The Effect of Functional Groups on the Adsorption of Light

Publication Date (Web): December 26, 2018. Copyright © 2018 American Chemical Society. Cite this:Cryst. Growth Des. XXXX, XXX, XXX-XXX ...
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Effect of Functional Groups on the Adsorption of Light Hydrocarbons in f mj-type Metal−Organic Frameworks Yutong Wang,† Xia Wang,† Xiaokang Wang,† Xiurong Zhang,† Weidong Fan,† Di Liu,‡ Liangliang Zhang,† Fangna Dai,*,† and Daofeng Sun† †

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School of Materials Science and Engineering, College of Science, China University of Petroleum (East China), Qingdao, Shandong 266580, People’s Republic of China ‡ College of Chemical and Environmental Engineering, Shandong University of Science and Technology, Qingdao Shandong 266590, People’s Republic of China S Supporting Information *

ABSTRACT: The functionalized modification of targeted porous metal−organic frameworks (MOFs) is important to improve the adsorption capacity of light hydrocarbon gases. Five isomorphic MOFs with different functional groups (F, Cl, NH2, CH3, and OCH3) are successfully synthesized by systematic functional modification of UMCM-151. By studying the adsorption properties of C2 and C3 hydrocarbons (C2H2, C2H4, C2H6, C3H6, and C3H8), it is found that the electron-withdrawing group functional UMCM-151-F and UMCM-151-Cl exhibit strong affinity for C2H2 (98.71 cm3 g−1 for UMCM-151-F and 90.29 cm3 g−1 for UMCM-151Cl), while the electron-donating group functional UMCM151-NH2, UMCM-151-CH3, and UMCM-151-OCH3 have strong affinity for C2H4 (97.89 cm3 g−1 for UMCM-151-NH2, 90.22 cm3 g−1 for UMCM-151-CH3 and 94.13 cm3 g−1 for UMCM-151-OCH3). The differences in affinity of electron effects for light hydrocarbon provide an experimental basis for porous MOFs to improve their light hydrocarbon storage capacity.

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INTRODUCTION C2 and C3 hydrocarbons (C2H2, C2H4, C2H6, C3H6, and C3H8) are important chemical raw materials.1,2 For example, C2H2, C2H4, and C3H6 are widely used in polymerization, oxidation, alkylation, hydration, oligomerization, hydroformylation, and so on.3−7 Compression and liquefaction are traditional methods of light hydrocarbon storage. However, expensive pressure vessels and six-stage high pressure are required during the compression process, which are significant safety hazards. Therefore, the effective and safe storage methods for C2 and C3 hydrocarbons are important. On the basis of the above considerations, adsorption-based storage is considered to be an effective method because it can be realized at atmospheric pressure and room temperature.8,9 Thus, it is valuable to design and synthesize efficacious light hydrocarbons adsorbent materials.10,11 The limited surface area, lower porosity, and unregulated structure make conventional porous materials, such as molecular sieves, zeolites, and activated carbon, difficult to achieve efficient gas storage.12,13 Therefore, excavating new promising adsorbents is important for the storage of light hydrocarbons. The metal−organic framework (MOF) is crystalline porous material with periodic network structure assembled from coordination bond by metal ions/clusters and organic ligands, which are considered as promising candidates for light © XXXX American Chemical Society

hydrocarbons adsorption because their regulated channel and modified skeleton.14−20 In fact, there have been some work exploring the factors that affect the storage of light hydrocarbons by MOFs.21−26 For example, by introducing amino groups, He. et al. increased 10% of C2H2 uptake compared to the parent compound.27 By methoxy modification, the ZJU-12 reported by Qian’s group exhibited a high gravimetric C2H2 uptake of 193 cm3 g−1 at atmospheric pressure and room temperature.28 Our group has designed and synthesized the methylation-MOFs material for high selectivity separation of propane and methane with a separation selectivity of 124.29 Besides the past research studies have been mainly focused on adsorption of C1−C2, with few reports on C3. It should be noted that studies on the effect of organic functional groups on the adsorption properties of light hydrocarbons have not been systematically performed. As is well-known, grafting functional groups into the organic linkers increases affinity with gas molecules, although the pore volume is reduced. In this article, we introduce five different electronic organic functional groups, including strongly electron-withdrawing groups (F and Cl) and electron-donating Received: September 18, 2018 Revised: December 19, 2018 Published: December 26, 2018 A

