Can COFs replace MOFs in flue gas separation? high-throughput computational screening of COFs for CO<sub>2</sub>/N<sub>2</sub> separation

Altundal, Omer Faruk; Altıntaş, Çiğdem; Keskın, Seda

doi:10.1039/d0ta04574h

Cited by 81 publications

(67 citation statements)

References 86 publications

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“… 56 Potential parameters of COF atoms were taken from the DRIEDING force field 57 since a good agreement between simulated and experimentally reported CO 2 isotherms of COFs was found in our previous works. 40 , 41 A good agreement between simulations and experimentally measured CH 4 adsorption isotherms of COFs 58 is also seen in Figure S1 of the Supporting Information ( SI ). Using the results obtained from GCMC simulations, we calculated various adsorbent performance evaluation metrics including adsorption selectivity ( S ads ), working capacity (Δ N ), adsorbent performance score (APS), and percent regenerability ( R %), as listed in Table 1 .…”

Section: Computational Detailssupporting

confidence: 74%

“…S ads,CH 4 /N 2 values do not significantly change when the electrostatic interactions were neglected, which can be attributed to the absence of strong metal atoms in COFs. 38 , 40 Therefore, we concluded that LJ interactions are the main contributors to the adsorption of N 2 molecules in COFs.…”

Section: Results and Discussionmentioning

confidence: 76%

“…Our group recently screened 295 COFs for CO 2 /N 2 separation at VSA, PSA, and TSA conditions and reported that COFs with pore sizes < 10 Å, 0.6 < porosity < 0.8, and surface area < 4500 m 2 /g are the most promising candidates for flue gas separation. 40 A total of 288 COFs were studied using HTCS methods for CO 2 /H 2 separation at five different operating conditions, and COFs with narrow pores and low porosities were identified as the best-performing candidates for CO 2 separation from H 2 . 41 …”

Section: Introductionmentioning

confidence: 99%

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Combined GCMC, MD, and DFT Approach for Unlocking the Performances of COFs for Methane Purification

Altundal

Haşlak

Keskın

2021

Ind. Eng. Chem. Res.

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Covalent organic frameworks (COFs) are promising materials for gas storage and separation; however, the potential of COFs for separation of CH 4 from industrially relevant gases such as H 2 , N 2 , and C 2 H 6 is yet to be investigated. In this work, we followed a multiscale computational approach to unlock both the adsorption- and membrane-based CH 4 /H 2 , CH 4 /N 2 , and C 2 H 6 /CH 4 separation potentials of 572 COFs by combining grand canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulations and density functional theory (DFT) calculations. Adsorbent performance evaluation metrics of COFs, adsorption selectivity, working capacity, regenerability, and adsorbent performance score were calculated for separation of equimolar CH 4 /H 2 , CH 4 /N 2 , and C 2 H 6 /CH 4 mixtures at vacuum swing adsorption (VSA) and pressure swing adsorption (PSA) conditions to identify the best-performing COFs for each mixture. Results showed that COFs could achieve selectivities of 2–85, 1–7, and 2–23 for PSA-based CH 4 /H 2 , CH 4 /N 2 , and C 2 H 6 /CH 4 separations, respectively, outperforming conventional adsorbents such as zeolites and activated carbons for each mixture. Structure–performance relations revealed that COFs with pore sizes <10 Å are promising adsorbents for all mixtures. We identified the gas adsorption sites in the three top-performing COFs commonly identified for each mixture by DFT calculations and computed the binding strength of gases, which were found to be on the order of C 2 H 6 > CH 4 > N 2 > H 2 , supporting the GCMC results. Nucleus-independent chemical shift (NICS) indexes of aromaticity for adsorption sites were calculated, and the results revealed that the degree of linker aromaticity could be a measure for the selection or design of highly alkane-selective COF adsorbents over N 2 and H 2 . Finally, COF membranes were shown to achieve high H 2 permeabilities, 4.57 × 10 3 – 1.25 × 10 6 Barrer, and decent membrane selectivities, as high as 4.3, outperforming polymeric and MOF-based membranes for separation of H 2 from CH 4 .

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Section: Computational Detailssupporting

confidence: 74%

Section: Results and Discussionmentioning

confidence: 76%

Section: Introductionmentioning

confidence: 99%

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Combined GCMC, MD, and DFT Approach for Unlocking the Performances of COFs for Methane Purification

Altundal

Haşlak

Keskın

2021

Ind. Eng. Chem. Res.

