Biomass-derived platform molecules,such as furfural,are abundant and renewable feedstock for valuable chemical production.It is critical to synthesize highly efficient photocatalysts for selective oxidation under visi...Biomass-derived platform molecules,such as furfural,are abundant and renewable feedstock for valuable chemical production.It is critical to synthesize highly efficient photocatalysts for selective oxidation under visible light.The Er@K-C_(3)N_(4)/UiO-66-NH_(2) catalyst was synthesized using a straight-forward hydrothermal technique,and exhibited exceptional efficiency in the photocatalytic oxidation of furfural to furoic acid.The catalyst was thoroughly characterized,confirming the effective adjustment of the band gap energy of Er@K-C_(3)N_(4)/UiO-66-NH_(2).Upon the optimized reaction conditions,the conversion rate of furfural reached 89.3%,with a corresponding yield of furoic acid at 79.8%.The primary reactive oxygen species was identified as·O_(2)^(-) from ESR spectra and scavenger tests.The incorporation of Er and K into the catalyst enhanced the photogenerated carriers transfer rate,hence increasing the separating efficiency of photogenerated electron-hole pairs.This study expands the potential applications of rare earth element doped g-C_(3)N_(4) in the photocatalytic selective oxidation of furfurans.展开更多
Implementing a new energy-saving electrochemical synthesis system with high commercial value is a strategy of the sustainable development for upgrading the bulk chemicals preparation technology in the future.Here,we r...Implementing a new energy-saving electrochemical synthesis system with high commercial value is a strategy of the sustainable development for upgrading the bulk chemicals preparation technology in the future.Here,we report a multiple redox-mediated linear paired electrolysis system,combining the hydrogen peroxide mediated cathode process with the I2 mediated anode process,and realize the conversion of furfural to furoic acid in both side of the dividedflow cell simultaneously.By reasonably controlling the cathode potential,the undesired water splitting reaction and furfural reduction side reactions are avoided.Under the galvanostatic electrolysis,the two-mediated electrode processes have good compatibility,which reduce the energy consumption by about 22%while improving the electronic efficiency by about 125%.This system provides a green electrochemical synthesis route with commercial prospects.展开更多
The paired electrolytic system is constructed by combining the valuable organic electro-oxidation and electro-reduction reactions,which can replace the ineffective water splitting half-reaction.By reducing the energy ...The paired electrolytic system is constructed by combining the valuable organic electro-oxidation and electro-reduction reactions,which can replace the ineffective water splitting half-reaction.By reducing the energy consumption of the electrolytic cell,the value-added electrolysis is realized.The indirect electrolysis method greatly reduces the dependence of the organic electrolysis reaction on electrode potential by introducing the redox mediators,which solves the problem on the matching of anode and cathode current under potentiostatic conditions.Here,we report a more stable,efficient and energy-saving linear paired electrochemical synthesis system that can simultaneously convert furfural to furoic acid at both the anode and cathode at higher current densities.Stable three-dimensional networked PbO_(2)is used as the anode and the catalytic amount of 2,2,6,6-tetramethyl-1-piperidinyloxy(TEMPO)is used as the mediator to realize the efficient conversion of furfural to furoic acid in a wide potential range.The cathode catalyzes two-electron oxygen reduction to hydrogen peroxide using Pb/RHPC gas-diffusion electrode,which mediates the oxidation of furfural to furoic acid simultaneously.In potentiostatic electrolysis,the selectivity of the furoic acid in the cathode and anode is 33.2%and 99.3%,respectively,and the total electron efficiency is 127.1%.The properties of the cathode and anode remain stable after the long-time electrolysis in a flow cell.By choosing a stable anode with high oxygen evolution overpotential and a gas-diffusion cathode with high hydrogen evolution overpotential,the electrolytic cell can be operated efficiently and stably by introducing reasonable mediated reactions.The two half-reactions have good compatibility during the electrolysis process,saving energy consumption by about 12.3%,for certain industrial application prospects.展开更多
A robust and green strategy for the selective upgrading of biomass-derived platform chemicals towards highly valuable products is important for the sustainable development.Herein,the efficient electrocatalytic oxidati...A robust and green strategy for the selective upgrading of biomass-derived platform chemicals towards highly valuable products is important for the sustainable development.Herein,the efficient electrocatalytic oxidation of biomass-derived furfuryl alcohol(FFA)into furoic acid(FurAc)catalyzed by the electrodeposited non-precious NiFe microflowers was successfully reached under the low temperature and ambient pressure.The 3D hierarchical NiFe microflowers assembled from ultrathin nanosheets were controllably synthesized by the electrodeposition method and uniformly grown on carbon fiber paper(CFP).Electrochemical analysis confirmed that NiFe nanosheets more preferred in the selective oxidation of FFA(FFAOR)than oxygen evolution reaction(OER).The linear sweep voltammetry(LSV)in FFAOR displayed a clear decrease towards lower potential,resulting in 30 mV reduction of overpotential at 20 mA cm^(-2) compared with that of OER.The optimal catalyst Ni_(1)Fe_(2) nanosheets exhibited the highest selectivity of FurAc(94.0%)and 81.4%conversion of FFA within 3 h.Besides,the influence of various reaction parameters on FFAOR was then explored in details.After that,the reaction pathway was investigated and rationally proposed.The outstanding performance for FFAOR can be ascribed to the unique structure of 3D flower-like NiFe nanosheets and oxygen vacancies,resulting in large exposure of active sites,faster electron transfer and enhanced adsorption of reactants.Our findings highlight a facile and convenient mean with a promising green future,which is promising for processing of various biomass-derived platform chemicals into value-added products.展开更多
基金supported by Natural Science Foundation of Shandong Province(ZR2022MB049)National Natural Science Foundation of China(22078174)。
文摘Biomass-derived platform molecules,such as furfural,are abundant and renewable feedstock for valuable chemical production.It is critical to synthesize highly efficient photocatalysts for selective oxidation under visible light.The Er@K-C_(3)N_(4)/UiO-66-NH_(2) catalyst was synthesized using a straight-forward hydrothermal technique,and exhibited exceptional efficiency in the photocatalytic oxidation of furfural to furoic acid.The catalyst was thoroughly characterized,confirming the effective adjustment of the band gap energy of Er@K-C_(3)N_(4)/UiO-66-NH_(2).Upon the optimized reaction conditions,the conversion rate of furfural reached 89.3%,with a corresponding yield of furoic acid at 79.8%.The primary reactive oxygen species was identified as·O_(2)^(-) from ESR spectra and scavenger tests.The incorporation of Er and K into the catalyst enhanced the photogenerated carriers transfer rate,hence increasing the separating efficiency of photogenerated electron-hole pairs.This study expands the potential applications of rare earth element doped g-C_(3)N_(4) in the photocatalytic selective oxidation of furfurans.