DOI: 10.1021/acs.cgd.8b01403 Cryst. Growth Des. XXXX, XXX, XXX−XXX

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Synthesis of UMCM-151. The UMCM-151 is prepared by a previously reported method.30 Elemental analysis calcd (%) for UMCM-151: C, 52.39; H, 2.89; found: C, 51.96; H, 2.50. Synthesis of UMCM-151-NH2. The UMCM-151-NH2 is prepared by a previously reported method.32 Elemental analysis calcd (%) for UMCM-151-NH2: C, 45.71; N, 2.96; H, 7.30; found: C, 45.36; N, 2.89; H, 7.32. Synthesis of [Cu3(L2)(H2O)3]·3DMF·3Diox·10H2O (UMCM151-F). H3L2 (0.03 mmol, 12.0 mg) and Cu(NO3)2·2.5H2O (0.1 mmol, 24.0 mg) was dissolved in a solution of DMF/Diox/H2O (3 mL, V/V/V = 5:2:1) in 10 mL vial. The mixture was heated to 75 °C over 2 h and kept for 12 h. The blue crystals were collected and washed with DMF several times (yield: 86%, based on H3L2). Elemental analysis calcd (%) for UMCM-151-F: C, 45.71; N, 2.96; H, 7.30; found: C, 45.36; N, 2.89; H, 7.32. IR spectrum data (KBr, cm−1): 3369(m), 2927(m), 1663(s), 1545(m), 1383(s), 1249(m), 1178(m), 1097(s), 870(w), 782(m), 729(m), 658(m). Synthesis of [Cu3(L3)(H2O)3]·3DMF·3Diox·9H2O (UMCM-151Cl). The synthesis process of UMCM-151-F was similar to that of UMCM-151-F except with H3L3 instead of H3L2. Yield: 81% (based on H3L3). Elemental analysis calcd (%) for UMCM-151-Cl: C, 44.10; H, 7.2; N, 3.67; found: C, 43.81; H, 7.26; N, 3.59. IR Spectrum data (KBr, cm−1): 3417(w), 1600(s), 1531(s), 1404(m), 1320(s), 1035(w), 781 (s), 712(m). Synthesis of [Cu3(L5)(H2O)3]·4DMF·4Diox·10H2O (UMCM151-CH3). The synthesis process of UMCM-151-CH3 was similar to that of UMCM-151-F except with H3L5 instead of H3L2. Yield: 78% (based on H3L5). Elemental analysis calcd (%) for UMCM-151CH3: C, 42.5; H, 7.20; N, 3.96; found: C, 41.5; H, 7.05; N, 3.88. IR Spectrum data (KBr, cm−1): 3420(m), 3065(m), 2954(m), 1660(s), 1553(s), 1402(s), 1312(m), 1254(m), 1180(m), 1099(s), 1019(w), 866(w), 790(m), 724(m), 665(m),514(m). Synthesis of [Cu3(L6)(H2O)3]·3DMF·4Diox·9H2O (UMCM-151OCH3). The synthesis process of UMCM-151-OCH3 was similar to that of UMCM-151-F except with H3L6 instead of H3L2. Yield: 80% (based on H3L6). Elemental analysis calcd (%) for UMCM-151OCH3: C, 41.71; H, 7.01; N, 2.96; found: C, 41.2; H, 6.78; N, 3.07. IR Spectrum data (KBr, cm−1): 3424(m), 2931(m),1657(s),1610(s), 1547(m), 1386(s), 1229(m), 1099(w), 1002(w), 865(w),786(m), 721(m), 663(m). X-ray Crystallography. The crystallographic diffraction data of UMCM-151-F, UMCM-151-Cl, UMCM-151-CH3 and UMCM-151OCH3 were collected by means of ω-2θ with a Copper microfocus Xray sources (Cu Kα λ= 1.54184 Å) on Agilent Xcalibur Eos Gemini diffractometer. Data were reduced by CrysAlisPro package and absorbed correction by SADABS program.33 Crystal structure data are imported into Olex2 and solved by Superflip program. All nonhydrogen atom coordinates and anisotropic parameters are obtained by using Shelxs program and full-matrix least-squares method to modify F2 continuously.34,35 The aromatic hydrogen atoms were placed in calculated ideal positions and refined using the riding model, and the difference maps method was used to determine the hydrogen atoms of coordinated water molecules. The disordered solvent molecules were removed by the PLATON/ SQUEEZE program.36 Then the data were refined to obtain the final crystallographic data. The crystallographic data for this paper have been deposited in the Cambridge Crystallographic Data Centre. The CCDC numbers are 1849596−1849599. Full crystallographic data analyses, selected bond lengths, and bond angles are given in the Table S1−S9 of Supporting Information. Gas Sorption Measurements. Gas adsorption−desorption measurements of N2, C2H2, C2H4, C2H6, C3H6, and C3H8 on UMCM-151, UMCM-151-F, UMCM-151-Cl, UMCM-151-NH2, UMCM-151-CH3, and UMCM-151-OCH3 were collected at different temperatures on the ASAP 2020. The temperatures of 77, 273, and 298 K were maintained through a liquid nitrogen bath, an ice− water bath, and a water bath, respectively.

