Efficient conversion of lignin to aromatic hydrocarbons via depolymerization and subsequent hydrodeoxygenation is important.Previously,we found that NbOx species played a key role in the activation and cleavage of C-O...Efficient conversion of lignin to aromatic hydrocarbons via depolymerization and subsequent hydrodeoxygenation is important.Previously,we found that NbOx species played a key role in the activation and cleavage of C-O bonds in lignin and its model compounds.In this study,commercial niobic acid(HY-340),niobium phosphate(NbPO-CBMM)and lab-made layered niobium oxide(Nb2O5-Layer)were chosen as supports to study the effect of Brosted and Lewis acids on the activation of C-O bonds in lignin conversion.A variety of Ru-loaded,Nb-based catalysts with different Ru particle sizes were prepared and applied to the conversion of p-cresol.The results show that all the Ru/Nb-based catalysts produce high mole yields of C7-C9 hydrocarbons(82.3%-9.1%).What's more,Ru/Nb2O5-Layer affords the best mole yield of C7-C9 hydrocarbons and selectivity for C7-C9 aromatic hydrocarbons,of up to 99.1% and 88.0%,respectively.Moreover,it was found that Lewis acid sites play important roles in the depolymerization of enzymatic lignin into phenolic monomers and the cleavage of the C-O bond of phenols.Additionally,the electronic state and particle size of Ru are significant factors which influence the selectivity for aromatic hydrocarbons.A partial positive charge on the metallic Ru surface and a smaller Ru particle size are beneficial in improving the selectivity for aromatic hydrocarbons.展开更多
A series of(Ce,Cr)xO2/Nb2O5 catalysts with different(Ce,Cr)xO2 to Nb2O5 mass ratios were synthesized by the deposition-precipitation method for use in deep catalytic oxidation of 1,2-dichloroethane(DCE), which is one ...A series of(Ce,Cr)xO2/Nb2O5 catalysts with different(Ce,Cr)xO2 to Nb2O5 mass ratios were synthesized by the deposition-precipitation method for use in deep catalytic oxidation of 1,2-dichloroethane(DCE), which is one of the typical chlorinated volatile organic compound pollutants. The textural properties were characterized by X-ray diffraction, N2 adsorption/desorption isotherms, UV-Raman spectroscopy, and scanning electron microscopy. The surface acidity and the redox properties were characterized by ammonia temperature-programmed desorption and H2 temperature-programmed reduction, respectively. The results show that the addition of a proper amount of(Ce,Cr)xO2 over Nb2O5 significantly improves the intrinsic catalytic activity towards the deep oxidation of DCE, and only a very small amount of C2H3Cl is detected as the byproduct of the oxidation process. Further study reveals the existence of an obvious synergistic effect between Nb2O5, with abundant strong acid sites, and(Ce,Cr)xO2, with strong oxidation sites, as the strong acid sites of Nb2O5 promote the adsorption and dehydrochlorination of DCE, while the strong oxidation sites of(Ce,Cr)xO2 contribute to the deep oxidation of the reactant, intermediates, and byproducts.展开更多
NbC-Sn composite powder was successfully prepared from SnO2,Nb2O5and carbon by electrochemical reduction andcarbonization in CaCl2-NaCl molten salt at900°C.The reaction pathway was investigated by terminating ele...NbC-Sn composite powder was successfully prepared from SnO2,Nb2O5and carbon by electrochemical reduction andcarbonization in CaCl2-NaCl molten salt at900°C.The reaction pathway was investigated by terminating electrochemicalexperiments for various durations.The influence of carbon on the final products was considered.NbC particles were obtained byleaching the composite with acid.The results showed that the aggregated NbC-Sn composite powdev contained NbC particles about50-100nm and Sn particles about200nm.SnO2was reduced to Sn in the sintering process.Nb2O5was electrochemically reduced toNb in molten salt,experiencing some intermediate products of calcium niobates and niobium suboxides.Nb metal obtained wasconverted to NbC with assistance of carbon.The reduction of Nb oxides may be incomplete and Nb3Sn would be formed if carbon isinsufficient in the cathodic pellet.NbC with good dispersity is produced by leaching NbC-Sn with HCl.展开更多
A low-toxicity and environment-friendly NaCl−KCl−CsCl−K_(2)NbF_(7) system was used to prepare Nb coatings on Mo substrates.The effects of temperature,current density and electrodeposition time on the micromorphologies...A low-toxicity and environment-friendly NaCl−KCl−CsCl−K_(2)NbF_(7) system was used to prepare Nb coatings on Mo substrates.The effects of temperature,current density and electrodeposition time on the micromorphologies and textures of the electrodeposited Nb coatings were studied.The results showed that Nb coatings obtained at 30−70 mA/cm^(2) in the temperature range of 700−750℃ were continuous and compact,with a hardness range of 2.16−2.45 GPa.As the columnar crystals grew with time,the preferential growth orientations of the Nb coatings changed from<200>to<211>and then became disordered.With increasing polarization,the morphologies of the Nb coatings changed from hexagonal star-like surface to conical or pyramid-like surface.展开更多
