With ongoing global warming and increasing energy demands,the CH_(4)-CO_(2)reforming reaction(dry reforming of methane,DRM)has garnered significant attention as a promising carbon capture and utilization technology.Ni...With ongoing global warming and increasing energy demands,the CH_(4)-CO_(2)reforming reaction(dry reforming of methane,DRM)has garnered significant attention as a promising carbon capture and utilization technology.Nickel-based catalysts are renowned for their outstanding activity and selectivity in this process.The impact of metal-support interaction(MSI),on Ni-based catalyst performance has been extensively researched and debated recently.This paper reviews the recent research progress of MSI on Ni-based catalysts and their characterization and modulation strategies in catalytic reactions.From the perspective of MSI,the effects of different carriers(metal oxides,carbon materials and molecular sieves,etc.)are introduced on the dispersion and surface structure of Ni active metal particles,and the effect of MSI on the activity and stability of DRM reactions on Ni-based catalysts is discussed in detail.Future research should focus on better understanding and controlling MSI to improve the performance and durability of nickel-based catalysts in CH_(4)-CO_(2)reforming,advancing cleaner energy technologies.展开更多
The preferential oxidation of CO(CO-PROX)reaction is a cost-effective method for eliminating trace amounts of CO from the fuel H2.Pt-based catalysts have been extensively studied for COPROX,with their activity influen...The preferential oxidation of CO(CO-PROX)reaction is a cost-effective method for eliminating trace amounts of CO from the fuel H2.Pt-based catalysts have been extensively studied for COPROX,with their activity influenced by the morphology of the support.Hydrothermal synthesis was employed to produce different morphologies ofγ-Al_(2)O_(3):flower-likeγ-Al_(2)O_(3)(f)exposing(110)crystal faces,sheet-likeγ-Al_(2)O_(3)(s)revealing(100)crystal faces,and rod-likeγ-Al_(2)O_(3)(r)displaying(111)crystal faces,followed by loading PtCo nanoparticles.The exposed crystal faces of the support impact the alloying degree of the PtCo nanoparticles,and an increase in the alloying degree correlates with enhanced catalyst reactivity.Pt_(3)Co intermetallic compounds were identified onγ-Al_(2)O_(3)(f)exposing(110)crystal faces,and PtCo/γ-Al_(2)O_(3)(f)showed high catalytic activity in the CO-PROX reaction,achieving 100%CO conversion across a broad temperature range of 50−225°C.In contrast,only partial alloying of PtCo was observed onγ-Al_(2)O_(3)(s).Furthermore,no alloying between Pt and Co occurred in PtCo/γ-Al_(2)O_(3)(r),resulting in a reaction rate at 50°C that was merely 11%of that of PtCo/γ-Al_(2)O_(3)(f).The formation of Pt3Co intermetallic compounds led to a more oxidized state of Pt,which significantly diminished the adsorption of CO on Pt and augmented the active oxygen species,thereby facilitating the selective oxidation of CO.展开更多
Leveraging the interplay between the metal component and the supporting material represents a cornerstone strategy for augmenting electrocatalytic efficiency,e.g.,electrocatalytic CO_(2)reduction reaction(CO_(2)RR).He...Leveraging the interplay between the metal component and the supporting material represents a cornerstone strategy for augmenting electrocatalytic efficiency,e.g.,electrocatalytic CO_(2)reduction reaction(CO_(2)RR).Herein,we employ freestanding porous carbon fibers(PCNF)as an efficacious and stable support for the uniformly distributed SnO_(2)nanoparticles(SnO_(2)PCNF),thereby capitalizing on the synergistic support effect that arises from their strong interaction.On one hand,the interaction between the SnO_(2)nanoparticles and the carbon support optimizes the electronic configuration of the active centers.This interaction leads to a noteworthy shift of the d-band center toward stronger intermediate adsorption energy,consequently lowering the energy barrier associated with CO_(2)reduction.As a result,the Sn O_(2)PCNF realizes a remarkable CO_(2)RR performance with excellent selectivity towards formate(98.1%).On the other hand,the porous carbon fibers enable the uniform and stable dispersion of SnO_(2)nanoparticles,and this superior porous structure of carbon supports can also facilitate the exposure of the SnO_(2)nanoparticles on the reaction interface to a great extent.Consequently,adequate contact between active sites,reactants,and electrolytes can significantly increase the metal utilization,eventually bringing forth a remarkable7.09 A/mg mass activity.This work might provide a useful idea for improving the utilization rate of metals in numerous electrocatalytic reactions.展开更多
