Synthesis, X-ray Crystal Structures, and Gas Sorption Properties of Pillared Square Grid Nets Based on Paddle-Wheel Motifs: Implications for Hydrogen Storage in Porous Materials

Chun, Hyungphil,Dybtsev, Danil N.,Kim, Hyunuk,Kim, Kimoon WILEY-VCH Verlag 2005 Chemistry Vol.11 No.12

<P>A systematic modulation of organic ligands connecting dinuclear paddle-wheel motifs leads to a series of isomorphous metal-organic porous materials that have a three-dimensional connectivity and interconnected pores. Aromatic dicarboxylates such as 1,4-benzenedicarboxylate (1,4-bdc), tetramethylterephthalate (tmbdc), 1,4-naphthalenedicarboxylate (1,4-ndc), tetrafluoroterephthalate (tfbdc), or 2,6-naphthalenedicarboxylate (2,6-ndc) are linear linkers that form two-dimensional layers, and diamine ligands, 4-diazabicyclo[2.2.2]octane (dabco) or 4,4′-dipyridyl (bpy), coordinate at both sides of Zn<SUB>2</SUB> paddle-wheel units to bridge the layers vertically. The resulting open frameworks [Zn<SUB>2</SUB>(1,4-bdc)<SUB>2</SUB>(dabco)] (1), [Zn<SUB>2</SUB>(1,4-bdc)(tmbdc)(dabco)] (2), [Zn<SUB>2</SUB>(tmbdc)<SUB>2</SUB>(dabco)] (3), [Zn<SUB>2</SUB>(1,4-ndc)<SUB>2</SUB>(dabco)] (4), [Zn<SUB>2</SUB>(tfbdc)<SUB>2</SUB>(dabco)] (5), and [Zn<SUB>2</SUB>(tmbdc)<SUB>2</SUB>(bpy)] (8) possess varying size of pores and free apertures originating from the side groups of the 1,4-bdc derivatives. [Zn<SUB>2</SUB>(1,4-bdc)<SUB>2</SUB>(bpy)] (6) and [Zn<SUB>2</SUB>(2,6-ndc)<SUB>2</SUB>(bpy)] (7) have two- and threefold interpenetrating structures, respectively. The non-interpenetrating frameworks (1–5 and 8) possess surface areas in the range of 1450–2090 m<SUP>2</SUP>g<SUP>−1</SUP> and hydrogen sorption capacities of 1.7–2.1 wt % at 78 K and 1 atm. A detailed analysis of the sorption data in conjunction with structural similarities and differences concludes that porous materials with straight channels and large openings do not perform better than those with wavy channels and small openings in terms of hydrogen storage through physisorption.</P> <B>Graphic Abstract</B> <P>Similarities and differences exist in the structures and gas sorption behavior of highly porous metal–organic frameworks systematically modulated from a prototype based on a paddle-wheel-based three-dimensional net (see picture). The similarities and differences are used to draw a conclusion that might be useful for the development of efficient hydrogen-storage materials. <img src='wiley_img/09476539-2005-11-12-CHEM200401201-content.gif' alt='wiley_img/09476539-2005-11-12-CHEM200401201-content'> </P>

Enantioselective sorption of alcohols in a homochiral metal–organic framework

Suh, Kyungwon,Yutkin, Maxim P.,Dybtsev, Danil N.,Fedin, Vladimir P.,Kim, Kimoon The Royal Society of Chemistry 2012 Chemical communications Vol.48 No.4

<p>Single-crystal X-ray diffraction study reveals the host–guest interactions between a homochiral metal–organic framework and two enantiomers of a chiral alcohol providing the key driving force for the enantioselective sorption of alcohols in the framework.</p> <P>Graphic Abstract</P><P>Single-crystal X-ray diffraction study reveals enantioselective recognition <I>via</I> H-bond interaction between a chiral substrate and an enantiopure porous metal–organic framework. <img src='http://pubs.rsc.org/ej/CC/2011/c1cc16209h/c1cc16209h-ga.gif'> </P>

Synthesis of phase-pure interpenetrated MOF-5 and its gas sorption properties.

