Cu/ZSM-5 and CeO_2-modified Cu/ZSM-5 catalysts were prepared by a wetness impregnation method. The addition of CeO_2 was found to enhance the NO_x selective catalytic reduction（SCR） activity of the catalyst at low t...Cu/ZSM-5 and CeO_2-modified Cu/ZSM-5 catalysts were prepared by a wetness impregnation method. The addition of CeO_2 was found to enhance the NO_x selective catalytic reduction（SCR） activity of the catalyst at low temperatures, but the high-temperature activity was weakened. The catalysts were characterized by X-ray diffraction（XRD）, nitrogen physisorption, inductively coupled plasma optical emission spectrometry（ICP-OES）, X-ray photoelectron spectroscopy（XPS）, electron paramagnetic resonance（EPR）, H_2 temperature-programmed reduction（TPR） and NH_3 temperature-programmed desorption（TPD）. The results showed that more CuO clusters instead of isolated Cu^（2＋） species were obtained on the modified catalyst. These active CuO clusters, as well as the Cu-Ce synergistic effect, improved the redox property of the catalyst and low-temperatures SCR activity via promoting the oxidation of NO to NO_2 and fast SCR reaction. The loss in high-temperatures activity was attributed to the enhanced competitive oxidation of NH_3 by O_2 and decreased surface acidity of the catalyst.展开更多
In this work, a series of Cu-ZSM-5 catalysts with different SiO2/Al2O3 ratios(25, 50, 100 and200) were synthesized and investigated in n-butylamine catalytic degradation. The n-butylamine can be completely catalytic d...In this work, a series of Cu-ZSM-5 catalysts with different SiO2/Al2O3 ratios(25, 50, 100 and200) were synthesized and investigated in n-butylamine catalytic degradation. The n-butylamine can be completely catalytic degradation at 350 ℃ over all Cu-ZSM-5 catalysts. Moreover, Cu-ZSM-5(25) exhibited the highest selectivity to N2, exceeding 90% at 350 ℃. These samples were investigated in detail by several characterizations to illuminate the dependence of the catalytic performance on redox properties, Cu species, and acidity. The characterization results proved that the redox properties and chemisorption oxygen primarily affect n-butylamine conversion. N2 selectivity was impacted by the Bronsted acidity and the isolated Cu^2+ species. Meanwhile, the surface acid sites over Cu-ZSM-5 catalysts could influence the formation of Cu species. Furthermore, in situ diffuse reflectance infrared Fourier transform spectra was adopted to explore the reaction mechanism. The Cu-ZSM-5 catalysts are the most prospective catalysts for nitrogen-containing volatile organic compounds removal, and the results in this study could provide new insights into catalysts design for VOC catalytic oxidation.展开更多
This study was aimed to investigate the effects of hydrothermal aging, propene and SO<sub>2</sub> poisoning on the ammonia-selective catalytic reduction (NH<sub>3</sub>-SCR) performance of both...This study was aimed to investigate the effects of hydrothermal aging, propene and SO<sub>2</sub> poisoning on the ammonia-selective catalytic reduction (NH<sub>3</sub>-SCR) performance of both Cu-SAPO-34 and Cu-ZSM-5. The catalytic activities of fresh, aged and poisoned samples were tested in ammonia-selective catalytic reduction (NH<sub>3</sub>-SCR) of NO<sub>x</sub> conditions. The XRD, TG and N<sub>2</sub>-desorption results showed that the structures of the Cu-SAPO-34 and Cu-ZSM-5 remained intact after 750˚C hydrothermally aged, SO<sub>2</sub> and propene poisoned. After hydrothermal aging at 750˚C for 12 h, the NO reduction performance of Cu-ZSM-5 was significantly reduced at lower temperatures, while that of Cu-SAPO-34 was less affected. Moreover, Cu-SAPO-34 catalyst showed high NO conversion with SO<sub>2</sub> or propene compared to Cu-ZSM-5. However, Cu-ZSM-5 showed a larger drop in catalytic activity with SO<sub>2</sub> or propene compared to Cu-SAPO-34 catalyst. The H<sub>2</sub>-TPR results showed that Cu<sup>2 </sup> ions could be reduced to Cu<sup> </sup> and Cu<sup>0</sup> for Cu-ZSM-5, while no significant transformation of copper species was observed for Cu-SAPO-34. Meanwhile, the UV-vis DRS results showed that CuO species were formed in Cu-ZSM-5, while little changes were observed for the Cu-SAPO-34. Cu-SAPO-34 showed high sulfur and hydrocarbon poison resistance compared to Cu-ZSM-5. In summary, Cu-SAPO-34 with small-pore zeolite showed higher hydrothermal stability and better hydrocarbon and sulfur poison resistant than Cu-ZSM-5 with medium-pore.展开更多
