The interfacial perimeter of gold nanocatalysts is popularly viewed as the active sites for a number of chemical reactions,while the geometrical structure of the interface at atomic scale is less known.Here,TiO2-nanos...The interfacial perimeter of gold nanocatalysts is popularly viewed as the active sites for a number of chemical reactions,while the geometrical structure of the interface at atomic scale is less known.Here,TiO2-nanosheets and nanospindles were adapted to accommodate Au particles(~2.2 nm),forming Au-TiO2{001}and Au-TiO2{101}interfaces.Upon calcination at 623 K in air,HAADF-STEM images evidenced that the Au particles on TiO2{101}enlarged to 3.1 nm and these on TiO2{001}remained unchanged,suggesting the stronger metal-support interaction on TiO2{001}.Au/TiO2{001}was more active for CO oxidation than Au/TiO2{101}system.展开更多
Nitrogen-doped carbon materials encapsulating 3 d transition metals are promising alternatives to replace noble metal Pt catalysts for efficiently catalyzing the oxygen reduction reaction(ORR). Herein, we use cobalt s...Nitrogen-doped carbon materials encapsulating 3 d transition metals are promising alternatives to replace noble metal Pt catalysts for efficiently catalyzing the oxygen reduction reaction(ORR). Herein, we use cobalt substituted perfluorosulfonic acid/polytetrafluoroethylene copolymer and dicyandiamide as the pyrolysis precursor to synthesize nitrogen-doped carbon nanotube(N–CNT) encapsulating cobalt nanoparticles hybrid material. The carbon layers and specific surface area of N–CNT have a critical role to the ORR performance due to the exposed active sites, determined by the mass ratio of the two precursors. The optimum hybrid material exhibits high ORR activity and stability, as well as excellent performance and durability in zinc–air battery.展开更多
Replacing platinum for catalyzing hydrogen evolution reaction (HER) in acidic medium remains great chal- lenges. Herein, we prepared few-layered MoS2 by ball milling as an efficient catalyst for HER in acidic medium...Replacing platinum for catalyzing hydrogen evolution reaction (HER) in acidic medium remains great chal- lenges. Herein, we prepared few-layered MoS2 by ball milling as an efficient catalyst for HER in acidic medium, The activity of as-prepared MoS2 had a strong dependence on the ball milling time, Furthermore, Ketjen Black EC 300J was added into the ball-milled MoS2 followed by a second ball milling, and the resultant MoS2/carbon black hybrid material showed a much higher HER activity than MoS2 and carbon black alone. The enhanced activity of the MoS2/carbon black hybrid material was attributed to the increased abundance of catalytic edge sites of MoS) and excellent electrical coupling to the underlving carbon network.展开更多
Active-phase engineering is regularly utilized to tune the selectivity of metal nanoparticles (NPs) in heterogeneous catalysis. However, the lack of understanding of the active phase in electrocatalysis has hampered...Active-phase engineering is regularly utilized to tune the selectivity of metal nanoparticles (NPs) in heterogeneous catalysis. However, the lack of understanding of the active phase in electrocatalysis has hampered the development of efficient catalysts for CO2 electroreduction. Herein, we report the systematic engineering of active phases of Pd NPs, which are exploited to select reaction pathways for CO2 electroreduction. In situ X-ray absorption spectroscopy, in situ attenuated total reflection-infrared spectroscopy, and density functional theory calculations suggest that the formation of a hydrogen-adsorbed Pd surface on a mixture of the α- and β-phases of a palladium-hydride core (α+β PdHx@PdHx) above -0.2 V (vs. a reversible hydrogen electrode) facilitates formate production via the HCOO intermediate, whereas the formation of a metallic Pd surface on the β-phase Pd hydride core (β PdHx@Pd) below -0.5 V promotes CO production via the COOH" intermediate. The main product, which is either formate or CO, can be selectively produced with high Faradaic efficiencies (〉90%) and mass activities in the potential window of 0.05 to -0.9 V with scalable application demonstration.展开更多
A PtFe/C catalyst has been synthesized by impregnation and high-temperature reduction followed by acid-leaching. X-ray diffraction, X-ray photoelectron spectroscopy and X-ray atomic near edge spectroscopy characteriza...A PtFe/C catalyst has been synthesized by impregnation and high-temperature reduction followed by acid-leaching. X-ray diffraction, X-ray photoelectron spectroscopy and X-ray atomic near edge spectroscopy characterization reveal that PtgFe alloy formation occurs during high-temperature reduction and that unstable Fe species are dissolved into acid solution. The difference in Fe concentration from the core region to the surface and strong O-Fe bonding may drive the outward diffusion of Fe to the highly corrugated Pt-skeleton, and the resulting highly dispersed surface FeOx is stable in acidic medium, leading to the construction of a PtBFe@Pt-FeOx architecture. The as prepared PtFe/C catalyst demonstrates a higher activity and comparable durability for the oxygen reduction reaction compared with a Pt/C catalyst, which might be due to the synergetic effect of surface and subsurface Fe species in the PtFe/C catalyst.展开更多