The expandable graphite(EG)modified TiO_(2) nanocomposites were prepared by the high shearmethod using the TiO_(2) nanoparticles(NPs)and EG as precursors,in which the amount of EG doped in TiO_(2) was 10 wt.%.Followed...The expandable graphite(EG)modified TiO_(2) nanocomposites were prepared by the high shearmethod using the TiO_(2) nanoparticles(NPs)and EG as precursors,in which the amount of EG doped in TiO_(2) was 10 wt.%.Followed by the impregnation method,adjusting the pH of the solution to 10,and using the electrostatic adsorption to achieve spatial confinement,the Pt elementswere mainly distributed on the exposed TiO_(2),thus generating the Pt/10EG-TiO_(2)-10 catalyst.The best CO oxidation activity with the excellent resistance to H_(2)O and SO_(2) was obtained over the Pt/10EG-TiO_(2)-10 catalyst:CO conversion after 36 hr of the reaction was ca.85%under the harsh condition of 10 vol.%H_(2)O and 100 ppm SO_(2) at a high gaseous hourly space velocity(GHSV)of 400,000 hr−1.Physicochemical properties of the catalystswere characterized by various techniques.The results showed that the electrostatic adsorption,which riveted the Pt elements mainly on the exposed TiO_(2) of the support surface,reduced the dispersion of Pt NPs on EG and achieved the effective dispersion of Pt NPs,hence significantly improving CO oxidation activity over the Pt/10EG-TiO_(2)-10 catalyst.The 10 wt.%EG doped in TiO_(2) caused the TiO_(2) support to form a more hydrophobic surface,which reduced the adsorption of H_(2)O and SO_(2) on the catalyst,greatly inhibited deposition of the TiOSO_(4) and formation of the PtSO4 species as well as suppressed the oxidation of SO_(2),thus resulting in an improvement in the resistance to H_(2)O and SO_(2) of the Pt/10EG-TiO_(2)-10 catalyst.展开更多
Selective hydrogenation of furfural to furfuryl alcohol is a great challenge in the hydrogenation field due to thermodynamic preference for hydrogenation of C=C over C=O.Herein,a novel Al_(2)O_(3)/C-u hybrid catalyst,...Selective hydrogenation of furfural to furfuryl alcohol is a great challenge in the hydrogenation field due to thermodynamic preference for hydrogenation of C=C over C=O.Herein,a novel Al_(2)O_(3)/C-u hybrid catalyst,composed of N-modified dendritic carbon networks supporting Al_(2)O_(3)nanoparticles,was successfully prepared via carbonizing the freeze-dried gel from spontaneous cross-linking of alginate,Al3+and urea.The obtained carbon-supported Al_(2)O_(3)hybrid catalyst has a high ratio (31%) of Al species in pentahedral-coordinated state.The introduction of urea enhances the surface N content,the ratio of pyrrolic N,and specific surface area of catalyst,leading to improved adsorption capacity of C=O and the accessibility of active sites.In the furfural hydrogenation reaction with isopropyl alcohol as hydrogen donor,Al_(2)O_(3)/C-u catalyst achieved a 90%conversion of furfural with 98.0% selectivity to furfuryl alcohol,outperforming that of commercial γ-Al_(2)O_(3).Moreover,Al_(2)O_(3)/C-u demonstrates excellent catalytic stability in the recycling tests attributed to the synergistic effect of abundant weak Lewis acid sites and the anchoring effect of the carbon network on Al_(2)O_(3)nanoparticles.This work provides an innovative and facile strategy for fabrication of carbon-supported Al_(2)O_(3)hybrid catalysts with rich AlVspecies,serving as a high selective hydrogenation catalyst through MPV reaction route.展开更多
基金supported by the Natural Science Foundation of Shanxi Province(202203021221155)the Foundation of National Key Laboratory of High Efficiency and Low Carbon Utilization of Coal(J23-24-902)。
文摘With ongoing global warming and increasing energy demands,the CH_(4)-CO_(2)reforming reaction(dry reforming of methane,DRM)has garnered significant attention as a promising carbon capture and utilization technology.Nickel-based catalysts are renowned for their outstanding activity and selectivity in this process.The impact of metal-support interaction(MSI),on Ni-based catalyst performance has been extensively researched and debated recently.This paper reviews the recent research progress of MSI on Ni-based catalysts and their characterization and modulation strategies in catalytic reactions.From the perspective of MSI,the effects of different carriers(metal oxides,carbon materials and molecular sieves,etc.)are introduced on the dispersion and surface structure of Ni active metal particles,and the effect of MSI on the activity and stability of DRM reactions on Ni-based catalysts is discussed in detail.Future research should focus on better understanding and controlling MSI to improve the performance and durability of nickel-based catalysts in CH_(4)-CO_(2)reforming,advancing cleaner energy technologies.
