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Exceptional Packing Density of Ammonia in a Dual-Functionalized Metal-Organic Framework.

ABSTRACT: We report the reversible adsorption of ammonia (NH₃) up to 9.9 mmol g^-1 in a robust Al-based metal-organic framework, MFM-303(Al), which is functionalized with free carboxylic acid and hydroxyl groups. The unique pore environment decorated with these acidic sites results in an exceptional packing density of NH₃ at 293 K (0.801 g cm^-3) comparable to that of solid NH₃ at 193 K (0.817 g cm^-3). In situ synchrotron X-ray diffraction and inelastic neutron scattering reveal the critical role of free -COOH and -OH groups in immobilizing NH₃ molecules. Breakthrough experiments confirm the excellent performance of MFM-303(Al) for the capture of NH₃ at low concentrations under both dry and wet conditions.

SUBMITTER: Marsh C

PROVIDER: S-EPMC8154541 | biostudies-literature | 2021 May

REPOSITORIES: biostudies-literature

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Exceptional Packing Density of Ammonia in a Dual-Functionalized Metal-Organic Framework.

Marsh Christopher C Han Xue X Li Jiangnan J Lu Zhenzhong Z Argent Stephen P SP da Silva Ivan I Cheng Yongqiang Y Daemen Luke L LL Ramirez-Cuesta Anibal J AJ Thompson Stephen P SP Blake Alexander J AJ Yang Sihai S Schröder Martin M

Journal of the American Chemical Society 20210422 17

We report the reversible adsorption of ammonia (NH3) up to 9.9 mmol g-1 in a robust Al-based metal-organic framework, MFM-303(Al), which is functionalized with free carboxylic acid and hydroxyl groups. The unique pore environment decorated with these acidic sites results in an exceptional packing density of NH3 at 293 K (0.801 g cm-3) comparable to that of solid NH3 at 193 K (0.817 g cm-3). In situ synchrotron X-ray diffrac ...[more]

PMID: 33885294

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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

Exceptional Packing Density of Ammonia in a Dual-Functionalized Metal-Organic Framework.

Publications

Exceptional Packing Density of Ammonia in a Dual-Functionalized Metal-Organic Framework.

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