Strategic Fast Induction Heating to Combat Hysteresis Barriers in a Flexible MOF for Rapid CO2 Desorption in Biogas Upgrading

A major challenge in Cyclic Swing Separation using flexible adsorbents that have high equilibrium CO₂ adsorption capacity is their very low-pressure hysteresis that hinders efficient desorption. Mg-Gallate MOF is such a flexible adsorbent that only begins to release CO₂ at its pore closing pressure at 0.08 bar and 30 °C, showing very slow and inefficient desorption in pressure or temperature swing. Therefore, a novel strategy is presented that combines state of art technique Magnetic Induction Heating with a vacuum swing for fast and efficient CO₂ desorption from flexible adsorbents at a moderately elevated temperature (70 °C).     

Optimizing Sieving Effect for CO2 Capture from Humid Air Using an Adaptive Ultramicroporous Framework

Excessive CO₂ in the air can not only lead to serious climate problems but also cause serious damage to humans in confined spaces. Here, a novel metal–organic framework (FJI-H38) with adaptive ultramicropores and multiple active sites is prepared. It can sieve CO₂ from air with the very high adsorption capacity/selectivity but the lowest adsorption enthalpy among the reported physical adsorbents. Such excellent adsorption performances can be retained even at high humidity. Mechanistic studies show that the polar ultramicropore is very suitable for molecular sieving of CO₂ from N₂, and the distinguishable adsorption sites for H₂O and CO₂ enable them to be co-adsorbed. Notably, the adsorbed-CO₂-driven pore shrinkage can further promote CO₂ capture while the adsorbed-H₂O-induced phase transitions in turn inhibit H₂O adsorption. Moreover, FJI-H38 has excellent stability and recyclability and can be synthesized on a large scale, making it a practical trace CO₂ adsorbent. This will provide a new strategy for developing practical adsorbents for CO₂ capture from the air.     

Clover leaf-shaped Al2O3 extrudate as a support for high-capacity and cost-effective CO2 sorbent

Amine-functionalized clover leaf-shaped Al₂O₃ extrudates (CA) were prepared for use as CO₂ sorbent. The as-synthesized materials were characterized by N₂ adsorption, XRD, SEM and elemental analysis followed by testing for CO₂ capture using simulated flue gas containing 15.1% CO₂. The results showed that a significant enhancement in CO₂ uptake was achieved with the introduction of amines into CA materials. A remarkably high volume-based capacity of 70.1 mg/mL of sorbent of this hybrid material suggests that it can be potentially used for CO₂ capture from flue gases and other stationary sources, especially those with low CO₂ concentration. The novel adsorbent reported here performed well during prolonged cyclic operations of adsorption-desorption of CO₂.     

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.     

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.     

Metal‐Organic Frameworks for CO2 Chemical Transformations

Carbon dioxide (CO₂), as the primary greenhouse gas in the atmosphere, triggers a series of environmental and energy related problems in the world. Therefore, there is an urgent need to develop multiple methods to capture and convert CO₂ into useful chemical products, which can significantly improve the environment and promote sustainable development. Over the past several decades, metal‐organic frameworks (MOFs) have shown outstanding heterogeneous catalytic activity due in part to their high internal surface area and chemical functionalities. These properties and the ability to synthesize MOF platforms allow experiments to test structure‐function relationships for transforming CO₂ into useful chemicals. Herein, recent developments are highlighted for MOFs participating as catalysts for the chemical fixation and photochemical reduction of CO₂. Finally, opportunities and challenges facing MOF catalysts are discussed in this ongoing research area.     

改性5A分子筛吸附分离CO2/N2的研究

考察了低浓度CO2[7.3%（V/V）]在不同种类吸附剂上的动态吸附性能;讨论了吸附剂表面极性、孔道结构、载水预处理及金属盐改性等因素对吸附过程的影响。结果表明,5A分子筛经铝溶胶粘合剂成型后对CO2的吸附性能最佳;重复使用6次,对CO2吸附容量无明显下降;金属离子改性处理会造成其孔道的堵塞而导致CO2吸附容量下降。     

Multishelled CaO Microspheres Stabilized by Atomic Layer Deposition of Al2O3 for Enhanced CO2 Capture Performance

CO₂ capture and storage is a promising concept to reduce anthropogenic CO₂ emissions. The most established technology for capturing CO₂ relies on amine scrubbing that is, however, associated with high costs. Technoeconomic studies show that using CaO as a high‐temperature CO₂ sorbent can significantly reduce the costs of CO₂ capture. A serious disadvantage of CaO derived from earth‐abundant precursors, e.g., limestone, is the rapid, sintering‐induced decay of its cyclic CO₂ uptake. Here, a template‐assisted hydrothermal approach to develop CaO‐based sorbents exhibiting a very high and cyclically stable CO₂ uptake is exploited. The morphological characteristics of these sorbents, i.e., a porous shell comprised of CaO nanoparticles coated by a thin layer of Al₂O₃ (<3 nm) containing a central void, ensure (i) minimal diffusion limitations, (ii) space to accompany the substantial volumetric changes during CO₂ capture and release, and (iii) a minimal quantity of Al₂O₃ for structural stabilization, thus maximizing the fraction of CO₂‐capture‐active CaO.     

