Multiwall carbon nanotubes （MWNTs） and alumina are combined to give a new type of nanohybrid for Fisher-Tropsch synthesis （FTS） catalyst support. Alumina nano-particles （10 wt%） were introduced directly on funct...Multiwall carbon nanotubes （MWNTs） and alumina are combined to give a new type of nanohybrid for Fisher-Tropsch synthesis （FTS） catalyst support. Alumina nano-particles （10 wt%） were introduced directly on functionalized MWNTs by a modified sol-gel method. Microstructure observations show that alumina particles were homogeneously dispersed on the inside and outside of modified MWNTs surfaces. 15 wt% cobalt loading catalysts were prepared with this nanohybrid and γ-alumina as a reference, using a sol-gel technique and wet impregnation method respectively. These catalysts were characterized by TEM, XRD, N2-adsorption, H2 chemisorption and TPR. The deposition of cobalt nanoparticles synthesized by sol-gel technique on the MWNTs nanohybrid shift the reduction peaks to a low temperature, indicating higher reducibility for uniform cobalt particles. Nanohybrid also aided in high dispersion of metal clusters and high stability and performance of catalyst. The proposed MWNTs nanohybrid-supported cobalt catalysts showed the improved FTS rate （gHc/（gcat.min））, CO conversion （%）, and water gas shift rate （WGS）（gcoz/（gcat.h）） of 0.012, 52, and 30E-3, respectively, as compared to those of 0.007, 25, and 18E-3, respectively, on the γ-alumina-supported cobalt catalysts with the same Co loading.展开更多
The catalysts of Co/Zr-SiO2 were prepared by precipitation and the promoter of Pt was supported by impregnation.The reducibility of the cobalt oxide and the other physicochemical properties of the catalysts were chara...The catalysts of Co/Zr-SiO2 were prepared by precipitation and the promoter of Pt was supported by impregnation.The reducibility of the cobalt oxide and the other physicochemical properties of the catalysts were characterized by TPR,TPD,BET and XPS.With the evaluation of the reduction temperature,the reduction degree increased but the surface area of the catalysts and the adsorption property for reactant CO distinctly decreased;The addition of Pt resulted in the improvement of the reducibility by decreasing the reduction temperature of cobalt oxide species.The FT-synthesis has been performed in a quartz fixed-bed reactor,and the experimental results showed that the best activity for promoted catalyst has been found at the reduction temperature of 400℃,in spite of its uncompleted reduction.展开更多
The conversion of CO_(2) into high value added chemicals via the Fischer-Tropsch synthesis(FTS)reaction has attracted significant attention.The surface oxygenation environment is a significant factor influencing the p...The conversion of CO_(2) into high value added chemicals via the Fischer-Tropsch synthesis(FTS)reaction has attracted significant attention.The surface oxygenation environment is a significant factor influencing the performance of the catalyst.In this work,spin-polarized density-functional theory calculations have been used to investigate the adsorption and reactions of CO_(2) and H to generate CH4 and CH3OH on Fe_(5)C_(2)(100)surfaces with varying OH∗coverage.On the pure Fe_(5)C_(2)(100)surface,surface C^(∗) preferentially reacts with hydrogen to form CH4,exposing C^(∗) vacancy.CO_(2) favors adsorbing on the C^(∗) vacancy to further dissociating and activating.The co-adsorption of OH∗promotes the C^(∗) cycle process by facilitating the hydrogenation of C^(∗).The Fe_(5)C_(2) surface with an oxide interface is favorable for reducing FexOy,thereby maintaining the dynamic stability of the surface.Therefore,surface oxidation is inevitably involved in the entire C^(∗) cycle of the FTS reaction and regulates the relative content of iron oxides and iron carbides.Our work can contribute to the rational modulation of the surface C^(∗) cycle,thereby enhancing catalyst performance.展开更多