groups (NH2, CH3, and OCH3), with an increased atomic radius (from 0.710 to 1.897 Å), into the parent compound UMCM-151, which is a prototypical f mj-type MOF (with the point symbol {62.82.102}{62.84}{63}8{64.102}4) consisting of dicopper paddlewheel and [1,1′:3′,1′′-terphenyl]-4,4′′,5′-tricarboxylic acid (H3L),30 and systematically explored their light hydrocarbons adsorption properties. Among the six compounds (UMCM-151, UMCM-151-F, UMCM-151-Cl, UMCM-151-NH 2, UMCM-151-CH 3, and UMCM-151OCH3), functionalized compounds UMCM-151-F, UMCM151-Cl, UMCM-151-NH 2 exhibit a higher Brunauer− Emmett−Teller (BET) surface area than UMCM-151-CH3 and UMCM-151-OCH3. With the incorporation of functional groups, the adsorption capacity of light hydrocarbons is significantly increased. For example, modified UMCM-151-F with a strong electron-withdrawing group exhibited the highest C2H2 uptake, reaching 98.71 cm3 g−1 at 273 K and atmospheric pressure. However, UMCM-151-NH2 was modified by a strong electron-donating group, which exhibited a higher C2H4 uptake, reaching 97.89 cm3 g−1 at 273 K and atmospheric pressure. The adsorption heat (Qst) of light hydrocarbons in the compounds is calculated by the Clausius− Clapeyron equation,31 UMCM-151-CH3 exhibits the highest Qst for C3H6, while UMCM-151-OCH3 has the highest Qst for C3H8.

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EXPERIMENTAL SECTION

Materials and Methods. All chemical reagents and solvents employed are commercially available except H3L1−6 and were not purified before use. The H3L1−6 was synthesized by the Suzuki coupling reaction and purified by column chromatography, and then hydrolyzed with dilute HCl. The purity of H3L1−6 was determined on a 400 MHz Varian INOVA spectrometer by 1H NMR spectrum. The phase purity of the compounds was determined on an analytical XPert pro diffractometer with CuKa radiation (λ = 1.54184 Å) by powder X-ray diffraction. Thermogravimetric (TG) curves were measured with a Mettler Toledo TGA heated from 40 to 900 °C (at 10 °C min−1) under nitrogen atmosphere. The PerkinElmer 240 elemental analyzer was used to obtained the elemental analyses (C, N, H) of compounds. Infrared spectra were collected on a Nicolet 330 FTIR spectrometer using KBr pellets in the 4000−400 cm−1 region. The gas adsorption experiments at different temperatures were performed on the surface area analyzer Micromeritics ASAP 2020. Synthesis of Compounds. The synthesis of H3L1−6 is outlined in Scheme 1. Detailed synthesis process in Supporting Information. UMCM-151 and UMCM-151-NH2 are reported by Matzger et. al and our group, respectively.30,32 The other four compounds of UMCM-151-F, -Cl, -CH3, -OCH3 are first reported here.

