It is widely recognized that the development of ZABs is impeded by the kinetic bottleneck of oxygen evolution reaction(OER)and oxygen reduction reaction(ORR).The application of conformational entropy strategy to oxide...It is widely recognized that the development of ZABs is impeded by the kinetic bottleneck of oxygen evolution reaction(OER)and oxygen reduction reaction(ORR).The application of conformational entropy strategy to oxides often involves introducing multiple elements with different properties,thereby providing outstanding bifunctional catalytic activity for OER/ORR.Nevertheless,the possible underlying catalytic pathways and potential interactions between various components are still poorly understood.This paper presents an excellent medium-entropy perovskite oxide,Sr(FeCoNiMo)_(1/4)O_(3−δ)(lower overpotential of 301 mV at 10 mA cm^(−2)).Zinc-air batteries employing it as a cathode catalyst demonstrate excellent round-trip efficiency(62%).By combining theoretical calculation with experiments,we aim to establish the link between the electronic structure of perovskite oxides with different elemental compositions and their OER mechanism.Research reveals that the conformational entropy strategy can simultaneously shift the O 2p-band center and metal d-band center of perovskite oxide towards the vicinity of the Fermi energy level,thereby triggering a more favorable lattice oxygen-participated mechanism(LOM)during the OER process.The outcomes of this work provide crucial insights into the role of conformational entropy strategies in oxygen catalysis and offer potential avenues for constructing efficient and stable electrocatalysts.展开更多
Cu nanoparticles supported on a variety of oxide supports, including SiO2, TiO2, ZrO2, Al2O3, MgO and ZnO, were investigated for the hydrogenolysis of biomass‐derived furfuryl alcohol to1,2‐pentanediol and 1,5‐pent...Cu nanoparticles supported on a variety of oxide supports, including SiO2, TiO2, ZrO2, Al2O3, MgO and ZnO, were investigated for the hydrogenolysis of biomass‐derived furfuryl alcohol to1,2‐pentanediol and 1,5‐pentanediol. A Cu‐Al2O3 catalyst with 10 wt% Cu loading prepared by a co‐precipitation method exhibited the best performance in terms of producing pentanediols compared with the other materials. This catalyst generated an 85.8% conversion and a 70.3% combined selectivity for the target pentanediols at 413 K and 8 MPa H2 over an 8‐h reaction. The catalyst could also be recycled over repeated reaction trials without any significant decrease in productivity. Characterizations with X‐ray diffraction, NH3/CO2‐temperature programmed desorption, N2 adsorption,transmission electron microscopy and N2 O chemisorption demonstrated that intimate and effective interactions between Cu particles and the acidic Al2O3 support in this material greatly enhanced its activity and selectivity. The promotion of the hydrogenolysis reaction was found to be especially sensitive to the Cu particle size, and the catalyst with Cu particles 1.9 to 2.4 nm in size showed the highest turnover frequency during the synthesis of pentanediols.展开更多
基金the financial support from the National Natural Science Foundation of China (51872067 and 21773048)
文摘It is widely recognized that the development of ZABs is impeded by the kinetic bottleneck of oxygen evolution reaction(OER)and oxygen reduction reaction(ORR).The application of conformational entropy strategy to oxides often involves introducing multiple elements with different properties,thereby providing outstanding bifunctional catalytic activity for OER/ORR.Nevertheless,the possible underlying catalytic pathways and potential interactions between various components are still poorly understood.This paper presents an excellent medium-entropy perovskite oxide,Sr(FeCoNiMo)_(1/4)O_(3−δ)(lower overpotential of 301 mV at 10 mA cm^(−2)).Zinc-air batteries employing it as a cathode catalyst demonstrate excellent round-trip efficiency(62%).By combining theoretical calculation with experiments,we aim to establish the link between the electronic structure of perovskite oxides with different elemental compositions and their OER mechanism.Research reveals that the conformational entropy strategy can simultaneously shift the O 2p-band center and metal d-band center of perovskite oxide towards the vicinity of the Fermi energy level,thereby triggering a more favorable lattice oxygen-participated mechanism(LOM)during the OER process.The outcomes of this work provide crucial insights into the role of conformational entropy strategies in oxygen catalysis and offer potential avenues for constructing efficient and stable electrocatalysts.
基金supported by the National Natural Science Foundation of China(2113301121203221+1 种基金21473224)the Natural Science Foundation of Gansu Province(1308RJZA281)~~
文摘Cu nanoparticles supported on a variety of oxide supports, including SiO2, TiO2, ZrO2, Al2O3, MgO and ZnO, were investigated for the hydrogenolysis of biomass‐derived furfuryl alcohol to1,2‐pentanediol and 1,5‐pentanediol. A Cu‐Al2O3 catalyst with 10 wt% Cu loading prepared by a co‐precipitation method exhibited the best performance in terms of producing pentanediols compared with the other materials. This catalyst generated an 85.8% conversion and a 70.3% combined selectivity for the target pentanediols at 413 K and 8 MPa H2 over an 8‐h reaction. The catalyst could also be recycled over repeated reaction trials without any significant decrease in productivity. Characterizations with X‐ray diffraction, NH3/CO2‐temperature programmed desorption, N2 adsorption,transmission electron microscopy and N2 O chemisorption demonstrated that intimate and effective interactions between Cu particles and the acidic Al2O3 support in this material greatly enhanced its activity and selectivity. The promotion of the hydrogenolysis reaction was found to be especially sensitive to the Cu particle size, and the catalyst with Cu particles 1.9 to 2.4 nm in size showed the highest turnover frequency during the synthesis of pentanediols.