基金supported by the National Natural Science Foundation of China(22376063,21976057)the Fund of the National Engineering Laboratory for Mobile Source Emission Control Technology(NELMS2020A05)Fundamental Research Funds for the Central Universities.
文摘The preferential oxidation of CO(CO-PROX)reaction is a cost-effective method for eliminating trace amounts of CO from the fuel H2.Pt-based catalysts have been extensively studied for COPROX,with their activity influenced by the morphology of the support.Hydrothermal synthesis was employed to produce different morphologies ofγ-Al_(2)O_(3):flower-likeγ-Al_(2)O_(3)(f)exposing(110)crystal faces,sheet-likeγ-Al_(2)O_(3)(s)revealing(100)crystal faces,and rod-likeγ-Al_(2)O_(3)(r)displaying(111)crystal faces,followed by loading PtCo nanoparticles.The exposed crystal faces of the support impact the alloying degree of the PtCo nanoparticles,and an increase in the alloying degree correlates with enhanced catalyst reactivity.Pt_(3)Co intermetallic compounds were identified onγ-Al_(2)O_(3)(f)exposing(110)crystal faces,and PtCo/γ-Al_(2)O_(3)(f)showed high catalytic activity in the CO-PROX reaction,achieving 100%CO conversion across a broad temperature range of 50−225°C.In contrast,only partial alloying of PtCo was observed onγ-Al_(2)O_(3)(s).Furthermore,no alloying between Pt and Co occurred in PtCo/γ-Al_(2)O_(3)(r),resulting in a reaction rate at 50°C that was merely 11%of that of PtCo/γ-Al_(2)O_(3)(f).The formation of Pt3Co intermetallic compounds led to a more oxidized state of Pt,which significantly diminished the adsorption of CO on Pt and augmented the active oxygen species,thereby facilitating the selective oxidation of CO.
基金supported by the National Natural Science Foundation of China(Nos.22172099,U21A20312)Guangdong Basic and Applied Basic Research Foundation(Nos.2023A1515012776,2022B1515120084)the Shenzhen Science and Technology Program(No.RCYX20200714114535052)。
文摘Leveraging the interplay between the metal component and the supporting material represents a cornerstone strategy for augmenting electrocatalytic efficiency,e.g.,electrocatalytic CO_(2)reduction reaction(CO_(2)RR).Herein,we employ freestanding porous carbon fibers(PCNF)as an efficacious and stable support for the uniformly distributed SnO_(2)nanoparticles(SnO_(2)PCNF),thereby capitalizing on the synergistic support effect that arises from their strong interaction.On one hand,the interaction between the SnO_(2)nanoparticles and the carbon support optimizes the electronic configuration of the active centers.This interaction leads to a noteworthy shift of the d-band center toward stronger intermediate adsorption energy,consequently lowering the energy barrier associated with CO_(2)reduction.As a result,the Sn O_(2)PCNF realizes a remarkable CO_(2)RR performance with excellent selectivity towards formate(98.1%).On the other hand,the porous carbon fibers enable the uniform and stable dispersion of SnO_(2)nanoparticles,and this superior porous structure of carbon supports can also facilitate the exposure of the SnO_(2)nanoparticles on the reaction interface to a great extent.Consequently,adequate contact between active sites,reactants,and electrolytes can significantly increase the metal utilization,eventually bringing forth a remarkable7.09 A/mg mass activity.This work might provide a useful idea for improving the utilization rate of metals in numerous electrocatalytic reactions.
