Electro-oxidation of 5-hydroxymethylfurfural(HMFOR)is a promising green approach to realize the conversion of biomass into value-added chemicals.However,considering the complexity of the molecular structure of HMF,an ...Electro-oxidation of 5-hydroxymethylfurfural(HMFOR)is a promising green approach to realize the conversion of biomass into value-added chemicals.However,considering the complexity of the molecular structure of HMF,an in-depth understanding of the electrocatalytic behavior of HMFOR has rarely been investigated.Herein,the electrocatalytic mechanism of HMFOR on nickel nitride(Ni3 N)is elucidated by operando X-ray absorption spectroscopy(XAS),in situ Raman,quasi in situ X-ray photoelectron spectroscopy(XPS),and operando electrochemical impedance spectroscopy(EIS),respectively.The activity origin is proved to be Ni^(2+δ)N(OH)ads generated by the adsorbed hydroxyl group.Moreover,HMFOR on Ni3 N relates to a two-step reaction:Initially,the applied potential drives Ni atoms to lose electrons and adsorb OH-after 1.35 VRHE,giving rise to Ni^(2+δ)N(OH)ads with the electrophilic oxygen;then Ni^(2+δ)N(OH)ads seizes protons and electrons from HMF and leaves as H_(2) O spontaneously.Furthermore,the high electrolyte alkalinity favors the HMFOR process due to the increased active species(Ni^(2+δ)N(OH)ads)and the enhanced adsorption of HMF on the Ni3 N surface.This work could provide an in-depth understanding of the electrocatalytic mechanism of HMFOR on Ni3 N and demonstrate the alkalinity effect of the electrolyte on the electrocatalytic performance of HMFOR.展开更多
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
The 3-dimensional(3D)modeling of crop canopies is fundamental for studying functional-structural plant models.Existing studies often fail to capture the structural characteristics of crop canopies,such as organ overla...The 3-dimensional(3D)modeling of crop canopies is fundamental for studying functional-structural plant models.Existing studies often fail to capture the structural characteristics of crop canopies,such as organ overlapping and resource competition.To address this issue,we propose a 3D maize modeling method based on computational intelligence.An initial 3D maize canopy is created using the t-distribution method to reflect characteristics of the plant architecture.展开更多
Electrocatalytic dehydrogenative cross-coupling of various alcohols in aqueous electrolytes functionalizes alcohols to form structurally diverse long-carbon-chain chemicals.However,it remains challenging to achieve th...Electrocatalytic dehydrogenative cross-coupling of various alcohols in aqueous electrolytes functionalizes alcohols to form structurally diverse long-carbon-chain chemicals.However,it remains challenging to achieve the high selectivity because of the high reactivity of involved carbonyl intermediates and different oxidation rates for the alcohols.Herein,the synthesis ofα,β-unsaturated ketones from alcohols was realized by the electro-oxidation cross-coupling in aqueous solutions by a“salting-out”strategy to engineer the micro-environment at electrocatalytic reaction interfaces.Theoretical calculations and electrochemical measurements demonstrated that concentrated local intermediates could inhibit the over-oxidation of alcohols and accelerate the coupling reaction kinetics between the intermediates.This strategy can couple primary and secondary alcohols to formα,β-unsaturated carbonyl compounds with a selectivity of 87% and be easily scaled up to gram scales.This study provides an attractive strategy for broadening the diversity of organic products in electrocatalysis.展开更多
基金supported by the National Key R&D Program of China(2020YFA0710000)the National Natural Science Foundation of China(Grant No.:21902047)+1 种基金the Provincial Natural Science Foundation of Hunan(2020JJ5045)the Fundamental Research Funds for the Central Universities(Grant No.531118010127)。
文摘Electro-oxidation of 5-hydroxymethylfurfural(HMFOR)is a promising green approach to realize the conversion of biomass into value-added chemicals.However,considering the complexity of the molecular structure of HMF,an in-depth understanding of the electrocatalytic behavior of HMFOR has rarely been investigated.Herein,the electrocatalytic mechanism of HMFOR on nickel nitride(Ni3 N)is elucidated by operando X-ray absorption spectroscopy(XAS),in situ Raman,quasi in situ X-ray photoelectron spectroscopy(XPS),and operando electrochemical impedance spectroscopy(EIS),respectively.The activity origin is proved to be Ni^(2+δ)N(OH)ads generated by the adsorbed hydroxyl group.Moreover,HMFOR on Ni3 N relates to a two-step reaction:Initially,the applied potential drives Ni atoms to lose electrons and adsorb OH-after 1.35 VRHE,giving rise to Ni^(2+δ)N(OH)ads with the electrophilic oxygen;then Ni^(2+δ)N(OH)ads seizes protons and electrons from HMF and leaves as H_(2) O spontaneously.Furthermore,the high electrolyte alkalinity favors the HMFOR process due to the increased active species(Ni^(2+δ)N(OH)ads)and the enhanced adsorption of HMF on the Ni3 N surface.This work could provide an in-depth understanding of the electrocatalytic mechanism of HMFOR on Ni3 N and demonstrate the alkalinity effect of the electrolyte on the electrocatalytic performance of HMFOR.
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partially supported by the National Science and Technology Major Project(2022ZD0115705)the National Natural Science Foundation of China(32071891)+2 种基金the Science and Technology Innovation Special Construction Funded Program of Beijing Academy of Agriculture and Forestry Sciences(KJCX20220401)the China Postdoctoral Science Foundation(2023M730314)the earmarked fund(CARS-02 and CARS-054).
文摘The 3-dimensional(3D)modeling of crop canopies is fundamental for studying functional-structural plant models.Existing studies often fail to capture the structural characteristics of crop canopies,such as organ overlapping and resource competition.To address this issue,we propose a 3D maize modeling method based on computational intelligence.An initial 3D maize canopy is created using the t-distribution method to reflect characteristics of the plant architecture.
基金supported by the National Key R&D Program of China(2020YFA0710000)the National Natural Science Foundation of China(22122901)+2 种基金the Provincial Natural Science Foundation of Hunan(2021JJ0008,2021JJ20024,2021RC3054)the Provincial Natural Science Foundation of Hunan(2022JJ40043)Hunan Provincial Innovation Foundation For Postgraduate(CX20220386)。
文摘Electrocatalytic dehydrogenative cross-coupling of various alcohols in aqueous electrolytes functionalizes alcohols to form structurally diverse long-carbon-chain chemicals.However,it remains challenging to achieve the high selectivity because of the high reactivity of involved carbonyl intermediates and different oxidation rates for the alcohols.Herein,the synthesis ofα,β-unsaturated ketones from alcohols was realized by the electro-oxidation cross-coupling in aqueous solutions by a“salting-out”strategy to engineer the micro-environment at electrocatalytic reaction interfaces.Theoretical calculations and electrochemical measurements demonstrated that concentrated local intermediates could inhibit the over-oxidation of alcohols and accelerate the coupling reaction kinetics between the intermediates.This strategy can couple primary and secondary alcohols to formα,β-unsaturated carbonyl compounds with a selectivity of 87% and be easily scaled up to gram scales.This study provides an attractive strategy for broadening the diversity of organic products in electrocatalysis.
