Catalytic activity and hydrothermal stability are both crucial for the application of the selective catalytic reduction of NO_(x)with NH_(3)(NH_(3)-SCR)catalyst in diesel vehicles.In this study,a tin(Sn)-modified Ce-N...Catalytic activity and hydrothermal stability are both crucial for the application of the selective catalytic reduction of NO_(x)with NH_(3)(NH_(3)-SCR)catalyst in diesel vehicles.In this study,a tin(Sn)-modified Ce-Nb mixed-oxide catalyst was synthesized as an NH_(3)-SCR catalyst for NO_(x)emission control.After the intro-duction of Sn,both the NH_(3)-SCR activity and the hydrothermal stability of the catalyst were remarkably promoted.Even after hydrothermal aging at 1000℃,the developed Ce_(1)Sn_(2)Nb_(1)O_(x)catalyst achieved more than 90%NO_(x)conversion at 325-500℃.Various methods,including N2-physisorption,X-ray diffraction,in-situ high-temperature X-ray diffraction,high-resolution transmission electron microscopy,X-ray pho-toelectron spectroscopy,X-ray absorption fine-structure spectroscopy,temperature-programmed reduc-tion of hydrogen,temperature-programmed desorption of ammonia,and density functional theory calculations were used to investigate the promotional effects induced by the Sn species.The characteri-zation results showed that the addition of Sn not only promoted the formation of the Ce-Nb active phase but also improved its thermal stability,contributing to the excellent NH_(3)-SCR performance and hydrothermal stability.This study provides an excellent sintering-resistance catalyst for the application of diesel engine NO_(x)emission control.展开更多
Based on the previous findings that the presence of hydroxyl groups on the outer surface is crucial for maintaining skeletal stability,we propose a strategy modified Cu/SAPO-34 using Pr ions in this study.Therefore,we...Based on the previous findings that the presence of hydroxyl groups on the outer surface is crucial for maintaining skeletal stability,we propose a strategy modified Cu/SAPO-34 using Pr ions in this study.Therefore,we conducted several measurements to investigate the effect of Pr ions on the lowtemperature hydrothermal stability of Cu/SAPO-34.We find that Pr exists only on the surface of Cu/SAPO-34 as ions and oxides,with Pr^(3+)ions playing a protective role in occupying surface acidic sites.The addition of small amounts of Pr leads to the re-dispersion of Cu,resulting in improved lowtemperature selective catalytic reduction(SCR)activity in the as-synthesized samples.Furthermore,it enhances the resistance to decomposition of the Si-(OH)-Al framework during low-temperature hydrothermal aging,thereby preserving the framework structure and allowing detached active Cu species to return to exchangeable positions,ultimately restoring SCR activity.However,as the Pr content increases,the enhanced acidity causes some structural damage,gradually weakening the protective effect.Our work demonstrates that Pr modification is a simple and effective solution to the issue of poor lowtemperature hydrothermal stability in Cu/SAPO-34,providing a promising way for the application of light rare earth elements.展开更多
In this study, phosphorus modification by trimethyl phosphate impregnation was employed to enhance the hydrothermal stability of nano‐sized HZSM‐5 zeolites. A parallel modification was studied by ammonium dihydrogen...In this study, phosphorus modification by trimethyl phosphate impregnation was employed to enhance the hydrothermal stability of nano‐sized HZSM‐5 zeolites. A parallel modification was studied by ammonium dihydrogen phosphate impregnation. The modified zeolites were subjected to steam treatment at 800 °C for 4 h (100% steam) and employed as catalysts for olefin catalyticcracking (OCC) of full‐range fluid catalytic cracking (FCC) gasoline. X‐ray diffraction, N2 physicaladsorption and NH3 temperature‐programmed desorption analysis indicated that, although significantimprovements to the hydrothermal stability of nano‐sized HZSM‐5 zeolites can be observedwhen adopting both phosphorus modification strategies, impregnation with trimethyl phosphatedisplays further enhancement of the hydrothermal stability. This is because higher structural crystallinityis retained, larger specific surface areas/micropore volumes form, and there are greaternumbers of surface acid sites. Reaction experiments conducted using a fixed‐bed micro‐reactor(catalyst/oil ratio = 4, time on stream = 4 s) showed OCC of full‐range FCC gasoline-under a fluidized‐bed reaction mode configuration-to be a viable solution for the olefin problem of FCC gasoline.This reaction significantly decreased the olefin content in the full‐range FCC gasoline feed, andspecifically heavy‐end olefins, by converting the olefins into value‐added C2–C4 olefins and aromatics.At the same time, sulfide content of the gasoline decreased via a non‐hydrodesulfurization process.Nano‐sized HZSM‐5 zeolites modified with trimethyl phosphate exhibited enhanced catalytic performance for OCC of full‐range FCC gasoline.展开更多
A reconstruction strategy has been developed to synthesize Cu-SAPO-34 with a wide crystallization phase region,high solid yield,and tunable Si and Cu contents.Cu-rich SAPO-34 was prepared from a Cu-amine complex,which...A reconstruction strategy has been developed to synthesize Cu-SAPO-34 with a wide crystallization phase region,high solid yield,and tunable Si and Cu contents.Cu-rich SAPO-34 was prepared from a Cu-amine complex,which acted as a precursor and Cu source for the reconstruction synthesis.The role of the Cu-amine complex as a template was restricted,which allowed easier control over the Cu and Si contents than in the previously reported"one-pot"synthesis method.Characterization of the material revealed that the Si(4Al)coordination environment dominates the synthesized Cu-SAPO-34 catalysts.High-temperature hydrothermal treatment increased the isolated Cu2+content slightly,and the acid sites in the low-silica catalyst are more resistant to hydrothermal treatment than those of the existing catalysts.The obtained materials,especially the low-silica Cu-SAPO-34 sample,exhibit excellent catalytic activity and hydrothermal stability for the selective catalytic reduction of NOx by NH3(NH3-SCR).In addition,the influence of the catalyst acidity on the NH3-SCR reaction was also investigated and is discussed.The high synthetic efficiency and outstanding catalytic performance make Cu-SAPO-34 synthesized by the reconstruction method a promising catalyst for the NH3-SCR process.展开更多
The mesoporous Al-SBA-15 zeolite was obtained via impregnation of pure silica-based SBA-15 zeolite with aluminum nitrate.The Al-SBA-15 sample was calcined in air at 800℃for 6 h and hydrothermally treated at near 100...The mesoporous Al-SBA-15 zeolite was obtained via impregnation of pure silica-based SBA-15 zeolite with aluminum nitrate.The Al-SBA-15 sample was calcined in air at 800℃for 6 h and hydrothermally treated at near 100℃for 120 h,respectively,and then the thermal and hydrothermal stability of Al-SBA-15 sample was investigated by X-ray diffractometry(XRD),scanning electron microscopy(SEM),transmission electron microscopy(TEM)and nitrogen adsorption and desorption techniques.The Al-SBA-15 sample was also studied by 27 Al nuclear magnetic resonance(27 Al NMR)and ammonia temperature programmed desorption(NH 3-TPD)techniques.In addition,the catalytic activity of Al-SBA-15 zeolite was investigated by the Friedel-Crafts reactions of 2,4-di-tert-butylphenol with cinnamyl alcohol.The test results showed that the thermal and hydrothermal stability of Al-SBA-15 zeolite was better than that of SBA-15 zeo-lite.The Al-SBA-15 zeolite sample prepared by impregnation method exhibits more framework aluminum species and Al-O-Si units.Therefore,the number of the surface hydroxyl groups was reduced,resulting in the stabilization of framework structure ofAl-SBA-15 zeolite.The aluminum species can form weak and medium-strong acid sites with catalytic activity.展开更多
