Design of Highly Connected Cd-Tetrazolate-Dicarboxylate

Sep 30, 2016 - Notably, SNNU-12 decorated with uncoordinated nitrogen sites shows not only high CO2 uptake capacity (87.9 cm3 g–1, 1 atm, and 273 K)...
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Design of Highly Connected Cd-Tetrazolate-Dicarboxylate Frameworks with Enhanced CO2/CH4 and C2 Hydrocarbons/CH4 Separation Performance Jian-Wei Zhang, Man-Cheng Hu,* Shu-Ni Li, Yu-Cheng Jiang, and Quan-Guo Zhai* Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi’an, Shaanxi 710062, P. R. China S Supporting Information *

ABSTRACT: Highly connected crystalline porous materials are rare but promising for gas adsorption and separation since varying pore shape and size as well as high framework stability may be achieved by tuning the framework connectivity. We demonstrate herein two highly connected frameworks, namely, {[Cd7(BDC)6(MTAZ)2(DMF)6]·3DMF}n (SNNU11) and {[Cd5(BDC) (PTAZ)8(DMF)2]·4DMF}n (SNNU-12) (BDC = 1,4-benzenedicarboxylic acid, MTAZ = 5-methyl-tetrazole, and PTAZ = 5(4-pyridyl)-tetrazole). In SNNU-11, BDC ligands link S-shaped [Cd7(MTAZ)2] motifs to form a novel 10-connected framework, which is related to but different from the reported 10-connected bct and gpu nets. Under the similar synthesis condition, the utilization of 5-(4-pyridyl)tetrazole produced SNNU-12, which is constructed from zigzag Cd5 clusters and exhibits a 12-connected fcu net. Notably, SNNU-12 decorated with uncoordinated nitrogen sites shows not only high CO2 uptake capacity (87.9 cm3 g−1, 1 atm, and 273 K) but also high CO2 over CH4 and C2 hydrocarbons over CH4 selectivity, which is among the highest values of highly connected MOF materials (connectivity ≥10) including famous UiO-66 and rare-earth fcu-MOFs under the same temperature and pressure.

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INTRODUCTION Methane has been widely utilized as an energy source and raw material. Compared to other conventional automobile fuels such as gasoline (petrol) and diesel, methane can be considered as a cleaner energy alternative due to its clean burning characteristics. In general, natural gas often contains impurities such as CO2, along with C2-hydrocarbons: C2H2, C2H4, and C2H6. Thus, the separation of methane from C2-hydrocarbons and CO2 is a very important industrial process.1−6 Traditionally, light hydrocarbon separations are performed by cryogenic distillation, which entails large energy costs. To compensate for the above deficiency, it is urgent to develop new microporous adsorbents as superior candidates because of its mild regeneration and energy- and cost-efficiency for separation of methane from CO2 and C2-hydrocarbons in a mild environment. A new class of designable porous materials, coordination polymers (PCPs) or metal organic frameworks (MOFs),7−17 have demonstrated significant promise for adsorption and separation because of their chemical tailorability, which results in high BET surface areas and specific recognition ability for components in the gas mixture.18−21 However, one of the limitations of most MOFs is their low chemical stability, which undoubtedly hampers their application in industry. To construct robust MOFs, the utilization of high-valence metals has become the focus of some recent research efforts. However, very few stable materials have been obtained up to now because © XXXX American Chemical Society

MOFs based on these metal ions of high valence are difficult to crystallize although 12-connected UiO-66 and related MOFs have been well developed. These led us to consider the highly connected MOFs on the base of 3d metals as an option for the preparation of robust MOFs. Usually, metal clusters act as the highly connected nodes, and multidentate carboxylate ligands are employed to connect them to form highly connected networks.22−24 Much effort has been devoted to the creation of such solids based on polynuclear metal clusters, which contribute a lot of novel topological structures.25−27 However, it is still a great challenge to create the frameworks of highly connected MOFs. As an extension of our successful construction of metal-carboxylate-polyazolate pillar-layered frameworks and nanoscopic polyhedral cages, we speculate that the combinations of dicarboxylate ligands and polyazolate derivatives should be an effective way for functional highly connected MOFs. The reasons are listed as follows: (1) polyazolate derivatives tend to form polynuclear clusters through three or four aromatic nitrogen electron-donating atoms;28−37 (2) dicarboxyl groups manifest various bonding modes and its phenyl ring provides structural rigidity to extend the structure to highly connected network;38−44 (3) the pore surface of MOFs can be decorated by the bare nitrogen atoms, Received: July 24, 2016 Revised: September 29, 2016