Scheme 1. Synthetic Procedures of Functional Ligands

B

DOI: 10.1021/acs.cgd.8b01403 Cryst. Growth Des. XXXX, XXX, XXX−XXX

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Figure 1. (a−f) Twist angle between the central benzene ring and the side benzene ring of UMCM-151, UMCM-151-F, UMCM-151-Cl, UMCM151-NH2, UMCM-151-CH3 and UMCM-151-OCH3, respectively.

Figure 2. (a−f) The pore sizes along the a-axis of UMCM-151, UMCM-151-F, UMCM-151-Cl, UMCM-151-NH2, UMCM-151-CH3, and UMCM-151-OCH3, respectively.

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RESULTS AND DISCUSSION Crystal Structure. Single-crystal X-ray diffraction analysis show that UMCM-151-F, UMCM-151-Cl, UMCM-151-NH2, UMCM-151-CH3, and UMCM-151-OCH3 are isostructural with UMCM-151, crystallizing in the orthorhombic space group of Immm. The crystal structure of UMCM-151-F is described representatively. A typical dicopper paddlewheel [Cu2(COO)4] secondary building unit (SBU) is formed by two adjacent copper and four carboxylate groups from four different organic ligands. There are two kinds of SBUs in the structure, one coordinated by four m-carboxylate groups, and the other coordinated by four p-benzoate groups (Figure 3a,b). If the dicopper paddlewheel SBUs are simplified as 4connected, and the organic linkers are considered as 3connected nodes, the three-dimensional (3D) frameworks can be simplified as the typical f mj-type topology structure. With the introduction of different functional groups, there are subtle transformations of other isomorphism due to the differences in size and electron cloud density. As shown in Figure 1, the twist angles between the central benzene ring and the side benzene ring have changed (39.490°, 47.032°, 57.157°, 56.479°, 57.180°, and 56.479° for UMCM-151, UMCM-151-F, UMCM-151-Cl, UMCM-151-NH2, UMCM-151-CH3, and UMCM-151-OCH3, respectively). With the addition of functional groups, the diameter of the channel along the aaxis changes, and the pore size decreases accordingly (Figure

2). Notably, all of the modified functional groups extend into the pores, and the surface of the framework is decorated with potential Lewis basic (nitrogen donor sites) and Lewis acid (fluorine or chlorine sites), which are favorable for gas adsorption. The total accessible volumes are calculated by PLATON (the guest and coordinated water molecules are removed), which are 76.6, 75.7, 73.2, 75.5, 74.4 and 73.7% for UMCM-151, UMCM-151-F, UMCM-151-Cl, UMCM-151NH2, UMCM-151-CH3, and UMCM-151-OCH3, respectively. The crystallographic data and selective bond lengths and angles are summarized in Tables S1−S9. Gas-Adsorption. Gas-uptake measurements of desolvated UMCM-151, UMCM-151-F, UMCM-151-Cl, UMCM-151NH2, UMCM-151-CH3, and UMCM-151-OCH3 are performed. As shown in Figure 5a, all six compounds exhibited Type-I reversible sorption isotherms, which is defined as the characteristic of microporous materials in the IUPAC classification. The maximum N2 uptakes at 77 K are 195.67, 236.41, 228.68, 215.75, 163.86, and 146.63 cm3 g−1 for UMCM-151, UMCM-151-F, UMCM-151-Cl, UMCM-151NH2, UMCM-151-CH3, and UMCM-151-OCH3, respectively. The BET surface areas based on the N2 adsorption isotherms are calculated to be 697.35, 803.12, 781.65, 746.19, 589.76, and 502.18 m2 g−1 for UMCM-151, UMCM-151-F, UMCM151-Cl, UMCM-151-NH2, UMCM-151-CH3, and UMCM151-OCH3, respectively. It should be noted that the porosities of the six compounds vary slightly with the maximum C

