High CO2 Capture Capacity Research Articles

Amine/vermiculite composite aerogels fabricated by polyethyleneimine-induced vermiculite nanosheet gelation for efficient direct air capture

Direct air capture (DAC), being able to remove the accumulated CO2 in atmosphere and CO2 carbon emission from discrete sources, is a promising technology for mitigating the global greenhouse effect and achieving carbon neutrality. However, achieving high-capacity, low-cost DAC of CO2 through simple methods remains a significant challenge. In this study, a simple, cost-effective, and environmentally friendly method for fabricating amine/vermiculite composite aerogels is proposed for capturing CO2 from ambient air. Natural two-dimensional material, vermiculite nanosheets with exposed surface and intrinsic negative charge, was utilized as the the building blocks for fabricating aerogel as solid amine adsorbents, via the fast gelatin between vermiculite and amine, significantly reducing the cost of adsorbent preparation while achieving promising CO2 capture capability. The effects of amine loading, amine molecular weight, and porosity on CO2 capture capacity and amine efficiency were investigated. It is found that the amine with larger molecular weights endows more stable amine anchoring in the composite aerogel, the aerogels using amine with higher molecular weights demonstrated higher residual amine ratios under vacuum conditions during the aerogel adsorbent synthesis, consequently enhancing the CO2 capture capacity of the adsorbents. By optimizing synthesis strategy and the amine loading of the composite aerogels, the highest CO2 capture capacity (0.72 mmol/g) and amine efficiency (0.29) were achieved. The monolithic structure of the aerogels ensures low pressure drop of 0.35 hPa during gas flow-through, enhancing their integration and applicability in adsorption devices. The vermiculite-based adsorbents exhibit unique advantages in practical DAC processes, including lower cost, higher amine efficiency, and stable cyclic performance. These findings hold significant promise for the application and advancement of DAC technologies.

Optimized Porous Carbon Particles from Sucrose and Their Polyethyleneimine Modifications for Enhanced CO2 Capture

Carbon dioxide (CO2), one of the primary greenhouse gases, plays a key role in global warming and is one of the culprits in the climate change crisis. Therefore, the use of appropriate CO2 capture and storage technologies is of significant importance for the future of planet Earth due to atmospheric, climate, and environmental concerns. A cleaner and more sustainable approach to CO2 capture and storage using porous materials, membranes, and amine-based sorbents could offer excellent possibilities. Here, sucrose-derived porous carbon particles (PCPs) were synthesized as adsorbents for CO2 capture. Next, these PCPs were modified with branched- and linear-polyethyleneimine (B-PEI and L-PEI) as B-PEI-PCP and L-PEI-PCP, respectively. These PCPs and their PEI-modified forms were then used to prepare metal nanoparticles such as Co, Cu, and Ni in situ as M@PCP and M@L/B-PEI-PCP (M: Ni, Co, and Cu). The presence of PEI on the PCP surface enables new amine functional groups, known for high CO2 capture ability. The presence of metal nanoparticles in the structure may be used as a catalyst to convert the captured CO2 into useful products, e.g., fuels or other chemical compounds, at high temperatures. It was found that B-PEI-PCP has a larger surface area and higher CO2 capture capacity with a surface area of 32.84 m2/g and a CO2 capture capacity of 1.05 mmol CO2/g adsorbent compared to L-PEI-PCP. Amongst metal-nanoparticle-embedded PEI-PCPs (M@PEI-PCPs, M: Ni, Co, Cu), Ni@L-PEI-PCP was found to have higher CO2 capture capacity, 0.81 mmol CO2/g adsorbent, and a surface area of 225 m2/g. These data are significant as they will steer future studies for the conversion of captured CO2 into useful fuels/chemicals.