The activity and hydrothermal stability of the Rh/Ce_(x)Zr_(1-x)O_(2)(x=0,0.05,0.3,0.5) model three-way catalysts for gasoline vehicle emissions control were investigated in this work.Among the Rh/Ce_(x)Zr_(1-x)O_(2) ...The activity and hydrothermal stability of the Rh/Ce_(x)Zr_(1-x)O_(2)(x=0,0.05,0.3,0.5) model three-way catalysts for gasoline vehicle emissions control were investigated in this work.Among the Rh/Ce_(x)Zr_(1-x)O_(2) samples with different Ce/Zr ratios,the Rh/ZrO_(2) sample exhibits a significantly better activity and hydrothermal stability than the rest of the samples.The impacts of having more Ce components in the Rh/Ce_(x)Zr_(1-x)O_(2) catalysts are associated with the strong Rh-O-Ce interaction that tends to over stabilize the rhodium species.A significant amount of such rhodium atoms can be found in the bulk of the support oxides after a hydrothermal aging at 1050℃ with 10% H_(2)O in air for 12 h.Differently,the sintering of rhodium on the surface of Rh/ZrO_(2) catalysts is the main reason for the catalyst deactivation during the hydrothermal aging.These findings provide an example where high dispersion of supported metal induced by strong metal-support interactions does not necessarily lead to high catalytic activity.展开更多
To probe the function of Ce on enhancing low-temperature stability of SAPO-34,Ce/SAPO-34 with different Ce contents was prepared via one-pot method and further treated at 70℃in 80%relative humidity for 24 h.The struc...To probe the function of Ce on enhancing low-temperature stability of SAPO-34,Ce/SAPO-34 with different Ce contents was prepared via one-pot method and further treated at 70℃in 80%relative humidity for 24 h.The structural results prove that the one-pot synthesis is an effective way to introduce Ce(Ce<0.325 wt%)without influencing micro-structural and chemical composition.The lowtemperature hydrothermal stability of Ce/SAPO-34 is enhanced by Ce loading.More than 92%CHA structure and total acidity are maintained over 0.188 wt%Ce/SAPO-34,while only about 20%of that left on pure H/SAPO-34.As Ce exists as Ce^(3+)at exchange sites on the surface of SAPO-34,the results of the linear relationship between protected surface acidity and structure/acidity conservation manifest that Ce^(3+))effectively hinders the structural collapse.This study provides new insight into surface acidity protection for solving the problem of low-temperature hydrothermal stability of SAPO-34.展开更多
A series of CeO2–ZrO2–WO3（CZW）catalysts prepared by a hydrothermal synthesis method showed excellent catalytic activity for selective catalytic reduction（SCR）of NO with NH3 over a wide temperature of 150–550℃....A series of CeO2–ZrO2–WO3（CZW）catalysts prepared by a hydrothermal synthesis method showed excellent catalytic activity for selective catalytic reduction（SCR）of NO with NH3 over a wide temperature of 150–550℃.The effect of hydrothermal treatment of CZW catalysts on SCR activity was investigated in the presence of 10% H2O.The fresh catalyst showed above 90% NOx conversion at 201–459℃,which is applicable to diesel exhaust NOx purification（200–440℃）.The SCR activity results indicated that hydrothermal aging decreased the SCR activity of CZW at low temperatures（below 300℃）,while the activity was notably enhanced at high temperature（above 450℃）.The aged CZW catalyst（hydrothermal aging at 700℃ for 8 hr）showed almost 80% NOx conversion at 229–550℃,while the V2O5–WO3/TiO2 catalyst presented above 80% NOx conversion at 308–370℃.The effect of structural changes,acidity,and redox properties of CZW on the SCR activity was investigated.The results indicated that the excellent hydrothermal stability of CZW was mainly due to the CeO2–ZrO2 solid solution,amorphous WO3 phase and optimal acidity.In addition,the formation of WO3 clusters increased in size as the hydrothermal aging temperature increased,resulting in the collapse of structure,which could further affect the acidity and redox properties.展开更多
Hydrothermal stability is crucial for the practical application of deNO_(x)catalyst on diesel vehicles,for the selective catalytic reduction of NO_(x)with NH_(3)(NH_(3)-SCR).SnO_(2)-based materials possess superior hy...Hydrothermal stability is crucial for the practical application of deNO_(x)catalyst on diesel vehicles,for the selective catalytic reduction of NO_(x)with NH_(3)(NH_(3)-SCR).SnO_(2)-based materials possess superior hydrothermal stability,which is attractive for the development of NH_(3)-SCR catalyst.In this work,a series of Ce-Nb/SnO_(2)catalysts,with Ce and Nb loading on SnO_(2)support,were prepared by impregnation method.It was found that,the NH_(3)-SCR activities and hydrothermal stabilities of the Ce-Nb/SnO_(2)catalysts significantly varied with the impregnation sequences,and the Ce-Nb(f)/SnO_(2) catalyst that firstly impregnated Nb and then impregnated Ce exhibited the best performance.The characterization results revealed that CeNb(f)/SnO_(2)possessed appropriate acidity and redox capability.Furthermore,the strong synergistic effect between Nb and Sn species stabilized the structure and maintained the dispersion of acid sites.This study may provide a new understanding for the effect of impregnation sequence on activity and hydrothermal stability and a new environmental-friendly NH_(3)-SCR catalyst with potential applications for NO_(x)removal from diesel and hydrogenfueled engines.展开更多
A microporous zirconia membrane with hydrogen permeance about 5 × 10-8mol·m-2·s-1·Pa-1, H2/CO2 permselectivity of ca. 14, and excellent hydrothermal stability under steam pressure of 100 k Pa was f...A microporous zirconia membrane with hydrogen permeance about 5 × 10-8mol·m-2·s-1·Pa-1, H2/CO2 permselectivity of ca. 14, and excellent hydrothermal stability under steam pressure of 100 k Pa was fabricated via polymeric sol–gel process. The effect of calcination temperature on single gas permeance of sol–gel derived zirconia membranes was investigated. Zirconia membranes calcined at 350 °C and 400 °C showed similar single gas permeance, with permselectivities of hydrogen towards other gases, such as oxygen, nitrogen, methane, and sulfur hexa fluoride, around Knudsen values. A much lower CO2permeance（3.7 × 10-9mol·m-2·s-1·Pa-1）was observed due to the interaction between CO2 molecules and pore wall of membrane. Higher calcination temperature, 500 °C, led to the formation of mesoporous structure and, hence, the membrane lost its molecular sieving property towards hydrogen and carbon dioxide. The stability of zirconia membrane in the presence of hot steam was also investigated. Exposed to 100 k Pa steam for 400 h, the membrane performance kept unchanged in comparison with freshly prepared one, with hydrogen and carbon dioxide permeances of 4.7 × 10-8and ~ 3 × 10-9mol·m-2·s-1·Pa-1, respectively. Both H2 and CO2permeances of the zirconia membrane decreased with exposure time to 100 k Pa steam. With a total exposure time of 1250 h, the membrane presented hydrogen permeance of 2.4 × 10-8mol·m-2·s-1·Pa-1and H2/CO2 permselectivity of 28, indicating that the membrane retains its microporous structure.展开更多