DOI: 10.1021/acs.cgd.8b01403 Cryst. Growth Des. XXXX, XXX, XXX−XXX

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Figure 5. (a) N2 adsorption−desorption isotherms at 77 K, (b) pore size distributions of the six compounds.

isotherms tested are completely reversible, indicating rapid adsorption and desorption kinetics. At 273 K and atmospheric pressure, the C2H2 uptake values are UMCM-151-F (98.71) > UMCM-151-Cl (90.29) > UMCM-151-NH2 (87.5) > UMCM-151-OCH3 (80.06) > UMCM-151-CH3 (74.51) > UMCM-151 (49.7) cm3 g−1 (Table 1). It can be observed that the C2H2 uptake increased after the insertion of the electronwithdrawing and electron-donating functional groups. While the UMCM-151-F shows the highest value among the six compounds, and the storage capacity of C2H2 increases significantly due to the electron-withdrawing groups (F and Cl). The C2H4 uptake values are UMCM-151-NH2 (97.89) > UMCM-151-CH3 (90.22) > UMCM-151-OCH3 (94.13) > UMCM-151-F (72.24) > UMCM-151-Cl (67.32) > UMCM151 (60.18) cm3 g−1 at 273 K, which are higher than UPC-33, FJI-C4, 1-FA, and comparable to that of 1-pim and 1buim.37−40 There is no significant difference on the adsorption capacity of C2H6, C3H6, and C3H8 between the two electronwithdrawing groups (F, Cl), which is also present in the electron-donating groups (NH2, CH3, OCH3) (Table 1). Compared with the parent compound, the C2H2 uptake of UMCM-151-F increased by 1.98 times, while the C2H4 uptake of UMCM-151-NH2 increased by 1.62 times. Adsorption

Figure 3. X-ray Single-crystal structure of UMCM-151-F. (a) and (b) Secondary building unit formed by the coordination of four mcarboxylate groups and four p-benzoate groups; (c) view of 3D open framework along the c-axis; (d) topology structure.

difference of 2 Å, but the platform does not change (Figure 5b). With the introduction of functional groups, the BET surface area of the modified crystal increases as the N2 adsorption capacity increases, except for UMCM-151-CH3 and UMCM-151-OCH3 (Table S10). This can indicate that the introduction of functional groups enhances the interaction of gas molecules with framework; however, they tend to reduce the porosity of the compounds and thus have a negative impact on gas adsorption performance. Adsorption Isotherms of Hydrocarbons. In order to explore the effect of different functional groups on the adsorption of light hydrocarbons. We have carried out light hydrocarbon adsorption isomers on the six compounds. As shown in Figure 4 and Table 1, the adsorption−desorption

Figure 4. (a−e) Adsorption−desorption isotherms of UMCM-151, UMCM-151-F, UMCM-151-Cl, UMCM-151-NH2, UMCM-151-CH3, and UMCM-151-OCH3 for C2H2, C2H4, C2H6, C3H6, and C3H8 at 273 K. D

DOI: 10.1021/acs.cgd.8b01403 Cryst. Growth Des. XXXX, XXX, XXX−XXX

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Table 1. Adsorption Data at 1 atm and 273 K for the Six Compounds MOFs uptake (cm3/g)

UMCM-151

UMCM-151-F

UMCM-151-Cl

UMCM-151-NH2

UMCM-151-CH3

UMCM-151-OCH3

C2H2 C2H4 C2H6 C3H6 C3H8

49.7(6) 60.18(6) 51.79 (6) 68.74(6) 66.86(6)

98.71(1) 72.24(4) 68.36(4) 105.75(2) 97.61(3)

90.29(2) 67.32(5) 66.91(5) 96.14(5) 88.74(5)

87.5(3) 97.89(1) 82.73(1) 109.39(1) 100.36(1)