We present a facile and versatile method for introducing various non-precious metal nanoparticles (NPs) in small nanotubes, such as single-walled carbon nanotubes (SWNTs), including 3d-metals (V, Mn, Fe and Co),...We present a facile and versatile method for introducing various non-precious metal nanoparticles (NPs) in small nanotubes, such as single-walled carbon nanotubes (SWNTs), including 3d-metals (V, Mn, Fe and Co), 4d-metals (Mo), and 5d-metals (W). This is realized by oxidizing encapsulated cycloalkene metal carbonyl complexes below their sublimation temperatures. This novel technique is significant because it avoids the diffusion and deposition of metal species on the outer walls of nanotubes, which has been challenging to achieve using the conventional filling methods. High-resolution transmission electron microscopy (HRTEM), high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), energy-dispersive X-ray spectroscopy (EDX), Raman, and X-ray photoelectron spectroscopy (XPS) analyses revealed high filling efficiencies (〉 95% SWNTs filled with metal NPs). This method also provides a unique approach to fabricate highly dispersed and uniform SWNT-metal nanoparficle encapsulates with lower valence states, which are often not stable in the bulk.展开更多
The grain morphology, nano-oxide particles and mechanical properties of oxide dispersion strengthened (ODS)-316L austenitic steel synthesized by electron beam selective melting (EBSM) technique with different post...The grain morphology, nano-oxide particles and mechanical properties of oxide dispersion strengthened (ODS)-316L austenitic steel synthesized by electron beam selective melting (EBSM) technique with different post-working processes, were explored in this study. The ODS-316L austenitic steel with superfine nano-sized oxide particles of 30-40 nm exhibits good tensile strength (412 MPa) and large total elongation (about 51%) due to the pinning effect of uniform distributed oxide particles on dislocations. After hot rolling, the specimen exhibits a higher tensile strength of 482 MPa, but the elongation decreases to 31.8% owing to the introduction of high-density dislocations. The subsequent heat treatment eliminates the grain defects induced by hot rolling and increases the randomly orientated grains, which further improves the strength and ductility of EBSM ODS-316L steel.展开更多
An effective solvent-free method based on a solid-reduction process was developed to fabricate ultrafine gold catalysts. By this method we revealed a strong size-dependent activity of Au species in which subnanometer-...An effective solvent-free method based on a solid-reduction process was developed to fabricate ultrafine gold catalysts. By this method we revealed a strong size-dependent activity of Au species in which subnanometer-sized clusters exhibited the best activity in the hydrogenation of CO_2 to formate, with a turnover number of up to 9278 over 7 h at 90 ℃.展开更多
In this paper the tungsten-fibre-net-reinforced tungsten composites were produced by spark plasma sintering (SPS) using fine W powders and commercial tungsten fibres. The relative density of the samples is above 95%...In this paper the tungsten-fibre-net-reinforced tungsten composites were produced by spark plasma sintering (SPS) using fine W powders and commercial tungsten fibres. The relative density of the samples is above 95%. It was found that the recrystallization area in the fibres became bigger with increasing sintering temperature and pressure. The tungsten grains of fibres kept stable when sintered at 1350℃/16 kN while grown up when sintered at 1800℃/16 kN. The composite sintered at 1350℃/16 kN have a Vickers-hardness of -610 HV, about 2 times that of the 1800℃/16 kN sintered one. Tensile tests imply that the temperature at which the composites (1350℃/16 kN) begin to exhibit plastic deformation is about 200℃-250℃, which is 400℃ lower than that of SPSed pure W. The tensile fracture surfaces show that the increasing fracture ductility comes from pull-out, interface debonding and fracture of fibres.展开更多
基金supported by Liaoning Revitalization Talents Program (XLYC1807121)National Natural Science Foundation of China (20673054)~~
文摘The interfacial perimeter of gold nanocatalysts is popularly viewed as the active sites for a number of chemical reactions,while the geometrical structure of the interface at atomic scale is less known.Here,TiO2-nanosheets and nanospindles were adapted to accommodate Au particles(~2.2 nm),forming Au-TiO2{001}and Au-TiO2{101}interfaces.Upon calcination at 623 K in air,HAADF-STEM images evidenced that the Au particles on TiO2{101}enlarged to 3.1 nm and these on TiO2{001}remained unchanged,suggesting the stronger metal-support interaction on TiO2{001}.Au/TiO2{001}was more active for CO oxidation than Au/TiO2{101}system.