Various acidic components（MOx：phosphate,sulfate,tungstate and niobate） were loaded on Ce0.75 Zr0.25 O2 powders by an impregnation method.The as-prepared catalysts were hydrothermally treated at 760 oC for 48 h in a...Various acidic components（MOx：phosphate,sulfate,tungstate and niobate） were loaded on Ce0.75 Zr0.25 O2 powders by an impregnation method.The as-prepared catalysts were hydrothermally treated at 760 oC for 48 h in air containing 10 vol.% H2 O to obtain the aged catalysts.The catalysts were characterized by X-ray diffraction,Fourier transform infrared spectroscopy,H2 programmed-reduction,NH3 adsorption and deNOx activity measurements.The results showed that,among the catalysts investigated,the phosphated Ce0.75 Zr0.25 O2 catalyst showed the highest hydrothermal stability.The remained high acidity of the phosphated catalyst with moderate redox property helped to maintain the excellent NH3-SCR activity of hydrothermally aged catalyst.Cerium tungstate led to the poor redox property of the tungstated catalyst although the acidity of catalyst was still high.The decomposition of sulfates at temperatures higher than 600 °C restrained the usage of sulfated catalysts in high temperature conditions.The overall dehydration of niobate to niobium oxides led to the low acidity of hydrothermally aged Nb2 O5-Ce0.75 Zr0.25 O2 catalyst.展开更多
1 Introduction Since its first discovery in 1992, ordered mesoporous silica material with large pore size, high surface area, and high pore volume has attracted great attention for the potentially wide application in...1 Introduction Since its first discovery in 1992, ordered mesoporous silica material with large pore size, high surface area, and high pore volume has attracted great attention for the potentially wide application in catalysis, adsorption, separation, and ion exchange, etc. However, the poor hydrothermal stability of mesoporous silica has limited its wide application in industry. Therefore, in the last 10 years, many studies have been dedicated to improving the hydrothermal stability of mesoporous silica. Xiao et al.展开更多
Cu-SSZ-13(CHA topology)zeolites are commonly used in diesel engines for the selective catalytic reduction(NH3-SCR)of nitrogen oxides(NO_(x)).However,their synthesis typically requires long crystallization times and th...Cu-SSZ-13(CHA topology)zeolites are commonly used in diesel engines for the selective catalytic reduction(NH3-SCR)of nitrogen oxides(NO_(x)).However,their synthesis typically requires long crystallization times and their durability in NH3-SCR is limited.Herein,we achieved a significant reduction in crystallization time,synthesizing SSZ-13 zeolites in just 6 h by using SAPO-18 seeds and a minimal amount of an organic structure-directing agent(OSDA).The OSDA/Si ratio was reduced by a factor of 16 compared to conventional methods.Crystallization studies revealed that SAPO-18 seeds promoted the formation of four-membered rings(4MRs),which quickly combined into double 6-membered rings(D6Rs)with the assistance of the OSDA,enabling rapid crystallization of SSZ-13.The resulting Cu-SSZ-13 demonstrated comparable NH3-SCR performance to conventionally synthesized Cu-SSZ-13(Cuconv-SSZ-13).Moreover,we introduced Ce ions into Cu-SSZ-13 to enhance its hydrothermal stability and explored the effects of different metal precursors on the catalytic performance.The optimized CuCe(Ⅲ)0.5-SSZ-13 exhibited superior hydrothermal stability compared to Cu-SSZ-13.Conversely,CuCe(Ⅳ)1.0-SSZ-13 and CuCe(Ⅲ)0.5Ce(Ⅳ)1.0-SSZ-13 displayed reduced hydrothermal stability.Characterization revealed that using the Ce(Ⅲ)precursor inhibited CuO_(x) formation during hydrothermal ageing,while the Ce(Ⅳ)precursor favored the formation of CeO2,decreasing the zeolite stability and promoting CuO_(x) formation.This work presents a novel approach for rapid SSZ-13 synthesis and highlights the critical role of metal precursors in the performance of bimetallic SSZ-13 zeolites.展开更多
Cu-based Al-rich zeolite catalysts(e.g.,Cu-SSZ-13,CHA)exhibit excellent catalytic activity in the ammonia-selective catalytic reduction of nitrogen oxides(NH3-SCR),particularly at low temperatures,but their applicatio...Cu-based Al-rich zeolite catalysts(e.g.,Cu-SSZ-13,CHA)exhibit excellent catalytic activity in the ammonia-selective catalytic reduction of nitrogen oxides(NH3-SCR),particularly at low temperatures,but their application is hindered by inferior hydrothermal stability.In this study,CHA/OFF-ERI zeolites with cocrystallized interfaces between small CHA zeolite crystals and OFF-ERI intergrowth zeolite rods were synthesized,which demonstrated superior hydrothermal stability compared to Cu-SSZ-13,Cu-OFF-ERI,and a physical mixture of Cu-SSZ-13 and Cu-OFF-ERI(denoted as Cu-Mixture).Studies on the evolution of the crystallinity and Brønsted acid sites of Cu-CHA/OFF-ERI,Cu-SSZ-13,Cu-OFF-ERI,and Cu-Mixture before and after hydrothermal aging suggested that the cocrystallized interfaces accounted for the enhanced hydrothermal stability of Cu-CHA/OFF-ERI zeolite.During hydrothermal aging,the cocrystallized interfaces locked the Al(OH)3 species detached from the zeolitic framework within the zeolitic micropores.After hydrothermal aging,the detached Al(OH)3 species were reincorporated into the defects as the temperature decreased,thereby inhibiting dealumination and improving the hydrothermal stability of Cu-CHA/OFF-ERI zeolite.This work unravels the role of cocrystallized interfaces in boosting the hydrothermal stability of Cu-based cocrystallized zeolites,providing valuable guidance for designing catalysts with excellent NH3-SCR performance taking advantage of the cocrystallized zeolite interfaces.展开更多
Selective catalytic reduction with NH3(NH3-SCR)is an important means of NO_(x) abatement from stationary and mobile sources,and the key element is efficient and stable NH3-SCR catalysts.In this study,we propose a meth...Selective catalytic reduction with NH3(NH3-SCR)is an important means of NO_(x) abatement from stationary and mobile sources,and the key element is efficient and stable NH3-SCR catalysts.In this study,we propose a method to construct superior Fe-Beta catalysts based on Al-rich zeolites.This strategy successfully promotes the formation of NH3-SCR-active isolated Fe^(3+)species,thus effectively improving the low-temperature activity of the Fe-Beta catalysts.Thanks to the abundant Brønsted acid sites of the Al-rich zeolite,the Fe_(2)O_(3) particles are redispersed and anchored as isolated Fe^(3+)during hydrothermal aging.This dynamic evolution of Fe species makes up for the adverse effect of dealumination of the Al-rich zeolite framework and achieves high stability for the Al-rich Fe-Beta catalyst.This study may promote the understanding of highly efficient and stable catalyst design using Al-rich zeolites.展开更多
