Annealing study of the Al/GaSb system was performed by using a slow positron beam and the measurement of X-ray diffraction. The S parameter against positron energy data were fitted by a three layer model （Al/interfac...Annealing study of the Al/GaSb system was performed by using a slow positron beam and the measurement of X-ray diffraction. The S parameter against positron energy data were fitted by a three layer model （Al/interface/GaSb）. It was found there was a ～5 nm interfacial at the region between the Al layer and bulk in the sample of as-deposited. After the 400 ℃ annealing, this interfacial region extends to over 40 nm and S parameter dramatically drops. This is possibly due to a new phase formation induced by the atoms＇inter-diffusion at the interface. The annealing out of the open volume defects in the Al layer was revealed by the decrease of the S parameter and the increase of the effective diffusion length of the Al layer. Annealing behaviors of Sb and Lb of the GaSb bulk showed the annealing out of positron traps at 250 ℃. However,further annealing at 400 ℃ induces formation of positron traps, which are possibly another kind of VGarelated defect and the positron shallow trap GaSb anti-site. The results of the X-ray diffraction experiment verified the conclusion of obtained by using positron technology.展开更多
Heterogeneous-structured Cu samples composed of coarse-grained(CG) and ultrafine-grained(UFG) domains with a transitional interface were fabricated by friction stir processing, in order to investigate the effect of in...Heterogeneous-structured Cu samples composed of coarse-grained(CG) and ultrafine-grained(UFG) domains with a transitional interface were fabricated by friction stir processing, in order to investigate the effect of interface constraint on the yielding and fracture behaviors. Tensile test revealed that the synergetic strengthening induced by elastic/plastic interaction between incompatible domains increases with increasing the area of constraint interface. The strain distribution near interface and the fracture morphology were characterized using digital image correlation technique and scanning electron microscopy, respectively. Fracture dimples preferentially formed at the interface, possibly due to extremely high triaxial stress and strain accumulation near the interface. Surprisingly, the CG domain was fractured by pure shear instead of the expected voids growth caused by tensile stress.展开更多
Although photocatalytic water splitting has excellent potential for converting solar energy into chemical energy,the challenging charge separation process and sluggish surface catalytic reactions significantly limit p...Although photocatalytic water splitting has excellent potential for converting solar energy into chemical energy,the challenging charge separation process and sluggish surface catalytic reactions significantly limit progress in solar energy conversion using semiconductor photocatalysts.Herein,we demonstrate a feasible strategy involving the surface assembly of cobalt oxide species(CoO_(x))on a visible-light-responsive Cd_(0.9)Zn_(0.1)S(CZS)photocatalyst to fabricate a hierarchical CZS@CoO_(x) heterostructure.The unique hierarchical structure effectively accelerates the directional transfer of photogenerated charges,reducing charge recombination through the smooth interfacial heterojunction between CZS and CoO_(x),as evidenced by photoluminescence(PL)spectroscopy and various electrochemical characterizations.The surface cobalt species on the CZS material also act as efficient cocatalysts for photocatalytic hydrogen production,with activity even higher than that of noble metals.The well-defined CZS@CoO_(x) heterostructure not only enhances the interfacial separation of photoinduced charges,but also improves surface catalytic reactions.This leads to superior photocatalytic performances,with an apparent quantum efficiency of 20%at 420 nm for visible-light-driven hydrogen generation,which is one of the highest quantum efficiencies measured among noble-metal-free photocatalysts.Our work presents a potential pathway for controlling complex charge separation and catalytic reaction processes in photocatalysis,guiding the practical development of artificial photocatalysts for successful transformation of solar to chemical energy.展开更多
Boosting the alkaline hydrogen evolution and oxidation reaction(HER/HOR)kinetics is vital to practicing the renewable hydrogen cycle in alkaline media.Recently,intensive research has demonstrated that interface engine...Boosting the alkaline hydrogen evolution and oxidation reaction(HER/HOR)kinetics is vital to practicing the renewable hydrogen cycle in alkaline media.Recently,intensive research has demonstrated that interface engineering is of critical significance for improving the performance of heterostructured electrocatalysts particularly toward the electrochemical reactions involving multiple reaction intermediates like alkaline hydrogen electrocatalysis,and the research advances also bring substantial non-trivial fundamental insights accordingly.Herein,we review the current