Preparation of microporous polyamide networks for carbon dioxide capture and nanofiltration

For the first time, microporous polyamide networks have been synthesized via the interfacial polymerization of piperazine and acyl chloride monomers containing tetrahedral carbon and silicon cores. These polyamides, with Brunauer–Emmett–Teller surface area between 488 and 584 m² g^?1, show a CO₂ uptake of up to 9.81 wt% and a CO₂/N₂ selectivity of up to 51 at 1 bar and 273 K, suggesting their great potential in the area of carbon capture and storage applications. We have developed the interfacial polymerization on the surface of the porous polyacrylonitrile substrate, resulting in the formation of ultrathin microporous membranes with thicknesses of about 100 nm. These nanofiltration (NF) membranes exhibited an attractive water flux of 82.8 L m^?2 h^?1 at 0.4 MPa and a high CaCl₂ (500 mg/L) rejection of 93.3%. These NF membranes follow the salt rejection sequence of CaCl₂ > NaCl > Na₂SO₄, demonstrating the positively charged character of these membranes.     

Solution‐reprocessable microporous polymeric adsorbents for carbon dioxide capture

Solution‐processable microporous polymers are promising materials for CO₂ capture because of their low synthetic cost and high processability. In this work, we for the first time systematically evaluate the feasibility of two microporous polymers, namely PIM‐1 and its hydrolyzed form hPIM‐1, as adsorbent materials for postcombustion CO₂ capture. By conducting ternary CO₂/N₂/H₂O breakthrough experiments, PIM‐1 demonstrates several promising features: moderate CO₂ working capacity, low water vapor uptake capacity, good moisture resistance, and easy regeneration process. In addition, we have pioneeringly studied the multiple‐cycle CO₂ adsorption–desorption induced relaxation effect on soft PIM‐1 polymers. Through a simple dissolution–precipitation approach, PIM‐1 can restore its BET surface area, CO₂ uptake capacity, and pore‐size distribution. The solution reprocessability of PIM‐1 demonstrated in this study distinguishes it from other rigid adsorbents and thus offers a new insight for the future design of economically‐viable and facilely regenerable adsorbents. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3376–3389, 2018     

Chemical functionalization strategies for carbon dioxide capture in microporous organic polymers

We review the design and use of microporous polymers for pre‐ and post‐combustion capture of CO₂. Microporous organic polymers are promising candidates for CO₂ capture materials. They have good physicochemical stabilities and high surface areas. Ultrahigh‐surface‐area microporous organic polymers could find use in pre‐combustion capture, while networks with lower surface areas but higher heats of sorption for CO₂ might be more relevant for lower pressure, post‐combustion capture. We discuss strategies for enhancing CO₂ uptakes including increasing surface area, chemical functionalization to provide high‐enthalpy binding sites and the potential for pore size tuning. © 2013 Society of Chemical Industry     

PVP-assisted synthesis of monodisperse UiO-66 crystals with tunable sizes

A polyvinylpyrrolidone (PVP)-assisted synthesis method was reported to prepare monodisperse UiO-66 octahedral crystals with tunable sizes. In this acetic acid/PVP co-modulated synthesis system, the relatively weak coordination of PVP to Zr(IV) played an important role in manipulating the sizes of UiO-66 crystals instead of their shapes. With the optimized PVP concentrations, sizes of the monodisperse UiO-66 crystals could be effectively tuned from ~ 1900 nm to ~ 700 nm. These uniform MOF crystals could be assembled into monolayers on water surface and further transferred onto a solid substrate to yield MOF films with preferential orientation and controlled thicknesses.     

UiO-66的合成、结构及应用技术进展

金属有机框架（MOFs）材料因具有比表面积大、孔隙率高及孔道易调、易功能化等特点而应用于各研究领域。然而，多数MOFs材料的化学稳定性和水热稳定性较差，极大地限制其应用。锆基MOFs材料UiO-66的骨架坍塌温度高于500 ℃、可承受1.0 MPa的机械压力并且具有超高稳定性从而引起了人们的关注。该文系统介绍了UiO-66制备方法的研究进展，其中干凝胶转化法具有产品收率高、反应体积小及可连续生产等优点更具优势；详细介绍了有机配体、金属节点和掺杂等改性方式对UiO-66结构的影响，结果表明对UiO-66结构进行改性可进一步提高其性能；总结了UiO-66在催化、气体储存和分离等方面的应用；最后，对UiO-66的未来发展方向进行了展望。     

