研究了以离子交换法制备的Fe/ZSM-5上聚合态的Fe氧化物(FeOx)在催化N2O直接分解中的作用。 Fe/ZSM-5催化剂利用600–900 oC的高纯Ar处理,使催化剂中的FeOx发生聚合。利用一系列的表征手段(XRD, BET, DRIFTS, UV/vis-DRS, XAFS, N2O脉冲和O2-TPD)对催化剂进行了表征。结果发现,分子筛骨架外的FeOx在Fe/ZSM-5催化N2O分解中起重要作用；通过研究高温处理的Fe/ZSM-5催化剂中不同FeOx的比例与催化剂活性的关系,得到多核的FeOx是催化N2O分解的主要活性物种；并且,无定形态的FeOx中键长较长的Fe–O键((Fe–O)2)是参与反应的重要物种。
The effects of aggregated Fe oxo (FeOx) species on N2O decomposition activity of aqueous ion‐exchanged Fe/ZSM‐5 were investigated. Aggregation of FeOx species was achieved by thermal treatment of the Fe/ZSM‐5 catalysts at different temperatures (600–900 °C) in pure Ar. The charac‐terizations were carried out using X‐ray diffraction, N2 physisorption, UV‐Vis diffuse reflectance spectroscopy, X‐ray absorption fine structure spectroscopy, pulse‐response analysis, and O2‐temperature‐programmed desorption. The FeOx species on the external framework of the ZMS‐5 zeolite played a dominant role in N2O decomposition over Fe/ZSM‐5. By studying the relationship between the contents of the various existing iron species and activity of the different catalysts, pol‐ynuclear FeOx appeared to be the main active phase for N2O decomposition. Additionally, Fe–O with a long bond length ((Fe–O)2) in amorphous polynuclear FeOx was positively correlated to the activi‐ty of the catalysts, indicating that (Fe–O)2 was the active species for N2O decomposition.
参考文献
| [1] | Pérez-Ramírez J;Kapteijn F;Sch?ffel K;Moulijn J A .[J].Applied Catalysis B:Environmental,2003,44:117. |
| [2] | Stott L;Poulsen C;Lund S;Thunell R .Super ENSO and global climate oscillations at millennial time scales[J].Science,2002(5579):222-226. |
| [3] | Pérez-Ramírez J;Kapteijn F;Mul G;Xu X D Moulijn J A .[J].Catal To-day,2002,76:55. |
| [4] | Pérez-Ramírez J;Kapteijn F;Mul G;Moulijn J A .[J].Applied Catalysis B:Environmental,2002,35:227. |
| [5] | Pérez-Ramírez J;Kapteijn F;Mul G;Moulijn J A.[J].Chemistry Communications,2001:693. |
| [6] | Sun K Q;Xia H A;Feng Z C;van Santen R Hensen E Li C .[J].Journal of Catalysis,2008,254:383. |
| [7] | Sun K Q;Zhang H D;Xia H A;Lian Y X, Li Y, Feng Z C, Ying P L, Li C.[J].Chemistry Communications,2004:2480. |
| [8] | Sazama, P.;Sathu, N.K.;Tabor, E.;Wichterlová, B.;Sklenák, ?.;Sobalík, Z..Structure and critical function of Fe and acid sites in Fe-ZSM-5 in propane oxidative dehydrogenation with N_2O and N_2O decomposition[J].Journal of Catalysis,2013:188-203. |
| [9] | Sazama P;Wichterlová B;Tábor E;??astny P,Sathu N K,Sobalik Z,D?de?ek J,Sklenák S,Klein P,Vondrova A .[J].Journal of Catalysis,2014,312:123. |
| [10] | Berlier G;Spoto G;Bordiga S;Ricchiardi G Fisicaro P Zecchina A Rossetti I Selli E Forni L Giamello E Lamberti C .[J].Journal of Catalysis,2002,208:64. |
| [11] | Ferretti A M;Oliva C;Forni L;Berlier G Zecchina A Lamberti C .[J].Journal of Catalysis,2002,208:83. |
| [12] | Kiwi-Minsker L.;Bulushev DA.;Renken A. .Active sites in HZSM-5 with low Fe content for the formation of surface oxygen by decomposing N2O: is every deposited oxygen active?[J].Journal of Catalysis,2003(2):273-285. |
