Article pubs.acs.org/IC
Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX
A Lanthanum Carboxylate Framework with Exceptional Stability and Highly Selective Adsorption of Gas and Liquid Yun-Nan Gong,† Peng Xiong,† Chun-Ting He,‡ Ji-Hua Deng,† and Di-Chang Zhong*,† †
Key Laboratory of Jiangxi University for Functional Material Chemistry, College of Chemistry & Chemical Engineering, Gannan Normal University, Ganzhou 341000, People’s Republic of China ‡ MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, People’s Republic of China S Supporting Information *
ABSTRACT: The development of porous metal−organic frameworks that can retain structural integrity under harsh physical and chemical conditions is essential from the perspective of their use in adsorption, catalysis, and sensors. Herein, a lanthanum carboxylate framework was found to exhibit exceptional stability, not only robust in boiling aqueous solutions at pH 2− 12 and in boiling common organic solvents over 24 h but also stable upon ball milling for 1 h. Furthermore, this framework displayed highly selective separation for CO2 over N2 (Sads = 940), as well as size-dependent selective adsorption behavior of water and alcohols.
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INTRODUCTION Metal−organic frameworks (MOFs) have attracted tremendous attention for their intriguing structures and potential applications in gas adsorption/separation, catalysis, and sensing.1 The stability of MOFs is of special significance because many applications involve harsh conditions such as liquid water, high humidity, acidic and basic media, and even extreme temperatures and pressures.2 However, most of the reported MOFs are unstable due to their weak coordination bonds.3 In order to overcome the vulnerability of MOFs, one of the extensively explored methods is to construct highly connected metal clusters with high-valent metal ions and carboxylate groups. For example, zirconium carboxylate MOFs based on 8-connected, 12-connected Zr6 clusters and/or infinite Zr−O chains exhibit exceptional chemical and thermal stabilities.4 On the other hand, the development of effective technologies to capture and separate CO2 have attracted broad interest because the atmospheric CO2 concentration has increased significantly over the past decade.5 Traditionally, CO2 is chemically absorbed using aqueous amine solutions, but this technology has several limitations such as difficult recycling and corrosion to processing equipment.6 To overcome these drawbacks of the traditional method, physical adsorption based on molecular sieves, hybrid zeolite−polymer systems, porous organic materials, and MOFs has attracted widespread attention.7 In particular, MOFs have been extensively studied to capture and separate CO2 due to their easy synthesis and high porosity.8 Nevertheless, only a few MOFs show high CO2 selectivity over N2 at room temperature.9 The exploration of © XXXX American Chemical Society
stable MOFs that can selectively and efficiently eliminate CO2 remains a huge challenge. In this article, we report the chemical and mechanical stabilities as well as the selective adsorption for gas and vapor of a lanthanum carboxylate MOF, [La(TTCA)(H2O)]·DMF·H2O (1) (TTCA3− = triphenylene-2,6,10-tricarboxylate, DMF = N,N-dimethylformamide). We find that 1 not only exhibits high chemical stability in boiling aqueous solutions at pH 2−12 and in boiling common organic solvents for 24 h but also shows a high mechanical stability upon ball milling for 1 h. Gas and vapor sorption investigations demonstrated that 1 shows exceptional CO2 selectivity over N2 (Sads = 940) and sizedependent selective adsorption behavior of water and alcohols.
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RESULTS AND DISCUSSION Structural investigations revealed that 1 is a 3D porous framework containing 10-coordinated La(III) ions and 1dimensional La(CO2)n chains connected by μ3-CO2 groups (Figure S1). The 1D size of the channel of 1 is 6 × 8 Å2. 1 exhibits extremely high thermal and chemical stabilities.10 To further thoroughly investigate the chemical stability, 1 was soaked in boiling aqueous solutions with different pH values and in a variety of boiling organic solvents, respectively. The powder XRD results show that the framework integrity of 1 is well retained, not only in boiling aqueous solutions at pH 2−12 but also in diverse boiling organic solvents (methanol, ethanol, 1-propanol, chloroform, acetonitrile, acetone, toluene, ethyl Received: January 9, 2018
A
DOI: 10.1021/acs.inorgchem.8b00082 Inorg. Chem. XXXX, XXX, XXX−XXX
Article
Inorganic Chemistry
Figure 1. Powder XRD patterns of 1 treated with boiling (a) aqueous solutions at pH 2−12 and (b) organic solvents for 24 h.
