According to the principles of simultaneous equilibrium and mass equilibrium, the thermodynamics model of the precipitation-coordination equilibrium of Ni2+-C2H8N2- 2-2 4C O -H2O system was established, and calculati...According to the principles of simultaneous equilibrium and mass equilibrium, the thermodynamics model of the precipitation-coordination equilibrium of Ni2+-C2H8N2- 2-2 4C O -H2O system was established, and calculation for the relationships between concentration of each substance in solution and parameters was carried out, including pH value, concentrations of ethylenediamine and oxalate by MATLAB program. The results show that Ni exists as Ni2+and [Ni(C2O4)n]2-2n mainly at pH〈1 and pH=1-6, respectively. When pH〉6, the complex between Ni2+and ethylenediamine is predominant. The precursor of Ni microfiber was prepared by an oxalate precipitation process using ethylenediamine as a coordination agent, and the role of ethylenediamine in the growth of the precursor fiber was discussed. The Ni microfiber can be obtained by a thermal decomposition-reduction process of the precursor in N2 and H2 mixed atmosphere. The diameters and aspect ratios of the obtained Ni microfibers are 0.2-1 μm and 20-30, respectively.展开更多
The preparation of Cu nanoparticles by the aqueous solution reduction method was investigated. The effects of different reaction parameters on the preparation of Cu nanoparticles were studied. The optimum conditions f...The preparation of Cu nanoparticles by the aqueous solution reduction method was investigated. The effects of different reaction parameters on the preparation of Cu nanoparticles were studied. The optimum conditions for preparing well-dispersed nanoparticles were found as follows: 0.4 mol/L NaBH4 was added into solution containing 0.2 mol/L Cu2+, 1.0% gelatin dispersant in mass fraction, and 1.2 mol/L NH3?H2O at pH 12 and 313 K. In addition, a series of experiments were performed to discover the reaction process. NH3?H2O was found to be able to modulate the reaction process. At pH=10, Cu2+ was transformed to Cu(NH3)42+ as precursor after the addition of NH3?H2O, and then Cu(NH3)42+ was reduced by NaBH4 solution. At pH=12, Cu2+ was transformed to Cu(OH)2 as precursor after the addition of NH3?H2O, and Cu(OH)2 was then reduced by NaBH4 solution.展开更多
Fe-N compounds with excellent electrocatalytic oxygen reduction activity are considered to be one of the most promising non-precious metal materials for fuel cells.Fe-N compounds with excellent electrocatalytic oxygen...Fe-N compounds with excellent electrocatalytic oxygen reduction activity are considered to be one of the most promising non-precious metal materials for fuel cells.Fe-N compounds with excellent electrocatalytic oxygen reduction activity are considered to be one of the most promising non-precious metal materials for fuel cells,which focuses on the Fe-N4 single-atom catalysts and the iron nitride materials(such as Fe2N and Fe3N).A hybridized catalyst having a hierarchical porous structure with regular macropores could enable the desired mass transfer efficiency in the catalytic process.In this study,we have constructed a new type of hybrid catalyst having iron and iron-nitrogen alloy nanoparticles(Fe-N austenite,termed as Fe-NA)embedded in the three-dimensional ordered macroporous N-doped carbon(3DOM Fe/Fe-NA@NC)by direct pyrolysis of single-source dicyandiamide-based iron metal-organic frameworks.The as-synthesized composites preserve the hierarchical porous carbon framework with ordered macropores and high specific surface area,incorporating the uniformly dispersed iron/iron-nitrogen austenite nanoparticles.Thereby,the striking architectural configuration embedded with highly active catalytic species delivers a superior oxygen reduction activity with a half-wave potential of 0.88 V and a subsequent superior Zn-air battery performance with high open-circuit voltage and continuous stability as compared to those using a commercial 20%Pt/C catalyst.展开更多
In this letter, we report a quantitative analysis of how a Pt(II) precursor is reduced to atoms at different temperatures for the formation of Pt nanocrystals with different morphologies and sizes. Our results sugge...In this letter, we report a quantitative analysis of how a Pt(II) precursor is reduced to atoms at different temperatures for the formation of Pt nanocrystals with different morphologies and sizes. Our results suggest that in the early stage of a synthesis, the Pt(II) precursor is reduced to atoms exclusively in the solution phase, followed by homogeneous nucleation to generate nuclei and then seeds. At a relatively low reaction temperature such as 22℃, the growth of the seeds is dominated by autocatalytic surface reduction that involves the adsorption and then reduction of the Pt(II) precursor on the surface of the just-formed seeds. This particular growth pathway results in relatively large assemblies of Pt nanocrystals. When the reaction temperature is increased to 100 ℃, the dominant reduction pathway will be switched from surface to solution phase, producing much smaller asselnblies of Pt nanocrystals. Our results also demonstrate that a similar trend applies to the seed-rnediated growth of Pt nanocrystals in the presence of Pd nanocubes.展开更多
