Mesoporous Hexanuclear Copper Cluster-Based MetalâOrganic

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Energy, Environmental, and Catalysis Applications

A Mesoporous Hexa-Nuclear Copper Cluster-Based MOF with Highly Selective Adsorption of Gas and Organic Dye Molecule Dongmei Wang, Jian Zhang, Guanghua Li, Yuan Jiaqi, Jiantang Li, Qisheng Huo, and Yunling Liu ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b06340 • Publication Date (Web): 27 Aug 2018 Downloaded from http://pubs.acs.org on August 27, 2018

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ACS Applied Materials & Interfaces

A Mesoporous Hexa-Nuclear Copper Cluster-Based MOF with Highly Selective Adsorption of Gas and Organic Dye Molecule Dongmei Wang,b Jian Zhang,a Guanghua Li,a Jiaqi Yuan,a Jiantang Li,a Qisheng Huoa and Yunling Liu*a a

State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of

Chemistry, Jilin University, Changchun 130012, P. R. China b

College of Chemistry and Life Sciences, Zhejiang Normal University, Jinhua

321004, P. R. China.

KEYWORDS: mesoporous metal-organic frameworks, cluster cooperative assembly strategy, hexa-nuclear Cu cluster, gas adsorption and separation, dye adsorption.

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ABSTRACT

Despite many advances in design and assembly of mesoporous metal-organic frameworks (meso-MOFs), it is still challenging to obtain the desired structure. Here, we utilized an effective cluster cooperative assembly strategy by introducing SO42ions as chelating binding sites to construct a novel mesoporous MOF, [Cu8(SO4)(TBA)6(OH)2(DMA)4]·12DMA·12CH3OH

(JLU-MOF51,

H2TBA

=

4-(1H-tetrazol-5-yl)-benzoic acid). Remarkably, the cooperative assembly of infrequent hexa-nuclear [Cu6SO4(OH)2] cluster and classical paddlewheel [Cu2(CO2)4] via linear hetero-N, O donor ligand results in an open three-dimensional framework which possesses 1D nanometer tube channels with the diameter of 24 Å and 28 Å. Fascinatingly, JLU-MOF51 displays exceptional large Langmuir surface area (5443 m2 g-1) and exhibits high capacity of selective adsorption of C3H8 (C3H8: 348 cm3 g-1 at 273K, C3H8/CH4 = 220 at 298K). In addition, JLU-MOF51 can selectively adsorb fluorescein disodium salt (FS) dye among numerous organic dyes. Extremely high surface area and unique structural characteristics make JLU-MOF51 a promising meso-MOF material for the adsorption and separation of hydrocarbon gases and organic dyes. Moreover, this strategy will provide an effective mean of constructing meso-MOFs via one-step synthesis.

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INTRODUCTION

Metal-organic frameworks (MOFs), as one of the most actively research fields in porous materials, have received great attention on account of their potential applications in catalysis,1-5 luminescence,6-8 drug delivery,9 sensing,10-11 and especially gas storage and separation.12-19 As an abundant and clean energy source, natural gas consists primarily of CH4 and a small quantity of other light hydrocarbons such as C2H6 and C3H8. The existence of impurities greatly decreases the utilization efficiency of CH4. Hence, it is significant to purify natural gas for more efficient utilization. Recently, MOFs have been regarded as a underlying candidate of solid sorbents for light hydrocarbon separation.20-23 Nevertheless, most MOF materials possess micropore structure, in which the narrow pores work against not only hosting large catalytic substrate and biomolecules, but also fast diffusion and transfer of large molecules, which results in the disappointing test performance of many MOFs in applications such as catalysis and drug delivery. Consequently, mesoporous-MOFs (meso-MOFs) may become the go-to options for industrial processes involving large molecules, thanks to their large pore volumes and ingenious cage constructions.24-29 However, only several meso-MOFs have been reported due to the lack of appropriate synthetic strategies.30 Besides complicated surfactant template method which was widely used for fabricating mesoporous silica and carbon materials,31-33 ligand extension synthetic strategy has been explored to synthesize meso-MOFs.34-35 Through prolonging the length of organic ligands can increase the pore size to form meso-MOFs, sometimes it also causes interpenetration of frameworks to yield 3



unstable products. Based on these synthetic strategy, a few successful examples have been reported in recent years, such as UMCM-1 and DUT-6,36-37 IRMOF-16,38 NU-100.39 However, more effective strategies to construct meso-MOFs with open framework and extra high surface area are still in demand.

