Nanocage-Based Porous MetalâOrganic Frameworks Constructed

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Nanocage-based porous MOFs constructed from icosahedrons and tetrahedrons for selective gas adsorption Da-Shuai Zhang, Yong-Zheng Zhang, Xiuling Zhang, Fei Wang, Jian Zhang, Hui Hu, Jun Gao, Hui Yan, Hui-Ling Liu, Huiyan Ma, Longlong Geng, and Yunwu Li ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.9b05655 • Publication Date (Web): 14 May 2019 Downloaded from http://pubs.acs.org on May 16, 2019

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ACS Applied Materials & Interfaces

Nanocage-Based Porous MOFs Constructed from Icosahedrons and Tetrahedrons for Selective Gas Adsorption Da-Shuai Zhang,a Yong-Zheng Zhang,a Xiuling Zhang,*a,c Fei Wang,e Jian Zhange, Hui Hu,a Jun Gao,d Hui Yan,b Hui-Ling Liu,a,c Hui-Yan Ma,b Long-Long Genga and Yun-Wu Li*b a

College of Chemistry and Chemical Engineering, Dezhou University, Dezhou, 253023, P. R.

China. E-mail: [email protected]. b

Shandong Provincial Key Laboratory / Collaborative Innovation Center of Chemical Energy

Storage and Novel Cell Technology, and School of Chemistry and Chemical Engineering Liaocheng University, Liaocheng, 252000, P. R. China. E-mail: [email protected] c

College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao,

266000, P. R. China. d

College of College of Chemical and Environmental Engineering, Shandong University of

Science and Technology, Qingdao, 266590, P. R. China

e

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of

Matter, Chinese Academy of Sciences, Fuzhou, P. R. China.

ACS Paragon Plus Environment

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KEYWORDS：Cage-based metal-organic framework; selective gas adsorption; carbon dioxide capture; polyhedron cages

ABSTRACT: Two isostructural nanocage-based porous Ni/Co(II)-MOFs have been hydrothermally synthesized, which were interestingly composed of icosahedron and tetrahedron cages with a new (3,8)-connected 3D topology. Moreover, the stable NiMOF exhibits good selective CO2/CH4 and CO2/N2 adsorption owing to its exposed nitrogen active sites.


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Porous metal-organic frameworks (MOFs) are a new class of hybrid crystalline materials, which are built from metal ions or metal clusters and organic linking ligands through self-assembly. Compared with traditional inorganic porous materials, such as zeolites, MOFs often possess larger specific surface areas and higher porosity, especially adjustable pores (shapes and size) and variable functional groups by selecting targeted organic ligands. Therefore, MOFs could be endowed with plenty of topological structures with various applications by tuning different types of metal centers (various coordination modes) and organic linkers (various symmetries).1 Among them, one special kind is cage-based MOFs, which have caused great attention over the past decades, due to their special cavity structures and potential applications in many research areas such as storage,2-4 separation,5,6 sensing,7-9 drug delivery,10-11 catalysis12,13 and so on. Besides these perspectives, our particular interest lies in the construction of functional cage-based MOFs towards gas storage and separation. Compared with MOFs bearing open channels, cage-based MOFs offer several attractive features: i) the unique pore structures possessing large cavities with controllable sizes could benefit the interactions between the host frameworks and guest


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molecules; ii) the cages bearing small windows and closed faces could enhance the sieve effect for size-based separation;14 iii) additionally, pore walls of these polyhedron cages could also be decorated by the introduction of uncoordinated functional groups like –NH2 or –CH3,15,16 further enhancing the interaction between the cavities and certain adsorbed molecules. Therefore, cage-based MOFs often exhibit unique adsorption and separation properties.

To construct cage-based MOFs with desired properties, one classic design strategy is combining angular organic linkers with inorganic secondary building units (SBUs), such as the paddlewheel {Cu(II)2} clusters with isophthalate units. Usually, the cagestructures derived from this method mainly include polyhedral types like tetrahedron,17 cube,18 octahedron and dodecahedron.19-21 On the other hand, it has been proved in our previous works and others that using mixed ligands strategy might be another effective way to synthesize unique cage-based MOFs, which importantly could not only enrich the structure topologies but endow MOFs with more property features.22,23 For example, several wonderful kinds of cage-based MOFs with special pores (cage-in-cage


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structure,24 multi-polyhedron based structure25 and pore space partition,26,27 etc.) and excellent gas adsorption properties have been reported by combining 2,4,6-tri(4pyridinyl)-1,3,5-triazine (tpt) and different kinds of benzene polycarboxylic acids ligands. These studies prove that the selection of proper mixed ligands is a key factor. Recently, the ligands containing multidentate O and/or N donors, especially, including both carboxyl and N-rich groups, have been frequently used in the construction of diverse MOFs.28-33 Since this kind of ligands can not only provide abundant coordination modes but also act as guest binding sites inside the resulting frameworks, it is quite interesting for the construction of cage-based MOFs with such ligands. Based on the above considerations, the ligands containing angular dicarboxylic groups and functional azole groups must be a good choice to achieve this purpose.

