency for removing iodine vapor was acquired for NDB‐S (≈425 wt %), ADB‐HS (≈345 wt %), and ADB‐S (≈342 wt %). Remarkably, NDB‐H exhibited an iodine capture capacity up to ≈443 wt %. Excellent reusability was obtained as well. Amorphous NDB‐H has accomplished an extremely high iodine capture performance, illustrating the great chance to exploit versatile amorphous POPs for iodine enrichment and removal based on Schiff‐base chemistry.     

High CO2‐Capture Ability of a Porous Organic Polymer Bifunctionalized with Carboxy and Triazole Groups

A new porous organic polymer, SNU‐C1 , incorporating two different CO₂‐attracting groups, namely, carboxy and triazole groups, has been synthesized. By activating SNU‐C1 with two different methods, vacuum drying and supercritical‐CO₂ treatment, the guest‐free phases, SNU‐C1‐va and SNU‐C1‐sca , respectively, were obtained. Brunauer–Emmett–Teller (BET) surface areas of SNU‐C1‐va and SNU‐C1‐sca are 595 and 830 m²g^?1, respectively, as estimated by the N₂‐adsorption isotherms at 77 K. At 298 K and 1 atm, SNU‐C1‐va and SNU‐C1‐sca show high CO₂ uptakes, 2.31 mmol g^?1 and 3.14 mmol g^?1, respectively, the high level being due to the presence of abundant polar groups (carboxy and triazole) exposed on the pore surfaces. Five separation parameters for flue gas and landfill gas in vacuum‐swing adsorption were calculated from single‐component gas‐sorption isotherms by using the ideal adsorbed solution theory (IAST). The data reveal excellent CO₂‐separation abilities of SNU‐C1‐va and SNU‐C1‐sca , namely high CO₂‐uptake capacity, high selectivity, and high regenerability. The gas‐cycling experiments for the materials and the water‐treated samples, experiments that involved treating the samples with a CO₂‐N₂ gas mixture (15:85, v/v) followed by a pure N₂ purge, further verified the high regenerability and water stability. The results suggest that these materials have great potential applications in CO₂ separation.     

有机微孔聚合物研究进展

有机微孔聚合物(MOPs)是一类新型的多孔材料,具有合成方法多样、化学和物理性质稳定、孔尺寸可调控、表面可修饰等优点。近年来,MOPs在物理吸附储存气体方面表现出巨大潜力,从而在储氢和温室气体封存方面成为研究的热点之一。本文首先介绍了MOPs的结构类型及特点,分别介绍了自具微孔聚合物、超交联聚合物、共价有机网络以及共轭微孔聚合物的最新进展,分析结构与性能间的关系,并对其在催化、分离和气体储存方面的应用做了简单总结。最后对MOPs未来的研究进行了展望。     

Directing the Structural Features of N2‐Phobic Nanoporous Covalent Organic Polymers for CO2 Capture and Separation

A family of azo‐bridged covalent organic polymers (azo‐COPs) was synthesized through a catalyst‐free direct coupling of aromatic nitro and amine compounds under basic conditions. The azo‐COPs formed 3D nanoporous networks and exhibited surface areas up to 729.6 m² g^?1, with a CO₂‐uptake capacity as high as 2.55 mmol g^?1 at 273 K and 1 bar. Azo‐COPs showed remarkable CO₂/N₂ selectivities (95.6–165.2) at 298 K and 1 bar. Unlike any other porous material, CO₂/N₂ selectivities of azo‐COPs increase with rising temperature. It was found that azo‐COPs show less than expected affinity towards N₂ gas, thus making the framework “N₂‐phobic”, in relative terms. Our theoretical simulations indicate that the origin of this unusual behavior is associated with the larger entropic loss of N₂ gas molecules upon their interaction with azo‐groups. The effect of fused aromatic rings on the CO₂/N₂ selectivity in azo‐COPs is also demonstrated. Increasing the π‐surface area resulted in an increase in the CO₂‐philic nature of the framework, thus allowing us to reach a CO₂/N₂ selectivity value of 307.7 at 323 K and 1 bar, which is the highest value reported to date. Hence, it is possible to combine the concepts of “CO₂‐philicity” and “N₂‐phobicity” for efficient CO₂ capture and separation. Isosteric heats of CO₂ adsorption for azo‐COPs range from 24.8–32.1 kJ mol^?1 at ambient pressure. Azo‐COPs are stable up to 350 °C in air and boiling water for a week. A promising cis/trans isomerization of azo‐COPs for switchable porosity is also demonstrated, making way for a gated CO₂ uptake.     