The use of supported Co-based catalysts is widespread in various catalytic reactions due to their unique structures.The structural sensitivity of these catalysts is closely linked to their particle size and crystal fo...The use of supported Co-based catalysts is widespread in various catalytic reactions due to their unique structures.The structural sensitivity of these catalysts is closely linked to their particle size and crystal form.Consequently,comprehending the structure–activity relationship requires the development of well-defined Co-based catalysts.Herein,we employed a colloidal wet chemical process and a heterogeneous nucleation method to prepare well-defined Co-based catalysts supported by inert carbon nanospheres.The nanospheres’surface possesses abundant functional groups that efficiently capture metal complexes and facilitate the nucleation and growth of CoO nanoparticles.By adjusting the Co source concentration,solvent molar ratio,and nucleation growth kinetics,we successfully prepared CoO/carbon sphere(CS)catalysts with different particle sizes and crystal forms.The influence of metallic face-centered cubic(fcc)-Co^(0) particle size in the range of 6.6–17.6 nm on the performance of Fischer–Tropsch synthesis(FTS)using well-defined CoO/CS catalysts has been investigated.The result demonstrated that the turnover frequency(TOF)remained constant for CoO/CS catalysts with metallic fcc-Co^(0) particle size larger than 7.7 nm.However,both the selectivity and the activity changed for CoO/CS catalysts with smaller particles(<7.7 nm).Significantly,when metallic fcc-Co^(0) particle size was reduced from 17.6 to 7.7 nm,the cobalt time yield increased to 6.7μmolCO·gCo^(-1)·s^(-1),indicating improved catalytic activity.At the same time,the CH_(4) selectivity decreased to 4.9%,suggesting a higher preference for hydrocarbon production.These findings demonstrate the importance of particle size in Co catalyzed Fischer–Tropsch synthesis.The use of well-defined CoO/CS catalysts offers valuable insights into the structure–activity relationship,leading to a better understanding of Co catalyzed Fischer–Tropsch synthesis.展开更多
基金supported by the Research Council of the Research Institute of Petroleum Industrythe Research and Development of the National Iranian Oil Company
文摘Multiwall carbon nanotubes （MWNTs） and alumina are combined to give a new type of nanohybrid for Fisher-Tropsch synthesis （FTS） catalyst support. Alumina nano-particles （10 wt%） were introduced directly on functionalized MWNTs by a modified sol-gel method. Microstructure observations show that alumina particles were homogeneously dispersed on the inside and outside of modified MWNTs surfaces. 15 wt% cobalt loading catalysts were prepared with this nanohybrid and γ-alumina as a reference, using a sol-gel technique and wet impregnation method respectively. These catalysts were characterized by TEM, XRD, N2-adsorption, H2 chemisorption and TPR. The deposition of cobalt nanoparticles synthesized by sol-gel technique on the MWNTs nanohybrid shift the reduction peaks to a low temperature, indicating higher reducibility for uniform cobalt particles. Nanohybrid also aided in high dispersion of metal clusters and high stability and performance of catalyst. The proposed MWNTs nanohybrid-supported cobalt catalysts showed the improved FTS rate （gHc/（gcat.min））, CO conversion （%）, and water gas shift rate （WGS）（gcoz/（gcat.h）） of 0.012, 52, and 30E-3, respectively, as compared to those of 0.007, 25, and 18E-3, respectively, on the γ-alumina-supported cobalt catalysts with the same Co loading.
基金Supported by the National High Technology Research and Development Program of China(863Program)(No.:2004AA649240)
文摘The catalysts of Co/Zr-SiO2 were prepared by precipitation and the promoter of Pt was supported by impregnation.The reducibility of the cobalt oxide and the other physicochemical properties of the catalysts were characterized by TPR,TPD,BET and XPS.With the evaluation of the reduction temperature,the reduction degree increased but the surface area of the catalysts and the adsorption property for reactant CO distinctly decreased;The addition of Pt resulted in the improvement of the reducibility by decreasing the reduction temperature of cobalt oxide species.The FT-synthesis has been performed in a quartz fixed-bed reactor,and the experimental results showed that the best activity for promoted catalyst has been found at the reduction temperature of 400℃,in spite of its uncompleted reduction.