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DOI: 10.1021/acs.cgd.6b01097 Cryst. Growth Des. XXXX, XXX, XXX−XXX

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which provide potential adsorption sites to improve gas adsorption and selective properties of MOFs. As a result, we report herein the synthesis and characterization of two novel highly connected Cd-tetrazolate-dicarboxylate frameworks, namely, {[Cd7(BDC)6(MTAZ)2(DMF)6]· 3DMF}n (SNNU-11) and {[Cd5(BDC) (PTAZ)8(DMF)2]· 4DMF}n (SNNU-12) (BDC = 1,4-benzenedicarboxylic acid, MTAZ = 5-methyl-tetrazole and PTAZ = 5-(4-pyridyl)tetrazole) SNNU = Shaanxi Normal University. [Cd7(TAZ)2] and [Cd5(TAZ)8] polynuclear clusters are connected by dicarboxylate ligands to give the 10- and 12-connected frameworks for SNNU-11 and -12, respectively. These two highly connected MOFs demonstrate both high stability and permanent porosity. Specifically, SNNU-12 shows remarkable CO2 uptake capacity and high separation of CH4 from CO2, C2H2, and C2H4, which outperforms most similar highly connected MOF materials.

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q = qm ×

b × p1/ n 1 + b × p1/ n

(1)

where p is the pressure of the bulk gas at equilibrium with the adsorbed phase (kPa), q is the adsorbed amount per mass of adsorbent (mmol g−1), qm is the saturation capacities of site (mmol g−1), b is the affinity coefficients of site (1/kPa), and n represent the deviations from an ideal homogeneous surface. Table S3 presents the fitting parameters of LF equation as well as the correlation coefficients (R2). Based on the above equation parameters of pure gas adsorption, we used the IAST model to investigate the separation of CO2/CH4, C2H2/CH4, and C2H4/CH4 in compound SNNU-12, the adsorption selectivity is defined by sA/B =

xA /yA x B/yB

(2)

where xi and yi are the mole fractions of component i (i = A and B) in the adsorbed and bulk phases, respectively. Note that in the Henry regime SA/B is identical to the ratio of the Henry constants of the two species.

EXPERIMENTAL SECTION

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Materials and Methods. All chemicals were obtained from commercial sources and used without further purification. Thermogravimetric analyses (TGA) were carried out on a NETSCHZ STA449C thermal analyzer at a ramp rate of 5 °C min−1 in nitrogen and air atmosphere for SNNU-11 and -12, respectively. Powder X-ray diffraction (PXRD) studies were carried out with a Japan Rigaku D/ Max2550VB+/PC diffractometer equipped with Cu Kα radiation (λ = 1.5406 Å). Synthesis. {[Cd7(BDC)6(MTAZ)2(DMF)6]·3DMF}n (SNNU-11). A mixture of Cd(NO3)2·4H2O (0.062 g, 0.2 mmol), H2BDC (0.033 g, 0.2 mmol), MTAZ (0.017 g, 0.4 mmol), and 6 mL DMF/1,4-dioxane (v/v = 2:1) in a 20 mL vial, while stirring at room temperature. After a few minutes, the mixed solution was sealed, heated at 100 °C for 6 days and then slowly cooled to room temperature. Light yellow blockshaped crystals of as-synthesized 1 were collected in 45% yield based on Cd(II). The phase purity of compound was checked by powder Xray diffraction (Figure S1). {[Cd5(BDC) (PTAZ)8(DMF)2]·4DMF}n (SNNU-12). A mixture of Cd(NO3)2·4H2O 0.062 g (0.2 mmol), H2BDC 0.033 g (0.2 mmol), PTAZ 0.06 g (0.4 mmol), and 6 mL DMF in a 20 mL vial, while stirring at room temperature. After a few minutes, the mixed solution was sealed, heated at 100 °C for 5 days and then slowly cooled to room temperature. Colorless block-shaped crystals of as-synthesized 2 were collected in 37% yield based on Cd(II). The phase purity of compound was checked by powder X-ray diffraction (Figure S1). X-ray Crystallographic Determination. Single crystal X-ray data collection for coordination compounds was performed on a Gemini E diffractometer equipped with a graphite-monochromated Mo Kα radiation (λ = 0.71075 Å). Intensity data for all compounds were collected at 296 K. All structures were solved by direct methods using the SHELXS-97 program and refined by the SHELXL-97 program.45−47 All non-hydrogen atoms were refined anisotropically by the full-matrix least-squares method. The C−H and O−H hydrogen atoms were also found and refined. The detailed crystallographic data and the structure refinement parameters of compounds are summarized in Table S1. Selected bond lengths are given in Table S2. Gas Adsorption and Selectivity Prediction for Binary Mixture Adsorption. Gas sorption isotherms were measured on a Micromeritics ASAP 2020 HD88 surface-area and pore-size analyzer up to 1 atm of gas pressure by the static volumetric method. All gases used were of 99.99% purity. The gas sorption isotherms for N2 and H2 were measured at 77 K. The gas sorption isotherms for CO2, CH4, C2H2, and C2H4 were measured at 273 and 298 K, respectively. To perform the integrations required by Ideal Adsorbed Solution Theory (IAST),48,49 the single-component isotherms should be fitted by a proper model. Several isotherm models were tested to fit the experimental pure isotherms for CO2, C2H2, and C2H4 and CH4 of SNNU-12, and the Langmuir−Freundlich (LF) equation were found to the best fit to the experimental data