Nowadays, cluster cooperative assembly, as a powerful strategy, has been employed to design and synthesize stable MOFs with high porosity.40-41 Taking this strategy into account, some MOF materials with multiple building units have been successfully prepared for gas capture and separation. For example, CPM-5 comprises of both single-metal building blocks [In(CO2)4] and trimeric clusters [In3O(CO2)6] with opposite charges in the structure, giving rise to an unique cage-within-cage framework with high CO2 uptake capacity.42 For the same purpose, our target products should contain multiple building units in the framework. Referring to our previous work,43-44 sulfates can chelate copper (II) centers to assemble tetra-nuclear and hexa-nuclear clusters which can further be cross-linked to generate a porous network. Hence, we choose copper (II) sulfate as a metal source in combination to form coordination networks owing to their multiple coordination modes. Accordingly, linear type tetrazolyl-carboxylates have been confirmed as suitable ligand to avoid interpenetration owing to their appropriate size and flexible coordination styles.

Herein, we introduce a successful example of applying the cluster cooperative assembly strategy to prepare a meso-MOF JLU-MOF51 with ternary building units, which include two inorganic SBUs: hexa-nuclear [Cu6O2(SO4)6] cluster and classical 4


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[Cu2(CO2)4] paddlewheel, and one linear organic SBU. Benefited from the coordinated diversity of sulfates and multidentate ligand, compound JLU-MOF51 exhibits unique coordination modes and possesses 1D nanometer tube channel in the framework, which is rarely reported for MOFs materials. Most notably, JLU-MOF51 exhibits extremely high porosity with Langmuir surface area of 5443 m2 g-1. Noticeably, through CO2, light hydrocarbon adsorption measurement, JLU-MOF51 was found to be a potential candidate for gas adsorption applications. Additionally, attributing to its large pore size, JLU-MOF51 showed selective adsorption performances on organic dye molecules.

EXPERIMENTAL SECTION

Materials and methods. All organic solvent and copper sulfate were purchased from commercial sources, and the ligand was obtained from Jinan Camolai Trading Company. Powder X-ray diffraction (PXRD) data were measured on a Rigaku D/max-2550 diffractometer with CuKα radiation (λ = 1.5418 Å). The data of elemental analyses (C, H, and N) were collected by vario MICRO (Elementar, Germany). In the atmosphere, under a heating rate of 10 °C min-1, the TGA data were recorded on a thermal gravimetric analyses (TGA) Q500 thermogravimetric analyser. Utilized SHIMADZU UV-2450 UV-visible spectrophotometer, the liquid state UV-vis spectra for the samples were measured. Synthesis of JLU-MOF51. CuSO4 5H2O (0.04 mmol, 10 mg), H2TBA (0.026 mmol, 5 mg), DMA (1 mL), MeOH (1 mL) were added to a 20 mL vial, and the reaction 5



mixture was heated to 65 oC for 48 h and cooled down, yielding blue crystals. Analysis for C124H218Cu8N40O46S: Found (wt%): C, 44.68; H, 5.28; N, 19.84. Calcd (wt%): C, 44.85; H, 5.33; N, 19.61. The consistency of the experimental and simulated PXRD patterns revealed the pure phase of the as-synthesized compound (Figure S8).

Single Crystal X-ray Crystallography. The single crystal X-ray diffraction measurement for JLU-MOF51 was performed on a Bruker Apex II CCD diffractometer using graphite-monochromated Mo-Kα (λ = 0.71073 Å) radiation. The structure was solved by direct method and refined by full-matrix least-squares on F2 using SHELXTL program.45 All non-hydrogen atoms were refined with anisotropic thermal parameters. Because there exist plenty of disordered solvent molecules in the channels, which could not be modeled, and they were processed with SQUEEZE routine. The results indicate that the checkcif showed an A-alert, which may be caused by the non-assignment of solvent molecules in the nano-pores. The final formula was obtained by combining crystallographic data with elements and thermogravimetric analysis data. The details of the crystallographic data for JLU-MOF51 are shown in Table S1. Crystallographic data of JLU-MOF51 (1587688) was provided by the Cambridge Crystallographic Data Centre. The topological information of JLU-MOF51 was obtained by TOPOS 4.0.46