From low-cost mineral to high-performance Li4SiO4 for solar energy storage and CO2 capture

The huge consumption of fossil fuels results in excessive CO2 emissions and its reduction has become a common concern. The combination of renewable energies (i.e., solar energy) and carbon capture, utilization, and sequestration are well recognized as two major routes to achieving carbon neutrality. Lithium orthosilicate (Li4SiO4) has been identified as one of the most promising candidates for solar energy storage and CO2 capture. However, the cost reduction and performance enhancement remain to be the main obstacles for its practical application. In this work, high-performance Li4SiO4 heat carriers have been synthesized using low-cost mineral as silicon source for solar energy storage and CO2 capture. Li4SiO4 derived from diatomite exhibited cyclic energy storage densities above 500 kJ/kg. The performance was further improved by doping alkali carbonates, particularly doping 3 wt% K2CO3 (LD-P-3K), which exhibited high and stable energy storage density of approximately 700 kJ/kg in the tested 10 cycles. Then, the mechanism of alkali doping was revealed through experiments and DFT calculations. The DSC results demonstrated that the improved performance was attributed to the formation of a eutectic melt which reduced the CO2 diffusion resistance. The DFT calculations showed that K-doped Li4SiO4 had lower adsorption energy and more significant charge migration, which meant stronger interaction. Additionally, diatomite-derived Li4SiO4 material is also a promising candidate for high-temperature CO2 capture, evidenced by its relatively high cyclic CO2 capture capacity (∼0.25 g/g). In general, satisfactory density/capacity and stability endows diatomite-derived Li4SiO4 with great prospects for both thermochemical energy storage and high-temperature CO2 capture.

Adsorption capability and regenerability of carbon slit micropores for CO2 capture

To date, the exceptional performance of microporous carbon in CO2 capture has been widely acknowledged as a crucial step towards achieving global zero carbon emissions. In this molecular simulation study, we employ grand canonical Monte Carlo simulation (GCMC) to shed light on the significant influence of micropores on CO2 adsorption capability and regenerability, emphasizing the need for a rigorous selection of the swing adsorption process based on pore size. Our findings corroborate numerous experimental and numerical studies that the ultramicropore (pore size < 7 Å) is the appropriate range for CO2 capture, as it facilitates the formation of a horizontal monolayer of CO2 molecules. Furthermore, we highlight the importance of designing porous carbon materials with a large pore volume at the optimal ultramicropore sizes (approximately 5.8-6.4 Å depending on adsorption and desorption conditions) for obtaining high CO2 capture capacity and effective adsorbent regeneration. For the first time, taking into account the operational parameters of practical swing adsorption processes, our simulation study provides valuable guidance for selecting the most appropriate technology tailored to each specific range of micropore size in porous carbon. For porous carbon materials with an abundant volume of ultramicropores, pressure swing adsorption (PSA) and pressure-temperature swing adsorption (PTSA), as conventional and hybrid swing adsorption processes respectively, are the most effective practices, achieving high CO2 working capacity and regenerability exceeding 80%.

Versatile Activated Carbon Fibers Derived from the Cotton Fibers Used as CO2 Solid-State Adsorbents and Electrode Materials.

Activated carbon has an excellent porous structure and is considered a promising adsorbent and electrode material. In this study, activated carbon fibers (ACFs) with abundant microporous structures, derived from natural cotton fibers, were successfully synthesized at a certain temperature in an Ar atmosphere and then activated with KOH. The obtained ACFs were characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), elemental analysis, nitrogen and carbon dioxide adsorption-desorption analysis, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and N2 adsorption-desorption measurement. The obtained ACFs showed high porous qualities and had a surface area from 673 to 1597 m2/g and a pore volume from 0.33 to 0.79 cm3/g. The CO2 capture capacities of prepared ACFs were measured and the maximum capture capacity for CO2 up to 6.9 mmol/g or 4.6 mmol/g could be achieved at 0 °C or 25 °C and 1 standard atmospheric pressure (1 atm). Furthermore, the electrochemical capacitive properties of as-prepared ACFs in KOH aqueous electrolyte were also studied. It is important to note that the pore volume of the pores below 0.90 nm plays key roles to determine both the CO2 capture ability and the electrochemical capacitance. This study provides guidance for designing porous carbon materials with high CO2 capture capacity or excellent capacitance performance.

Why does CaX zeolite have such a high CO2 capture capacity and how is it affected by water?

