The Co@NC catalysts with different morphologies were prepared by two step process,solvent control growth and pyrolysis method.The polyhedral Co@NC-67P-450 catalyst has a relatively high CoNx content and exhibits excel...The Co@NC catalysts with different morphologies were prepared by two step process,solvent control growth and pyrolysis method.The polyhedral Co@NC-67P-450 catalyst has a relatively high CoNx content and exhibits excellent phenol hydrogenation activity(conversion 96.9%)at 160℃,3 MPa,which is higher than that of leaf shaped Co@NC-67L-450 catalyst(conversion 75.4%).We demonstrated Co_(3)O_(4)was reduced to the Co^(0)during the reaction.Moreover,CoNx species contribute to the superior hydrogenation activity of phenol.The Co-based catalysts can be easily recovered through the magnetic separation and performed the high stability.展开更多
The hydrogen evolution reaction(HER)is a promising way to produce hydrogen,and the use of non-precious metals with an excellent electrochemical performance is vital for this.Carbon-based transition metal catalysts hav...The hydrogen evolution reaction(HER)is a promising way to produce hydrogen,and the use of non-precious metals with an excellent electrochemical performance is vital for this.Carbon-based transition metal catalysts have high activity and stability,which are important in reducing the cost of hydrogen production and promoting the development of the hydrogen production industry.However,there is a lack of discussion regarding the effect of carbon components on the performance of these electrocatalysts.This review of the literature discusses the choice of the carbon components in these catalysts and their impact on catalytic performance,including electronic structure control by heteroatom doping,morphology adjustment,and the influence of self-supporting materials.It not only analyzes the progress in HER,but also provides guidance for synthesizing high-performance carbon-based transition metal catalysts.展开更多
The shape impact of nanostructured ceria on the dispersion of Pd species was investigated by analyzing the atomic configuration and the bonding environment of Pd species over spherical and cubic ceria particles,using ...The shape impact of nanostructured ceria on the dispersion of Pd species was investigated by analyzing the atomic configuration and the bonding environment of Pd species over spherical and cubic ceria particles,using STEM and XPS.Amorphous Pd particles of about 2.0 nm,with a substantial amount of tiny Pd species,dispersed on spherical ceria,primarily due to the enriched surface oxygen vacancies that bonded the Pd species tightly.While faceted Pd particles of about 2.9 nm located on cubic ceria with distinct interfaces where Pd atoms embedded into the ceria lattice.The crystalline Pd particles on ceria cubes were highly active and stable for methane combustion that occurred on the metal surface via a facile PdO/Pd redox cycle;while the amorphous Pd particles on spherical ceria particles were featured by a significantly higher activity and stability towards CO oxidation,where the Pd-ceria interface served as the active sites.展开更多
Cobalt-based phosphate/phosphonates are a class of promising water oxidation catalysts at neutralpH.Herein,we reported a facile hydrothermal synthesis of various nanostructured cobalt phe-nylphosphonates.It is found t...Cobalt-based phosphate/phosphonates are a class of promising water oxidation catalysts at neutralpH.Herein,we reported a facile hydrothermal synthesis of various nanostructured cobalt phe-nylphosphonates.It is found that the number of hydroxyl group of structure-directing reagent iscrucial for the construction of 3D hierarchical structures including hierarchical nanosheet flow-er-like assemblies and nanothorn microsphere.These samples were characterized by scanningelectron microscopy,transmission electron microscopy,X-ray diffraction,infrared,and X-ray pho-toelectron spectroscopy techniques.They can act as highly efficient electrocatalysts for the oxygenevolution reaction at neutral pH.Among these,hierarchical cobalt phenylphosphonate nanothornflowers present excellent performance,affording a current density of 1 mA cm^-2 required a smalloverpotential of 393 mV.This work offers a new clue to develop high-performance metal phospho-nate/phosphate catalysts toward electrochemical water oxidation.展开更多
Ruthenium(Ru)serves as a promising catalyst for ammonia synthesis via the Haber-Bosch process,identification of the structure sensitivity to improve the activity of Ru is important but not fully explored yet.We presen...Ruthenium(Ru)serves as a promising catalyst for ammonia synthesis via the Haber-Bosch process,identification of the structure sensitivity to improve the activity of Ru is important but not fully explored yet.We present here density functional theory calculations combined with microkinetic simulations on nitrogen molecule activation,a crucial step in ammonia synthesis,over a variety of hexagonal close-packed(hcp)and face-center cubic(fcc)Ru facets.Hcp{2130}facet exhibits the highest activity toward N_(2) dissociation in hcp Ru,followed by the(0001)monatomic step sites.The other hcp Ru facets have N_(2) dissociation rates at least three orders lower.Fcc{211}facet shows the best performance for N_(2) activation in fcc Ru,followed by{311},which indicates stepped surfaces make great contributions to the overall reactivity.Although hcp Ru{2130}facet and(0001)monatomic step sites have lower or comparable activation barriers compared with fcc Ru{211}facet,fcc Ru is proposed to be more active than hcp Ru for N_(2) conversion due to the exposure of the more favorable active sites over step surfaces in fcc Ru.This work provides new insights into the crystal structure sensitivity of N_(2) activation for mechanistic understanding and rational design of ammonia synthesis over Ru catalysts.展开更多
