Capture of nitrogen dioxide and conversion to nitric acid in a porous metal–organic framework

Li, Jiangnan; Han, Xue; Zhang, Xinran; Sheveleva, Alena M.; Cheng, Yongqiang; Tuna, Floriana; McInnes, Eric J. L.; McPherson, Laura J. McCormick; Teat, Simon J.; Daemen, Luke L.; Ramirez‐Cuesta, Anibal J.; Schröder, Martin; Yang, Sihai

doi:10.1038/s41557-019-0356-0

Cited by 137 publications

(110 citation statements)

References 30 publications

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“…[10,11] By tuning the composition of the MOF's metal nodes and organic linkers, selective chemical adsorption and/or catalysis can be achieved. [12] Indeed, several groups have demonstrated the selective capture of NO x using different MOFs, including [Zr 6 O 4 (OH) 4 (FA) 6 ] 2 (calixarene) 3, [13] MFM-300(Al), [14] MFM-520, [15] MOF-74, [16][17][18] RE-DOBDC, [19] UiO-66, and UiO-67. [20,21] MOFs have previously been used for direct electrical sensing of gases.…”

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confidence: 99%

Near‐Zero Power MOF‐Based Sensors for NO₂ Detection

Small

Henkelis

Rademacher

et al. 2020

Adv Funct Materials

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Detection and capture of toxic nitrogen oxides (NO x) is important for emissions control of exhaust gases and general public health. The ability to directly electrically detect trace (0.5-5 ppm) NO 2 by a metal-organic framework (MOF)-74-based sensor at relatively low temperatures (50 °C) is demonstrated via changes in electrical properties of M-MOF-74, M = Co, Mg, Ni. The magnitude of the change is ordered Ni > Co > Mg and explained by each variant's NO 2 adsorption capacity and specific chemical interaction. Ni-MOF-74 provides the highest sensitivity to NO 2 ; a 725× decrease in resistance at 5 ppm NO 2 and detection limit <0.5 ppm, levels relevant for industry and public health. Furthermore, the Ni-MOF-74-based sensor is selective to NO 2 over N 2 , SO 2 , and air. Linking this fundamental research with future technologies, the high impedance of MOF-74 enables applications requiring a near-zero power sensor or dosimeter, with the active material drawing <15 pW for a macroscale device 35 mm 2 with 0.8 mg MOF-74. This represents a 10 4-10 6 × decrease in power consumption compared to other MOF sensors and demonstrates the potential for MOFs as active components for long-lived, near-zero power chemical sensors in smart industrial systems and the internet of things.

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confidence: 99%

Near‐Zero Power MOF‐Based Sensors for NO₂ Detection

Small

Henkelis

Rademacher

et al. 2020

Adv Funct Materials

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“…The peaks representing N 2 O 4 at 1716, 1380, and 1278 cm À1 (n(NO)) [17] suggest NO 2 partially transform into N 2 O 4 upon adsorption, which was also observed in other MOF, that is, MFM-300(Al) and MFM-520. [1,18] Those (Figure 4 a), clearly suggesting pbackbonding between Ni and NO 2 , in contrast to the blueshift observed in the MOFs via a Lewis acidic mechanism. [13,19] The depletion of bands representing the hydroxy (OH) group at 3708 and 3710 cm À1 (Supporting Information, Figure S6), respectively, was ascribed to the formation of hydrogen bonding between the Al-OH metal node and NO 2 .…”

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confidence: 83%

“…Nitrogen dioxide (NO 2 ) pollution causes serious environmental problems and poses substantial health threats to human beings. [1] Various NO 2 emission sources, such as exhaust from vehicles, flue gas from burning of fossil fuels, contribute to the accumulation of NO 2 in the atmosphere. [2] Although the selective catalytic reduction (SCR) applicable for NO 2 conversion at high temperatures (523-873 K) has been widely used in industry, [3] the control and abatement of ambient NO 2 emission is still an elusive challenge.…”

