Insights into the Oxidative Degradation Mechanism of Solid Amine Sorbents for CO<sub>2</sub> Capture from Air: Roles of Atmospheric Water

Carneiro, Juliana; Innocenti, Giada; Moon, Hyun June; Guta, Yoseph A.; Proaño, Laura; Sievers, Carsten; Sakwa-Novak, Miles A.; Ping, Eric W.; Jones, Christopher W.

doi:10.1002/ange.202302887

Cited by 9 publications

(23 citation statements)

References 102 publications

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“…The 100% RH samples are clear outliers, being much higher in magnitude than all the other T 1 values. We believe that this phenomenon is likely due to the phase separation of large amounts of water in the 100% RH samples, which could give rise to an altogether different T 1 signal, and was recently invoked to explain other observations in humidified PEI composites . That hypothesis is further supported by the DRIFTS measurements in the next section, which illustrate a dramatic increase in the stretching frequency associated with hydroxyl groups near 3650 cm –1 for the 100% RH sample.…”

Section: Resultssupporting

confidence: 58%

“…We believe that this phenomenon is likely due to the phase separation of large amounts of water in the 100% RH samples, which could give rise to an altogether different T 1 signal, and was recently invoked to explain other observations in humidified PEI composites. 24 That hypothesis is further supported by the DRIFTS measurements in the next section, which illustrate a dramatic increase in the stretching frequency associated with hydroxyl groups near 3650 cm −1 for the 100% RH sample. Regardless, the T 1 and T 2 data as a whole serve to corroborate the fluorescence mobility data and the interpretation of structure−property−performance relationships.…”

Section: The Journal Of Physical Chemistry Cmentioning

confidence: 54%

“…Here, we develop these probes further to study branched PEI mobility in model DAC systems as a function of real-world operating conditions, beginning with moisture uptake as a function of RH exposure. PEI composites with γ-Al 2 O 3 are quite hygroscopic; a composite that is 40 wt % PEI can uptake as much 1.7 equivalents in weight of water relative to PEI when allowed to equilibrate in a stream of humid N 2 ( vide infra ). This amount of moisture can significantly alter the mobility of the PEI matrix.…”

Section: Resultsmentioning

confidence: 99%

“…The physical state of the polymer adsorbent not only affects optimal cycle times for CO 2 sorption; it also governs subsequent O 2 diffusion in and out of the material. As residual oxygen in the sorbent chamber during the CO 2 desorption step can lead to fast sorbent degradation, 24 selective O 2 removal prior to CO 2 desorption plays a key role in optimizing amine-based sorbent lifetimes. This optimization requires fundamental understanding of gas diffusion in these materials and hence polymer mobility.…”

Section: ■ Introductionmentioning

confidence: 99%

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Fundamental Insight into Humid CO₂ Uptake in Direct Air Capture Nanocomposites Using Fluorescence and Portable NMR Relaxometry

et al. 2023

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Direct air capture (DAC) technology is being explored as a pathway for reducing greenhouse gas emissions through the efficient removal of CO2 from the atmosphere. However, there remains a knowledge gap regarding structure–property–performance factors that impact the behavior of these systems in diverse, real-world environments. In aminopolymer-based DAC systems, gas diffusion is tightly coupled with polymer mobility, which is in turn affected by a large matrix of variables, including interactions with the pore wall of the support, nanoconfinement, the presence of co-adsorbates (moisture), and electrostatic cross-links that develop as a function of CO2 chemisorption. Higher-throughput, benchtop techniques for studying and understanding mobility in these systems would lead to more rapid advances in the field. Here, we demonstrate the value of a fluorescence technique for monitoring polymer mobility within nanocomposite capture materials as a function of CO2 and water adsorption in a series of humidified polyethylenimine-Al2O3 composite materials. The approach allows us to correlate changes in mobility with CO2 adsorption kinetics as a function of relative humidity. We further couple this information with NMR relaxometry data attained using a portable single-sided magnetic resonance device, and we employ diffuse reflectance infrared Fourier transform spectroscopy to correlate the formation of different relative amounts of carbamates and carbonates with the environmental conditions. These results provide a blueprint for using benchtop techniques to promote fundamental understanding in DAC systems that can in turn enable more efficient operation in real-world conditions.

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Section: Resultssupporting

confidence: 58%

Section: The Journal Of Physical Chemistry Cmentioning

confidence: 54%

Section: Resultsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Fundamental Insight into Humid CO₂ Uptake in Direct Air Capture Nanocomposites Using Fluorescence and Portable NMR Relaxometry

et al. 2023

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“…Sorbents with low stability necessitate continuous replenishment, leading to a significant increase in the capture costs and operation complexity. Generally, amine-supported materials are susceptible to degradation through various mechanisms, including steam-induced degradation of supports and amines, − thermal degradation with or without oxygen presence, − irreversible urea formation, − and irreversible sulfur adsorption . Fortunately, urea formation occurs only in CO 2 -rich streams, and sulfur adsorption requires SO 2 , more typical in flue gas rather than DAC applications .…”

Section: Introductionmentioning

confidence: 99%

Amine Sorbents for Sustainable Direct Air Capture: Long-Term Stability and Extended Aging Study

