Selective conversion of fructose to 1,2-propanediol(1,2-PDO)is considered as a sustainable and cost-effective alternative to petroleum-based processes,however,this approach still faces challenges associated with low e...Selective conversion of fructose to 1,2-propanediol(1,2-PDO)is considered as a sustainable and cost-effective alternative to petroleum-based processes,however,this approach still faces challenges associated with low efficiency and harsh reaction conditions.Here,we have successfully synthesized a novel bifunctional Ru-WO_(x)-MgO_(y) catalyst through a facile'one-pot'solvothermal method.Remarkably,this catalyst exhibits exceptional catalytic performances in the conversion of fructose to 1,2-PDO under mild reaction conditions.The yield of 1,2-PDO is up to 56.2%at 140°C for 4 h under an ultra-low hydrogen pressure of only 0.2 MPa,surpassing the reported results in recent literature(below 51%).Comprehensive characterizations and density functional theory(DFT)calculations reveal that the presence of oxygen vacancies in the Ru-WO_(x)-MgO_(y) catalyst,serving as active acidic sites,facilitates the chemoselective cleavage of C-C bonds in fructose,which leads to the generation of active intermediates and ultimately resulted in the high yield of 1,2-PDO.展开更多
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
基金the financial support from the Natural Science Foundation of Chongqing(CSTB2022NSCQ-MSX0458)the State Key Laboratory of Coal Mine Disaster Dynamics and Control(2011DA105287-MS202203)+4 种基金the Joint Fund for Innovation and Development of Chongqing(CSTB2022NSCQ-LZX0030)the financial support from the National Natural Science Foundation of China(22168027 and 22308169)the financial support from the Natural Science Foundation of Chongqing(cstc2021jcyj-msxmX0741)the financial support from the National Natural Science Foundation of China(22105028)the Natural Science Foundation of Chongqing(cstc2021jcyj-msxmX0572)。
文摘Selective conversion of fructose to 1,2-propanediol(1,2-PDO)is considered as a sustainable and cost-effective alternative to petroleum-based processes,however,this approach still faces challenges associated with low efficiency and harsh reaction conditions.Here,we have successfully synthesized a novel bifunctional Ru-WO_(x)-MgO_(y) catalyst through a facile'one-pot'solvothermal method.Remarkably,this catalyst exhibits exceptional catalytic performances in the conversion of fructose to 1,2-PDO under mild reaction conditions.The yield of 1,2-PDO is up to 56.2%at 140°C for 4 h under an ultra-low hydrogen pressure of only 0.2 MPa,surpassing the reported results in recent literature(below 51%).Comprehensive characterizations and density functional theory(DFT)calculations reveal that the presence of oxygen vacancies in the Ru-WO_(x)-MgO_(y) catalyst,serving as active acidic sites,facilitates the chemoselective cleavage of C-C bonds in fructose,which leads to the generation of active intermediates and ultimately resulted in the high yield of 1,2-PDO.
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.