Synthesis of Two‐dimensional Microporous Carbonaceous Polymer Nanosheets and Their Application as High‐performance CO2 Capture Sorbent

The synthesis of two‐dimensional (2D) polymer nanosheets with a well‐defined microporous structure remains challenging in materials science. Here, a new kind of 2D microporous carbonaceous polymer nanosheets was synthesized through polymerization of a very low concentration of 1,4‐dicyanobenzene in molten zinc chloride at 400–500 °C. This type of nanosheets has a thickness in the range of 3–20 nm, well‐defined microporosity, a high surface area (～537 m² g^?1), and a large micropore volume (～0.45 cm³ g^?1). The microporous carbonaceous polymer nanosheets exhibit superior CO₂ sorption capability (8.14 wt % at 298 K and 1 bar) and a relatively high CO₂ selectivity toward N₂ (25.6). Starting from different aromatic nitrile monomers, a variety of 2D carbonaceous polymer nanosheets can be obtained showing a certain universality of the ionothermal method reported herein.     

Cationic Nonporous Macrocyclic Organic Compounds for Multimedia Iodine Capture

Over the past two decades, progress in chemistry has generated various types of porous materials for removing iodine (¹²⁹I or ¹³¹I) that can be formed during nuclear energy generation or nuclear waste storage. However, most studies for iodine capture are based on the weak host-guest interactions of the porous materials. Here, we present two cationic nonporous macrocyclic organic compounds, namely, MOC-1 and MOC-2 , in which 6I^- and 8I⁻ were as counter anions, for highly efficient iodine capture. MOC-1 and MOC-2 were formed by reacting 1,1′-diamino-4,4′-bipyridylium di-iodide with 1,2-diformylbenzene or 1,3-diformylbenzene, respectively. The presence of a large number of I⁻ anions results in high I₂ affinity with uptake capacities up to 2.15 g ⋅ g⁻¹ for MOC-1 and 2.25 g ⋅ g⁻¹ for MOC-2 .     

Imidazolium-Functionalized Chemically Robust Ionic Porous Organic Polymers (iPOPs) toward Toxic Oxo-Pollutants Capture from Water

Fabricating new and efficient materials aimed at containment of water contamination, in particular removing toxic heavy metal based oxo-anions (e. g. CrO₄²⁻, TcO₄⁻) holds paramount importance. In this work, we report two new highly stable imidazolium based ionic porous organic polymers (iPOPs) decorated with multiple interaction sites along with electrostatics driven adsorptive removal of such oxo-anions from water. Both the iPOPs (namely, iPOP-3 and iPOP-4) exhibited rapid sieving kinetics and very high saturation uptake capacity for CrO₄²⁻ anions (170 and 141 mg g⁻¹ for iPOP-3 and iPOP-4 respectively) and ReO₄⁻ (515.5 and 350.3 mg g⁻¹ for iPOP-3 and iPOP-4 respectively), where ReO₄⁻ anions being the non-radioactive surrogative counterpart of radioactive TcO₄⁻ ions. Noticeably, both iPOPs showed exceptional selectivity towards CrO₄²⁻ and ReO₄⁻ even in presence of several other concurrent anions such as Br⁻, Cl⁻, SO₄²⁻, NO₃⁻ etc. The theoretical binding energy calculations via DFT method further confirmed the preferential interaction sites as well as binding energies of both iPOPs towards CrO₄²⁻ and ReO₄⁻ over all other competing anions which corroborates with the experimental high capacity and selectivity of iPOPs toward such oxo-anions.     

CO2高效资源化利用的高温熔盐电化学技术研究

高温熔融盐具有CO₂吸收容量大、电化学窗口宽、高温下反应动力学快等特点,是利用清洁电能大规模捕集和资源化利用CO₂颇具实用化潜力的电解液体系. 本文主要介绍作者课题组近十年关于高温熔盐CO₂捕集与电化学资源化转化(MSCC-ET)技术的相关研究工作,包括熔融盐电解质对CO₂的吸收、阴极过程动力学、电解条件对产物的影响、析氧阳极、电解过程能量效率和CO₂捕获潜力,并展望了MSCC-ET技术的发展前景.     