Two series of Mn/beta and Mn/ZSM‐5catalysts were prepared to study the influence of how different Mn precursors,introduced to the respective parent zeolites by wet impregnation,affected the selective catalytic reduct...Two series of Mn/beta and Mn/ZSM‐5catalysts were prepared to study the influence of how different Mn precursors,introduced to the respective parent zeolites by wet impregnation,affected the selective catalytic reduction(SCR)of NO by NH3across a low reaction temperature window of50–350°C.In this study,the catalysts were characterized using N2adsorption/desorption,X‐ray diffraction,X‐ray fluorescence,H2temperature‐programmed reduction,NH3temperature‐programmed desorption and X‐ray photoelectron spectroscopy.As the manganese chloride precursor only partially decomposed this primarily resulted in the formation of MnCl2in addition to the presence of low levels of crystalline Mn3O4,which resulted in poor catalytic performance.However,the manganese nitrate precursor formed crystalline MnO2as the major phase in addition to a minor presence of unconverted Mn‐nitrate.Furthermore,manganese acetate resulted principally in a mixture of amorphous Mn2O3and MnO2,and crystalline Mn3O4.From all the catalysts screened,the test performance data showed Mn/beta‐Ac to exhibit the highest NO conversion(97.5%)at240°C,which remained>90%across a temperature window of220–350°C.The excellent catalytic performance was ascribed to the enrichment of highly dispersed MnOx(Mn2O3and MnO2)species that act as the active phase in the NH3‐SCR process.Furthermore,together with a suitable amount of weakly acidic centers,higher concentration of surface manganese and a greater presence of surface labile oxygen groups,SCR performance was collectively enhanced at low temperature.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.展开更多
Cu nanoparticles were prepared by reducing Cu2+ ions with NaBH4 in alkaline solution. The effects of NaBH4 concentration and dripping rate on the formation of Cu nanoparticles were studied. The optimum conditions are...Cu nanoparticles were prepared by reducing Cu2+ ions with NaBH4 in alkaline solution. The effects of NaBH4 concentration and dripping rate on the formation of Cu nanoparticles were studied. The optimum conditions are found to be 0.2 mol/L Cu2+, solution with pH=12, temperature of 313 K and 1% gelatin as dispersant, to which 0.4 mol/L NaBH4 is added at a dripping rate of 50 mL/min. NH3-H2O is found to be the optimal complexant to form the Cu precursor. A series experiments were conducted to study the reaction process at different time points.展开更多
Aniline,pyrrole and phenanthroline,which have different nitrogen compositions,are used as carbon precursors to synthesize nitrogen-doped ordered mesoporous carbons(NOMCs) by the nanocasting method.The effect of the ...Aniline,pyrrole and phenanthroline,which have different nitrogen compositions,are used as carbon precursors to synthesize nitrogen-doped ordered mesoporous carbons(NOMCs) by the nanocasting method.The effect of the precursor on the resultant NOMC is extensively investigated by nitrogen adsorption-desorption measurements,scanning electron microscopy,X-ray photoelectron spectroscopy(XPS),cyclic voltammetry and rotating ring-disk electrode measurements.Salient findings are as follows.First,the precursor has a significant influence on the specific surface area and textural properties.The NOMC materials derived from pyrrole(C-PY-900:765 m^2/) and phenanthroline(C-Phen-900:746 m^2/) exhibit higher specific surface areas than the aniline analog(C-PA-900:569 m^2/).Second,the XPS results indicate that the total nitrogen content(ca.3.1–3.3 at%) is similar for the three carbon sources,except for a slight difference in the nitrogen configuration.Furthermore,the content of the nitrogen-activated carbon atoms is found to closely depend on the precursor,which is the highest for the phenanthroline-derived carbon.Third,the electrochemical results reveal that the electrocatalytic activity follows in the order C-PA-900 C-PY-900 C-Phen-900,confirming that the nitrogen-activated carbon atoms are the active sites for the oxygen reduction reaction(ORR).In summary,the precursor has considerable influence on the composition and textural properties of the NOMC materials,of which the ORR electrocatalytic activity can be enhanced through optimization of the NOMCs.展开更多
