Computational screening of porous carbons, zeolites, and metal organic frameworks for desulfurization and decarburization of biogas, natural gas, and flue gas

Carbon capture from flue gas and natural gas offers a green path to construct a net-zero emissions economic system. Selective adsorption-based gas separation by employing metal-organic frameworks (MOFs) is regarded as a promising technology due to the advantages of simple processing, easy regeneration and high efficiency. We synthesized two Zirconium MOFs (UiO-66 and UiO-66-NH2) nanocrystals for selective capture and further removal of CO2 from flue gas and natural gas. In particular, UiO-66-NH2 nanocrystals have a smaller grain size, a large amount of defects, and pending –NH2 groups inside their pores which display effective CO2 selective adsorption abilities over CH4 and N2 with the theoretical separation factors of 20 and 7. This breakthrough experiment further verified the selective adsorption-based separation process of natural gas and flue gas. In one further step, we used the Monte Carlo simulation to investigate the optimized adsorption sites and energy of CO2, N2 and CH4 molecules in the gas mixture. The significantly large adsorption energy of CO2 (0.32 eV) over N2 (0.19 eV) and N2 (0.2 eV) may help us to reveal the selective adsorption mechanism.

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Metal–Organic Frameworks for Helium Recovery from Natural Gas via N2/He Separation: A Computational Screening

The Journal of Physical Chemistry C ◽

10.1021/acs.jpcc.8b07804 ◽

2019 ◽

Vol 123 (6) ◽

pp. 3469-3475 ◽

Cited By ~ 4

Author(s):

Pezhman Zarabadi-Poor ◽

Radek Marek

Keyword(s):

Natural Gas ◽

Metal Organic Frameworks ◽

Computational Screening ◽

Metal Organic

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Cooperative carbon capture and steam regeneration with tetraamine-appended metal–organic frameworks

Science ◽

10.1126/science.abb3976 ◽

2020 ◽

Vol 369 (6502) ◽

pp. 392-396

Author(s):

Eugene J. Kim ◽

Rebecca L. Siegelman ◽

Henry Z. H. Jiang ◽

Alexander C. Forse ◽

Jung-Hoon Lee ◽

...

Keyword(s):

Natural Gas ◽

Flue Gas ◽

Carbon Capture ◽

Power Plants ◽

Metal Organic Frameworks ◽

The United States ◽

Carbon Intensity ◽

Extreme Conditions ◽

Metal Organic ◽

Adsorption Desorption

Natural gas has become the dominant source of electricity in the United States, and technologies capable of efficiently removing carbon dioxide (CO2) from the flue emissions of natural gas–fired power plants could reduce their carbon intensity. However, given the low partial pressure of CO2 in the flue stream, separation of CO2 is particularly challenging. Taking inspiration from the crystal structures of diamine-appended metal–organic frameworks exhibiting two-step cooperative CO2 adsorption, we report a family of robust tetraamine-functionalized frameworks that retain cooperativity, leading to the potential for exceptional efficiency in capturing CO2 under the extreme conditions relevant to natural gas flue emissions. The ordered, multimetal coordination of the tetraamines imparts the materials with extraordinary stability to adsorption-desorption cycling with simulated humid flue gas and enables regeneration using low-temperature steam in lieu of costly pressure or temperature swings.

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Computational screening of hydrophobic metal–organic frameworks for the separation of H2S and CO2 from natural gas

Journal of Materials Chemistry A ◽

10.1039/c8ta04939d ◽

2018 ◽

Vol 6 (39) ◽

pp. 18898-18905 ◽

Cited By ~ 27

Author(s):

Zhiwei Qiao ◽

Qisong Xu ◽

Jianwen Jiang

Keyword(s):

Natural Gas ◽

Computational Study ◽

Metal Organic Frameworks ◽

Computational Screening ◽

Metal Organic

A computational study is reported to screen metal–organic frameworks for H2S and CO2 separation from natural gas under humid conditions.

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Computational Screening of Metal–Organic Frameworks for Membrane-Based CO2/N2/H2O Separations: Best Materials for Flue Gas Separation

The Journal of Physical Chemistry C ◽

10.1021/acs.jpcc.8b05416 ◽

2018 ◽

Vol 122 (30) ◽

pp. 17347-17357 ◽

Cited By ~ 34

Author(s):

Hilal Daglar ◽

Seda Keskin

Keyword(s):

Gas Separation ◽

Flue Gas ◽

Metal Organic Frameworks ◽

Computational Screening ◽

Metal Organic

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Tuning the Redox Activity of Metal−Organic Frameworks for Enhanced, Selective O2 Binding

10.26434/chemrxiv.10316681.v1 ◽

2019 ◽

Author(s):

Andrew Rosen ◽

M. Rasel Mian ◽

Timur Islamoglu ◽

Haoyuan Chen ◽

Omar Farha ◽

...

