The electrocatalytic oxidation of biomass-derived furfural(FF)feedstocks into 2-furoic acid(FA)holds immense industrial potential in optics,cosmetics,polymers,and food.Herein,we fabricated Co O/Ni O/nickel foam(NF)and...The electrocatalytic oxidation of biomass-derived furfural(FF)feedstocks into 2-furoic acid(FA)holds immense industrial potential in optics,cosmetics,polymers,and food.Herein,we fabricated Co O/Ni O/nickel foam(NF)and Cu_(2)O/Ni O/NF electrodes via in situ pulsed laser irradiation in liquids(PLIL)for the bifunctional electrocatalysis of oxygen evolution reaction(OER)and furfural oxidation reaction(FOR),respectively.Simultaneous oxidation of NF surface to NiO and deposition of CoO and/or Cu_(2)O on NF during PLIL offer distinct advantages for enhancing both the OER and FOR.CoO/NiO/NF electrocatalyst provides a consistently low overpotential of~359 m V(OER)at 10 m A/cm^(2),achieving the maximum FA yield(~16.37 m M)with 61.5%selectivity,79.5%carbon balance,and a remarkable Faradaic efficiency of~90.1%during 2 h of FOR at 1.43 V(vs.reversible hydrogen electrode).Mechanistic pathway via in situ electrochemical-Raman spectroscopy on CoO/NiO/NF reveals the involvement of phase transition intermediates(NiOOH and CoOOH)as surface-active centers during electrochemical oxidation.The carbonyl carbon in FF is attacked by hydroxyl groups to form unstable hydrates that subsequently undergo further oxidation to yield FA products.This method holds promise for large-scale applications,enabling simultaneous production of renewable building materials and fuel.展开更多
Microreactors are increasingly used for green and safe chemical processes owing to their benefits of superior mass and heat transfer,increased yield,safety,and simplicity of control.However,immobilizing catalysts in m...Microreactors are increasingly used for green and safe chemical processes owing to their benefits of superior mass and heat transfer,increased yield,safety,and simplicity of control.However,immobilizing catalysts in microreactors remains challenging.In this investigation,a technique for creating Cu_(2)O/montmorillonite catalyst coating,using electrostatic attraction for layer-by-layer self-assembly,was proposed.The montmorillonite film's morphology and thickness could be efficiently regulated by adjusting the degree of exfoliation and surface charge of montmorillonite,alongside layer-by-layer coating times.The Cu_(2)O nanoparticles were immobilized using the flow deposition approach.The resulting Cu_(2)O@montmorillonite-film-coated capillary microreactor successfully transformed glycerol into dihydroxyacetone.The conversion of glycerol and product selectivity could be controlled by adjusting the molar ratio of reactants,temperature,residence time,and Cu_(2)O loading.The maximum glycerol conversion observed was 47.6%,with a 27%selectivity toward dihydroxyacetone.The study presents a technique for immobilizing montmorillonite-based catalyst coatings in capillary tubing,which can serve as a foundation for the future application of microreactors in glycerol conversion.展开更多
This work describes the use of TiO_(2)nanotubes-based electrodes(TNT)modified with Cu_(2)O nanostructures and gold nanoparticles for the photoelectroreduction of CO_(2)to produce value-added compounds.A thin layer of ...This work describes the use of TiO_(2)nanotubes-based electrodes(TNT)modified with Cu_(2)O nanostructures and gold nanoparticles for the photoelectroreduction of CO_(2)to produce value-added compounds.A thin layer of polydopamine was used as both an adherent agent and an electron transfer mediator,due to itsπ-conjugated electron system.The highest production yield was achieved using a TNT@PDA/Nc/Au40%electrode,with Faradaic efficiencies of 47.4%(110.5μM cm^(-2))and 27.8%(50.4μM cm^(-2))for methanol and methane,respectively.The performance of the photoelectrodes was shown to be Cu_(2)O facet-dependent,with cubic structures leading to greater conversion of CO_(2)to methanol(43%)and methane(27%),compared to the octahedral morphology,while a higher percentage of metallic gold on the nanostructured Cu_(2)O surface was mainly important for CH4production.Density functional theory(DFT)calculations supported these findings,attributing the superior photoelectrocatalytic performance of the TNT@PDA/Nc/Au40%electrode for CH4generation to the formation of an OCH3intermediate bonded to Au atoms.Studies using isotope-labeling and analysis by gas chromatograph-mass(GC-MS)demonstrated that13CO_(2)was the source for photoelectrocatalytic generation of13CH3OH and13CH313CH2OH.展开更多
基金supported by the Korea Basic Science Institute(National research Facilities and Equipment Center)grant funded by the Ministry of Education(2019R1A6C1010042,2021R1A6C103A427)the financial support from the National Research Foundation of Korea(NRF)(2022R1A2C2010686,2022R1A4A3033528,2021R1I1A1A01060380,2021R1C1C2010726,2019H1D3A1A01071209)。
文摘The electrocatalytic oxidation of biomass-derived furfural(FF)feedstocks into 2-furoic acid(FA)holds immense industrial potential in optics,cosmetics,polymers,and food.Herein,we fabricated Co O/Ni O/nickel foam(NF)and Cu_(2)O/Ni O/NF electrodes via in situ pulsed laser irradiation in liquids(PLIL)for the bifunctional electrocatalysis of oxygen evolution reaction(OER)and furfural oxidation reaction(FOR),respectively.Simultaneous oxidation of NF surface to NiO and deposition of CoO and/or Cu_(2)O on NF during PLIL offer distinct advantages for enhancing both the OER and FOR.CoO/NiO/NF electrocatalyst provides a consistently low overpotential of~359 m V(OER)at 10 m A/cm^(2),achieving the maximum FA yield(~16.37 m M)with 61.5%selectivity,79.5%carbon balance,and a remarkable Faradaic efficiency of~90.1%during 2 h of FOR at 1.43 V(vs.reversible hydrogen electrode).Mechanistic pathway via in situ electrochemical-Raman spectroscopy on CoO/NiO/NF reveals the involvement of phase transition intermediates(NiOOH and CoOOH)as surface-active centers during electrochemical oxidation.The carbonyl carbon in FF is attacked by hydroxyl groups to form unstable hydrates that subsequently undergo further oxidation to yield FA products.This method holds promise for large-scale applications,enabling simultaneous production of renewable building materials and fuel.
