Korean Chemical Engineering Research

The Korean Institute of Chemical Engineers (한국화학공학회)
권호 표지

Adsorption of Nitrogen Dioxide on Transition-Metal-Oxide-Incorporated Hydrotalcites

전이금속 산화물이 고정된 하이드로탈사이트에 이산화질소 흡착

  • Park, Ji Won (School of Applied Chemical Engineering, Chonnam National University) ;
  • Seo, Gon (Institute for Catalysis Research, Chonnam National University)
  • 박지원 (전남대학교 응용화학공학부) ;
  • 서곤 (전남대학교 촉매연구소)
  • Received : 2008.08.06
  • Accepted : 2008.10.03
  • Published : 2008.12.31
Download PDF
⟨ Previous Next ⟩

Abstract

Transition-metal-oxide-incorporated hydrotalcites were prepared by hydrothermal reaction of their synthetic mixtures containing precursors of transition metal oxides and their properties of nitrogen dioxide adsorption was investigated. The dispersion of transition metal oxides on the hydrotalcites and the amount and the state of nitrogen dioxide adsorbed on them were examined by using XRD, SEM, XPS, nitrogen adsorption, a gravimetric adsorption system, FT-IR spectroscopy and temperature programmed desorption techniques. Transition metal oxides were mainly incorporated on their surface and the incorporation of iron and nickel oxides to the hydrotalcites increased their adsorption amounts of nitrogen dioxide. The dispersion of iron oxide on the hydrotalcites was effective in increasing the amount of nitrogen dioxide adsorption, while too much amount of iron oxide incorporation reduced the amount of nitrogen dioxide adsorption due to masking of surface basic sites by agglomerated iron oxide. Although the incorporation of iron oxide to the hydrotalcites lowered the adsorption strength of nitrogen dioxide, the incorporation of it with a proper amount enhanced the amount of nitrogen dioxide adsorption and the stability against the hydrothermal treatment.

전이금속 산화물의 전구체가 들어있는 합성모액을 수열 반응시켜 전이금속 산화물이 고정된 하이드로탈사이트를 제조하여 이들에 대한 이산화질소의 흡착 성질을 조사하였다. 전이금속 산화물의 분산도, 이산화질소의 흡착량 및 흡착상태를 XRD, SEM, XPS, 질소 흡착등온선, 중량식 흡착법, FT-IR, 승온탈착법으로 조사하였다. 전이금속 산화물은 주로 하이드로탈사이트의 표면에 분산 담지되었으며, 철과 니켈 산화물이 고정된 하이드로탈사이트에 이산화질소가 많이 흡장되었다. 철 산화물이 표면에 분산되어 담지되면 이산화질소의 흡장량이 많지만, 철 산화물이 지나치게 많이 담지되면 덩어리져서 표면의 염기점을 차폐하므로 이산화질소의 흡장량이 오히려 줄어들었다. 철 산화물의 고정량이 적절하면 하이드로탈사이트에서 이산화질소의 흡장세기는 약해지지만, 흡장량은 많아지고 수열 안정성이 증진되었다.