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“…A total of 295 CoRE COFs were recently screened for CO 2 /N 2 separation, and it was concluded that many COF adsorbents can compete with MOFs in CO 2 capture from flue gas. 51 A total of 296 CURATED COFs were also screened with a workflow algorithm to evaluate their postcombustion CO 2 capture performances, and the COF with the lowest parasitic energy was identified for the PTSA process. 48 Hypothetical (computer-generated but not yet synthesized) COFs were studied for CH 4 storage.…”

Section: Introductionmentioning

confidence: 99%

Computational Selection of High-Performing Covalent Organic Frameworks for Adsorption and Membrane-Based CO₂/H₂ Separation

et al. 2020

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Covalent organic frameworks (COFs) have high potential in gas separation technologies because of their porous structures, large surface areas, and good stabilities. The number of synthesized COFs already reached several hundreds, but only a handful of materials were tested as adsorbents and/or membranes. We used a high-throughput computational screening approach to uncover adsorption-based and membrane-based CO 2 /H 2 separation potentials of 288 COFs, representing the highest number of experimentally synthesized COFs studied to date for precombustion CO 2 capture. Grand canonical Monte Carlo (GCMC) simulations were performed to assess CO 2 /H 2 mixture separation performances of COFs for five different cyclic adsorption processes: pressure swing adsorption, vacuum swing adsorption, temperature swing adsorption (TSA), pressure−temperature swing adsorption (PTSA), and vacuum−temperature swing adsorption (VTSA). The results showed that many COFs outperform traditional zeolites in terms of CO 2 selectivities and working capacities and PTSA is the best process leading to the highest adsorbent performance scores. Combining GCMC and molecular dynamics (MD) simulations, CO 2 and H 2 permeabilities and selectivities of COF membranes were calculated. The majority of COF membranes surpass Robeson’s upper bound because of their higher H 2 permeabilities compared to polymers, indicating that the usage of COFs has enormous potential to replace current materials in membrane-based H 2 /CO 2 separation processes. Performance analysis based on the structural properties showed that COFs with narrow pores [the largest cavity diameter (LCD) < 15 Å] and low porosities (ϕ < 0.75) are the top adsorbents for selective separation of CO 2 from H 2 , whereas materials with large pores (LCD > 20 Å) and high porosities (ϕ > 0.85) are generally the best COF membranes for selective separation of H 2 from CO 2 . These results will help to speed up the engineering of new COFs with desired structural properties to achieve high-performance CO 2 /H 2 separations.

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“…50 A recent independent study compared the gas-separation performances as computed from the structures of this database and the original COF structures, highlighting the importance of the curation process. 51 …”

Section: Databases Of Nanoporous Materialsmentioning

confidence: 99%

Too Many Materials and Too Many Applications: An Experimental Problem Waiting for a Computational Solution

2020

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Finding the best material for a specific application is the ultimate goal of materials discovery. However, there is also the reverse problem: when experimental groups discover a new material, they would like to know all the possible applications this material would be promising for. Computational modeling can aim to fulfill this expectation, thanks to the sustained growth of computing power and the collective engagement of the scientific community in developing more efficient and accurate workflows for predicting materials’ performances. We discuss the impact that reproducibility and automation of the modeling protocols have on the field of gas adsorption in nanoporous crystals. We envision a platform that combines these tools and enables effective matching between promising materials and industrial applications.

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Can COFs replace MOFs in flue gas separation? high-throughput computational screening of COFs for CO₂/N₂ separation

Abstract: Adsorption and membrane-based gas separation performances of 295 COFs are evaluated for CO2/N2 separation using high-throughput computational screening.

Cited by 81 publications

References 86 publications

Combined GCMC, MD, and DFT Approach for Unlocking the Performances of COFs for Methane Purification

Combined GCMC, MD, and DFT Approach for Unlocking the Performances of COFs for Methane Purification

Computational Selection of High-Performing Covalent Organic Frameworks for Adsorption and Membrane-Based CO₂/H₂ Separation

Too Many Materials and Too Many Applications: An Experimental Problem Waiting for a Computational Solution

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Can COFs replace MOFs in flue gas separation? high-throughput computational screening of COFs for CO2/N2 separation

Abstract: Adsorption and membrane-based gas separation performances of 295 COFs are evaluated for CO2/N2 separation using high-throughput computational screening.

Cited by 81 publications

References 86 publications

Combined GCMC, MD, and DFT Approach for Unlocking the Performances of COFs for Methane Purification

Combined GCMC, MD, and DFT Approach for Unlocking the Performances of COFs for Methane Purification

Computational Selection of High-Performing Covalent Organic Frameworks for Adsorption and Membrane-Based CO2/H2 Separation

Too Many Materials and Too Many Applications: An Experimental Problem Waiting for a Computational Solution

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Product

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Can COFs replace MOFs in flue gas separation? high-throughput computational screening of COFs for CO₂/N₂ separation

Computational Selection of High-Performing Covalent Organic Frameworks for Adsorption and Membrane-Based CO₂/H₂ Separation