The effect of ultrasonic treatment on the formation of primary Al3Zr was investigated by applying ultrasound to an Al?0.4Zr alloy.Three temperature ranges were selected,i.e.,830to790°C(above liquidus),790to750...The effect of ultrasonic treatment on the formation of primary Al3Zr was investigated by applying ultrasound to an Al?0.4Zr alloy.Three temperature ranges were selected,i.e.,830to790°C(above liquidus),790to750°C(cross liquidus)and750to710°C(below liquidus)for ultrasonication.Using the scanning electron microscopy,both the size and morphology of the primary Al3Zr particles were examined.It was found that the size was significantly reduced and the morphology changed from large throwing-star shape to small compact tablet shape.The mechanisms for refinement of primary Al3Zr were discussed.It is suggested that sonocrystallization theory via activation of aluminium oxide particles is responsible for the refinement of primary Al3Zr when ultrasonic melt treatment(UST)is applied within the fully liquid state.The refinement of primary Al3Zr particles when UST is applied in the slurry(growth stage)is due to the sonofragmentation.展开更多
The design and fabrication of solid nanomaterials are the key issues in heterogeneous catalysis to achieve desired performance. Traditionally, the main theme is to reduce the size of the catalyst particles as small as...The design and fabrication of solid nanomaterials are the key issues in heterogeneous catalysis to achieve desired performance. Traditionally, the main theme is to reduce the size of the catalyst particles as small as possible for maximizing the number of active sites. In recent years, the rapid advancement in materials science has enabled us to fabricate catalyst particles with tuna- ble morphology. Consequently, both size modulation and morphology control of the catalyst particles can be achieved inde- pendently or synergistically to optimize their catalytic properties. In particular, morphology control of solid catalyst particles at the nanometer level can selectively expose the reactive crystal facets, and thus drastically promote their catalytic performance. In this review, we summarize our recent work on the morphology impact of Co304, CeO2 and Fe203 nanomaterials in catalytic reactions, together with related literature on morphology-dependent nanocatalysis of metal oxides, to demonstrate the importance of tuning the shape of oxide-nanocatalysts for prompting their activity, selectivity and stability, which is a rapidly growing topic in heterogeneous catalysis. The fundamental understanding of the active sites in morphology-tunable oxides that are enclosed by reactive crystal facets is expected to direct the development of highly efficient nanocatalysts.展开更多
The Al-Si coating of ultra-high strength steel has been applied to hot stamping more and more widely, owing to solving the problem of oxidation and decarburization. However, the evolution of Al-Si coating during the h...The Al-Si coating of ultra-high strength steel has been applied to hot stamping more and more widely, owing to solving the problem of oxidation and decarburization. However, the evolution of Al-Si coating during the heating process was rarely studied in the previous study. The tests about the influence of heating parameters, such as heating temperature, heating rates and dwell time, on properties of the Al-Si coating were carried out on the Gleeble-3500 thermal simulator. The properties of the Al-Si coating, for instance, volume fraction of FeAl intermetallics, α-Fe layer as well as porosity and 3D surface topography, were explored in the study. Results showed that more and more Kirkendall voids and cracks appeared in the Al-Si coating when the heating temperature exceeded 600°C. The heating rates almost had no influence on properties of the Al-Si coating when the temperature was equal to or lower than 500°C. The volume fraction of FeAl intermetallics in the coating with dwell time from 3 s to 8 min at 930°C was0, 6.19%, 17.03% and 20.65%, separately. The volume fraction of the α-Fe layer in the coating changed from zero to 31.52%with the prolonged dwell time. The porosity of the coating ranged from 0.51% to 4.98% with the extension of dwell time. The unsmooth degree of the surface of the coating rose gradually with the increasing of heating rates and the extension of dwell time.The 3D surface topography of the coating was determined by the comprehensive effect of atoms diffusion, new formed phases,surface tension and the degree of oxidation of the coating surface. Experiments indicated that rapid heating was not suitable for the coating when the temperature exceeded 500°C. Experiments also demonstrated that enough dwell time was essential to obtain the superior properties of the coating.展开更多
基金The National Natural Science Foundation of China(22102194)The Science and Technology Plan of Gansu Province(20JR10RA044)The Youth Innovation Promotion Association of CAS(2022427).
