PtSnSr/HZSM-5 catalysts with different amounts of strontium were prepared by sequential impregnation method, and characterized by BET analysis, TEM, NH3-TPD, Hz-TPR, TPO and TG techniques. The results showed that the ...PtSnSr/HZSM-5 catalysts with different amounts of strontium were prepared by sequential impregnation method, and characterized by BET analysis, TEM, NH3-TPD, Hz-TPR, TPO and TG techniques. The results showed that the addition of strontium could modify the characteristics and properties of both acid function and metal function of Pt-Sn-based cata- lysts. In this case, PtSnSr/HZSM-5 catalyst with an appropriate amount of Sr （1.2%） showed higher catalytic activity and lower amount of coke deposits than PtSn/HZSM-5 catalyst. However, excessive loading of Sr could facilitate the reduction of Sn, which was unfavorable to the reaction. Afterwards, 1.0 m% of Na was added into the PtSnSr（1.2%）/HZSM-5 catalyst to improve the catalytic performance in propane dehydrogenation, and this catalyst displayed the best catalytic performance during our experiments. After having been subjected to reaction for 5 h, the PtSnNa（1.0%）Sr（1,2%）/HZSM-5 catalyst had achieved a higher than 95% selectivity towards propene along with a corresponding propane conversion rate of 32.2%.展开更多
A series of the Pt-Sn/SBA-15 catalysts were prepared and their properties characterized by using X-ray powder diffraction （XRD）, N2 adsorption-desorption, high resolution transmission electron microscope, X-ray phot...A series of the Pt-Sn/SBA-15 catalysts were prepared and their properties characterized by using X-ray powder diffraction （XRD）, N2 adsorption-desorption, high resolution transmission electron microscope, X-ray photoelectron spectroscopy （XPS） and H2-temperature programmed reduction. Their performances in long chain alkane dehydrogenation were evaluated in a fixed-bed microreactor with dodecane as a model alkane. The results indicated that SBA-15 maintained the well-order mesoporous structure during the reaction. The performance of the catalyst was found not dominated by its textural properties, but by the molar ratio of Sn to Pt which governed the degree of Sn reduction. Owing to the highest degree of Sn reduction, 1% （by mass） Pt-1.8% （by mass） Sn/SBA-15 showed the best catalytic activity. At 0.1 MPa and 470℃, the molar ratio of hydrogen to alkane at 4, and liquid hourly space velocity （LHSV） 20 h^-1, the dodecane conversion is 10%, and the dodecene selectivity is about 70%.展开更多
Propane dehydrogenation(PDH),an atom-economic reaction to produce high-value-added propylene and hydrogen with high efficiency,has recently attracted extensive attention.The severe deactivation of Pt-based catalysts t...Propane dehydrogenation(PDH),an atom-economic reaction to produce high-value-added propylene and hydrogen with high efficiency,has recently attracted extensive attention.The severe deactivation of Pt-based catalysts through sintering and coking remains a major challenge in this high-temperature reaction.The introduction of Sn as a promoter has been widely applied to improve the stability and selectivity of the catalysts.However,the selectivity and stability of PtSn catalysts have been found to vary considerably with synthesis methods,and the role of Sn is still far from fully understanding.To gain in-depth insights into this issue,we synthesized a series of PtSn/SiO_(2)and SnPt/SiO_(2)catalysts by varying the deposition sequence and Pt:Sn ratios using atomic layer deposition with precise control.We found that PtSn/SiO_(2)catalysts fabricated by the deposition of SnO_(x)first and then Pt,exhibited much better propylene selectivity and stability than the SnPt/SiO_(2)catalysts synthesized the other way around.We demonstrate that the presence of Sn species at the Pt-SiO_(2)interface is of essential importance for not only the stabilization of PtSn clusters against sintering under reaction conditions but also the promotion of charge transfers to Pt for high selectivity.Besides the above,the precise regulation of the Sn content is also pivotal for high performance,and the excess amount of Sn might generate additional acidic sites,which could decrease the propylene selectivity and lead to heavy coke formation.These findings provide deep insight into the design of highly selective and stable PDH catalysts.展开更多