Gas adsorption measurements. Before collected the gas adsorption data (N2, H2, CO2, CnH2n+2 (n = 1, 2, 3)) on a Micromeritics ASAP 2020, JLU-MOF51 was soaked in ethanol for a week, then heated under the vacuum to get the activated sample. It can 6


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be confirmed by the TGA data (Figure S9). The PXRD pattern of activated sample is the same as that simulated one, which further supported the sustained porosity (Fig. S8).

Dye Adsorption Measurement. Six dyes including positively charged Rhodamine B (RhB), electrically neutral Sudan III (SD III), and negatively charged Methyl Orange (MO), Fluorescein disodium salt (FS), Orange G (OG) and Acid Fuchsin (AF) (Table S4) were employed to assess the ability of JLUMOF51 for dyes selective adsorption. Under the condition of shaking and avoiding light, all the tests were executed in ethanol solvent. The adsorption measurements of dyes were carried out on a SHIMADZU UV-2450 spectrophotometer.

RESULTS AND DISCUSSION

Single-crystal X-ray diffraction analysis shows that JLU-MOF51 crystallizes in the trigonal crystal system and combined with R-3m space group (Table S1). The fascinating structure is constructed by multiple inorganic-organic SBUs with rich coordination modes. Besides the familiar paddlewheel SBUs, it is worth mentioning that the innovative and infrequent hexa-nuclear [Cu6O2(SO4)] cluster is also deployed to construct this meso-MOF, as represented in Fig. 1. The hexa-nuclear cluster is composed of one SO42- ions chelated by two tri-nuclear [Cu3O] sharing one O atom. Each of tri-nuclear cluster [Cu3O] linked by three ligands outspread to one paddlewheel and two hexa-nuclear clusters, and then the two tri-nuclear clusters are

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bridged by one SO42- ion and two ligands through four N atoms. In contrast, there is a gigantic difference between the structure of JLU-MOF51 and the reported tri-nuclear cluster [M3O],47 all of Cu atoms in the tri-nuclear cluster being five-coordinated in quadrangular

pyramids

instead

of

the

reported

six-coordinated

octahedral

configuration. Therein, the Cu1 atom is constructed to two N atoms and one N/O from three ligands and two O atoms from OH- and SO42- ions, respectively; the Cu2 atom is coordinated by one N/O atom from one ligand and three O atoms from OH- ions, SO42- ions, and DMA molecule, respectively; the Cu3 atom is coordinated by one N atoms and two N/O atom from three ligands and two O atoms from OH- and SO42ions, respectively. Additionally, the linear ligand also displays abundant coordination modes. With the first two kinds, the ligand linked paddlewheel through O atom and hexa-nuclear cluster through N(2,3) or N(7,8) atoms. The third kind is the ligand associated two hexa-nuclear clusters by N/O atoms (Figure S1).

Fig. 1 3D framework constructed by hexa-nuclear [Cu6O2(SO4)] cluster.

As a whole, the hexa-nuclear clusters are chelated by ligands to extend a 2D layer, which are further pillared by Cu2(TBA)4 SBUs to create a 3D network. The 8


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framework possesses 1D nanometer tube channels with the diameter of 24 Å and 28 Å, which rarely appears in the field of MOFs constructed of such small ligands. Simultaneously, the framework exists hierarchical pores with multiple sizes and shapes (Figure S2). In light of topological analysis, the ligand and the 4-connected paddlewheel can be regarded separately as a linear node and a square geometry, and the hexa-nuclear cluster connected by eight ligands but simplified as 7-connected node can be regarded as a polyhedral architecture. Therefore, the simplified (4, 7)-connected network of JLU-MOF51 belongs to a new topology with a Schlafli symbol of (32.42.52)(34.43.54.69.7) (Fig. 2, Figure S3-S5).