RESULTS AND DISCUSSION Crystal Structures. Single crystal X-ray analysis reveals that SNNU-11 crystallizes in the monoclinic space group C2/c and has a 10-connected 3D framework constructed from S-shaped heptanuclear clusters linking through BDC ligands. The asymmetric unit consists three and half crystallographically independent Cd(II), one MTAZ, three BDC ligands, three coordinated DMF, and three entrapped DMF molecules (Figure S2). The Cd1 and Cd3 atoms display similar sevencoordinated distorted-pentagonal bipyramidal geometry, which is bound to six O atoms from four BDC ligands and one N atom from MTAZ ligand. The Cd2 and Cd4 atoms display sixcoordinated octahedral geometry. Cd2 is surrounded by two N atoms from MTAZ ligand, and four O atoms from four BDC ligands. However, Cd4 is bound to one N atom from MTAZ ligands and one O atom from BDC ligands and three DMF molecules. The bond distances range from 2.20 to 2.47 Å and 2.26 to 2.40 Å for Cd−O and Cd−N, respectively. As we speculated above, two MTAZ ligands link seven Cd atoms through eight N sites, and thus produces an S-shaped [Cd7(MTAZ)2] heptanuclear cationic cluster with Cd4 as the center of symmetry. The Cd···Cd separations are of about 3.8 Å. Each heptanuclear cluster is further surrounded by 12 carboxylate groups from 12 BDC linkers to complete the distorted-pentagonal bipyramidal or octahedral geometries of seven Cd centers. Then, the neutral [Cd7(MTAZ)2(COO)12] building blocks are connected by BDC phenyl groups to generate the 3D porous framework of SNNU-11 (Figure S2). Overall, each heptanuclear motif connects 10 adjacent ones through 12 BDC ligands as depicted in Figure 1. From the topological view, the [Cd7(MTAZ)2(COO)12] building blocks can be regarded as 10-connected nodes, and BDC ligands can be simplified as linkers; thus, the whole network can be simplified to a uninodal 10-connected net with the short Schläfli symbol of 312.424.58.6 (Figure 2). Under similar synthesis conditions, the utilization of 5-(4pyridyl)-tetrazole instead of 5-methyl-tetrazole produced the other highly connected MOF, SNNU-12, which is constructed from zigzag Cd5 clusters and exhibits a fcu net. SNNU-12 crystallizes in the monoclinic space group P2(1)/n. As illustrated in Figure S3 the asymmetric unit contains two and a half crystallographically independent Cd(II) cations, half BDC anion, four PTAZ ligands, one coordinated DMF, and B