基金support from the National Natural Science Foundation of China(2207213641672033)+2 种基金the research grants from Engineering Research Center of Non-metallic Minerals of Zhejiang Province(ZD2023K01)the projects from Qing Yang Institute for Industrial Minerals(KYYHX-20220336KYY-HX-20170557).
文摘Microreactors are increasingly used for green and safe chemical processes owing to their benefits of superior mass and heat transfer,increased yield,safety,and simplicity of control.However,immobilizing catalysts in microreactors remains challenging.In this investigation,a technique for creating Cu_(2)O/montmorillonite catalyst coating,using electrostatic attraction for layer-by-layer self-assembly,was proposed.The montmorillonite film's morphology and thickness could be efficiently regulated by adjusting the degree of exfoliation and surface charge of montmorillonite,alongside layer-by-layer coating times.The Cu_(2)O nanoparticles were immobilized using the flow deposition approach.The resulting Cu_(2)O@montmorillonite-film-coated capillary microreactor successfully transformed glycerol into dihydroxyacetone.The conversion of glycerol and product selectivity could be controlled by adjusting the molar ratio of reactants,temperature,residence time,and Cu_(2)O loading.The maximum glycerol conversion observed was 47.6%,with a 27%selectivity toward dihydroxyacetone.The study presents a technique for immobilizing montmorillonite-based catalyst coatings in capillary tubing,which can serve as a foundation for the future application of microreactors in glycerol conversion.
基金FAPESP,Brazil(#2023/10027-5,#2014/50945-4,#2020/15230-5,and#2021/000675-4)CNPq,Brazil(#465571/2014-0,#303269/2021-9,and#307837/2014-9)+6 种基金Instituto Serrapilheira(grant number Serra-2211-41925)FAPEMIG,Brazil(#PPM-00831-15)for support of this workCNPq,Brazil(#105944/2022-0)and PROPEUNESP(13/2022)FAPESP(#2019/00463-7,#2018/22845-6,and#2021/08007-0,respectively)for scholarshipsthe National Institute for Alternative Technologies of Detection,Toxicological Evaluation and Removal of Micropollutants and Radioactives(INCT-DATREM)the support of the Research Centre for Greenhouse Gas Innovation(RCGI),hosted by the University of Sao Paulo(USP)and sponsored by FAPESP and Shell Brasilthe strategic support given by ANP,Brazil(Brazilian National Oil,Natural Gas,and Biofuels Agency)through the R&D levy regulation。
文摘This work describes the use of TiO_(2)nanotubes-based electrodes(TNT)modified with Cu_(2)O nanostructures and gold nanoparticles for the photoelectroreduction of CO_(2)to produce value-added compounds.A thin layer of polydopamine was used as both an adherent agent and an electron transfer mediator,due to itsπ-conjugated electron system.The highest production yield was achieved using a TNT@PDA/Nc/Au40%electrode,with Faradaic efficiencies of 47.4%(110.5μM cm^(-2))and 27.8%(50.4μM cm^(-2))for methanol and methane,respectively.The performance of the photoelectrodes was shown to be Cu_(2)O facet-dependent,with cubic structures leading to greater conversion of CO_(2)to methanol(43%)and methane(27%),compared to the octahedral morphology,while a higher percentage of metallic gold on the nanostructured Cu_(2)O surface was mainly important for CH4production.Density functional theory(DFT)calculations supported these findings,attributing the superior photoelectrocatalytic performance of the TNT@PDA/Nc/Au40%electrode for CH4generation to the formation of an OCH3intermediate bonded to Au atoms.Studies using isotope-labeling and analysis by gas chromatograph-mass(GC-MS)demonstrated that13CO_(2)was the source for photoelectrocatalytic generation of13CH3OH and13CH313CH2OH.