基金This study is supported by the National Key Research and Development Program of China(2017YFB0307500).
文摘Implementing a new energy-saving electrochemical synthesis system with high commercial value is a strategy of the sustainable development for upgrading the bulk chemicals preparation technology in the future.Here,we report a multiple redox-mediated linear paired electrolysis system,combining the hydrogen peroxide mediated cathode process with the I2 mediated anode process,and realize the conversion of furfural to furoic acid in both side of the dividedflow cell simultaneously.By reasonably controlling the cathode potential,the undesired water splitting reaction and furfural reduction side reactions are avoided.Under the galvanostatic electrolysis,the two-mediated electrode processes have good compatibility,which reduce the energy consumption by about 22%while improving the electronic efficiency by about 125%.This system provides a green electrochemical synthesis route with commercial prospects.
基金supported by the National Key Research and Development Program of China(2017YFB0307500).
文摘The paired electrolytic system is constructed by combining the valuable organic electro-oxidation and electro-reduction reactions,which can replace the ineffective water splitting half-reaction.By reducing the energy consumption of the electrolytic cell,the value-added electrolysis is realized.The indirect electrolysis method greatly reduces the dependence of the organic electrolysis reaction on electrode potential by introducing the redox mediators,which solves the problem on the matching of anode and cathode current under potentiostatic conditions.Here,we report a more stable,efficient and energy-saving linear paired electrochemical synthesis system that can simultaneously convert furfural to furoic acid at both the anode and cathode at higher current densities.Stable three-dimensional networked PbO_(2)is used as the anode and the catalytic amount of 2,2,6,6-tetramethyl-1-piperidinyloxy(TEMPO)is used as the mediator to realize the efficient conversion of furfural to furoic acid in a wide potential range.The cathode catalyzes two-electron oxygen reduction to hydrogen peroxide using Pb/RHPC gas-diffusion electrode,which mediates the oxidation of furfural to furoic acid simultaneously.In potentiostatic electrolysis,the selectivity of the furoic acid in the cathode and anode is 33.2%and 99.3%,respectively,and the total electron efficiency is 127.1%.The properties of the cathode and anode remain stable after the long-time electrolysis in a flow cell.By choosing a stable anode with high oxygen evolution overpotential and a gas-diffusion cathode with high hydrogen evolution overpotential,the electrolytic cell can be operated efficiently and stably by introducing reasonable mediated reactions.The two half-reactions have good compatibility during the electrolysis process,saving energy consumption by about 12.3%,for certain industrial application prospects.
基金supported by Key Area Research and Development Program of Guangdong Province (2019B110209003)Guangdong Basic and Applied Basic Research Foundation (2019B1515120058,2020A1515011149)+2 种基金National Natural Science Foundation of China (22078374,21776324)National Key R&D Program of China (2018YFD0800703)National Ten Thousand Talent Plan,the Fundamental Research Funds for the Cornell University (19lgzd25)and Hundred Talent Plan (201602)from Sun Yat-sen University.
文摘A robust and green strategy for the selective upgrading of biomass-derived platform chemicals towards highly valuable products is important for the sustainable development.Herein,the efficient electrocatalytic oxidation of biomass-derived furfuryl alcohol(FFA)into furoic acid(FurAc)catalyzed by the electrodeposited non-precious NiFe microflowers was successfully reached under the low temperature and ambient pressure.The 3D hierarchical NiFe microflowers assembled from ultrathin nanosheets were controllably synthesized by the electrodeposition method and uniformly grown on carbon fiber paper(CFP).Electrochemical analysis confirmed that NiFe nanosheets more preferred in the selective oxidation of FFA(FFAOR)than oxygen evolution reaction(OER).The linear sweep voltammetry(LSV)in FFAOR displayed a clear decrease towards lower potential,resulting in 30 mV reduction of overpotential at 20 mA cm^(-2) compared with that of OER.The optimal catalyst Ni_(1)Fe_(2) nanosheets exhibited the highest selectivity of FurAc(94.0%)and 81.4%conversion of FFA within 3 h.Besides,the influence of various reaction parameters on FFAOR was then explored in details.After that,the reaction pathway was investigated and rationally proposed.The outstanding performance for FFAOR can be ascribed to the unique structure of 3D flower-like NiFe nanosheets and oxygen vacancies,resulting in large exposure of active sites,faster electron transfer and enhanced adsorption of reactants.Our findings highlight a facile and convenient mean with a promising green future,which is promising for processing of various biomass-derived platform chemicals into value-added products.
