Cooperative insertion of CO2 in diamine-appended metal-organic frameworks

McDonald, Thomas M.; Mason, Jarad A.; Kong, Xueqian; Bloch, Eric D.; Gygi, David; Dani, Alessandro; Crocellà, Valentina; Giordanino, Filippo; Odoh, Samuel O.; Drisdell, Walter S.; Vlaisavljevich, Bess; Dzubak, Allison L.; Poloni, Roberta; Schnell, Sondre K.; Planas, Nora; Lee, Kyuho; Pascal, Tod A.; Wan, Liwen F.; Prendergast, David; Neaton, Jeffrey B.; Smit, Berend; Kortright, Jeffrey B.; Gagliardi, Laura; Bordiga, Silvia; Reimer, Jeffrey A.; Long, Jeffrey R.

doi:10.1038/nature14327

Cited by 1,068 publications

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“…Mg 2 (dobpdc) was prepared as previously reported. 36 In a dry, argon-filled glovebox, 50 mg (0.16 mmol) of Mg 2 (dobpdc) was suspended in ∼6 mL of acetonitrile and stirred vigorously in a 20 mL glass scintillation vial. In another vial, 27 mg (0.16 mmol) of NOPF 6 (Aldrich) was dissolved in ∼4 mL of acetonitrile.…”

Section: Pfmentioning

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A Dual−Ion Battery Cathode via Oxidative Insertion of Anions in a Metal–Organic Framework

2015

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A redox−active metal−organic framework, Fe 2 (dobpdc) (dobpdc 4− = 4,4′-dioxidobiphenyl-3,3′-dicarboxylate), is shown to undergo a topotactic oxidative insertion reaction with a variety of weakly coordinating anions, including BF 4 − and PF 6 − . The reaction results in just a minor lattice contraction, and a broad intervalence charge-transfer band emerges, indicative of charge mobility. Although both metaland ligand-based oxidations can be accessed, only the former were found to be fully reversible and, importantly, proceed stoichiometrically under both chemical and electrochemical conditions. Electrochemical measurements probing the effects of nanoconfinement on the insertion reaction revealed strong anion size and solvent dependences. Significantly, the anion insertion behavior of Fe 2 (dobpdc) enabled its use in the construction of a dual-ion battery prototype incorporating a sodium anode. As a cathode, the material displays a particularly high initial reduction potential and is further stable for at least 50 charge/discharge cycles, exhibiting a maximum specific energy of 316 Wh/ kg.

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Section: Pfmentioning

confidence: 99%

A Dual−Ion Battery Cathode via Oxidative Insertion of Anions in a Metal–Organic Framework

2015

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“…Metal organic frameworks (MOFs), a tunable class of porous solid-state materials, are regarded to offer prospective solutions to various challenges pertaining to gas storage and gas separation. [20][21][22][23][24][25][26][27][28][29] Evidently, the modular and hybrid character of MOFs permit the fine-tuning of their affinity for CO 2 , via the introduction of appropriate pre-functionalized ligands and/or the grafting of judiciously selected amine moieties on the open metal sites, and subsequently explore their potential for the CCS. 22,[25][26][27][28] Nevertheless, only a limited number of functionalized MOFs, affording the CO 2 -chemisorption, showed promise for DAC and low-concentration CO 2 capture from confined spaces (<0.5 %).…”

Section: Introductionmentioning

confidence: 99%

“…[20][21][22][23][24][25][26][27][28][29] Evidently, the modular and hybrid character of MOFs permit the fine-tuning of their affinity for CO 2 , via the introduction of appropriate pre-functionalized ligands and/or the grafting of judiciously selected amine moieties on the open metal sites, and subsequently explore their potential for the CCS. 22,[25][26][27][28] Nevertheless, only a limited number of functionalized MOFs, affording the CO 2 -chemisorption, showed promise for DAC and low-concentration CO 2 capture from confined spaces (<0.5 %). 22,26 Outwardly, it was intuited that chemisorption based sorbents are the foremost option for traces CO 2 capture, 8 and atypically put forward that physical adsorbents are prone to be ineffective for carbon capture at the low CO 2 concentration of 400 ppm due to their plausibly weak interactions with the adsorbed CO 2 molecules.…”

Section: Introductionmentioning

confidence: 99%

A Fine-Tuned Fluorinated MOF Addresses the Needs for Trace CO₂ Removal and Air Capture Using Physisorption

