Adsorbents For Capture Research Articles

A general Energy-Efficient strategy for optimizing CO2 Capture: Designing and harnessing the rapid adsorption kinetics of Amine-Impregnated adsorbents

This study aims to optimize the performance of amine-impregnated CO2 adsorbents for both direct air capture (DAC) and point source CO2 capture (PSC) applications. The main objective of this study is to investigate the relationship between the weight fraction of amine loading and the efficiency of CO2 uptake on the designated support, aiming to find a straightforward method to design effective amine support materials. To this end, a composite material denoted as PEI/CNT@ZIF-8 has been developed. This composite is comprised of polyethylenimine (PEI), multi-walled carbon nanotubes (CNTs), and zeolitic imidazolate frameworks (ZIF-8). CNTs offer several advantages for enhancing CO2 uptake, including rearranging the ZIF-8 particles to facilitate PEI loading, creating strong electrostatic interaction for amine anchoring, and establishing CO2 diffusion channels to improve CO2 capture kinetics. In DAC scenarios, with a CO2 concentration of 400 ppm balanced with N2, the 25.0 wt% PEI/CNT(1)@ZIF-8(5) demonstrates superior CO2 uptake, achieving 4.08 mmol g−1 within a one-hour interval by harnessing the rapid kinetic region and exhibiting a low desorption energy of 55.8 kJ mol−1 for releasing CO2. In PSC scenarios, with a CO2 concentration of 15 vol% under both dry and wet conditions, the 37.5 wt% PEI/CNT(1)@ZIF-8(5) exhibits excellent CO2 uptake of 2.21 and 2.58 mmol g−1, respectively, at 50 ℃. The findings suggest that adjusting the balance between CO2 uptake and adsorption kinetics by considering the amine weight fraction can optimize the performance of solid amine CO2 adsorbents across diverse operational conditions. Furthermore, rather than relying on a single support material, this study reveals the potential of combining CNTs with materials such as SiO2 nanoparticles, Al2O3, or metal–organic frameworks (MOFs) to enhance CO2 capture performance. This approach holds promise as an effective and straightforward strategy.

Ultra-highly efficient adsorbent for CO2 capture from air by directional deprotonation regulation of MOFs-based amine grafting

In recent years, the solid amine of Metal-Organic Frameworks (MOFs) has shown promise as a direct air capture (DAC) adsorbent. However, the efficiency of amine groups under ultra-low CO2 concentrations requires improvement. In this study, we propose a novel method to regulate proton migration through solvent effects during amine grafting, to enhance the synthesis of MOFs as solid amine adsorbents and improve amine group utilization. This approach yielded outstanding results with a MIL-100(Cr)-based DAC adsorbent, demonstrating a CO2 adsorption capacity of 2.15 mmol/g and an ultra-high amine group utilization of 89.6 % at ambient conditions. By directional deprotonation regulation, the CO2 adsorption performance of the UiO-66(Zr)-based adsorbent significantly increased from 0.06 mmol/g of using H2O as solvent to 1.71 mmol/g of using NMP, with a 27.5-fold increase. Specifically, organic polar aprotic solvents enhanced the binding energy and reduced the energy barrier for deprotonation during the grafting process, thereby improving CO2 adsorption performance and amine group utilization, which shed a new light on the development of MOFs based CO2 adsorbent. Furthermore, due to the coordination of secondary amine groups with metal sites leads to the decrease of hydrophilic functional groups in the CO2 adsorption products, the hydrophobicity of products was reduced significantly resulting in an increase in the ΔS of the hydrated ion pairs after the adsorption, which reduced the heat of CO2 adsorption about 15 % than that reported in the literature. Based on changes in humidity conditions, the regeneration energy consumption of the MF-Cr-AEEA is less than 2.5 GJ/t CO2 under a relatively lower humidity, demonstrating outstanding industrial applications potential of the adsorbent.

Recent Progress on Porous Carbons for Carbon Capture.

