Catalysis by a zinc-porphyrin-based metal-organic framework: From theory to computational design

Sharani Roy, Christopher B. George, Mark A Ratner

Research output: Contribution to journalArticle

21 Citations (Scopus)

Abstract

Catalytic metal-organic frameworks (MOFs) have captured widespread attention for displaying shape, size, chemical, and enantiomeric selectivity characteristic of biological enzymes. Nguyen and co-workers [J. Am. Chem. Soc.2009, 131, 4204-4205] synthesized a stable, crystalline, microporous, zinc-porphyrin-based metal-organic framework (ZnPO-MOF) that incorporates the catalytic activity of metalloporphyrins. They observed a 236-fold initial acceleration of an acyl-transfer reaction between 3-pyridylcarbinol and N-acetylimidazole by ZnPO-MOF, and attributed this catalysis primarily to a high local concentration or "preconcentration" of reactants at the porphyrin-Zn active sites of the framework. We report a detailed theoretical investigation of the framework-promoted reaction using the full atomic structure of the MOF. The three-step first-principles-based method developed for this purpose can be applied to study other catalytically active MOFs, and can help in the computational design of frameworks with optimum preconcentration and chemical sensing properties. Calculations show that reactants bind to the closely packed porphyrin-Zn sites of ZnPO-MOF, resulting in a high local concentration of catalyst-bound reactant. Our model predicts that reactant preconcentration in ZnPO-MOF can increase the initial rate of the acyl-transfer reaction by about 2 orders of magnitude relative to the uncatalyzed reaction, and can be the dominant catalytic mechanism in this system.

Original languageEnglish
Pages (from-to)23494-23502
Number of pages9
JournalJournal of Physical Chemistry C
Volume116
Issue number44
DOIs
Publication statusPublished - Nov 8 2012

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Porphyrins
porphyrins
Catalysis
catalysis
Zinc
zinc
Metals
metals
Nicotinyl Alcohol
Metalloporphyrins
Catalyst selectivity
zinc hematoporphyrin
atomic structure
catalytic activity
enzymes
Catalyst activity
Enzymes
selectivity
Crystalline materials
catalysts

ASJC Scopus subject areas

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

Cite this

Catalysis by a zinc-porphyrin-based metal-organic framework : From theory to computational design. / Roy, Sharani; George, Christopher B.; Ratner, Mark A.

In: Journal of Physical Chemistry C, Vol. 116, No. 44, 08.11.2012, p. 23494-23502.

Research output: Contribution to journalArticle

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