Excellent catalysts with low-temperature activity and relatively wide temperature window for selective catalytic reduction of NO with ammonia(NH_(3)-SCR) are highly demanded in view of the practical treatment of NO.He...Excellent catalysts with low-temperature activity and relatively wide temperature window for selective catalytic reduction of NO with ammonia(NH_(3)-SCR) are highly demanded in view of the practical treatment of NO.Herein,we have designed a highly active VOx-MnOx/CeO_(2) material based on the intrinsic requirement of SCR reaction for catalyst,namely redox sites and surface acid sites.The vanadium oxide and manganese oxide are highly dispersed over the ceria mesosphere via simple incipient wetness impregnation.The loading of manganese could introduce acid sites and enhance the redox property remarkably,while the loading of vanadium increases acid sites and weakens redox property.Through tentatively controlling the appropriate loading ratio of the two components,the optimal catalyst achieves a balance between redox property and surface acidity.The work shed light on the development of new SCR catalyst with superior low temperature activity,wide work temperature window and good hydrothermal stability.展开更多
Galena(PbS)and chalcopyrite(CuFeS_(2))are sulfide minerals that exhibit good floatability characteristics.Thus,efficiently separating them via common flotation is challenging.Herein,a new method of surface sulfuric ac...Galena(PbS)and chalcopyrite(CuFeS_(2))are sulfide minerals that exhibit good floatability characteristics.Thus,efficiently separating them via common flotation is challenging.Herein,a new method of surface sulfuric acid corrosion in conjunction with flotation separation was proposed,and the efficient separation of galena and chalcopyrite was successfully realized.Contact angle test results showed a substantial decrease in surface contact angle and a selective inhibition of surface floatability for corroded galena.Meanwhile,the contact angle and floatability of corroded chalcopyrite remained almost unaffected.Scanning electron microscope results confirmed that sulfuric acid corrosion led to the formation of a dense oxide layer on the galena surface,whereas the chalcopyrite surface remained unaltered.X-ray photoelectron spectroscopy results showed that the chemical state of S^(2-)on the surface of corroded galena was oxidized to SO_(4)^(2-).A layer of hydrophilic PbSO4was formed on the surface,leading to a sharp decrease in galena floatability.Meanwhile,new hydrophobic CuS_(2),CuS,and Cu_(1-x)Fe_(1-y)S_(2-z)species exhibiting good floatability were generated on the chalcopyrite surface.Finally,theoretical analysis results were further verified by corrosion–flotation separation experiments.The galena–chalcopyrite mixture was completely separated via flotation separation under appropriate corrosion acidity,corrosion temperature,and corrosion time.A novel approach has been outlined in this study,providing potential applications in the efficient separation of refractory copper–lead sulfide ore.展开更多
This article discussed the benzoic acid activated carbons which have changed the types and content of acid oxygen-function groups on the surface of activated carbons and their effect on the adsorption for Hg^0 in simu...This article discussed the benzoic acid activated carbons which have changed the types and content of acid oxygen-function groups on the surface of activated carbons and their effect on the adsorption for Hg^0 in simulated flue gas at 140 ℃. These surface acid oxygen function groups were identified by Boehm titration, Fourier transformation infrared spectrum, temperature programmed desorption and X-ray photoelectron spectroscopy. It indicates that the carboxyl, lactone and phenolic were formed when the benzoic acid is loaded on the surface of activated carbons. Among the surface acid oxygen function groups, the carboxyl groups enhance the adsorption capacities of Hg^0 for activated carbons to a greater extent.展开更多
Tuning the surface acidity of ZSM-5 catalyst is essential to achieve desired propene selectivity and yield.Here several ratios of Zr were utilized to modify ZSM-5 via flame spray pyrolysis technique coupled with a pul...Tuning the surface acidity of ZSM-5 catalyst is essential to achieve desired propene selectivity and yield.Here several ratios of Zr were utilized to modify ZSM-5 via flame spray pyrolysis technique coupled with a pulse spray evaporation system.The interaction between Zr and ZSM-5 in the flame influenced the physicochemical and acidity properties of the Zr/ZSM-5.The increasing Zr ratio in ZSM-5 shows coated layers of irregular nano-sized Zr with an increase in crystallite sizes due to the synergetic effect between Zr and ZSM-5.The surface chemical analysis