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confidence: 99%

Transition‐Metal‐Containing Porphyrin Metal–Organic Frameworks as π‐Backbonding Adsorbents for NO₂ Removal

et al. 2020

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Mitigating ambient nitrogen dioxide (NO 2) pollution via selective adsorption on porous materials is a promising approach to tackle such an increasingly pressing environmental health issue. However, very few porous adsorbents have sufficiently high NO 2 adsorption capacity and good regenerability simultaneously. Here we attempt to address this challenge by developing p-backbonding adsorbents in the transition metal (TM) incorporated porphyrin metal-organic frameworks (PMOFs). Breakthrough experiments show that PMOFs with inserted TMs achieve appreciable NO 2 capacity and good regenerability. Combined in situ DRIFTS, synchrotron powder XRD, and DFT calculations reveal the adsorption mechanism: NO 2 partially transforms to N 2 O 4 and interacts with transition metal via p-backbonding and Al-node via hydrogen bonding. This work affords new insights for designing next-generation adsorbents for ambient NO 2 removal and presents PMOFs as a platform to tailor p-backbonding adsorbents.

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“…[53][54][55][56][57][58][59][60] In some cases, the profound structural and electronic changes induced by guest molecules enable the characterization/monitoring of the sorption process using EPR spectroscopy. This can be done directly in the case of paramagnetic guests [61][62][63][64][65] or indirectly by analyzing the g-factor shift of paramagnetic metal centers as in some Cu II -based porous materials. 58,[66][67][68] Noteworthy, EPR spectroscopy is commonly applied to study the state of the paramagnetic active sites doped into the mesoporous hosts such as zeolites in various catalytic processes.…”

Section: Introductionmentioning

confidence: 99%

Large Breathing Effect Induced by Water Sorption in the Exceptionally Stable Nonporous Non-MOF Crystalline Material

Magott¹,

Gaweł²,

Sarewicz³

et al. 2021

Preprint

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We report a non-MOF crystalline material {[Mn(imH)]2[Mo(CN)8]}n (imH = imidazole) with exceptional water sorption properties and a very large breathing effect accompanied by an outstanding stability and cyclability – properties that are absolutely unique for this class of compounds (Prussian Blue Analogs). Some previously published PBAs indeed show some sorption properties, but their cyclability is extremely limited - usually 1-3 cycles - followed by significant decomposition/amorphization. Our compound can be cycled more than 50 times without any fatigue and the sorption/desorption proceeds through four different crystal phases, which we have fully characterized structurally enabling the complete understanding of the sorption and breathing mechanism in this material - an achievement rarely reported for MOFs or PBAs. <br>The unique structure of {[Mn(imH)]2[Mo(CN)8]}n enables very strong coupling of its exceptional water sorption performance with the magnetic and photomagnetic properties of the framework, e.g. the sorption process can be followed by in-situ EPR spectroscopy with huge changes in the EPR signal intensity depending on the hydration level.<br><br>

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Capture of nitrogen dioxide and conversion to nitric acid in a porous metal–organic framework

Cited by 137 publications

References 30 publications

Near‐Zero Power MOF‐Based Sensors for NO₂ Detection

Near‐Zero Power MOF‐Based Sensors for NO₂ Detection

Transition‐Metal‐Containing Porphyrin Metal–Organic Frameworks as π‐Backbonding Adsorbents for NO₂ Removal

Large Breathing Effect Induced by Water Sorption in the Exceptionally Stable Nonporous Non-MOF Crystalline Material

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Capture of nitrogen dioxide and conversion to nitric acid in a porous metal–organic framework

Cited by 137 publications

References 30 publications

Near‐Zero Power MOF‐Based Sensors for NO2 Detection

Near‐Zero Power MOF‐Based Sensors for NO2 Detection

Transition‐Metal‐Containing Porphyrin Metal–Organic Frameworks as π‐Backbonding Adsorbents for NO2 Removal

Large Breathing Effect Induced by Water Sorption in the Exceptionally Stable Nonporous Non-MOF Crystalline Material

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Near‐Zero Power MOF‐Based Sensors for NO₂ Detection

Near‐Zero Power MOF‐Based Sensors for NO₂ Detection

Transition‐Metal‐Containing Porphyrin Metal–Organic Frameworks as π‐Backbonding Adsorbents for NO₂ Removal