attributed to six μ3-CO2 groups of six TTCA3− connecting one La(III) with other La(III) ions to form stable 1-dimensional La(CO2)n chains. Due to this excellent thermal stability, the CO2, N2, and CH4 sorption properties of desolvated 1 were measured by a volumetric measurement method. The CO 2 adsorption amounts were found to be 71.1 cm3 g−1 at 1 bar and 273 K and 53.8 cm3 g−1 at 1 bar and 298 K. In contrast, N2 adsorption amounts are 5.1 and 2.7 cm3 g−1 at 273 and 298 K, respectively, and CH4 adsorption amounts are 25.2 and 15.4 cm3 g−1 at 273 and 298 K, respectively (Figure 3 and Figure S5). These results
acetate, and triethylamine) for 24 h (Figure 1). Moreover, there was hardly any dissociated TTCA3− ligand detected by UV−vis results in the filtrate (Figure S2), which further proved the intactness of 1 under these harsh conditions. These results may originate from the large rigidity of TTCA3− ligands and high connectivity of 1-dimensional La(CO2)n chains within 1.4h The mechanical stability of 1 was further studied by a ballmilling method. The results of scanning electron microscopy (SEM) show that the particle size of 1 decreased upon ball milling. It is clearly observed that, after ball milling for 1 h, the particle size is rapidly decreased from 100 μm to approximately 1 μm (Figure 2). A powder XRD measurement shows that 1
Figure 3. CO2, N2, and CH4 adsorption isotherms of 1.
suggest that 1 possesses potential applications for CO2/N2 and CO2/CH4 separations. The selective adsorption of CO2 rather than N2 and CH4 may originate from the CO2 quadrupole moment (−1.4 × 10−39), implying that the framework possesses strong interactions with CO2 molecules.14 The CO2 adsorption enthalpy (Qst) of 1 was calculated using the virial equation to understand the interactions between the framework and CO2 molecules. As shown in Figures S6 and S7, it is noted that the initial Qst vlaue is 34.5 kJ mol−1, which then decreased slowly to 32.8 kJ mol−1 at 1 mmol g−1; after that it increased slowly to 35.4 kJ mol−1 at 3.1 mmol g−1. These results demonstrate that the framework of 1 has two or more binding sites within 1 toward CO2.15 The binding interactions of the framework to CO2 were further observed using a grand canonical Monte Carlo (GCMC) simulation. As shown in Figure 4, there are multiple interactions between CO 2 molecules and the pore surface, which is in accordance with the result of experiments at 1 bar and 298 K.
Figure 2. SEM images of 1: (a, (b) without ball-milling; (c, d) after ball milling for 1 h.
retains structural integrity after ball milling (Figure S3). The results of N2 sorption further confirm that 1 retains its porosity after ball milling (Figure S4). These results indicate that 1 is a mechanically stable MOF that is more stable than most reported MOFs,11 including some reported Zr-MOFs that can remain stable after ball milling for 15 min.12 From the perspective of topology, the structural model of MOFs was comprised of vertices and linkers, and the mechanical property of MOFs can be determined by the number of linkers.13 Therefore, the exceptional mechanical stability of 1 can be B
DOI: 10.1021/acs.inorgchem.8b00082 Inorg. Chem. XXXX, XXX, XXX−XXX
Article
Inorganic Chemistry
Figure 4. Host−guest structure of 1 simulated by GCMC at 1 bar and 298 K. Figure 6. Sorption isotherms of water, methanol, ethanol, and 1propanol vapors of 1.
To predict the separation performance of 1, we calculated the selectivities for CO2/N2 (15/85) and CO2/CH4 (50/50) binary mixtures via ideal adsorbed solution theory (IAST).14a At 100 kPa, the selectivity factors are the proportion of the CO2 uptake at 15 kPa to the adsorbed amount of N2 at 85 kPa and the CO2 uptake at 50 kPa to the adsorbed amount of CH4 at 50 kPa, which are then normalized for the given pressures. As shown in Figure 5 and Figure S8, IAST calculations indicated
molecules, the amounts of adsorbed vapor molecules per formula unit decrease.17 The guest molecule size-dependent adsorption behavior indicates that 1 may be a candidate for guest separation.