revealed increased lattice oxygen on the Zr modified ZSM-5(1:4) sample compared to other catalysts.The acidity analysis revealed the Lewis and Br?nsted acid distribution in the weak and medium acid sites on the catalyst surface.However,the increase in Zr loading decreased the concentration of Br?nsted acid sites and tuned the catalyst surface to more Lewis acidity,promoting propene selectivity and hindering the over-oxidation of propene.The modified ZSM-5 catalysts were examined in a fixed bed reactor within 300℃-700℃ at a gas hourly space velocity(GHSV) of 6000 mL·g(catalysts)^(-1)·h^(-1) for the oxidative dehydrogenation of propane(ODHP) to propene.Among the catalysts,Zr/ZSM-5(1:4) exhibited the best propene yield, with 57.19% propane conversion and 75.54% selectivity to propene and the highest stability.This work provides a promising strategy for tuning the surface acidity of ZSM-5 with Zr for ODHP applications.展开更多
In the study,the catalyst precursors of Ce-modifiedγ-MnO2 were washed with deionized water until the pH value of the supernatant was 1,2,4 and 7,and the obtained catalysts were named accordingly.Under space velocity ...In the study,the catalyst precursors of Ce-modifiedγ-MnO2 were washed with deionized water until the pH value of the supernatant was 1,2,4 and 7,and the obtained catalysts were named accordingly.Under space velocity of 300,000 hr-1,the ozone conversion over the pH=7 catalyst under dry conditions and relative humidity of 65%over a period of 6 hr was 100%and 96%,respectively.However,the ozone decomposition activity of the pH=2 and 4 catalysts distinctly decreased under relative humidity of 65%compared to that under dry conditions.Detailed physical and chemical characterization demonstrated that the residual sulfate ions on the pH=2 and 4 catalysts decreased their hydrophobicity and then restrained humid ozone decomposition activity.The pH=2 and 4 catalysts had inferior resistance to high space velocity under dry conditions,because the residual sulfate ion on their surface reduced their adsorption capacity for ozone molecules and increased their apparent activation energies,which was proved by temperature programmed desorption of O2 and kinetic experiments.Long-term activity testing,X-ray photoelectron spectroscopy and density functional theory calculations revealed that there were two kinds of oxygen vacancies on the manganese dioxide catalysts,one of which more easily adsorbed oxygen species and then became deactivated.This study revealed the detrimental effect of surface acid ions on the activity of catalysts under humid and dry atmospheres,and provided guidance for the development of highly efficient catalysts for ozone decomposition.展开更多
Sulfation treatment has been widely used to promote the catalytic performance of ceria(CeO_(2))based catalysts for the selective catalytic reduction of NO by NH_(3)(NH_(3)-SCR of NO).Praseodymium oxide(PrO_(x)),anothe...Sulfation treatment has been widely used to promote the catalytic performance of ceria(CeO_(2))based catalysts for the selective catalytic reduction of NO by NH_(3)(NH_(3)-SCR of NO).Praseodymium oxide(PrO_(x)),another commonly used rare earth material with similar structural properties as CeO_(2),also shows satistactory redox properties due to the facile redox cycle of Pr^(3+)■Pr^(4+).In this work,gas phase sulfation treatment with varied duration was performed on PrO_(x) at 200℃,and the NH_(3)-SCR activity of sulfated PrO_(x) was evaluated.Based on the results of systematic characterizations(e.g.,N_(2)-physisorption,NH_(3) oxidation,NO oxidation,in situ diffuse Fourier transform infrared spectroscopy),it is revealed that the catalytic performance of sulfated PrO_(x)is highly dependent on the sulfation time(or the amount of sulfate species deposited on PrO_(x)),which has a significant impact on the competitive reaction between NH_(3) oxidation and NH_(3)-SCR of NO,thus determining the NH_(3)-SCR activity of PrO_(x).This work provides new insight into tuning the interaction between PrO_(x) surface and reactants(NO,NH_(3))via sulfation treatment,which cam guide the design and application of PrO_(x)based catalysts for NH_(3)-SCR of NO in the future.展开更多