Cu-ZSM-5 type molecular sieves were synthesized hydrothermally in weak acid medium in the presence of F- ions. The structures of these samples were investigated.Increasing the amount of copper in synthesized samples t...Cu-ZSM-5 type molecular sieves were synthesized hydrothermally in weak acid medium in the presence of F- ions. The structures of these samples were investigated.Increasing the amount of copper in synthesized samples the unit cell volumes of Cu-ZSM-5 zeolites increase, while the adsorption peaks of Cu-ZSM-5 shift to lower wavenumbers.These facts and the results of the electron probe micrograph and XPS analyese indicate that copper was introduced into the framework of molecular sieve.展开更多
Five Cu-ZSM-5 catalysts were obtained by treating Na-ZSM-5 （Si/Al ratio = 15） with aqueous solutions of differ- ent Cu precursors （CuCl2, Cu（NO3）2, CuSO4, Cu（CH3COO）2, and ammoniacal copper （II） complex ion）...Five Cu-ZSM-5 catalysts were obtained by treating Na-ZSM-5 （Si/Al ratio = 15） with aqueous solutions of differ- ent Cu precursors （CuCl2, Cu（NO3）2, CuSO4, Cu（CH3COO）2, and ammoniacal copper （II） complex ion）. After being pretreated in flowing He at 500 ℃ to form active Cu＋, these catalysts exhibited quite different activities in cata- lytic decomposition of N2O. CZM-AC（II） （prepared by ammoniacal copper （II） complex ion） with 9.4 wt% Cu con- tent was the most active among these Cu-ZSM-5 catalysts, achieving almost complete N2I conversion at 400 ℃. CZM-CA （prepared using Cu（ CH3COO）2 as the Cu precursor） with 2.8 wt% Cu content was the second most active catalyst among these Cu-ZSM-5 catalysts, achieving almost complete N2I conversion at 425 ℃. CZM-CC, CZM- CN, and CZM-CS prepared by using CuCl2, Cu（NO3）2, or CuSO4 as the Cu precursor with similar Cu contents （≈1.7 wt%） were the least active among these Cu-ZSM-5 catalysts, achieving ca. 90% N2O conversion at 500 ℃. XRD, ICP, SEM, TEM, EDX-mapping, and CO-IR experiments were conducted to characterize relevant samples. The superior activity of CZM-AC（II） can be attributed to the high contents of total Cu＋ and dimeric Cu＋ among these samples. The influence of co-fed O2 or H2O on the catalytic performance of typical samples was also studied.展开更多
基金Project supported by the the National Natural Science Foundation of China(51372137)Ministry of Science and Technology,China(2015AA034603)
文摘Cu/ZSM-5 and CeO_2-modified Cu/ZSM-5 catalysts were prepared by a wetness impregnation method. The addition of CeO_2 was found to enhance the NO_x selective catalytic reduction（SCR） activity of the catalyst at low temperatures, but the high-temperature activity was weakened. The catalysts were characterized by X-ray diffraction（XRD）, nitrogen physisorption, inductively coupled plasma optical emission spectrometry（ICP-OES）, X-ray photoelectron spectroscopy（XPS）, electron paramagnetic resonance（EPR）, H_2 temperature-programmed reduction（TPR） and NH_3 temperature-programmed desorption（TPD）. The results showed that more CuO clusters instead of isolated Cu^（2＋） species were obtained on the modified catalyst. These active CuO clusters, as well as the Cu-Ce synergistic effect, improved the redox property of the catalyst and low-temperatures SCR activity via promoting the oxidation of NO to NO_2 and fast SCR reaction. The loss in high-temperatures activity was attributed to the enhanced competitive oxidation of NH_3 by O_2 and decreased surface acidity of the catalyst.
基金supported by the National Natural Science Foundation of China (Nos. 21477149,21677160,and 21707152)Beijing Municipal Science and Technology Commission (Nos. Z181100000118003 and Z181100005418011)。
文摘In this work, a series of Cu-ZSM-5 catalysts with different SiO2/Al2O3 ratios(25, 50, 100 and200) were synthesized and investigated in n-butylamine catalytic degradation. The n-butylamine can be completely catalytic degradation at 350 ℃ over all Cu-ZSM-5 catalysts. Moreover, Cu-ZSM-5(25) exhibited the highest selectivity to N2, exceeding 90% at 350 ℃. These samples were investigated in detail by several characterizations to illuminate the dependence of the catalytic performance on redox properties, Cu species, and acidity. The characterization results proved that the redox properties and chemisorption oxygen primarily affect n-butylamine conversion. N2 selectivity was impacted by the Bronsted acidity and the isolated Cu^2+ species. Meanwhile, the surface acid sites over Cu-ZSM-5 catalysts could influence the formation of Cu species. Furthermore, in situ diffuse reflectance infrared Fourier transform spectra was adopted to explore the reaction mechanism. The Cu-ZSM-5 catalysts are the most prospective catalysts for nitrogen-containing volatile organic compounds removal, and the results in this study could provide new insights into catalysts design for VOC catalytic oxidation.