Keyword(s):

Density Functional ◽

Metal Organic Frameworks ◽

Redox Activity ◽

Screening Methods ◽

Bridging Ligands ◽

Metal Centers ◽

Computational Screening ◽

Open Metal Sites ◽

Metal Organic ◽

Unsaturated Metal Sites

Metal−organic frameworks (MOFs) with coordinatively unsaturated metal sites are appealing as adsorbent materials due to their tunable functionality and ability to selectively bind small molecules. Through the use of computational screening methods based on periodic density functional theory, we investigate O2 and N2 adsorption at the coordinatively unsaturated metal sites of several MOF families. A variety of design handles are identified that can be used to modify the redox activity of the metal centers, including changing the functionalization of the linkers (replacing oxido donors with sulfido donors), anion exchange of bridging ligands (considering μ-Br-, μ-Cl-, μ-F-, μ-SH-, or μ-OH- groups), and altering the formal oxidation state of the metal. As a result, we show that it is possible to tune the O2 affinity at the open metal sites of MOFs for applications involving the strong and/or selective binding of O2. In contrast with O2 adsorption, N2 adsorption at open metal sites is predicted to be relatively weak across the MOF dataset, with the exception of MOFs containing synthetically elusive V2+ open metal sites. As one example from the screening study, we predict that exchanging the μ-Cl- ligands of M2Cl2(BBTA) (H2BBTA = 1H,5H-benzo(1,2-d:4,5-d′)bistriazole) with μ-OH- groups would significantly enhance the strength of O2 adsorption at the open metal sites without a corresponding increase in the N2 affinity. Experimental investigation of Co2Cl2(BBTA) and Co2(OH)2(BBTA) confirms that the former exhibits only weak physisorption, whereas the latter is capable of chemisorbing O2 at room temperature. The chemisorption behavior is attributed to the greater electron-donating character of the μ-OH- ligands and the presence of H-bonding interactions between the μ-OH- bridging ligands and the O2 adsorbate.

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High-Throughput Computational Screening of Metal–Organic Frameworks for the Separation of Methane from Ethane and Propane

The Journal of Physical Chemistry C ◽

10.1021/acs.jpcc.0c09117 ◽

2021 ◽

Vol 125 (3) ◽

pp. 1839-1854

Author(s):

Yadava Krishnan Ponraj ◽

Bhaskarjyoti Borah

Keyword(s):

High Throughput ◽

Metal Organic Frameworks ◽

Computational Screening ◽

Metal Organic

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C2s/C1 hydrocarbon separation: The major step towards natural gas purification by metal-organic frameworks (MOFs)

Coordination Chemistry Reviews ◽

10.1016/j.ccr.2021.213998 ◽

2021 ◽

Vol 442 ◽

pp. 213998

Author(s):

Rupam Sahoo ◽

Madhab C. Das

Keyword(s):

Natural Gas ◽

Metal Organic Frameworks ◽

Gas Purification ◽

Major Step ◽

Natural Gas Purification ◽

Metal Organic

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Porphyrin MOF-Derived Porous Carbons: Preparation and Applications

C – Journal of Carbon Research ◽

10.3390/c7020047 ◽

2021 ◽

Vol 7 (2) ◽

pp. 47

Author(s):

Flávio Figueira ◽

Filipe A. Almeida Paz

Keyword(s):

Chemical Composition ◽

Carbon Material ◽

Metal Organic Frameworks ◽

Electrochemical Reactions ◽

Porous Carbon Material ◽

Important Class ◽

Porous Carbons ◽

Preparation Methods ◽

Crystalline Materials ◽

Metal Organic

Metal–organic frameworks (MOFs) are crystalline materials with permanent porosity, composed of metal nodes and organic linkers whose well-ordered arrangement enables them to act as ideal templates to produce materials with a uniform distribution of heteroatom and metal elements. The hybrid nature of MOFs, well-defined pore structure, large surface area and tunable chemical composition of their precursors, led to the preparation of various MOF-derived porous carbons with controlled structures and compositions bearing some of the unique structural properties of the parent networks. In this regard, an important class of MOFs constructed with porphyrin ligands were described, playing significant roles in the metal distribution within the porous carbon material. The most striking early achievements using porphyrin-based MOF porous carbons are here summarized, including preparation methods and their transformation into materials for electrochemical reactions.

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