High emission of carbon dioxide (CO2) has caused CO2 levels to reach more than 400 ppm in air and led to a serious climate problem. In addition, in confined spaces such as submarines and aircraft, the CO2 concentration increase in the air caused by human respiration also affects human health. In order to protect the environment and human health, the search for high-performance adsorbents for carbon capture from high and low concentration gas is particularly important. Porous carbon materials, possessing the advantages of low cost and renewability, have set off a boom in the research of porous adsorbents, which have the opportunity to be utilized on a large scale for industrial carbon capture in the future. In this review, we summarize the recent research progress of porous carbons for carbon capture from flue gas and directly from air in the last five years, including activated carbon (AC), heteroatom-modified porous carbon, carbon molecular sieves (CMS), and other porous carbon materials, with a focus on the effects of temperature, water content, and gas flow rate of industrial flue gas on the performance of porous carbon adsorbents. We summarize the preparation strategies of various porous carbons and seek environmental friendly porous carbon materials preparation strategies under the premise of improving the CO2 adsorption capacity and selectivity of porous carbon adsorbents. Based on the effects of real industrial flue gas on adsorbents, we provide new ideas and evaluation methods for the development and preparation of porous carbon materials.

Facilely tuning the morphologies of tertiary amine-functionalized SBA-15 for optimizing selective SO2 capture

The amine-based materials pose high potential for the adsorption of sulfur dioxide (SO2). This work is aimed at modulating the morphologies of SBA-15 adsorbents by controlling the precursor self-assembly processes, for the sake of optimizing the utilization efficiency of amine species in the polytertiary amine (PTA)-functionalized SBA-15. It results that worm-like SBA-15 (WLS) material shows a better particle aspect ratio and well-defined pore structure, which helps to optimize the adsorption sites invoked by the preferable dispersion and exposure of PTA, thus amplifying the chemisorption of SO2 on the adsorbent. Consequently, the functionalized WLS-PTA adsorbent exhibits remarkable SO2 adsorption performance (15.43 mmol/g), exceptionally high selectivities of SO2/N2 (27522) and SO2/CO2 (652). Surprisingly, the desulfurization capacity can be further enhanced by the positive effect of the water vapor co-fed. It is unveiled that the whole SO2 adsorption process mainly follows the dual site Langmuir-Freundlich isotherm model and Bangham model. This work sheds light on the design of polymer-solid composite adsorbents for selective capture of SO2.

Modified mesoporous silica derived from bamboo leaf using cetyltrimethylammonium bromide and 3-aminopropyl triethoxysilane as CO2 adsorbentinbiogas purification.

The calorific value of post-fermentation biogas is a way down below standard and quite low due to the presence of high amount level of carbon dioxide (CO2) biogas mixture. Therefore, it raises the need to process the biogas, separating it from CO2 in order to obtain high-purity biogas as well as to maximize its calorific value. One widely available material that can be used as a sustainable carbon capture adsorbent is silica extracted from bamboo leaves. However, so that silica can act as CO2 adsorber, it is necessary to modify the surface of silica with CTAB and APTES (3-aminopropyl triethoxysilane). In this study, 2-stage method was carried out, namely preparation of mesoporous silica and surface modification using APTES on the mesoporous silica. Experiments in synthesizing APTES-modified silica were obtained by varying its composition: CTAB (1.5-5%w), (HCl 1.5-5 N), and APTES (10-30%). A central composite design (CCD) was employed in exploring the interaction between all variables and also performed for the optimization. Through analysis of variance, it shows that optimum CO2 adsorption capacity reaches 47.02mgg-1, by applying 4.98% of CTAB, 4.28N of HCl and 10.08% of APTES. Pseudo-second-order kinetic and Redlich-Peterson isotherm models are more representative to show the adsorption behavior of CO2 into the modified silica. The results show that the modified silica with APTES shows a prospective application of silica for CO2 removal from biogas.

Experimental and theoretical study on recovered nano amorphous selenium as efficient adsorbents for mercury capture from flue gas

The cost-effective removal of gaseous elemental mercury from coal-fired flue gas is crucial for environmental protection. In this study, nano amorphous selenium (nano-a-Se) adsorbent was recovered from desulfurization wastewater to remove Hg0 in flue gas. The results indicate that nano-a-Se has a high efficiency in the amorphous form with a saturated adsorption capacity of 2034.32 mg g−1. The Se utilization ratio of nano-a-Se reached 80% of the theoretical limit. Meanwhile, nano-a-Se exhibited high resistance to NO and SO2 poisoning. Moreover, the Hg0 removal mechanism of nano-a-Se was analyzed by experimental analysis and density functional theory (DFT) calculations. The results demonstrate that nano-a-Se can convert Hg0 into stable mercury selenide, a high-value by-product with little risk of mercury re-release. Therefore, nano-a-Se is expected to be a novel adsorbent with high efficiency in capturing Hg0, which can help realize the resource utilization of toxic elements from the environment.