Al-Absi,

Benneker,

Mahinpey

2024

Energy Fuels

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The emerging technology of direct air capture (DAC) holds promise for the extraction of CO 2 from the air, offering a potential avenue to reverse climate change. However, DAC is still in its early stages of development, particularly on the sorbent material side, and the long-term stability of sorbents remains inadequately understood. This study investigates the impact of thermal degradation, hydrothermal treatment, long-term cyclic operation, and extended aging over 3 years on amine-supported sorbents and its effect on the adsorption capacity at DAC conditions. Sorbents were synthesized through various methods (impregnation, chemical grafting, and in situ polymerization) into two supports: large-pore AlMCM-41 (LPAlSi) and mesoporous silica foam (MSF). LPAlSi support demonstrates superior stability compared to MSF support under thermal and hydrothermal treatments. Impregnated sorbents with physically bonded amines exhibit the lowest stability, with a significant amine loss during all treatments, confirmed through porosity analysis, thermogravimetric analysis (TGA) decomposition, scanning electron microscopy (SEM), and Fourier-transform infrared spectroscopy (FTIR). Additionally, they experience a notable 6% decrease in CO 2 uptake after 50 cycles. In contrast, chemically bonded amines through grafting and in situ polymerization display better stability due to stronger bonding, maintaining CO 2 uptake despite harsh treatments. In situ-polymerized sorbents into LPAlSi exhibit remarkable stability under thermal and hydrothermal treatments, experiencing drops of 17 and 27% over 3 days, respectively. Furthermore, they demonstrate outstanding stability over 50 cycles under DAC conditions, with only a 0.3% drop in CO 2 uptake. Extended aging of class III sorbent for 3 years indicates good stability in CO 2 uptake, with only an 11% drop compared to impregnated ones, which showed a larger decrease over a shorter time. The presented results suggest that in situ-polymerized amines into LPAlSi are promising materials for DAC, offering good capacity and significant long-term stability. With opportunities for further sorbent optimization, there is substantial potential to deploy DAC at a scalable level and mitigate global warming effects.

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Amine‐Functionalized Amyloid Aerogels for CO₂ Capture

Dong,

Peydayesh,

Donat

et al. 2023

ChemSusChem

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Climate change caused by excessive CO2 emissions constitutes an increasingly dire threat to human life. Reducing CO2 emissions alone may not be sufficient to address this issue, so that the development of emerging adsorbents for the direct capture of CO2 from the air becomes essential. Here, we apply amyloid fibrils derived from different food proteins as the solid adsorbent support and develop aminosilane‐modified amyloid fibril‐templated aerogels for CO2 capture applications. The results indicate that the CO2 sorption properties of the aerogels depend on the mixing ratio of aminosilane featuring different amine groups and the type of amyloid fibril used. Notably, amine‐functionalized β‐lactoglobulin (BLG) fibril‐templated aerogels show the highest CO2 adsorption capacity of 51.52 mg (1.17 mmol) CO2/g at 1 bar CO2 and 25.5 mg (0.58 mmol) CO2/g at 400 ppm; similarly, the CO2 adsorption capacity of chitosan‐BLG fibril hybrid aerogels is superior to that of pure chitosan. This study provides a proof‐of‐concept design for an amyloid fibril‐templated hybrid material facilitating applications of protein‐based adsorbents for CO2 capture, including direct air capture.

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Insights into the Oxidative Degradation Mechanism of Solid Amine Sorbents for CO₂ Capture from Air: Roles of Atmospheric Water

Cited by 9 publications

References 102 publications

Fundamental Insight into Humid CO₂ Uptake in Direct Air Capture Nanocomposites Using Fluorescence and Portable NMR Relaxometry

Fundamental Insight into Humid CO₂ Uptake in Direct Air Capture Nanocomposites Using Fluorescence and Portable NMR Relaxometry

Amine Sorbents for Sustainable Direct Air Capture: Long-Term Stability and Extended Aging Study

Amine‐Functionalized Amyloid Aerogels for CO₂ Capture

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Insights into the Oxidative Degradation Mechanism of Solid Amine Sorbents for CO2 Capture from Air: Roles of Atmospheric Water

Cited by 9 publications

References 102 publications

Fundamental Insight into Humid CO2 Uptake in Direct Air Capture Nanocomposites Using Fluorescence and Portable NMR Relaxometry

Fundamental Insight into Humid CO2 Uptake in Direct Air Capture Nanocomposites Using Fluorescence and Portable NMR Relaxometry

Amine Sorbents for Sustainable Direct Air Capture: Long-Term Stability and Extended Aging Study

Amine‐Functionalized Amyloid Aerogels for CO2 Capture

Contact Info

Product

Resources

About

Insights into the Oxidative Degradation Mechanism of Solid Amine Sorbents for CO₂ Capture from Air: Roles of Atmospheric Water

Fundamental Insight into Humid CO₂ Uptake in Direct Air Capture Nanocomposites Using Fluorescence and Portable NMR Relaxometry

Fundamental Insight into Humid CO₂ Uptake in Direct Air Capture Nanocomposites Using Fluorescence and Portable NMR Relaxometry

Amine‐Functionalized Amyloid Aerogels for CO₂ Capture