To reveal how cerium stabilizes Cu/SAPO-34 at low-temperature hydrothermal aging,various amounts of cerium were introduced into Cu/SAPO-34 via impregnation method and treated at 70℃with RH 80%for 96 h.Cerium as Ce^(3...To reveal how cerium stabilizes Cu/SAPO-34 at low-temperature hydrothermal aging,various amounts of cerium were introduced into Cu/SAPO-34 via impregnation method and treated at 70℃with RH 80%for 96 h.Cerium as Ce^(3+)and CeO_(2)nanoparticle is located on the surface of Cu/SAPO-34,and Ce^(3+)plays a vital role on gradually decreasing surface acidity and blocking defect sites with an increase of Ce loading.After hydrothermal aging,Cu/SAPO-34 with high Ce loading shows the superior SCR activity comparable to fresh samples.It is proven that the surface acidity determines the stability of the structure during hydrothermal aging process,and lower surface acidity prevents the number of Cu(Ⅱ)ions from decreasing significantly.Furthermore,the structure's stability helps the recovery of Cu(Ⅱ)ions and renders an outstanding regene ration ability.Our finding paves the way for the design of new Cu/SAPO-34catalysts with good SCR activity and long-term stability in real application.展开更多
Based on monolayer dispersion theory,Co_(3)O_(4)/ZSM-5 catalysts with different loadings have been prepared for selective catalytic reduction of nitrogen oxides by ammonia.Co_(3)O_(4)can spontaneously disperse on HZSM...Based on monolayer dispersion theory,Co_(3)O_(4)/ZSM-5 catalysts with different loadings have been prepared for selective catalytic reduction of nitrogen oxides by ammonia.Co_(3)O_(4)can spontaneously disperse on HZSM-5 support with a monolayer dispersion threshold of 0.061 mmol 100 m^(-2),equaling to a weight percentage around 4.5%.It has been revealed that the quantities of surface active oxygen(O_(2)^(-))and acid sites are crucial for the reaction,which can adsorb and activate NO_(x)and NH_(3)reactants effectively.Below the monolayer dispersion threshold,Co_(3)O_(4)is finely dispersed as sub-monolayers or monolayers and in an amorphous state,which is favorable to generate the two kinds of active sites,hence promoting the performance of ammonia selective catalytic reduction of nitrogen oxide.However,the formation of crystalline Co_(3)O_(4)above the capacity is harmful to the reaction performance.4%Co_(3)O_(4)/ZSM-5,the catalyst close to the monolayer dispersion capacity,possesses the most abundant active O_(2)^(-)species and acidic sites,thereby demonstrating the best reaction performance in all the samples.It is proposed the optimal Co_(3)O_(4)/ZSM-5 catalyst can be prepared by loading the capacity amount of Co_(3)O_(4)onto HZSM-5 support.展开更多
CuSO4/TiO2 catalysts with high catalytic activity and excellent resistant to SO2 and H2 O,were thought to be promising catalysts used in Selective catalytic reduction of nitrogen oxides by NH3.The performance of catal...CuSO4/TiO2 catalysts with high catalytic activity and excellent resistant to SO2 and H2 O,were thought to be promising catalysts used in Selective catalytic reduction of nitrogen oxides by NH3.The performance of catalysts is largely affected by calcination temperature.Here,effects of calcination temperature on physicochemical property and catalytic activity of CuSO4/TiO2 catalysts were investigated in depth.Catalyst samples calcined at different temperatures were prepared first and then physicochemical properties of the catalyst were characterized by N2 adsorption-desorption,X-ray diffraction,thermogravimetric analysis,Raman spectra,Fourier-transform infrared spectroscopy,X-ray photoelectron spectroscopy,temperature-pro grammed desorption of NH3,temperature-programmed reduction of H2 and in situ diffuse reflectance infrared Fourier transform spectroscopy.Results revealed that high calcination temperature had three main effects on the catalyst.First,sintering and anatase transform into rutile with increase of calcination temperature,causing a decrement of specific surface area.Second,decomposition of CuSO4 under higher calcination temperature,resulting in disappears of Br(?)nsted acid sites(S-OH),which had an adverse effect on surface acidity.Third,CuO from the decomposition of CuSO4 changed surface reducibility of the catalyst and favored the process of NH3 oxidation to nitrogen oxides(NOx).Thus,catalytic activity of the catalyst calcined under high temperatures(≥600℃)decreased largely.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 cerium phosphate catalysts with different crystal phases were synthesized by hydrothermal method and co-precipitation method.Hexagonal cerium phosphate(CePO_(4)-H)shows better NH_(3)-SCR denitration activi...A series of cerium phosphate catalysts with different crystal phases were synthesized by hydrothermal method and co-precipitation method.Hexagonal cerium phosphate(CePO_(4)-H)shows better NH_(3)-SCR denitration activity than monoclinic cerium phosphate(CePO_(4)-M)and mixed phases of CePO_(4)-H and CePO_(4)-M.Moreover,CePO_(4)-H also exhibits excellent activity stability with stream time and cycling stability.Various characterizations were carried out to explain the effects of different crystal phases of CePO_(4)on the activity.Among these catalysts,CePO_(4)-H has much stronger surface acidity that is conducive to the adsorption and activation of NH_(3),and more surface adsorbed oxygen species that can effectively improve SCR activity.In situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)were performed to investigate the adsorption and reaction of NH_(3)and NO_(x)on CePO_(4)-H and CePO_(4)-M,and the results suggest that the better activity over CePO_(4)-H follows mainly the Eley-Rideal mechanism in the activity temperature window(300-500℃)with 100%NO conversion.展开更多
