Dataset Information

Amides Do Not Always Work: Observation of Guest Binding in an Amide-Functionalized Porous Metal-Organic Framework.

ABSTRACT: An amide-functionalized metal organic framework (MOF) material, MFM-136, shows a high CO₂ uptake of 12.6 mmol g^-1 at 20 bar and 298 K. MFM-136 is the first example of an acylamide pyrimidyl isophthalate MOF without open metal sites and, thus, provides a unique platform to study guest binding, particularly the role of free amides. Neutron diffraction reveals that, surprisingly, there is no direct binding between the adsorbed CO₂/CH₄ molecules and the pendant amide group in the pore. This observation has been confirmed unambiguously by inelastic neutron spectroscopy. This suggests that introduction of functional groups solely may not necessarily induce specific guest-host binding in porous materials, but it is a combination of pore size, geometry, and functional group that leads to enhanced gas adsorption properties.

SUBMITTER: Benson O

PROVIDER: S-EPMC5152937 | biostudies-literature | 2016 Nov

REPOSITORIES: biostudies-literature

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Amides Do Not Always Work: Observation of Guest Binding in an Amide-Functionalized Porous Metal-Organic Framework.

Benson Oguarabau O da Silva Ivan I Argent Stephen P SP Cabot Rafel R Savage Mathew M Godfrey Harry G W HG Yan Yong Y Parker Stewart F SF Manuel Pascal P Lennox Matthew J MJ Mitra Tamoghna T Easun Timothy L TL Lewis William W Blake Alexander J AJ Besley Elena E Yang Sihai S Schröder Martin M

Journal of the American Chemical Society 20161101 45

An amide-functionalized metal organic framework (MOF) material, MFM-136, shows a high CO2 uptake of 12.6 mmol g-1 at 20 bar and 298 K. MFM-136 is the first example of an acylamide pyrimidyl isophthalate MOF without open metal sites and, thus, provides a unique platform to study guest binding, particularly the role of free amides. Neutron diffraction reveals that, surprisingly, there is no direct binding between the adsorbed CO2/CH4 molecules and the pe ...[more]

PMID: 27665845

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Project description:The electrochemical reduction reaction of nitrate (NO3RR) is an attractive route to produce ammonia at ambient conditions, but the conversion from nitrate to ammonia, which requires nine protons, has to compete with both the two-proton process of nitrite formation and the hydrogen evolution reaction. Extensive research efforts have thus been made in recent studies to develop electrocatalysts for the NO3RR facilitating the production of ammonia. Rather than designing another better electrocatalyst, herein, we synthesize an electrochemically inactive, porous, and chemically robust zirconium-based metal-organic framework (MOF) with enriched intraframework sulfonate groups, SO3-MOF-808, as a coating deposited on top of the catalytically active copper-based electrode. Although both the overall reaction rate and electrochemically active surface area of the electrode are barely affected by the MOF coating, with negatively charged sulfonate groups capable of enriching more protons near the electrode surface, the MOF coating significantly promotes the selectivity of the NO3RR toward the production of ammonia. In contrast, the use of MOF coating with positively charged trimethylammonium groups to repulse protons strongly facilitates the conversion of nitrate to nitrite, with selectivity of more than 90% at all potentials. Under the optimal operating conditions, the copper electrocatalyst with SO3-MOF-808 coating can achieve a Faradaic efficiency of 87.5% for ammonia production, a nitrate-to-ammonia selectivity of 95.6%, and an ammonia production rate of 97 μmol/cm2 h, outperforming all of those achieved by both the pristine copper (75.0%; 93.9%; 87 μmol/cm2 h) and copper with optimized Nafion coating (83.3%; 86.9%; 64 μmol/cm2 h). Findings here suggest the function of MOF as an advanced alternative to the commercially available Nafion to enrich protons near the surface of electrocatalyst for NO3RR, and shed light on the potential of utilizing such electrochemically inactive MOF coatings in a range of proton-coupled electrocatalytic reactions.

Dataset Information

Amides Do Not Always Work: Observation of Guest Binding in an Amide-Functionalized Porous Metal-Organic Framework.

Publications

Amides Do Not Always Work: Observation of Guest Binding in an Amide-Functionalized Porous Metal-Organic Framework.

Similar Datasets

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