基金financial support from the Ministry of Science and Technology of China(Grants 2016YFB0600901 and 2013CB933100)the National Natural Science Foundation of China(Grants 21573222 and 91545202)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB17020200)financial support from CAS Youth Innovation Promotion(Grant No.2015145)
文摘Nitrogen-doped carbon materials encapsulating 3 d transition metals are promising alternatives to replace noble metal Pt catalysts for efficiently catalyzing the oxygen reduction reaction(ORR). Herein, we use cobalt substituted perfluorosulfonic acid/polytetrafluoroethylene copolymer and dicyandiamide as the pyrolysis precursor to synthesize nitrogen-doped carbon nanotube(N–CNT) encapsulating cobalt nanoparticles hybrid material. The carbon layers and specific surface area of N–CNT have a critical role to the ORR performance due to the exposed active sites, determined by the mass ratio of the two precursors. The optimum hybrid material exhibits high ORR activity and stability, as well as excellent performance and durability in zinc–air battery.
基金the financial support from the Ministry of Science and Technology of China (grants 2012CB215500 and 2013CB933100)the National Natural Science Foundation of China (grants 21573222 and 21103178)
文摘Replacing platinum for catalyzing hydrogen evolution reaction (HER) in acidic medium remains great chal- lenges. Herein, we prepared few-layered MoS2 by ball milling as an efficient catalyst for HER in acidic medium, The activity of as-prepared MoS2 had a strong dependence on the ball milling time, Furthermore, Ketjen Black EC 300J was added into the ball-milled MoS2 followed by a second ball milling, and the resultant MoS2/carbon black hybrid material showed a much higher HER activity than MoS2 and carbon black alone. The enhanced activity of the MoS2/carbon black hybrid material was attributed to the increased abundance of catalytic edge sites of MoS) and excellent electrical coupling to the underlving carbon network.
文摘Active-phase engineering is regularly utilized to tune the selectivity of metal nanoparticles (NPs) in heterogeneous catalysis. However, the lack of understanding of the active phase in electrocatalysis has hampered the development of efficient catalysts for CO2 electroreduction. Herein, we report the systematic engineering of active phases of Pd NPs, which are exploited to select reaction pathways for CO2 electroreduction. In situ X-ray absorption spectroscopy, in situ attenuated total reflection-infrared spectroscopy, and density functional theory calculations suggest that the formation of a hydrogen-adsorbed Pd surface on a mixture of the α- and β-phases of a palladium-hydride core (α+β PdHx@PdHx) above -0.2 V (vs. a reversible hydrogen electrode) facilitates formate production via the HCOO intermediate, whereas the formation of a metallic Pd surface on the β-phase Pd hydride core (β PdHx@Pd) below -0.5 V promotes CO production via the COOH" intermediate. The main product, which is either formate or CO, can be selectively produced with high Faradaic efficiencies (〉90%) and mass activities in the potential window of 0.05 to -0.9 V with scalable application demonstration.
基金This work was financially supported by the Ministry of Science and Technology of China (Grants 2012CB215500 and 2013CB933100) and the National Natural Science Foundation of China (Grants 21103178 and 21033009).
