Enhancement of CO2 binding and mechanical properties upon diamine functionalization of M2(dobpdc) metal–organic frameworks

Jung-Hoon Lee; Rebecca L. Siegelman; Lorenzo Maserati; Tonatiuh Rangel; Brett A. Helms; Jeffrey R. Long; Jeffrey B. Neaton

doi:10.1039/C7SC05217K

Enhancement of CO₂ binding and mechanical properties upon diamine functionalization of M₂(dobpdc) metal–organic frameworks†

Jung-Hoon Lee,

^ab Rebecca L. Siegelman,

^cd Lorenzo Maserati,

^a Tonatiuh Rangel,^ab Brett A. Helms,

^ad Jeffrey R. Long

^cde and Jeffrey B. Neaton*^abf

Author affiliations

* Corresponding authors

^a Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA
E-mail: jbneaton@lbl.gov

^b Department of Physics, University of California, Berkeley, California 94720, USA

^c Department of Chemistry, University of California, Berkeley, California 94720, USA

^d Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA

^e Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720, USA

^f Kavli Energy Nanosciences Institute at Berkeley, Berkeley, California 94720, USA

Abstract

The family of diamine-appended metal–organic frameworks exemplified by compounds of the type mmen–M₂(dobpdc) (mmen = N,N′-dimethylethylenediamine; M = Mg, Mn, Fe, Co, Zn; dobpdc⁴⁻ = 4,4′-dioxidobiphenyl-3,3′-dicarboxylate) are adsorbents with significant potential for carbon capture, due to their high working capacities and strong selectivity for CO₂ that stem from a cooperative adsorption mechanism. Herein, we use first-principles density functional theory (DFT) calculations to quantitatively investigate the role of mmen ligands in dictating the framework properties. Our van der Waals-corrected DFT calculations indicate that electrostatic interactions between ammonium carbamate units significantly enhance the CO₂ binding strength relative to the unfunctionalized frameworks. Additionally, our computed energetics show that mmen–M₂(dobpdc) materials can selectively adsorb CO₂ under humid conditions, in agreement with experimental observations. The calculations further predict an increase of 112% and 124% in the orientationally-averaged Young's modulus E and shear modulus G, respectively, for mmen–Zn₂(dobpdc) compared to Zn₂(dobpdc), revealing a dramatic enhancement of mechanical properties associated with diamine functionalization. Taken together, our calculations demonstrate how functionalization with mmen ligands can enhance framework gas adsorption and mechanical properties.

This article is part of the themed collection: Chemistry of polymers - Chemical Science symposium collection

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Article information

DOI: https://doi.org/10.1039/C7SC05217K
Article type: Edge Article
Submitted: 08 Dec 2017
Accepted: 15 May 2018
First published: 23 May 2018
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry

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Chem. Sci., 2018,9, 5197-5206

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Enhancement of CO₂ binding and mechanical properties upon diamine functionalization of M₂(dobpdc) metal–organic frameworks

J. Lee, R. L. Siegelman, L. Maserati, T. Rangel, B. A. Helms, J. R. Long and J. B. Neaton, Chem. Sci., 2018, 9, 5197 DOI: 10.1039/C7SC05217K

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