Small-sized nanoclusters exhibit catalytic activity in electrochemical reactions distinct from the bulk-like properties of nanoparticles 2 nm or larger,yet their surfactant-free synthesis remains a formidable challeng...Small-sized nanoclusters exhibit catalytic activity in electrochemical reactions distinct from the bulk-like properties of nanoparticles 2 nm or larger,yet their surfactant-free synthesis remains a formidable challenge.A scalable microchannel-confined synthesis method enables rapid,controlled formation of 1.12 nm Pt nanoclusters without additional surfactants.Kinetic control achieves a nucleation and growth time of approximately 18.6 s,with heat transfer simulations confirming uniform temperature attainment within 0.5 s.Half-cell and single-cell tests,corroborated by density functional theory(DFT)calculations,demonstrate exceptional performance of these Pt nanoclusters in proton exchange membrane fuel cell(PEMFC),achieving a mass activity 1.9 times that of commercial samples and a rated power density of 1.55 W cm-2.This method can employ multiple capillaries assembled into a capillary bundle to enable parallel experiments,highlighting its scalability and potential to advance hydrogen-electricity conversion technologies.展开更多
Atomic-level catalysts hold immense promise for advancing the atomic economy and facilitating targeted design in catalysis and energy applications.Nevertheless,conventional synthetic approaches have fallen short in at...Atomic-level catalysts hold immense promise for advancing the atomic economy and facilitating targeted design in catalysis and energy applications.Nevertheless,conventional synthetic approaches have fallen short in attaining the utmost synergy among activity,selectivity,and stability.In this innovative study,a groundbreaking photo-induced neighbour-deposition strategy is introduced to construct diatomic Pt sites on highly dispersed CeO2 nests for the reverse water-gas shift(RWGS)reaction.In stark contrast to traditional electrostatic adsorption and impregnation techniques,our strategy enables the precise and directional deposition of diatomic sites onto designated regions,effectively circumventing the adverse effects of residual chlorine on catalytic performance.The resultant dualatom Pt catalyst showcases remarkable RWGS capabilities across a broad temperature spectrum,with CO2 conversion approaching thermodynamic equilibrium and near-100%CO selectivity.The enhanced catalytic performance is primarily attributed to electron coupling at diatomic Pt sites,which significantly accelerates H2dissociation and thence promotes the formation of oxygen vacancies on CeO2 nests,ultimately improving the hydrogenation process.Furthermore,it exhibits exceptional stability over a 100-h reaction period owing to the strong confinement effect at CeO2 nests.This research provides a universal strategy for precisely controlling the configuration and coordination structure of active sites in the synthesis of various low-nuclearity cluster catalysts.展开更多
Deep hydrogenation of polycyclic aromatic hydrocarbons(PAHs)into jet fuel is an important strategy for the upgrading of light cycle oil(LCO).Zeolite-supported metal catalysts have exhibited good catalytic performance ...Deep hydrogenation of polycyclic aromatic hydrocarbons(PAHs)into jet fuel is an important strategy for the upgrading of light cycle oil(LCO).Zeolite-supported metal catalysts have exhibited good catalytic performance for hydrogenation of PAHs under relatively mild conditions.However,the impacts of acidity variations in zeolite supports,arising from the differences in framework Al(AlF)distribution on the catalytic behavior of zeolite-sup ported metal catalysts in the deep hydrogenation of PAHs remains unclear.Herein,two series of mesoporous ZSM-5 samples,that is ZSM-5-E-x and ZSM-5-F-x,with the differences in AlFdistribution but similar Si/Al ratios,were prepared in the crystallization system with or without NaOH.The results of NH3-TPD,Pyridine-IR,N2 adsorption-desorption and SEM reveal that two series of HZSM-5 samples have similar acid density and acid strength,textural properties,morphology and particle size.However,the results of XPS,27Al MAS NMR,2,6-Ditert-butylpyridine-IR,catalytic cracking of 1,3,5-triisopropylbenzene and the controlled reactions as well as DFT calculation indicate that the higher enrichment degree of AlFon the external surface and the suitable arrangement mode of Alp in ten-membered ring(10-MR)of HZSM-5-F-x compared to HZSM-5-E-x in case of the similar Si/Al ratios,result in Pt/HZSM-5-F-x exhibiting remarkably-improved deep hydrogenation performance of phenanthrene(PHE)compared to Pt/HZSM-5-E-x.Particularly,the selectivity to perhydrophenanthrene(PHP)over Pt/HZSM-5-F-50 can reach above 99.0%at a conversion of PHE(>99.0%).Furthermore,Pt/HZSM-5-F-50 exhibits well reusability.This work helps to clarify the impact of AlFdistribution in ZSM-5 on catalytic hydrogenation performance for PAHs,providing valuable guidance for design and development of efficient catalysts for the hydrogenation of PAHs.展开更多
