MnO_x-CeO_2 catalysts were synthesized to investigate the active sites for NO oxidation by varying the calcination temperature. XRD and TEM results showed that cubic CeO_2 and amorphous MnO_x existed in MnO_x-CeO_2 ca...MnO_x-CeO_2 catalysts were synthesized to investigate the active sites for NO oxidation by varying the calcination temperature. XRD and TEM results showed that cubic CeO_2 and amorphous MnO_x existed in MnO_x-CeO_2 catalysts. High temperature calcination caused the sintering of amorphous MnO_x and transforming to bulk crystalline Mn_2O_3, H_2-TPR and XPS results suggested the valence of Mn in MnO_x-CeO_2 was higher than pure MnO_x, and decreased with the increasing calcination temperature, The turnover frequency(TOF) was calculated based on the initial reducibility according to H_2-TPR quantitation and kinetic study. The TOF results indicated that the initial reducibility of amorphous MnO_x with high valence manganese ions was equivalent to the active sites for NO oxidation. It can be inferred that the amorphous MnO_x plays a key role in low-temperature NO oxidation.展开更多
Thermally stable Zr4+, Al3+, and Si4+ cations were incorporated into the lattice of CeO2 nano‐rods (i.e., CeO2‐NR) in order to improve the specific surface area. The undoped and Zr4+, Al3+, and Si4+ doped nano‐rods...Thermally stable Zr4+, Al3+, and Si4+ cations were incorporated into the lattice of CeO2 nano‐rods (i.e., CeO2‐NR) in order to improve the specific surface area. The undoped and Zr4+, Al3+, and Si4+ doped nano‐rods were used as supports to prepare MnOx/CeO2‐NR, MnOx/CZ‐NR, MnOx/CA‐NR, and MnOx/CS‐NR catalysts, respectively. The prepared supports and catalysts were comprehensively characterized by transmission electron microscopy (TEM), high‐resolution TEM, X‐ray diffraction, Raman and N2‐physisorption analyses, hydrogen temperature‐programmed reduction, ammonia temperature‐programmed desorption, in situ diffuse reflectance infrared Fourier‐transform spectroscopic analysis of the NH3 adsorption, and X‐ray photoelectron spectroscopy. Moreover, the catalytic performance and H2O+SO2 tolerance of these samples were evaluated through NH3‐selective catalytic reduction (NH3‐SCR) in the absence or presence of H2O and SO2. The obtained results show that the MnOx/CS‐NR catalyst exhibits the highest NOx conversion and the lowest N2O concentration, which result from the largest number of oxygen vacancies and acid sites, the highest Mn4+ content, and the lowest redox ability. The MnOx/CS‐NR catalyst also presents excellent resistance to H2O and SO2. All of these phenomena suggest that Si4+ is the optimal dopant for the MnOx/CeO2‐NR catalyst.展开更多
MnOx-CeO2 composite catalysts were prepared by a coprecipitation method and tested for formaldehyde (HCHO) and carbon monoxide (CO) oxidation. X-ray photon spectroscopy (XPS) results indicated that the average o...MnOx-CeO2 composite catalysts were prepared by a coprecipitation method and tested for formaldehyde (HCHO) and carbon monoxide (CO) oxidation. X-ray photon spectroscopy (XPS) results indicated that the average oxidation state of surface Mn species in CeMn composite catalyst was higher compared to the pure MnOx. The enhancement of reactivity for HCHO oxidation was due to the activation of the lattice oxygen species in MnOx by the addition of CeO2, which was confirmed by the H2 temperature programmed reduction (HE-TPR) results. The remarkable enhancement of reactivity for CO oxidation by the addition of CeO2 was due to the active oxygen species generated on the CeO2 surface which directly participated in the reaction.展开更多
This work examines the influence of preparation methods on the physicochemical properties and catalytic performance of MnOx‐CeO2 catalysts for selective catalytic reduction of NO by NH3 (NH3‐SCR) at low temperature....This work examines the influence of preparation methods on the physicochemical properties and catalytic performance of MnOx‐CeO2 catalysts for selective catalytic reduction of NO by NH3 (NH3‐SCR) at low temperature. Five different methods, namely, mechanical mixing, impregnation,hydrothermal treatment, co‐precipitation, and a sol‐gel technique, were used to synthesizeMnOx‐CeO2 catalysts. The catalysts were characterized in detail, and an NH3‐SCR model reaction waschosen to evaluate the catalytic performance. The results showed that the preparation methodsaffected the catalytic performance in the order: hydrothermal treatment > sol‐gel > co‐precipitation> impregnation > mechanical mixing. This order correlated with the surface Ce3+ and Mn4+ content,oxygen vacancies and surface adsorbed oxygen species concentration, and the amount of acidic sitesand acidic strength. This trend is related to redox interactions between MnOx and CeO2. The catalystformed by a hydrothermal treatment exhibited excellent physicochemical properties, optimal catalyticperformance, and good H2O resistance in NH3‐SCR reaction. This was attributed to incorporationof Mnn+ into the CeO2 lattice to form a uniform ceria‐based solid solution (containing Mn‐O‐Cestructures). Strengthening of the electronic interactions between MnOx and CeO2, driven by thehigh‐temperature and high‐pressure conditions during the hydrothermal treatment also improved the catalyst characteristics. Thus, the hydrothermal treatment method is an efficient and environment‐friendly route to synthesizing low‐temperature denitrification (deNOx) catalysts.展开更多
The NO oxidation reaction was studied over MnOx-CeO2 catalysts prepared by co-precipitation, impregnation and mechanical mixing method, respectively. It was found that the co-precipitation was the most active and a 60...The NO oxidation reaction was studied over MnOx-CeO2 catalysts prepared by co-precipitation, impregnation and mechanical mixing method, respectively. It was found that the co-precipitation was the most active and a 60% NO conversion was achieved at 250 oC. X-ray diffraction (XRD), Brumauer-Emmett (BET), H2-temperature programmed reduction (H2-TPR) and oxygen storage capacity (OSC) techniques were employed to characterize the physical and chemical properties of the catalysts. XRD results showed that amorphous MnOx or Mn-O-Ce solid solution existed in co-precipitation and impregnation prepared sample, while crystalline MnOx was found in mechanical mixing catalyst. A larger surface area was observed on co-precipitation prepared catalyst compared to those prepared by impregnation and mechanical mixing. The strong interaction between MnOx and CeO2 enhanced the reducibility of the oxides and increased the amount of Mn4+ and activated oxygen, which are favorable for NO oxidation to NO2.展开更多
MnOx-CeO2-Al2O3 mixed oxides were prepared by impregnating manganese and cerium precursors on alumina powders via a sol- gel deposition method. The oxide catalyst exhibited a poor resistance to sulfur dioxide after th...MnOx-CeO2-Al2O3 mixed oxides were prepared by impregnating manganese and cerium precursors on alumina powders via a sol- gel deposition method. The oxide catalyst exhibited a poor resistance to sulfur dioxide after the treatment in 100 ppm SO2/air at 350 °C for 50 h. The formation of manganese sulfate and especially cerium sulfate reduced the availability of surface active metal oxides, blocked the pore structure and decreased the surface area of the catalyst. These changes in chemical and structural and textural properties resulted in a severe loss in the activities of the sulfated catalyst for NO and soot oxidation. The decomposition of sulfates was almost complete during the calcina-tion in air at 800 °C for 30 min, which partially recovered the surface active sites and the catalyst surface area despite the significant sintering of metal oxides. Consequently, the NOx-assisted soot oxidation activity of the catalyst was regenerated to some extent by the oxidation treatment.展开更多
基金Project supported by the National key research and development program(2016YFC0204901)the National Natural Science Foundation of China(21576207)the introduction of talent and technology cooperation plan of Tianjin(14RCGFGX00849)
摘要MnO_x-CeO_2 catalysts were synthesized to investigate the active sites for NO oxidation by varying the calcination temperature. XRD and TEM results showed that cubic CeO_2 and amorphous MnO_x existed in MnO_x-CeO_2 catalysts. High temperature calcination caused the sintering of amorphous MnO_x and transforming to bulk crystalline Mn_2O_3, H_2-TPR and XPS results suggested the valence of Mn in MnO_x-CeO_2 was higher than pure MnO_x, and decreased with the increasing calcination temperature, The turnover frequency(TOF) was calculated based on the initial reducibility according to H_2-TPR quantitation and kinetic study. The TOF results indicated that the initial reducibility of amorphous MnO_x with high valence manganese ions was equivalent to the active sites for NO oxidation. It can be inferred that the amorphous MnO_x plays a key role in low-temperature NO oxidation.