With

this

in

mind,

a

three-connection

ligand

4,4'-((H-1,2,4-triazol-1-

yl)methylene)dibenzoic acid (H2tmdb) has been selected as main ligand to construct cage-based MOFs towards gas storage and separation. In this ligand, it both contains two angular dicarboxylic groups and one N-rich triazole group (Scheme S1, Supporting


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Information (SI)). Notably, the N-donors in the triazole group can not only act as coordination nodes, but also, importantly, provide optimal N active sites for benefiting enhanced functionality. Furthermore, previous study reveals that i) H2tmdb presents a trigonal pyramidal configuration rather than a planar triangle structure; ii) the flexible carboxyphenyl and rigid triazolyl groups could provide more flexibility and diverse coordination modes for satisfying the geometric requirement of metal centers.34-36 All these features indicate that H2tmdb should be a good candidate for the construction of new type cage-based MOFs with unique performances.

Herein, we report two isostructural cage-based Ni/Co(II) MOFs, namely {[Co2(tmdb)2(4,4'-bpy)(H2O)]·solvents}n (YZ-5; here YZ = Yong-Zheng Zhang) and {[Ni2(tmdb)2(4,4'-bpy)(H2O)]·solvents}n (YZ-6), synthesized by using H2tmdb and 4,4'bipyridine (4,4'-bpy) mixture ligands under solvothermal conditions. Interestingly, the frameworks are composed of two kinds of cages, icosahedrons and tetrahedrons, to generate a new (3,8)-connected 3D topology, which is very uncommon as we know. More importantly, the exposed uncoordinated nitrogen atoms of triazole groups could


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afford effective active sites that can increase the CO2-framework interaction to facilitate the adsorption selectivity. Thus, as expected, the stable YZ-6 shows a remarkable CO2 uptake and good CO2/CH4 and CO2/N2 selectivities. Moreover, the Grand Canonical Monte Carlo (GCMC) simulations were also executed to provide a clear visualization on the preferential stronger interactions of CO2 with N active sites.

X-ray single-crystal analyses revealed that both YZ-5 and YZ-6 crystallize in the rhombohedral R-3c space group and show isostructure, so YZ-6 is selected for structure description. In YZ-6, there exists one crystallographically distinct Ni(II) ion, which is six-coordinated by four oxygen atoms from three tmdb2- ligands and one water molecule, two nitrogen atoms from one tmdb2- ligand and 4,4'-bpy into a distorted octahedral geometry (Figure S1a, SI). As shown in Figure S1b, two adjacent Ni(II) are bonded together by two carboxylates and one water molecule to form a binuclear {Ni2(COO)2(H2O)} cluster with the Ni···Ni distance being 3.5121 Å. The Ni–O bond distances are in the range of 2.0273(13) Å to 2.0814(9) Å. The Ni–N1 and Ni–N4#3 bond lengths are 2.0764(15) Å and 2.1171(14) Å, respectively. The bond angles


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between the donor atoms around the Ni(II) centres range from 85.74(6)° to 176.64(4)°. As for the tmdb2- ligand, it contains one monodentate carboxylate group, one bidentate carboxylate group in a µ2−O;O´ mode and one monodentate triazol group exposing another N as uncoordinated active site. Each {Ni2(COO)2(H2O)} cluster is connected to ten neighbouring clusters through six tmdb2- and two 4,4'-bipy ligands, further extending into a microporous 3D framework (Figure 1a) with 1D hexagonal channels (side length is ca. 2.97 Å) running along c axis. Considering the tmdb2- ligands and {Ni2(COO)2(H2O)} clusters as three and eight nodes respectively, the framework of YZ-6 could be simplified into a new (3,8)-connected topology with the Schläfli symbol of (42·5)2(44·59·610·73·82) (Figure S1e, SI). Remarkably, the free void volume of YZ-6 estimated by PLATON is 58.4% of the total volume (YZ-5 also is 58.4 %) when the solvent molecules are removed.