锆基金属有机骨架UiO-66的合成及在化学防护领域中的研究进展

UiO-66除了具备其他MOFs材料的比表面积大、孔隙率高及孔道易调、易功能化等特点外，与大多数MOFs 材料不同，还具有优异的化学稳定性、机械稳定性、热稳定性和抗水性能，使其在吸附及催化领域具有巨大的应用前景。本文详细介绍了UiO-66的合成方法最新研究进展，包括溶剂热法、机械研磨法、微波辅助法、持续流法及干胶转化法，同时指出干胶转化法产品收率高，纯化、活化过程简单且不产生有机废液，是UiO-66合成及未来工业化生产的发展方向。同时综述了改性UiO-66材料近年来在有毒工业化学品吸附及化学战剂催化降解领域中的研究进展，展望了静电纺纳米纤维负载UiO-66在化学防护领域应用的发展趋势。     

Adsorption Behavior of Rhodamine B on UiO-66 Adsorption Behavior of Rhodamine B on UiO-66

The adsorption characteristics of UiO-66 (a Zr-containing metal–organic framework formed by terephthalate) for Rhodamine B (RhB), such as isotherms, kinetics and thermodynamics, were investigated syste...     

In situ nitrogen enriched carbon for carbon dioxide capture

In situ nitrogen enriched carbon was synthesized from locally available low cost soybean as the proteinaceous source. The material was synthesized by chemical activation using zinc chloride followed by physical activation using CO₂. The surface area of synthesized nitrogen enriched carbon was found to be 811 m²/g which is comparable with commercially available activated carbon. The nitrogen enriched carbon was having a breakthrough adsorption capacity of 23 mg/g at 120 °C which was almost three times higher in comparison with the commercially available activated carbon for a gas mixture comprising 15% CO₂ balanced with helium. This high adsorption capacity was attributed to the presence of nitrogen group within the carbon matrix, which was estimated to be about 0.64% as determined using the Kjeldahl’s method. The presence of different nitrogen containing groups assisting the adsorption of CO₂ in the synthesized sample was also confirmed by infrared analysis. For checking the consistent performance of the synthesized carbon, multi-cycle adsorption-desorption studies were carried out at 30 and 75 °C in binary mixture of CO₂/N₂.     

Facile synthesis of amine-functionalized UiO-66 by microwave method and application for methylene blue adsorption

The metal–organic frameworks UiO-66 with amine functional groups were synthesized by microwave irradiation, their structures and properties were characterized. The results show that NH₂-UiO-66 can be prepared quickly and well-crystallized by microwave-assisted method within 15 min. The amine-functionalized UiO-66 was octahedral crystals of well defined sizes (500–900 nm) and had a high specific surface area about 924.37 m² g^?1 and micropore range from 2.0 to 11 nm. The amine-functionalized UiO-66 was thermally stable up to 540 °C stability and exhibited a good combination of methylene blue adsorption. The maximum adsorption capacity reached up to 203.95 mg g^?1. The kinetics and equilibrium of the adsorption process were found to follow the pseudo-second-order kinetic and Langmuir adsorption model, respectively.     

功能化离子液体在二氧化碳吸收分离中的应用

吸收及分离二氧化碳是降低碳排放和应对全球气候变化的主要策略之一,这就必然要求全球科技工作者注重开发具有选择性高效吸收分离二氧化碳的新材料和新路线。作为近20多年来发展的一类代表性的新材料,离子液体（尤其是功能化离子液体）具有独特的物理化学性质,例如几乎没有蒸气压、液态温度范围大、热稳定性和化学稳定性好、电化学窗口宽、不可燃、结构-性质可调控等。这些性质使离子液体在二氧化碳吸收及分离领域受到广泛关注。重点综述了近5年（2015~2019）来功能化离子液体吸收分离二氧化碳的研究进展, 主要内容包括单位点离子液体、多位点离子液体、基于功能化离子液体的混合物、功能化离子液体杂化材料对二氧化碳的吸收分离。同时, 对目前该领域的发展所面临的主要问题和进一步的研究工作进行了分析讨论。     

Enhanced CO2 selectivity of polyimide membranes through dispersion of polyethyleneimine decorated UiO-66 particles

Branched polyethyleneimine (PEI) functionalized UiO-66 were synthesized and used as fillers to fabricated mixed-matrix membranes (MMMs) for CO₂/CH₄ separation. The purpose of introducing amino-functional groups in the filler is to improve the interfacial compatibility of the filler with the polymer through the formation of hydrogen bonds with the carbonyl group of 6FDA-ODA. Additionally, the amino group can facilitate CO₂ transport through a reversible reaction, enhancing the CO₂/CH₄ separation properties of MMM. The chemical structure and morphology of fillers and membranes were characterized by employing X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectrometer (FTIR), X-ray diffraction (XRD), thermogravimetric (TGA), Derivative thermogravimetry (DTG) and scanning electron microscope (SEM). Furthermore, the effects of filler loading and feed pressure on CO₂ permeability and CO₂/CH₄ selectivity have been investigated. MMMs present higher gas separation performance than pure 6FDA-ODA due to the presence of amino groups and the improvement of interface morphology. In particular, the MMM with 15 wt% loading of UiO-66-PEI shows optimum CO₂ permeability of 28.23 Barrer and CO₂/CH₄ selectivity of 56.49. Therefore, post-synthetic modification of UiO-66 particle with PEI is a promising alternative to improved membrane performance.     