基金supported by National Natural Science Foundation of China (21876168, 21507130)Youth Innovation Promotion Association of CAS (2019376)the Chongqing Science & Technology Commission (cstc2016jcyjA0070, cstckjcxljrc13)~~
摘要Thermally stable Zr4+, Al3+, and Si4+ cations were incorporated into the lattice of CeO2 nano‐rods (i.e., CeO2‐NR) in order to improve the specific surface area. The undoped and Zr4+, Al3+, and Si4+ doped nano‐rods were used as supports to prepare MnOx/CeO2‐NR, MnOx/CZ‐NR, MnOx/CA‐NR, and MnOx/CS‐NR catalysts, respectively. The prepared supports and catalysts were comprehensively characterized by transmission electron microscopy (TEM), high‐resolution TEM, X‐ray diffraction, Raman and N2‐physisorption analyses, hydrogen temperature‐programmed reduction, ammonia temperature‐programmed desorption, in situ diffuse reflectance infrared Fourier‐transform spectroscopic analysis of the NH3 adsorption, and X‐ray photoelectron spectroscopy. Moreover, the catalytic performance and H2O+SO2 tolerance of these samples were evaluated through NH3‐selective catalytic reduction (NH3‐SCR) in the absence or presence of H2O and SO2. The obtained results show that the MnOx/CS‐NR catalyst exhibits the highest NOx conversion and the lowest N2O concentration, which result from the largest number of oxygen vacancies and acid sites, the highest Mn4+ content, and the lowest redox ability. The MnOx/CS‐NR catalyst also presents excellent resistance to H2O and SO2. All of these phenomena suggest that Si4+ is the optimal dopant for the MnOx/CeO2‐NR catalyst.
基金supported by the Zhejiang Provincial Natural Science Foundation (Y407020)the Qianjiang Talent Program of Zhejiang Province (QJD0702098)Xinmiao Talent Program of Zhejiang Province (2007R40G2030045)
摘要MnOx-CeO2 composite catalysts were prepared by a coprecipitation method and tested for formaldehyde (HCHO) and carbon monoxide (CO) oxidation. X-ray photon spectroscopy (XPS) results indicated that the average oxidation state of surface Mn species in CeMn composite catalyst was higher compared to the pure MnOx. The enhancement of reactivity for HCHO oxidation was due to the activation of the lattice oxygen species in MnOx by the addition of CeO2, which was confirmed by the H2 temperature programmed reduction (HE-TPR) results. The remarkable enhancement of reactivity for CO oxidation by the addition of CeO2 was due to the active oxygen species generated on the CeO2 surface which directly participated in the reaction.