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Figure 1. (a) The 3D porous framework for YZ-6 with 1D hexagonal channels along the c axis. Formation of the tetrahedron (b) and icosahedron (c) cages inside the framework of YZ-6. (d) The packing modes for two kinds of cages in YZ-6. (Color codes for ball-and-stick model: C, gray; O, red; N, blue; Ni, green. H atoms are omitted for clarity)

Notably, it is very interesting to find that there exist two type of cages with narrow windows inside the framework. As shown in Figure 1c, twelve {Ni2(COO)2(H2O)} clusters are bridged and linked by twelve tmdb2- and six 4,4'-bipy ligands to form the first type of oblate icosahedron cage by considering six external edge tmdb2- ligands as twoconnection linkers. By excluding the van der Waals radius, the height of these cages is about ca. 10.0 Å (Figure S1f, SI) along c axis. Adjacent icosahedron cages along c axis are arranged in rows by sharing their top and bottom open faces, directly leading to the


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formation of the 1D channels of the framework (Figure S1g, SI). The icosahedron rows are further neighboured together through edge- and face-sharing, which result in the generation of the final 3D framework of YZ-6 (Figure 1d). Then, through the packing of the icosahedron cages, the second type of smaller tetrahedron cages (Figure 1b) which contain four {Ni2(COO)2(H2O)} clusters, two tmdb2- and one 4,4'-bipy ligands, are formed with two open faces. As we know, this unique framework both containing internal icosahedron and tetrahedron cavities has not been reported before, although some icosahedron metal clusters based MOFs were reported by other groups.37-40 Moreover, the triazolate μ2 N-donors (N3) are uncoordinated and exposed on the internal surface of the cages which can offer active function sites for property studies. In order to evaluate the permanent porosity of the two compounds, N2 adsorption experiments were performed at 77 K. The adsorption experiment result of YZ-5a shows no adsorption performance for N2, indicating the low porosity of YZ-5a. Further studies reveal that the framework of YZ-5a collapsed after activated, as confirmed by the PXRD patterns (Figure S3a, SI). However, YZ-6a still maintains its framework after gas adsorption measurements (Figure S3b, SI). The higher stability of the framework for YZ-


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6a than that of YZ-5a agrees with the Irving–Williams order (complex stability: Ni2+ > Co2+).41 The uptake amount of N2 is 486.4 cm3g-1 (STP), and it shows a reversible type I isotherm (Figure 2a), suggesting the microporosity of YZ-6a. The H-K (HorvathKawazoe) pore diameter distribution (Figure 2a insert) is mainly around 6.0 Å (range from ca. 4.0 to 10.0 Å) corresponding to the pore sizes from single-crystal X-ray diffraction. In addition, based on the N2 adsorption isotherm, the Brunauer-EmmettTeller (BET) and Langmuir surface area of guest-free framework are estimated to be 1598 and 2048 m2g-1, respectively, and the pore volume is 0.535 cm3g-1. H2 adsorption isotherms were also measured at 77 K and 87 K, respectively, in order to explore the hydrogen adsorption capacity of YZ-6a. As shown in Figure 2b, YZ-6a can adsorb a considerable amount of H2, that is 238.6 cm3g-1 (2.13 wt%) at 77 K and 1 atm, with a Qst value of 8.3-5.3 kJ mol-1 depending on the degree of H2 loading. The result is comparable to many reported MOFs (Figure S5 and Table S3, SI).


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Figure 2. Gas adsorption isotherms for YZ-6a: (a) N2 at 77 K; Inset: pore size distribution plots. (b) H2 at 77 K and 87 K.

The permanent porosity and the unique cage structure of YZ-6a encouraged us to further study the CO2 capture ability. Firstly, at 195 K, the amounts of adsorbed CO2 increase abruptly at the beginning and reach to 480 cm3g-1 (STP) (94.3 wt%) at 1 atm, approximately 355 CO2 molecules adsorbed per cell volume. Moreover, the isotherm presents typical type I curves with obvious hysteresis on desorption (Figure 3a), which might be attributed to the enhanced interactions between the significant quadrupole moment of CO2 molecules and active sites, the unique arrangement of the cages and narrow windows compared to the critical dimensions of a CO2 molecules.42 Subsequently, CO2 adsorption experiments at 273 K and 298 K were performed to


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evaluate the potential application of YZ-6a in CO2 selective adsorption. As shown in Figure 3b,c, YZ-6a has a maximum CO2 uptake of 112.2 cm3g-1 at 273 K and 45.3 cm3g-1 at 298 K, and the Qst value is calculated ranging from 33.3-27.8 kJ mol-1 (Figure S6b, SI). Furthermore, the adsorption isotherms of CH4 and N2 for YZ-6a at 273 K and 298 K were experimentally measured, respectively. As can be seen from Figure 3b,c, the amount of CH4 uptake at 273 K and 298 K (P = 760 torr) are 35.9 cm3g-1 and 8.8 cm3g-1, respectively, and the amounts of N2 uptake at the same temperatures are only 16.6 cm3g-1 and 0.76 cm3g-1, in spite of that the channel size of YZ-6a is larger than the kinetic diameter of N2 (3.64 Å). Obviously, YZ-6a exhibits distinct selective adsorption of CO2 over CH4 and N2 from the above data.