A series of PtSn/hierarchical ZSM-5 catalysts were developed for propane dehydrogenation,in which the PtSn bimetallic particles are confined in the mesopores of hierarchical ZSM-5 zeolite.The synthesis of PtSn/hierarc...A series of PtSn/hierarchical ZSM-5 catalysts were developed for propane dehydrogenation,in which the PtSn bimetallic particles are confined in the mesopores of hierarchical ZSM-5 zeolite.The synthesis of PtSn/hierarchical ZSM-5 catalysts was achieved via the loading of Pt and Sn species onto the hierarchical ZSM-5 catalysts that are obtained through a desilication of conventional ZSM-5.The PtSn/hierarchical ZSM-5 catalysts were fully characterized by XRD,N_(2) adsorption,STEM,XPS,and CO-IR techniques,which reveals that highly dispersed PtSn bimetallic nanoparticles are enclosed into mesopores of hierarchical ZSM-5.The catalytic performance of PtSn/hierarchical ZSM-5 is greatly affected by the concentrations of alkali solution in the desilication process and Sn/Pt ratios in PtSn bimetallic particles.The PtSn1.00/ZSM-5(0.8)catalyst shows the highest efficiency in propane dehydrogenation,which gives an initial conversion of 46%and selectivity of 98%at 570℃.The high efficiency in these PtSn/hierarchical ZSM-5 catalysts for propane dehydrogenation is mainly ascribed to the confinement of PtSn particles in the mesopores of hierarchical ZSM-5 zeolite.展开更多
PtSnNa/AlSBA-15 catalysts with different amounts of Sn were prepared for propane dehydrogenation.The catalysts were characterized by XRF,BET,H2 chemisorption,NH3-TPD,H2-TPR,and TPO techniques.Test results indicated th...PtSnNa/AlSBA-15 catalysts with different amounts of Sn were prepared for propane dehydrogenation.The catalysts were characterized by XRF,BET,H2 chemisorption,NH3-TPD,H2-TPR,and TPO techniques.Test results indicated that the presence of tin not only modified the acid function and the interfacial character between metal and support,but also reduced the coke deposition effectively.Among these catalysts investigated thereby,the PtSn(0.7%)Na/AlSBA-15 catalyst had the best catalytic performance in terms of propane conversion and stability.With the continuous addition of Sn,more amounts of Sn0 species appeared,which was unfavorable to the reaction.The PtSn(0.7%)Na/AlSBA-15 catalyst was parametrically characterized in order to obtain necessary information to integrate the process operating conditions.A weight hourly space velocity of 3 h-1,a reaction temperature of 610 ℃ and a H2/C3H8 molar ratio of 0.25 were found to be optimum conditions for achieving a higher dehydrogenation activity of the catalyst.展开更多
The oxidative dehydrogenation of propane with CO_(2)(CO_(2)-ODP)is a promising technology for the efficient production of propene in tandem with CO_(2)reduction to CO.However,the rational design of high-performance ca...The oxidative dehydrogenation of propane with CO_(2)(CO_(2)-ODP)is a promising technology for the efficient production of propene in tandem with CO_(2)reduction to CO.However,the rational design of high-performance catalysts for this green process is still challenged by limited understanding of the nature of active sites and the reaction mechanism.In this work,the effects of SnO_(2) promoter on Pt/CeO_(2)activity and propene selectivity in CO_(2)-ODP are elucidated through varying the Sn/Pt molar ratio.When the ratio increases,propane conversion gradually decreases,while the propene selectivity increases.These dependences are explained by increasing the electron density of Pt through the promoter.The strength of this effect is determined by the Sn/Pt ratio.Owing to the electronic changes of Pt,CO_(2)-ODP becomes more favorable than the undesired CO_(2)reforming of propane.Sn-modified Pt–O–Ce bonds are reasonably revealed as the active sites for CO_(2)-ODP occurring through a redox mechanism involving the activation of CO_(2)over oxygen vacancies at Sn-modified Pt and CeO_(2)boundaries.These atomic-scale understandings are important guidelines for purposeful development of high-performance Pt-based catalysts for CO_(2)-ODP.展开更多