CO2 capture is important in solving one of the major current environmental problems, namely global warming. Among the different approaches, adsorption is considered the most promising and CaX zeolite is one of the materials with the highest capacity. However, the knowledge on the mechanism of its interaction with CO2 is still not complete which hinders further optimization. In this work we report the results of a combined study of CO2 adsorption on a CaX zeolite by in-situ FTIR spectroscopy, adsorption measurements and DFT calculations. It was found that at ambient temperature CO2 initially forms linear Ca2+−OCO species which, with increasing equilibrium pressure, are first converted to Ca2+(CO2)2 and then to Ca2+(CO2)3 species. This is the reason for the very high CO2 adsorption capacity of the material. Because of the practical importance, the effect of H2O on the processes was also studied. Water suppress CO2 adsorption but the effect is softened by the formation of mixed ligand Ca2+(CO2)x(H2O)y complexes (x + y = 2 or 3). In agreement with the spectroscopic results it was found that the adsorption capacity of the material increases with the rise of activation temperature up to 673 K due to dehydration. Its value, 22.2 wt% at 273 K and 490 mbar, is among the highest values reported in the literature at similar conditions.

Characteristics of cold-adapted carbonic anhydrase and efficient carbon dioxide capture based on cell surface display technology

Carbonic anhydrase (CA) is currently under investigation because of its potential to capture CO2. A novel N-domain of ice nucleoproteins (INPN)-mediated surface display technique was developed to produce CA with low-temperature capture CO2 based on the mining and characterization of Colwellia sp. CA (CsCA) with cold-adapted enzyme structural features and catalytic properties. CsCA and INPN were effectively integrated into the outer membrane of the cell as fusion proteins. Throughout the display process, the integrity of the membrane of engineered bacteria BL21/INPN-CsCA was maintained. Notably, the study affirmed positive applicability, wherein 94 % activity persisted after 5 d at 15 °C, and 73 % of the activity was regained after 5 cycles of CO2 capture. BL21/INPN-CsCA displayed a high CO2 capture capacity of 52 mg of CaCO3/mg of whole-cell biocatalysts during CO2 mineralization at 25 °C. Therefore, the CsCA functional cell surface display technology could contribute significantly to environmentally friendly CO2 capture.

Crystal Engineering of Hydrogen Bonding for Direct Air Capture of CO2: A Quantum Crystallography Perspective

Rising atmospheric CO2 levels demand efficient and sustainable carbon capture solutions. Direct air capture (DAC) via crystallizing hydrogen-bonded frameworks such as carbonate salts has emerged as a promising approach. This review explores the potential of crystal engineering, in tandem with advanced quantum crystallography techniques and computational modeling, to unlock the full potential of DAC materials. We examine the critical role of hydrogen bonding and other noncovalent interactions within a family of bis-guanidines that governs the formation of carbonate salts with high CO2 capture capacity and low regeneration energies for utilization. Quantum crystallography and charge density analysis prove instrumental in elucidating these interactions. A case study of a highly insoluble carbonate salt of a 2,6-pyridine-bis-(iminoguanidine) exemplifies the effectiveness of these approaches. However, challenges remain in the systematic and precise determination of hydrogen atom positions and atomic displacement parameters within DAC materials using quantum crystallography, and limitations persist in the accuracy of current energy estimation models for hydrogen bonding interactions. Future directions lie in exploring diverse functional groups, designing advanced hydrogen-bonded frameworks, and seamlessly integrating experimental and computational modeling with machine learning. This synergistic approach promises to propel the design and optimization of DAC materials, paving the way for a more sustainable future.

Self-Assembled Core-Shell Structure MgO@TiO2 as a K2CO3 Support with Superior Performance for Direct Air Capture CO2.

Traditional carbon capture and storage technologies for large point sources can at best slow the rate of increase in atmospheric CO2 concentrations. In contrast, direct capture of CO2 from ambient air, or "direct air capture" (DAC), offers the potential to become a truly carbon-negative technology. Composite solid adsorbents fabricated by impregnating a porous matrix with K2CO3 are promising adsorbents for the adsorption capture of CO2 from ambient air. Nevertheless, the adsorbent can be rapidly deactivated during continuous adsorption/desorption cycles. In this study, MgO-supported, TiO2-stabilized MgO@TiO2 core-shell structures were prepared as supports using a novel self-assembled (SA) method and then impregnated with 50 wt % K2CO3 (K2CO3/MgO@TiO2, denoted as SA-KM@T). The adsorbent exhibits a high CO2 capture capacity of ∼126.6 mg CO2/g sorbent in direct air adsorption and maintained a performance of 20 adsorption/desorption cycles at 300 °C mid-temperature, which was much better than that of K2CO3/MgO. Analysis proved that the core-shell structure of the support effectively inhibited the reaction between the active component (K2CO3) and the main support (MgO) by the addition of TiO2, resulting in higher reactivity, thermal stability, and antiagglomeration properties. This work provides an alternative strategy for DAC applications using adsorbents.