Kim, Hyunuk,Das, Sunirban,Kim, Min Gyu,Dybtsev, Danil N,Kim, Yonghwi,Kim, Kimoon American Chemical Society 2011 Inorganic Chemistry Vol.50 No.8

<P>For the first time, phase-pure interpenetrated MOF-5 (1) has been synthesized and its gas sorption properties have been investigated. The phase purity of the material was confirmed by both single-crystal and powder X-ray diffraction studies and TGA analysis. A systematic study revealed that controlling the pH of the reaction medium is critical to the synthesis of phase-pure 1, and the optimum apparent pH (pH*) for the formation of 1 is 4.0-4.5. At higher or lower pH*, [Zn(2)(BDC)(2)(DMF)(2)] (2) or [Zn(5)(OH)(4)(BDC)(3)] (3), respectively, was predominantly formed. The pore size distribution obtained from Ar sorption experiments at 87 K showed only one peak, at ~6.7 ?, which is consistent with the average pore size of 1 revealed by single crystal X-ray crystallography. Compared to MOF-5, 1 exhibited higher stability toward heat and moisture. Although its surface area is much smaller than that of MOF-5 due to interpenetration, 1 showed a significantly higher hydrogen capacity (both gravimetric and volumetric) than MOF-5 at 77 K and 1 atm, presumably because of its higher enthalpy of adsorption, which may correlate with its higher volumetric hydrogen uptake compared to MOF-5 at room temperature, up to 100 bar. However, at high pressures and 77 K, where the saturated H(2) uptake mostly depends on the surface area of a porous material, the total hydrogen uptake of 1 is notably lower than that of MOF-5.</P>

Microporous sensor: gas sorption, guest exchange and guest-dependant luminescence of metal–organic framework

Sapchenko, Sergey A.,Samsonenko, Denis G.,Dybtsev, Danil N.,Melgunov, Maxim S.,Fedin, Vladimir P. Royal Society of Chemistry 2011 Dalton transactions Vol.40 No.10

<P>Zn(<SMALL>II</SMALL>)-containing metal–organic framework (MOF) [Zn<SUB>4</SUB>(dmf)(ur)<SUB>2</SUB>(ndc)<SUB>4</SUB>] (ndc<SUP>2−</SUP> = 2,6-naphtalenedicarboxylate, ur = urotropin, dmf = N,N′-dimethylformamide) was synthesized and characterized by X-ray crystallography and gas sorption analysis. Host MOF retains its crystallinity after guest removal and exchange. Single-crystal to single-crystal formation of different host–guest systems with benzene and ferrocene was investigated. Interesting guest-depended luminescence properties of the porous host framework were observed.</P> <P>Graphic Abstract</P><P>A Zn(<SMALL>II</SMALL>)-containing MOF was synthesized and characterized by X-ray crystallography and gas sorption analysis. <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=c0dt00999g'> </P>

Imparting High Proton Conductivity to a Metal–Organic Framework Material by Controlled Acid Impregnation

Ponomareva, Valentina G.,Kovalenko, Konstantin A.,Chupakhin, Alexei P.,Dybtsev, Danil N.,Shutova, Elena S.,Fedin, Vladimir P. American Chemical Society 2012 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY - Vol.134 No.38

<P>The extensive implementation of hydrogen-powered technology today is limited by a number of fundamental problems related to materials research. Fuel-cell hydrogen conversion technology requires proton-conducting materials with high conductivity at intermediate temperatures up to 120 °C. The development of such materials remains challenging because the proton transport of many promising candidates is based on extended microstructures of water molecules, which deteriorate at temperatures above the boiling point. Here we show the impregnation of the mesoporous metal–organic framework (MOF) MIL-101 by nonvolatile acids H<SUB>2</SUB>SO<SUB>4</SUB> and H<SUB>3</SUB>PO<SUB>4</SUB>. Such a simple approach affords solid materials with potent proton-conducting properties at moderate temperatures, which is critically important for the proper function of on-board automobile fuel cells. The proton conductivities of the H<SUB>2</SUB>SO<SUB>4</SUB>@MIL-101 and H<SUB>3</SUB>PO<SUB>4</SUB>@MIL-101 at <I>T</I> = 150 °C and low humidity outperform those of any other MOF-based materials and could be compared with the best proton conductors, such as Nafion.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/jacsat/2012/jacsat.2012.134.issue-38/ja305587n/production/images/medium/ja-2012-05587n_0005.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ja305587n'>ACS Electronic Supporting Info</A></P>

Porous carbon materials with a controllable surface area synthesized from metal–organic frameworks

Lim, Seunghoon,Suh, Kyungwon,Kim, Yelin,Yoon, Minyoung,Park, Hyeran,Dybtsev, Danil N.,Kim, Kimoon The Royal Society of Chemistry 2012 Chemical communications Vol.48 No.60