基金Project(CX2012B046)supported by Hunan Provincial Innovation Foundation for Postgraduate,ChinaProject(20090162120080)supported by the Doctorate Fund of Education Minister of China
文摘According to the principles of simultaneous equilibrium and mass equilibrium, the thermodynamics model of the precipitation-coordination equilibrium of Ni2+-C2H8N2- 2-2 4C O -H2O system was established, and calculation for the relationships between concentration of each substance in solution and parameters was carried out, including pH value, concentrations of ethylenediamine and oxalate by MATLAB program. The results show that Ni exists as Ni2+and [Ni(C2O4)n]2-2n mainly at pH〈1 and pH=1-6, respectively. When pH〉6, the complex between Ni2+and ethylenediamine is predominant. The precursor of Ni microfiber was prepared by an oxalate precipitation process using ethylenediamine as a coordination agent, and the role of ethylenediamine in the growth of the precursor fiber was discussed. The Ni microfiber can be obtained by a thermal decomposition-reduction process of the precursor in N2 and H2 mixed atmosphere. The diameters and aspect ratios of the obtained Ni microfibers are 0.2-1 μm and 20-30, respectively.
文摘The preparation of Cu nanoparticles by the aqueous solution reduction method was investigated. The effects of different reaction parameters on the preparation of Cu nanoparticles were studied. The optimum conditions for preparing well-dispersed nanoparticles were found as follows: 0.4 mol/L NaBH4 was added into solution containing 0.2 mol/L Cu2+, 1.0% gelatin dispersant in mass fraction, and 1.2 mol/L NH3?H2O at pH 12 and 313 K. In addition, a series of experiments were performed to discover the reaction process. NH3?H2O was found to be able to modulate the reaction process. At pH=10, Cu2+ was transformed to Cu(NH3)42+ as precursor after the addition of NH3?H2O, and then Cu(NH3)42+ was reduced by NaBH4 solution. At pH=12, Cu2+ was transformed to Cu(OH)2 as precursor after the addition of NH3?H2O, and Cu(OH)2 was then reduced by NaBH4 solution.
文摘Fe-N compounds with excellent electrocatalytic oxygen reduction activity are considered to be one of the most promising non-precious metal materials for fuel cells.Fe-N compounds with excellent electrocatalytic oxygen reduction activity are considered to be one of the most promising non-precious metal materials for fuel cells,which focuses on the Fe-N4 single-atom catalysts and the iron nitride materials(such as Fe2N and Fe3N).A hybridized catalyst having a hierarchical porous structure with regular macropores could enable the desired mass transfer efficiency in the catalytic process.In this study,we have constructed a new type of hybrid catalyst having iron and iron-nitrogen alloy nanoparticles(Fe-N austenite,termed as Fe-NA)embedded in the three-dimensional ordered macroporous N-doped carbon(3DOM Fe/Fe-NA@NC)by direct pyrolysis of single-source dicyandiamide-based iron metal-organic frameworks.The as-synthesized composites preserve the hierarchical porous carbon framework with ordered macropores and high specific surface area,incorporating the uniformly dispersed iron/iron-nitrogen austenite nanoparticles.Thereby,the striking architectural configuration embedded with highly active catalytic species delivers a superior oxygen reduction activity with a half-wave potential of 0.88 V and a subsequent superior Zn-air battery performance with high open-circuit voltage and continuous stability as compared to those using a commercial 20%Pt/C catalyst.
基金supported in part by a grant from National Science Foundation of the United States(DMR-1505441)startup funds from the Georgia Institute of Technology
文摘In this letter, we report a quantitative analysis of how a Pt(II) precursor is reduced to atoms at different temperatures for the formation of Pt nanocrystals with different morphologies and sizes. Our results suggest that in the early stage of a synthesis, the Pt(II) precursor is reduced to atoms exclusively in the solution phase, followed by homogeneous nucleation to generate nuclei and then seeds. At a relatively low reaction temperature such as 22℃, the growth of the seeds is dominated by autocatalytic surface reduction that involves the adsorption and then reduction of the Pt(II) precursor on the surface of the just-formed seeds. This particular growth pathway results in relatively large assemblies of Pt nanocrystals. When the reaction temperature is increased to 100 ℃, the dominant reduction pathway will be switched from surface to solution phase, producing much smaller asselnblies of Pt nanocrystals. Our results also demonstrate that a similar trend applies to the seed-rnediated growth of Pt nanocrystals in the presence of Pd nanocubes.
