Electrocatalytic N2 reduction to NH3 under ambient conditions is an eco-friendly and sustainable alternative to the traditional Haber-Bosch process. However, inhibited by the high activation barrier of N2, this proces...Electrocatalytic N2 reduction to NH3 under ambient conditions is an eco-friendly and sustainable alternative to the traditional Haber-Bosch process. However, inhibited by the high activation barrier of N2, this process needs efficient electrocatalysts to adsorb and activate the N2, enabling the N2 reduction reaction(NRR). Herein, we report that porous LaFeO3 nanofiber with oxygen vacancies acts as an efficient NRR electrocatalyst with abundant active sites to enhance the adsorption and activation of N2. When tested in 0.1 M HCl, such electrocatalyst achieves a high Faradaic efficiency of 8.77% and a large NH3 yield rate of 18.59 μg h–1 mgcat–1.at-0.55 V versus reversible hydrogen electrode. This catalyst also shows high long-term electrochemical stability and excellent selectivity for NH3 formation. Density functional theory calculations reveal that, by introducing oxygen vacancy on LaFeO3, the subsurface metallic ions are exposed with newly localized electronic states near the Fermi level, which facilitates the adsorption and activation of N2 molecules as well as the subsequent hydrogenation reactions.展开更多
Electrochemical nitrogen reduction reaction(NRR)is considered as an alternative to the industrial Haber-Bosch process for NH3 production due to both low energy consumption and environment friendliness.However,the majo...Electrochemical nitrogen reduction reaction(NRR)is considered as an alternative to the industrial Haber-Bosch process for NH3 production due to both low energy consumption and environment friendliness.However,the major problem of electrochemical NRR is the unsatisfied efficiency and selectivity of electrocatalyst.As one group of the cheapest and most abundant transition metals,iron-group(Fe,Co,Ni and Cu)electrocatalysts show promising potential on cost and performance advantages as ideal substitute for traditional noble-metal catalysts.In this minireview,we summarize recent advances of iron-group-based materials(including their oxides,hydroxides,nitrides,sulfides and phosphides,etc.)as non-noble metal electrocatalysts towards ambient N2-to-NH3 conversion in aqueous media.Strategies to boost NRR performances and perspectives for future developments are discussed to provide guidance for the field of NRR studies.展开更多
Achieving full densification of some ceramic materials,such as Y_(2)O_(3),without sintering aids by spark plasma sintering(SPS)is a great challenge when plastic deformation contributes limitedly to the densification a...Achieving full densification of some ceramic materials,such as Y_(2)O_(3),without sintering aids by spark plasma sintering(SPS)is a great challenge when plastic deformation contributes limitedly to the densification as the yield stress of the material at an elevated temperature is higher than the applied sintering pressure.Herein,we demonstrate that particle fracture and rearrangement is an effective strategy to promote the densification during the pressure-assisted sintering process.Specifically,Y_(2)O_(3) nanocrystalline powders composed of nanorod and near-spherical particles were synthesized and sintered at various temperatures by the SPS.The results show that the relative density of the ceramics prepared by the nanorod powders is higher than the density of the ceramics from the near-spherical powders after 600℃ due to the fracture and rearrangement of the nanorods at low temperatures,which leads to the decrease of particle size and the increase of density and homogeneity.Based on this novel densification mechanism,ultrafine-grained Y_(2)O_(3) transparent ceramics with good optical and mechanical properties were fabricated successfully from the nanorod powders.展开更多
基金the National Natural Science Foundation of China(Nos.21575137 and 11704005)。
文摘Electrocatalytic N2 reduction to NH3 under ambient conditions is an eco-friendly and sustainable alternative to the traditional Haber-Bosch process. However, inhibited by the high activation barrier of N2, this process needs efficient electrocatalysts to adsorb and activate the N2, enabling the N2 reduction reaction(NRR). Herein, we report that porous LaFeO3 nanofiber with oxygen vacancies acts as an efficient NRR electrocatalyst with abundant active sites to enhance the adsorption and activation of N2. When tested in 0.1 M HCl, such electrocatalyst achieves a high Faradaic efficiency of 8.77% and a large NH3 yield rate of 18.59 μg h–1 mgcat–1.at-0.55 V versus reversible hydrogen electrode. This catalyst also shows high long-term electrochemical stability and excellent selectivity for NH3 formation. Density functional theory calculations reveal that, by introducing oxygen vacancy on LaFeO3, the subsurface metallic ions are exposed with newly localized electronic states near the Fermi level, which facilitates the adsorption and activation of N2 molecules as well as the subsequent hydrogenation reactions.
文摘Electrochemical nitrogen reduction reaction(NRR)is considered as an alternative to the industrial Haber-Bosch process for NH3 production due to both low energy consumption and environment friendliness.However,the major problem of electrochemical NRR is the unsatisfied efficiency and selectivity of electrocatalyst.As one group of the cheapest and most abundant transition metals,iron-group(Fe,Co,Ni and Cu)electrocatalysts show promising potential on cost and performance advantages as ideal substitute for traditional noble-metal catalysts.In this minireview,we summarize recent advances of iron-group-based materials(including their oxides,hydroxides,nitrides,sulfides and phosphides,etc.)as non-noble metal electrocatalysts towards ambient N2-to-NH3 conversion in aqueous media.Strategies to boost NRR performances and perspectives for future developments are discussed to provide guidance for the field of NRR studies.
基金supported by the National Natural Science Foundation of China(Nos.11802042 and 51672100)the Key Research and Development Program of Sichuan Provence(No.2020YFG0192)International Cooperation Project of Guangdong Province(No.2019A050510049).
文摘Achieving full densification of some ceramic materials,such as Y_(2)O_(3),without sintering aids by spark plasma sintering(SPS)is a great challenge when plastic deformation contributes limitedly to the densification as the yield stress of the material at an elevated temperature is higher than the applied sintering pressure.Herein,we demonstrate that particle fracture and rearrangement is an effective strategy to promote the densification during the pressure-assisted sintering process.Specifically,Y_(2)O_(3) nanocrystalline powders composed of nanorod and near-spherical particles were synthesized and sintered at various temperatures by the SPS.The results show that the relative density of the ceramics prepared by the nanorod powders is higher than the density of the ceramics from the near-spherical powders after 600℃ due to the fracture and rearrangement of the nanorods at low temperatures,which leads to the decrease of particle size and the increase of density and homogeneity.Based on this novel densification mechanism,ultrafine-grained Y_(2)O_(3) transparent ceramics with good optical and mechanical properties were fabricated successfully from the nanorod powders.