文摘A PtFe/C catalyst has been synthesized by impregnation and high-temperature reduction followed by acid-leaching. X-ray diffraction, X-ray photoelectron spectroscopy and X-ray atomic near edge spectroscopy characterization reveal that PtgFe alloy formation occurs during high-temperature reduction and that unstable Fe species are dissolved into acid solution. The difference in Fe concentration from the core region to the surface and strong O-Fe bonding may drive the outward diffusion of Fe to the highly corrugated Pt-skeleton, and the resulting highly dispersed surface FeOx is stable in acidic medium, leading to the construction of a PtBFe@Pt-FeOx architecture. The as prepared PtFe/C catalyst demonstrates a higher activity and comparable durability for the oxygen reduction reaction compared with a Pt/C catalyst, which might be due to the synergetic effect of surface and subsurface Fe species in the PtFe/C catalyst.
文摘We present a facile and versatile method for introducing various non-precious metal nanoparticles (NPs) in small nanotubes, such as single-walled carbon nanotubes (SWNTs), including 3d-metals (V, Mn, Fe and Co), 4d-metals (Mo), and 5d-metals (W). This is realized by oxidizing encapsulated cycloalkene metal carbonyl complexes below their sublimation temperatures. This novel technique is significant because it avoids the diffusion and deposition of metal species on the outer walls of nanotubes, which has been challenging to achieve using the conventional filling methods. High-resolution transmission electron microscopy (HRTEM), high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), energy-dispersive X-ray spectroscopy (EDX), Raman, and X-ray photoelectron spectroscopy (XPS) analyses revealed high filling efficiencies (〉 95% SWNTs filled with metal NPs). This method also provides a unique approach to fabricate highly dispersed and uniform SWNT-metal nanoparficle encapsulates with lower valence states, which are often not stable in the bulk.
基金Acknowledgements This work was subsidized by the National Natural Science Foundation of China (Grant Nos. 11175203 and 11375230).
文摘The grain morphology, nano-oxide particles and mechanical properties of oxide dispersion strengthened (ODS)-316L austenitic steel synthesized by electron beam selective melting (EBSM) technique with different post-working processes, were explored in this study. The ODS-316L austenitic steel with superfine nano-sized oxide particles of 30-40 nm exhibits good tensile strength (412 MPa) and large total elongation (about 51%) due to the pinning effect of uniform distributed oxide particles on dislocations. After hot rolling, the specimen exhibits a higher tensile strength of 482 MPa, but the elongation decreases to 31.8% owing to the introduction of high-density dislocations. The subsequent heat treatment eliminates the grain defects induced by hot rolling and increases the randomly orientated grains, which further improves the strength and ductility of EBSM ODS-316L steel.
基金This work was supported by the National Natural Science Foun- dation of China (Nos. 21676045, 21476226, 21203182, 21176037), the National Key R&D Program of China (No. 2016YFB0600902), the Strategic Priority Research Program of the Chinese Academy of Sciences (Nos. XDB17020400), Dalian Science Foundation for Distinguished Young Scholars (No. 2016RJ04), the Youth Innova- tion Promotion Association CAS and the Natural Science Founda- tion of Liaoning province (No. 201602169).
文摘An effective solvent-free method based on a solid-reduction process was developed to fabricate ultrafine gold catalysts. By this method we revealed a strong size-dependent activity of Au species in which subnanometer-sized clusters exhibited the best activity in the hydrogenation of CO_2 to formate, with a turnover number of up to 9278 over 7 h at 90 ℃.
文摘In this paper the tungsten-fibre-net-reinforced tungsten composites were produced by spark plasma sintering (SPS) using fine W powders and commercial tungsten fibres. The relative density of the samples is above 95%. It was found that the recrystallization area in the fibres became bigger with increasing sintering temperature and pressure. The tungsten grains of fibres kept stable when sintered at 1350℃/16 kN while grown up when sintered at 1800℃/16 kN. The composite sintered at 1350℃/16 kN have a Vickers-hardness of -610 HV, about 2 times that of the 1800℃/16 kN sintered one. Tensile tests imply that the temperature at which the composites (1350℃/16 kN) begin to exhibit plastic deformation is about 200℃-250℃, which is 400℃ lower than that of SPSed pure W. The tensile fracture surfaces show that the increasing fracture ductility comes from pull-out, interface debonding and fracture of fibres.