基金supported by the National Key R&D Program of China (No.2017YFC0210303).
文摘The expandable graphite(EG)modified TiO_(2) nanocomposites were prepared by the high shearmethod using the TiO_(2) nanoparticles(NPs)and EG as precursors,in which the amount of EG doped in TiO_(2) was 10 wt.%.Followed by the impregnation method,adjusting the pH of the solution to 10,and using the electrostatic adsorption to achieve spatial confinement,the Pt elementswere mainly distributed on the exposed TiO_(2),thus generating the Pt/10EG-TiO_(2)-10 catalyst.The best CO oxidation activity with the excellent resistance to H_(2)O and SO_(2) was obtained over the Pt/10EG-TiO_(2)-10 catalyst:CO conversion after 36 hr of the reaction was ca.85%under the harsh condition of 10 vol.%H_(2)O and 100 ppm SO_(2) at a high gaseous hourly space velocity(GHSV)of 400,000 hr−1.Physicochemical properties of the catalystswere characterized by various techniques.The results showed that the electrostatic adsorption,which riveted the Pt elements mainly on the exposed TiO_(2) of the support surface,reduced the dispersion of Pt NPs on EG and achieved the effective dispersion of Pt NPs,hence significantly improving CO oxidation activity over the Pt/10EG-TiO_(2)-10 catalyst.The 10 wt.%EG doped in TiO_(2) caused the TiO_(2) support to form a more hydrophobic surface,which reduced the adsorption of H_(2)O and SO_(2) on the catalyst,greatly inhibited deposition of the TiOSO_(4) and formation of the PtSO4 species as well as suppressed the oxidation of SO_(2),thus resulting in an improvement in the resistance to H_(2)O and SO_(2) of the Pt/10EG-TiO_(2)-10 catalyst.
基金China Postdoctoral Science Foundation (2023M733451)Dalian Innovation Team in Key Areas(2020RT06)Engineering Research Center for Key Aromatic Compounds and LiaoNing Key Laboratory,Liaoning Provincial Natural Science Foundation (Doctoral Research Start-up Fund 2024-BSBA-37)。
文摘Selective hydrogenation of furfural to furfuryl alcohol is a great challenge in the hydrogenation field due to thermodynamic preference for hydrogenation of C=C over C=O.Herein,a novel Al_(2)O_(3)/C-u hybrid catalyst,composed of N-modified dendritic carbon networks supporting Al_(2)O_(3)nanoparticles,was successfully prepared via carbonizing the freeze-dried gel from spontaneous cross-linking of alginate,Al3+and urea.The obtained carbon-supported Al_(2)O_(3)hybrid catalyst has a high ratio (31%) of Al species in pentahedral-coordinated state.The introduction of urea enhances the surface N content,the ratio of pyrrolic N,and specific surface area of catalyst,leading to improved adsorption capacity of C=O and the accessibility of active sites.In the furfural hydrogenation reaction with isopropyl alcohol as hydrogen donor,Al_(2)O_(3)/C-u catalyst achieved a 90%conversion of furfural with 98.0% selectivity to furfuryl alcohol,outperforming that of commercial γ-Al_(2)O_(3).Moreover,Al_(2)O_(3)/C-u demonstrates excellent catalytic stability in the recycling tests attributed to the synergistic effect of abundant weak Lewis acid sites and the anchoring effect of the carbon network on Al_(2)O_(3)nanoparticles.This work provides an innovative and facile strategy for fabrication of carbon-supported Al_(2)O_(3)hybrid catalysts with rich AlVspecies,serving as a high selective hydrogenation catalyst through MPV reaction route.