Catalytic hydrodesulfurization(HDS)technique is widely used for clean gasoline production.However,traditional HDS catalyst(CoMo/γ-Al_(2)O_(3))exhibits high hydrogenation performance of olefins(HYDO),resulting in the ...Catalytic hydrodesulfurization(HDS)technique is widely used for clean gasoline production.However,traditional HDS catalyst(CoMo/γ-Al_(2)O_(3))exhibits high hydrogenation performance of olefins(HYDO),resulting in the loss of gasoline octane number.To achieve high HDS/HYDO ratio,the key issue is to reduce the interaction between active metals and the support,therefore,in this research,the modified CoMo/γ-Al_(2)O_(3)catalysts with various boron amounts were investigated under traditional or microwave heating.The effects of preparing methods as well as boron amounts on the active phase,acidic properties and HDS catalytic activities were examined.Results show that the modification,especially under microwave treatment,can significantly weaken the interaction between the active component and the support by enlarging the surface area and pore diameter,and reducing the acidity of the support.As a result,the stacking numbers of MoS_(2) slabs were obviously improved by the modification and microwave treatment,contributing to higher edge/rim ratio,and resulting in higher HDS performance and selectivity to olefin.展开更多
A detailed investigation on the effect of preparation method on the structural,magnetic,and acidic properties of cobalt ferrite nanoparticles prepared by sol-gel and co-precipitation is presented.Citric acid and ethyl...A detailed investigation on the effect of preparation method on the structural,magnetic,and acidic properties of cobalt ferrite nanoparticles prepared by sol-gel and co-precipitation is presented.Citric acid and ethylene glycol were used as gelling agents,while sodium hydroxide and aqueous ammonia were used as precipitating agents.The resulting ferrites were calcined at 450℃ and 750℃.Sharper X-ray diffraction(XRD)peaks were observed for the samples calcined at 750℃,indicating greater crystallinity of the samples calcined at higher temperature.Average crystallite sizes fell in the ranges of 7.1-21.1 nm and 30.4-42.1 nm for the samples calcined at 450℃ and 750℃,respectively.The infrared spectra revealed two main absorption bands,the high frequency bandν1 around 600 cm^(-1) and the low frequency bandν2 around 400 cm^(-1) arising from stretching vibrations of the oxygen bond with the metal in the tetrahedral(A)and octahedral(B)sites in the spinel lattice.Agglomeration of particles was observed in the scanning electron microscopy(SEM)images.Magnetic parameters of CoFe_(2)O_(4) nanoparticles greatly depended on calcination temperature and preparation techniques.Ammonia temperature programmed desorption(TPD)measurements indicated that weak acid sites predominate medium strength sites,while the number of strong acid sites is the least.Cumulative acidity decreased for the samples calcined at higher temperature.The results underline the effect of preparation conditions on the morphology,crystallite size,and magnetic properties of nano ferrites.展开更多
基金Project supported by the National Natural Science Foundation of China (21576054)Science and Technology Planning of Guangdong Province (2016B020241003)+1 种基金Natural Science Foundation of Guangdong Province(2018A030310563)Foundation of Higher Education of Guangdong Province(2018KZDXM031)。
文摘Excellent catalysts with low-temperature activity and relatively wide temperature window for selective catalytic reduction of NO with ammonia(NH_(3)-SCR) are highly demanded in view of the practical treatment of NO.Herein,we have designed a highly active VOx-MnOx/CeO_(2) material based on the intrinsic requirement of SCR reaction for catalyst,namely redox sites and surface acid sites.The vanadium oxide and manganese oxide are highly dispersed over the ceria mesosphere via simple incipient wetness impregnation.The loading of manganese could introduce acid sites and enhance the redox property remarkably,while the loading of vanadium increases acid sites and weakens redox property.Through tentatively controlling the appropriate loading ratio of the two components,the optimal catalyst achieves a balance between redox property and surface acidity.The work shed light on the development of new SCR catalyst with superior low temperature activity,wide work temperature window and good hydrothermal stability.