Uncoordinated amino groups of MIL-101 anchoring cobalt porphyrins for highly selective CO2 electroreduction

Electrocatalytic carbon dioxide reduction reaction (CO2RR) presents a sustainable route to address energy crisis and environmental issues, where the rational design of catalysts remains crucial. Metal–organic frameworks (MOFs) with high CO2 capture capacities have immense potential as CO2RR electrocatalysts but suffer from poor activity. Herein we report a redox-active cobalt protoporphyrin grafted MIL-101(Cr)–NH2 for CO2 electroreduction. Material characterizations reveal that porphyrin molecules are covalently attached to uncoordinated amino groups of the parent MOF without compromising its well-defined porous structure. Furthermore, in situ spectroscopic techniques suggest inherited CO2 concentrate ability and more abundant adsorbed carbonate species on the modified MOF. As a result, a maximum CO Faradaic efficiency (FECO) up to 97.1% and a turnover frequency of 0.63 s−1 are achieved, together with FECO above 90% within a wide potential window of 300 mV. This work sheds new light on the coupling of MOFs with molecular catalysts to enhance catalytic performances.

Challenges and Opportunities: Metal–Organic Frameworks for Direct Air Capture

AbstractGlobal reliance on fossil fuel combustion for energy production has contributed to the rising concentration of atmospheric CO2, creating significant global climate challenges. In this regard, direct air capture (DAC) of CO2 from the atmosphere has emerged as one of the most promising strategies to counteract the harmful effects on the environment, and the further development and commercialization of this technology will play a pivotal role in achieving the goal of net‐zero emissions by 2050. Among various DAC adsorbents, metal–organic frameworks (MOFs) show great potential due to their high porosity and ability to reversibly adsorb CO2 at low concentrations. However, the adsorption efficiency and cost‐effectiveness of these materials must be improved to be widely deployed as DAC sorbents. To that end, this perspective provides a critical discussion on several types of benchmark MOFs that have demonstrated high CO2 capture capacities, including an assessment of their stability, CO2 capture mechanism, capture‐release cycling behavior, and scale‐up synthesis. It then concludes by highlighting limitations that must be addressed for these MOFs to go from the research laboratory to implementation in DAC devices on a global scale so they can effectively mitigate climate change.

Artificial switches induce the bespoke production of functional compounds in marine microalgae Chlorella by neutralizing CO2

To improve the CO2 tolerance of a marine microalga Chlorella sp. of which the production capacity has been demonstrated industrially, a mutant library was created and a strain hct53 was screened. Compared to the parental strain, hct53 shows a high CO2 capture capacity, while starch biosynthesis is compromised, with increases in health beneficial metabolites and antioxidant capacity. Global gene expression and genome-wide mutation distribution revealed that transcript choreography was concomitant with more active CO2 sequestration, an increase in the lipid synthesis, and a decrease in the starch and protein synthesis. These results suggest that artificial trait improvement via mutagenesis, couple with multiomics analysis, helps discover genetic switches that induce the bespoke conversion of carbon flow from “redundant metabolites” to valuable ones for functional food.

The Effect of Alkali Metals (Li, Na, and K) on Ni/CaO Dual-Functional Materials for Integrated CO2 Capture and Hydrogenation.