K ions were introduced onto Cu/SAPO-34 catalysts via the ion-exchange process in order to improve their stability under low-temperature hydrothermal aging.The changes in structure and copper-species contents of these ...K ions were introduced onto Cu/SAPO-34 catalysts via the ion-exchange process in order to improve their stability under low-temperature hydrothermal aging.The changes in structure and copper-species contents of these catalysts upon hydrothermal aging were probed in order to investigate their effects on selective catalytic reduction(SCR)activity.For the fresh Cu/SAPO-34 catalysts,K ions had little influence on the chabazite framework but effected their acidities by exchanging with acid sites.After hydrothermal aging,the structural integrity and amount of active sites decreased on pure Cu/SAPO-34.While the K-loaded catalysts showed improved chabazite structure,acidity,and active site conservation with increasing K loading.However,although the 0.7 wt%K catalyst maintained the same crystallinity,active site abundance,and low-temperature SCR activity as the fresh catalyst upon aging,an apparent decrease in SCR activity at high temperature was observed because of the inevitable decrease in the number of Brönsted acid sites.To compensate for the activity disadvantage of K-loaded Cu/SAPO-34 at high temperature,Fe/Beta catalysts were co-employed with K-loaded Cu/SAPO-34,and a wide active temperature window of SCR activity was obtained.Thus,our study reveals that a combined system comprising Fe/Beta and K-loaded Cu/SAPO-34 catalysts shows promise for the elimination of NOx in real-world applications.展开更多
The pore structure of spherical alumina supports is closely related to the dispersion of catalytically active components and the diffusion of reactants.Maintaining excellent pore structure under strict reaction condit...The pore structure of spherical alumina supports is closely related to the dispersion of catalytically active components and the diffusion of reactants.Maintaining excellent pore structure under strict reaction conditions is of utmost importance.In this work,sphericalγ-Al_(2)O_(3)support with a bimodal pore structure,composed of macropores and mesopores,was successfully synthesized using dodecane as the pore-forming agent through the oil–ammonia column-shaping method.The morphology and internal pore structure of the alumina were found to be influenced by the amount of surfactant added and ultrasound treatment conditions.Notably,when concentration of surfactant was 4‰and ultrasound voltage of 20 V was applied,the resultingγ-Al_(2)O_(3)-4‰-20 displayed a highly concentrated distribution of macropores with an average pore size of 100 nm,resulting in an impressive porosity of 69.21%.In contrast,the untreated sample ofγ-Al_(2)O_(3)-0-0 only exhibited a mesoporous distribution with a porosity of 54.03%.Moreover,after being subjected to a hydrothermal treatment in a high temperature(600°C)and high humidity(water vapor)environment for 120 h,theγ-Al_(2)O_(3)-4‰-20 sample maintained a high BET specific surface area of 170.9 m^(2)g^(−1)and mercury intrusion porosimetry specific surface area of 263.3 m^(2)g^(−1).展开更多
Reducing pollution and carbon emissions is an important step toward peaking CO_(2)emissions before 2030 and reaching carbon neutrality before 2060,and heavy diesel vehicle pollution,particularly nitrogen oxides(NOx)em...Reducing pollution and carbon emissions is an important step toward peaking CO_(2)emissions before 2030 and reaching carbon neutrality before 2060,and heavy diesel vehicle pollution,particularly nitrogen oxides(NOx)emissions,is an essential part.CuSAPO-34 is a CHA-type small pore molecular sieve with excellent ammonia(NH_(3))selective catalytic reduction(NH_(3)-SCR)catalytic activity,but it cannot be stored or applied because of severe degradation caused by low-temperature hydrothermal aging.To improve the hydrothermal stability,TiO_(2)was coated on the surface of Cu-SAPO-34 by the ALD method to form a uniform nanolayer.Though this ultrathin TiO_(2)nanolayer has little effect on NH_(3)-SCR catalytic activity of Cu-SAPO-34,the resistance to low-temperature hydrothermal aging in liquid water at 80℃for 24 h has greatly been improved.A study carried out by SEM,XRD,NH_(3)-TPD,and EPR,showed that the ultra-thin TiO_(2)nanolayers were covered uniformly and hydrolysis of frameworks silicon and the migration of Cu^(2+)was retarded.This method has some implications for the future preparation of highly robust Cu-SAPO-34 catalysts for industrial applications.This research could inspire the development of highly robust CuSAPO-34 catalysts to control the NOx emissions from diesel engines.展开更多
Hydrothermal liquefaction(HTL)is one of the most promising technologies for conversion of microalgae,and catalysts with high hydrothermal stability are required for controllable HTL.In this article,SBA-15 incorporated...Hydrothermal liquefaction(HTL)is one of the most promising technologies for conversion of microalgae,and catalysts with high hydrothermal stability are required for controllable HTL.In this article,SBA-15 incorporated with transition metals(Ni,Pd,Co and Ru)were synthetized via double-template method for catalytic HTL of microalgae.The results showed that metal incorporated SBA-15 represented high hydrothermal stability at 613 K.The incorporated Ni,Co and Ru was dispersed in SBA-15 enhancing the hydrothermal stability.The catalysts greatly influenced the chemical composition of the obtained bio-oil,which contained a higher percentage of furfural derivatives and a lower content of fatty acids and N-containing compounds,thus bio-oil quality was improved significantly.Higher hydrothermal stability and specific surface areas of Co-SBA-15 contribute to the highest preformation with 78.78%conversion and 24.11 wt%bio-oil yield.Metal incorporated SBA-15 provides a potential application for biomass conversion in high-temperature aqueous phase.展开更多
V2O5/WO3‐TiO2 and V2O5/WO3‐TiO2‐SiO2 catalysts were prepared by a wetness impregnation method, and both the catalysts were hydrothermally aged at 750℃ in 10 vol%H2O/air for 24 h. The catalysts were evaluated for N...V2O5/WO3‐TiO2 and V2O5/WO3‐TiO2‐SiO2 catalysts were prepared by a wetness impregnation method, and both the catalysts were hydrothermally aged at 750℃ in 10 vol%H2O/air for 24 h. The catalysts were evaluated for NOx conversion using NH3 as the reductant. Hydrothermal ageing decreased the NOx conversion of V2O5/WO3‐TiO2 catalyst severely over the entire measured tem‐perature range. Interestingly, the NH3‐SCR activity of the silica‐modified catalyst at 220–480℃ is enhanced after ageing. The catalysts were characterized by X‐ray diffraction, nitrogen adsorption, X‐ray fluorescence, Raman spectroscopy, H2 temperature‐programmed reduction, and NH3 temper‐ature‐programmed desorption. The addition of silica inhibited the phase transition from anatase to rutile titania, growth of TiO2 crystallite size and shrinkage of catalyst surface area. Consequently, the vanadia species remained highly dispersed and the hydrothermal stability of the V2O5/WO3‐TiO2 catalyst was significantly improved.展开更多
基金supported by the National Natural Science Foundation of China(52225004 and 22276202)the National Key Research and Development Program of China(2022YFC3701804)the Youth Innovation Promotion Association of Chinese Academy of Sciences(2019045).