文摘This study was aimed to investigate the effects of hydrothermal aging, propene and SO<sub>2</sub> poisoning on the ammonia-selective catalytic reduction (NH<sub>3</sub>-SCR) performance of both Cu-SAPO-34 and Cu-ZSM-5. The catalytic activities of fresh, aged and poisoned samples were tested in ammonia-selective catalytic reduction (NH<sub>3</sub>-SCR) of NO<sub>x</sub> conditions. The XRD, TG and N<sub>2</sub>-desorption results showed that the structures of the Cu-SAPO-34 and Cu-ZSM-5 remained intact after 750˚C hydrothermally aged, SO<sub>2</sub> and propene poisoned. After hydrothermal aging at 750˚C for 12 h, the NO reduction performance of Cu-ZSM-5 was significantly reduced at lower temperatures, while that of Cu-SAPO-34 was less affected. Moreover, Cu-SAPO-34 catalyst showed high NO conversion with SO<sub>2</sub> or propene compared to Cu-ZSM-5. However, Cu-ZSM-5 showed a larger drop in catalytic activity with SO<sub>2</sub> or propene compared to Cu-SAPO-34 catalyst. The H<sub>2</sub>-TPR results showed that Cu<sup>2 </sup> ions could be reduced to Cu<sup> </sup> and Cu<sup>0</sup> for Cu-ZSM-5, while no significant transformation of copper species was observed for Cu-SAPO-34. Meanwhile, the UV-vis DRS results showed that CuO species were formed in Cu-ZSM-5, while little changes were observed for the Cu-SAPO-34. Cu-SAPO-34 showed high sulfur and hydrocarbon poison resistance compared to Cu-ZSM-5. In summary, Cu-SAPO-34 with small-pore zeolite showed higher hydrothermal stability and better hydrocarbon and sulfur poison resistant than Cu-ZSM-5 with medium-pore.
文摘Cu-ZSM-5 type molecular sieves were synthesized hydrothermally in weak acid medium in the presence of F- ions. The structures of these samples were investigated.Increasing the amount of copper in synthesized samples the unit cell volumes of Cu-ZSM-5 zeolites increase, while the adsorption peaks of Cu-ZSM-5 shift to lower wavenumbers.These facts and the results of the electron probe micrograph and XPS analyese indicate that copper was introduced into the framework of molecular sieve.
基金Supported by the National Natural Science Foundation of China(Grant No.21477022)
文摘Five Cu-ZSM-5 catalysts were obtained by treating Na-ZSM-5 （Si/Al ratio = 15） with aqueous solutions of differ- ent Cu precursors （CuCl2, Cu（NO3）2, CuSO4, Cu（CH3COO）2, and ammoniacal copper （II） complex ion）. After being pretreated in flowing He at 500 ℃ to form active Cu＋, these catalysts exhibited quite different activities in cata- lytic decomposition of N2O. CZM-AC（II） （prepared by ammoniacal copper （II） complex ion） with 9.4 wt% Cu con- tent was the most active among these Cu-ZSM-5 catalysts, achieving almost complete N2I conversion at 400 ℃. CZM-CA （prepared using Cu（ CH3COO）2 as the Cu precursor） with 2.8 wt% Cu content was the second most active catalyst among these Cu-ZSM-5 catalysts, achieving almost complete N2I conversion at 425 ℃. CZM-CC, CZM- CN, and CZM-CS prepared by using CuCl2, Cu（NO3）2, or CuSO4 as the Cu precursor with similar Cu contents （≈1.7 wt%） were the least active among these Cu-ZSM-5 catalysts, achieving ca. 90% N2O conversion at 500 ℃. XRD, ICP, SEM, TEM, EDX-mapping, and CO-IR experiments were conducted to characterize relevant samples. The superior activity of CZM-AC（II） can be attributed to the high contents of total Cu＋ and dimeric Cu＋ among these samples. The influence of co-fed O2 or H2O on the catalytic performance of typical samples was also studied.