基金financially supported by the National Natural Science Foundation of China(No.52064027)Yunnan Major Scientific and Technological Projects,China(No.202202AG050015)。
文摘Galena(PbS)and chalcopyrite(CuFeS_(2))are sulfide minerals that exhibit good floatability characteristics.Thus,efficiently separating them via common flotation is challenging.Herein,a new method of surface sulfuric acid corrosion in conjunction with flotation separation was proposed,and the efficient separation of galena and chalcopyrite was successfully realized.Contact angle test results showed a substantial decrease in surface contact angle and a selective inhibition of surface floatability for corroded galena.Meanwhile,the contact angle and floatability of corroded chalcopyrite remained almost unaffected.Scanning electron microscope results confirmed that sulfuric acid corrosion led to the formation of a dense oxide layer on the galena surface,whereas the chalcopyrite surface remained unaltered.X-ray photoelectron spectroscopy results showed that the chemical state of S^(2-)on the surface of corroded galena was oxidized to SO_(4)^(2-).A layer of hydrophilic PbSO4was formed on the surface,leading to a sharp decrease in galena floatability.Meanwhile,new hydrophobic CuS_(2),CuS,and Cu_(1-x)Fe_(1-y)S_(2-z)species exhibiting good floatability were generated on the chalcopyrite surface.Finally,theoretical analysis results were further verified by corrosion–flotation separation experiments.The galena–chalcopyrite mixture was completely separated via flotation separation under appropriate corrosion acidity,corrosion temperature,and corrosion time.A novel approach has been outlined in this study,providing potential applications in the efficient separation of refractory copper–lead sulfide ore.
文摘This article discussed the benzoic acid activated carbons which have changed the types and content of acid oxygen-function groups on the surface of activated carbons and their effect on the adsorption for Hg^0 in simulated flue gas at 140 ℃. These surface acid oxygen function groups were identified by Boehm titration, Fourier transformation infrared spectrum, temperature programmed desorption and X-ray photoelectron spectroscopy. It indicates that the carboxyl, lactone and phenolic were formed when the benzoic acid is loaded on the surface of activated carbons. Among the surface acid oxygen function groups, the carboxyl groups enhance the adsorption capacities of Hg^0 for activated carbons to a greater extent.