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but μN1,N2 and μN1,N2,N3, and the Cd···Cd separations are about 4.1 Å. Furthermore, six pyridine groups from another six PTAZ and two carboxylate groups from different BDC ligands help to complete the octahedral sphere of five Cd centers. Thus, each pentanuclear motif is surrounding by 14 PTAZ and two BDC ligands, of which, two PTAZ act as terminal ligands. Overall, each Cd5 building blocks connects 12 adjacent ones as depicted in Figure 1 to generate the 3D porous framework of SNNU-12. The pentanuclear cluster can be simplified as a 12-connected nodes, thus the whole network can be extended to a uninodal fcu net with the short Schläfli symbol of 324.436.56 (Figure 2). To the best of our knowledge, only two uninodal 10connected nets (bct23 and gpu24) had been reported to date. It is interesting that these two frameworks are both constructed from polyazolate and dicarboxylate mixed ligands. The Schläfli symbols are of 312.428.55 for bct and 312.426.57 for gpu, respectively (Figure 2). Clearly, SNNU-11 possesses an unprecedented topology and appears to be close to the two reported 10-connected nets. In fact, the gross topologies of these three 10-connected nets are quite similar and their Schläfli symbols indicate that only some of the rings formed at each node differ in size. The topological relationship between SNNU-11, bct, gpu, and well-known 12-connected fcu net for SNNU-12 is schematically illustrated in Figure 2. Due to the complex nature of visualizing high-connectivity nets, they are most easily described in terms of interconnected simpler subnets. All of these nets can be described in terms of 36 sheets, which are bridged by different modes to give different stacking patterns. This may provide a new insight for targeting new highly connected frameworks through interconnected simpler subnets. Gas Adsorption. PLATON calculations show that the guest-accessible volumes of highly connected MOFs SNNU-11 and -12 are 23.6% and 37.3%, respectively. Thermogravimetric analyses (TGA) shows that the framework of as-synthesized samples starts to collapse at above 300 °C for both compounds. Such porosity and thermal stability render them suitable candidates for gas sorption applications (Figure S4). To activate these two MOF materials, as-synthesized SNNU11 and -12 were subjected to solvent exchange by soaking in fresh acetone for over 1 week. After the removal of acetone by decanting, the sample was air-dried and loaded into the sample tube of the sorption instrument. Then the samples were degassed at 60 °C for SNNU-11 and 100 °C for SNNU-12. As shown in Figure S5, the N2 and H2 adsorption for SNNU11 at 77 K is neglectable. One possible reason is that three terminal coordinated DMF molecules around each Cd3 centers block the pores. However, for SNNU-12, the N2 sorption isotherms at 77 K indicate typical type I sorption behavior, characteristic of microporous materials with a saturated sorption amount of N2 of 190.5 cm3/g (8.5 mmol/g). The BET and Langmuir surface areas and pore volume are 519.5 and 815.1 m2/g, and 0.28 cm3 g−1, respectively. Notably, the pore width of SNNU-12 is about 4.9 Å by Horvath−Kawazoe (H−K) method, suggesting that this framework may a suitable candidate for small molecular gas uptake and separations. Therefore, the sorption behaviors of SNNU-12 toward H2, CO2, C2H2, C2H4, and CH4 were further investigated. The H2 sorption isotherms for SNNU-12 were given in Figure 3b. The uptake of H2 is 155.4 cm3 g−1 (1.38 wt %) at 1 atm and 77 K, which surpasses the values of most highly connected MOFs (connectivity ≥10) and a lot of famous MOF materials such as MOF-5 and MOF-177 under the same

Figure 1. S-Shaped heptanuclear and zigzag pentanuclear building blocks, and corresponding 10- and 12-connected frameworks of SNNU-11 (left) and -12 (right).

Figure 2. Illustration for three types of 10-connected uninodal nets and 12-connected fcu net.

two lattice DMF molecules. All Cd atoms display sixcoordinated octahedral geometry, whereas there are three different environments. The Cd1 is bound to one O atom from BDC ligand and five N atoms from five PTAZ ligands. The Cd2 is bound to six N atoms from six PTAZ ligands. The Cd3 is bound to four N atoms from four PTAZ ligands and two O atoms from one carboxylate oxygen atom and DMF molecule. The bond distances are ranging from 2.22 to 2.39 Å and 2.30 to 2.49 Å for Cd−O and Cd−N, respectively (Figure S3). Eight tetrazole groups from PTAZ ligands connect five cadmium atoms to give a zigzag [Cd5(TAZ)8] pentanuclear cluster with Cd2 as the center of symmetry. However, the bridging mode of tetrazole is not μN1,N2,N3,N4 as in SNNU-11, C

DOI: 10.1021/acs.cgd.6b01097 Cryst. Growth Des. XXXX, XXX, XXX−XXX

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Figure 3. Adsorption isotherms of N2 (a) and H2 (b) at 77 K, CO2 (c), C2H2 (d), C2H4 (d), and CH4 (d) for SNNU-12.

CH4, C2H2−CH4, and C2H4−CH4 binary mixture selectivity, an ideal adsorbed solution theory (IAST) calculation based on a Langmuir−Freundlich simulation was employed on the basis of the single-component CO 2 , C 2 H 2 , C 2 H 4 , and CH 4 adsorption isotherms. Figures 4b shows the adsorption selectivity of MOFs SNNU-12 for CO2 (50%) and CH4 (50%) at 273 K. The initial CO2/CH4 selectivity values are estimated to be 15.5, which is much higher than the reported values for many MOF materials.65−68 Figure 4d shows the predicted mixture adsorption selectivity of SNNU-12 for C2H2/ CH4 (50:50), and C2H4/CH4 (50:50) at 273 K. The initial C2H2/CH4 and C2H4/CH4 selectivity values are estimated to be 92.3 and 79.4. At 273 K and 1 bar, the selectivities increase to 35.5, 394.1, and 227.2 for the CO2/CH4, C2H2/CH4, and C2H4/CH4, respectively. These values are considered very high selectivity among the limited MOFs investigated so far for separations of the C2 hydrocarbons (C2H2, C2H4, or C2H6) over CH4.25−27 Overall, the tunable CO2 and C2 hydrocarbon selectivity over CH4 for SNNU-12 could be due to the synergistic effect of bare pyridine and tetrazole N Lewis base sites, narrow cross pores, and open metal sites. Importantly, the 12-connectivity of SNNU-12 enforces the chemical stability of this cadmium-tetrazolate-dicarboxylate framework, which is favorable for their potential application in separation of CO2 and C2 hydrocarbons from CH4.