Keywords

Acknowledgement

Grant : 미래형 자동차의 배기가스 제로화 기술 개발

Supported by : 지식경제부

References

  1. Garin, F., 'Mechanism of $No_x$ Decomposition,' Appl. Catal. A: Gen., 222, 183-219(2001) https://doi.org/10.1016/S0926-860X(01)00827-4
  2. Botas, J. A., Gutierrez-Ortiz, M. A., Gonzalez-Marcos, M. P., Gonzalez-Marcos, J. A. and Gonzalez-Velasco, J. R., 'Kinetic Consideration of Three-way Catalysis in Automobile Exhaust Converters,' Appl. Catal. B: Environ., 32, 243-256(2001) https://doi.org/10.1016/S0926-3373(01)00144-8
  3. Larrubia, M. A., Ramis, G. and Busca, G., 'An FT-IR Study of the Adsorption of Urea and Ammonia over $V_2O_5-MoO_3-TiO_2$ SCR Catalysts,' Appl. Catal. B: Environ., 27, L145-L151(2000) https://doi.org/10.1016/S0926-3373(00)00150-8
  4. Koebel, M., Elsener, M. and Kleemann, M., 'Urea-SCR: A Promising Technique to $No_x$ Emissions from Automotive Diesel Engines,' Catal. Today, 59, 335-345(2000) https://doi.org/10.1016/S0920-5861(00)00299-6
  5. Takahashi, N., Shinjoh, H., Iijima, T., Suzuki, T., Yamazaki, K., Yokota, K., Suzuki, H., Miyoshi, N., Matsumoto, S., Tanizawa, T., Tanaka, T., Tateishi, S. and Kasahara, K., 'The New Concept 3-way Catalyst for Automotive Lean-burn Engine: $No_x$ Storage and Reduction Catalyst,' Catal. Today, 27, 63-69(1996) https://doi.org/10.1016/0920-5861(95)00173-5
  6. Epling, W. S., Parks, J. E., Campbell, G. C., Yezerets, A., Currier, N. W. and Campbell, L. E., 'Further Evidence of Multiple NOx Sorption Sites on $No_x$ Storage/reduction Catalysts,' Catal. Today, 96, 21-39(2004) https://doi.org/10.1016/j.cattod.2004.05.004
  7. Salasc, S., Skoglundh, M. and Fridell, E., 'A Comparison Between Pt and Pd in $No_x$ Storage Catalysts,' Appl. Catal. B: Environ., 36, 145-160(2002) https://doi.org/10.1016/S0926-3373(01)00300-9
  8. Sedlmair, C., Seshan, K., Jentys, A. and Lercher, J. A., 'Studies on the Deactivation of $No_x$ Storage-reduction Catalysts by Sulfur Dioxide,' Catal. Today, 75, 413-419(2002) https://doi.org/10.1016/S0920-5861(02)00091-3
  9. Amberntsson, A., Fridell, E. and Skoglundh, M., 'Influence of Platinum and Rhodium Composition on the NOx Storage and Sulphur Tolerance of a Barium Based $No_x$ Storage Catalyst,' Appl. Catal. B: Environ., 46, 429-439(2003) https://doi.org/10.1016/S0926-3373(03)00269-8
  10. Cavani, F., Trifiro, F. and Vaccari, A., 'Hydrotalcite-type Anionic Clays: Preparation Properties and Applications,' Catal. Today, 11, 173-301(1991) https://doi.org/10.1016/0920-5861(91)80068-K
  11. Vaccari, A., 'Clays and Catalysis: A Promising Future,' Appl. Clay Sci., 14, 161-198(1999) https://doi.org/10.1016/S0169-1317(98)00058-1
  12. Kannan, S., 'Catalytic Applications of Hydrotalcite-like Materials and Their Derived Forms,' Catal. Surv. Asia, 10, 117-137(2006) https://doi.org/10.1007/s10563-006-9015-8
  13. Chmielarz, L., Kustrowski, P., Rafalska-Lasocha, A., Majda, D. and Dziembaj, R., 'Catalytic Activity of Co-Mg-Al, Cu-Mg-Al and Cu-Co-Mg-Al Mixed Oxides Derived from Hydrotalcites in SCR of NO with Ammonia,' Appl. Catal. B: Environ., 35, 195-210(2002) https://doi.org/10.1016/S0926-3373(01)00244-2
