Korean Chemical Engineering Research

The Korean Institute of Chemical Engineers (한국화학공학회)
권호 표지
DOI QR코드

DOI QR Code

Sonochemical Synthesis of UiO-66 for CO2 Adsorption and Xylene Isomer Separation

초음파 합성법을 이용한 UiO-66의 합성 및 이산화탄소 흡착/자일렌 이성체 분리 연구

  • Kim, Hee-Young (Department of Chemical Engineering, Inha University) ;
  • Kim, Se-Na (Department of Chemical Engineering, Inha University) ;
  • Kim, Jun (Department of Chemical Engineering, Inha University) ;
  • Ahn, Wha-Seung (Department of Chemical Engineering, Inha University)
  • 김희영 (인하대학교 화학공학과) ;
  • 김세나 (인하대학교 화학공학과) ;
  • 김준 (인하대학교 화학공학과) ;
  • 안화승 (인하대학교 화학공학과)
  • Received : 2013.04.19
  • Accepted : 2013.05.17
  • Published : 2013.08.01
Download PDF
⟨ Previous Next ⟩

Abstract

Zr-benzendicarboxylate structure, UiO-66 was prepared in 1-L batch scale by using a unique sonochemical-solvothermal combined synthesis method. The produced UiO-66 showed uniform particles of ca. $0.2{\mu}m$ in size with the BET surface area of $1,375m^2/g$ in high product yield (>95%). The UiO-66 showed 198 and 84 mg/g $CO_2$ adsorption capacity at 273 K and 298 K, respectively, with excellent $CO_2$ selectivity ($CO_2:N_2=32:1$) at ambient conditions. The isosteric heat of $CO_2$ adsorption varied from 33 to 25 kJ/mol as the adsorption progressed. The UiO-66 tested for xylene isomer separation in a liquid-phase batch mode confirmed preferential adsorption of the adsorbent for o-xylene over m-, and p-xylene.

초음파-용매열 혼합방법으로 염화지르코늄과 1,4-benzenedicarboxylic acid를 사용하여 다공성 금속유기 구조체인 UiO-66을 1-L 규모로 제조하였다. 합성 개시 2시간 뒤 약 $0.2{\mu}m$의 작고 고른 형태와 $1,375m^2/g$의 높은 비표면적을 갖는 결정을 95%의 높은 수율로 얻을 수 있었다. 제조된 UiO-66 물질의 이산화탄소 흡착 거동을 조사한 결과, 1기압 273 K 및 298K에서 각각 198 및 84 mg/g의 흡착량과 32:1 이상의 높은 질소 대비 이산화탄소 흡착 선택성을 갖는 것을 확인하였다. 흡착이 진행됨에 따라 흡착열은 33에서 25 kJ/mol 로 감소하였다. 또한 UiO-66 물질을 사용하여 액상 회분식 조건에서 자일렌 이성체의 분리 연구를 수행하였으며, o-자일렌이 단일성분 최대 흡착능 및 경쟁흡착에서도 m-, p-자일렌 대비 약 2배 이상의 높은 흡착 선호도를 갖는 것을 확인할 수 있었다.