Supported noble-metal catalysts often suffer from nanoparticle sintering,resulting in rapid deactivation under high-temperature conditions.We report hierarchically porous spinel type high-entropy oxide(SHEO)nanofibers...Supported noble-metal catalysts often suffer from nanoparticle sintering,resulting in rapid deactivation under high-temperature conditions.We report hierarchically porous spinel type high-entropy oxide(SHEO)nanofibers,(CrMnFeCoMg)3O4,as robust supports for Pt nanoparticles.The porous structure(38.5m2/g)endows thermal stability,preserving porosity after 880℃calcination.The porous Pt/S-HEO-500exhibits exceptional sinter-resistance.Under 500℃calcination,Pt exhibits only a 0.2 nm growth increment,owing to the physical confinement and strong metal-support interactions.For Pt/S-HEO-500,the T50(50%conversion temperature)for CO oxidation was merely 9℃higher than that without calcination,with 100%conversion retained over 100 h of steady-state operation.These findings position porous spinel HEO nanofibers as a versatile platform for designing sinter-resistant noble-metal catalysts in hightemperature applications.展开更多
Optimizing metal-support interactions(MSI)can significantly enhance catalytic activity,as the characteristics of the support play a decisive role in governing these interactions.Herein,this study systematically invest...Optimizing metal-support interactions(MSI)can significantly enhance catalytic activity,as the characteristics of the support play a decisive role in governing these interactions.Herein,this study systematically investigated the properties and catalytic performance of Pt/CeO2 catalysts prepared by atomic layer deposition(ALD)on three distinct supports:metal-organic framework(MOF)-derived CeO2(CeO2-M),ceria nanorods(CeO2-N),and ceria cubes(CeO2-C).Comprehensive characterization reveals that CeO2-M possesses the highest concentration of coordinatively unsaturated cerium(Ce)sites and surface oxygen vacancies,allowing for higher platinum(Pt)loading.Furthermore,the defect-rich structure of the support creates a unique coordination microenvironment for Pt species,which leads to optimized MSI as well as redox property.Therefore,Pt/CeO2-M catalyst achieves 99%acetone conversion at 200℃with the lowest activation energy of 57.9 kJ/mol.In situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)studies demonstrate that Pt/CeO2-M follows a distinct reaction pathway during acetone oxidation due to its unique coordination structure.These findings establish MOF-derived CeO2 as an ideal ALD support,where defect-mediated Pt anchoring can enhance both oxygen activation capacity and catalytic stability,providing new insights for the design of highperformance oxidation catalysts.展开更多
Pt/C catalysts are widely used for the oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs)but suffer from limited stability.Herein,we demonstrate that the introduction of Fe-N-C layers onto th...Pt/C catalysts are widely used for the oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs)but suffer from limited stability.Herein,we demonstrate that the introduction of Fe-N-C layers onto the surface of Pt/C catalysts can significantly bolster both the ORR stability and activity of Pt/C in the harsh working environment of PEMFCs.Whilst Fe-N-C catalysts typically exhibit poor ORR activity and durability in acidic media,the obtained PtFe/C@Fe-N-C catalyst exhibits a very high peak power density of 2.03 W cm-2and an excellent mass activity(MA)of 0.75 A mgPt-1in a H2-O2fuel cell,with only 2.7%decay after 30000 cycles,far superior to the Pt/C(0.176 A mgPt-1and 54.0% decay)and the U.S.Department of Energy 2025 targets.Experimental and density functional theory investigations unequivocally confirm that the Pt coated with optimized Fe-N-C layer contributes to a more delocalized electronic structure and stronger bonding between Pt and FeNx via strong hybridization of 5d-3d/2p orbitals,resulting in the excellent activity and stability of the PtFe/C@Fe-N-C catalyst.展开更多