The porous material ATZ with micro-mesopore hierarchical porosity was prepared by alkali treatment of parent HZSM-5 zeolite and applied for propane dehydrogenation. The zeolite samples were characterized by XRD, N2- p...The porous material ATZ with micro-mesopore hierarchical porosity was prepared by alkali treatment of parent HZSM-5 zeolite and applied for propane dehydrogenation. The zeolite samples were characterized by XRD, N2- physisorption, and NH3-TPD analysis. The results showed that the alkali treatment can modify the physicochemical prop- erties of HZSM-5 zeolite. In this case, the porous material ATZ showed larger extemal surface area with less acid sites as compared to the HZSM-5 zeolite. It was found out that the alkali treatment of HZSM-5 zeolite could promote the catalytic performance of PtSn/ATZ catalyst. The possible reason was ascribed to the low acidity of ATZ. Furthermore, the presence of mesopores could reduce the carbon deposits on the metallic surface, which was also favorable for the dehydrogenation reaction.展开更多
Solid-state grinding is a simple and effective method to introduce guest species into the channels of microporous materials through filling.The structure and the surface acidity of the materials were obtained from BET...Solid-state grinding is a simple and effective method to introduce guest species into the channels of microporous materials through filling.The structure and the surface acidity of the materials were obtained from BET isotherms and NH3-TPD,respectively.XRD,UV-vis,UV diffuse-reflectance,and TEM were used to characterize the phases,and the morphology,respectively.The clustered layers of MgO-Al2O3phases were formed in the internal pore surface and were highly dispersed inside the channels of the ZSM-5 host.So the volume of MgO-Al2O3/ZSM-5 composite was larger than the ZSM-5 zeolite itself and some mesoporous channels appeared when Mg/Al species entered the channels.Meanwhile,new acid sites emerged in MgO-Al2O3/ZSM-5 composite and the acid amount of the sample changed.The improved Pt dispersion and the increased acid content would cause the increase of propane conversion and the modification of selectivity during the reaction.展开更多
In addition to the theoretical research,direct ethanol fuel cells have great potential in practical applications.The performance of direct ethanol fuel cells largely depends on the electrocatalysts.Ptbased electrocata...In addition to the theoretical research,direct ethanol fuel cells have great potential in practical applications.The performance of direct ethanol fuel cells largely depends on the electrocatalysts.Ptbased electrocatalysts have been promising candidates for advancing direct ethanol fuel cells for its high catalytic activity and great durability.Here,a PtSn catalyst with unique three-dimensional porous nanostructure has been designed and synthesized via a two-step liquid phase reduction reaction.Sn formed a self-supporting framework in PtSn alloy particles(~3.5 nm).In ethanol electro-oxidation reaction,the PtSn catalyst exhibited high mass activity and excellent recycling time compared with that of Pt/C.After the morphology characterization before and after potential cycling,the PtSn alloy-based nano-catalyst showed good stability.The PtSn catalysts effectively avoid structural instability due to the external carriers,and prolong the leaching time of Sn.In addition,the introduction of a certain amount of Sn can also solve the poisoning phenomenon of active sites on Pt surface.The design strategy of porous alloy nano-catalyst sheds light on its applications in direct ethanol fuel cells.展开更多
基金The Production and Research Prospective Joint Research Project (BY2009153)The Science and Technology Support Program (BE2008129) of Jiangsu Province of Chinathe National Nature Science Foundation of China (50873026,21106017) for financial support
文摘PtSnSr/HZSM-5 catalysts with different amounts of strontium were prepared by sequential impregnation method, and characterized by BET analysis, TEM, NH3-TPD, Hz-TPR, TPO and TG techniques. The results showed that the addition of strontium could modify the characteristics and properties of both acid function and metal function of Pt-Sn-based cata- lysts. In this case, PtSnSr/HZSM-5 catalyst with an appropriate amount of Sr （1.2%） showed higher catalytic activity and lower amount of coke deposits than PtSn/HZSM-5 catalyst. However, excessive loading of Sr could facilitate the reduction of Sn, which was unfavorable to the reaction. Afterwards, 1.0 m% of Na was added into the PtSnSr（1.2%）/HZSM-5 catalyst to improve the catalytic performance in propane dehydrogenation, and this catalyst displayed the best catalytic performance during our experiments. After having been subjected to reaction for 5 h, the PtSnNa（1.0%）Sr（1,2%）/HZSM-5 catalyst had achieved a higher than 95% selectivity towards propene along with a corresponding propane conversion rate of 32.2%.
