With oil-soluble molybdenum compound and sublimed sulfur serving as raw materials, two dispersed Mo-based catalysts were prepared, characterized and then applied to the hydrogenation conversion of phenanthrene. The te...With oil-soluble molybdenum compound and sublimed sulfur serving as raw materials, two dispersed Mo-based catalysts were prepared, characterized and then applied to the hydrogenation conversion of phenanthrene. The test results showed that under the conditions specified by this study, the catalyst prepared in a higher sulfiding atmosphere was more catalytically active due to its higher content of MoS2 and stronger intrinsic catalytic activity of MoS2 unit, which demonstrated that the sulfiding atmosphere for the preparation of catalysts not only could influence the yield of MoS2 but also the structure of MoS2.The analysis on the selectivity of octahydrophenanthrene isomers revealed that the catalyst prepared in a lower sulfiding atmosphere had a relatively higher catalytic selectivity to the hydrogenation of outer aromatic ring and the structure of catalysts could be modified under the specific reaction conditions. Moreover, the selectivity between the isomers of as-octahydrophenanthrene at different reaction time and temperature was analyzed and, based on the results, a hydrogenation mechanism over dispersed Mo-based catalysts was suggested, with monatomic hydrogen transfer and catalytic surface desorption of the half-addition intermediates functioning as the key points. In addition, it is concluded that the catalyst prepared in a lower sulfiding atmosphere was more capable of adsorption than the other one.展开更多
Low-overpotential layered hydroxides(LDHs)with high theoretical capacity are promising electrodes for supercapaterry and oxygen evolution reaction;however,the low electronic conductivity and insufficient active sites ...Low-overpotential layered hydroxides(LDHs)with high theoretical capacity are promising electrodes for supercapaterry and oxygen evolution reaction;however,the low electronic conductivity and insufficient active sites of bulk LDHs increase the internal resistance and reduce the capacity and oxygen-production efficiency of electrodes.Herein,we prepared a polyaniline-coated Ni-Co-layered double hydroxide intercalated with MoO_(4)^(2−)(M-LDH@PANI)composite electrode using a two-step method.As the amount of MoO_(4)^(2−)in the LDH increases,acicular microspheres steadily evolve into flaky microspheres with a high surface area,providing more active electrochemical sites.Moreover,the amorphous PANI coating of M-LDH boosts the electronic conductivity of the composite electrode.Accordingly,the M-LDH@PANI at an appropriate level of MoO_(4)^(2−)exhibits significantly enhanced energy storage and catalytic performance.Experimental analyses and theoretical calculations reveal that a small amount of MoO_(4)^(2−)is conducive to the expansion of LDH interlayer spacing,while an excessive amount of MoO_(4)^(2−)combines with the H atoms of LDH,thus competing with OH^(−),resulting in reduced electrochemical performance.Moreover,M-LDH flaky microspheres can efficiently modulate deprotonation energy,greatly accelerating surface redox reactions.This study provides an explanation for an unconventional mechanism,and a method for the modification of LDH-based materials for anion intercalation.展开更多
The reduction of an aqueous solution of sodium molybdate by iron powder at low pH value (～0.83), in the presence of ethylenediaminetetraacetate (EDTA) ligand, gives the title compound [Fe(H 2O) 6][Mo 2O 4(EDTA)]·...The reduction of an aqueous solution of sodium molybdate by iron powder at low pH value (～0.83), in the presence of ethylenediaminetetraacetate (EDTA) ligand, gives the title compound [Fe(H 2O) 6][Mo 2O 4(EDTA)]·5H 2O 1, which was characterized by elemental analysis, IR and X ray single crystal diffraction techniques. Compound 1 crystallizes in monoclinic system, space group P2 1/c, C 10 H 34 N 2FeMo 2O 23 , M r=798.12, a=8.781(1), b=14.081(1), c=21.353(1) , β= 92\^688(1)°, V = 2637.2(3) 3, Z = 4, D c = 2.010 g·cm -3 , μ = 1.579 mm -1 , F (000)=1608, the final R =0.0530 and wR =0.1271 for 3312 observed reflections. The binuclear oxomolybdenum(V) anion and the six coordinated Fe(II) cation are linked to infinite three dimensional network through several hydrogen bonds towards different directions between crystal waters, Fe(II) cation and Mo(V) anion.展开更多