Fig. 2 Doubly-layer pillared by Cu2(TBA)4 SBUs further to outspread a 3D framework, and topological feature. 9



Specifically, the TBA2- ligands and hexa-nuclear clusters are connected each other to generate two types of hexagons: type A is formed by interlocking hexa-nuclear clusters through single- and double- connected ligands; type B represents the hexagon formed by viewing six hexa-nuclear clusters and six ligands as the vertices and edges (Figure S6). More interestingly, hexagons in the form of AA-stacking mode supported by six paddlewheels SBUs can generate the hexagonal prisms 1 (yellow); however, hexagons in the manner of AB-stacking mode fabricated by three paddlewheels SBUs assemble the other hexagonal prisms 2 (pink) (Fig. 3, Figure S7). It is undoubtedly worth noting that such a large pore 3D framework of JLU-MOF51 constructed by short linear linkers is rarely reported in the field of MOFs.

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Fig. 3 Schematic showing the new topology and the construction of hexagonal prisms observed in JLU-MOF51.

Thermal Stability Analysis

TGA of JLU-MOF51 was performed in the temperature range of 30-800 oC. The TGA curve of JLU-MOF51 displays a weight loss of nearly 50 % before 300 oC, indicating the release of guest molecules and terminal coordinated DMA molecules (calcd. 47.8 %) (Figure S9).

Gas Adsorption of JLU-MOF51

The total accessible volume of desolvated JLU-MOF51 is 80.4% calculated using PLATON. Due to its very low framework density (0.48 cm3 g-1) and high theoretical pore volume (1.68 cm3 g-1), JLU-MOF51 exhibits ultra-empty framework and even could be compared with IR-MOFs materials.48-49 In order to thoroughly investigate the permanent porosity and surface area of JLU-MOF51, the N2 adsorption experiments at 77 K were carried out (Fig. 4). The N2 adsorption of activated JLU-MOF51 reveals a reversible type-IV isotherm with a steep increase at P/P0 = 0.2 characteristic of mesoporous material. And, the Langmuir and BET surface areas of JLU-MOF51 are 5443 and 3317 m2 g-1, respectively, which is close to the milestone materials MIL-101(Cr) and MOF-177.47,

50

The pore size distribution

further suggests its mesoporosity. Compared with the reported materials with ultra-high surface area (Table S2).24 JLU-MOF51 constructed by small ligand 11



amazingly exhibits outstanding Langmuir surface area, and can even surpass many materials built by large ligands. Meanwhile, the low-pressure H2 uptake of JLU-MOF51 is also explored to be 177 (1.6 wt%) and 114 (1.0 wt%) cm3 g-1 at 77 and 87 K under 1 bar, which are quite analogous to PCN-66 material with excellent high BET surface (4000 m2 g-1) under the same conditions (Figure S10).49

Fig. 4 N2 sorption isotherms and the pore size distribution (DFT method) of JLU-MOF51.

Furthermore, on account of its high surface area and permanent porosity, the pure component adsorption isotherms of CO2, CH4, C2H6 and C3H8 for JLU-MOF51 were measured to investigate its application in small gas molecules adsorption and separation. As shown in Fig. 5, at 273 and 298 K (1 bar), the maximum adsorption for CO2 is 88 and 47 cm3 g-1, CH4 is 19 and 11 cm3 g-1, C2H6 is 107 and 61 cm3 g-1 and C3H8 is 348 and 173 cm3 g-1. It is noteworthy that the adsorption capacity of JLU-MOF51 for C3H8 has a great improvement compared with the previously 12


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reported work of our group43, 51-54 and the ultrahigh adsorption capacity is beyond that of most of other MOF materials (Table S3), such as FJI-C4.20 At zero loading, the Qst of CO2, CH4, C2H6 and C3H8 is 22, 15, 22 and 29 kJ mol-1, respectively, indicating the existence of strong interactions between the framework and the gas molecules (Figure S11-S14).

Fig. 5 The gas sorption isotherms of JLU-MOF51 under 1 bar: a) CO2; b) CH4; c) C2H6; d) C3H8.