基金supported by the National Science and Technology Program of China(CDGC01-KT16)~~
文摘Two series of Mn/beta and Mn/ZSM‐5catalysts were prepared to study the influence of how different Mn precursors,introduced to the respective parent zeolites by wet impregnation,affected the selective catalytic reduction(SCR)of NO by NH3across a low reaction temperature window of50–350°C.In this study,the catalysts were characterized using N2adsorption/desorption,X‐ray diffraction,X‐ray fluorescence,H2temperature‐programmed reduction,NH3temperature‐programmed desorption and X‐ray photoelectron spectroscopy.As the manganese chloride precursor only partially decomposed this primarily resulted in the formation of MnCl2in addition to the presence of low levels of crystalline Mn3O4,which resulted in poor catalytic performance.However,the manganese nitrate precursor formed crystalline MnO2as the major phase in addition to a minor presence of unconverted Mn‐nitrate.Furthermore,manganese acetate resulted principally in a mixture of amorphous Mn2O3and MnO2,and crystalline Mn3O4.From all the catalysts screened,the test performance data showed Mn/beta‐Ac to exhibit the highest NO conversion(97.5%)at240°C,which remained>90%across a temperature window of220–350°C.The excellent catalytic performance was ascribed to the enrichment of highly dispersed MnOx(Mn2O3and MnO2)species that act as the active phase in the NH3‐SCR process.Furthermore,together with a suitable amount of weakly acidic centers,higher concentration of surface manganese and a greater presence of surface labile oxygen groups,SCR performance was collectively enhanced at low temperature.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.
文摘Cu nanoparticles were prepared by reducing Cu2+ ions with NaBH4 in alkaline solution. The effects of NaBH4 concentration and dripping rate on the formation of Cu nanoparticles were studied. The optimum conditions are found to be 0.2 mol/L Cu2+, solution with pH=12, temperature of 313 K and 1% gelatin as dispersant, to which 0.4 mol/L NaBH4 is added at a dripping rate of 50 mL/min. NH3-H2O is found to be the optimal complexant to form the Cu precursor. A series experiments were conducted to study the reaction process at different time points.
基金supported by the National Natural Science Foundation of China(21476087,21576101)the Innovation Project of Guangdong Department of Education(2014KTSCX016)+1 种基金the Science&Technology Research Project of Guangdong Province(2013B010405005,2014A010105041)the Fundamental Research Funds for the Central Universities~~
文摘Aniline,pyrrole and phenanthroline,which have different nitrogen compositions,are used as carbon precursors to synthesize nitrogen-doped ordered mesoporous carbons(NOMCs) by the nanocasting method.The effect of the precursor on the resultant NOMC is extensively investigated by nitrogen adsorption-desorption measurements,scanning electron microscopy,X-ray photoelectron spectroscopy(XPS),cyclic voltammetry and rotating ring-disk electrode measurements.Salient findings are as follows.First,the precursor has a significant influence on the specific surface area and textural properties.The NOMC materials derived from pyrrole(C-PY-900:765 m^2/) and phenanthroline(C-Phen-900:746 m^2/) exhibit higher specific surface areas than the aniline analog(C-PA-900:569 m^2/).Second,the XPS results indicate that the total nitrogen content(ca.3.1–3.3 at%) is similar for the three carbon sources,except for a slight difference in the nitrogen configuration.Furthermore,the content of the nitrogen-activated carbon atoms is found to closely depend on the precursor,which is the highest for the phenanthroline-derived carbon.Third,the electrochemical results reveal that the electrocatalytic activity follows in the order C-PA-900 C-PY-900 C-Phen-900,confirming that the nitrogen-activated carbon atoms are the active sites for the oxygen reduction reaction(ORR).In summary,the precursor has considerable influence on the composition and textural properties of the NOMC materials,of which the ORR electrocatalytic activity can be enhanced through optimization of the NOMCs.