status of interface engineering with respect to developing efficient heterostructured electrocatalysts for alkaline HER and HOR.Two major subjects—how interface engineering promotes the reaction kinetics and what fundamental insights interface engineering has brought into alkaline HER and HOR—are discussed.Specifically,heterostructured electrocatalysts with abundant interfaces have shown substantially accelerated alkaline hydrogen electrocatalysis kinetics owing to the synergistic effect from different components,which could balance the adsorption/desorption behaviors of the intermediates at the interfaces.Meanwhile,interface engineering can effectively tune the electronic structures of the active sites via electronic interaction,interfacial bonding,and lattice strain,which would appropriately optimize the binding energy of targeted intermediates like hydrogen.Furthermore,the confinement effect is critical for delivering high durability by sustaining high density of active sites.At last,our own perspectives on the challenges and opportunities toward developing efficient heterostructured electrocatalysts for alkaline hydrogen electrocatalysis are provided.展开更多
Remarkable phenomena arise at well-defined heterostructures, composed of transition metal oxides, which is absent in the bulk counterpart, providing us a paradigm for exploring the various electron correlation effects...Remarkable phenomena arise at well-defined heterostructures, composed of transition metal oxides, which is absent in the bulk counterpart, providing us a paradigm for exploring the various electron correlation effects. The functional properties of such heterostructures have attracted much attention in the microelectronic and renewable energy fields. Exotic and unexpected states of matter could arise from the reconstruction and coupling among lattice, charge, orbital and spin at the interfaces. Aberration-corrected scanning transmission electron microscopy （STEM） is a powerful tool to visualize the lattice structure and electronic structure at the atomic scale. In the present study some novel phenomena of oxide heterostructures at the atomic scale are summarized and pointed out from the perspective of electron microscopy.展开更多
Developing highly efficient,cost-effective,and stable electrocatalysts for hydrogen evolution reaction(HER)is of considerable importance but remains challenging.Herein,we report the fabrication of a robust Ru-based el...Developing highly efficient,cost-effective,and stable electrocatalysts for hydrogen evolution reaction(HER)is of considerable importance but remains challenging.Herein,we report the fabrication of a robust Ru-based electrocatalyst,which comprises heterostructured Ru-Ru_(2)P nanoparticles that are embedded in the N,P-codoped carbon nanofibers(CNFs),through a synthetic strategy involving electrospinning and temperature-controlled pyrolysis treatment.The as-prepared Ru-Ru_(2)P catalyst(Ru-Ru_(2)P@CNFs)shows excellent HER catalytic activities with low overpotentials of 11 and 14 mV in acidic and alkaline media,respectively,to achieve a current density of 10 mA cm^(−2),which are superior to the individual components of pure Ru and Ru_(2)P catalysts.Density functional theory calculations demonstrate the existence of electronic coupling effect between Ru and Ru_(2)P at the heterointerfaces,leading to a well-modulated electronic structure with optimized hydrogen adsorption strength and enhanced electrical conductivity for efficient HER electrocatalysis.In addition,the overall synthetic strategy can be generalized for the synthesis of a series of transitional metal phosphide-based nanofibers,thereby holding a remarkable capacity for various potential applications.展开更多
The reliable information about interface energetics of organic materials, especially the energy level alignment at organic heterostructures is of pronounced importance for unraveling the photon harvesting and charge s...The reliable information about interface energetics of organic materials, especially the energy level alignment at organic heterostructures is of pronounced importance for unraveling the photon harvesting and charge separation process in organic photovoltaic(OPV) cells. This article provides an overview of interface energetics at typical planar and mixed donor-acceptor heterostructures, perovskite/organic hybrid interfaces, and their contact interfaces with charge collection layers. The substrate effect on energy level offsets at organic heterostructures and the processes that control and limit the OPV operation are presented. Recent efforts on interface engineering with electrical doping are also discussed.展开更多