文摘Catalytic activity and hydrothermal stability are both crucial for the application of the selective catalytic reduction of NO_(x)with NH_(3)(NH_(3)-SCR)catalyst in diesel vehicles.In this study,a tin(Sn)-modified Ce-Nb mixed-oxide catalyst was synthesized as an NH_(3)-SCR catalyst for NO_(x)emission control.After the intro-duction of Sn,both the NH_(3)-SCR activity and the hydrothermal stability of the catalyst were remarkably promoted.Even after hydrothermal aging at 1000℃,the developed Ce_(1)Sn_(2)Nb_(1)O_(x)catalyst achieved more than 90%NO_(x)conversion at 325-500℃.Various methods,including N2-physisorption,X-ray diffraction,in-situ high-temperature X-ray diffraction,high-resolution transmission electron microscopy,X-ray pho-toelectron spectroscopy,X-ray absorption fine-structure spectroscopy,temperature-programmed reduc-tion of hydrogen,temperature-programmed desorption of ammonia,and density functional theory calculations were used to investigate the promotional effects induced by the Sn species.The characteri-zation results showed that the addition of Sn not only promoted the formation of the Ce-Nb active phase but also improved its thermal stability,contributing to the excellent NH_(3)-SCR performance and hydrothermal stability.This study provides an excellent sintering-resistance catalyst for the application of diesel engine NO_(x)emission control.
基金supported by the National Key R&D Program of China(2021YFB3503200)the Innovative Research Groups of the National Natural Science Foundation of China(51921004)+1 种基金Young Elite Scientists Sponsorship Program by CAST(2021QNRC001)the Key R&D project of Shandong Province(2021CXGC010703,2022CXGC020311)。
文摘Based on the previous findings that the presence of hydroxyl groups on the outer surface is crucial for maintaining skeletal stability,we propose a strategy modified Cu/SAPO-34 using Pr ions in this study.Therefore,we conducted several measurements to investigate the effect of Pr ions on the lowtemperature hydrothermal stability of Cu/SAPO-34.We find that Pr exists only on the surface of Cu/SAPO-34 as ions and oxides,with Pr^(3+)ions playing a protective role in occupying surface acidic sites.The addition of small amounts of Pr leads to the re-dispersion of Cu,resulting in improved lowtemperature selective catalytic reduction(SCR)activity in the as-synthesized samples.Furthermore,it enhances the resistance to decomposition of the Si-(OH)-Al framework during low-temperature hydrothermal aging,thereby preserving the framework structure and allowing detached active Cu species to return to exchangeable positions,ultimately restoring SCR activity.However,as the Pr content increases,the enhanced acidity causes some structural damage,gradually weakening the protective effect.Our work demonstrates that Pr modification is a simple and effective solution to the issue of poor lowtemperature hydrothermal stability in Cu/SAPO-34,providing a promising way for the application of light rare earth elements.
基金supported by the National Natural Science Foundation of China (21603023)the Petro China Innovation Foundation, China (2014D-5006-0501)~~
文摘In this study, phosphorus modification by trimethyl phosphate impregnation was employed to enhance the hydrothermal stability of nano‐sized HZSM‐5 zeolites. A parallel modification was studied by ammonium dihydrogen phosphate impregnation. The modified zeolites were subjected to steam treatment at 800 °C for 4 h (100% steam) and employed as catalysts for olefin catalyticcracking (OCC) of full‐range fluid catalytic cracking (FCC) gasoline. X‐ray diffraction, N2 physicaladsorption and NH3 temperature‐programmed desorption analysis indicated that, although significantimprovements to the hydrothermal stability of nano‐sized HZSM‐5 zeolites can be observedwhen adopting both phosphorus modification strategies, impregnation with trimethyl phosphatedisplays further enhancement of the hydrothermal stability. This is because higher structural crystallinityis retained, larger specific surface areas/micropore volumes form, and there are greaternumbers of surface acid sites. Reaction experiments conducted using a fixed‐bed micro‐reactor(catalyst/oil ratio = 4, time on stream = 4 s) showed OCC of full‐range FCC gasoline-under a fluidized‐bed reaction mode configuration-to be a viable solution for the olefin problem of FCC gasoline.This reaction significantly decreased the olefin content in the full‐range FCC gasoline feed, andspecifically heavy‐end olefins, by converting the olefins into value‐added C2–C4 olefins and aromatics.At the same time, sulfide content of the gasoline decreased via a non‐hydrodesulfurization process.Nano‐sized HZSM‐5 zeolites modified with trimethyl phosphate exhibited enhanced catalytic performance for OCC of full‐range FCC gasoline.
文摘A reconstruction strategy has been developed to synthesize Cu-SAPO-34 with a wide crystallization phase region,high solid yield,and tunable Si and Cu contents.Cu-rich SAPO-34 was prepared from a Cu-amine complex,which acted as a precursor and Cu source for the reconstruction synthesis.The role of the Cu-amine complex as a template was restricted,which allowed easier control over the Cu and Si contents than in the previously reported"one-pot"synthesis method.Characterization of the material revealed that the Si(4Al)coordination environment dominates the synthesized Cu-SAPO-34 catalysts.High-temperature hydrothermal treatment increased the isolated Cu2+content slightly,and the acid sites in the low-silica catalyst are more resistant to hydrothermal treatment than those of the existing catalysts.The obtained materials,especially the low-silica Cu-SAPO-34 sample,exhibit excellent catalytic activity and hydrothermal stability for the selective catalytic reduction of NOx by NH3(NH3-SCR).In addition,the influence of the catalyst acidity on the NH3-SCR reaction was also investigated and is discussed.The high synthetic efficiency and outstanding catalytic performance make Cu-SAPO-34 synthesized by the reconstruction method a promising catalyst for the NH3-SCR process.
文摘The mesoporous Al-SBA-15 zeolite was obtained via impregnation of pure silica-based SBA-15 zeolite with aluminum nitrate.The Al-SBA-15 sample was calcined in air at 800℃for 6 h and hydrothermally treated at near 100℃for 120 h,respectively,and then the thermal and hydrothermal stability of Al-SBA-15 sample was investigated by X-ray diffractometry(XRD),scanning electron microscopy(SEM),transmission electron microscopy(TEM)and nitrogen adsorption and desorption techniques.The Al-SBA-15 sample was also studied by 27 Al nuclear magnetic resonance(27 Al NMR)and ammonia temperature programmed desorption(NH 3-TPD)techniques.In addition,the catalytic activity of Al-SBA-15 zeolite was investigated by the Friedel-Crafts reactions of 2,4-di-tert-butylphenol with cinnamyl alcohol.The test results showed that the thermal and hydrothermal stability of Al-SBA-15 zeolite was better than that of SBA-15 zeo-lite.The Al-SBA-15 zeolite sample prepared by impregnation method exhibits more framework aluminum species and Al-O-Si units.Therefore,the number of the surface hydroxyl groups was reduced,resulting in the stabilization of framework structure ofAl-SBA-15 zeolite.The aluminum species can form weak and medium-strong acid sites with catalytic activity.
