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Facile Uptake and Release of Ammonia by Nickel Halide Ammines.

ABSTRACT: Although major difficulties are experienced for hydrogen- storage materials to meet performance requirements for mobile applications, alternative fuel cell feedstocks such as ammonia can be stored in the solid state safely at high capacity. We herein describe the NiX2 -NH3 (X=Cl, Br, I) systems and demonstrate their exceptional suitability for NH3 storage (up to 43?wt?% NH3 with desorption that begins at 400?K). The structural effects that result from the uptake of NH3 were studied by powder X-ray diffraction (PXD), FTIR spectroscopy and SEM. NH3 release at elevated temperatures was followed by in?situ PXD. The cycling capabilities and air stability of the systems were also explored. NH3 is released from the hexaammines in a three-step process to yield the diammine, monoammine and NiX2 dihalides respectively and (re)ammoniation occurs readily at room temperature. The hexaammines do not react with air after several hours of exposure.

SUBMITTER: Breternitz J

PROVIDER: S-EPMC5084821 | biostudies-other | 2016 Jun

REPOSITORIES: biostudies-other

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Facile Uptake and Release of Ammonia by Nickel Halide Ammines.

Breternitz Joachim J Vilk Yury E YE Giraud Elsa E Reardon Hazel H Hoang Tuan K A TK Godula-Jopek Agata A Gregory Duncan H DH

ChemSusChem 20160503 11

Although major difficulties are experienced for hydrogen- storage materials to meet performance requirements for mobile applications, alternative fuel cell feedstocks such as ammonia can be stored in the solid state safely at high capacity. We herein describe the NiX2 -NH3 (X=Cl, Br, I) systems and demonstrate their exceptional suitability for NH3 storage (up to 43 wt % NH3 with desorption that begins at 400 K). The structural effects that result from the uptake of NH3 were studied by powder X-r ...[more]

PMID: 27137479

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Project description:The uptake of aqueous Ni(II) by synthetic mackinawite (FeS) was examined in anaerobic batch experiments at near-neutral pH (5.2 to 8.4). Initial molar ratios of Ni(II) to FeS ranged from 0.008 to 0.83 and maximum Ni concentrations in mackinawite, expressed as the cation mol fraction, were as high as XNi = 0.56 (Fe1 - x Ni x S; 0 ≤ x ≤ 1). Greater than 99% Ni removal from solution occurred when Ni loading remained below 0.13 ± 0.03 (1σ) mol Ni per mol FeS due to sorption of Ni at the mackinawite surface. Characterization of experimental solids using X-ray diffraction and Raman spectroscopy showed patterns characteristic of nanocrystalline mackinawite; no evidence of nickel monosulfide (α-NiS or millerite), polydymite (Ni3S4), or godlevskite [(Ni,Fe)9S8] formation was indicated regardless of the amount of Ni loading. Slight expansion of the c-axis correlated with increasing Ni content in synthetic mackinawite, from c = 5.07 ± 0.01 Å at XNi = 0.02 to c = 5.10 ± 0.01 Å at XNi = 0.38. Ni K-edge extended X-ray absorption fine structure (EXAFS) spectra of synthetic Ni-bearing mackinawite are similar in phase and amplitude to the Fe K-edge EXAFS spectrum of Ni-free mackinawite, indicating that the molecular environment of Ni2+ in Ni-bearing mackinawite is similar to that of Fe2+ in Ni-free mackinawite. EXAFS data fitting of Ni-bearing mackinawite with XNi = 0.42 indicated a coordination number of 4.04 ± 0.30 and an average Ni_S bond distance of 2.28 Å, in good agreement with the Fe_S bond distance of 2.26 Å in mackinawite, tetrahedral Fe coordination, and slight lattice expansion along the c-axis. At lower Ni loadings (XNi = 0.05-0.11), EXAFS analysis showed a decrease in Ni_S coordination towards CN = 3, which reflects the influence of sorbed Ni. Continued Ni uptake, past the maximum amount of sorption, was accompanied by proportional molar release of Fe to solution. Interstitial occupancy of Ni within the mackinawite interlayer may be transitional to structural substitution of Fe. The Ni-mackinawite solid-solution is described by a one-site binary mixing model: LnKd=lnKe-(W/RT)(1-2XNi) where Kd is the distribution coefficient, Ke is the ratio of equilibrium constants for Ni-mackinawite and mackinawite (14.4 ± 1.3), W is an ion interaction parameter, and XNi is the mole fraction of end-member NiS in the solid solution. The experimentally determined value of W is 17.74 ± 1.15 kJ/mol and indicates significant non-ideality of the solid solution. Transformation processes were evaluated by aging Ni-mackinawite with polysulfides and solutions saturated with air. Reaction of Ni-mackinawite with polysulfides led to the formation of pyrite (FeS2) and Ni retention in the solid phase. When Ni-mackinawite was aged in the presence of dissolved oxygen, transformation to goethite (FeOOH) and violarite (FeNi2S4) was observed.

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Facile Uptake and Release of Ammonia by Nickel Halide Ammines.

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Facile Uptake and Release of Ammonia by Nickel Halide Ammines.

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