Supporting Information Cooperative Template-Directed Assembly of Mesoporous Metal-Organic Frameworks Lin-Bing Sun, Jian-Rong Li, Jinhee Park, and Hong-Cai Zhou* Department of Chemistry, Texas A&M University, P.O. Box 312, College Station, Texas 77842-312 * Corresponding author. Email: zhou@mail.chem.tamu.edu S1
Experimental Details Chemicals. Copper nitrate hemipentahydrate (> 98%, benzene,3,5-tricarboxylic acid (H 3 BTC, > 98%, citric acid (CA, > 99%, and ammonium nitrate (> 95% were purchased from Alfa Aesar Chemicals. Cetyltrimethylammonium bromide (CTAB, > 99% was purchased from Acros. Ethanol and N,N-dimethylformamide (DMF were obtained from Koptech and Mallinckrodt Chemicals, respectively. All starting materials were used without further purification. Materials Synthesis. In a typical synthesis,.232 g (1. mmol of copper nitrate hemipentahydrate,.116 g (.56 mmol of H 3 BTC were dissolved in 1 ml of DMF. After a given amount of surfactant CTAB (-.6 g and chelating agent CA (-.1 g were added, the mixture was sonicated for 1 min to form a homogeneous solution. The solution was then heated to 75 o C and held at this temperature for 24 h under static conditions. The resulting solid was washed with DMF to remove unreacted starting materials. Finally, the as-synthesized sample was subjected to an ion-exchange process at 6 o C for 24 h with 1 M ammonium nitrate ethanol/water solution (volume ratio of 1:2 to remove the template, followed by washing with an ethanol/water mixture (volume ratio of 1:2. Mesostructured MOFs were obtained and denoted as mesomof(smcn, where m and n represent the amount of surfactant and chelating agent in gram, respectively. Instrumentation. X-ray diffraction (XRD patterns of the materials were recorded using a BRUKER D8-Focus Bragg-Brentano X-ray Powder Diffractometer equipped with a Cu sealed tube (λ = 1.54178 at 4 kv and 4 ma. Transmission electron microscopy (TEM analysis were performed on a FEI Tecnai G 2 -F2 transmission electron microscope. Thermogravimetry analysis (TGA was conducted on a TGA-5 (SHIMADZU thermogravimetric analyzer. About 1 mg of sample was heated from room temperature to 5 C in a N 2 flow (25 ml g 1. Fourier transform infrared (IR measurements were performed on a SHIMADZU IRAffinity spectrometer. The spectra were collected with a 2 cm 1 resolution. N 2 adsorption-desorption isotherms were measured using a Micrometritics ASAP22 system at 196 o C. The samples were degassed at 18 o C for 12 h prior to analysis. The Langmuir surface area was estimated using the adsorption data accoding to the Langmuir equation. 1 The S2
Brunauer-Emmett-Teller (BET surface area was calculated using adsorption data in a relative pressure ranging from.1 to.3. The total pore volume was determined from the amount adsorbed at a relative pressure of about.95. The mesopore pore volume was obtained from the Barrett-Joyner-Halenda (BJH cumulative specific adsorption volume according to the literature. 2 The mesopore size distributions were calculated using the BJH method. Discussion on CA-Derived Crystal Phase and Synthetic Mechanism As described in manuscript, one CA molecule can interact with two CTAB molecules. Hence, the optimum CTAB/CA molar ratio is about 2. In the presence of.8 and.1 g CA, the CTAB/CA ratio is 1.4 and 1.2, respectively, and is obviously lower than 2. As a results, their XRD patterns show several new diffraction lines with the strongest one at 2 of 1.1 o besides those from Cu 3 (BTC 2 (Figure S1. Also, their IR spectra display new bands with a typical one at 1567 cm 1 (Figure S3. Because both XRD patterns and IR spectra are apparently different from those of CA itself (Figures S7 and S8, the residue of CA in the samples can be excluded. That means, an excess of CA leads to the formation a new phase (denote as 1. This phase cannot be identified, owing to the difficulty in obtaining a pure crystal. The