基金the financial support from the National Basic Research Program of China (Grant 2012CB224801)
文摘With oil-soluble molybdenum compound and sublimed sulfur serving as raw materials, two dispersed Mo-based catalysts were prepared, characterized and then applied to the hydrogenation conversion of phenanthrene. The test results showed that under the conditions specified by this study, the catalyst prepared in a higher sulfiding atmosphere was more catalytically active due to its higher content of MoS2 and stronger intrinsic catalytic activity of MoS2 unit, which demonstrated that the sulfiding atmosphere for the preparation of catalysts not only could influence the yield of MoS2 but also the structure of MoS2.The analysis on the selectivity of octahydrophenanthrene isomers revealed that the catalyst prepared in a lower sulfiding atmosphere had a relatively higher catalytic selectivity to the hydrogenation of outer aromatic ring and the structure of catalysts could be modified under the specific reaction conditions. Moreover, the selectivity between the isomers of as-octahydrophenanthrene at different reaction time and temperature was analyzed and, based on the results, a hydrogenation mechanism over dispersed Mo-based catalysts was suggested, with monatomic hydrogen transfer and catalytic surface desorption of the half-addition intermediates functioning as the key points. In addition, it is concluded that the catalyst prepared in a lower sulfiding atmosphere was more capable of adsorption than the other one.
文摘Low-overpotential layered hydroxides(LDHs)with high theoretical capacity are promising electrodes for supercapaterry and oxygen evolution reaction;however,the low electronic conductivity and insufficient active sites of bulk LDHs increase the internal resistance and reduce the capacity and oxygen-production efficiency of electrodes.Herein,we prepared a polyaniline-coated Ni-Co-layered double hydroxide intercalated with MoO_(4)^(2−)(M-LDH@PANI)composite electrode using a two-step method.As the amount of MoO_(4)^(2−)in the LDH increases,acicular microspheres steadily evolve into flaky microspheres with a high surface area,providing more active electrochemical sites.Moreover,the amorphous PANI coating of M-LDH boosts the electronic conductivity of the composite electrode.Accordingly,the M-LDH@PANI at an appropriate level of MoO_(4)^(2−)exhibits significantly enhanced energy storage and catalytic performance.Experimental analyses and theoretical calculations reveal that a small amount of MoO_(4)^(2−)is conducive to the expansion of LDH interlayer spacing,while an excessive amount of MoO_(4)^(2−)combines with the H atoms of LDH,thus competing with OH^(−),resulting in reduced electrochemical performance.Moreover,M-LDH flaky microspheres can efficiently modulate deprotonation energy,greatly accelerating surface redox reactions.This study provides an explanation for an unconventional mechanism,and a method for the modification of LDH-based materials for anion intercalation.
文摘The reduction of an aqueous solution of sodium molybdate by iron powder at low pH value (～0.83), in the presence of ethylenediaminetetraacetate (EDTA) ligand, gives the title compound [Fe(H 2O) 6][Mo 2O 4(EDTA)]·5H 2O 1, which was characterized by elemental analysis, IR and X ray single crystal diffraction techniques. Compound 1 crystallizes in monoclinic system, space group P2 1/c, C 10 H 34 N 2FeMo 2O 23 , M r=798.12, a=8.781(1), b=14.081(1), c=21.353(1) , β= 92\^688(1)°, V = 2637.2(3) 3, Z = 4, D c = 2.010 g·cm -3 , μ = 1.579 mm -1 , F (000)=1608, the final R =0.0530 and wR =0.1271 for 3312 observed reflections. The binuclear oxomolybdenum(V) anion and the six coordinated Fe(II) cation are linked to infinite three dimensional network through several hydrogen bonds towards different directions between crystal waters, Fe(II) cation and Mo(V) anion.