  14. Corma, A., Palomares, A. E., Rey, F. and M'arquez, F., 'Simultaneous Catalytic Removal of $So_x$ and $No_x$ with Hydrotalcitederived Mixed Oxides Containing Copper, and Their Possibilities to be Used in FCC Units,' J. Catal., 170, 140-149(1997) https://doi.org/10.1006/jcat.1997.1750
  15. Fornasari, G., Trifiro, F., Vaccari, A., Prinetto, F., Ghiotti, G. and Centi, G., 'Novel Low Temperature $No_x$ Storage-reduction Catalysts for Diesel Light-duty Engine Emissions Based on Hydrotalcite Compounds,' Catal. Today, 75, 421-429(2002) https://doi.org/10.1016/S0920-5861(02)00092-5
  16. Silletti, B. A., Adams, R. T., Sigmon, S. M., Nikolopoulos, A., Spivey, J. J. and Lamb, H. H., 'A Novel $Pd/MgAlO_x$ Catalyst for $No_x$ Storage-reduction,' Catal. Today, 114, 64-71(2006) https://doi.org/10.1016/j.cattod.2006.02.003
  17. Li, L.D., Yu, J. J., Hao, Z. P. and Xu, Z. P., 'Novel Ru-Mg-Al-O Catalyst Derived from Hydrotalcites-like Compound for NO Storage/ decomposition/reduction,' J. Phys. Chem. C, 111, 10552-10559(2007) https://doi.org/10.1021/jp0662000
  18. Fornasari, G., Glockler, R., Livi, M. and Vaccari, A., 'Role of the Mg/Al Atomic Ratio in Hydrotalcite-based Catalysts for $No_x$ Storage/reduction,' Appl. Clay Sci., 29, 258-266(2005) https://doi.org/10.1016/j.clay.2005.02.002
  19. Morandi, S., Prinetto, F., Ghiotti, G., Livi, M. and Vaccari, A., 'FT-IR Investigation of $No_x$ Storage Properties of Pt-Mg(Al)O and Pt/Cu-Mg(Al)O Catalysts Obtained from Hydrotalcite Compounds,' Micropor. Mesopor. Mater., 107, 31-38(2008) https://doi.org/10.1016/j.micromeso.2007.03.014
  20. Jun, J. Y., Zheng, J., Ling, Z., Zheng, P. H. and Zhi, P. X., 'Adsorption/desorption Studies of NOx on Well-mixed Oxides Derived from Co-Mg/Al Hydrotalcite-like Compounds,' J. Phys. Chem. B, 110, 4291-4300(2006)
  21. Yu, J. J., Wang, X. P., Tao, Y. X. and Hao, Z. P., 'Effective $No_x$ Decomposition and Storage/reduction over Mixed Oxides Derived From Layered Double Hydroxide,' Ind. Eng. Chem. Res., 46, 5794-5797(2007) https://doi.org/10.1021/ie0705958
  22. Obalova, L., Pacultova, K., Balabanova, J., Jiratova, K., Bastl, Z., Valaskova, M., Lacny, Z. and Kovanda, F., 'Effect of Mn/Al Ratio in Co-Mn-Al Mixed Oxide Catalysts Prepared from Hydrotalcite-like Precursors on Catalytic Decomposition of $N_2Ox$,' Catal. Today, 119, 233-238(2007) https://doi.org/10.1016/j.cattod.2006.08.027
  23. Centi, G., Arena, G. E. and Perathoner, S., 'Nanostructured Catalysts for $No_x$ Storage-reduction and $N_2Ox$ Decomposition,' J. Catal., 216, 443-454(2003) https://doi.org/10.1016/S0021-9517(02)00072-6
  24. Climent, M. J., Corma, A., Iborra, S., Epping, K. and Velty, A., 'Increasing the Basicity and Catalytic Activity of Hydrotalcites by Different Synthesis Procedures,' J. Catal., 225, 316-326(2004) https://doi.org/10.1016/j.jcat.2004.04.027
