Catalytic oxidation of benzene with N_(2)O to phenol over the hierarchical and microporous Fe/ZSM-5-based catalysts in a continuous fixedbed reactor was investigated.The spent catalyst was in-situ regenerated by an ox...Catalytic oxidation of benzene with N_(2)O to phenol over the hierarchical and microporous Fe/ZSM-5-based catalysts in a continuous fixedbed reactor was investigated.The spent catalyst was in-situ regenerated by an oxidative treatment using N_(2)O and in total 10 reaction-regeneration cycles were performed.A 100% N_(2)O conversion,93.3% phenol selectivity,and high initial phenol formation rate of 16.49±0.06mmol_(phenol gcatalyst)^(-1)h^(-1)at time on stream(TOS) of 5 min,and a good phenol productivity of 147.06 mmol_(phenol gcatalyst)^(-1)during catalyst lifetime of 1800 min were obtained on a fresh hierarchical Fe/ZSM-5-Hi2.8 catalyst.With the reaction-regeneration cycle,N_(2)O conversion is fully recovered within TOS of 3 h,moreover,the phenol productivity was decreased ca.2.2±0.8% after each cycle,leading to a total phenol productivity of ca.0.44 ton_(pheol kg_(catalyst)^(-1)estimated for 300 cycles.Catalyst characterizations imply that the coke is rapidly deposited on catalyst surface in the initial TOS of 3 h(0.28 mgc_(gcatalyst)^(-1)min^(-1)) and gradually becomes graphitic during the TOS of 30 h with a slow formation rate of 0.06 mgc g_(catalyst)^(-1)min^(-1).Among others(e.g.,the decrease of textural property and acidity),the nearly complete coverage of the active Fe-O-Al sites by coke accounts for the main catalyst deactivation.Besides these reversible deactivation characteristics related to coking,the irreversible catalyst deactivation is also observed with the reaction-regeneration cycle.The latter is reflected by a further decreased amount of the active Fe-O-Al sites,which agglomerate on catalyst surface with the cycle,likely associated with the hard coke residue that is not completely removed by the regeneration.展开更多
Temperature-programmed reduction (H2-TPR) was employed to quantitatively characterize the active oxygen species generated from a high Fe-loading Fe/ZSM-5 catalyst exposed to N2O at 250 ℃. Fe-O-Fe2+ dimer was determin...Temperature-programmed reduction (H2-TPR) was employed to quantitatively characterize the active oxygen species generated from a high Fe-loading Fe/ZSM-5 catalyst exposed to N2O at 250 ℃. Fe-O-Fe2+ dimer was determined as the active iron complex for N2O decomposition to produce the active oxygen. Reduction of Fe3+ to Fe2+ by H2 in the dimer and removal of OH- groups from Fe2+ dimer by heating Fe/ZSM-5 to 700 ℃ were the prerequisites for the formation of this active Fe complex. A linear correlation with a slope of 1.0 between the amount of Fe-O-Fe2+ and that of active oxygen species was observed. Maximum amount of active oxygen species can be generated by reducing Fe/ZSM-5 catalyst with H2 at the temperatures over 500 ℃ and then heating the resulting product in Ar to 700 ℃, followed by N2O exposure at 250 ℃.The ratio of the total number of oxygen atoms (Ode) deposited by interaction of Fe-O-Fe2+ with N2O to the amount of Fe-O-Fe2+ was 2. However, not all the deposited oxygen atoms were active oxygen (Oa); the ratio of Oa and Ode was 0.5. The iron dimer complex composing active oxygen is a five-atom ion Fe2O32+; the most probable structure is as follows:展开更多
层状KTi Nb O5因具有离子可交换、层间结构均一可控等优点而引起了广泛的关注。采用高温固相法制备的KTi Nb O5为前驱体,经H+交换、剥离改性制备出HTi Nb O5纳米片并以其作为基体材料与Fe2O3纳米粒子复合制备出e-HTi Nb O5@Fe2O3纳米复...层状KTi Nb O5因具有离子可交换、层间结构均一可控等优点而引起了广泛的关注。采用高温固相法制备的KTi Nb O5为前驱体,经H+交换、剥离改性制备出HTi Nb O5纳米片并以其作为基体材料与Fe2O3纳米粒子复合制备出e-HTi Nb O5@Fe2O3纳米复合材料。采用XRD、Raman、BET、HRTEM、TG-DSC和UV-vis DRS对样品的结构和光响应特征进行表征。结果表明,e-HTi Nb O5@Fe2O3保留了主体纳米片聚集体的孔隙结构特征,客体材料分散于主体材料表面,并与主体纳米片上的活性官能团之间发生相互作用,导致主体纳米片的热稳定性增加。另外,e-HTi Nb O5@Fe2O3的BET表面积明显增加的同时,其在可见光区有明显的吸收,禁带宽度为2.08 e V,该纳米复合材料在自然光辐射下可将乙硫醇光催化氧化为磺酸盐。展开更多
We investigate the electronic structure and magnetic properties of layered compound Sr_(3)Fe_(2)O_(5) based on firstprinciples calculations in the framework of density functional theory with GGA+U method.Under high pr...We investigate the electronic structure and magnetic properties of layered compound Sr_(3)Fe_(2)O_(5) based on firstprinciples calculations in the framework of density functional theory with GGA+U method.Under high pressure,the ladder-type layered structure of Sr_(3)Fe_(2)O_(5) is transformed into the infinite layered structure accompanied by a transition from G-type anti-ferromagnetic(AFM)insulator to ferromagnetic(FM)metal and a spin transition from S=2 to S=1.We reproduce these transformations in our calculations and give a clear physical interpretation.展开更多