为强化石油回采捕集CO2的全周期评估

The development and deployment of Carbon dioxide Capture and Storage （CCS） technology is a cornerstone of the Norwegian government＇s climate strategy. A number of projects are currently evaluated/planned along the Norwegian West Coast, one at Tjeldbergodden. COe from this project will be utilized in part for enhanced oil recovery in the Halten oil field, in the Norwegian Sea. We study a potential design of such a system. A combined cycle power plant with a gross power output of 832 MW is combined with CO2 capture plant based on a post-combustion capture using amines as a solvent. The captured CO2 is used for enhanced oil recovery （EOR）. We employ a hybrid life-cycle assessment （LCA） method to assess the environmental impacts of the system. The study focuses on the modifications and operations of the platform during EOR. We allocate the impacts connected to the capture of CO2 to electricity production, and the impacts connected to the transport and storage of CO2 to the oil produced. Our study shows a substantial reduction of the greenhouse gas emissions from power production by 80% to 75 g·（kW·h）^-1. It also indicates a reduction of the emissions associated with oil production per unit oil produced, mostly due to the increased oil production. Reductions are especially significant if the additional power demand due to EOR leads to power supply from the land.     

燃烧后CO_2捕集技术研究

对燃烧前、燃烧后CO2捕集以及富氧燃烧3种CO2捕集技术的特点,以及适用于燃煤电厂的燃烧后CO2捕集技术进行了介绍,分析了吸收分离法、吸附分离法和膜分离法的原理及优缺点。其中,化学吸收法应用最广,但再生能耗大,运行成本高;吸附法虽再生能耗小,但对CO2选择性低,吸附能力有限;膜分离法目前仍处于实验室研究阶段,但应用前景巨大。对上述技术整合形成复合技术以及对新材料进行开发将有助于克服现有CCS技术面临的困难。     

Synthesis and characterization of triphenylamine-containing microporous organic copolymers for carbon dioxide uptake

This article describes the synthesis and characterization of microporous organic copolymers (PP-N-x, where “x” is the molar percent of triphenylamine) prepared from triphenylamine and dichloro-p-xylene using a combination of oxidative polymerization and Friedel–Crafts alkylation process promoted by anhydrous FeCl₃. The samples possessed BET specific surface areas from 318 to 1530 m² g⁻¹ with the increasing content of dichloro-p-xylene. The highest CO₂ uptake of 4.60 mmol g⁻¹ was observed for PP-N-25, which was one of the highest values among MOPs reported to date under these conditions. The polymers possessed stable and reversible CO₂ adsorption–desorption performance in at least 5 consecutive runs without noticeable deterioration of CO₂ uptake capacities.     

Highly selective CO2 capture by S-doped microporous carbon materials

S-doped microporous carbon materials were synthesized by the chemical activation of a reduced-graphene-oxide/poly-thiophene material. The material displayed a large CO₂ adsorption capacity of 4.5 mmol g⁻¹ at 298 K and 1 atm, as well as an impressive CO₂ adsorption selectivity over N₂, CH₄ and H₂. The material was shown to exhibit a stable recycling adsorption capacity of 4.0 mmol g⁻¹. The synthesized material showed a maximum specific surface area of 1567 m² g⁻¹ and an optimal CO₂ adsorption pore size of 0.6 nm. The microporosity, surface area and oxidized S content of the material were found to be the determining factors for CO₂ adsorption. These properties show that the as synthesized S-doped microporous carbon material can be more effective than similarly prepared N-doped microporous carbons in CO₂ capture.     