Ni/CaO, a low-cost dual-functional material (DFM), has been widely studied for integrated CO2 capture and hydrogenation. The core of this dual-functional material should possess both good CO2 capture-conversion performance and structural stability. Here, we synthesized Ni/CaO DFMs modified with alkali metals (Na, K, and Li) through a combination of precipitation and combustion methods. It was found that Na-modified Ni/CaO (Na-Ni/CaO) DFM offered stable CO2 capture-conversion activity over 20 cycles, with a high CO2 capture capacity of 10.8 mmol/g and a high CO2 conversion rate of 60.5% at the same temperature of 650 °C. The enhanced CO2 capture capacity was attributed to the improved surface basicity of Na-Ni/CaO. In addition, the incorporation of Na into DFMs had a favorable effect on the formation of double salts, which shorten the CO2 capture and release process and promoted DFM stability by hindering their aggregation and the sintering of DFMs.

Hierarchically Porous SIFSIX‐3‐Ni/PAN Composite Beads for Carbon Dioxide Adsorption

AbstractThe increase in CO2 concentration in the atmosphere has led to global warming, which draws great attention all over the world. Adsorption is considered as an effective method for CO2 capture and stabilizing the increasing CO2 concentration. Metal–organic frameworks (MOFs) are promising materials for carbon capture. However, the direct use of MOF powders may lead to issues such as high pressure drop, pipe clogging, and handling difficulties in applications. Herein, a phase inversion strategy is reported to prepare SIFSIX‐3‐Ni@PAN composite beads. The prepared composites exhibit hierarchically porous structure with uniform MOF distribution inside the materials and good mechanical stability. The MOF content can be well controlled and composites with up to 70% loading are prepared. Finally, the obtained materials possess high CO2 capture capacity, even at low CO2 concentrations (1.19 mmol g−1 at 0.01 bar and 298 K).

Synthetic silico-metallic particles-SSMMP-Ni and SSMMP-Ni-IL: CO2 capture and utilization

Synthetic silico-metallic mineral particles (SSMMP) containing different amounts of Ni (SSMMP-Ni) and SSMMP-Ni functionalized with different IL (SSMMP-Ni-IL) were obtained and successfully used as solid adsorbents for CO2 sorption, CO2/N2 separation and highly recyclable heterogeneous catalysts active in the synthesis of different cyclic carbonates using CO2 as a starting reagent. Samples were characterized by infrared spectroscopy (FTIR), RAMAN spectroscopy, X-ray diffraction (XRD), thermal analysis (TGA), specific surface area measurements (BET) and scanning electron microscopy (SEM). Samples containing IL demonstrated high CO2 capture capacity (1.18–1.91 mmol CO2/g adsorbent − 1 bar CO2), CO2 selectivity (7.5–14.7) and stability. As catalysts, SSMMP-Ni 50% achieved a yield of 93.3% in propylene carbonate production (20 bar, 100 °C and 7 h) and constant yield up to 10 cycles. These materials are easy to synthesize, with low energy demand, high stability and versatile to be used as adsorbent in CO2 capture and catalyst for CO2 transformation.

Enhancing hydrophobicity via core–shell metal organic frameworks for high-humidity flue gas CO2 capture

Developing metal–organic framework (MOF) materials with the moisture-resistant feature is highly desirable for CO2 capture from highly humid flue gas. In this work, a new core–shell MOF@MOF composite using Mg-MOF-74 with high CO2 capture capacity as a functional core and hydrophobic zeolitic imidazolate framework-8 (ZIF-8) as a protective shell is fabricated by the epitaxial growth method. Experimental results show that the CO2 adsorption performance of the core–shell structured Mg-MOF-74@ZIF-8 composites from water-containing flue gas is enhanced along with their improved hydrophobicity. The dynamic breakthrough results show that the Mg-MOF-74@ZIF-8 with three assembled layers (Mg-MOF-74@ZIF-8-3) can capture 3.56 mmol·g−1 CO2 from wet CO2/N2 (VCO2: VN2 = 15:85) mixtures, which outperforms Mg-MOF-74 (0.37 mmol·g−1) and most of the reported physisorbents.