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CONCLUSION In summary, a lanthanum carboxylate framework demonstrates several interesting features: (a) it shows high thermal stability up to 570 °C, (b) it exhibits exceptional chemical stability, remaining stable in boiling aqueous solutions at pH 2−12 as well as in boiling organic solvents for 24 h, (c) it displays high mechanical stability, retaining structural integrity upon ball milling for 1 h, and (d) it shows exceptional selective separation for CO2 over N2, as well as size-dependent adsorption behavior with water and alcohols. Given the above outstanding properties, this lanthanum carboxylate framework may be an excellent material for gas and vapor separation and purification under harsh physical and chemical conditions.
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EXPERIMENTAL SECTION
Materials and Instruments. All chemical reagents were purchased from commercially available sources and were used without further purification. Powder XRD data were collected on a D8 ADVANCE X-ray diffractometer. UV−vis spectra were recorded on a Shimadzu UV-2501PC spectrophotometer. Scanning electron microscopy (SEM) measurements were recorded on an FEI Quanta 450 instrument. The gas and vapor sorption isotherms were carried out on a BELSORP-max instrument. Synthesis of [La(TTCA)(H2O)]·DMF·H2O (1). 1 was prepared according to the reported method.10 Briefly, 0.043 g of La(NO3)3· 6H2O, 0.018 g of H3TTCA, and 1 drop of concentrated hydrochloric acid were dissolved in 8 mL of DMF in a sealed Teflon-lined autoclave. The autoclave was heated to 120 °C for 24 h and then cooled to room temperature. Yellow block crystals were obtained by filtration. Chemical Stability Test. A 150 mg portion of crystals of 1 was immersed in pH 2−6 HCl and pH 8−12 NaOH boiling aqueous solutions and soaked in diverse boiling organic solvents (methanol, ethanol, 1-propanol, chloroform, acetonitrile, acetone, toluene, ethyl acetate, triethylamine) for 24 h and then filtered and dried. Powder XRD data were collected to analysis their crystallinity. UV−vis data of the filtrate were collected to analyze the intactness of the frameworks. Mechanical Stability Test. The mechanical stability of 1 was performed by a ball-milling method. A 100 mg portion of the crystals was placed in a plastic pipe (volume 3 mL) with two steel balls (diameter 4 mm), and the crystals were ball-milled for 1 h continuously in a Retsch MM400 grinder mill operating at 30 Hz. SEM images were conducted to investigate the particle size of the
Figure 5. CO2/N2 and CO2/CH4 adsorption selectivities of 1.
that the selectivities are 940 and 188 for CO2/N2 at 273 and 298 K, respectively, and those for CO2/CH4 are 24 and 11 at 273 and 298 K, respectively. The high separation ratio for CO2/ N2 can be attributed to the multiple interactions of the framework of 1 with CO2. To our knowledge, only a few reported MOFs show a selectivity of over 900 for CO2/N2 near room temperature.9b−g Considering the exceptional chemical stability of 1 in boiling organic solvents, the vapor sorption properties of 1 were also studied. A series of alcohol (methanol, ethanol, 1-propanol) and water vapor sorption measurements were carried out at 298 K.16 The results indicate that 1 can adsorb water, methanol, and ethanol, showing typical type I adsorption isotherms. As shown in Figure 6, the initial adsorption amounts increase dramatically and then gradually reach plateaus of 270, 149, and 91 cm3 (STP) g−1 at 1 bar, corresponding to 2.43 water, 1.34 methanol, and 0.82 ethanol molecule per formula unit, respectively. However, for 1-propanol, only limited surface adsorption has occurred in the adsorption measurement. Obviously, the absorption behavior of 1 to vapor molecules is size-dependent. With an increase of the kinetic diameters of these vapor C
DOI: 10.1021/acs.inorgchem.8b00082 Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
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sample. Powder XRD data were collected to analysis the crystallinity and N2 adsorption data were collected to analysis the porosity after ball milling. Gas and Vapor Adsorption Measurements. N2, CO2, CH4, water, methanol, ethanol, and 1-propanol adsorption isotherms of 1 were carried out on a BELSORP-Max instrument. The 77, 273, and 298 K temperatures for gas and vapor adsorption measurements were controlled by liquid nitrogen, ice, and water baths, respectively. Before the measurements, the sample was degassed at 453 K for 4 h and then transferred to the adsorption intrument. Adsorption Enthalpy Calculation. The CO2 adsorption enthalpy (Qst) of 1 was calculated using adsorption data at 273 and 298 K. A virial-type expression (eq S1) was used to fit these data, and then the Qst was then calculated by the expression given by eq S2.