基金financial support from the National Natural Science Foundation of China (No. 52161145105/51888103/51976216)Ministry of Science and Technology of China (2017YFA0402800)+5 种基金Beijing Municipal Natural Science Foundation (JQ20017)K.C. Wong Education Foundation (GJTD-2020-07)Recruitment of Global Youth Expertsthe financial support of the Belt and Road scholarshipthe financial support of the ANSO scholarshipthe support of the Chinese Academy of Sciences for the CAS project (Grant No.2018/43)。
文摘Tuning the surface acidity of ZSM-5 catalyst is essential to achieve desired propene selectivity and yield.Here several ratios of Zr were utilized to modify ZSM-5 via flame spray pyrolysis technique coupled with a pulse spray evaporation system.The interaction between Zr and ZSM-5 in the flame influenced the physicochemical and acidity properties of the Zr/ZSM-5.The increasing Zr ratio in ZSM-5 shows coated layers of irregular nano-sized Zr with an increase in crystallite sizes due to the synergetic effect between Zr and ZSM-5.The surface chemical analysis revealed increased lattice oxygen on the Zr modified ZSM-5(1:4) sample compared to other catalysts.The acidity analysis revealed the Lewis and Br?nsted acid distribution in the weak and medium acid sites on the catalyst surface.However,the increase in Zr loading decreased the concentration of Br?nsted acid sites and tuned the catalyst surface to more Lewis acidity,promoting propene selectivity and hindering the over-oxidation of propene.The modified ZSM-5 catalysts were examined in a fixed bed reactor within 300℃-700℃ at a gas hourly space velocity(GHSV) of 6000 mL·g(catalysts)^(-1)·h^(-1) for the oxidative dehydrogenation of propane(ODHP) to propene.Among the catalysts,Zr/ZSM-5(1:4) exhibited the best propene yield, with 57.19% propane conversion and 75.54% selectivity to propene and the highest stability.This work provides a promising strategy for tuning the surface acidity of ZSM-5 with Zr for ODHP applications.
基金supported by the National Key R&D Program of China(Nos.2016YFC0207104 and 2017YFC0211802)the National Natural Science Foundation of China(NSFC)(No.21876191)the Youth Innovation Promotion Association,CAS(No.2017064)
文摘In the study,the catalyst precursors of Ce-modifiedγ-MnO2 were washed with deionized water until the pH value of the supernatant was 1,2,4 and 7,and the obtained catalysts were named accordingly.Under space velocity of 300,000 hr-1,the ozone conversion over the pH=7 catalyst under dry conditions and relative humidity of 65%over a period of 6 hr was 100%and 96%,respectively.However,the ozone decomposition activity of the pH=2 and 4 catalysts distinctly decreased under relative humidity of 65%compared to that under dry conditions.Detailed physical and chemical characterization demonstrated that the residual sulfate ions on the pH=2 and 4 catalysts decreased their hydrophobicity and then restrained humid ozone decomposition activity.The pH=2 and 4 catalysts had inferior resistance to high space velocity under dry conditions,because the residual sulfate ion on their surface reduced their adsorption capacity for ozone molecules and increased their apparent activation energies,which was proved by temperature programmed desorption of O2 and kinetic experiments.Long-term activity testing,X-ray photoelectron spectroscopy and density functional theory calculations revealed that there were two kinds of oxygen vacancies on the manganese dioxide catalysts,one of which more easily adsorbed oxygen species and then became deactivated.This study revealed the detrimental effect of surface acid ions on the activity of catalysts under humid and dry atmospheres,and provided guidance for the development of highly efficient catalysts for ozone decomposition.
基金Project supported by the National Natural Science Foundation of China(21972063)the Natural Science Foundation of Jiangsu Province(BK20200012).
文摘Sulfation treatment has been widely used to promote the catalytic performance of ceria(CeO_(2))based catalysts for the selective catalytic reduction of NO by NH_(3)(NH_(3)-SCR of NO).Praseodymium oxide(PrO_(x)),another commonly used rare earth material with similar structural properties as CeO_(2),also shows satistactory redox properties due to the facile redox cycle of Pr^(3+)■Pr^(4+).In this work,gas phase sulfation treatment with varied duration was performed on PrO_(x) at 200℃,and the NH_(3)-SCR activity of sulfated PrO_(x) was evaluated.Based on the results of systematic characterizations(e.g.,N_(2)-physisorption,NH_(3) oxidation,NO oxidation,in situ diffuse Fourier transform infrared spectroscopy),it is revealed that the catalytic performance of sulfated PrO_(x)is highly dependent on the sulfation time(or the amount of sulfate species deposited on PrO_(x)),which has a significant impact on the competitive reaction between NH_(3) oxidation and NH_(3)-SCR of NO,thus determining the NH_(3)-SCR activity of PrO_(x).This work provides new insight into tuning the interaction between PrO_(x) surface and reactants(NO,NH_(3))via sulfation treatment,which cam guide the design and application of PrO_(x)based catalysts for NH_(3)-SCR of NO in the future.