基金Financial support by the Specialized Research Fund for Doctoral Program of Higher Education,China (No.20120010110003)。
文摘Catalytic oxidation of benzene with N_(2)O to phenol over the hierarchical and microporous Fe/ZSM-5-based catalysts in a continuous fixedbed reactor was investigated.The spent catalyst was in-situ regenerated by an oxidative treatment using N_(2)O and in total 10 reaction-regeneration cycles were performed.A 100% N_(2)O conversion,93.3% phenol selectivity,and high initial phenol formation rate of 16.49±0.06mmol_(phenol gcatalyst)^(-1)h^(-1)at time on stream(TOS) of 5 min,and a good phenol productivity of 147.06 mmol_(phenol gcatalyst)^(-1)during catalyst lifetime of 1800 min were obtained on a fresh hierarchical Fe/ZSM-5-Hi2.8 catalyst.With the reaction-regeneration cycle,N_(2)O conversion is fully recovered within TOS of 3 h,moreover,the phenol productivity was decreased ca.2.2±0.8% after each cycle,leading to a total phenol productivity of ca.0.44 ton_(pheol kg_(catalyst)^(-1)estimated for 300 cycles.Catalyst characterizations imply that the coke is rapidly deposited on catalyst surface in the initial TOS of 3 h(0.28 mgc_(gcatalyst)^(-1)min^(-1)) and gradually becomes graphitic during the TOS of 30 h with a slow formation rate of 0.06 mgc g_(catalyst)^(-1)min^(-1).Among others(e.g.,the decrease of textural property and acidity),the nearly complete coverage of the active Fe-O-Al sites by coke accounts for the main catalyst deactivation.Besides these reversible deactivation characteristics related to coking,the irreversible catalyst deactivation is also observed with the reaction-regeneration cycle.The latter is reflected by a further decreased amount of the active Fe-O-Al sites,which agglomerate on catalyst surface with the cycle,likely associated with the hard coke residue that is not completely removed by the regeneration.
基金supported by National 863 Program Emphasis Project (Nanometer Biology Ware Study, No.2007AA0222006)National Natural Science Foundation of P.R. China(No.30740062 and No.30872970)High School Doctor Subjec Special-purpose Scientific Research Foundation(No.20070286042)
基金supported by the National High Technology Research and Development Program of China(863 Program,2013AA065301)the National Basic Research Program of China(973 Program,2010CB732304)the National Natural Science Found for Creative Research Groups of China(51221892)~~
文摘Temperature-programmed reduction (H2-TPR) was employed to quantitatively characterize the active oxygen species generated from a high Fe-loading Fe/ZSM-5 catalyst exposed to N2O at 250 ℃. Fe-O-Fe2+ dimer was determined as the active iron complex for N2O decomposition to produce the active oxygen. Reduction of Fe3+ to Fe2+ by H2 in the dimer and removal of OH- groups from Fe2+ dimer by heating Fe/ZSM-5 to 700 ℃ were the prerequisites for the formation of this active Fe complex. A linear correlation with a slope of 1.0 between the amount of Fe-O-Fe2+ and that of active oxygen species was observed. Maximum amount of active oxygen species can be generated by reducing Fe/ZSM-5 catalyst with H2 at the temperatures over 500 ℃ and then heating the resulting product in Ar to 700 ℃, followed by N2O exposure at 250 ℃.The ratio of the total number of oxygen atoms (Ode) deposited by interaction of Fe-O-Fe2+ with N2O to the amount of Fe-O-Fe2+ was 2. However, not all the deposited oxygen atoms were active oxygen (Oa); the ratio of Oa and Ode was 0.5. The iron dimer complex composing active oxygen is a five-atom ion Fe2O32+; the most probable structure is as follows:
文摘层状KTi Nb O5因具有离子可交换、层间结构均一可控等优点而引起了广泛的关注。采用高温固相法制备的KTi Nb O5为前驱体,经H+交换、剥离改性制备出HTi Nb O5纳米片并以其作为基体材料与Fe2O3纳米粒子复合制备出e-HTi Nb O5@Fe2O3纳米复合材料。采用XRD、Raman、BET、HRTEM、TG-DSC和UV-vis DRS对样品的结构和光响应特征进行表征。结果表明,e-HTi Nb O5@Fe2O3保留了主体纳米片聚集体的孔隙结构特征,客体材料分散于主体材料表面,并与主体纳米片上的活性官能团之间发生相互作用,导致主体纳米片的热稳定性增加。另外,e-HTi Nb O5@Fe2O3的BET表面积明显增加的同时,其在可见光区有明显的吸收,禁带宽度为2.08 e V,该纳米复合材料在自然光辐射下可将乙硫醇光催化氧化为磺酸盐。
基金Project supported by the National Natural Science Foundation of China(Grant No.11964039)Xinjiang“Hundred Young Doctors Introduction Program”Project,China(Grant No.3010010111).
文摘We investigate the electronic structure and magnetic properties of layered compound Sr_(3)Fe_(2)O_(5) based on firstprinciples calculations in the framework of density functional theory with GGA+U method.Under high pressure,the ladder-type layered structure of Sr_(3)Fe_(2)O_(5) is transformed into the infinite layered structure accompanied by a transition from G-type anti-ferromagnetic(AFM)insulator to ferromagnetic(FM)metal and a spin transition from S=2 to S=1.We reproduce these transformations in our calculations and give a clear physical interpretation.