High interfacial energy Li^(0)-electrolyte interface contributes to larger Li^(0) nucleation embryos and a more stable interface,so the interfacial energy is essential for highly reversible Li^(0) deposition/stripping...High interfacial energy Li^(0)-electrolyte interface contributes to larger Li^(0) nucleation embryos and a more stable interface,so the interfacial energy is essential for highly reversible Li^(0) deposition/stripping.Herein,a high interfacial-energy artificial solid electrolyte interphase(SEI)with rich LiF embedded in lithiated poly-2-acrylamido-2-methylpropane sulfonic acid(PAMPS-Li)network is designed to realize favorable Li^(0) nucleation and rapid desolvation of Li+simultaneously.The Li-F bonds in LiF(001)exhibit stronger ion-dipole interactions with Li atoms,offering higher interfacial energies.When the growth surface energy and total interfacial energy of Li^(0) are balanced,the high interfacial energy SEI with abundant LiF can promote the formation of larger Li^(0) nucleation embryos.In addition,the PAMPS-Li with immobilized anions presents weaker interaction with Li^(0) and possesses higher polymer-Li interfacial energy,and its amide and sulfonic acid groups exhibit higher binding energies with Li^(+).Therefore,PAMPS-Li can easily promote the Li+to escape from the solvent sheath and weaken the desolvation energy barrier.The highly reversible Li^(0) deposition behavior with restricted side reactions is achieved based on the synergistic modification of high interfacial energy SEI with heterostructure.Most importantly,lifespan of multi-layered Li^(0) pouch cell(330 Wh kg-1)with a low N/P ratio(1.67)is over 100 cycles,verifying its potential practical application.展开更多
Direct growth of graphene on insulators is expected to yield significant improvements in performance of graphene-based electronic and spintronic devices. In this study, we successfully reveal the atomic arrangement an...Direct growth of graphene on insulators is expected to yield significant improvements in performance of graphene-based electronic and spintronic devices. In this study, we successfully reveal the atomic arrangement and electronic properties of a coherent heterostructure of single-layer graphene and α-Al2O3（0001）. The analysis of the atomic arrangement of single-layer graphene on α-Al2O3（0001） revealed an apparentcontradiction. The in-plane analysis shows that single-layer graphene grows not in a single-crystalline epitaxial manner, but rather in polycrystalline form, with two strongly pronounced preferred orientations. This suggests relatively weak interfacial interactions are operative. However, we demonstrate that unusually strong physical interactions between graphene and α-Al2O3（0001） exist, as evidenced by the small separation between the graphene and the α-Al2O3（0001） surface. The interfacial interaction is shown to be dominated by the electrostatic forces involved in the graphene n-system and the unsaturated electrons of the topmost O layer of α-Al2O3（0001）, rather than the van der Waals interactions. Such features causes graphene hole doping and enable the graphene to slide on the α-Al2O3（0001） surface with only a small energy barrier despite the strong interfacial interactions.展开更多
基金This work was supported by the CERG, RGC, HKSAR （projects 7134/99P and 7107/02P）the National Science Foundation of China （No.10425072）.
文摘Annealing study of the Al/GaSb system was performed by using a slow positron beam and the measurement of X-ray diffraction. The S parameter against positron energy data were fitted by a three layer model （Al/interface/GaSb）. It was found there was a ～5 nm interfacial at the region between the Al layer and bulk in the sample of as-deposited. After the 400 ℃ annealing, this interfacial region extends to over 40 nm and S parameter dramatically drops. This is possibly due to a new phase formation induced by the atoms＇inter-diffusion at the interface. The annealing out of the open volume defects in the Al layer was revealed by the decrease of the S parameter and the increase of the effective diffusion length of the Al layer. Annealing behaviors of Sb and Lb of the GaSb bulk showed the annealing out of positron traps at 250 ℃. However,further annealing at 400 ℃ induces formation of positron traps, which are possibly another kind of VGarelated defect and the positron shallow trap GaSb anti-site. The results of the X-ray diffraction experiment verified the conclusion of obtained by using positron technology.
基金Projects(11672195,51301092) supported by the National Natural Science Foundation of ChinaProject(2016JQ0047) supported by Sichuan Youth Science and Technology Foundation,China
文摘Heterogeneous-structured Cu samples composed of coarse-grained(CG) and ultrafine-grained(UFG) domains with a transitional interface were fabricated by friction stir processing, in order to investigate the effect of interface constraint on the yielding and fracture behaviors. Tensile test revealed that the synergetic strengthening induced by elastic/plastic interaction between incompatible domains increases with increasing the area of constraint interface. The strain distribution near interface and the fracture morphology were characterized using digital image correlation technique and scanning electron microscopy, respectively. Fracture dimples preferentially formed at the interface, possibly due to extremely high triaxial stress and strain accumulation near the interface. Surprisingly, the CG domain was fractured by pure shear instead of the expected voids growth caused by tensile stress.