Single-atom catalysts(SACs)with a two-dimensional(2D)material as the support offer peculiar active sites at edges and in planes,which differ significantly in their chemical environments and consequently in their catal...Single-atom catalysts(SACs)with a two-dimensional(2D)material as the support offer peculiar active sites at edges and in planes,which differ significantly in their chemical environments and consequently in their catalytic performances in reactions.Herein,we report that Pt single atoms anchored at the edges of 2D MoS2nanosheets deliver dramatically high activity for CO2hydrogenation to CO,in contrast to Pt single atoms as well as their aggregations of 2D-rafts on the in-plane MoS2showing inferior activity.By a combination of experimental and theoretical studies,it was found that the activation of CO2was significantly facilitated on the Pt single atoms with the synergetic effect of its neighboring Mo at the edges,which readily dissociates into gaseous CO with a low energy barrier.Pt,which is isolated by the Scoordinated surroundings on the in-planes,is inert toward CO2adsorption and activation,thus leading to poor activity.This research reveals the close association between the catalytic performance of SACs with their chemical environments,and provides insights into the mechanism modulated by the synergetic effect between single-atom active sites and the support.展开更多
基金National Key Research and Development Program of China(2022YFE0207600)。
摘要Small-sized nanoclusters exhibit catalytic activity in electrochemical reactions distinct from the bulk-like properties of nanoparticles 2 nm or larger,yet their surfactant-free synthesis remains a formidable challenge.A scalable microchannel-confined synthesis method enables rapid,controlled formation of 1.12 nm Pt nanoclusters without additional surfactants.Kinetic control achieves a nucleation and growth time of approximately 18.6 s,with heat transfer simulations confirming uniform temperature attainment within 0.5 s.Half-cell and single-cell tests,corroborated by density functional theory(DFT)calculations,demonstrate exceptional performance of these Pt nanoclusters in proton exchange membrane fuel cell(PEMFC),achieving a mass activity 1.9 times that of commercial samples and a rated power density of 1.55 W cm-2.This method can employ multiple capillaries assembled into a capillary bundle to enable parallel experiments,highlighting its scalability and potential to advance hydrogen-electricity conversion technologies.
基金supported by the National Natural Science Foundation of China(51972306)the Educational and Scientific Research Project of Young and Middle-aged Teachers in Fujian Province(JAT220203)。
摘要Atomic-level catalysts hold immense promise for advancing the atomic economy and facilitating targeted design in catalysis and energy applications.Nevertheless,conventional synthetic approaches have fallen short in attaining the utmost synergy among activity,selectivity,and stability.In this innovative study,a groundbreaking photo-induced neighbour-deposition strategy is introduced to construct diatomic Pt sites on highly dispersed CeO2 nests for the reverse water-gas shift(RWGS)reaction.In stark contrast to traditional electrostatic adsorption and impregnation techniques,our strategy enables the precise and directional deposition of diatomic sites onto designated regions,effectively circumventing the adverse effects of residual chlorine on catalytic performance.The resultant dualatom Pt catalyst showcases remarkable RWGS capabilities across a broad temperature spectrum,with CO2 conversion approaching thermodynamic equilibrium and near-100%CO selectivity.The enhanced catalytic performance is primarily attributed to electron coupling at diatomic Pt sites,which significantly accelerates H2dissociation and thence promotes the formation of oxygen vacancies on CeO2 nests,ultimately improving the hydrogenation process.Furthermore,it exhibits exceptional stability over a 100-h reaction period owing to the strong confinement effect at CeO2 nests.This research provides a universal strategy for precisely controlling the configuration and coordination structure of active sites in the synthesis of various low-nuclearity cluster catalysts.