reaction of Cu(NO 3 2 with CA, under the similar conditions as Cu 3 (BTC 2 synthesis except that BTC was replaced by CA, yielded a phase (denote as 2 with a strongest diffraction line at 2 of 8.5 o (Figures S9, which is different from phase 1. Moreover, this sample shows a very poor porosity with a BET surface area of 16 m 2 g 1 and a pore volume of.17 cm 3 g 1 (Figure S1. Thus, phase 1 should not be a mixture of MOFs constructed from BTC and CA. It is interesting to note that a pure Cu 3 (BTC 2 phase can be obtained even if g CA was introduced to the synthetic system of Cu 3 (BTC 2, in the absence of CTAB (Figure S2. This reveals the preferential coordination of copper ions with BTC rather than CA. Nevertheless, the introduction of small amount of CTAB (in the case of CTAB/CA molar ratios lower than 2 results in the formation of phase 1. This indicates that the existence of CTAB plays an important role in the produce of phase 1. The effect of bromine ion was evaluated by using CuBr 2 with the same amount of bromine instead of CTAB. As presented in Figure S11, pure Cu 3 (BTC 2 phase was obtained under the same conditions as the synthesis S3
of mesomof(sc. That means, bromine does not favor the generation of phase 1. In other words, the micelles derived from cetyltrimethylammonium ions (CTA +, together with CA, are responsible for the generation of phase 1. It is possible that micelles produce some available microspace, so that CA has the opportunity to react with copper ions. It is worthy of noting that further increasing CTAB dosage, the amount of phase 1 decreases gradually and disappears finally. This gives evidence of the strong interaction between CTAB and CA, which decline the interaction of CA with copper ions, and subsequently pure Cu 3 (BTC 2 phase is created. Further evidence can be provided by the results shown in Figure S9. The reaction of Cu(NO 3 2 with CA leads to the formation of phase 2 in the absence of CTAB. However, the diffraction lines were weakened after the introduction of g CTAB, and no diffraction can be observed in the presence of.2 g CTAB. On the basis of the description above, it can be tentatively concluded that the formation of phase 1 is derived from CA, while the presence of CTAB is also necessary. The molar ratio of CTAB-to-CA affects the content of phase 1 in the final samples. A low CTAB/CA ratio favors the generation of phase 1, while a high CTAB/CA ratio is beneficial to the formation of pure Cu 3 (BTC 2 phase. Aiming to obtain mesostructured MOFs with pure Cu 3 (BTC 2 phase, a CTAB/CA molar ratio higher than 2 is suggested, from the standpoint of avoiding an excess of CA. It is worth noting that Qiu et al. reported the fabrication of mesoporous MOFs in the presence of CTAB individually. 2 In the present study, we employed DMF as solvent and conducted the reaction at 75 o C. The mesoporous MOFs reported by Qiu et al. were synthesized in ethanol/h 2 O mixed solvents at 12 o C. It is known that DMF can favor the deprotonation of carboxylic acid; in the meanwhile, dimethylammonium cations are produced. These cations may compete with surfactants (cetyltrimethylammonium cations from CTAB to interact with MOF precursors. As a result, the structure-directing role of surfactants is seriously degraded, which will certainly affect the formation of mesopores. However, there is no competition existed in the ethanol/h 2 O synthetic system, so surfactants can interact with MOF precursors despite that the direct interaction is relatively weak. Therefore, different solvents should be responsible for the difference between Qiu s results and ours. Due to the S4