<P>Carbonization of zinc containing metal–organic frameworks produces porous carbon materials with an interesting linear relationship between the Zn/C ratio of the precursors and the surface area of the resulting carbon materials.</P> <P>Graphic Abstract</P><P>Carbonization of zinc containing metal–organic frameworks produces porous carbon materials with an interesting linear relationship between the Zn/C ratio of the precursors and the surface area of the resulting carbon materials. <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=c2cc33439a'> </P>

Structure of a framework coordination polymer Zn2(dmf)(H2O)(atc)]·0.75DMF·0.5H2O

Zavakhina, M. S.,Samsonenko, D. G.,Yutkin, M. P.,Dybtsev, D. N.,Fedin, V. P. Pleiades Publishing 2012 Journal of structural chemistry Vol.53 No.2

Synthesis and characterization of expected and unexpected topologies of homochiral porous metal(II) malate frameworks

Yutkin, M.P.,Zavakhina, M.S.,Samsonenko, D.G.,Dybtsev, D.N.,Fedin, V.P. Elsevier Sequoia [etc.] 2013 Inorganica chimica acta Vol.394 No.-

Three new homochiral metal-organic frameworks (MOFs) based on malate anions and N-donor linkers of different length have been prepared. [Co<SUB>2</SUB>(mal)<SUB>2</SUB>(bpy)].2H<SUB>2</SUB>O (1), [Ni<SUB>2</SUB>(mal)<SUB>2</SUB>(bpy)].2H<SUB>2</SUB>O (2), [Ni<SUB>2</SUB>(mal)<SUB>2</SUB>(bpe)].3H<SUB>2</SUB>O (3) (mal=S-malate, bpy=4,4'-bipyridyl, bpe=trans-1,2-bis(4-pyridyl)ethylene) were characterized by a number of analytical methods including single crystal X-ray analysis. Optical purity of compounds 2 and 3 was confirmed by polarimetry experiments. Compounds 1 and 2 contribute to the family of isoreticular M(II) malates and aspartates ([M<SUB>2</SUB>(asp)<SUB>2</SUB>L] and [M<SUB>2</SUB>(mal)<SUB>2</SUB>L], M=Cu, Co, Ni; L=ditopic rigid organic ligand) where all structural units (metal cations, chiral ligands and bridging ligands) could be changed with retention of the topology in the resulting framework. Compound 3 has a different structure and contributes to a different family of isoreticular homochiral MOFs.

Methane Sorption and Structural Characterization of the Sorption Sites in Zn₂(bdc)₂(dabco) by Single Crystal X-ray Crystallography

Kim, Hyunuk,Samsonenko, Denis G.,Das, Sunirban,Kim, Ghyung-Hwa,Lee, Heung-Soo,Dybtsev, Danil N.,Berdonosova, Elena A.,Kim, Kimoon Wiley (John WileySons) 2009 Chemistry - An Asian Journal Vol.4 No.6

<P>Sorption isotherms of methane in Zn(2)(bdc)(2)(dabco) are measured up to a pressure of 35 bar in the temperature range between 198-296 K. The methane sorption measurements at 296 K showed an uptake of 137 cm(3) cm(-3) at 35 bar. The enthalpy of methane adsorption for Zn(2)(bdc)(2)(dabco) estimated by the virial equation is 13.6 kJ mol(-1) at zero coverage. X-ray structure analysis of methane-adsorbed Zn(2)(bdc)(2)(dabco) by synchrotron radiation at 90 K revealed that methane molecules occupy three independent sorption sites (A, B, and C) with a stoichiometry of Zn(2)(bdc)(2)(dabco) x 6.69 CH(4), which is consistent with the results of the gas sorption measurements at 198 K. In a cavity, eight symmetry-related methane sorption sites A are located near the {Zn(2)(CO(2))(4)} paddle-wheel units, while four symmetry-related methane sorption sites B are near the center of the small windows along the a and b axes. Both A and B sites are half-occupied. Methane molecules occupying sites A are not only in van der Waals contact with the paddle-wheel units, but also interact with the phenyl rings of bdc ligands through partial pi-HC interactions. Methane molecules in B sites interact with the side of the phenyl rings through van der Waals interaction. The site C, located at the center of the cavity, is a secondary sorption site; methane molecules occupying sites C are in van der Waals contact with those in sites A and B.</P>