Fabrication of metal oxides-based adsorbents for SO2 capture with equimolar adsorption

A series of novel porous metal oxides (MO, M = Mg, Ca, Ba, Mn and Zn) adsorbents were synthesized through simple thermal treatment of the corresponding metal sulfite for the remotion of sulfur dioxide (SO2). The obtained MO adsorbents were characterized by various techniques including scanning electron microscopy (SEM), thermal gravimetric analyzer (TGA), X-ray diffraction (XRD) and nitrogen adsorption studies. The results show that the SO2 adsorption capacity of manganese oxide (MnO) is much higher than that of other MO. And due to its highly dispersed and large specific surface area, especially its well-developed pore structure, equimolar adsorption of SO2 can be achieved for the first time among similar SO2 adsorbents. In addition, different sources of MnO were explored and it was found that the MnO obtained from the decomposition of MnSO3 had the highest SO2 adsorption capacity. Adsorption kinetic studies show that the reaction between MnO and SO2 conforms to the pseudo-second-order kinetic equation. Furthermore, it was found through seven-cycle experiments that the adsorption amount tended to stabilize in each of the following cycles, except for the first high temperature, which led to changes in the adsorbent and a decrease in cycling performance. This strategy has three advantages: one-step preparation at low temperatures, equimolar adsorption of SO2 as well as good reusability and selectivity.

Techno-economic analysis on temperature vacuum swing adsorption system integrated with pre-dehumidification for direct air capture

In addressing the practical application of direct air capture (DAC) technology to achieve net-zero greenhouse gas emissions by 2050, the intricate climatic environment presents a significant challenge in selecting capture adsorbents with excellent adsorption performance, high moisture tolerance and stability. This study seeks to assess the efficacy of a temperature vacuum swing adsorption (TVSA) system for DAC, integrated with two distinct pre-dehumidification methods: condensation dehumidification and solid desiccant dehumidification. Initially, to balance enhanced adsorption capacity with the energy required for regeneration in the presence of water vapor, the optimal techno-economic performance is achieved at a 40 % relative humidity (RH). This corresponds to 15.49 GJ/t of heat consumption and 194.08 $/tonCO2 of CO2 the levelized cost of DAC (LCOD). Following dynamic simulation, the dehumidification system effectively controlled the outlet RH. Furthermore, economic analysis indicates that reducing environmental air to 40 % RH is more suitable and cost-efficient for both integrated systems. The optimal LCODs are 200.29 $/tonCO2 for the solid desiccant dehumidification system and 197.16 $/tonCO2 for the condensation dehumidification system, which could effectively save 7.09 % and 5.61 % of LCOD, respectively, compared to systems without a dehumidification process.

Nitrogen-rich porous organic polymer as a promising adsorbent for iodine capture from organic solvents

A perylene and triazine-based polymer called PT-POP demonstrates exceptional efficiency in iodine adsorption capacity, indicating its potential for effective iodine removal and storage.

Integrated fabrication of CMC@UiO-66–NH2@PEI composite adsorbents for efficient batch and dynamic phosphate capture

A separable bio-adsorbent was created through a straightforward cross-linking process, leading to effective capture of phosphate in both static and dynamic aqueous systems.

Highly selective capture of SO2 with supported micro-mesoporous silica sphere from CO2-rich environment

Selective adsorption of sulfur dioxide (SO2) is an important clean technology for purification of exhaust gas from fossil fuel combustion. The widely applied zeolite-based adsorbents interact with SO2 through weakly physical adsorption, resulting in low adsorption capacity and selectivity for SO2. Herein, a facile strategy that combines improving the textural property of zeolite and optimizing adsorption sites is developed for efficient and stable SO2 adsorption. The micro-mesoporous silica sphere (MS) with high specific surface area and well-defined pore structure is obtained through a micelle expander assisted soft-template method, which can facilitate the dispersion and exposure of designed adsorption sites- methylated polyethyleneimine (mPEI). Since the Lewis basic sites of N in mPEI can strongly interact with the π-receptor SO2, and the tertiary amine groups exhibit a weak attraction for CO2, the optimized MS supported mPEI adsorbent exhibits remarkable SO2 adsorption performance (7.5 mmol/g), exceptionally high SO2/N2 selectivity (16673) and SO2/CO2 selectivity (551). Moreover, it presents an outstanding stability in the adsorption-regeneration test. This work sheds light on the design of high-performance organic-solid composite adsorbent for selective capture of SO2.