strong interaction between template and MOF precursors established by chelating agent, our strategy might be applicable in synthetic systems with different solvents. References (1 Yuan, D.; Lu, W.; Zhao, D.; Zhou, H.-C. Adv. Mater. 211, 23, 3723. (2 Qiu, L.-G.; Xu, T.; Li, Z.-Q.; Wang, W.; Wu, Y.; Jiang, X.; Tian, X.-Y.; Zhang, L.-D. Angew. Chem. Int. Ed. 28, 47, 9487; Complete reference 2g: Horcajada, P.; Chalati, T.; Serre, C.; Gillet, B.; Sebrie, C.; Baati, T.; Eubank, J. F.; Heurtaux, D.; Clayette, P.; Kreuz, C.; Chang, J.-S.; Hwang, Y. K.; Marsaud, V.; Bories, P.-N.; Cynober, L.; Gil, S.; Ferey, G.; Couvreur, P.; Gref, R. Nat. Mater. 21, 9, 172; S5
Table S1. Structural Properties of mesomofs Synthesized with Different Amount of CTAB and CA Sample a CTAB/CA BET Surface Langmuir Pore Mesopore Mesopore molar ratio area surface area volume diameter volume (m 2 g 1 (m 2 g 1 (cm 3 g 1 (nm (cm 3 g 1 mesomof(sc 1261 1957.696 mesomof(s.2c 1181 1831.65 mesomof(s.2c.1 11.6 1183 1848.657 4.7.44 mesomof(s.2c.2 5.8 1112 1744.62 4.7 2 mesomof(s.2c 2.3 1162 1915.694 19.6.13 mesomof(s.2c.8 1.4 94 1569.566 19.6.9 mesomof(s.2c.1 1.2 783 1297.465 19.6.69 mesomof(sc 126 1954.696 mesomof(sc.6 184 1754.628 16.7 5 mesomof(s.1c 1.1 122 1877.672 14.5.6 mesomof(s.4c 4.6 1273 1966.71 19.6.71 mesomof(s.6c 6.9 1229 194.692 17.6 6 a mesomof(smcn denotes mesostructured metal-organic frameworks, where m and n represent the amount of surfactant and chelating agent in gram, respectively. S6
CA CTAB =.2g Intensity (a.u..1.2.8.1 4 8 12 16 2 2 (degrees Figure S1. XRD patterns of mesomofs synthesized with different amount of CA. Intensity (a.u. CTAB.1.2.4.6 CA = g 4 8 12 16 2 2 (degrees Figure S2. XRD patterns of mesomofs synthesized with different amount of CTAB. S7
CA CTAB =.2g Transmittance (a.u..1.2.8.1 4 3 2 1 Wavenumber (cm Figure S3. IR spectra of mesomofs synthesized with different amount of CA. Transmittance (a.u. CTAB CA = g.1.2.4.6 4 3 2 1 Wavenumber (cm Figure S4. IR spectra of mesomofs synthesized with different amount of CTAB. S8
Weight (a.u. CTAB =.2g 5% CA.1.2.8.1 1 2 3 4 5 Temperature ( o C Figure S5. TGA curves of mesomofs synthesized with different amount of CA. Weight (a.u. CA = g 5% CTAB.1.2.4.6 1 2 3 4 5 Temperature ( o C Figure S6. TGA curves of mesomofs synthesized with different amount of CTAB. S9
Intensity (a.u. 4 8 12 16 2 2 (degrees Figure S7. XRD pattern of pure CA. Transmittance (a.u. 4 3 2 1 Wavenumber (cm Figure S8. IR spectrum of pure CA. S1
Intensity (a.u. CTAB.2 4 8 12 16 2 2 (degrees Figure S9. XRD patterns of the samples derived from the reaction of Cu(NO 3 2 and CA in the presence of -.2 g of CTAB. Volume adsorbed (cm 3. g, STP 15 1 5..2.4.6.8 1. Relative pressure (p/p Figure S1. N 2 adsorption-desorption isotherm of the sample derived from the reaction of Cu(NO 3 2 and CA. The reaction conditions are similar to the synthesis of Cu 3 (BTC 2 except that the ligand BTC was replaced by CA. S11
Intensity (a.u. 4 8 12 16 2 2 (degrees Figure S11. XRD pattern of the sample derived from the reaction of Cu(NO 3 2 and BTC in the presence of CA and CuBr 2. The reaction conditions are similar to the synthesis of mesomof(sc except that CTAB was replaced by CuBr 2 with the same molar amount of Br. (a Pore volume (cm 3. g CTAB =.2g.25 CA.1.2.8.15.1.2.1. 2 1 3 Pore diameter (A o (b Pore volume (cm 3. g CTAB =.2g.25 CA.1.2.8.15.1.2.1. 2 1 3 Pore diameter (A o (c Pore volume (cm 3. g CTAB =.2g CA.3.1.8.2.1.2.1. 2 1 3 Pore diameter (A o Figure S12. Pore size distributions of mesomofs synthesized in the presence of different amount of CA. Pore size distributions were calculated from adsorption braches by using (a BJH, (b BJH-KJS, and (c DFT models. S12
(a CA = g (b CA = g (c CA = g Pore volume (cm 3. g.25.2.15.1 CTAB.6.4.2.1 Pore volume (cm 3. g.25.2.15.1 CTAB.6.4.2.1 Pore volume (cm 3. g.3.2.1 CTAB.6.4.2.1. 2 1 3 Pore diameter (A o. 2 1 3 Pore diameter (A o. 2 1 3 Pore diameter (A o Figure S13. Pore size distributions of mesomofs synthesized in the presence of different amount of CTAB. Pore size distributions were calculated from adsorption braches by using (a BJH, (b BJH-KJS, and (c DFT models. S13