文摘Although photocatalytic water splitting has excellent potential for converting solar energy into chemical energy,the challenging charge separation process and sluggish surface catalytic reactions significantly limit progress in solar energy conversion using semiconductor photocatalysts.Herein,we demonstrate a feasible strategy involving the surface assembly of cobalt oxide species(CoO_(x))on a visible-light-responsive Cd_(0.9)Zn_(0.1)S(CZS)photocatalyst to fabricate a hierarchical CZS@CoO_(x) heterostructure.The unique hierarchical structure effectively accelerates the directional transfer of photogenerated charges,reducing charge recombination through the smooth interfacial heterojunction between CZS and CoO_(x),as evidenced by photoluminescence(PL)spectroscopy and various electrochemical characterizations.The surface cobalt species on the CZS material also act as efficient cocatalysts for photocatalytic hydrogen production,with activity even higher than that of noble metals.The well-defined CZS@CoO_(x) heterostructure not only enhances the interfacial separation of photoinduced charges,but also improves surface catalytic reactions.This leads to superior photocatalytic performances,with an apparent quantum efficiency of 20%at 420 nm for visible-light-driven hydrogen generation,which is one of the highest quantum efficiencies measured among noble-metal-free photocatalysts.Our work presents a potential pathway for controlling complex charge separation and catalytic reaction processes in photocatalysis,guiding the practical development of artificial photocatalysts for successful transformation of solar to chemical energy.
基金funding support from “Hundred Talents Program” of Zhejiang University, Chinapartially supported by the Australian Research Council (ARC) Discovery Project (DP200100365)
文摘Boosting the alkaline hydrogen evolution and oxidation reaction(HER/HOR)kinetics is vital to practicing the renewable hydrogen cycle in alkaline media.Recently,intensive research has demonstrated that interface engineering is of critical significance for improving the performance of heterostructured electrocatalysts particularly toward the electrochemical reactions involving multiple reaction intermediates like alkaline hydrogen electrocatalysis,and the research advances also bring substantial non-trivial fundamental insights accordingly.Herein,we review the current status of interface engineering with respect to developing efficient heterostructured electrocatalysts for alkaline HER and HOR.Two major subjects—how interface engineering promotes the reaction kinetics and what fundamental insights interface engineering has brought into alkaline HER and HOR—are discussed.Specifically,heterostructured electrocatalysts with abundant interfaces have shown substantially accelerated alkaline hydrogen electrocatalysis kinetics owing to the synergistic effect from different components,which could balance the adsorption/desorption behaviors of the intermediates at the interfaces.Meanwhile,interface engineering can effectively tune the electronic structures of the active sites via electronic interaction,interfacial bonding,and lattice strain,which would appropriately optimize the binding energy of targeted intermediates like hydrogen.Furthermore,the confinement effect is critical for delivering high durability by sustaining high density of active sites.At last,our own perspectives on the challenges and opportunities toward developing efficient heterostructured electrocatalysts for alkaline hydrogen electrocatalysis are provided.
基金supported by the National Key Basic Research Program of China(Grant No.2014CB921002)the Strategic Priority Research Program of Chinese Academy of Sciences(Grant No.XDB07030200)the National Natural Science Foundation of China(Grant Nos.51522212 and51421002)
文摘Remarkable phenomena arise at well-defined heterostructures, composed of transition metal oxides, which is absent in the bulk counterpart, providing us a paradigm for exploring the various electron correlation effects. The functional properties of such heterostructures have attracted much attention in the microelectronic and renewable energy fields. Exotic and unexpected states of matter could arise from the reconstruction and coupling among lattice, charge, orbital and spin at the interfaces. Aberration-corrected scanning transmission electron microscopy （STEM） is a powerful tool to visualize the lattice structure and electronic structure at the atomic scale. In the present study some novel phenomena of oxide heterostructures at the atomic scale are summarized and pointed out from the perspective of electron microscopy.