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.     

Artificial versus Natural Reuse of CO2 for DME Production: Are We Any Closer?

This work uses a mathematical optimization approach to analyze and compare facilities that either capture carbon dioxide (CO₂) artificially or use naturally captured CO₂ in the form of lignocellulosic biomass toward the production of the same product, dimethyl ether (DME). In nature, plants capture CO₂ via photosynthesis in order to grow. The design of the first process discussed here is based on a superstructure optimization approach in order to select technologies that transform lignocellulosic biomass into DME. Biomass is gasified; next, the raw syngas must be purified using reforming, scrubbing, and carbon capture technologies before it can be used to directly produce DME. Alternatively, CO₂ can be captured and used to produce DME via hydrogenation. Hydrogen (H₂) is produced by splitting water using solar energy. Facilities based on both photovoltaic (PV) solar or concentrated solar power (CSP) technologies have been designed; their monthly operation, which is based on solar availability, is determined using a multi-period approach. The current level of technological development gives biomass an advantage as a carbon capture technology, since both water consumption and economic parameters are in its favor. However, due to the area required for growing biomass and the total amount of water consumed (if plant growing is also accounted for), the decision to use biomass is not a straightforward one.     

Adsorption and separation of carbon dioxide and methane on carbonaceous adsorbents

Adsorption and separation of carbon dioxide and methane on different carbonaceous adsorbents were analyzed and compared. Coconut shell-based activated carbon has the highest adsorption capacity for two gases. Sips model describes the adsorption isotherms best. The separation factor on coconut shell-based activated carbon is the highest under various conditions, reaching about 3.8. The adsorption capacity of the two gases is closely related to the specific surface area and micropore volume of the adsorbent. The adsorbed amount of each component in the mixture is less than that of the pure component under the same condition, indicating that there is a competition in the adsorption process. The total adsorbed amount of the two gases decreases as the proportion of carbon dioxide decreases, implying that the adsorption process is dominated by carbon dioxide adsorption. Additionally, the separation factor decreases with increasing temperature. Understanding the adsorption behaviors of pure and binary carbon dioxide and methane is important in treating biomass gas using carbonaceous adsorbents.     

Customizing Metal-Organic Frameworks by Lego-Brick Strategy for One-Step Purification of Ethylene from a Quaternary Gas Mixture

One-step purification of ethylene (C₂H₄) from a quaternary gas mixture of C₂H₆/C₂H₄/C₂H₂/CO₂ by adsorption is a promising separation process, yet developing adsorbents that synergistically capture various gas impurities remains challenging. Herein, a Lego-brick strategy is proposed to customize pore chemistry in a unified framework material. The ethane-selective MOF platform is further modified with customized binding sites to specifically adsorb acetylene and carbon dioxide, thus one-step purification of C₂H₄ with high productivity of polymer-grade product (134 mol kg⁻¹) is achieved on the assembly of porous coordination polymer-2,5-furandicarboxylic acid (PCP-FDCA) and PCP-5-aminoisophthalic acid (IPA-NH₂). Computational studies verify that the low-polarity surface of this MOFs-based platform provides a delicate environment for C₂H₆ recognition, and the specific binding sites (FDCA and IPA-NH₂) exhibit favorable trapping of C₂H₂ and CO₂ via C H^δ+···O^δ− and C^δ+···N^δ− electrostatic interactions, respectively. The proposed Lego-brick strategy to customize binding sites within the MOFs structure provides new ideas for the design of adsorbents for compounded separation tasks.     

烟气中低浓度二氧化碳吸附捕集中试试验研究

采用廉价的工业硅胶,通过三塔八步工业试验,对燃煤烟道气中低浓度CO2进行了吸附捕集,探讨了置换时间、吸附周期、顺放时间等工艺条件对产品气中CO2浓度的影响,结果表明,置换时间与吸附周期对CO2浓度影响最大,其次为顺放时间与产品气流量,返流工艺影响最小.采用工业硅胶可以在保证产品气流量的情况下,将产品气浓度提高至74%以上,有利于进一步降低CO2减排成本.     

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.     

