The d-d orbital coupling induced by crystal-phase engineering can effectively adjust the electronic structure of electrocatalysts,thus showing significant catalytic performance,while it has been rarely explored in ele...The d-d orbital coupling induced by crystal-phase engineering can effectively adjust the electronic structure of electrocatalysts,thus showing significant catalytic performance,while it has been rarely explored in electrochemical acetonitrile reduction reaction(ARR)to date.Herein,we successfully realize the structural transformation of Pd Cu metallic aerogels(MAs)from face-centered cubic(FCC)to body-centered cubic(BCC)through annealing treatment.Specifically,the BCC Pd Cu MAs exhibit excellent ARR performance with high ethylamine selectivity of 90.91%,Faradaic efficiency of 88.60%,yield rate of 316.0 mmol h^(-1)g^(-1)_(Pd+Cu)and long-term stability for consecutive electrolysis within 20 h at-0.55 V vs.reversible hydrogen electrode,outperforming than those of FCC Pd Cu MAs.Under the membrane electrode assembly system,BCC Pd Cu MAs also demonstrate excellent ethylamine yield rate of 389.5 mmol h^(-1)g^(-1)_(Pd+Cu).Density functional theory calculation reveals that the d-d orbital coupling in BCC Pd Cu MAs results in an evident correlation effect for the interaction of Pd and Cu sites,which boosts up the Cu sites electronic activities to enhance ARR performance.Our work opens a new route to develop efficient ARR electrocatalysts from the perspective of crystalline structure transformation.展开更多
Crystal-phase low-dimensional structures offer great potential for the implementation of photonic devices of interest for quantum information processing.In this context,unveiling the fundamental parameters of the crys...Crystal-phase low-dimensional structures offer great potential for the implementation of photonic devices of interest for quantum information processing.In this context,unveiling the fundamental parameters of the crystal phase structure is of much relevance for several applications.Here,we report on the anisotropy of the g-factor tensor and diamagnetic coefficient in wurtzite/zincblende(WZ/ZB)crystal-phase quantum dots(QDs)realized in single InP nanowires.The WZ and ZB alternating axial sections in the NWs are identified by high-angle annular dark-field scanning transmission electron microscopy.The electron(hole)g-factor tensor and the exciton diamagnetic coefficients in WZ/ZB crystal-phase QDs are determined through micro-photoluminescence measurements at low temperature(4.2 K)with different magnetic field configurations,and rationalized by invoking the spin-correlated orbital current model.Our work provides key parameters for band gap engineering and spin states control in crystal-phase low-dimensional structures in nanowires.展开更多
III-V compound semiconductor nanowires are generally characterized by the coexistence of zincblende and wurtzite structures. So far, this polytypism has impeded the determination of the electronic properties of the me...III-V compound semiconductor nanowires are generally characterized by the coexistence of zincblende and wurtzite structures. So far, this polytypism has impeded the determination of the electronic properties of the metastable wurtzite phase of GaAs, which thus remain highly controversial. In an effort to obtain new insights into this topic, we cross-correlate nanoscale spectral imaging by near-field scanning optical microscopy with a transmission electron microscopy analysis of the very same polytypic GaAs nanowire dispersed onto a Si wafer. Thus, spatially resolved photoluminescence spectra could be unambiguously assigned to nanowire segments whose structure is known with lattice-resolved accuracy. An emission energy of 1.528 eV was observed from extended zincblende segments, revealing that the dispersed nanowire was under uniaxial strain presumably due to interaction with its supporting substrate. These crucial information and the emission energy obtained for extended pure wurtzite segments were used to perform envelope function calculations of zincblende quantum disks in a wurtzite matrix as well as the inverse structure. In these calculations, we varied the fundamental bandgap, the electron mass, and the band offset between zincblende and wurtzite GaAs. From this multi-parameter comparison with the experimental data, we deduced that the bandgap between the F8 conduction and A valence band ranges from 1.532 to 1.539 eV in strain-free wurtzite GaAs, and estimated values of 1.507 to 1.514 eV for the F7-A bandgap.展开更多