基金supported by the National Natural Science Foundation of China (No. 21507130)the Open Project Program of Beijing National Laboratory for Molecular Sciences (No. 20140142)+3 种基金the Open Project Program of Chongqing Key Laboratory of Environmental Materials and Remediation Technology from Chongqing University of Arts and Sciences (No. CEK1405)the Open Project Program of Jiangsu Key Laboratory of Vehicle Emissions Control (No. OVEC001)the Open Project Program of Chongqing Key Laboratory of Catalysis and Functional Organic Molecules from Chongqing Technology and Business University (1456029)the Chongqing Science & Technology Commission (Nos. cstc2016jcyj A0070, cstc2014pt-gc20002, cstckjcxljrc13)~~
摘要This work examines the influence of preparation methods on the physicochemical properties and catalytic performance of MnOx‐CeO2 catalysts for selective catalytic reduction of NO by NH3 (NH3‐SCR) at low temperature. Five different methods, namely, mechanical mixing, impregnation,hydrothermal treatment, co‐precipitation, and a sol‐gel technique, were used to synthesizeMnOx‐CeO2 catalysts. The catalysts were characterized in detail, and an NH3‐SCR model reaction waschosen to evaluate the catalytic performance. The results showed that the preparation methodsaffected the catalytic performance in the order: hydrothermal treatment > sol‐gel > co‐precipitation> impregnation > mechanical mixing. This order correlated with the surface Ce3+ and Mn4+ content,oxygen vacancies and surface adsorbed oxygen species concentration, and the amount of acidic sitesand acidic strength. This trend is related to redox interactions between MnOx and CeO2. The catalystformed by a hydrothermal treatment exhibited excellent physicochemical properties, optimal catalyticperformance, and good H2O resistance in NH3‐SCR reaction. This was attributed to incorporationof Mnn+ into the CeO2 lattice to form a uniform ceria‐based solid solution (containing Mn‐O‐Cestructures). Strengthening of the electronic interactions between MnOx and CeO2, driven by thehigh‐temperature and high‐pressure conditions during the hydrothermal treatment also improved the catalyst characteristics. Thus, the hydrothermal treatment method is an efficient and environment‐friendly route to synthesizing low‐temperature denitrification (deNOx) catalysts.
基金supported by National High Technology Research and Development Program of China(863Program,2011AA03A405)grant support from GM Global Research & Development
摘要The NO oxidation reaction was studied over MnOx-CeO2 catalysts prepared by co-precipitation, impregnation and mechanical mixing method, respectively. It was found that the co-precipitation was the most active and a 60% NO conversion was achieved at 250 oC. X-ray diffraction (XRD), Brumauer-Emmett (BET), H2-temperature programmed reduction (H2-TPR) and oxygen storage capacity (OSC) techniques were employed to characterize the physical and chemical properties of the catalysts. XRD results showed that amorphous MnOx or Mn-O-Ce solid solution existed in co-precipitation and impregnation prepared sample, while crystalline MnOx was found in mechanical mixing catalyst. A larger surface area was observed on co-precipitation prepared catalyst compared to those prepared by impregnation and mechanical mixing. The strong interaction between MnOx and CeO2 enhanced the reducibility of the oxides and increased the amount of Mn4+ and activated oxygen, which are favorable for NO oxidation to NO2.
基金Project supported by National Natural Science Foundation of China (51072096)National Program on Key Basic Research Project (973 program)(2010CB732304)
摘要MnOx-CeO2-Al2O3 mixed oxides were prepared by impregnating manganese and cerium precursors on alumina powders via a sol- gel deposition method. The oxide catalyst exhibited a poor resistance to sulfur dioxide after the treatment in 100 ppm SO2/air at 350 °C for 50 h. The formation of manganese sulfate and especially cerium sulfate reduced the availability of surface active metal oxides, blocked the pore structure and decreased the surface area of the catalyst. These changes in chemical and structural and textural properties resulted in a severe loss in the activities of the sulfated catalyst for NO and soot oxidation. The decomposition of sulfates was almost complete during the calcina-tion in air at 800 °C for 30 min, which partially recovered the surface active sites and the catalyst surface area despite the significant sintering of metal oxides. Consequently, the NOx-assisted soot oxidation activity of the catalyst was regenerated to some extent by the oxidation treatment.