The molecular structures of metal precursors in the impregnating solution were designed so as to prepare efficient Ni Mo/Al_2O_3 hydrodesulfurization(HDS) catalysts. At first, five typical impregnating solutions were ...The molecular structures of metal precursors in the impregnating solution were designed so as to prepare efficient Ni Mo/Al_2O_3 hydrodesulfurization(HDS) catalysts. At first, five typical impregnating solutions were designed; the existing metal precursors, such as [Mo4(citrate)2O11]^(4-)-like, [P2Mo18O62]^(6-)-like and [P2Mo5O23]^(6-)-like species in the solutions were confirmed by laser Raman spectroscopy(LRS). The UV-Vis spectra results indicated that the solutions containing both phosphoric acid and citric acid could change the existing form of nickel species. Five corresponding Ni Mo/Al_2O_3 catalysts were prepared by the incipient wetness impregnation method. The LRS analysis results of dried catalysts showed that the above metal precursors could be partly retained on alumina support after impregnation and drying, although the interface reaction between different metal precursors and alumina support unavoidably took place. Then the catalysts were sulfided and characterized by N2 physisorption, TEM and XPS analyses. The results showed that different metal precursors in impregnating solution could mainly result in the difference in both the morphology of(Ni)Mo S2 slabs and the promoting effect of Ni species. The catalyst prepared mainly with [P2Mo5O23]^(6-)-like species used as precursors exhibited worse dispersion of(Ni)Mo S2 slabs and lower ratio of Ni–Mo–S active phases than the one with [Mo4(citrate)2O11]^(4-)-like species. Promisingly, the catalyst prepared with co-existing [Mo4(citrate)2O11]^(4-)-like, [P2Mo18O62]^(6-)-like and [P2Mo5O23]^(6-)-like species showed better hydrodesulfurization activity for 4,6-DMDBT thanks to its more well-dispersed Ni–Mo–S active phases.展开更多
Cost-efficient electrocatalysts composed of earth-abundant elements are highly desired for enhanced oxygen evolution reaction (OER).As a promising candidate,metallic Co4N already demonstrated electrocatalytic performa...Cost-efficient electrocatalysts composed of earth-abundant elements are highly desired for enhanced oxygen evolution reaction (OER).As a promising candidate,metallic Co4N already demonstrated electrocatalytic performance relying on specific nanostructures and electronic configurations.Herein,nickel was introduced as the dopant into one-dimensional (1D) hierarchical Co4N structures,achieving effective electronic regulation of Co4N toward high OER performance.The amount of Co3+increased after Ni-doping,and the in-situ formed surface oxyhydroxide during OER enhanced the electrocatalytic kinetics.Meanwhile,the 1D hierarchical structure further promoted the performances of Co4N owing to the high electrical conductivity and abundant activesites on the rough surface.As expected,the optimal Ni-doped Co4N with a Ni/Co molar ratio of 0.25 provides a small overpotential of 233 mV at a current density of 10 mA cm^(-2),with a low Tafel slope of 61 mV dec^(-1),and high long-term stability in 1.0 mol L^(-1)KOH.Following these results,the enhancement by doping the Co4N nanowire bundles with Fe and Cu was further evidenced for the OER.展开更多
In the research of bio-molecular chips and sensors, extra electric biases are most often employed to control and manipulate the DNA and protein molecules moving through micro/nano-fluidic channels. In order to accurat...In the research of bio-molecular chips and sensors, extra electric biases are most often employed to control and manipulate the DNA and protein molecules moving through micro/nano-fluidic channels. In order to accurately and flexibly control the bio-molecules as they move within the channels, a clear understanding of how the current changes within the buffer solution caused by an applied bias is fundamental. In this report, the current changed value of different buffer solutions, e.g., KC1, TE, and TBE was systematically studied with real-time monitoring and quantitative analysis in the situation of the buffers moving through a fluidic channel with a 5 μm inner diameter, driven by biases of 50 or 100 mV. The results revealed that the relation- ship between the current changed value and the pause interval of the applied electric field is highly consistent with the Hill Equation, which is helpful for accurately detecting and manipulating single biomolecules in microfluidic sensors and biochips.展开更多