基金the National Natural Science Foundation of China for Youths(21908207)National Key R&D Program of China(2021YFB3503200)+3 种基金the Key R&D project of Shandong Province(2021CXGC010703)China Postdoctoral Science Foundation(2020M670659)Shanxi Province Science Foundation for Youths(201901D211224)Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi(2019L0575)。
文摘To reveal how cerium stabilizes Cu/SAPO-34 at low-temperature hydrothermal aging,various amounts of cerium were introduced into Cu/SAPO-34 via impregnation method and treated at 70℃with RH 80%for 96 h.Cerium as Ce^(3+)and CeO_(2)nanoparticle is located on the surface of Cu/SAPO-34,and Ce^(3+)plays a vital role on gradually decreasing surface acidity and blocking defect sites with an increase of Ce loading.After hydrothermal aging,Cu/SAPO-34 with high Ce loading shows the superior SCR activity comparable to fresh samples.It is proven that the surface acidity determines the stability of the structure during hydrothermal aging process,and lower surface acidity prevents the number of Cu(Ⅱ)ions from decreasing significantly.Furthermore,the structure's stability helps the recovery of Cu(Ⅱ)ions and renders an outstanding regene ration ability.Our finding paves the way for the design of new Cu/SAPO-34catalysts with good SCR activity and long-term stability in real application.
基金the financial supporting by the National Natural Science Foundation of China(Grant Nos.21962009,22172071,22102069,22062013)the Natural Science Foundation of Jiangxi Province(Grant Nos.20202BAB203006,20181ACB20005)the Key Laboratory Foundation of Jiangxi Province for Environment and Energy Catalysis(Grant No.20181BCD40004).
文摘Based on monolayer dispersion theory,Co_(3)O_(4)/ZSM-5 catalysts with different loadings have been prepared for selective catalytic reduction of nitrogen oxides by ammonia.Co_(3)O_(4)can spontaneously disperse on HZSM-5 support with a monolayer dispersion threshold of 0.061 mmol 100 m^(-2),equaling to a weight percentage around 4.5%.It has been revealed that the quantities of surface active oxygen(O_(2)^(-))and acid sites are crucial for the reaction,which can adsorb and activate NO_(x)and NH_(3)reactants effectively.Below the monolayer dispersion threshold,Co_(3)O_(4)is finely dispersed as sub-monolayers or monolayers and in an amorphous state,which is favorable to generate the two kinds of active sites,hence promoting the performance of ammonia selective catalytic reduction of nitrogen oxide.However,the formation of crystalline Co_(3)O_(4)above the capacity is harmful to the reaction performance.4%Co_(3)O_(4)/ZSM-5,the catalyst close to the monolayer dispersion capacity,possesses the most abundant active O_(2)^(-)species and acidic sites,thereby demonstrating the best reaction performance in all the samples.It is proposed the optimal Co_(3)O_(4)/ZSM-5 catalyst can be prepared by loading the capacity amount of Co_(3)O_(4)onto HZSM-5 support.
基金supported by the National Natural Science Foundation of China(Nos.21906127,21677114,21876139 and 21922606)the Key R&D Program of Shaanxi Province(Nos.2019SF-244 and 2019ZDLSF05-05-02)+4 种基金the China PostdoctoralScience Foundation(No.2016M602831)Natural Science Foundation of Shaanxi Province,China(No.2019JQ-502)the Fundamental Research Funds for the Central Universities(Nos.xjj2017113 and xjj2017170)financial supports from the China Scholarship Councilthe support of K.C.Wong Education Foundation
文摘CuSO4/TiO2 catalysts with high catalytic activity and excellent resistant to SO2 and H2 O,were thought to be promising catalysts used in Selective catalytic reduction of nitrogen oxides by NH3.The performance of catalysts is largely affected by calcination temperature.Here,effects of calcination temperature on physicochemical property and catalytic activity of CuSO4/TiO2 catalysts were investigated in depth.Catalyst samples calcined at different temperatures were prepared first and then physicochemical properties of the catalyst were characterized by N2 adsorption-desorption,X-ray diffraction,thermogravimetric analysis,Raman spectra,Fourier-transform infrared spectroscopy,X-ray photoelectron spectroscopy,temperature-pro grammed desorption of NH3,temperature-programmed reduction of H2 and in situ diffuse reflectance infrared Fourier transform spectroscopy.Results revealed that high calcination temperature had three main effects on the catalyst.First,sintering and anatase transform into rutile with increase of calcination temperature,causing a decrement of specific surface area.Second,decomposition of CuSO4 under higher calcination temperature,resulting in disappears of Br(?)nsted acid sites(S-OH),which had an adverse effect on surface acidity.Third,CuO from the decomposition of CuSO4 changed surface reducibility of the catalyst and favored the process of NH3 oxidation to nitrogen oxides(NOx).Thus,catalytic activity of the catalyst calcined under high temperatures(≥600℃)decreased largely.
