Framework reduction and alkali-metal doping of a triply catenating metal-organic framework enhances and then diminishes H 2 uptake

Karen L. Mulfort, Thea M. Wilson, Michael R Wasielewski, Joseph T Hupp

Research output: Contribution to journalArticle

82 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)503-508
Number of pages6
JournalLangmuir
Volume25
Issue number1
DOIs
Publication statusPublished - Jan 6 2009

Fingerprint

Alkali Metals
Alkali metals
alkali metals
Metals
Doping (additives)
cations
Cations
augmentation
Positive ions
organic compounds
metals
isotherms
anions
Organic compounds
nitrogen
heat
adsorption
Anions
Isotherms
Nitrogen

ASJC Scopus subject areas

  • Electrochemistry
  • Condensed Matter Physics
  • Surfaces and Interfaces
  • Materials Science(all)
  • Spectroscopy

Cite this

Framework reduction and alkali-metal doping of a triply catenating metal-organic framework enhances and then diminishes H 2 uptake. / Mulfort, Karen L.; Wilson, Thea M.; Wasielewski, Michael R; Hupp, Joseph T.

In: Langmuir, Vol. 25, No. 1, 06.01.2009, p. 503-508.

Research output: Contribution to journalArticle

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