基金Supported by the National Natural Science Foundation of China （20376005）.
文摘A series of the Pt-Sn/SBA-15 catalysts were prepared and their properties characterized by using X-ray powder diffraction （XRD）, N2 adsorption-desorption, high resolution transmission electron microscope, X-ray photoelectron spectroscopy （XPS） and H2-temperature programmed reduction. Their performances in long chain alkane dehydrogenation were evaluated in a fixed-bed microreactor with dodecane as a model alkane. The results indicated that SBA-15 maintained the well-order mesoporous structure during the reaction. The performance of the catalyst was found not dominated by its textural properties, but by the molar ratio of Sn to Pt which governed the degree of Sn reduction. Owing to the highest degree of Sn reduction, 1% （by mass） Pt-1.8% （by mass） Sn/SBA-15 showed the best catalytic activity. At 0.1 MPa and 470℃, the molar ratio of hydrogen to alkane at 4, and liquid hourly space velocity （LHSV） 20 h^-1, the dodecane conversion is 10%, and the dodecene selectivity is about 70%.
基金supported by the National Natural Science Foundation of China(22102168)the National Science Fund for Distinguished Young Scholars(22025205)+4 种基金the Anhui Natural Science Foundation of China(2108085QB59)Project funded by the China Postdoctoral Science Foundation(BX20190312,2020M671867)the University of Science and Technology of China Youth Innovation Key Fund(YD9990002015)the Fundamental Research Funds for the Central Universities(WK2060000038,WK3430000005)the National Synchrotron Radiation Laboratory(KY2340000135).
文摘Propane dehydrogenation(PDH),an atom-economic reaction to produce high-value-added propylene and hydrogen with high efficiency,has recently attracted extensive attention.The severe deactivation of Pt-based catalysts through sintering and coking remains a major challenge in this high-temperature reaction.The introduction of Sn as a promoter has been widely applied to improve the stability and selectivity of the catalysts.However,the selectivity and stability of PtSn catalysts have been found to vary considerably with synthesis methods,and the role of Sn is still far from fully understanding.To gain in-depth insights into this issue,we synthesized a series of PtSn/SiO_(2)and SnPt/SiO_(2)catalysts by varying the deposition sequence and Pt:Sn ratios using atomic layer deposition with precise control.We found that PtSn/SiO_(2)catalysts fabricated by the deposition of SnO_(x)first and then Pt,exhibited much better propylene selectivity and stability than the SnPt/SiO_(2)catalysts synthesized the other way around.We demonstrate that the presence of Sn species at the Pt-SiO_(2)interface is of essential importance for not only the stabilization of PtSn clusters against sintering under reaction conditions but also the promotion of charge transfers to Pt for high selectivity.Besides the above,the precise regulation of the Sn content is also pivotal for high performance,and the excess amount of Sn might generate additional acidic sites,which could decrease the propylene selectivity and lead to heavy coke formation.These findings provide deep insight into the design of highly selective and stable PDH catalysts.