et al. 2016

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CitationA fine-tuned fluorinated MOF addresses the needs for trace CO2 removal and air capture using physisorption. Just Accepted "Just Accepted" manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides "Just Accepted" as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. "Just Accepted" manuscripts appear in full in PDF format accompanied by an HTML abstract. "Just Accepted" manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). "Just Accepted" is an optional service offered to authors. Therefore, the "Just Accepted" Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the "Just Accepted" Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these "Just Accepted" manuscripts.A fine-tuned fluorinated MOF addresses the needs for trace CO 2 removal and air capture using physisorption. ABSTRACT:The development of functional solid-state materials for carbon capture at low carbon dioxide (CO 2 ) concentrations, namely from confined spaces (<0.5 %) and in particular from air (400 ppm), is of prime importance with respect to energy and environment sustainability. Herein, we report the deliberate construction of a hydrolytically stable fluorinated metal-organic framework (MOF), NbOFFIVE-1-Ni, with the appropriate pore system (size, shape and functionality), ideal for the effective and energyefficient traces carbon dioxide removal. Markedly, the CO 2 -selective NbOFFIVE-1-Ni exhibits the highest CO 2 gravimetric and volumetric uptake (ca. 1.3 mmol/g and 51.4 cm 3 (STP).cm -3 ) for a physical adsorbent at 400 ppm CO 2 and 298 K. Practically, the NbOFFIVE-1-Ni offers the complete CO 2 desorption at 328 K under vacuum with an associated moderate energy input of 54 kJ/mol, typical for the full CO 2 desorption in conventional physical adsorbents but considerably lower than chemical sorbents. Noticeably, the contracted square-like channels, affording the close proximity of the fluorine centers, permitted the enhancement of the CO 2 -framework interactions and subsequently the attainment of an unprecedented CO 2 -selectivity at very low CO 2 concentrations. The precise localization of the adsorbed CO 2 at the vicinity of the periodically aligned fluorine centers, promoting the selective adsorption of CO 2 , is evidenced by the single-crystal X-ray diffraction study on t...

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“…23 ). Moreover, accurate computational models can provide detailed information about gasframework interactions resolved to the atomic level, providing an unprecedented level of molecular information supporting the design of next generation materials 24,25 .The idea of augmenting discovery programs with computation is not new. For example, computational screening is frequently used in the pharmaceutical industry as an initial step to identify molecules as potential drug candidates 26 .…”

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Computational development of the nanoporous materials genome

2017

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H1 Abstract.There is currently a large push towards big data and data mining in materials research to accelerate discovery. Zeolites, metal-organic frameworks (MOFs) and other related crystalline porous materials are not immune to this recent phenomenon, as evidenced by the proliferation of porous structure databases and computational gas adsorption screening studies over the past decade. The strive to identify the best materials for a variety of gas separation and storage applications has not only led to collections of thousands of synthesised structures, but the development of hypothetical material building algorithms.The materials databases assembled with these algorithms expand greatly on the range of complex pore structures that have been synthesised, with the rationale that we have discovered only a small fraction of realisable structures and expanding upon these will accelerate rational design. In this review, we highlight some of the methods developed to build these databases, and some of the important outcomes resulting from large-scale computational screening efforts. SummaryIn the field of nanoporous materials discovery, we are witnessing the emergence of big data analytics combined with traditional computational thermodynamics calculations. This review turns a critical eye on the current state of the art, with a focus on computational database generation and results from large-scale screening for gas separations. H1 Introduction.The discovery, in the late 19 th century, that zeolites could trap interesting and valuable particles in their pores opened up an entire field of research 1,2 . This seemingly simple phenomenon was an enormous boon to the oil and gas industry, seeing as how cheap, but effective porous materials could serve as a catalyst for hydrocarbon cracking. From their humble beginnings (being carved out of rock faces), zeolites, and their ability to selectively trap guests in their pores, have become integral in not only the oil and gas industry, but in detergents (as ion exchangers) and natural gas purification to name a few 1 .Zeolites have since enjoyed an almost exclusive dominance in porous materials research until the late 20 th century, when we began to observe the creation of more diverse materials in terms of chemistry, network connectivity, and physical properties.At present, there are a little over 200 known zeolite structures, which is only a small fraction of the total number of structures that have been predicted 3 . In addition, if we were also able to expand the chemical diversity of these materials beyond the conventional Si 4+ , O 2-, and Al 3+ ions found in zeolites, one could envision designing materials for virtually any gas separation application. Thus when the first articles arose in the 1990's characterising Metal-Organic Frameworks (MOFs) [4][5][6][7][8] , and later Covalent Organic Frameworks (COFs) 9,10 , Zeolitic Imidazolate Frameworks (ZIFs) 11 , and Porous Polymer Networks (PPNs) 12 the excitement was palpable. It was recognised early-on by Yaghi, O'Keeffe, ...

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Cooperative insertion of CO2 in diamine-appended metal-organic frameworks

Cited by 1,068 publications

References 56 publications

A Dual−Ion Battery Cathode via Oxidative Insertion of Anions in a Metal–Organic Framework

A Dual−Ion Battery Cathode via Oxidative Insertion of Anions in a Metal–Organic Framework

A Fine-Tuned Fluorinated MOF Addresses the Needs for Trace CO₂ Removal and Air Capture Using Physisorption

Computational development of the nanoporous materials genome

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Cooperative insertion of CO2 in diamine-appended metal-organic frameworks

Cited by 1,068 publications

References 56 publications

A Dual−Ion Battery Cathode via Oxidative Insertion of Anions in a Metal–Organic Framework

A Dual−Ion Battery Cathode via Oxidative Insertion of Anions in a Metal–Organic Framework

A Fine-Tuned Fluorinated MOF Addresses the Needs for Trace CO2 Removal and Air Capture Using Physisorption

Computational development of the nanoporous materials genome

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A Fine-Tuned Fluorinated MOF Addresses the Needs for Trace CO₂ Removal and Air Capture Using Physisorption