Hollow spherical nano-traps using pillararene-based polymer for efficient uranium extraction from seawater.

Herein, a hollow spherical pillar[5]arene-based polymer (P5-AO) adsorbent was synthesized. The P5-AO adsorbent was capable of effectively capturing uranium from simulated seawater (139.5 mg g-1) and real seawater (8.1 mg g-1). We also elucidated the uranium adsorption mechanism of P5-AOvia extended X-ray absorption fine structure (EXAFS). This study provides a novel direction for the development of uranium capture adsorbents.

Amino-modified biochar-silica hybrid aerogels with ordered pore structure templated by cellulose nanocrystals for highly efficient and selective CO2 capture

Carbon dioxide (CO2) emissions from the combustion of fossil fuels are contributing to global climate change and ocean acidification, and the development of low-cost, highly efficient CO2 capture adsorbents for the reduction of CO2 concentrations is now a matter of urgency. Herein, we developed amine-modified biochar-silica hybrid aerogels template cellulose nanocrystals (CNCs) for CO2 capture. CNCs can self-assemble into an ordered lamellar structure and maintain their original structure after calcination in N2 atmosphere. At the same time, we chemically modified the hybrid aerogels with amines. The ordered pore structure and chemical modification effectively enhanced the CO2 adsorption capacity and rate of hybrid aerogels. The test showed that our material exhibited high adsorption properties of 2.81 mmol g−1 (0 °C, 1 bar). This work offers research ideas and methods for fabricating amine-modified biochar-silica hybrid aerogels for CO2 capture.

Importance of Bridging Molecular and Process Modeling to Design Optimal Adsorbents for Large-Scale CO2 Capture.

ConspectusCarbon capture, utilization, and storage have been identified as key technologies to decarbonize the energy and industrial sectors. Although postcombustion CO2 capture by absorption in aqueous amines is a mature technology, the required high regeneration energy, losses due to degradation and evaporation, and corrosion carry a high economic cost, precluding this technology to be used today at the scale required to mitigate climate change. Solid adsorbent-based systems with high CO2 capacities, high selectivity, and lower regeneration energy are becoming an attractive alternative for this purpose. Conscious of this opportunity, the search for optimal adsorbents for the capture of CO2 has become an urgent task. To accurately assess the performance of CO2 separation by adsorption at the needed scale, adsorbents should be synthesized and fully characterized under the required operating conditions, and the proper design and simulation of the process should be implemented along with techno-economic and environmental assessments. Several works have examined pure CO2 single-component adsorption or binary mixtures of CO2 with nitrogen for different families of adsorbents, primarily addressing their CO2 adsorption capacity and selectivity; however, very limited data is available under other conditions and/or with impurities, mainly due to the intensive experimental (modeling) efforts required for the large number of adsorbents to be studied, posing a challenge for their assessment under the needed conditions. In this regard, molecular simulations can be employed in synergy with experiments, reliably generating missing adsorption properties of mixtures while providing understanding at the molecular level of the mechanism of the adsorption process.This Account provides an outlook on strategies used for the rational design of materials for CO2 capture from different sources from the understanding of the adsorption mechanism at the molecular level. We illustrate with practical examples from our work and others' work how molecular simulations can be reliably used to link the molecular knowledge of novel adsorbents for which limited data exist for CO2 capture adsorption processes. Molecular simulation results of different adsorbents, including MOFs, zeolites, and carbon-based and silica-based materials, are discussed, focusing on understanding the role of physical and chemical adsorption obtained from simulations and quantifying the impact of impurities in the performance of the materials. Furthermore, simulation results can be used for screening adsorbents from basic key performance indicators, such as cycling the working capacity, selectivity, and energy requirement, or for feeding detailed dynamic models to assess their performance in swing adsorption processes on the industrial scale, additionally including monetized performance indicators such as operating expenses, equipment sizes, and compression cost. Moreover, we highlight the role of molecular simulations in guiding strategies for improving the performance of these materials by functionalization with amines or creating hybrid solid materials. We show how integrating models at different scales provides a robust and reliable assessment of the performance of the adsorbent materials under the required industrial conditions, rationally guiding the search for best performers. Trends in additional computational resources that can be used, including machine learning, and perspectives on practical requirements for leveraging CO2 capture adsorption technologies on the needed scale are also discussed.