Keywords

References

  1. Rowsell, J. L. C., Spencer, E. C., Eckert, J., Howard, J. A. K. and Yaghi, O. M., "Gas Adsorption Sites in a Large-pore Metalorganic Framework," Science, 309, 1350-1354(2005). https://doi.org/10.1126/science.1113247
  2. Li, H. L., Eddaoudi, M., O'Keeffe, M. and Yaghi, O. M., "Design and Synthesis of An Exceptionally Stable and Highly Porous Metal-organic Framework," Nature, 402, 276-279(1999). https://doi.org/10.1038/46248
  3. Ferey, G., Latroche, M., Serre, C., Millange, F., Loiseau, T. and Guegan, A. P., "Hydrogen Adsorption in the Nanoporous Metalbenzenedicarboxylate $M(OH)(O_{2}C-C_{6}H_{4}-CO_{2})$ (M=$Al^{3+}$, $Cr^{3+}$), MIL-53," Chem. Commun., 24, 2976-2977(2003).
  4. Kitaura, R., Seki, K., Akiyama, G. and Kitagawa, S., "Porous Coordination-Polymer Crystals with Gated Channels Specific for Supercritical Gases," Angew. Chem. Int. Ed., 42, 428-431(2003). https://doi.org/10.1002/anie.200390130
  5. Yang, D. A., Cho, H. Y., Kim, J., Yang, S. T. and Ahn, W. S., "$CO_{2}$ Capture and Conversion Using Mg-MOF-74 Prepared by a Sonochemical Method," Energy Environ. Sci., 5, 6465-6473(2012). https://doi.org/10.1039/c1ee02234b
  6. Kim, J., Kim, W. Y. and Ahn, W. S., "Amine-functionalized MIL- 53(Al) for $CO_{2}$/$N_{2}$ Separation: Effect of Textural Properties," Fuel, 102, 574-579(2012). https://doi.org/10.1016/j.fuel.2012.06.016
  7. Kim, J., Bhattacharjee, S., Jeong, K. E., Jeong, S. Y. and Ahn, W. S., "Selective Oxidation of Tetralin over a Chromium Terephthalate Metal Organic Framework, MIL-101," Chem. Commun., 3904- 3906(2009).
  8. Lee, J. Y., Farha, O. K., Roberts, J., Scheidt, K. A., Nguyen, S. B. T. and Hupp, J. T., "Metal-organic Framework Materials as Catalysts," Chem. Soc. Rev., 38, 1450-1459(2009). https://doi.org/10.1039/b807080f
  9. 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., Cynober, L., Gil, S., Ferey, G., Couvreur, P. and Gref, R., "Porous Metal-organic-framework Nanoscale Carriers as a Potential Platform for Drug Delivery and Imaging," Nat. Mater., 9, 172-178(2010). https://doi.org/10.1038/nmat2608
  10. Achmann, S., Hagen, G., Kita, J., Malkowsky, I. M., Kiener, C. and Moos, R., "Metal-organic Frameworks for Sensing Applications in the Gas Phase," Sensors, 9, 1574-1589(2009). https://doi.org/10.3390/s90301574
  11. Liu, B., Shioyama, H., Akita, T. and Xu, Q., "Metal-organic Framework as a Template for Porous Carbon Synthesis," J. Am. Chem. Soc., 130, 5390-5391(2008). https://doi.org/10.1021/ja7106146
  12. Cho, H. Y., Yang, D. A., Kim, J., Jeong, S. Y. and Ahn, W. S., "$CO_{2}$ Adsorption and Catalytic Application of Co-MOF-74 Synthesized by Microwave Heating," Catal. Today, 185, 35-40(2012). https://doi.org/10.1016/j.cattod.2011.08.019
  13. Kim, J., Kim, S. H., Yang, S. T. and Ahn, W. S., "Bench-scale Preparation of $Cu_{3}(BTC)_{2}$ by Ethanol Reflux: Synthesis Optimization and Adsorption/catalytic Applications," Micropor. Mesopor. Mater., 161, 48-55(2012). https://doi.org/10.1016/j.micromeso.2012.05.021
  14. Dhakshinamoorthy, A., Alvaro, M. and Garcia, H., "Metal-Organic Frameworks as Efficient Heterogeneous Catalysts for the Regioselective Ring Opening of Epoxides," Chem. Eur. J., 16, 8530- 8536(2010). https://doi.org/10.1002/chem.201000588
  15. Dhakshinamoorthy, A., Alvaro, M. and Garcia, H., "Metal Organic Frameworks as Solid Acid Catalysts for Acetalization of Aldehydes with Methanol," Adv. Synth. Catal., 352, 3022-3030(2010). https://doi.org/10.1002/adsc.201000537
  16. Liu, Y. D., Kim, J., Ahn, W. S. and Choi, H. J., "Novel Electrorheological Properties of a Metal-organic Framework $Cu_{3}(BTC)_{2}$," Chem. Commun., 48, 5635-5637(2012). https://doi.org/10.1039/c2cc30367a