基金Project supported by the National Key Research and Development Program(2017YFC0211003)GM Global Research and Development(GAC 2696)。
文摘The activity and hydrothermal stability of the Rh/Ce_(x)Zr_(1-x)O_(2)(x=0,0.05,0.3,0.5) model three-way catalysts for gasoline vehicle emissions control were investigated in this work.Among the Rh/Ce_(x)Zr_(1-x)O_(2) samples with different Ce/Zr ratios,the Rh/ZrO_(2) sample exhibits a significantly better activity and hydrothermal stability than the rest of the samples.The impacts of having more Ce components in the Rh/Ce_(x)Zr_(1-x)O_(2) catalysts are associated with the strong Rh-O-Ce interaction that tends to over stabilize the rhodium species.A significant amount of such rhodium atoms can be found in the bulk of the support oxides after a hydrothermal aging at 1050℃ with 10% H_(2)O in air for 12 h.Differently,the sintering of rhodium on the surface of Rh/ZrO_(2) catalysts is the main reason for the catalyst deactivation during the hydrothermal aging.These findings provide an example where high dispersion of supported metal induced by strong metal-support interactions does not necessarily lead to high catalytic activity.
基金Project supported by the National Key R&D Program(2017YFC0211302)the National Natural Science Foundation of China(21676195)+1 种基金the National Natural Science Foundation for Youth of China(21908207)The work was supported by the academic collaboration with G M Global Research and Development,USA.
文摘To probe the function of Ce on enhancing low-temperature stability of SAPO-34,Ce/SAPO-34 with different Ce contents was prepared via one-pot method and further treated at 70℃in 80%relative humidity for 24 h.The structural results prove that the one-pot synthesis is an effective way to introduce Ce(Ce<0.325 wt%)without influencing micro-structural and chemical composition.The lowtemperature hydrothermal stability of Ce/SAPO-34 is enhanced by Ce loading.More than 92%CHA structure and total acidity are maintained over 0.188 wt%Ce/SAPO-34,while only about 20%of that left on pure H/SAPO-34.As Ce exists as Ce^(3+)at exchange sites on the surface of SAPO-34,the results of the linear relationship between protected surface acidity and structure/acidity conservation manifest that Ce^(3+))effectively hinders the structural collapse.This study provides new insight into surface acidity protection for solving the problem of low-temperature hydrothermal stability of SAPO-34.
基金supported by the National Natural Science Foundation of China(Nos.U1137603,21307047)the Opening Project of Key Laboratory of Green Catalysis of Sichuan Institutes of High Education(No.LYJ1309)
文摘A series of CeO2–ZrO2–WO3（CZW）catalysts prepared by a hydrothermal synthesis method showed excellent catalytic activity for selective catalytic reduction（SCR）of NO with NH3 over a wide temperature of 150–550℃.The effect of hydrothermal treatment of CZW catalysts on SCR activity was investigated in the presence of 10% H2O.The fresh catalyst showed above 90% NOx conversion at 201–459℃,which is applicable to diesel exhaust NOx purification（200–440℃）.The SCR activity results indicated that hydrothermal aging decreased the SCR activity of CZW at low temperatures（below 300℃）,while the activity was notably enhanced at high temperature（above 450℃）.The aged CZW catalyst（hydrothermal aging at 700℃ for 8 hr）showed almost 80% NOx conversion at 229–550℃,while the V2O5–WO3/TiO2 catalyst presented above 80% NOx conversion at 308–370℃.The effect of structural changes,acidity,and redox properties of CZW on the SCR activity was investigated.The results indicated that the excellent hydrothermal stability of CZW was mainly due to the CeO2–ZrO2 solid solution,amorphous WO3 phase and optimal acidity.In addition,the formation of WO3 clusters increased in size as the hydrothermal aging temperature increased,resulting in the collapse of structure,which could further affect the acidity and redox properties.
基金supported by the National Natural Science Foundation of China(Nos.52225004 and 22276182)the National Key R&D Program of China(Nos.2022YFC3701804 and 2022YFC3704400)the Science and Technology Innovation“2025”major program in Ningbo(No.2020Z103)。
文摘Hydrothermal stability is crucial for the practical application of deNO_(x)catalyst on diesel vehicles,for the selective catalytic reduction of NO_(x)with NH_(3)(NH_(3)-SCR).SnO_(2)-based materials possess superior hydrothermal stability,which is attractive for the development of NH_(3)-SCR catalyst.In this work,a series of Ce-Nb/SnO_(2)catalysts,with Ce and Nb loading on SnO_(2)support,were prepared by impregnation method.It was found that,the NH_(3)-SCR activities and hydrothermal stabilities of the Ce-Nb/SnO_(2)catalysts significantly varied with the impregnation sequences,and the Ce-Nb(f)/SnO_(2) catalyst that firstly impregnated Nb and then impregnated Ce exhibited the best performance.The characterization results revealed that CeNb(f)/SnO_(2)possessed appropriate acidity and redox capability.Furthermore,the strong synergistic effect between Nb and Sn species stabilized the structure and maintained the dispersion of acid sites.This study may provide a new understanding for the effect of impregnation sequence on activity and hydrothermal stability and a new environmental-friendly NH_(3)-SCR catalyst with potential applications for NO_(x)removal from diesel and hydrogenfueled engines.
基金Supported by the National Natural Science Foundation of China(21276123,21490581)the National High Technology Research and Development Program of China(2012AA03A606)+3 种基金State Key Laboratory of Materials-Oriented Chemical Engineering(ZK201002)the Natural Science Research Plan of Jiangsu Universities(11KJB530006)the "Summit of the Six Top Talents" Program of Jiangsu Provincea Project Funded by the Priority Academic Program development of Jiangsu Higher Education Institutions(PAPD)
文摘A microporous zirconia membrane with hydrogen permeance about 5 × 10-8mol·m-2·s-1·Pa-1, H2/CO2 permselectivity of ca. 14, and excellent hydrothermal stability under steam pressure of 100 k Pa was fabricated via polymeric sol–gel process. The effect of calcination temperature on single gas permeance of sol–gel derived zirconia membranes was investigated. Zirconia membranes calcined at 350 °C and 400 °C showed similar single gas permeance, with permselectivities of hydrogen towards other gases, such as oxygen, nitrogen, methane, and sulfur hexa fluoride, around Knudsen values. A much lower CO2permeance（3.7 × 10-9mol·m-2·s-1·Pa-1）was observed due to the interaction between CO2 molecules and pore wall of membrane. Higher calcination temperature, 500 °C, led to the formation of mesoporous structure and, hence, the membrane lost its molecular sieving property towards hydrogen and carbon dioxide. The stability of zirconia membrane in the presence of hot steam was also investigated. Exposed to 100 k Pa steam for 400 h, the membrane performance kept unchanged in comparison with freshly prepared one, with hydrogen and carbon dioxide permeances of 4.7 × 10-8and ~ 3 × 10-9mol·m-2·s-1·Pa-1, respectively. Both H2 and CO2permeances of the zirconia membrane decreased with exposure time to 100 k Pa steam. With a total exposure time of 1250 h, the membrane presented hydrogen permeance of 2.4 × 10-8mol·m-2·s-1·Pa-1and H2/CO2 permselectivity of 28, indicating that the membrane retains its microporous structure.