基金supports of the National Natural Science Foundation of China(21878050,22178062)Foundation of State Key Labora-tory of Coal Conversion(J21-22-620)Green Petrochemical Engineering Base of Intelligence Introduction for Innovation(111 Project D17005)are gratefully acknowledged.
文摘A series of PtSn/hierarchical ZSM-5 catalysts were developed for propane dehydrogenation,in which the PtSn bimetallic particles are confined in the mesopores of hierarchical ZSM-5 zeolite.The synthesis of PtSn/hierarchical ZSM-5 catalysts was achieved via the loading of Pt and Sn species onto the hierarchical ZSM-5 catalysts that are obtained through a desilication of conventional ZSM-5.The PtSn/hierarchical ZSM-5 catalysts were fully characterized by XRD,N_(2) adsorption,STEM,XPS,and CO-IR techniques,which reveals that highly dispersed PtSn bimetallic nanoparticles are enclosed into mesopores of hierarchical ZSM-5.The catalytic performance of PtSn/hierarchical ZSM-5 is greatly affected by the concentrations of alkali solution in the desilication process and Sn/Pt ratios in PtSn bimetallic particles.The PtSn1.00/ZSM-5(0.8)catalyst shows the highest efficiency in propane dehydrogenation,which gives an initial conversion of 46%and selectivity of 98%at 570℃.The high efficiency in these PtSn/hierarchical ZSM-5 catalysts for propane dehydrogenation is mainly ascribed to the confinement of PtSn particles in the mesopores of hierarchical ZSM-5 zeolite.
基金the Production and Research Prospective Joint Research Project(BY2009153)the Science and Technology Support Program(BE2008129) of Jiangsu Province of Chinathe National Nature Science Foundation of China(50873026) for financial supports
文摘PtSnNa/AlSBA-15 catalysts with different amounts of Sn were prepared for propane dehydrogenation.The catalysts were characterized by XRF,BET,H2 chemisorption,NH3-TPD,H2-TPR,and TPO techniques.Test results indicated that the presence of tin not only modified the acid function and the interfacial character between metal and support,but also reduced the coke deposition effectively.Among these catalysts investigated thereby,the PtSn(0.7%)Na/AlSBA-15 catalyst had the best catalytic performance in terms of propane conversion and stability.With the continuous addition of Sn,more amounts of Sn0 species appeared,which was unfavorable to the reaction.The PtSn(0.7%)Na/AlSBA-15 catalyst was parametrically characterized in order to obtain necessary information to integrate the process operating conditions.A weight hourly space velocity of 3 h-1,a reaction temperature of 610 ℃ and a H2/C3H8 molar ratio of 0.25 were found to be optimum conditions for achieving a higher dehydrogenation activity of the catalyst.
基金the National Natural Science Foundation of China(No.21636006)the Fundamental Research Funds for the Central Universities(No.GK201901001).G.Q.Y.acknowledges support from the China Scholarship Council.
文摘The oxidative dehydrogenation of propane with CO_(2)(CO_(2)-ODP)is a promising technology for the efficient production of propene in tandem with CO_(2)reduction to CO.However,the rational design of high-performance catalysts for this green process is still challenged by limited understanding of the nature of active sites and the reaction mechanism.In this work,the effects of SnO_(2) promoter on Pt/CeO_(2)activity and propene selectivity in CO_(2)-ODP are elucidated through varying the Sn/Pt molar ratio.When the ratio increases,propane conversion gradually decreases,while the propene selectivity increases.These dependences are explained by increasing the electron density of Pt through the promoter.The strength of this effect is determined by the Sn/Pt ratio.Owing to the electronic changes of Pt,CO_(2)-ODP becomes more favorable than the undesired CO_(2)reforming of propane.Sn-modified Pt–O–Ce bonds are reasonably revealed as the active sites for CO_(2)-ODP occurring through a redox mechanism involving the activation of CO_(2)over oxygen vacancies at Sn-modified Pt and CeO_(2)boundaries.These atomic-scale understandings are important guidelines for purposeful development of high-performance Pt-based catalysts for CO_(2)-ODP.
