In the selective oxidation of biomass-based 1,2-propanediol(PDO)with oxygen as the terminal oxidant,it is challenging to improve the lactic acid(LA)selectivity for nonnoble metal nanoparticles(NPs)due to their limited...In the selective oxidation of biomass-based 1,2-propanediol(PDO)with oxygen as the terminal oxidant,it is challenging to improve the lactic acid(LA)selectivity for nonnoble metal nanoparticles(NPs)due to their limited oxygen reduction rate and easy C-C cleavage.Given the high economic feasibility of nonnoble metals,i.e.,Cu,in this work,copper and nitrogen codoped porous carbon nanosheets encapsulating ultrafine Cu nanoparticles(Cu@Cu-N-C)were developed to realize highly selective of PDO oxidation to LA.The carbon-encapsulated ultrasmall Cu^(0)NPs in Cu@Cu-N-C have high PDO dehydrogenation activity while N-coordinated Cu(Cu-N)sites are responsible for the high oxygen reduction efficacy.Therefore,the performance of catalytic PDO conversion to LA is optimized by a proposed pathway of PDO→hydroxylacetone→lactaldehyde→LA.Specifically,the enhanced LA selectivity is 88.5%,and the PDO conversion is up to 75.1%in an O_(2)-pressurized reaction system(1.0 MPa O_(2)),superior to other Cu-based catalysts,while in a milder nonpressurized system(O_(2)flow rate of 100 mL min-1),a remarkable LA selectivity(94.2%)is obtained with 39.8%PDO conversion,2.2 times higher than that of supported Au nanoparticles(1%Au/C).Moreover,carbon encapsulation offers Cu@Cu-N-C with strong leaching resistance for better recycling.展开更多
This study investigated the influence of graded Zn content on the evolution of precipitated and iron-rich phases and grain struc-ture of the alloys,designed and developed the Al–8.0Zn–1.5Mg–1.5Cu–0.2Fe(wt%)alloy w...This study investigated the influence of graded Zn content on the evolution of precipitated and iron-rich phases and grain struc-ture of the alloys,designed and developed the Al–8.0Zn–1.5Mg–1.5Cu–0.2Fe(wt%)alloy with high strength and formability.With the increase of Zn content,forming the coupling distribution of multiscale precipitates and iron-rich phases with a reasonable matching ratio and dispersion distribution characteristics is easy.This phenomenon induces the formation of cell-like structures with alternate distribu-tion of coarse and fine grains,and the average plasticity–strain ratio(characterizing the formability)of the pre-aged alloy with a high strength is up to 0.708.Results reveal the evolution and influence mechanisms of multiscale second-phase particles and the corresponding high formability mechanism of the alloys.The developed coupling control process exhibits considerable potential,revealing remarkable improvements in the room temperature formability of high-strength Al–Zn–Mg–Cu alloys.展开更多
基金supported by the National Natural Science Foundation of China(32371407,82160421)the Natural Science Foundation of Jiangsu Province(BK20211322)。
文摘In the selective oxidation of biomass-based 1,2-propanediol(PDO)with oxygen as the terminal oxidant,it is challenging to improve the lactic acid(LA)selectivity for nonnoble metal nanoparticles(NPs)due to their limited oxygen reduction rate and easy C-C cleavage.Given the high economic feasibility of nonnoble metals,i.e.,Cu,in this work,copper and nitrogen codoped porous carbon nanosheets encapsulating ultrafine Cu nanoparticles(Cu@Cu-N-C)were developed to realize highly selective of PDO oxidation to LA.The carbon-encapsulated ultrasmall Cu^(0)NPs in Cu@Cu-N-C have high PDO dehydrogenation activity while N-coordinated Cu(Cu-N)sites are responsible for the high oxygen reduction efficacy.Therefore,the performance of catalytic PDO conversion to LA is optimized by a proposed pathway of PDO→hydroxylacetone→lactaldehyde→LA.Specifically,the enhanced LA selectivity is 88.5%,and the PDO conversion is up to 75.1%in an O_(2)-pressurized reaction system(1.0 MPa O_(2)),superior to other Cu-based catalysts,while in a milder nonpressurized system(O_(2)flow rate of 100 mL min-1),a remarkable LA selectivity(94.2%)is obtained with 39.8%PDO conversion,2.2 times higher than that of supported Au nanoparticles(1%Au/C).Moreover,carbon encapsulation offers Cu@Cu-N-C with strong leaching resistance for better recycling.
基金financially supported by the National Key Research and Development Program of China(No.2020YFB0311201)the National Natural Science Foundation of China(No.51627802)。
基金supported by the National Key Research and Development Program of China(No.2021YFE0115900)the National Natural Science Foundation of China(Nos.52371016,51871029,and 51571023)the Opening Project of State Key Laboratory for Advanced Metals and Materials(Nos.2020-ZD02 and No.2022-Z03).
文摘This study investigated the influence of graded Zn content on the evolution of precipitated and iron-rich phases and grain struc-ture of the alloys,designed and developed the Al–8.0Zn–1.5Mg–1.5Cu–0.2Fe(wt%)alloy with high strength and formability.With the increase of Zn content,forming the coupling distribution of multiscale precipitates and iron-rich phases with a reasonable matching ratio and dispersion distribution characteristics is easy.This phenomenon induces the formation of cell-like structures with alternate distribu-tion of coarse and fine grains,and the average plasticity–strain ratio(characterizing the formability)of the pre-aged alloy with a high strength is up to 0.708.Results reveal the evolution and influence mechanisms of multiscale second-phase particles and the corresponding high formability mechanism of the alloys.The developed coupling control process exhibits considerable potential,revealing remarkable improvements in the room temperature formability of high-strength Al–Zn–Mg–Cu alloys.