基金supported by National Natural Science Foundation of China(51202126)Strategic Emerging Industry Development Funds of Shenzhen(JCYJ20120619152738634)
文摘Various acidic components（MOx：phosphate,sulfate,tungstate and niobate） were loaded on Ce0.75 Zr0.25 O2 powders by an impregnation method.The as-prepared catalysts were hydrothermally treated at 760 oC for 48 h in air containing 10 vol.% H2 O to obtain the aged catalysts.The catalysts were characterized by X-ray diffraction,Fourier transform infrared spectroscopy,H2 programmed-reduction,NH3 adsorption and deNOx activity measurements.The results showed that,among the catalysts investigated,the phosphated Ce0.75 Zr0.25 O2 catalyst showed the highest hydrothermal stability.The remained high acidity of the phosphated catalyst with moderate redox property helped to maintain the excellent NH3-SCR activity of hydrothermally aged catalyst.Cerium tungstate led to the poor redox property of the tungstated catalyst although the acidity of catalyst was still high.The decomposition of sulfates at temperatures higher than 600 °C restrained the usage of sulfated catalysts in high temperature conditions.The overall dehydration of niobate to niobium oxides led to the low acidity of hydrothermally aged Nb2 O5-Ce0.75 Zr0.25 O2 catalyst.
基金Supported by the National Natural Science Foundation of China(Nos.20401015 and 50574082)Beijing(China) Municipal Natural Science Foundation(No.2082022)the Innovation Project of the Chinese Academy of Sciences(Nos.CXJJ-171 and CXJJ-210)
文摘1 Introduction Since its first discovery in 1992, ordered mesoporous silica material with large pore size, high surface area, and high pore volume has attracted great attention for the potentially wide application in catalysis, adsorption, separation, and ion exchange, etc. However, the poor hydrothermal stability of mesoporous silica has limited its wide application in industry. Therefore, in the last 10 years, many studies have been dedicated to improving the hydrothermal stability of mesoporous silica. Xiao et al.
基金the National Natural Science Foundation of China(22301209,22476147,22288101,22405293)the Zhejiang Province Science Technology Planning Project(no.2021C03023)+1 种基金the Zhejiang Provincial Natural Science Foundation of China(no.ZCLQ24B0101)the‘111 Center’(B17020)for supporting this work.
文摘Cu-SSZ-13(CHA topology)zeolites are commonly used in diesel engines for the selective catalytic reduction(NH3-SCR)of nitrogen oxides(NO_(x)).However,their synthesis typically requires long crystallization times and their durability in NH3-SCR is limited.Herein,we achieved a significant reduction in crystallization time,synthesizing SSZ-13 zeolites in just 6 h by using SAPO-18 seeds and a minimal amount of an organic structure-directing agent(OSDA).The OSDA/Si ratio was reduced by a factor of 16 compared to conventional methods.Crystallization studies revealed that SAPO-18 seeds promoted the formation of four-membered rings(4MRs),which quickly combined into double 6-membered rings(D6Rs)with the assistance of the OSDA,enabling rapid crystallization of SSZ-13.The resulting Cu-SSZ-13 demonstrated comparable NH3-SCR performance to conventionally synthesized Cu-SSZ-13(Cuconv-SSZ-13).Moreover,we introduced Ce ions into Cu-SSZ-13 to enhance its hydrothermal stability and explored the effects of different metal precursors on the catalytic performance.The optimized CuCe(Ⅲ)0.5-SSZ-13 exhibited superior hydrothermal stability compared to Cu-SSZ-13.Conversely,CuCe(Ⅳ)1.0-SSZ-13 and CuCe(Ⅲ)0.5Ce(Ⅳ)1.0-SSZ-13 displayed reduced hydrothermal stability.Characterization revealed that using the Ce(Ⅲ)precursor inhibited CuO_(x) formation during hydrothermal ageing,while the Ce(Ⅳ)precursor favored the formation of CeO2,decreasing the zeolite stability and promoting CuO_(x) formation.This work presents a novel approach for rapid SSZ-13 synthesis and highlights the critical role of metal precursors in the performance of bimetallic SSZ-13 zeolites.
基金the National Key Research and Development Program of China(grant nos.2021YFA1501202 and 2021YFA1500401)the National Natural Science Foundation of China(grant nos.22288101,21920102005,and 22201095)+1 种基金the“111 Center”(grant no.B17020)the National Engineering Laboratory for Mobile Source Emission Control Technology(grant no.NELMS2020A01)for financially supporting this work.
文摘Cu-based Al-rich zeolite catalysts(e.g.,Cu-SSZ-13,CHA)exhibit excellent catalytic activity in the ammonia-selective catalytic reduction of nitrogen oxides(NH3-SCR),particularly at low temperatures,but their application is hindered by inferior hydrothermal stability.In this study,CHA/OFF-ERI zeolites with cocrystallized interfaces between small CHA zeolite crystals and OFF-ERI intergrowth zeolite rods were synthesized,which demonstrated superior hydrothermal stability compared to Cu-SSZ-13,Cu-OFF-ERI,and a physical mixture of Cu-SSZ-13 and Cu-OFF-ERI(denoted as Cu-Mixture).Studies on the evolution of the crystallinity and Brønsted acid sites of Cu-CHA/OFF-ERI,Cu-SSZ-13,Cu-OFF-ERI,and Cu-Mixture before and after hydrothermal aging suggested that the cocrystallized interfaces accounted for the enhanced hydrothermal stability of Cu-CHA/OFF-ERI zeolite.During hydrothermal aging,the cocrystallized interfaces locked the Al(OH)3 species detached from the zeolitic framework within the zeolitic micropores.After hydrothermal aging,the detached Al(OH)3 species were reincorporated into the defects as the temperature decreased,thereby inhibiting dealumination and improving the hydrothermal stability of Cu-CHA/OFF-ERI zeolite.This work unravels the role of cocrystallized interfaces in boosting the hydrothermal stability of Cu-based cocrystallized zeolites,providing valuable guidance for designing catalysts with excellent NH3-SCR performance taking advantage of the cocrystallized zeolite interfaces.
基金supported by the National Key R&D Program of China(No.2023YFC3707200)the National Natural Science Foundation of China(Nos.22306191 and 52270112).
文摘Selective catalytic reduction with NH3(NH3-SCR)is an important means of NO_(x) abatement from stationary and mobile sources,and the key element is efficient and stable NH3-SCR catalysts.In this study,we propose a method to construct superior Fe-Beta catalysts based on Al-rich zeolites.This strategy successfully promotes the formation of NH3-SCR-active isolated Fe^(3+)species,thus effectively improving the low-temperature activity of the Fe-Beta catalysts.Thanks to the abundant Brønsted acid sites of the Al-rich zeolite,the Fe_(2)O_(3) particles are redispersed and anchored as isolated Fe^(3+)during hydrothermal aging.This dynamic evolution of Fe species makes up for the adverse effect of dealumination of the Al-rich zeolite framework and achieves high stability for the Al-rich Fe-Beta catalyst.This study may promote the understanding of highly efficient and stable catalyst design using Al-rich zeolites.