Surface functionalization of microporous carbon fibers by vapor phase methods for CO2 capture

The removal of excess CO2 from the atmosphere is expected to play a major role in the mitigation of global warming. Solid-state adsorbents, consisting of CO2-binding functionalities on porous supports, can provide high CO2 capture capacities with low energy requirements. In this contribution, we report on the vapor-phase functionalization of porous carbon fibers with amine functionalities. Functionalization occurs either via direct exposure to cyclic azasilane molecules (2,2-dimethoxy-1,6-diaza-2-silacyclooctane) or by the atomic layer deposition of Al2O3 followed by exposure to azasilane. XPS analysis and SEM/energy-dispersive x-ray spectroscopy (EDX) measurements confirmed Al2O3 deposition and amine functionalization. Yet, the two different functionalization approaches led to different amine loadings and distinct differences in porosity upon functionalization, which affected CO2 capture. Combining Al2O3 and amine functionalization resulted in fast CO2 sorption with superior capturing efficiency. In contrast, direct functionalization resulted in strong reduction of the surface area of the porous support and limited gas exchange. We attribute the superior capture efficiency to the porosity level achieved when combining Al2O3 and amine functionalization demonstrating that this approach might be valuable for compact high-throughput direct air, CO2 capture systems.

Direct air capture (DAC) and sequestration of CO 2 : Dramatic effect of coordinated Cu(II) onto a chelating weak base ion exchanger

Direct air capture (DAC) is important for achieving net-zero greenhouse gas emissions by 2050. However, the ultradilute atmospheric CO2 concentration (~400 parts per million) poses a formidable hurdle for high CO2 capture capacities using sorption-desorption processes. Here, we present a Lewis acid-base interaction-derived hybrid sorbent with polyamine-Cu(II) complex enabling over 5.0 mol of CO2 capture/kg sorbent, nearly two to three times greater capacity than most of the DAC sorbents reported to date. The hybrid sorbent, such as other amine-based sorbents, is amenable to thermal desorption at less than 90°C. In addition, seawater was validated as a viable regenerant, and the desorbed CO2 is simultaneously sequestered as innocuous, chemically stable alkalinity (NaHCO3). The dual-mode regeneration offers unique flexibility and facilitates using oceans as decarbonizing sinks to widen DAC application opportunities.

Construction of multifunctional histidine-based hypercrosslinked hierarchical porous ionic polymers for efficient CO2 capture and conversion

Several novel multifunctional histidine-based hypercrosslinked ionic polymers (HIPs) were constructed via a one-pot copolymerization strategy. The resultant HIPs were characterized by various technologies and investigated for the CO2 adsorption and conversion. Plentiful hydrogen bond donors, nucleophilic ionic sites, and Lewis bases were successfully integrated into the HIPs skeletons. As-prepared histidine-based HIPs possess excellent hierarchical pore structure. The optimal HIP-Br-His exhibits a high CO2 capture capacity of 2.90 mmol/g at 273 K and 1 bar, much higher than that of corresponding hypercrosslinked polymer HCP-Br without histidine units. Meanwhile, the HIP-Br-His achieves an excellent catalytic activity of 95 % product yield with 99 % product selectivity in CO2 cycloaddition to propylene oxide under metal-, cocatalyst- and solvent-free and mild conditions (70 °C and 1.0 MPa). Particularly, HIP-Br-His can efficiently capture and convert dilute CO2 into cyclic carbonates with a satisfactory catalytic performance. The excellent catalytic activity associating with the confirmed good stability, recyclability, and substrate compatibility make the developed histidine-based HIPs a promising heterogeneous catalyst for efficient CO2 capture and conversion.

Identifying the Point of Attachment in the Hypercrosslinking of Benzene for the Synthesis of a Nanoporous Polymer as a Superior Adsorbent for High-Pressure CO2 Capture Application

The point of attachment in the hypercrosslinking of benzene using formaldehyde dimethyl acetal as the crosslinker, anhydrous ferric chloride as the catalyst, and 1,2 dichloroethane as the solvent for the synthesis of poly-benz is reported. A fast microwave-assisted synthesis, within a reaction time of 60 min, resulted in the formation of nanoporous poly-benz having a specific surface area of 1168 m2 g–1. A thorough analysis of poly-benz using 13C cross-polarization magic angle spinning nuclear magnetic resonance and X-ray photoelectron spectra has revealed the hypercrosslinking at the meta position of the benzene ring. The synthesized poly-benz further shows a high CO2 capture capacity of 65.3 wt % at 298 K and 30 bar. Various adsorption isotherm models have been fitted at different temperatures up to 30 bar to represent the equilibrium CO2 adsorption data.