基金supported by the National Science Foundation of China(No.22378293)Fundamental Research Program of Shanxi Province(No.20210302123398)。
摘要Deep hydrogenation of polycyclic aromatic hydrocarbons(PAHs)into jet fuel is an important strategy for the upgrading of light cycle oil(LCO).Zeolite-supported metal catalysts have exhibited good catalytic performance for hydrogenation of PAHs under relatively mild conditions.However,the impacts of acidity variations in zeolite supports,arising from the differences in framework Al(AlF)distribution on the catalytic behavior of zeolite-sup ported metal catalysts in the deep hydrogenation of PAHs remains unclear.Herein,two series of mesoporous ZSM-5 samples,that is ZSM-5-E-x and ZSM-5-F-x,with the differences in AlFdistribution but similar Si/Al ratios,were prepared in the crystallization system with or without NaOH.The results of NH3-TPD,Pyridine-IR,N2 adsorption-desorption and SEM reveal that two series of HZSM-5 samples have similar acid density and acid strength,textural properties,morphology and particle size.However,the results of XPS,27Al MAS NMR,2,6-Ditert-butylpyridine-IR,catalytic cracking of 1,3,5-triisopropylbenzene and the controlled reactions as well as DFT calculation indicate that the higher enrichment degree of AlFon the external surface and the suitable arrangement mode of Alp in ten-membered ring(10-MR)of HZSM-5-F-x compared to HZSM-5-E-x in case of the similar Si/Al ratios,result in Pt/HZSM-5-F-x exhibiting remarkably-improved deep hydrogenation performance of phenanthrene(PHE)compared to Pt/HZSM-5-E-x.Particularly,the selectivity to perhydrophenanthrene(PHP)over Pt/HZSM-5-F-50 can reach above 99.0%at a conversion of PHE(>99.0%).Furthermore,Pt/HZSM-5-F-50 exhibits well reusability.This work helps to clarify the impact of AlFdistribution in ZSM-5 on catalytic hydrogenation performance for PAHs,providing valuable guidance for design and development of efficient catalysts for the hydrogenation of PAHs.
基金financially supported by the National Key Research and Development Program of China(No.2022YFA1505700)the National Natural Science Foundation of China(No.22475044)+1 种基金the Project of Qinglan Talent of Jiangsu,Pre-Research Fund of Ministry of Education of China(No.8091B022212)the Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX22_0261)。
摘要Supported noble-metal catalysts often suffer from nanoparticle sintering,resulting in rapid deactivation under high-temperature conditions.We report hierarchically porous spinel type high-entropy oxide(SHEO)nanofibers,(CrMnFeCoMg)3O4,as robust supports for Pt nanoparticles.The porous structure(38.5m2/g)endows thermal stability,preserving porosity after 880℃calcination.The porous Pt/S-HEO-500exhibits exceptional sinter-resistance.Under 500℃calcination,Pt exhibits only a 0.2 nm growth increment,owing to the physical confinement and strong metal-support interactions.For Pt/S-HEO-500,the T50(50%conversion temperature)for CO oxidation was merely 9℃higher than that without calcination,with 100%conversion retained over 100 h of steady-state operation.These findings position porous spinel HEO nanofibers as a versatile platform for designing sinter-resistant noble-metal catalysts in hightemperature applications.