基金the funding from National Key Research and Development Program of China(No.2017YFC0211302)National Natural Science Foundation for Youth of China(Grant No.21908207)+1 种基金China Postdoctoral Science Foundation(No.2020M670659)Shanxi Province Science Foundation for Youths(Nos.201901D211224 and 201801D221351).
文摘K ions were introduced onto Cu/SAPO-34 catalysts via the ion-exchange process in order to improve their stability under low-temperature hydrothermal aging.The changes in structure and copper-species contents of these catalysts upon hydrothermal aging were probed in order to investigate their effects on selective catalytic reduction(SCR)activity.For the fresh Cu/SAPO-34 catalysts,K ions had little influence on the chabazite framework but effected their acidities by exchanging with acid sites.After hydrothermal aging,the structural integrity and amount of active sites decreased on pure Cu/SAPO-34.While the K-loaded catalysts showed improved chabazite structure,acidity,and active site conservation with increasing K loading.However,although the 0.7 wt%K catalyst maintained the same crystallinity,active site abundance,and low-temperature SCR activity as the fresh catalyst upon aging,an apparent decrease in SCR activity at high temperature was observed because of the inevitable decrease in the number of Brönsted acid sites.To compensate for the activity disadvantage of K-loaded Cu/SAPO-34 at high temperature,Fe/Beta catalysts were co-employed with K-loaded Cu/SAPO-34,and a wide active temperature window of SCR activity was obtained.Thus,our study reveals that a combined system comprising Fe/Beta and K-loaded Cu/SAPO-34 catalysts shows promise for the elimination of NOx in real-world applications.
基金National Key R&D Program of China(grant No.2022YFA1503400)Lanzhou Petrochemical Research Center project,and Programs for Foreign Talent(grant No.G2021106012L).
文摘The pore structure of spherical alumina supports is closely related to the dispersion of catalytically active components and the diffusion of reactants.Maintaining excellent pore structure under strict reaction conditions is of utmost importance.In this work,sphericalγ-Al_(2)O_(3)support with a bimodal pore structure,composed of macropores and mesopores,was successfully synthesized using dodecane as the pore-forming agent through the oil–ammonia column-shaping method.The morphology and internal pore structure of the alumina were found to be influenced by the amount of surfactant added and ultrasound treatment conditions.Notably,when concentration of surfactant was 4‰and ultrasound voltage of 20 V was applied,the resultingγ-Al_(2)O_(3)-4‰-20 displayed a highly concentrated distribution of macropores with an average pore size of 100 nm,resulting in an impressive porosity of 69.21%.In contrast,the untreated sample ofγ-Al_(2)O_(3)-0-0 only exhibited a mesoporous distribution with a porosity of 54.03%.Moreover,after being subjected to a hydrothermal treatment in a high temperature(600°C)and high humidity(water vapor)environment for 120 h,theγ-Al_(2)O_(3)-4‰-20 sample maintained a high BET specific surface area of 170.9 m^(2)g^(−1)and mercury intrusion porosimetry specific surface area of 263.3 m^(2)g^(−1).
基金supported by the National Natural Science Foundation of China(Grant Nos.22072141,22176185,and 22002150)the Youth Innovation Promotion Association of Chinese Academy of Sciences(Grant No.2018263)+1 种基金the Key Research Program of the Chinese Academy of Sciences(Grant No.ZDRW-CN-2021-3)the Self-deployed Projects of Ganjiang Innovation Academy,Chinese Academy of Sciences(Grant No.E055C003)。
文摘Reducing pollution and carbon emissions is an important step toward peaking CO_(2)emissions before 2030 and reaching carbon neutrality before 2060,and heavy diesel vehicle pollution,particularly nitrogen oxides(NOx)emissions,is an essential part.CuSAPO-34 is a CHA-type small pore molecular sieve with excellent ammonia(NH_(3))selective catalytic reduction(NH_(3)-SCR)catalytic activity,but it cannot be stored or applied because of severe degradation caused by low-temperature hydrothermal aging.To improve the hydrothermal stability,TiO_(2)was coated on the surface of Cu-SAPO-34 by the ALD method to form a uniform nanolayer.Though this ultrathin TiO_(2)nanolayer has little effect on NH_(3)-SCR catalytic activity of Cu-SAPO-34,the resistance to low-temperature hydrothermal aging in liquid water at 80℃for 24 h has greatly been improved.A study carried out by SEM,XRD,NH_(3)-TPD,and EPR,showed that the ultra-thin TiO_(2)nanolayers were covered uniformly and hydrolysis of frameworks silicon and the migration of Cu^(2+)was retarded.This method has some implications for the future preparation of highly robust Cu-SAPO-34 catalysts for industrial applications.This research could inspire the development of highly robust CuSAPO-34 catalysts to control the NOx emissions from diesel engines.
基金National Natural Science Foundation of China(No.21576155 and No.21776159)Research Project of Guangdong Provincial Department of Science and Technology Department(No.2015B020215004)Program for Changjiang Scholars and Innovative Research Team in University(No.IRT13026).
文摘Hydrothermal liquefaction(HTL)is one of the most promising technologies for conversion of microalgae,and catalysts with high hydrothermal stability are required for controllable HTL.In this article,SBA-15 incorporated with transition metals(Ni,Pd,Co and Ru)were synthetized via double-template method for catalytic HTL of microalgae.The results showed that metal incorporated SBA-15 represented high hydrothermal stability at 613 K.The incorporated Ni,Co and Ru was dispersed in SBA-15 enhancing the hydrothermal stability.The catalysts greatly influenced the chemical composition of the obtained bio-oil,which contained a higher percentage of furfural derivatives and a lower content of fatty acids and N-containing compounds,thus bio-oil quality was improved significantly.Higher hydrothermal stability and specific surface areas of Co-SBA-15 contribute to the highest preformation with 78.78%conversion and 24.11 wt%bio-oil yield.Metal incorporated SBA-15 provides a potential application for biomass conversion in high-temperature aqueous phase.
基金supported by the National Natural Science Foundation of China (51372137)the National High Technology Research and Development Program of China (863 Program,2015AA034603)~~
文摘V2O5/WO3‐TiO2 and V2O5/WO3‐TiO2‐SiO2 catalysts were prepared by a wetness impregnation method, and both the catalysts were hydrothermally aged at 750℃ in 10 vol%H2O/air for 24 h. The catalysts were evaluated for NOx conversion using NH3 as the reductant. Hydrothermal ageing decreased the NOx conversion of V2O5/WO3‐TiO2 catalyst severely over the entire measured tem‐perature range. Interestingly, the NH3‐SCR activity of the silica‐modified catalyst at 220–480℃ is enhanced after ageing. The catalysts were characterized by X‐ray diffraction, nitrogen adsorption, X‐ray fluorescence, Raman spectroscopy, H2 temperature‐programmed reduction, and NH3 temper‐ature‐programmed desorption. The addition of silica inhibited the phase transition from anatase to rutile titania, growth of TiO2 crystallite size and shrinkage of catalyst surface area. Consequently, the vanadia species remained highly dispersed and the hydrothermal stability of the V2O5/WO3‐TiO2 catalyst was significantly improved.