基金the National Natural Science Foundation of China(22002008,22202226,22468042)Ningxia Key Research and Development Project(2022BEE03002,2022 BSB03056)+1 种基金the Fourth Batch of Ningxia Youth Talents Supporting Program(TJGC2019022)West Light Foundation of the Chinese Academy of Sciences(XAB2019AW02).
文摘The conversion of CO_(2) into high value added chemicals via the Fischer-Tropsch synthesis(FTS)reaction has attracted significant attention.The surface oxygenation environment is a significant factor influencing the performance of the catalyst.In this work,spin-polarized density-functional theory calculations have been used to investigate the adsorption and reactions of CO_(2) and H to generate CH4 and CH3OH on Fe_(5)C_(2)(100)surfaces with varying OH∗coverage.On the pure Fe_(5)C_(2)(100)surface,surface C^(∗) preferentially reacts with hydrogen to form CH4,exposing C^(∗) vacancy.CO_(2) favors adsorbing on the C^(∗) vacancy to further dissociating and activating.The co-adsorption of OH∗promotes the C^(∗) cycle process by facilitating the hydrogenation of C^(∗).The Fe_(5)C_(2) surface with an oxide interface is favorable for reducing FexOy,thereby maintaining the dynamic stability of the surface.Therefore,surface oxidation is inevitably involved in the entire C^(∗) cycle of the FTS reaction and regulates the relative content of iron oxides and iron carbides.Our work can contribute to the rational modulation of the surface C^(∗) cycle,thereby enhancing catalyst performance.
基金supported by the National Natural Science Foundation of China(Nos.22072184,22372199,and 21972170)the Young Top-notch Talent Cultivation Program of Hubei Provincethe Fundamental Research Funds for the Central Universities of South-Central Minzu University(No.CZZ23005).
文摘The use of supported Co-based catalysts is widespread in various catalytic reactions due to their unique structures.The structural sensitivity of these catalysts is closely linked to their particle size and crystal form.Consequently,comprehending the structure–activity relationship requires the development of well-defined Co-based catalysts.Herein,we employed a colloidal wet chemical process and a heterogeneous nucleation method to prepare well-defined Co-based catalysts supported by inert carbon nanospheres.The nanospheres’surface possesses abundant functional groups that efficiently capture metal complexes and facilitate the nucleation and growth of CoO nanoparticles.By adjusting the Co source concentration,solvent molar ratio,and nucleation growth kinetics,we successfully prepared CoO/carbon sphere(CS)catalysts with different particle sizes and crystal forms.The influence of metallic face-centered cubic(fcc)-Co^(0) particle size in the range of 6.6–17.6 nm on the performance of Fischer–Tropsch synthesis(FTS)using well-defined CoO/CS catalysts has been investigated.The result demonstrated that the turnover frequency(TOF)remained constant for CoO/CS catalysts with metallic fcc-Co^(0) particle size larger than 7.7 nm.However,both the selectivity and the activity changed for CoO/CS catalysts with smaller particles(<7.7 nm).Significantly,when metallic fcc-Co^(0) particle size was reduced from 17.6 to 7.7 nm,the cobalt time yield increased to 6.7μmolCO·gCo^(-1)·s^(-1),indicating improved catalytic activity.At the same time,the CH_(4) selectivity decreased to 4.9%,suggesting a higher preference for hydrocarbon production.These findings demonstrate the importance of particle size in Co catalyzed Fischer–Tropsch synthesis.The use of well-defined CoO/CS catalysts offers valuable insights into the structure–activity relationship,leading to a better understanding of Co catalyzed Fischer–Tropsch synthesis.