conditions.50 The low-pressure CO2 adsorption−desorption isotherms were measured at 273 and 298 K for SNNU-12. As shown in Figure 3, at 1 atm, the CO2 uptakes are 3.92 mmol/g (87.9 cm3 g−1, 273 K) and 2.83 mmol/g (63.4 cm3 g−1, 298 K). To the best of our knowledge, the CO2 uptake of SNNU-12 is among the highest values of reported 12-connected MOFs including famous UiO-66 and rare-earth fcu-MOFs under the same temperature and pressure.51−56 Moreover, C2H2 and C2H4 gas are selected in this work to evaluate the C2 hydrocarbons over CH4 separation ability of SNNU-12. At 273 K and 1 atm, the C2H2 and C2H4 uptakes are 98.7 and 84.0 cm3 g−1. At 298 K and 1 atm, the values are 72.0 and 71.8 cm3 g−1. The CH4 uptake capacities of SNNU-12 are 1.46 mmol/g (32.7 cm3 g−1) at 273 K and 1 atm. To further understand the adsorption properties of SNNU12, the isosteric heat of adsorption (Qst) was studied at 273 and 298 K by the virial model.57 At zero coverage, the Qst for CH4 is about 2.9 kJ mol−1, whereas the Qst for C2H2, C2H4, and CO2 are 41.1, 22.8, and 21.3 kJ/mol (Figures 4a and S6−S9). The higher adsorption heats for C2 hydrocarbons and CO2 might be mainly due to the existence of a large number of uncoordinated pyridine and tetrazole N sites around each pentanuclear cluster. Moreover, the comparable pore sizes and open metal sites in SNNU-12 further enforce the interactions between the host framework and C2 hydrocarbons or CO2 molecules.58−64 CO2/CH4 and C2 Hydrocarbons/CH4 Selectivity. The previously mentioned isothermal adsorption results indicate that SNNU-12 can selectively adsorb CO2 and C2 hydrocarbons (C2H2 and C2H4) over CH4. In order to predict CO2−

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CONCLUSIONS In summary, two novel robust highly connected porous metal− organic frameworks have been successfully synthesized by D

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Figure 4. Isosteric heats of adsorption (Qst) for C2H2, C2H4, CO2, and CH4 (a) and selectivity predicted by IAST of SNNU-12 at 273 K (b−d).

Accession Codes

utilization of the dicarboxylate and tetrazolate mixed ligands. As expected, Cd2+ ions are bridged by tetrazole groups to form Sshaped heptanuclear and zigzag pentanuclear clusters, which act as 10- or 12-connected building blocks to generate two 3D microporous frameworks. Specifically, the narrow cross pores together with the uncoordinated pyridine or tetrazole N Lewis base sites in SNNU-12 effectively tune the CO2 and C2 hydrocarbons uptakes and reduce the affinity with CH4, which demonstrate the potential of the highly connected MOFs to be promising candidate materials for separation from natural gas and fuel gas. The synthesis strategy demonstrated herein by combination of the polycarboxylate and polyazolate ligand system may be a promising strategy for not only the development of robust highly connected MOFs but also the enhancement of gas adsorption capacity and separation performance of MOFs.

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CCDC 1052721−1052722 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. *E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work is financially supported by the National Natural Science Foundation of China (21671126 and 21271123), the Natural Science Foundation of Shaanxi Province (2014KJXX50), and the Innovation Funds of Graduate Programs of Shaanxi Normal University (SNNU. No. 2015CXB012).

ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.cgd.6b01097. Powder X-ray diffraction patterns, TGA curves, gas adsorption isotherms, additional crystal structure figures, crystallographic table, and CIF files for SNNU-11 and -12 (PDF)

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DOI: 10.1021/acs.cgd.6b01097 Cryst. Growth Des. XXXX, XXX, XXX−XXX