Ammonia Storage by Reversible Host–Guest Site Exchange in a Robust Metal–Organic Framework

Godfrey, Harry G. W.; Silva, Iván da; Briggs, Lydia; Carter, Joseph H.; Morris, Christopher G.; Savage, Mathew; Easun, Timothy L.; Manuel, Pascal; Murray, Claire; Tang, Chiu C.; Frogley, Mark D.; Cinque, Gianfelice; Yang, Sihai; Schröder, Martin

doi:10.1002/anie.201808316

Cited by 96 publications

(116 citation statements)

References 26 publications

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“…Omitting this, the unit cell volume of all samples remains constant throughout the experiment, indicating the stability of the samples to these conditions. In addition to this evidence of stability, NO 2 ( Figures S10 and S11 ) and NH 3 18 cycling experiments have shown little change in maximum gas uptake after 50 and 100 cycles, respectively.…”

Section: Results and Discussionmentioning

confidence: 85%

“…It has previously been shown that NH 3 storage in porous adsorbents can effectively overcome the energy penalty of these storage media by achieving densities close to that of liquid NH 3 under ambient conditions. 18 …”

Section: Introductionmentioning

confidence: 99%

“…The material chosen for this experiment was MFM-300(Al) [Al 2 (μ 2 -OH) 2 (L), H 4 L = biphenyl-3,3′,5,5′-tetracarboxylic acid], which exhibits a 3D open framework consisting of 1D extended aluminum oxide [AlO 4 (μ 2 -OH) 2 ] ∞ chains, linked by organic linkers in a “wine-rack” mode. 27 MFM-300 materials have exhibited excellent sorption properties for NH 3 , 18 NO 2 , 24 and SO 2 . 26 − 29 The aluminum analogue specifically was selected for the LD-SXRD study as it is based upon an abundant metal source and well-known crystal structure and is particularly stable within the MFM-300 series.…”

Section: Introductionmentioning

confidence: 99%

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Long-Term Stability of MFM-300(Al) toward Toxic Air Pollutants

Carter

Morris

Godfrey

et al. 2020

ACS Appl. Mater. Interfaces

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Temperature- or pressure-swing sorption in porous metal–organic framework (MOF) materials has been proposed for new gas separation technologies. The high tunability of MOFs toward particular adsorbates and the relatively low energy penalty for system regeneration indicate that reversible physisorption in MOFs has the potential to create economic and environmental benefits compared with state-of-the-art chemisorption systems. However, for MOF-based sorbents to be commercialized, they have to show long-term stability under the conditions imposed by the application. Here, we demonstrate the structural stability of MFM-300(Al) in the presence of a series of industrially relevant toxic and corrosive gases, including SO 2 , NO 2 , and NH 3 , over 4 years using long-duration synchrotron X-ray powder diffraction. Full structural analysis of gas-loaded MFM-300(Al) confirms the retention of these toxic gas molecules within the porous framework for up to 200 weeks, and cycling adsorption experiments verified the reusability of MFM-300(Al) for the capture of these toxic air pollutants.

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Section: Results and Discussionmentioning

confidence: 85%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Long-Term Stability of MFM-300(Al) toward Toxic Air Pollutants

Carter

Morris

Godfrey

et al. 2020

ACS Appl. Mater. Interfaces

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“…MFM-300(In) responds to ab ase, NH 3 ,w hereas there was no response to NO 2 (Figure6)i n3%r elative humidity air.A lthough this exact system has not yet been studied in situ spectroscopically,a neutron diffraction studyo fM FM-300(Al) shows NH 3 binding occurring at the metal site. [36] Separate capacitance measurements of MFM MOFs show that there is negligible NO 2 adsorption in the concentration range we study. [35] The imidazole-containing framework ZIF-8 did not respond to NH 3 (Figure S13, Supporting Information), but as described above,d oes respond to NO 2 .T hese responses are in agreement with the predictions of well-knownc hemical resistance rules.…”

Section: Zif-8 No 2 Sensingmentioning

confidence: 72%

Transistor‐Based Work‐Function Measurement of Metal–Organic Frameworks for Ultra‐Low‐Power, Rationally Designed Chemical Sensors

Gardner

Gao

Fahad

et al. 2019

Chemistry A European J

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Ac lassic challenge in chemical sensingi ss electivity.M etal-organic frameworks (MOFs) are an exciting class of materials because they can be tuned for selective chemical adsorption. Adsorptione ventst riggerw ork-function shifts, which can be detectedw ith ac hemical-sensitive field-effect transistor (power % microwatts). In this work, several case studiesw ere used towards generalizing the sensing mechanism, ultimately towards our metal-centric hypothesis. HKUST-1 was used as ap roof-of-principle humidity sensor.The response is thickness independent, meaning the response is surfacel ocalized. ZIF-8 is demonstrated to be an NO 2 -sensing material,a nd the response is dominated by adsorptiona tm etal sites. Finally, MFM-300(In) shows how standard hard-soft acid-base theory can be used to qualitatively predict sensorr esponses. This paper sets the groundwork for using the tunability of metal-organic frameworks for chemicalsensing with distributed, scalable devices.[a] D.Supporting information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.

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“…TheN H 3 packing density in CPM-100b and CPM-100c (0.598 and 0.597 gcm À3 )i sc omparable to that of the top two materials MFM-300(Al) and Co 2 Cl 2 BBTA( 0.622 and 0.610 gcm À3 ; Figure 4b;s ee also Table S2). [17] According to DFT calculations,the adsorption site Bpossesses alarge binding energy of À43 kJ mol À1 .T he distance between Ni na mmonia and Bi n tpb is approximately 2.45 ,t hus indicating as trong interaction between Band N(see Figure S10), which results in an adsorption enhancement with respect to tpt-pacs materials. …”

Section: Angewandte Chemiementioning

confidence: 98%

A Tale of Two Trimers from Two Different Worlds: A COF‐Inspired Synthetic Strategy for Pore‐Space Partitioning of MOFs

et al. 2019

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The introduction of asymmetry-and size-matching pore-partitioning agent in the form of either am olecular ligand, such as 2,4,6-tri(4-pyridinyl)-1,3,5-triazine (tpt), or ametal-complex cluster,into the hexagonal channels of MIL-88/MOF-235-type (the acs net) to create pacs-type (partitioned acs)c rystalline porous materials is an effective strategy to develop high-performance gas adsorbents.W ehave developed an integrated COF-MOF coassembly strategy as anew method for pore-space partitioning through the coassembly of [(M 3 -(OH) 1Àx (O) x (COO) 6 ]M OF-type and [B 3 O 3 (py) 3 ]C OF-type trimers.Withthis strategy,the coordination-driven assembly of the acs framework occurred concurrently and synergistically with the COF-1-type condensation of pyridine-4-boronic acid into aC 3 -symmetric trimeric boroxine molecule.The resulting boroxine-based pacs materials exhibited dramatically enhanced gas-sorption properties as compared to nonpartitioned acs-type materials and are among the most efficient NH 3 -sorption materials.

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Ammonia Storage by Reversible Host–Guest Site Exchange in a Robust Metal–Organic Framework

Cited by 96 publications

References 26 publications

Long-Term Stability of MFM-300(Al) toward Toxic Air Pollutants

Long-Term Stability of MFM-300(Al) toward Toxic Air Pollutants

Transistor‐Based Work‐Function Measurement of Metal–Organic Frameworks for Ultra‐Low‐Power, Rationally Designed Chemical Sensors

A Tale of Two Trimers from Two Different Worlds: A COF‐Inspired Synthetic Strategy for Pore‐Space Partitioning of MOFs

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