Here we exquisitely fabricated Cu/ZrO_(2)-dp catalysts with plentiful Cu-ZrO_(2)interfaces by depositing amorphous ZrO_(2)onto Cu nanoparticles for the hydrogenation of levulinic acid(LA)to y-valerolactone(GVL).With t...Here we exquisitely fabricated Cu/ZrO_(2)-dp catalysts with plentiful Cu-ZrO_(2)interfaces by depositing amorphous ZrO_(2)onto Cu nanoparticles for the hydrogenation of levulinic acid(LA)to y-valerolactone(GVL).With the created plentiful CU-ZrO_(2)interfaces,the optimal catalyst 3 Cu/ZrO_(2)-dp exhibited exceptional catalytic performance under mild reaction conditions,and achieved the highest GVL mass productivity of 266.0 mmol GVL·h^(-1)·g^(-1)Cu,which was 12.5 and 2.3 times of CU/ZrO_(2)catalysts with equivalent Cu loadings prepared by traditional impregnation(3 Cu/ZrO_(2)-im)or co-precipitation(3 Cu/ZrO_(2)-cp).As far as we know,this GVL mass productivity stood at the highest level compared with those obtained using non-noble metal catalysts under similar reaction conditions.By systematic investigation with multiple characterizations,density functional theory(DFT)calculations,and kinetic studies,it was found that interfacial active centers were created at Cu-ZrO_(2)interfaces,which contained oxygen vacancies(O_(v)),negatively charged Cu^(δ)-and partially reduced Zr^(3+)The O_(v) favored the adsorption and activation of LA via its ketone group,while negatively charged Cu^(δ)-was able to enhance heterolysis of H2,which resulted in the formation of H^(+)-Cu^(δ)-and Zr^(3+)-H^(-)active species via hydrogen spillover.Also,plentiful acid sites,which derived from coordinatively unsaturated and defective Zr species,generated at Cu-ZrO_(2)interfaces.With the cooperation of interfacial active centers(Cu^(δ-)-O_(v)-Zr^(3+))and acid sites,the fabricated 3 Cu/ZrO_(2)-dp with plentiful Cu-ZrO_(2)interfaces achieved excellent catalytic performance for the hydrogenation of LA to GVL.Hence,the synergistic catalysis of Cu-ZrO_(2)interfaces provided an effective strategy for designing catalysts with a satisfactory performance for the hydrogenation of LA,which also can be expanded to other hydrodeoxygenation reactions.展开更多
Design and development of high-efficiency and durable oxygen evolution reaction(OER)electrocatalysts is crucial for hydrogen production from seawater splitting.Herein,we report the in situ electrochemical conversion o...Design and development of high-efficiency and durable oxygen evolution reaction(OER)electrocatalysts is crucial for hydrogen production from seawater splitting.Herein,we report the in situ electrochemical conversion of a nanoarray of Ni(TCNQ)2(TCNQ=tetracyanoquinodimethane)on graphite paper into Ni(OH)_(2) nanoparticles confined in a conductive TCNQ nanoarray(Ni(OH)_(2)-TCNQ/GP)by anode oxidation.The Ni(OH)_(2)-TCNQ/GP exhibits high OER performance and demands overpotentials of 340 and 382 mV to deliver 100 mA·cm^(−2) in alkaline freshwater and alkaline seawater,respectively.Meanwhile,the Ni(OH)_(2)-TCNQ/GP also demonstrates steady long-term electrochemical durability for at least 80 h under alkaline seawater.展开更多
基金financial support from the National Natural Science Foundation of China(21576161,21703133,21802076,and 21962013)the Fundamental Research Funds for the Central Universities(GK202003028)。
文摘Here we exquisitely fabricated Cu/ZrO_(2)-dp catalysts with plentiful Cu-ZrO_(2)interfaces by depositing amorphous ZrO_(2)onto Cu nanoparticles for the hydrogenation of levulinic acid(LA)to y-valerolactone(GVL).With the created plentiful CU-ZrO_(2)interfaces,the optimal catalyst 3 Cu/ZrO_(2)-dp exhibited exceptional catalytic performance under mild reaction conditions,and achieved the highest GVL mass productivity of 266.0 mmol GVL·h^(-1)·g^(-1)Cu,which was 12.5 and 2.3 times of CU/ZrO_(2)catalysts with equivalent Cu loadings prepared by traditional impregnation(3 Cu/ZrO_(2)-im)or co-precipitation(3 Cu/ZrO_(2)-cp).As far as we know,this GVL mass productivity stood at the highest level compared with those obtained using non-noble metal catalysts under similar reaction conditions.By systematic investigation with multiple characterizations,density functional theory(DFT)calculations,and kinetic studies,it was found that interfacial active centers were created at Cu-ZrO_(2)interfaces,which contained oxygen vacancies(O_(v)),negatively charged Cu^(δ)-and partially reduced Zr^(3+)The O_(v) favored the adsorption and activation of LA via its ketone group,while negatively charged Cu^(δ)-was able to enhance heterolysis of H2,which resulted in the formation of H^(+)-Cu^(δ)-and Zr^(3+)-H^(-)active species via hydrogen spillover.Also,plentiful acid sites,which derived from coordinatively unsaturated and defective Zr species,generated at Cu-ZrO_(2)interfaces.With the cooperation of interfacial active centers(Cu^(δ-)-O_(v)-Zr^(3+))and acid sites,the fabricated 3 Cu/ZrO_(2)-dp with plentiful Cu-ZrO_(2)interfaces achieved excellent catalytic performance for the hydrogenation of LA to GVL.Hence,the synergistic catalysis of Cu-ZrO_(2)interfaces provided an effective strategy for designing catalysts with a satisfactory performance for the hydrogenation of LA,which also can be expanded to other hydrodeoxygenation reactions.
基金supported by the National Natural Science Foundation of China(No.22072015)the Opening Fund of Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research(Hunan Normal University)Ministry of Education(2020-02).
文摘Design and development of high-efficiency and durable oxygen evolution reaction(OER)electrocatalysts is crucial for hydrogen production from seawater splitting.Herein,we report the in situ electrochemical conversion of a nanoarray of Ni(TCNQ)2(TCNQ=tetracyanoquinodimethane)on graphite paper into Ni(OH)_(2) nanoparticles confined in a conductive TCNQ nanoarray(Ni(OH)_(2)-TCNQ/GP)by anode oxidation.The Ni(OH)_(2)-TCNQ/GP exhibits high OER performance and demands overpotentials of 340 and 382 mV to deliver 100 mA·cm^(−2) in alkaline freshwater and alkaline seawater,respectively.Meanwhile,the Ni(OH)_(2)-TCNQ/GP also demonstrates steady long-term electrochemical durability for at least 80 h under alkaline seawater.