74.51(5) 90.22(3) 77.66(3) 103.06(3) 100.23(2)

80.06(4) 94.13(2) 79.55(2) 100.35(4) 92.07(4)

Figure 6. (a−e) Qst for C2H2, C2H4, C2H6, C3H6 and C3H8 of UMCM-151, UMCM-151-F, UMCM-151-Cl, UMCM-151-NH2, UMCM-151CH3, and UMCM-151-OCH3.

interaction between C3 light hydrocarbons (C3H6 and C3H8) and the frameworks. In general, the Qst of C3 are greater than those of C2 in the six compounds. For C2H2, the Qst values of electron-withdrawing groups (F and Cl) are stronger, while electron-donating groups (NH2, CH3, and OCH3) are more superior in C2H4 adsorption.

experiments show that these functional groups can enhance the affinity with light hydrocarbons, especially for C2H2. To explore the influence of functional groups on the light hydrocarbons adsorption, the adsorption isotherms of these six compounds at 273 and 298 K were collected, and the adsorption enthalpy (Qst) was calculated using the Clausius− Clapeyron equation. Figure 6 shows the adsorption enthalpy for these compounds. At near zero coverage, the Qst of C2H2 are UMCM-151-F (23.0) > UMCM-151-Cl (21.0) > UMCM151-OCH3 (19.5) > UMCM-151-NH2 (18.5) > UMCM-151CH3 (17.6) > UMCM-151(17.6) kJ mol−1. It can be notice that the growth of the Qst of the UMCM-151 modified with electron-withdrawing groups is greater than electron-donating groups. The Qst of C2H4 are UMCM-151-NH2 (20.7) > UMCM-151 (20.6) > UMCM-151-OCH3 (19.3) > UMCM151-Cl (18.4) > UMCM-151-F (18.1) > UMCM-151-CH3 (17.0) kJ mol−1. It should be pointed that the introduction of functional groups does not cause a collective increase in the Qst of C2H4. By comparison, the amino group with strong electron donor has the strongest adsorption. The Qst values of C3H6 are UMCM-151-CH3 (32.8) > UMCM-151-OCH3 (28.5) > UMCM-151 (31.8) > UMCM-151-NH2 (28.0) > UMCM151-F (26.4) > UMCM-151-Cl (25.0) kJ mol−1, and of C3H8 are UMCM-151-OCH3 (33.0) > UMCM-151-NH2 (31.5) > UMCM-151 (29.6) > UMCM-151-CH3 (28.7) > UMCM151-F (27.7) > UMCM-151-Cl (25.9) kJ mol−1. The introduction of electron-withdrawing groups reduces the

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CONCLUSION In conclusion, the effect of functional groups on the adsorption of light hydrocarbons was systematically investigated on the f mj-type MOFs platform, revealing that the electron-withdrawing groups are generally superior to the electron-donating groups to increase the C2H2 uptake capacity. The electrondonating groups perform better in improving C2H4 uptake capacity. This work investigated the effects of electronwithdrawing groups (F and Cl) and electron-donating groups (NH2, CH3, and OCH3) on the adsorption of light hydrocarbons, providing basic data support for the modification of MOFs, which provides a favorable platform for designing and synthesizing MOFs with high hydrocarbon storage performance.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.cgd.8b01403. E

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Full details for ligand synthesis, single-crystal data, PXRD, TGA, and FT-IR (PDF) Accession Codes

CCDC 1849596−1849599 contain 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 Author

*E-mail: [email protected]. ORCID

Yutong Wang: 0000-0001-8943-1832 Fangna Dai: 0000-0002-5300-5388 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (Grant Nos. 21571187, 21771191), Taishan Scholar Foundation (ts201511019), the Shandong Natural Science Foundation (ZR2017QB012), and the Fundamental Research Funds for the Central Universities (14CX02213A, 16CX05015A, 18CX06003A, YCX2018071).

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DOI: 10.1021/acs.cgd.8b01403 Cryst. Growth Des. XXXX, XXX, XXX−XXX