By taking tetragonal tungsten bronze(TTB)phase Nb_(18)W_(16)O_(93)as an example,an improved solid-state sintering method at lower temperature of 1000℃for 36 h was proposed via applying nanoscale raw materials.XRD,SEM...By taking tetragonal tungsten bronze(TTB)phase Nb_(18)W_(16)O_(93)as an example,an improved solid-state sintering method at lower temperature of 1000℃for 36 h was proposed via applying nanoscale raw materials.XRD,SEM and XPS confirm that the expected sample was produced.GITT results show that the lithium-ion diffusion coefficient of Nb_(18)W_(16)O_(93)(10−12 cm^(2)/s)is higher than that of the conventional titanium-based anode,ensuring a relatively superior electrochemical performance.The lithium-ion diffusion mechanism was thoroughly revealed by using density functional theory simulation.There are three diffusion paths in TTB phase,among which the interlayer diffusion with the smallest diffusion barrier(0.46 eV)has more advantages than other typical anodes(such as graphite,0.56 eV).The relatively smaller lithium-ion diffusion barrier makes TTB phase Nb_(18)W_(16)O_(93)become a potential highspecific-power anode material.展开更多
Aldol condensation is of significant importance for the production of fuel precursors from biomass- derived chemicals and has received increasing attention. Here we report a Nb2O5 catalyst with excellent activity and ...Aldol condensation is of significant importance for the production of fuel precursors from biomass- derived chemicals and has received increasing attention. Here we report a Nb2O5 catalyst with excellent activity and stability in the aldol condensation of biomass-derived carbonyl molecules. It is found that in the aldol condensation of furfural with 4-heptanone, Nb2O5 has obviously superior activity, which is not only better than that of other common solid acid catalysts (ZrO2 and Al2O3), more importantly, but also better than that of solid base catalysts (MgO, CaO, and magnesium- aluminum hydrotalcite). The detailed characterizations by N2 sorption/desorption, NH3-TPD, Py-FTIR and DRIFTS study of acetone adsorption reveal that Nb2O5 has a strong ability to activate the C=O bond in carbonyl molecules, which helps to generate a metal enolate intermediate and undergo the nucleophilic addition to form a new C–C bond. Furthermore, the applicability of Nb2O5 to aldol condensation is extended to other biomass-derived carbonyl molecules and high yields of target fuel precursors are obtained. Finally, a multifunctional Pd/Nb2O5 catalyst is prepared and successfully used in the one-pot synthesis of liquid alkanes from biomass-derived carbonyl molecules by combining the aldol condensation with the sequential hydrodeoxygenation.展开更多
基金supported by the National Natural Science Foundation of China(21832002,21872050,21808063)the Natural Science Foundation of Shanghai(18ZR1408500)~~
文摘Efficient conversion of lignin to aromatic hydrocarbons via depolymerization and subsequent hydrodeoxygenation is important.Previously,we found that NbOx species played a key role in the activation and cleavage of C-O bonds in lignin and its model compounds.In this study,commercial niobic acid(HY-340),niobium phosphate(NbPO-CBMM)and lab-made layered niobium oxide(Nb2O5-Layer)were chosen as supports to study the effect of Brosted and Lewis acids on the activation of C-O bonds in lignin conversion.A variety of Ru-loaded,Nb-based catalysts with different Ru particle sizes were prepared and applied to the conversion of p-cresol.The results show that all the Ru/Nb-based catalysts produce high mole yields of C7-C9 hydrocarbons(82.3%-9.1%).What's more,Ru/Nb2O5-Layer affords the best mole yield of C7-C9 hydrocarbons and selectivity for C7-C9 aromatic hydrocarbons,of up to 99.1% and 88.0%,respectively.Moreover,it was found that Lewis acid sites play important roles in the depolymerization of enzymatic lignin into phenolic monomers and the cleavage of the C-O bond of phenols.Additionally,the electronic state and particle size of Ru are significant factors which influence the selectivity for aromatic hydrocarbons.A partial positive charge on the metallic Ru surface and a smaller Ru particle size are beneficial in improving the selectivity for aromatic hydrocarbons.
基金supported by the National Key R&D Program of China(2016YFC0204300)the National Natural Science Foundation of China(21477109)~~
文摘A series of(Ce,Cr)xO2/Nb2O5 catalysts with different(Ce,Cr)xO2 to Nb2O5 mass ratios were synthesized by the deposition-precipitation method for use in deep catalytic oxidation of 1,2-dichloroethane(DCE), which is one of the typical chlorinated volatile organic compound pollutants. The textural properties were characterized by X-ray diffraction, N2 adsorption/desorption isotherms, UV-Raman spectroscopy, and scanning electron microscopy. The surface acidity and the redox properties were characterized by ammonia temperature-programmed desorption and H2 temperature-programmed reduction, respectively. The results show that the addition of a proper amount of(Ce,Cr)xO2 over Nb2O5 significantly improves the intrinsic catalytic activity towards the deep oxidation of DCE, and only a very small amount of C2H3Cl is detected as the byproduct of the oxidation process. Further study reveals the existence of an obvious synergistic effect between Nb2O5, with abundant strong acid sites, and(Ce,Cr)xO2, with strong oxidation sites, as the strong acid sites of Nb2O5 promote the adsorption and dehydrochlorination of DCE, while the strong oxidation sites of(Ce,Cr)xO2 contribute to the deep oxidation of the reactant, intermediates, and byproducts.
