Dopant-controlled crystallization in metal-organic frameworks

The role of copper(II) in zinc 1,4-benzenedicarboxylate

Cantwell G. Carson, Jason Ward, Xiao Tao Liu, Justin Schwartz, Rosario A. Gerhardt, Rina Tannenbaum

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

A series of Zn-Cu 1,4-benzenedicarboxylate(bdc) metal organic frameworks(MOF) have been synthesized by introducing N,N-dimethylformamide(DMF) solutions of 1,4-benzenedicarboxylic acid to metal salt solutions with a range of concentrations of Cu(NO 3) 2 and Zn(NO 3) 2 across the entire composition range. At the Zn-rich side of the range, the presence of Cu(II) had the effect of changing the polymorph of the solid from the predominantly P2 1/n structure, associated with MOF-2, to the C2/m structure, shared with Cu(bdc). There was an associated change in crystal morphology that accompanied the addition of a Cu salt impurity. BET surface area measurements of the thermally desolvated product showed that the surface area of the Zn(bdc) increased with the addition of Cu. At the Cu-rich side, magnetic susceptibility measurements indicated that the presence of the Zn impurity increased the fraction of paramagnetic Cu centers, suggesting the formation of a large fraction of heterometallic secondary building units(hSBU) in the framework.

Original languageEnglish (US)
Pages (from-to)15322-15328
Number of pages7
JournalJournal of Physical Chemistry C
Volume116
Issue number29
DOIs
StatePublished - Jul 26 2012

Fingerprint

Crystallization
Zinc
Copper
zinc
Metals
Doping (additives)
crystallization
copper
Salts
metals
Impurities
salts
Dimethylformamide
impurities
crystal morphology
Polymorphism
Magnetic susceptibility
magnetic permeability
Crystals
acids

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

Cite this

Carson, Cantwell G. ; Ward, Jason ; Liu, Xiao Tao ; Schwartz, Justin ; Gerhardt, Rosario A. ; Tannenbaum, Rina. / Dopant-controlled crystallization in metal-organic frameworks : The role of copper(II) in zinc 1,4-benzenedicarboxylate. In: Journal of Physical Chemistry C. 2012 ; Vol. 116, No. 29. pp. 15322-15328.
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abstract = "A series of Zn-Cu 1,4-benzenedicarboxylate(bdc) metal organic frameworks(MOF) have been synthesized by introducing N,N-dimethylformamide(DMF) solutions of 1,4-benzenedicarboxylic acid to metal salt solutions with a range of concentrations of Cu(NO 3) 2 and Zn(NO 3) 2 across the entire composition range. At the Zn-rich side of the range, the presence of Cu(II) had the effect of changing the polymorph of the solid from the predominantly P2 1/n structure, associated with MOF-2, to the C2/m structure, shared with Cu(bdc). There was an associated change in crystal morphology that accompanied the addition of a Cu salt impurity. BET surface area measurements of the thermally desolvated product showed that the surface area of the Zn(bdc) increased with the addition of Cu. At the Cu-rich side, magnetic susceptibility measurements indicated that the presence of the Zn impurity increased the fraction of paramagnetic Cu centers, suggesting the formation of a large fraction of heterometallic secondary building units(hSBU) in the framework.",
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Dopant-controlled crystallization in metal-organic frameworks : The role of copper(II) in zinc 1,4-benzenedicarboxylate. / Carson, Cantwell G.; Ward, Jason; Liu, Xiao Tao; Schwartz, Justin; Gerhardt, Rosario A.; Tannenbaum, Rina.

In: Journal of Physical Chemistry C, Vol. 116, No. 29, 26.07.2012, p. 15322-15328.

Research output: Contribution to journalArticle

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