Separation Behaviors of JLU-MOF51

To assess the actual separation ability of JLU-MOF51 for industrially light hydrocarbon, theoretical separation of C2H6/CH4 and C3H8/CH4 (50% and 50%) is 13



analysed by the ideal solution adsorbed theory (IAST) model by applying single-component adsorption isotherms. Adopting dual-site Langmuir-Freundlich equation for fiting (R2 > 0.999), the obtained fitting parameters are the basis for predicting multi-component adsorption (Table S4). At 298 K and 100 kPa, the selectivity of C2H6 and C3H8 over CH4 for JLU-MOF51 is 7.5 and 220 (Fig. 6). It is worthy of mention that the selectivity of JLU-MOF51 for C3H8/CH4 is far above UTSA-35a (80), and comparable to FJI-C4 (293).55, 20

Fig. 6 The selectivity of a) C2H6/CH4 and b) C3H8/CH4 for JLU-MOF51.

The Qualitative Selective Adsorption of Dye

The large surface area and mesoporous characteristic of JLU-MOF51 encourage us further to explore the potential application in the qualitative selective adsorption of dye pollutants. As few studies on the selective remove of the FS dye by MOFs absorbent materials were reported, we investigated the adsorption of FS by activated JLU-MOF51 in EtOH. 20 mg of JLU-MOF51 was soaked in EtOH solution of FS (3 mL, 20 ppm), and then the solution was detected by the UV-vis spectra at room temperature. As shown in Fig. 7a, the absorption intensity of FS declined rapidly with an increase in soaking time and FS dye was almost totally adsorbed just in 30 min, 14


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which exhibited the high-efficiency adsorption capacity of FS by JLU-MOF51. More exhilaratingly, this adsorption process of FS can even be easily perceived by the naked eye because of the conspicuous change in the color of the solution from fluorescent green to colourless. In order to prove JLU-MOF51 as the adsorbent material has the ability to selective remove FS, five other kinds of typical pollutant dye molecules with different charges were selected, including cationic RhB, neutral SD III, and anionic MO, OG, and AF. Procedures similar to previously described were used to investigate the adsorption capacity of FS by JLU-MOF51. As shown in Fig. 7b-f, JLU-MOF51 exhibits no evidence for the adsorption of cationic RhB, neutral SD III. Furthermore, anionic MO, OG, and AF with different charge and molecular structures were picked out for comparison. Surprisingly, JLU-MOF51 shows a certain adsorption uptake of AF, but negligible adsorption of MO and OG even over a prolonged time period of 150 min. The above results illustrate that JLU-MOF51 has potential for the discriminative removal of FS dye molecule.

In view of the above experimental results and related reports,56-60 we speculate that the selective adsorption mechanism of anionic dye FS involves the strong π-π interactions between the benzene rings of the framework and the FS dye. Furthermore, the high matching of geometry configuration (size and shape) of FS and channel may be another important reason for the increased adsorption capacity of JLU-MOF51.

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Fig.7 UV-vis spectra for JLU-MOF51 in different dye solutions a) FS (insets: the corresponding photographs), b) MO, c) SD III, d) RhB, e) OG and f) AF.

CONCLUSIONS

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In summary, based on cluster cooperative assembly strategy, a novel mesoporous MOF material JLU-MOF51 has been successfully synthesized. It is worth mentioning that the framework consists of ternary building units: an unprecedented hexa-nuclear cluster [Cu6(SO4)(OH)2], the classical paddlewheel [Cu2(CO2)4] and a linear hetero-N, O donor ligand H2TBA. Remarkably, JLU-MOF51 with ultra-empty framework displays high capacity of C3H8 adsorption, reaching 348 cm3 g-1 at 273 K and 1 atm. Furthermore, JLU-MOF51 has good performance in selective adsorption of C3H8 gas molecule and FS dye molecule. Based on the above characteristics, JLU-MOF51 has potential to be a candidate adsorbent material for natural gas purification, as well as selective adsorption of large-size organic dyes.

ASSOCIATED CONTENT

Supporting Information.

PXRD, TGA, additional structural figures, gas sorption data, dye molecules, crystallographic data. This material is available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION Corresponding Author * (Y. L.) Email: [email protected].

Notes The authors declare no competing financial interests. 17



ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China (Nos. 21771078, 21671074 and 21621001), the 111 Project (B17020), the National Key Research and Development Program of China (2016YFB0701100).

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Mesoporous Hexanuclear Copper Cluster-Based MetalâOrganic

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