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
We herein report two crystals based on 2-（imidazo[1,2-a]pyridin-2-yl）-2-oxoacetic acid rad- ical and its perchlorate, and investigate the relationship between magnetic properties and crystal stacking structures or s...We herein report two crystals based on 2-（imidazo[1,2-a]pyridin-2-yl）-2-oxoacetic acid rad- ical and its perchlorate, and investigate the relationship between magnetic properties and crystal stacking structures or supramolecular interactions. 2-（imidazo[1,2-a]pyridin-2-yl）- 2-oxoaeetic acid radical in two crystals mainly exist as diamagnetic dimer formed via short atomic contacts or supramolecular interactions （hydrogen bonds, anion-Tr or lone- pair-~r interactions）, leading to low magnetic susceptibilities. 2-（imidazo[1,2-a]pyridin-2-yl）- 2-oxoaeetic acid radical crystal exhibits quasi-one-dimensional columnar stacking chain and weak antiferromagnetism. However, its perchlorate crystal possesses one-dimensional double- stranded chain structure assembled through double hydrogen bonds and anion-To interactions, and reveals weak ferromagnetism.展开更多
Bimetallic CuPdx nanoparticles synthesized by the wet chemical reduction method were used as the catalysts in the catalytic oxidation of 1,2-propanediol with gaseous oxygen to aliphatic acids.The palladium and copper ...Bimetallic CuPdx nanoparticles synthesized by the wet chemical reduction method were used as the catalysts in the catalytic oxidation of 1,2-propanediol with gaseous oxygen to aliphatic acids.The palladium and copper nanoparticles in the bimetallic CuP dxnanoparticles had an alloying trend.The catalytic activity of the palladium nanoparticles in the bimetallic CuP dxnanoparticles was enhanced by the interaction between the palladium and copper nanoparticles.When the bimetallic CuPd7 nanoparticles catalyzed the oxidation of 1,2-propanediol in an alkaline aqueous solution at 100℃for 3h,lactic,formic,and acetic acids were dominantly produced with the total selectivity of above 99%at the 1,2-propanediol conversion of 85.9%.The simulation of the reaction kinetic equation on the CuPd7 catalyst showed that the reaction activation energy was 29.4kJ·mol^-1,indicating that the bimetallic CuPd7 nanoparticles had a high catalytic activity in the oxidation reaction between 1,2-propanediol and gaseous oxygen.展开更多
Result of ab initio SCF calculation of 1,2-dithiosquaric acid (3,4-dihydroxy-3-cyclobutene-1,2-dithione) are reported. The ZZ isomer is found to be the most stable of the three isomers. An isodesmic energy analysis ha...Result of ab initio SCF calculation of 1,2-dithiosquaric acid (3,4-dihydroxy-3-cyclobutene-1,2-dithione) are reported. The ZZ isomer is found to be the most stable of the three isomers. An isodesmic energy analysis has been carried out at the HF 6-31G*//6-31G* level for the three planar isomers. The three isomers have positive isodesmic energies or small negative ones, suggesting that 1,2-dithiosquaric acid is not aromatic. Vibrational frequencies have also been calculated for the three isomers.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This work was supported by the National Natural Science Foundation of China （No.21172210）.
文摘We herein report two crystals based on 2-（imidazo[1,2-a]pyridin-2-yl）-2-oxoacetic acid rad- ical and its perchlorate, and investigate the relationship between magnetic properties and crystal stacking structures or supramolecular interactions. 2-（imidazo[1,2-a]pyridin-2-yl）- 2-oxoaeetic acid radical in two crystals mainly exist as diamagnetic dimer formed via short atomic contacts or supramolecular interactions （hydrogen bonds, anion-Tr or lone- pair-~r interactions）, leading to low magnetic susceptibilities. 2-（imidazo[1,2-a]pyridin-2-yl）- 2-oxoaeetic acid radical crystal exhibits quasi-one-dimensional columnar stacking chain and weak antiferromagnetism. However, its perchlorate crystal possesses one-dimensional double- stranded chain structure assembled through double hydrogen bonds and anion-To interactions, and reveals weak ferromagnetism.
基金financially supported by the Funding of Jiangsu Science and Technology Department,China(FZ20180919)。
文摘Bimetallic CuPdx nanoparticles synthesized by the wet chemical reduction method were used as the catalysts in the catalytic oxidation of 1,2-propanediol with gaseous oxygen to aliphatic acids.The palladium and copper nanoparticles in the bimetallic CuP dxnanoparticles had an alloying trend.The catalytic activity of the palladium nanoparticles in the bimetallic CuP dxnanoparticles was enhanced by the interaction between the palladium and copper nanoparticles.When the bimetallic CuPd7 nanoparticles catalyzed the oxidation of 1,2-propanediol in an alkaline aqueous solution at 100℃for 3h,lactic,formic,and acetic acids were dominantly produced with the total selectivity of above 99%at the 1,2-propanediol conversion of 85.9%.The simulation of the reaction kinetic equation on the CuPd7 catalyst showed that the reaction activation energy was 29.4kJ·mol^-1,indicating that the bimetallic CuPd7 nanoparticles had a high catalytic activity in the oxidation reaction between 1,2-propanediol and gaseous oxygen.
文摘Result of ab initio SCF calculation of 1,2-dithiosquaric acid (3,4-dihydroxy-3-cyclobutene-1,2-dithione) are reported. The ZZ isomer is found to be the most stable of the three isomers. An isodesmic energy analysis has been carried out at the HF 6-31G*//6-31G* level for the three planar isomers. The three isomers have positive isodesmic energies or small negative ones, suggesting that 1,2-dithiosquaric acid is not aromatic. Vibrational frequencies have also been calculated for the three isomers.