基金the Production and Research Prospective Joint Research Project(BY2009153)Science and the National Nature Science Foundation of China(50873026,21106017)for financial supportthe Specialized Research Fund for the Doctoral Program of Higher Education of China(20100092120047)
文摘The porous material ATZ with micro-mesopore hierarchical porosity was prepared by alkali treatment of parent HZSM-5 zeolite and applied for propane dehydrogenation. The zeolite samples were characterized by XRD, N2- physisorption, and NH3-TPD analysis. The results showed that the alkali treatment can modify the physicochemical prop- erties of HZSM-5 zeolite. In this case, the porous material ATZ showed larger extemal surface area with less acid sites as compared to the HZSM-5 zeolite. It was found out that the alkali treatment of HZSM-5 zeolite could promote the catalytic performance of PtSn/ATZ catalyst. The possible reason was ascribed to the low acidity of ATZ. Furthermore, the presence of mesopores could reduce the carbon deposits on the metallic surface, which was also favorable for the dehydrogenation reaction.
基金the financial supports of the National Natural Science Foundation of China(Grant No.21376051,21106017,21306023 and 51077013)the Natural Science Foundation of Jiangsu(Grant No.BK20131288)+3 种基金the Fund Project for Transformation of Scientific and Technological Achievements of Jiangsu Province of China(Grant No.BA2011086)the Specialized Research Fund for the Doctoral Program of Higher Education of China(Grant No.20100092120047)the Key Program for the Scientific Research Guiding Fund of Basic Scientific Research Operation Expenditure of Southeast University(Grant No.3207043101)Instrumental Analysis Fund of Southeast University
文摘Solid-state grinding is a simple and effective method to introduce guest species into the channels of microporous materials through filling.The structure and the surface acidity of the materials were obtained from BET isotherms and NH3-TPD,respectively.XRD,UV-vis,UV diffuse-reflectance,and TEM were used to characterize the phases,and the morphology,respectively.The clustered layers of MgO-Al2O3phases were formed in the internal pore surface and were highly dispersed inside the channels of the ZSM-5 host.So the volume of MgO-Al2O3/ZSM-5 composite was larger than the ZSM-5 zeolite itself and some mesoporous channels appeared when Mg/Al species entered the channels.Meanwhile,new acid sites emerged in MgO-Al2O3/ZSM-5 composite and the acid amount of the sample changed.The improved Pt dispersion and the increased acid content would cause the increase of propane conversion and the modification of selectivity during the reaction.
基金supported by the National Natural Science Foundation of China(Nos.21705036,21975067,51974115,21476066 and 51271074)Natural Science Foundation of Hunan Province,China(No.2018JJ3035)Fundamental Research Funds for the Central Universities from Hunan University。
文摘In addition to the theoretical research,direct ethanol fuel cells have great potential in practical applications.The performance of direct ethanol fuel cells largely depends on the electrocatalysts.Ptbased electrocatalysts have been promising candidates for advancing direct ethanol fuel cells for its high catalytic activity and great durability.Here,a PtSn catalyst with unique three-dimensional porous nanostructure has been designed and synthesized via a two-step liquid phase reduction reaction.Sn formed a self-supporting framework in PtSn alloy particles(~3.5 nm).In ethanol electro-oxidation reaction,the PtSn catalyst exhibited high mass activity and excellent recycling time compared with that of Pt/C.After the morphology characterization before and after potential cycling,the PtSn alloy-based nano-catalyst showed good stability.The PtSn catalysts effectively avoid structural instability due to the external carriers,and prolong the leaching time of Sn.In addition,the introduction of a certain amount of Sn can also solve the poisoning phenomenon of active sites on Pt surface.The design strategy of porous alloy nano-catalyst sheds light on its applications in direct ethanol fuel cells.
