Framework reduction and alkali-metal doping of a triply catenating metal-organic framework enhances and then diminishes H2 uptake.
نویسندگان
چکیده
A permanently microporous metal-organic framework compound with the formula Zn(2)(NDC)(2)(diPyTz) (NDC = 2,6-naphthalenedicarboxylate, diPyTz = di-3,6-(4-pyridyl)-1,2,4,5-tetrazine) has been synthesized. The compound, which features a triply catenating, pillared-paddlewheel structure, was designed to be easily chemically reduced (diPyTz sites) by appropriate channel permeants. Reduction was achieved by using the naphthalenide anion, with the accompanying metal cation (Li(+), Na(+) or K(+)) serving to dope the compound in extraframework fashion. H(2) uptake at 1 atm and 77 K increases from 1.12 wt % for the neutral material to 1.45, 1.60, and 1.51 wt % for the Li(+)-, Na(+)-, and K(+)-doped materials, respectively. The isosteric heats of adsorption are similar for all four versions of the material despite the large uptake enhancements for the reduced versions. Nitrogen isotherms were also measured in order to provide insight into the mechanisms of uptake enhancement. The primary mechanism is believed to be dopant-facilitated displacement of catenated frameworks by sorbed H(2). More extensive cation doping decreases the H(2) loading.
منابع مشابه
Alkali metal cation effects on hydrogen uptake and binding in metal-organic frameworks.
A 2-fold interwoven metal-organic framework has been chemically reduced and doped with Li(+), Na(+), and K(+). At low pressures and temperatures, the reduced and doped materials exhibit enhanced H2 uptakeup to 65% higher than for the neutral framework. Notably, at similar doping levels, H2 binding is strongest with Li(+) and decreases as Li(+) > Na(+) > K(+). However, the uptake increases in th...
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عنوان ژورنال:
- Langmuir : the ACS journal of surfaces and colloids
دوره 25 1 شماره
صفحات -
تاریخ انتشار 2009