Synergy tetraethylenepentamine and diethanolamine impregnated within silica nanotubes derived from natural halloysite for efficient CO2 capture

Amine-impregnated porous solid adsorbents are promising commercial CO2 capture adsorbents for CO2 mitigation due to relatively large CO2 capacity and high CO2 selectivity. However, the intrinsic viscosity and aggregation of the polyamine leads to low amine efficiency and greatly limits its further development. In this work, a facile and efficient approach was carried out to manipulate the porosity of natural halloysite (HNTs) support with hollow tubular structure and impregnate mixed-polyamines, i.e., both tetraethylenepentamine (TEPA) and diethanolamine (DEA) to synergistically enhance CO2 adsorption capacity, fast adsorption kinetics and thermal/chemical stability compared to the individual supported TEPA and DEA. The effects of the blend amount for TEPA and DEA, adsorption temperature and CO2 partial pressure on CO2 adsorption capacity and adsorption kinetics were specifically discussed. Due to the auxiliary effect of DEA, the chemical reaction between non-hydroxylated TEPA and CO2 was altered thus improving amine efficiency and the agglomeration layer between protonated TEPA molecules and carbamate, which existed due to electrostatic interaction when TEPA was loaded alone, was loosened thus improving amine efficiency and adsorption kinetics. Therefore, the maximum CO2 adsorption capacity of MHNTs loaded with 20 wt% TEPA and 20 wt% DEA was 3.25 mmol/g at 75 °C in the flow of 40 vol% N2/60 vol% CO2. Compared with loading individual TEPA with multiple amino groups on MHNTs, individual DEA with hydroxyl groups could increase the utilization efficiency of the amino groups of TEPA and ultimately obtain excellent CO2 capture capacity and adsorption kinetics. The experimental results show that the adsorbents obtained in this study using mixed amine impregnated silica nanotubes derived from natural minerals have a promising application in practical CO2 capture and separation processes.

Solvent-free mechanochemical synthesis of a sodium disulfonate covalent organic framework for simultaneous highly efficient selective capture and sensitive fluorescence detection of fluoroquinolones

Covalent organic frameworks (COFs) have great adsorption potential due to their tunable pore size and pore architecture as well as tailorable functionalities. However, the green and rapid synthesis of COFs with excellent adsorption properties remains a great challenge. Here, we presented a solvent-free and facile mechanochemical approach for the synthesis of COFs. The as-prepared COF TpBD-(SO3Na)2 containing sulfonate ions exhibited good thermal and chemical stability and can serve as an effective adsorbent for selective capture of fluoroquinolone antibiotics (FQs) benefiting from the ionic interface and abundant negatively charged sites. The maximum adsorption capacities of norfloxacin, enoxacin, and ciprofloxacin were 1709.6, 1661.5, and 1362.8 mg g−1, respectively, which outperformed those of other reported adsorbents. The adsorption mechanism was deeply explored through characterizations combined with density functional theory calculations, proving the synergistic adsorption effects of TpBD-(SO3Na)2 and FQs, including π-π* interactions, electrostatic interactions, and hydrogen bonding. Moreover, a fluorescence detection platform for FQs was developed based on the fluorescence signal of sodium disulfonate TpBD-(SO3Na)2. The limit of detection of norfloxacin was 8 nmol/L with a linear range from 0.03 to 6 μmol/L. This research provides a new strategy for the green synthesis of COFs and expands their application in the synchronous detection and removal of FQs in aquatic environments.