| [13] | Dubkov K A;Ovanesyan N S;Shteinman A A;Starokon E V Panov G I .[J].Journal of Catalysis,2002,207:341. |
| [14] | Pérez-Ramírez J;Kapteijn F;Mul G;Moulijn J A .[J].CATALYSIS COMMUNICATIONS,2002,3:19. |
| [15] | Sun KQ;Xia H;Hensen E;van Santen R;Li C .Chemistry of N2O decomposition on active sites with different nature: Effect of high-temperature treatment of Fe/ZSM-5[J].Journal of Catalysis,2006(1):186-195. |
| [16] | Roy PK;Pirngruber GD .The surface chemistry of N2O decomposition on iron-containing zeolites(II) - The effect of high-temperature pretreatments[J].Journal of Catalysis,2004(1):164-174. |
| [17] | Zhu Q.;van Teeffelen RM.;van Santen RA.;Hensen EJM. .Effect of high-temperature treatment on Fe/ZSM-5 prepared by chemical vapor deposition of FeCl3II. Nitrous oxide decomposition, selective oxidation of benzene to phenol, and selective reduction of nitric oxide by isobutane[J].Journal of Catalysis,2004(2):575-583. |
| [18] | Zhu Q;Mojet B L;Janssen R A J;Hensen E J M van Grondelle J Magusin P C M M van Santen R A .[J].Catalysis Letters,2002,81:205. |
| [19] | Hensen E J M;Zhu Q;Hendrix M M R M;Overweg A R Kooyman P J Sychev M V van Santen R A .[J].Journal of Catalysis,2004,221:560. |
| [20] | Perez-Ramirez J;Kapteijn F;Groen J C;Domenech A Mul G Moulijn J A .[J].Journal of Catalysis,2003,214:33. |
| [21] | Perez-Ramirez J .Active iron sites associated with the reaction mechanism of N2O conversions over steam-activated FeMFI zeolites[J].Journal of Catalysis,2004(2):512-522. |
| [22] | Perez-Ramirez J;Mul G;Kapteijn F;Moulijn J A Overweg A R Domenech A Ribera A Arends I W C E .[J].Journal of Catalysis,2002,207:113. |
| [23] | Perez-Ramirez J;Groen J C;Brückner A;Kunar M S Bentrup U Debbagh M N Villaescusa L A .[J].Journal of Catalysis,2005,232:318. |
| [24] | Kauck?D;Sobalík Z;Schawarze M;Vondrová A Wichterlová B .[J].Journal of Catalysis,2006,238:293. |
| [25] | Joyner R;Stockenhuber M .[J].Journal of Physical Chemistry B,1999,103:5963. |
| [26] | Pirngruber GD;Roy PK;Prins R .The role of autoreduction and of oxygen mobility in N2O decomposition over Fe-ZSM-5[J].Journal of Catalysis,2007(1):147-157. |
| [27] | Pirngruber G D;Luechinger M;Roy P K;Cecchetto A Smirniotis P .[J].Journal of Catalysis,2004,224:429. |
| [28] | Koningsberger D C;Mojet B I;van Dorssen G E;Ramaker E E .[J].Topics in Catalysis,2000,10:143. |
| [29] | Sing K S W;Everett D H;Haul R A W;Moscou L Pierotti R A Rouquerol J Siemieniewska T .[J].Pure and Applied Chemistry,1985,57:603. |
| [30] | Perez-Ramirez J;Kumar M S;Brückner A .[J].Journal of Catalysis,2004,223:13. |
| [31] | Battiston A A;Bitter J H;de Groot F M F;Overweg A R Stephan O van Bokhoven J A Kooyman P J van der Spek C Vankó G Koningsberger D C .[J].Journal of Catalysis,2003,213:251. |
| [32] | The equitions quote from Wikipedia, the free encyclopedia[OL].http://en.wikipedia.org/wiki/Arrhenius_equation |
| [33] | McNaught A D;Wilkinson A.Compendium of Chemical Terminol-ogy[M].IUPAC.Blackwell Sci Inc,1997 |
- 下载量()
- 访问量()
- 您的评分：
-
10%
-
20%
-
30%
-
40%
-
50%