Amide is essential in biologically active compounds,synthetic materials,and building blocks.However,conventional amide production relies on energyintensive consumption and activating agents that modulate processes to ...Amide is essential in biologically active compounds,synthetic materials,and building blocks.However,conventional amide production relies on energyintensive consumption and activating agents that modulate processes to construct the C–N bond.Herein,for the first time,we have successfully realized the formation of amides at industrial current density via the anodic coelectrolysis of alcohol and ammonia under ambient conditions.We have proved thatmodulation of the interface microenvironment concentration of nucleophile by electrolyte engineering can regulate the reaction pathways of amides rather than acetic acids.The C-N coupling strategy can be further extended to the electrosynthesis of the long-chain and aryl-ring amide with high selectivity by replacing ammonia with amine.Our work opens up a vast store of information on the utilization of biomass alcohol for high-value N-containing chemicals via an electrocatalytic C-N coupling reaction.展开更多
Electrochemical hydrogenation(ECH)of furfural,which uses the proton from water and avoids the usage of gaseous hydrogen and high pressure,is an efficient way to utilize biomass energy.Cu-based catalysts are promising ...Electrochemical hydrogenation(ECH)of furfural,which uses the proton from water and avoids the usage of gaseous hydrogen and high pressure,is an efficient way to utilize biomass energy.Cu-based catalysts are promising catalysts for the ECH of furfural.However,their active sites and reaction mechanism have not been fully understood yet.This work unveils the active oxidation state of Cu-based electrocatalysts for the ECH of furfural.The co-existence of Cu^(+)and Cu^(0) on the CuO surface under the working potential is confirmed by a series of in situ characterizations.The poisoning experiment shows that the performance decreased heavily after the Cu^(+)was complexed with SCN−,indicating the decisive role of Cu^(+).Finally,the density functional theory(DFT)calculation suggests that the Cu^(0)−Cu^(+)synergistic effect is beneficial to both kinetics and thermodynamics:Cu^(+)accelerates the second step hydrogenation process of furfural,and Cu^(0) reduces the energy barrier for the desorption of furfuryl alcohol.This work demonstrates the synergistic effect of Cu^(0) and Cu^(+)states for the electrochemical hydrogenation of furfural and provides a deeper understanding of the furfural hydrogenation mechanism.展开更多
基金supported by the National Key R&D Program of China(grant no.2020YFA0710000)the National Natural Science Foundation of China(grant no.22122901)+1 种基金the Provincial Natural Science Foundation of Hunan(grant nos.2021JJ0008,2021JJ20024,2021RC3054,and 2020JJ5045)the Shenzhen Science and Technology Program(grant no.JCYJ20210324140610028).
文摘Amide is essential in biologically active compounds,synthetic materials,and building blocks.However,conventional amide production relies on energyintensive consumption and activating agents that modulate processes to construct the C–N bond.Herein,for the first time,we have successfully realized the formation of amides at industrial current density via the anodic coelectrolysis of alcohol and ammonia under ambient conditions.We have proved thatmodulation of the interface microenvironment concentration of nucleophile by electrolyte engineering can regulate the reaction pathways of amides rather than acetic acids.The C-N coupling strategy can be further extended to the electrosynthesis of the long-chain and aryl-ring amide with high selectivity by replacing ammonia with amine.Our work opens up a vast store of information on the utilization of biomass alcohol for high-value N-containing chemicals via an electrocatalytic C-N coupling reaction.
基金supported by the National Key R&D Program of China(2020YFA0710000)the National Natural Science Foundation of China(22122901,21902047,21825201,U19A2017)the Provincial Natural Science Foundation of Hunan(2020JJ5045,2021JJ20024,2021RC3054).
文摘Electrochemical hydrogenation(ECH)of furfural,which uses the proton from water and avoids the usage of gaseous hydrogen and high pressure,is an efficient way to utilize biomass energy.Cu-based catalysts are promising catalysts for the ECH of furfural.However,their active sites and reaction mechanism have not been fully understood yet.This work unveils the active oxidation state of Cu-based electrocatalysts for the ECH of furfural.The co-existence of Cu^(+)and Cu^(0) on the CuO surface under the working potential is confirmed by a series of in situ characterizations.The poisoning experiment shows that the performance decreased heavily after the Cu^(+)was complexed with SCN−,indicating the decisive role of Cu^(+).Finally,the density functional theory(DFT)calculation suggests that the Cu^(0)−Cu^(+)synergistic effect is beneficial to both kinetics and thermodynamics:Cu^(+)accelerates the second step hydrogenation process of furfural,and Cu^(0) reduces the energy barrier for the desorption of furfuryl alcohol.This work demonstrates the synergistic effect of Cu^(0) and Cu^(+)states for the electrochemical hydrogenation of furfural and provides a deeper understanding of the furfural hydrogenation mechanism.