文摘The Co@NC catalysts with different morphologies were prepared by two step process,solvent control growth and pyrolysis method.The polyhedral Co@NC-67P-450 catalyst has a relatively high CoNx content and exhibits excellent phenol hydrogenation activity(conversion 96.9%)at 160℃,3 MPa,which is higher than that of leaf shaped Co@NC-67L-450 catalyst(conversion 75.4%).We demonstrated Co_(3)O_(4)was reduced to the Co^(0)during the reaction.Moreover,CoNx species contribute to the superior hydrogenation activity of phenol.The Co-based catalysts can be easily recovered through the magnetic separation and performed the high stability.
文摘The hydrogen evolution reaction(HER)is a promising way to produce hydrogen,and the use of non-precious metals with an excellent electrochemical performance is vital for this.Carbon-based transition metal catalysts have high activity and stability,which are important in reducing the cost of hydrogen production and promoting the development of the hydrogen production industry.However,there is a lack of discussion regarding the effect of carbon components on the performance of these electrocatalysts.This review of the literature discusses the choice of the carbon components in these catalysts and their impact on catalytic performance,including electronic structure control by heteroatom doping,morphology adjustment,and the influence of self-supporting materials.It not only analyzes the progress in HER,but also provides guidance for synthesizing high-performance carbon-based transition metal catalysts.
文摘The shape impact of nanostructured ceria on the dispersion of Pd species was investigated by analyzing the atomic configuration and the bonding environment of Pd species over spherical and cubic ceria particles,using STEM and XPS.Amorphous Pd particles of about 2.0 nm,with a substantial amount of tiny Pd species,dispersed on spherical ceria,primarily due to the enriched surface oxygen vacancies that bonded the Pd species tightly.While faceted Pd particles of about 2.9 nm located on cubic ceria with distinct interfaces where Pd atoms embedded into the ceria lattice.The crystalline Pd particles on ceria cubes were highly active and stable for methane combustion that occurred on the metal surface via a facile PdO/Pd redox cycle;while the amorphous Pd particles on spherical ceria particles were featured by a significantly higher activity and stability towards CO oxidation,where the Pd-ceria interface served as the active sites.
文摘Cobalt-based phosphate/phosphonates are a class of promising water oxidation catalysts at neutralpH.Herein,we reported a facile hydrothermal synthesis of various nanostructured cobalt phe-nylphosphonates.It is found that the number of hydroxyl group of structure-directing reagent iscrucial for the construction of 3D hierarchical structures including hierarchical nanosheet flow-er-like assemblies and nanothorn microsphere.These samples were characterized by scanningelectron microscopy,transmission electron microscopy,X-ray diffraction,infrared,and X-ray pho-toelectron spectroscopy techniques.They can act as highly efficient electrocatalysts for the oxygenevolution reaction at neutral pH.Among these,hierarchical cobalt phenylphosphonate nanothornflowers present excellent performance,affording a current density of 1 mA cm^-2 required a smalloverpotential of 393 mV.This work offers a new clue to develop high-performance metal phospho-nate/phosphate catalysts toward electrochemical water oxidation.
基金supported by the National Natural Science Foundation of China(No.91645202 and No.91945302)the Key Technologies R&D Program of China(2017YFB0602205 and 2018YFA0208603)+1 种基金the Chinese Academy of Sciences Key Project(QYZDJSSW-SLH054)the Super Computing Center of USTC is gratefully acknowledged。
文摘Ruthenium(Ru)serves as a promising catalyst for ammonia synthesis via the Haber-Bosch process,identification of the structure sensitivity to improve the activity of Ru is important but not fully explored yet.We present here density functional theory calculations combined with microkinetic simulations on nitrogen molecule activation,a crucial step in ammonia synthesis,over a variety of hexagonal close-packed(hcp)and face-center cubic(fcc)Ru facets.Hcp{2130}facet exhibits the highest activity toward N_(2) dissociation in hcp Ru,followed by the(0001)monatomic step sites.The other hcp Ru facets have N_(2) dissociation rates at least three orders lower.Fcc{211}facet shows the best performance for N_(2) activation in fcc Ru,followed by{311},which indicates stepped surfaces make great contributions to the overall reactivity.Although hcp Ru{2130}facet and(0001)monatomic step sites have lower or comparable activation barriers compared with fcc Ru{211}facet,fcc Ru is proposed to be more active than hcp Ru for N_(2) conversion due to the exposure of the more favorable active sites over step surfaces in fcc Ru.This work provides new insights into the crystal structure sensitivity of N_(2) activation for mechanistic understanding and rational design of ammonia synthesis over Ru catalysts.