基金supported by the National Key Basic Research Program of China(973 Program,2012CB224802)the SINOPEC project(No.114013)
文摘The molecular structures of metal precursors in the impregnating solution were designed so as to prepare efficient Ni Mo/Al_2O_3 hydrodesulfurization(HDS) catalysts. At first, five typical impregnating solutions were designed; the existing metal precursors, such as [Mo4(citrate)2O11]^(4-)-like, [P2Mo18O62]^(6-)-like and [P2Mo5O23]^(6-)-like species in the solutions were confirmed by laser Raman spectroscopy(LRS). The UV-Vis spectra results indicated that the solutions containing both phosphoric acid and citric acid could change the existing form of nickel species. Five corresponding Ni Mo/Al_2O_3 catalysts were prepared by the incipient wetness impregnation method. The LRS analysis results of dried catalysts showed that the above metal precursors could be partly retained on alumina support after impregnation and drying, although the interface reaction between different metal precursors and alumina support unavoidably took place. Then the catalysts were sulfided and characterized by N2 physisorption, TEM and XPS analyses. The results showed that different metal precursors in impregnating solution could mainly result in the difference in both the morphology of(Ni)Mo S2 slabs and the promoting effect of Ni species. The catalyst prepared mainly with [P2Mo5O23]^(6-)-like species used as precursors exhibited worse dispersion of(Ni)Mo S2 slabs and lower ratio of Ni–Mo–S active phases than the one with [Mo4(citrate)2O11]^(4-)-like species. Promisingly, the catalyst prepared with co-existing [Mo4(citrate)2O11]^(4-)-like, [P2Mo18O62]^(6-)-like and [P2Mo5O23]^(6-)-like species showed better hydrodesulfurization activity for 4,6-DMDBT thanks to its more well-dispersed Ni–Mo–S active phases.
基金financial support from China Postdoctoral Science Foundation (2020M673056)the National Key Research and Development Program of China (2018YFA0209402)the National Natural Science Foundation of China (21773093)。
文摘Cost-efficient electrocatalysts composed of earth-abundant elements are highly desired for enhanced oxygen evolution reaction (OER).As a promising candidate,metallic Co4N already demonstrated electrocatalytic performance relying on specific nanostructures and electronic configurations.Herein,nickel was introduced as the dopant into one-dimensional (1D) hierarchical Co4N structures,achieving effective electronic regulation of Co4N toward high OER performance.The amount of Co3+increased after Ni-doping,and the in-situ formed surface oxyhydroxide during OER enhanced the electrocatalytic kinetics.Meanwhile,the 1D hierarchical structure further promoted the performances of Co4N owing to the high electrical conductivity and abundant activesites on the rough surface.As expected,the optimal Ni-doped Co4N with a Ni/Co molar ratio of 0.25 provides a small overpotential of 233 mV at a current density of 10 mA cm^(-2),with a low Tafel slope of 61 mV dec^(-1),and high long-term stability in 1.0 mol L^(-1)KOH.Following these results,the enhancement by doping the Co4N nanowire bundles with Fe and Cu was further evidenced for the OER.
基金supported by the Major Research Plan of the National Natural Science Foundation of China(Grant No.91123030)the Interna-tional Cooperation Foundation of the National Science and Technology Major Project of the Ministry of Science and Technology of China(Grant No.2011DFA12220)the National Natural Science Foundation of China(Grant No.61378083)
文摘In the research of bio-molecular chips and sensors, extra electric biases are most often employed to control and manipulate the DNA and protein molecules moving through micro/nano-fluidic channels. In order to accurately and flexibly control the bio-molecules as they move within the channels, a clear understanding of how the current changes within the buffer solution caused by an applied bias is fundamental. In this report, the current changed value of different buffer solutions, e.g., KC1, TE, and TBE was systematically studied with real-time monitoring and quantitative analysis in the situation of the buffers moving through a fluidic channel with a 5 μm inner diameter, driven by biases of 50 or 100 mV. The results revealed that the relation- ship between the current changed value and the pause interval of the applied electric field is highly consistent with the Hill Equation, which is helpful for accurately detecting and manipulating single biomolecules in microfluidic sensors and biochips.