Synthesis of a Triazaisotruxene-Based Porous Organic Polymer and Its Application in Iodine Capture

A new triazaisotruxene-based porous organic polymer (POP) was designed and successfully synthesized by a FeCl₃-promoted crosslinking reaction. As a result of its porosity and good thermal stability, the designed POP can be utilized as a promising adsorbent for iodine, not only in the gaseous phase, but also in organic and aqueous solutions. Compared to its triazatruxene (TN) analogue, the ITN-based POP shows equal iodine uptake in the gaseous phase and in hexane solution, and better uptake in aqueous solution.     

Molecular Expansion for Constructing Porous Organic Polymers with High Surface Areas and Well-Defined Nanopores

Construction of porous organic polymers (POPs) with high surface areas, well-defined nanopores, and excellent stability remains extremely challenging because of the unmanageable reaction process. Until now, only a few reported POPs have Brunauer-Emmett-Teller (BET) surface areas (S_BET) exceeding 3000 m² g⁻¹. Herein, we demonstrate a molecular expansion strategy to integrate high surface areas, large nanopore sizes, and outstanding stability into POPs. A series of hyper-crosslinked conjugated polymers ( HCCPs ) with exceptional porosity are synthesized through this strategy. Specially, HCCP-6 and HCCP-11 exhibit the highest surface areas (S_BET >3000 m² g⁻¹) and excellent total pore volumes (up to 3.98 cm³ g⁻¹) among these HCCPs . They present decent total CH₄ storage capacities of 491 and 421 mg g⁻¹ at 80 bar and 298 K, respectively. Meanwhile, they are highly stable in harsh environments. The facile and general molecular expansion strategy would lead to improved synthetic routes of POPs for desired functions.     

Hierarchical Mesoporous Metal–Organic Frameworks for Enhanced CO2 Capture

Hierarchical porous materials are promising for catalyst, separation and sorption applications. A ligand‐assisted etching process is developed for template‐free synthesis of hierarchical mesoporous MOFs as single crystals and well‐intergrown membranes at 40 °C. At 223 K, the hierarchical porous structures significantly improve the CO₂ capture capacity of HKUST‐1 by more than 44 % at pressures up to 20 kPa and 13 % at 100 kPa. Even at 323 K, the enhancement of CO₂ uptake is above 25 % at pressures up to 20 kPa and 7 % at 100 kPa. The mesoporous structures not only enhance the CO₂ uptake capacity but also improve the diffusion and mass transportation of CO₂. Similarly, well‐intergrown mesoporous HKUST‐1 membranes are synthesized, which hold the potential for film‐like porous devices. Mesoporous MOF‐5 crystals are also obtained by a similar ligand‐assisted etching process. This may provide a facile way to prepare hierarchical porous MOF single crystals and membranes for wide‐ranging applications.     

Porous Cationic Covalent Triazine‐Based Frameworks as Platforms for Efficient CO2 and Iodine Capture

Porous cationic covalent triazine‐based frameworks (CTFs) with imidazolium salts as tectons were prepared via ionothermal synthesis. The high‐PF₆^?‐content CTF shows the CO₂ adsorption of 44.7 cm³ g^?1 and I₂ capture capacity of 312 wt %. The influence of counterion species and contents on the porosities, CO₂ adsorptions, and I₂ capture capacities of the CTFs has been investigated.     

共价有机多孔聚合物合成新策略

共价有机多孔聚合物(COPs)是由有机结构单元通过共价键连接而形成的一类具有微孔或者介孔结构的新型高分子多孔材料, 在能源、物质吸附与分离、气体存储、光电器件、多相催化以及化学/生物传感等方面展现出巨大的应用潜能. 尽管其合成方法众多, 合成单体多样, 产物结构稳定, 但是传统方法合成的有机多孔材料大多是无定型的, 结构难以控制, 且通常不溶不熔, 很难再加工. 为了解决这些问题, 近年来很多新的合成方法和合成策略被开发出来, 为共价有机多孔聚合物的进一步发展指明了方向. 本文将对这些最新的研究进展做一简要的介绍.