基金Project supported by National Natural Science Foundation of China(52370123,22206185)the National Key Research and Development Program of China(2023YFC3707502)。
摘要Optimizing metal-support interactions(MSI)can significantly enhance catalytic activity,as the characteristics of the support play a decisive role in governing these interactions.Herein,this study systematically investigated the properties and catalytic performance of Pt/CeO2 catalysts prepared by atomic layer deposition(ALD)on three distinct supports:metal-organic framework(MOF)-derived CeO2(CeO2-M),ceria nanorods(CeO2-N),and ceria cubes(CeO2-C).Comprehensive characterization reveals that CeO2-M possesses the highest concentration of coordinatively unsaturated cerium(Ce)sites and surface oxygen vacancies,allowing for higher platinum(Pt)loading.Furthermore,the defect-rich structure of the support creates a unique coordination microenvironment for Pt species,which leads to optimized MSI as well as redox property.Therefore,Pt/CeO2-M catalyst achieves 99%acetone conversion at 200℃with the lowest activation energy of 57.9 kJ/mol.In situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)studies demonstrate that Pt/CeO2-M follows a distinct reaction pathway during acetone oxidation due to its unique coordination structure.These findings establish MOF-derived CeO2 as an ideal ALD support,where defect-mediated Pt anchoring can enhance both oxygen activation capacity and catalytic stability,providing new insights for the design of highperformance oxidation catalysts.
摘要Pt/C catalysts are widely used for the oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs)but suffer from limited stability.Herein,we demonstrate that the introduction of Fe-N-C layers onto the surface of Pt/C catalysts can significantly bolster both the ORR stability and activity of Pt/C in the harsh working environment of PEMFCs.Whilst Fe-N-C catalysts typically exhibit poor ORR activity and durability in acidic media,the obtained PtFe/C@Fe-N-C catalyst exhibits a very high peak power density of 2.03 W cm-2and an excellent mass activity(MA)of 0.75 A mgPt-1in a H2-O2fuel cell,with only 2.7%decay after 30000 cycles,far superior to the Pt/C(0.176 A mgPt-1and 54.0% decay)and the U.S.Department of Energy 2025 targets.Experimental and density functional theory investigations unequivocally confirm that the Pt coated with optimized Fe-N-C layer contributes to a more delocalized electronic structure and stronger bonding between Pt and FeNx via strong hybridization of 5d-3d/2p orbitals,resulting in the excellent activity and stability of the PtFe/C@Fe-N-C catalyst.
基金financial supports from the Natural Science Foundation of Jiangsu Province(BK20231075)the National Natural Science Foundation of China(22208021)+6 种基金the Fundamental Research Funds for the Central Universities(QNTD202506)the National Key Research and Development Program(2025YFE0117000)the Science and Technology Project of Jiangsu Provincial Department of Science and Technology(BE2023852)the Science and Technology Project of Jiangsu Provincial Department of Science and Technology(BE2022613)the Key Research Project of the Science and Technology Department of Xinjiang,Development and Industrial Validation of a New Low-Energy Carbon Capture Solventthe CO2 Phase Change Absorption Catalytic Desorption Coupled System Design and Molecular Mechanism Research(2023KYJD1004)the Zhejiang Province Science and Technology Plan Project(2023C03156)。
摘要Single-atom catalysts(SACs)with a two-dimensional(2D)material as the support offer peculiar active sites at edges and in planes,which differ significantly in their chemical environments and consequently in their catalytic performances in reactions.Herein,we report that Pt single atoms anchored at the edges of 2D MoS2nanosheets deliver dramatically high activity for CO2hydrogenation to CO,in contrast to Pt single atoms as well as their aggregations of 2D-rafts on the in-plane MoS2showing inferior activity.By a combination of experimental and theoretical studies,it was found that the activation of CO2was significantly facilitated on the Pt single atoms with the synergetic effect of its neighboring Mo at the edges,which readily dissociates into gaseous CO with a low energy barrier.Pt,which is isolated by the Scoordinated surroundings on the in-planes,is inert toward CO2adsorption and activation,thus leading to poor activity.This research reveals the close association between the catalytic performance of SACs with their chemical environments,and provides insights into the mechanism modulated by the synergetic effect between single-atom active sites and the support.