  17. Czaja, A. U., Trukhan, N. and Mller, U., "Industrial Applications of Metal-organic Frameworks," Chem. Soc. Rev., 38, 1284-1293(2009). https://doi.org/10.1039/b804680h
  18. Cavka, J. H., Jakobsen, S., Olsbye, U., Guillou, N., Lamberti, C., Bordiga, S. and Lillerud, K. P., "A New Zirconium Inorganic Building Brick Forming Metal Organic Frameworks with Exceptional Stability," J. Am. Chem. Soc., 130, 13850-13851(2008). https://doi.org/10.1021/ja8057953
  19. Puchberger, M., Kogler, F. R., Jupa, M., Gross, S., Fric, H., Kickelbick, G. and Schubert, U., "Can the Clusters $Zr_{6}O_{4}(OH)_{4}(OOCR)_{12}$ and $[Zr_{6}O_{4}(OH)_{4}(OOCR)_{12}]_{2}$ Be Converted into Each Other?," Eur. J. Inorg. Chem., 3283-3293(2006).
  20. Kandiah, M., Nilsen, M. H., Usseglio, S., Jakobsen, S., Olsbye, U., Tilset, M., Larabi, C., Quadrelli, E. A., Bonino, F. and Lillerud, K. P., "Synthesis and Stability of Tagged UiO-66 Zr-MOFs," Chem. Mater., 22, 6632-6640(2010). https://doi.org/10.1021/cm102601v
  21. Eddaoudi, M., Kim, J., Rosi, N. L., Vodak, D. T., Wachter, J., O'Keeffe, M. and Yaghi, O. M., "Systematic Design of Pore Size and Functionality in Isoreticular Metal-organic Frameworks and Application in Methane Storage," Science, 295, 469-472(2002). https://doi.org/10.1126/science.1067208
  22. Rosi, N. L., Eckert, J., Eddaoudi, M., Vodak, D. T., Kim, J., O'Keeffe, M. and Yaghi, O. M., "Hydrogen Storage in Microporous Metal-organic Frameworks," Science, 300, 1127-1129(2003). https://doi.org/10.1126/science.1083440
  23. Mueller, U., Schubert, M., Teich, F., Puetter, H., Schierle-Arndt, K. and Pastre, J., "Metal-organic Frameworks-prospective Industrial Applications," J. Mater. Chem., 16, 626-636(2006). https://doi.org/10.1039/b511962f
  24. Choi, J. S., Son, W. J., Kim, J. and Ahn, W. S., "Metal-organic Framework MOF-5 Prepared by Microwave Heating: Factors to be Considered," Micropor. Mesopor. Mater., 116, 727-731(2008). https://doi.org/10.1016/j.micromeso.2008.04.033
  25. Jhung, S. H., Lee, J. H., Yoon, J. W., Serre, C., Ferey, G. and Chang, J. S., "Microwave Synthesis of Chromium Terephthalate MIL-101 and Its Benzene Sorption Ability," Adv. Mater., 19, 121-124(2007). https://doi.org/10.1002/adma.200601604
  26. Frisceic, T., Reid, D. G., Halasz, I., Stein, R. S., Dinnebier, R. E. and Duer, M. J., "Ion- and Liquid-assisted Grinding: Improved Mechanochemical Synthesis of Metal-organic Frameworks Reveals Salt Inclusion and Anion Templating," Angew. Chem. Int. Ed., 49, 712-715(2010). https://doi.org/10.1002/anie.200906583
  27. Klimakow, M., Klobes, P., Thüunemann, A. F., Rademann, K. and Emmerling, F., "Mechanochemical Synthesis of Metal-organic Frameworks: A Fast and Facile Approach Toward Quantitative Yields and High Specific Surface Areas," Chem. Mater., 22, 5216-5221(2010). https://doi.org/10.1021/cm1012119
  28. Son, W. J. Kim, J., Kim, J. and Ahn, W. S., "Sonochemical Synthesis of MOF-5," Chem. Commun., 6336-6338(2008).
  29. Li, Z. Q., Qiu, L. G., Su, T., Wu, Y., Wang, W., Wu, Z. Y. and Jiang, X., "$Cu_{3}(BTC)_{2}$ At Ambient Temperature and Pressure: An Efficient and Environmentally Friendly Method,"Mater. Lett., 63, 78-80(2009). https://doi.org/10.1016/j.matlet.2008.09.010
  30. Suslick, K. S., Hammerton, D. A. and Cline, R. E., " Sonochem- Ical Hot Spot," J. Am. Chem. Soc., 108, 5641-5642(1986). https://doi.org/10.1021/ja00278a055
  31. Suslick, K. S., "Sonochemistry," Science, 247, 1439-1445(1990). https://doi.org/10.1126/science.247.4949.1439
  32. Yang, S. T., Kim, J., Cho, H. Y., Kim, S. and Ahn, W. S., "Facile Synthesis of Covalent Organic Frameworks COF-1 and COF-5 by Sonochemical Method," RSC Adv., 2, 10179-10181(2012). https://doi.org/10.1039/c2ra21531d
  33. Cho, H. Y., Kim, J., Kim, S. N. and Ahn, W. S., "High Yield 1-L Scale Synthesis of ZIF-8 Via a Sonochemical Route," Micropor. Mesopor. Mater., 169, 180-184(2013). https://doi.org/10.1016/j.micromeso.2012.11.012