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Figure 3. Gas adsorption isotherms for YZ-6a: (a) CO2 at 195 K. (b) CO2, CH4 and N2 at 273 K. (c) CO2, CH4 and N2 at 298 K. (d) The IAST adsorption selectivities of CO2/CH4 and CO2/N2 at 273 K and 298 K.

In order to clearly show the adsorption selectivities, the initial slopes of the adsorption isotherms were firstly calculated at very low pressure (Figure S7, SI).43 The calculated CO2/CH4 selectivity is 3.5 : 1 at 273 K and 5.1 : 1 at 298 K. Using the same method, the CO2/N2 selectivity is calculated to be 8 : 1 at 273 K and 39.4 : 1 at 298 K,


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respectively. Then, the popular ideal adsorbed solution theory (IAST) method is also executed for further investigating its selectivity of CO2 towards CH4 and N2.44 As shown in Figure 3d, CO2/CH4 selectivities at 273 K and 298 K both show a declining trend with the value of 3.7 (273 K) and 5.6 (298 K) at 1 atm, respectively. As for the CO2/N2, the selectivity at 273 K declines from a high value to 10.4 in the range of 0−1 atm. However, at 298 K, the selectivity increases from 47.9 to 51.4 at the pressure of 0.64−1 atm, in spite of the decreasing trend before 0.64 atm. It should be noted that both the selectivities of CO2/CH4 and CO2/N2 increase along the temperature rises, especially for CO2/N2 selectivity which increases five-times when the temperature goes up from 273 k to 298 K. The selectivity for CO2 over N2 at 298 K is indeed comparable to some reported MOFs with excellent CO2/N2 separation efficiency (Table S4, SI), indicating the bright prospect of YZ-6a towards CO2 separation. The observed selective sorption behaviours of CO2 over CH4 and N2 may be attributed to the strong host-guest interaction between the CO2 and the uncoordinated N active sites on the cage surface of YZ-6a.


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In order to understand the CO2-framework interactions and the selectivity of CO2 adsorption for YZ-6a, the potential field slice for CO2 and the most preferential CO2 binding sites were simulated with GCMC using Materials Studio.45-48 As shown in Figure 4a, the most preferential adsorption region is showed in the field. As anticipated and experimental results, the highest potential values are located around the exposed uncoordinated N sites of triazole groups. This results are also confirmed by the most preferential binding sites as shown in Figure 4b. In YZ-6a, the CO2 molecules locate around the uncoordinated N atoms hanging on the internal walls of the pores (Figure 4b) (the short distances of O···N are 3.397 Å and 4.329 Å), indicating that there are stronger binding interactions for them than the other active sites. Thus, the good CO2 adsorption selectivity for YZ-6a should be attributed to the exposed uncoordinated N sites of triazole groups that provide enhanced CO2 binding sites. All these simulated results show good agreement with the experimental values.


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Figure 4. (a) Slice through the calculated potential field for CO2 in YZ-6a. (b) the most preferential CO2 binding site simulated with GCMC.

In conclusion, two novel isostructural nanocages-based porous Co(II)/Ni(II)-MOFs have been hydrothermally synthesized, and interestingly, internal of their frameworks contain two kinds of cages (icosahedrons and tetrahedrons) with a new (3,8)-connected 3D topology. Importantly, the stable Ni(II)-MOF exhibits good selective uptakes for CO2 over CH4 and N2, owing to the preferential stronger interactions between the CO2 and exposed uncoordinated N active sites as illustrated by GCMC simulation results. Moreover, the IAST calculation also provides insight into the potential applications of the Ni(II)-MOF in gas separation for CO2/CH4 and CO2/N2 binary mixtures.


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ASSOCIATED CONTENT

Supporting Information

Full experimental details, including Crystal data, Crystal structure, TGA curves, PXRD patterns, adsorption data.

AUTHOR INFORMATION

Corresponding Author

E-mail: [email protected] (X.-L. Zhang); [email protected] (Y.-W. Li)

ACKNOWLEDGEMENTS

This work was financially supported by the NNSF of China (Nos.: 21601028, 21371028 and 21771095), and the NSF of Shandong Province (Nos.: ZR2019QB026, ZR2018LB018, ZR2017JL013 and ZR2016BM26). REFERENCES (1) Zhou, H.-C.; Long, J. R.; Yaghi, O. M. Introduction to Metal–Organic Frameworks.

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