Recent advances and challenges in ionic materials for post-combustion carbon capture

The massive combustion of fossil fuels has resulted in excessive emissions of carbon dioxide (CO2), which has become an urgent environmental problem worldwide. Post-combustion capture technology is one of the most promising carbon capture technologies with rapid growth potential. Ionic materials hold great promise as superior adsorbents for post-combustion capture, offering advantages such as increased adsorption capacity, adjustable adsorption rate, and enhanced operational stability. This review mainly summarized the rational design of pure ionic materials and ion hybrid materials for carbon capture. The relationship between the structural design of materials and the control of capacity, rate, and stability of carbon capture was focused on. A complete description of several emerging ionic materials and their potential for carbon capture is also given. Simultaneously, novel control concepts and rapid screening techniques are introduced. Finally, the article discusses the problems and solutions for the use of ionic materials in future post-combustion capture technology. This work deepens our comprehension of the construction and control of ionic materials, offering valuable insights for the advancement of industrial carbon capture.

Synergistic Nitrogen Binding Sites in a Metal‐Organic Framework for Efficient N2/O2 Separation

AbstractPorous materials with d3 electronic configuration open metal sites have been proved to be effective adsorbents for N2 capture and N2/O2 separation. However, the reported materials remain challenging to address the trade‐off between adsorption capacity and selectivity. Herein, we report a robust MOF, MIL‐102Cr, that features two binding sites, can synergistically afford strong interactions for N2 capture. The synergistic adsorption site exhibits a benchmark Qst of 45.0 kJ mol−1 for N2 among the Cr‐based MOFs, a record‐high volumetric N2 uptake (31.38 cm3 cm−3), and highest N2/O2 selectivity (13.11) at 298 K and 1.0 bar. Breakthrough experiments reveal that MIL‐102Cr can efficiently capture N2 from a 79/21 N2/O2 mixture, providing a record 99.99 % pure O2 productivity of 0.75 mmol g−1. In situ infrared spectroscopy and computational modelling studies revealed that a synergistic adsorption effect by open Cr(III) and fluorine sites was accountable for the strong interactions between the MOF and N2.

Synergistic Nitrogen Binding Sites in a Metal-Organic Framework for Efficient N2 /O2 Separation.

Porous materials with d3 electronic configuration open metal sites have been proved to be effective adsorbents for N2 capture and N2 /O2 separation. However, the reported materials remain challenging to address the trade-off between adsorption capacity and selectivity. Herein, we report a robust MOF, MIL-102Cr, that features two binding sites, can synergistically afford strong interactions for N2 capture. The synergistic adsorption site exhibits a benchmark Qst of 45.0 kJ mol-1 for N2 among the Cr-based MOFs, a record-high volumetric N2 uptake (31.38 cm3 cm-3 ), and highest N2 /O2 selectivity (13.11) at 298 K and 1.0 bar. Breakthrough experiments reveal that MIL-102Cr can efficiently capture N2 from a 79/21 N2 /O2 mixture, providing a record 99.99 % pure O2 productivity of 0.75 mmol g-1 . In situ infrared spectroscopy and computational modelling studies revealed that a synergistic adsorption effect by open Cr(III) and fluorine sites was accountable for the strong interactions between the MOF and N2 .

Defective copper-based metal-organic frameworks for the efficient extraction of organosulfur compounds from garlic-processing wastewater

Organosulfur compounds (OSCs) in garlic-processing wastewater are decomposed and generated to toxic and harmful substances with unpleasant odors under anaerobic conditions. Herein, were report the successful development of novel copper-based metal organic framework (Cu-MOF) adsorbents with high adsorption capacities for OSCs in aqueous media. Defect-rich Cu-MOF-X samples, with particle sizes between 360 and 750 nm, synthesized hydrothermal in the presence of acetic acid (where X denotes the molar ratio of acetic acid relative to the pentadentate MOF linker H4PPYD). OSC adsorption experiments using allicin, ajoene and 2-ethenyl-4H-1,3-dithiine (2-VDT) showed that Cu-MOF-200 delivered fast adsorption kinetics and high OSC adsorption capacities (149.02–171.33 mg g−1) owing to the pore accessibility and range of adsorption sites in the MOF. FT-IR, Raman, and XPS analyses, together with density functional theory (DFT) calculations, verified the strong yet reversible adsorption of OSCs in Cu-MOF-200. Results guide the development of improved adsorbents for OSC capture from garlic-processing wastewater.