  34. Maes, M., Alaerts, L., Vermoortele, F., Ameloot, R., Couck, S., Finsy, V., Denayer, J. F. M. and De Vos, D. E., "Separation of $C_{5}$-Hydrocarbons on Microporous Materials: Complementary Performance of MOFs and Zeolites," J. Am. Chem. Soc., 132, 2284-2292(2010). https://doi.org/10.1021/ja9088378
  35. Ruthven, D. M., "Fundamentals of Adsorption and Adsorption ProCesses," John Wiley and Sons, New York(1984).
  36. Fabri, J., Graeser, U. and Simo, T. A., "Xylenes. In Ullmann's Encyclopedia of Industrial Chemistry,"Wiley-VCH: Weinheim, Germany(2000).
  37. Alaerts, L., Kirschhock, C. E. A., Maes, M., van der Veen, M. A., Finsy, V., Depla, A., Martens, J. A., Baron, G. V., Jacobs, P. A., Denayer, J. E. M. and De Vos, D. E., "Selective Adsorption and Separation of Xylene Isomers and Ethylbenzene with the Microporous Vanadium(IV) Terephthalate MIL-47," Angew. Chem. Int. Ed., 46, 4293-4297(2007). https://doi.org/10.1002/anie.200700056
  38. Alaerts, L., Maes, M., Jacobs, P. A., Denayer, J. F. M. and De Vos, D. E., "Activation of the Metal-Organic Framework MIL- 47 for Selective Adsorption of Xylenes and Other Difunctionalized Aromatics," Phys. Chem. Chem. Phys., 10, 2979-2985(2008). https://doi.org/10.1039/b719513c
  39. Finsy, V., Kirschhock, C. E. A., Vedts, G., Maes, M., Alaerts, L., De Vos, D. E., Baron, G. V. and Denayer, J. F. M., "Framework Breathing in the Vapour-Phase Adsorption and Separation of Xylene Isomers with the Metal-Organic Framework MIL-53," Chem.-Eur. J., 15, 7724-7731(2009). https://doi.org/10.1002/chem.200802672
  40. Alaerts, L., Maes, M., Giebeler, L., Jacobs, P. A., Martens, J. A., Denayer, J. F. M., Kirschhock, C. E. A. and De Vos, D. E., "Selective Adsorption and Separation of ortho-Substituted Alkylaromatics with the Microporous Aluminum Terephthalate MIL-53," J. Am. Chem. Soc., 130, 14170-14178(2008). https://doi.org/10.1021/ja802761z
  41. Moreira, M. A., Santos, J. C., Ferreira, A. F. P., Loureiro, J. M., Ragon, F., Horcajada, P., Yot, P., Serre, C. and Rodrigues, A. E., "Toward Understanding the Influence of Ethylbenzene in P-Xylene Selectivitiy of the Porous Titanium Amino Terephthalate MIL- 125(Ti): Adsorption Equilibrium and Separation of Xylene Isomers," Langmuir., 28, 3494-3502(2012). https://doi.org/10.1021/la204969t
  42. Vermoortele, F., Maes, M., Moghadam, P. Z., Lennox, M. J., Ragon, F., Boulhout, M., Biswas, S., Laurier, K. G. M., Beurroies, I., Denoyel, R., Roeffaers, M. B. J., Stock, N., Duren, T., Serre, C. and De Vos, D. E., "p-Xylene-Selective Metal-Organic Frameworks: A Case of Topology-Directed Selectivity," J. Am. Chem. Soc., 133, 18526-18529(2011). https://doi.org/10.1021/ja207287h
  43. Barcia, P. S., Guimaraes, D., Mendes, P. A. P., Silva, J. A. C., Guillerm, V., Chevreau, H., Serre, C. and Rodrigues, A. E., "Reverse Shape Selectivity in the Adsorption of Hexane and Xylene Isomers in MOF UiO-66," Micropor. Mesopor. Mater., 139, 67-73(2011). https://doi.org/10.1016/j.micromeso.2010.10.019
  44. Smit, B. and Maesen, T. L. M., "Towards a Molecular Understanding of Shape Selectivity," Nature., 451, 671-678(2008). https://doi.org/10.1038/nature06552
  45. Moreira, M. A., Santos, J. C., Ferreira, A. F. P., Loureiro, J. M., Ragon, F., Horcajada, P., Shim, K. E., Hwang, Y. K., Lee, U. W., Chang, J. S., Serre, C. and Rodrigues, A. E., "Reverse Shape Selectivity in the Liquid-Phase Adsorption of Xylene Isomers in Zirconium Terephthalate MOF UiO-66," Langmuir, 28, 5715-5723(2012). https://doi.org/10.1021/la3004118

Cited by

  1. Metal–organic framework-based sorbents in analytical sample preparation vol.445, pp.None, 2021, https://doi.org/10.1016/j.ccr.2021.214107