  25. Kanezaki, E., 'A Thermally Induced Metastable Solid Phase of Mg/Al-layered Double Hydroxides by Means of in situ High Temperature Powder X-ray Diffraction,' J. Mater. Sci. Lett., 17, 371-374(1998) https://doi.org/10.1023/A:1006570730849
  26. PDF Card, #39-1346
  27. Dupin, J. C., Gonbeau, D., Vinatier, P. and Levasseur, A., 'Systematic XPS Studies of Metal Oxides, Hydroxides and Peroxides,' Phys. Chem. Chem. Phys., 2, 1319-1324(2000) https://doi.org/10.1039/a908800h
  28. Cantrell, D. G., Gillie, L. J., Lee, A. F. and Wilson, K., 'Structure- reactivity Correlations in MgAl Hydrotalcite Catalysts for Biodiesel Synthesis,' Appl. Catal. A: Gen., 287, 183-190(2005) https://doi.org/10.1016/j.apcata.2005.03.027
  29. Marquez, F., Palomares, A. E., Rey, F. and Corma, A., 'Characterisation of the Active Copper Species for the $No_x$ Removal on Cu/Mg/Al Mixed Oxides Derived from Hydrotalcites: an in situ XPS/XAES Study,' J. Mater. Chem., 11, 1675-1680(2001) https://doi.org/10.1039/b009166a
  30. Brik, Y., Kacimi, M., Ziyad, M. and Bozon-Verduraz, F., 'Titaniasupported Cobalt and Cobalt-phosphorus Catalysts: Characterization and Performances in Ethane Oxidative Dehydrogenation,' J. Catal., 202, 118-128(2001) https://doi.org/10.1006/jcat.2001.3262
  31. Lenglet, M., Hochu, F., Diirr J. and Tuilier, M. H., 'Investigation of the Chemical Bonding in $3d^8$ Nickel(II) Charge Transfer Insulators (NiO, oxidic spinels) from Ligand-field Spectroscopy, Ni 2p XPS and X-ray Absorption Spectroscopy,' Solid State Commun., 104, 793-798(1997) https://doi.org/10.1016/S0038-1098(97)00273-1
  32. Grosvenor, A. P., Kobe, B. A., Biesinger, M. C. and Mclntyre, N. S., 'Investigation of Multiple Splitting of Fe 2p XPS Spectra and Bonding in Iron Compounds,' Surf. Interface Anal., 36, 1564-1574(2004) https://doi.org/10.1002/sia.1766
  33. Kucherov, A. V. and Shelef, M., "Quantitative Determination of Isolated $Fe^{3+}$ Cations in FeHZSM-5 Catalysts by ESR," J. Catal., 195, 106-112(2000) https://doi.org/10.1006/jcat.2000.2976
  34. Kucherov, A. V., Montreuil, C. N., Jucherova, T. N. and Shelef, M., 'In Situ High-temperature ESR Characterization of FeZSM- 5 and FeSAPO-34 Catalysts in Flowing Mixtures of NO, $C_3H_6$, and $O_2$,' Catal. Lett., 56, 173-181(1998) https://doi.org/10.1023/A:1019002322340
  35. Ferreira, O. P., Alves, O. L., Gouveia, D. X., Souza Filho, A. G., de Paiva, J. A. C. and Mendes, F. J., 'Thermal Decomposition and Structural Reconstruction Effect on Mg-Fe-based Hydrotalcite Compounds,' J. Solid State Chem., 177, 3058-32069(2008) https://doi.org/10.1016/j.jssc.2004.04.030
  36. Hadjiivanov, K. I., 'Identification of Netural and Charged $N_xO_y$ Surface Species by IR Spectroscopy,' Catal. Rev. -Sci. Eng., 42, 71-144(2000) https://doi.org/10.1081/CR-100100260
  37. Di Cosimo, J. I., Diez, V. K., Xu, M., Iglesia, E. and Apesteguia, C. R., 'Structure and Surface and Catalytic Properties of Mg-Al Basic Oxides,' J. Catal., 178, 499-510(1998) https://doi.org/10.1006/jcat.1998.2161