Elucidating Gating Effects for Hydrogen Sorption in MFU-4-Type Triazolate-Based Metal-Organic Frameworks Featuring Different Pore Sizes

被引:221
作者
Denysenko, Dmytro [1 ]
Grzywa, Maciej [1 ]
Tonigold, Markus [2 ]
Streppel, Barbara [3 ]
Krkljus, Ivana [3 ]
Hirscher, Michael [3 ]
Mugnaioli, Enrico [4 ]
Kolb, Ute [4 ]
Hanss, Jan [1 ]
Volkmer, Dirk [1 ,2 ]
机构
[1] Univ Augsburg, Chair Solid State & Mat Sci, Inst Phys, D-86135 Augsburg, Germany
[2] Univ Ulm, Inst Inorgan Chem Mat & Catalysis 2, D-89081 Ulm, Germany
[3] Max Planck Inst Met Res, D-70569 Stuttgart, Germany
[4] Johannes Gutenberg Univ Mainz, Inst Phys Chem, D-55099 Mainz, Germany
关键词
adsorption; hydrogen; metal-organic frameworks; thermal desorption spectroscopy; triazolates; AUTOMATED DIFFRACTION TOMOGRAPHY; ELECTRON-DIFFRACTION; SURFACE-AREAS; ADSORPTION; STORAGE; COORDINATION; DESORPTION; DESIGN; SYSTEM; HEAT;
D O I
10.1002/chem.201001872
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A highly porous member of isoreticular MFU-4-type frameworks, [Zn5Cl4(BTDD)(3)] (MFU-4/(arge)) (H-2-BTDD = bis(1H-1,2,3-triazolo[4,5-b],- [4',5'-i])dibenzo[1,4]dioxin), has been synthesized using ZnCl2 and H-2-BTDD in N,N-dimethylformamide as a solvent. MFU-4l represents the first example of MFU-4-type frameworks featuring large pore apertures of 9.1 angstrom. Here, MFU-4l serves as a reference compound to evaluate the origin of unique and specific gas-sorption properties of MFU-4, reported previously. The latter framework features narrow-sized pores of 2.5 angstrom that allow passage of sufficiently small molecules only (such as hydrogen or water), whereas molecules with larger kinetic diameters (e.g., argon or nitrogen) are excluded from uptake. The crystal structure of MFU-4l has been solved ab initio by direct methods from 3D electron-diffraction data acquired from a single nanosized crystal through automated electron diffraction tomography (ADT) in combination with electron-beam precession. Independently, it has been solved using powder X-ray diffraction. Thermogravimetric analysis (TGA) and variable-temperature X-ray powder diffraction (XRPD) experiments carried out on MFU-4l indicate that it is stable up to 500 degrees C (N-2 atmosphere) and up to 350 degrees C in air. The framework adsorbs 4 wt % hydrogen at 20 bar and 77 K, which is twice the amount compared to MFU-4. The isosteric heat of adsorption starts for low surface coverage at 5 kJ mol(-1) and decreases to 3.5 kJ mol(-1) at higher H-2 uptake. In contrast, MFU-4 possesses a nearly constant isosteric heat of adsorption of ca. 7 kJ mol(-1) over a wide range of surface coverage. Moreover, MFU-4 exhibits a H-2 desorption maximum at 71 K, which is the highest temperature ever measured for hydrogen physisorbed on metal-organic frameworks (MOFs).
引用
收藏
页码:1837 / 1848
页数:12
相关论文
共 47 条
[1]   EXPO2009: structure solution by powder data in direct and reciprocal space [J].
Altomare, Angela ;
Camalli, Mercedes ;
Cuocci, Corrado ;
Giacovazzo, Carmelo ;
Moliterni, Anna ;
Rizzi, Rosanna .
JOURNAL OF APPLIED CRYSTALLOGRAPHY, 2009, 42 :1197-1202
[2]   Optimum conditions for adsorptive storage [J].
Bhatia, SK ;
Myers, AL .
LANGMUIR, 2006, 22 (04) :1688-1700
[3]   Homo- and Heteropentanuclear Coordination Compounds with Td Symmetry - the Solid State Structures of [MZn4(L)4(L′)6] (M = CoII or Zn; L = chloride or acac; L′=1,2,3-benzotriazolate) [J].
Biswas, Shyam ;
Tonigold, Markus ;
Volkmer, Dirk .
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE, 2008, 634 (14) :2532-2538
[4]   A cubic coordination framework constructed from benzobistriazolate ligands and zinc ions having selective gas sorption properties [J].
Biswas, Shyam ;
Grzywa, Maciej ;
Nayek, Hari Pada ;
Dehnen, Stefanie ;
Senkovska, Irena ;
Kaskel, Stefan ;
Volkmer, Dirk .
DALTON TRANSACTIONS, 2009, (33) :6487-6495
[5]   VAN DER WAALS VOLUMES + RADII [J].
BONDI, A .
JOURNAL OF PHYSICAL CHEMISTRY, 1964, 68 (03) :441-+
[6]   IL MILIONE:: a suite of computer programs for crystal structure solution of proteins [J].
Burla, Maria C. ;
Caliandro, Rocco ;
Camalli, Mercedes ;
Carrozzini, Benedetta ;
Cascarano, Giovanni L. ;
De Caro, Liberato ;
Giacovazzo, Carmelo ;
Polidori, Giampiero ;
Siliqi, Dritan ;
Spagna, Riccardo .
JOURNAL OF APPLIED CRYSTALLOGRAPHY, 2007, 40 :609-613
[7]   A new microporous MOF material based on Zn(II)-polycarboxylate coordination polymer synthesized with the aid of 1,6-diaminohexane as template [J].
Chandra, Debraj ;
Kasture, Mahesh W. ;
Bhaumik, Asim .
MICROPOROUS AND MESOPOROUS MATERIALS, 2008, 116 (1-3) :204-209
[8]  
Chichak K, 2002, EUR J INORG CHEM, P357
[9]  
Dinca M., 2008, Angew. Chem, V120, P6870, DOI DOI 10.1002/ANGE.200801163
[10]   Hydrogen storage in microporous metal-organic frameworks with exposed metal sites [J].
Dinca, Mircea ;
Long, Jeffrey R. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2008, 47 (36) :6766-6779