基金Projects(51404057,50874026)supported by the National Natural Science Foundation of ChinaProject(N150204014)supported by Fundamental Research Funds for the Central Universities,China
文摘NbC-Sn composite powder was successfully prepared from SnO2,Nb2O5and carbon by electrochemical reduction andcarbonization in CaCl2-NaCl molten salt at900°C.The reaction pathway was investigated by terminating electrochemicalexperiments for various durations.The influence of carbon on the final products was considered.NbC particles were obtained byleaching the composite with acid.The results showed that the aggregated NbC-Sn composite powdev contained NbC particles about50-100nm and Sn particles about200nm.SnO2was reduced to Sn in the sintering process.Nb2O5was electrochemically reduced toNb in molten salt,experiencing some intermediate products of calcium niobates and niobium suboxides.Nb metal obtained wasconverted to NbC with assistance of carbon.The reduction of Nb oxides may be incomplete and Nb3Sn would be formed if carbon isinsufficient in the cathodic pellet.NbC with good dispersity is produced by leaching NbC-Sn with HCl.
基金the Special Fund of Hunan Province for Innovative Province Building-Support Program for Young Talents of Hunan,China(No.2020RC3034).
文摘A low-toxicity and environment-friendly NaCl−KCl−CsCl−K_(2)NbF_(7) system was used to prepare Nb coatings on Mo substrates.The effects of temperature,current density and electrodeposition time on the micromorphologies and textures of the electrodeposited Nb coatings were studied.The results showed that Nb coatings obtained at 30−70 mA/cm^(2) in the temperature range of 700−750℃ were continuous and compact,with a hardness range of 2.16−2.45 GPa.As the columnar crystals grew with time,the preferential growth orientations of the Nb coatings changed from<200>to<211>and then became disordered.With increasing polarization,the morphologies of the Nb coatings changed from hexagonal star-like surface to conical or pyramid-like surface.
基金the Key R&D Program of Shaanxi Province,China(No.2019ZDLGY04-05)the Natural Science Foundation of Shaanxi Province,China(No.2019JLZ-01)+1 种基金the Fundamental Research Funds for the Central Universities of China(Nos.19GH020302,3102019JC005,3102021ZD0401,3102021TS0406)the Science,Technology,and Innovation Commission of Shenzhen Municipality,China(No.JCYJ20180508151856806).
文摘By taking tetragonal tungsten bronze(TTB)phase Nb_(18)W_(16)O_(93)as an example,an improved solid-state sintering method at lower temperature of 1000℃for 36 h was proposed via applying nanoscale raw materials.XRD,SEM and XPS confirm that the expected sample was produced.GITT results show that the lithium-ion diffusion coefficient of Nb_(18)W_(16)O_(93)(10−12 cm^(2)/s)is higher than that of the conventional titanium-based anode,ensuring a relatively superior electrochemical performance.The lithium-ion diffusion mechanism was thoroughly revealed by using density functional theory simulation.There are three diffusion paths in TTB phase,among which the interlayer diffusion with the smallest diffusion barrier(0.46 eV)has more advantages than other typical anodes(such as graphite,0.56 eV).The relatively smaller lithium-ion diffusion barrier makes TTB phase Nb_(18)W_(16)O_(93)become a potential highspecific-power anode material.
基金financially supported by the National Natural Science Foundation of China(No.21832002,21872050,and 21808063)the Fundamental Research Funds for the Central Universities(222201718003)+1 种基金the Science and Technology Commission of Shanghai Municipality(18ZR1408500,10dz2220500)the “Zhang Jiangshu” Excellent Ph.D.Project of ECUST~~
文摘Aldol condensation is of significant importance for the production of fuel precursors from biomass- derived chemicals and has received increasing attention. Here we report a Nb2O5 catalyst with excellent activity and stability in the aldol condensation of biomass-derived carbonyl molecules. It is found that in the aldol condensation of furfural with 4-heptanone, Nb2O5 has obviously superior activity, which is not only better than that of other common solid acid catalysts (ZrO2 and Al2O3), more importantly, but also better than that of solid base catalysts (MgO, CaO, and magnesium- aluminum hydrotalcite). The detailed characterizations by N2 sorption/desorption, NH3-TPD, Py-FTIR and DRIFTS study of acetone adsorption reveal that Nb2O5 has a strong ability to activate the C=O bond in carbonyl molecules, which helps to generate a metal enolate intermediate and undergo the nucleophilic addition to form a new C–C bond. Furthermore, the applicability of Nb2O5 to aldol condensation is extended to other biomass-derived carbonyl molecules and high yields of target fuel precursors are obtained. Finally, a multifunctional Pd/Nb2O5 catalyst is prepared and successfully used in the one-pot synthesis of liquid alkanes from biomass-derived carbonyl molecules by combining the aldol condensation with the sequential hydrodeoxygenation.
