The effectiveness of photoelectrochemical(PEC)water splitting is significantly restricted by insufficient light harvesting,rapid charge recombination,and slow water reduction kinetics.Since the presence of amorphous p...The effectiveness of photoelectrochemical(PEC)water splitting is significantly restricted by insufficient light harvesting,rapid charge recombination,and slow water reduction kinetics.Since the presence of amorphous phases in the interfaces hinders the overcome of these inherent limitations,a photoelectrode must be built strategically.Herein,we artificially controlled the crystallographic orientation of indium tin oxide(ITO)to determine the orientation with the smallest lattice mismatch at the Cu_(2)O interface,thus significantly reducing the amorphous phase in the early stage of electrodeposition nucleation.The[222]/[400]mixed orientation ITO primarily exposed the{400}surface planes and accelerated charge transfer by forming an optimal interface with preferentially grown(111)oriented Cu_(2)O and minimized amorphous region.In addition,the ITO surface energy was calculated using density functional theory to theoretically verify which plane is more active for growing the photoactivation layer.The rationally designed ITO/Cu_(2)O/Al-dope Zn O/TiO_(2)/Rh-P device,with each layer serving a specific purpose,achieved a photocurrent density of 8.23 mA cm^(-2)at 0 VRHEunder AM 1.5 G illumination,providing a standard method for effective solar-to-hydrogen conversion photocathodes.展开更多
For CO catalytic oxidation,Cu and Ce species are of great importance,between which the synergistic effect is worth investigating.In this work,CeO_(2)/Cu_(2)O with Cu_(2)O {111} and {100} planes were comparatively expl...For CO catalytic oxidation,Cu and Ce species are of great importance,between which the synergistic effect is worth investigating.In this work,CeO_(2)/Cu_(2)O with Cu_(2)O {111} and {100} planes were comparatively explored on CO catalytic oxidation to reveal the effects of interfacial electronic interactions and oxygen defects.The activity result demonstrates that CeO_(2)/o-Cu_(2)O {111} has superior performance compared with CeO_(2)/c-Cu_(2)O {100}.Credit to the coordination unsaturated copper atoms(Cu_(CUS)) on oCu_(2)O {111} surface,the interfacial electronic interactions on CeO_(2)/o-Cu_(2)O {111} are more obvious than those on CeO_(2)/c-Cu_(2)O {100},leading to richer oxygen defect generation,better redox and activation abilities of CO and O_(2) reactants.Furthermore,the reaction mechanism of CeO_(2)/o-Cu_(2)O {111} on CO oxidation is revealed,i.e.,CO and O_(2) are adsorbed on the Cucus on Cu_(2)O {111} and oxygen defect of CeO_(2),respectively,and then synergistically promote the CO oxidation to CO_(2).The work sheds light on the designing optimized ceria and copper-based catalysts and the mechanism of CO oxidation.展开更多
基金supported by the Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Education(2021R1A2C3011870,2022R1A6A3A13071182)supported by the Global Research and Development Center Program(2018K1A4A3A01064272)through the NRF funded by the Korea government(MSIT)。
文摘The effectiveness of photoelectrochemical(PEC)water splitting is significantly restricted by insufficient light harvesting,rapid charge recombination,and slow water reduction kinetics.Since the presence of amorphous phases in the interfaces hinders the overcome of these inherent limitations,a photoelectrode must be built strategically.Herein,we artificially controlled the crystallographic orientation of indium tin oxide(ITO)to determine the orientation with the smallest lattice mismatch at the Cu_(2)O interface,thus significantly reducing the amorphous phase in the early stage of electrodeposition nucleation.The[222]/[400]mixed orientation ITO primarily exposed the{400}surface planes and accelerated charge transfer by forming an optimal interface with preferentially grown(111)oriented Cu_(2)O and minimized amorphous region.In addition,the ITO surface energy was calculated using density functional theory to theoretically verify which plane is more active for growing the photoactivation layer.The rationally designed ITO/Cu_(2)O/Al-dope Zn O/TiO_(2)/Rh-P device,with each layer serving a specific purpose,achieved a photocurrent density of 8.23 mA cm^(-2)at 0 VRHEunder AM 1.5 G illumination,providing a standard method for effective solar-to-hydrogen conversion photocathodes.
基金Project supported by the National Natural Science Foundation of China (21707066,21677069)。
文摘For CO catalytic oxidation,Cu and Ce species are of great importance,between which the synergistic effect is worth investigating.In this work,CeO_(2)/Cu_(2)O with Cu_(2)O {111} and {100} planes were comparatively explored on CO catalytic oxidation to reveal the effects of interfacial electronic interactions and oxygen defects.The activity result demonstrates that CeO_(2)/o-Cu_(2)O {111} has superior performance compared with CeO_(2)/c-Cu_(2)O {100}.Credit to the coordination unsaturated copper atoms(Cu_(CUS)) on oCu_(2)O {111} surface,the interfacial electronic interactions on CeO_(2)/o-Cu_(2)O {111} are more obvious than those on CeO_(2)/c-Cu_(2)O {100},leading to richer oxygen defect generation,better redox and activation abilities of CO and O_(2) reactants.Furthermore,the reaction mechanism of CeO_(2)/o-Cu_(2)O {111} on CO oxidation is revealed,i.e.,CO and O_(2) are adsorbed on the Cucus on Cu_(2)O {111} and oxygen defect of CeO_(2),respectively,and then synergistically promote the CO oxidation to CO_(2).The work sheds light on the designing optimized ceria and copper-based catalysts and the mechanism of CO oxidation.