基金financially supported by the National Natural Science Foundation of China(Grant Nos.52161135302,22105087)the Postdoctoral Research Foundation of China(Grant No.2022M721360)the Natural Science Foundation of Jiangsu Province(Grant No.BK20210446)。
文摘The d-d orbital coupling induced by crystal-phase engineering can effectively adjust the electronic structure of electrocatalysts,thus showing significant catalytic performance,while it has been rarely explored in electrochemical acetonitrile reduction reaction(ARR)to date.Herein,we successfully realize the structural transformation of Pd Cu metallic aerogels(MAs)from face-centered cubic(FCC)to body-centered cubic(BCC)through annealing treatment.Specifically,the BCC Pd Cu MAs exhibit excellent ARR performance with high ethylamine selectivity of 90.91%,Faradaic efficiency of 88.60%,yield rate of 316.0 mmol h^(-1)g^(-1)_(Pd+Cu)and long-term stability for consecutive electrolysis within 20 h at-0.55 V vs.reversible hydrogen electrode,outperforming than those of FCC Pd Cu MAs.Under the membrane electrode assembly system,BCC Pd Cu MAs also demonstrate excellent ethylamine yield rate of 389.5 mmol h^(-1)g^(-1)_(Pd+Cu).Density functional theory calculation reveals that the d-d orbital coupling in BCC Pd Cu MAs results in an evident correlation effect for the interaction of Pd and Cu sites,which boosts up the Cu sites electronic activities to enhance ARR performance.Our work opens a new route to develop efficient ARR electrocatalysts from the perspective of crystalline structure transformation.
基金This work was supported by the National Natural Science Foundation of China(Nos.11934019,61675228,11721404,51761145104,and 11874419)the Strategic Priority Research Program,the Instrument Developing Project and the Interdisciplinary Innovation Team of the Chinese Academy of Sciences(Nos.XDB28000000 and YJKYYQ20180036)+2 种基金the Key RD Program of Guangdong Province(No.2018B030329001)the Key Laboratory Fund(No.614280303051701)We acknowledge financial support from the SUPERTOP project,QUANTERA ERA-NET Cofund in Quantum Technologies.
文摘Crystal-phase low-dimensional structures offer great potential for the implementation of photonic devices of interest for quantum information processing.In this context,unveiling the fundamental parameters of the crystal phase structure is of much relevance for several applications.Here,we report on the anisotropy of the g-factor tensor and diamagnetic coefficient in wurtzite/zincblende(WZ/ZB)crystal-phase quantum dots(QDs)realized in single InP nanowires.The WZ and ZB alternating axial sections in the NWs are identified by high-angle annular dark-field scanning transmission electron microscopy.The electron(hole)g-factor tensor and the exciton diamagnetic coefficients in WZ/ZB crystal-phase QDs are determined through micro-photoluminescence measurements at low temperature(4.2 K)with different magnetic field configurations,and rationalized by invoking the spin-correlated orbital current model.Our work provides key parameters for band gap engineering and spin states control in crystal-phase low-dimensional structures in nanowires.
文摘III-V compound semiconductor nanowires are generally characterized by the coexistence of zincblende and wurtzite structures. So far, this polytypism has impeded the determination of the electronic properties of the metastable wurtzite phase of GaAs, which thus remain highly controversial. In an effort to obtain new insights into this topic, we cross-correlate nanoscale spectral imaging by near-field scanning optical microscopy with a transmission electron microscopy analysis of the very same polytypic GaAs nanowire dispersed onto a Si wafer. Thus, spatially resolved photoluminescence spectra could be unambiguously assigned to nanowire segments whose structure is known with lattice-resolved accuracy. An emission energy of 1.528 eV was observed from extended zincblende segments, revealing that the dispersed nanowire was under uniaxial strain presumably due to interaction with its supporting substrate. These crucial information and the emission energy obtained for extended pure wurtzite segments were used to perform envelope function calculations of zincblende quantum disks in a wurtzite matrix as well as the inverse structure. In these calculations, we varied the fundamental bandgap, the electron mass, and the band offset between zincblende and wurtzite GaAs. From this multi-parameter comparison with the experimental data, we deduced that the bandgap between the F8 conduction and A valence band ranges from 1.532 to 1.539 eV in strain-free wurtzite GaAs, and estimated values of 1.507 to 1.514 eV for the F7-A bandgap.