基金support from UK Engineering and Physical Science Research Council (EPSRC) for the Ultra-Cast project (grant EP/L019884/1, EP/L019825/1, EP/L019965/1)
文摘The effect of ultrasonic treatment on the formation of primary Al3Zr was investigated by applying ultrasound to an Al?0.4Zr alloy.Three temperature ranges were selected,i.e.,830to790°C(above liquidus),790to750°C(cross liquidus)and750to710°C(below liquidus)for ultrasonication.Using the scanning electron microscopy,both the size and morphology of the primary Al3Zr particles were examined.It was found that the size was significantly reduced and the morphology changed from large throwing-star shape to small compact tablet shape.The mechanisms for refinement of primary Al3Zr were discussed.It is suggested that sonocrystallization theory via activation of aluminium oxide particles is responsible for the refinement of primary Al3Zr when ultrasonic melt treatment(UST)is applied within the fully liquid state.The refinement of primary Al3Zr particles when UST is applied in the slurry(growth stage)is due to the sonofragmentation.
基金supported by the National Natural Science Foundation of China(20923001,21025312)
文摘The design and fabrication of solid nanomaterials are the key issues in heterogeneous catalysis to achieve desired performance. Traditionally, the main theme is to reduce the size of the catalyst particles as small as possible for maximizing the number of active sites. In recent years, the rapid advancement in materials science has enabled us to fabricate catalyst particles with tuna- ble morphology. Consequently, both size modulation and morphology control of the catalyst particles can be achieved inde- pendently or synergistically to optimize their catalytic properties. In particular, morphology control of solid catalyst particles at the nanometer level can selectively expose the reactive crystal facets, and thus drastically promote their catalytic performance. In this review, we summarize our recent work on the morphology impact of Co304, CeO2 and Fe203 nanomaterials in catalytic reactions, together with related literature on morphology-dependent nanocatalysis of metal oxides, to demonstrate the importance of tuning the shape of oxide-nanocatalysts for prompting their activity, selectivity and stability, which is a rapidly growing topic in heterogeneous catalysis. The fundamental understanding of the active sites in morphology-tunable oxides that are enclosed by reactive crystal facets is expected to direct the development of highly efficient nanocatalysts.
基金supported by the National Natural Science Foundation of China(Grant Nos.51275185,51405171,U1564203)
文摘The Al-Si coating of ultra-high strength steel has been applied to hot stamping more and more widely, owing to solving the problem of oxidation and decarburization. However, the evolution of Al-Si coating during the heating process was rarely studied in the previous study. The tests about the influence of heating parameters, such as heating temperature, heating rates and dwell time, on properties of the Al-Si coating were carried out on the Gleeble-3500 thermal simulator. The properties of the Al-Si coating, for instance, volume fraction of FeAl intermetallics, α-Fe layer as well as porosity and 3D surface topography, were explored in the study. Results showed that more and more Kirkendall voids and cracks appeared in the Al-Si coating when the heating temperature exceeded 600°C. The heating rates almost had no influence on properties of the Al-Si coating when the temperature was equal to or lower than 500°C. The volume fraction of FeAl intermetallics in the coating with dwell time from 3 s to 8 min at 930°C was0, 6.19%, 17.03% and 20.65%, separately. The volume fraction of the α-Fe layer in the coating changed from zero to 31.52%with the prolonged dwell time. The porosity of the coating ranged from 0.51% to 4.98% with the extension of dwell time. The unsmooth degree of the surface of the coating rose gradually with the increasing of heating rates and the extension of dwell time.The 3D surface topography of the coating was determined by the comprehensive effect of atoms diffusion, new formed phases,surface tension and the degree of oxidation of the coating surface. Experiments indicated that rapid heating was not suitable for the coating when the temperature exceeded 500°C. Experiments also demonstrated that enough dwell time was essential to obtain the superior properties of the coating.