二氧化碳直接空气捕集材料与技术研究进展

直接空气捕集（DAC）等新兴负碳排放技术是实现“双碳”目标的托底技术保障,近年来受到广泛关注。本文简要分析了直接空气碳捕集技术的特性,归纳总结了胺功能化无机材料和聚合物、金属氢氧化物和碳酸盐、多孔材料等痕量二氧化碳捕集性能,初步分析了负载方式、载体结构等与吸附容量和动力学的关系。浅析了该领域发展面临的问题和机遇,从能耗和性能方面对捕集材料和技术的研发提出以下建议：相较于物理吸附材料,胺功能化材料和固体碱等化学吸附材料具有更好的应用前景;在工艺开发领域,可以借鉴其他低浓度气体深度脱除工艺的经验;另一方面,可以结合不同工艺优势,设计多种工艺耦合的流程;最后,在严峻的环境问题下,必须加快材料研发的步伐,未来的研究重点应集中在材料的设计和低能耗再生方式的开发上。     

缺陷UiO-66对水中塑化剂的吸附

金属有机骨架材料（metal-organic frameworks,MOFs）是一种具有骨架结构的新型多孔材料。本研究合成了金属有机框架化合物UiO-66和有缺陷的UiO-66（UiO-66-1）,并研究了其作为吸附剂吸附塑化剂邻苯二甲酸二甲酯（DMP）的性能及其吸附动力学,最后通过拟合吸附等温线和吸附动力学模型拟合了吸附剂的最大吸附量和最快吸附时间。实验结果表明,UiO-66-1对DMP有更好的吸附性能,在5~10min内快速达到吸附平衡,pH在3~10吸附率仍可保持稳定;分析测试结果表明,引入缺陷的UiO-66-1的比表面积比UiO-66大,达到了1438m²/g,孔容为0.58cm³/g,晶体的尺寸也明显增大,吸附量增大了近一倍,最大吸附量可达到404mg/g,且循环利用率高;通过吸附等温线模型和吸附动力学模型的拟合研究表明,UiO-66-1的吸附过程比较符合Langmuir模型和拟二级动力学模型。     

Preparation of sulfur-doped microporous carbons for the storage of hydrogen and carbon dioxide

Structurally well ordered, sulfur-doped microporous carbon materials have been successfully prepared by a nanocasting method using zeolite EMC-2 as a hard template. The carbon materials exhibited well-resolved diffraction peaks in powder XRD patterns and ordered micropore channels in TEM images. Adjusting the synthesis conditions, carbons possess a tunable sulfur content in the range of 1.3–6.6 wt.%, a surface area of 729–1627 m² g^?1 and a pore volume of 0.60–0.90 cm³ g^?1. A significant proportion of the porosity in the carbons (up to 82% and 63% for surface area and pore volume, respectively) is contributed by micropores. The sulfur-doped microporous carbons exhibit isosteric heat of hydrogen adsorption up to 9.2 kJ mol^?1 and a high hydrogen uptake density of 14.3 × 10^?3 mmol m^?2 at ?196 °C and 20 bar, one of the highest ever observed for nanoporous carbons. They also show a high CO₂ adsorption energy up to 59 kJ mol^?1 at lower coverages (with 22 kJ mol^?1 at higher CO₂ coverages), the highest ever reported for any porous carbon materials and one of the highest amongst all the porous materials. These findings suggest that S-doped microporous carbons are potential promising adsorbents for hydrogen and CO₂.     

UiO-66的制备、功能化及膜分离研究进展

UiO-66是一种具有优异物理化学稳定性的金属有机骨架（MOFs）材料,近年来引起了研究者们的强烈关注。本文详细介绍了UiO-66的结构,重点探讨了溶剂热法过程中的一系列影响因素,包括使用不同的金属前体,改变合成温度、溶剂、各组分配比以及模板剂等,制备各种性能的UiO-66。针对溶剂热法合成效率较低的问题,介绍了微波合成法、微流控、连续流和无溶剂法等其它UiO-66的制备方法。为了扩大UiO-66的应用范围,对其有机配体进行功能化改性或与其他材料复合改性,具体介绍了改性后UiO-66在气体吸附、水处理、催化、电化学和化学传感等方面的应用。最后综述了利用UiO-66具有多孔特性构建分离膜方面的研究进展,具体阐述了纯UiO-66膜和UiO-66复合膜在气体分离和水处理方面的应用。     

Adsorption Behavior of Rhodamine B on UiO-66

The adsorption characteristics of UiO-66 (a Zr-containing metal–organic framework formed by terephthalate) for Rhodamine B (RhB), such as isotherms, kinetics and thermodynamics, were investigated systematically. The batch adsorption data conform well to the Langmuir and Freundlich isotherms. The adsorption kinetics of UiO-66 for RhB can be well described by the pseudo first-order model, and the adsorption thermodynamic parameters ΔG₀, ΔH₀ and ΔS₀ at 273 K are − 6.282 kJ·mol^− 1, 15.096 kJ·mol^− 1 and 78.052 J·mol^− 1·K^− 1, respectively. The thermodynamic analyses show that the adsorption process of RhB on UiO-66 is more favorable at higher temperatures. UiO-66 can be regenerated by desorbing in DMF solution with ultrasonic for 1 h. UiO-66 can keep good performance for at least six cycles of sorption/desorption.