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

Abstract

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...

Oxidation‐Resistant, Cost‐Effective Epoxide‐Modified Polyamine Adsorbents for CO2 Capture from Various Sources Including Air

“…Another possibility is the use of quaternary ammonium‐functionalized anionic exchange resins, which are regenerated through moisture swing . Recently, adsorbents based on modified metal–organic frameworks (MOFs) and porous polymer networks have also been proposed but remain costly . Some of the most studied adsorbents for DAC are solid hybrid adsorbents based on polyamines impregnated or chemically bound on supports including silica, mesoporous solids (SBA‐15, MCM‐41, MCM‐48, etc.…”

Fluorine-functionalized metal–organic frameworks and porous coordination polymers

“…However, Eddaoudi and colleagues 29,30 succeeded in the preparation of a fine-tuned fluorinated MOF by modification of the inorganic fluorinated anions. They used a NbOF 5 2 − dianion instead of SiF 6 2 − to afford the three-dimensional MOF, [Ni(NbOF 5 )(pyz) 2 ].…”

Parametrical Study on CO2 Capture from Ambient Air Using Hydrated K2CO3 Supported on an Activated Carbon Honeycomb

“…23,24 In general, amines have been presented as more attractive adsorbents given their high CO 2 capture capacities; however, some chemical or physical instability issues have been reported. 25−27 …”