Polyethyleneimine functionalised nanocarbons for the efficient adsorption ofcarbon dioxide with a low temperature of regeneration

Polyethyleneimine (PEI) conjugates with a range of nanocarbons (NCs) have been prepared, and their performances with regard to carbon dioxide absorption and liberation are compared. PEI-functionalised multi-walled carbon nanotubes (PEI-MWNTs) prepared by the reaction of branched PEI (25,000 Da) with F-MWNTs in the presence of pyridine, showed a lower CO₂ capacity at 25 °C (5 wt%, 1.1 mmol CO₂/g adsorbent) as compared to PEI-SWNTs (9.2 wt%, 2.1 mmol CO₂/g adsorbent), consistent with the interior layers of the MWNTs adding weight to the base NC without adding functionality. PEI-functionalised graphite/graphene was prepared by three routes: fluorinated graphite intercalation compounds, prepared from natural graphite powder, were reacted with PEI in EtOH with pyridine; exfoliated natural graphite powder was reacted with Boc–Phe(4-N₃)–OH, and subsequently PEI to give PEI-Phe(4-N-G); graphite oxide (GO) was reacted with PEI in the presence of NEt₃ to give PEI-GO. The CO₂ capacity of PEI-GO at 25 °C (8 wt%, 1.8 mmol CO₂/g adsorbent) was comparable to that of PEI-SWNTs making GO a valid and cheaper alternative to the SWNT scaffold. The temperature of CO₂ desorption of the PEI-NCs was 75 °C, providing a lower energy load for regeneration compared to current amine-based scrubbing units. The rate of CO₂ uptake is seen to depend on the curvature of the NC substrate.     

Restricting Lattice Flexibility in Polycrystalline Metal–Organic Framework Membranes for Carbon Capture

Although polycrystalline metal‐organic framework (MOF) membranes offer several advantages over other nanoporous membranes, thus far they have not yielded good CO₂ separation performance, crucial for energy‐efficient carbon capture. ZIF‐8, one of the most popular MOFs, has a crystallographically determined pore aperture of 0.34 nm, ideal for CO₂/N₂ and CO₂/CH₄ separation; however, its flexible lattice restricts the corresponding separation selectivities to below 5. A novel postsynthetic rapid heat treatment (RHT), implemented in a few seconds at 360 °C, which drastically improves the carbon capture performance of the ZIF‐8 membranes, is reported. Lattice stiffening is confirmed by the appearance of a temperature‐activated transport, attributed to a stronger interaction of gas molecules with the pore aperture, with activation energy increasing with the molecular size (CH₄ > CO₂ > H₂). Unprecedented CO₂/CH₄, CO₂/N₂, and H₂/CH₄ selectivities exceeding 30, 30, and 175, respectively, and complete blockage of C₃H₆, are achieved. Spectroscopic and X‐ray diffraction studies confirm that while the coordination environment and crystallinity are unaffected, lattice distortion and strain are incorporated in the ZIF‐8 lattice, increasing the lattice stiffness. Overall, RHT treatment is a facile and versatile technique that can vastly improve the gas‐separation performance of the MOF membranes.     

Modeling the operation of a three-stage fluidized bed reactor for removing CO2 from flue gases

A bubbling counter-current multistage fluidized bed reactor for the sorption of carbon dioxide (CO(2)) by hydrated lime particles was simulated employing a two-phase model, with the bubble phase assumed to be in plug flow, and the emulsion phase in plug flow and perfectly mixed flow conditions. To meet prescribed permissible limit to emit carbon dioxide from industrial flue gases, dry scrubbing of CO(2) was realized. For the evaluation, a pilot plant was built, on which also the removal efficiency of CO(2) was verified at different solids flow rates. The model results were compared with experimental data in terms of percentage removal efficiency of carbon dioxide. The comparison showed that the EGPF model agreed well with the experimental data satisfactorily. The removal efficiency was observed to be mainly influenced by flow rates of adsorbent and CO(2) concentration.     

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。     

Exposing {001} Crystal Plane on Hexagonal Ni‐MOF with Surface‐Grown Cross‐Linked Mesh‐Structures for Electrochemical Energy Storage

Hexagonal nickel‐organic framework (Ni‐MOF) [Ni(NO₃)₂·6H₂O, 1,3,5‐benzenetricarboxylic acid, 4‐4′‐bipyridine] is fabricated through a one‐step solvothermal method. The {001} crystal plane is exposed to the largest hexagonal surface, which is an ideal structure for electron transport and ion diffusion. Compared with the surrounding rectangular crystal surface, the ion diffusion length through the {001} crystal plane is the shortest. In addition, the cross‐linked porous mesh structures growing on the {001} crystal plane strengthen the mixing with conductive carbon, inducing preferable conductivity, as well as increasing the area of ion contact and the number of active sites. These advantages enable the hexagonal Ni‐MOF to exhibit excellent electrochemical performance as supercapacitor electrode materials. In a three‐electrode cell, specific capacitance of hexagonal Ni‐MOF in the 3.0 m KOH electrolyte is 977.04 F g^?1 and remains at the initial value of 92.34% after 5,000 cycles. When the hexagonal Ni‐MOF and activated carbon are assembled into aqueous devices, the electrochemical performance remains effective.     

变压吸附系统吸附剂吸附容量的实验研究

运用实验的方法对变压吸附系统中吸附剂的吸附容量进行了研究.分析不同因素对吸附剂吸附容量的影响,包括吸附温度、吸附压力,给出吸附容量在这些因素影响下的变化规律,同时比较了不同吸附剂的吸附容量.实验结果可对工业选用吸附剂以及变压吸附系统的优化设计提供必要的数据.