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.
文摘A series of cerium phosphate catalysts with different crystal phases were synthesized by hydrothermal method and co-precipitation method.Hexagonal cerium phosphate(CePO_(4)-H)shows better NH_(3)-SCR denitration activity than monoclinic cerium phosphate(CePO_(4)-M)and mixed phases of CePO_(4)-H and CePO_(4)-M.Moreover,CePO_(4)-H also exhibits excellent activity stability with stream time and cycling stability.Various characterizations were carried out to explain the effects of different crystal phases of CePO_(4)on the activity.Among these catalysts,CePO_(4)-H has much stronger surface acidity that is conducive to the adsorption and activation of NH_(3),and more surface adsorbed oxygen species that can effectively improve SCR activity.In situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)were performed to investigate the adsorption and reaction of NH_(3)and NO_(x)on CePO_(4)-H and CePO_(4)-M,and the results suggest that the better activity over CePO_(4)-H follows mainly the Eley-Rideal mechanism in the activity temperature window(300-500℃)with 100%NO conversion.
基金the National Natural Science Foundation of China(Grant No.21476258).
文摘Catalytic hydrodesulfurization(HDS)technique is widely used for clean gasoline production.However,traditional HDS catalyst(CoMo/γ-Al_(2)O_(3))exhibits high hydrogenation performance of olefins(HYDO),resulting in the loss of gasoline octane number.To achieve high HDS/HYDO ratio,the key issue is to reduce the interaction between active metals and the support,therefore,in this research,the modified CoMo/γ-Al_(2)O_(3)catalysts with various boron amounts were investigated under traditional or microwave heating.The effects of preparing methods as well as boron amounts on the active phase,acidic properties and HDS catalytic activities were examined.Results show that the modification,especially under microwave treatment,can significantly weaken the interaction between the active component and the support by enlarging the surface area and pore diameter,and reducing the acidity of the support.As a result,the stacking numbers of MoS_(2) slabs were obviously improved by the modification and microwave treatment,contributing to higher edge/rim ratio,and resulting in higher HDS performance and selectivity to olefin.
文摘A detailed investigation on the effect of preparation method on the structural,magnetic,and acidic properties of cobalt ferrite nanoparticles prepared by sol-gel and co-precipitation is presented.Citric acid and ethylene glycol were used as gelling agents,while sodium hydroxide and aqueous ammonia were used as precipitating agents.The resulting ferrites were calcined at 450℃ and 750℃.Sharper X-ray diffraction(XRD)peaks were observed for the samples calcined at 750℃,indicating greater crystallinity of the samples calcined at higher temperature.Average crystallite sizes fell in the ranges of 7.1-21.1 nm and 30.4-42.1 nm for the samples calcined at 450℃ and 750℃,respectively.The infrared spectra revealed two main absorption bands,the high frequency bandν1 around 600 cm^(-1) and the low frequency bandν2 around 400 cm^(-1) arising from stretching vibrations of the oxygen bond with the metal in the tetrahedral(A)and octahedral(B)sites in the spinel lattice.Agglomeration of particles was observed in the scanning electron microscopy(SEM)images.Magnetic parameters of CoFe_(2)O_(4) nanoparticles greatly depended on calcination temperature and preparation techniques.Ammonia temperature programmed desorption(TPD)measurements indicated that weak acid sites predominate medium strength sites,while the number of strong acid sites is the least.Cumulative acidity decreased for the samples calcined at higher temperature.The results underline the effect of preparation conditions on the morphology,crystallite size,and magnetic properties of nano ferrites.