1 ln P = ln N + T
m i=0
i=0
* Supporting Information
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.8b00082. Crystal structure, UV−vis spectra, PXRD patterns, gas adsorption isotherms, isosteric heat isotherm, and additional figures (PDF)
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i=0
*E-mail for D.-C.Z.:
[email protected]. ORCID
Di-Chang Zhong: 0000-0002-5504-249X (S1)
Notes
(S2)
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The authors declare no competing financial interest.
ACKNOWLEDGMENTS This work was financially supported by the NSFC (21401026 and 21563004), the Natural Science Foundation of Jiangxi Province (20171BAB213001), the Science Fund for Distinguished Young Scholars of Jiangxi Province (20162BCB23052), the Open Fund of Key Laboratory of Jiangxi University for Functional Materials Chemistry (FMC15101), and the bidding Project of Gannan Normal University (16zb06).
Here, P, N, and T are the pressure, amount adsorbed, and temperature, respectively. m and n determine the number of terms required to adequately describe the isotherm. ai and bi are virial coefficients. Computational Details. A grand canonical Monte Carlo (GCMC) simulation was performed to model CO2 adsorption using the Materials studio 5.0 package.15 Briefly, before the simulation, the model structure from the X-ray diffraction data was geometrically optimized by fixing the cell parameters using density functional theory (DFT). For CO2, the CO bond length of 1.177 Å was optimized, and O and C atom charges are −0.292 and 0.584 e as calculated by ESP fitted charges, respectively. For the GCMC simulation, the simulation box was set as 2 × 2 × 2 unit cells, but the material framework and CO2 molecule were considered to be rigid and described by the universal force field (UFF). The cutoff distance was set to 18.5 Å for the Lennard−Jones (LJ) interactions; the van der Waals and electrostatic interactions were handled using the atombased and Ewald summation methods, respectively. The fixed loading task and Metropolis method were used to simulate the favorable adsorption sites at 298 K. The loading steps, equilibration steps, and production steps were all set to 2.0 × 107. The saturation/maximum uptakes were modeled at 298 K by the fixed pressure task. Calculation of Gas Selectivity. The CO2/N2 and CO2/CH4 selectivities of 1 were estimated by ideal adsorbed solution theory (IAST) theory.18 In this work, the pure CO2, CH4, and N2 experimental isotherms were fitted using a single-site Langmuir− Freundlich equation (eq S3).
Q=
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(S3)
Here, Q, B, P, and Qsat are the adsorbed amount of adsorbent (mmol g−1), parameter in the pure component Langmuir isotherm (kPa−1), bulk gas phase pressure of species (kPa), and saturation capacity of species (mmol g−1), respectively. Then the adsorption isotherms of each component in the mixture were predicted by the fitted parameters (eq S4).
⎛ ⎛ B Py ⎞ B P(1 − y) ⎞ Q sat,a ln⎜1 + a ⎟ − Q sat,b ln⎜1 + b ⎟=0 ⎝ ⎝ x ⎠ 1−x ⎠
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Q satBP 1 + BP
AUTHOR INFORMATION
Corresponding Author
m
Q st = − R ∑ aiN i
ASSOCIATED CONTENT
S
n
∑ aiN i + ∑ biN i
Article
(S4)
The predicted CO2/N2 and CO2/CH4 adsorption selectivities for binary mixtures are defined as (x1/y1)/(x2/y2); here x1 and x2 are the mole fractions of adsorbed phases and y1 and y2 are the mole fractions of bulk phases. D
DOI: 10.1021/acs.inorgchem.8b00082 Inorg. Chem. XXXX, XXX, XXX−XXX
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DOI: 10.1021/acs.inorgchem.8b00082 Inorg. Chem. XXXX, XXX, XXX−XXX