基金financially supported by the Natural Science Foundation of Zhejiang Province (LQ20B030001 and LY20E020002)China Postdoctoral Science Foundation (2021M702305)。
文摘Developing highly efficient,cost-effective,and stable electrocatalysts for hydrogen evolution reaction(HER)is of considerable importance but remains challenging.Herein,we report the fabrication of a robust Ru-based electrocatalyst,which comprises heterostructured Ru-Ru_(2)P nanoparticles that are embedded in the N,P-codoped carbon nanofibers(CNFs),through a synthetic strategy involving electrospinning and temperature-controlled pyrolysis treatment.The as-prepared Ru-Ru_(2)P catalyst(Ru-Ru_(2)P@CNFs)shows excellent HER catalytic activities with low overpotentials of 11 and 14 mV in acidic and alkaline media,respectively,to achieve a current density of 10 mA cm^(−2),which are superior to the individual components of pure Ru and Ru_(2)P catalysts.Density functional theory calculations demonstrate the existence of electronic coupling effect between Ru and Ru_(2)P at the heterointerfaces,leading to a well-modulated electronic structure with optimized hydrogen adsorption strength and enhanced electrical conductivity for efficient HER electrocatalysis.In addition,the overall synthetic strategy can be generalized for the synthesis of a series of transitional metal phosphide-based nanofibers,thereby holding a remarkable capacity for various potential applications.
基金supported by the National Basic Research Program of China (2014CB932600)the National Natural Science Foundation of China (91433116, 11474214)+2 种基金Jiangsu Science and Technology Department (BK20140053)Bureau of Science and Technology of Suzhou Municipality (SYG201525, ZXG201422)the project of the Priority Academic Program Development (PAPD) of Jiangsu Higher Education Institutions
文摘The reliable information about interface energetics of organic materials, especially the energy level alignment at organic heterostructures is of pronounced importance for unraveling the photon harvesting and charge separation process in organic photovoltaic(OPV) cells. This article provides an overview of interface energetics at typical planar and mixed donor-acceptor heterostructures, perovskite/organic hybrid interfaces, and their contact interfaces with charge collection layers. The substrate effect on energy level offsets at organic heterostructures and the processes that control and limit the OPV operation are presented. Recent efforts on interface engineering with electrical doping are also discussed.
基金supported by the National Natural Science Foundation of China(22109030 and 21875195)Guangdong Basic and Applied Basic Research Foundation(2019A1515111069 and 2021A1515010177)the Key Research and Development Program of Yunnan Province(202103AA080019)。
文摘High interfacial energy Li^(0)-electrolyte interface contributes to larger Li^(0) nucleation embryos and a more stable interface,so the interfacial energy is essential for highly reversible Li^(0) deposition/stripping.Herein,a high interfacial-energy artificial solid electrolyte interphase(SEI)with rich LiF embedded in lithiated poly-2-acrylamido-2-methylpropane sulfonic acid(PAMPS-Li)network is designed to realize favorable Li^(0) nucleation and rapid desolvation of Li+simultaneously.The Li-F bonds in LiF(001)exhibit stronger ion-dipole interactions with Li atoms,offering higher interfacial energies.When the growth surface energy and total interfacial energy of Li^(0) are balanced,the high interfacial energy SEI with abundant LiF can promote the formation of larger Li^(0) nucleation embryos.In addition,the PAMPS-Li with immobilized anions presents weaker interaction with Li^(0) and possesses higher polymer-Li interfacial energy,and its amide and sulfonic acid groups exhibit higher binding energies with Li^(+).Therefore,PAMPS-Li can easily promote the Li+to escape from the solvent sheath and weaken the desolvation energy barrier.The highly reversible Li^(0) deposition behavior with restricted side reactions is achieved based on the synergistic modification of high interfacial energy SEI with heterostructure.Most importantly,lifespan of multi-layered Li^(0) pouch cell(330 Wh kg-1)with a low N/P ratio(1.67)is over 100 cycles,verifying its potential practical application.
基金We are grateful to the ＇Chebishev＇ and ＇Lomonosov＇ supercomputers of Moscow State University for providing the chance of using a cluster computer for quantum-chemical calculations. S.E. thanks Prof. H. Kondo （Keio University） and Prof. T. Shimada （Hirosaki University） for NIXSW measurements. This work was partly supported by Grants-in-Aid for Young Scientists B （Grant No. 22760033） from the Japan Society for the Promotion of Science. The present work has been performed under the approval of the Photon Factory Program Advisory Committee （PF PAC Nos. 2010G660 and 2012G741）. P.V.A., P.B.S. and L.Y.A. acknowledge the support from the Russian Science Foundation （project No. 14-13-00139）.
文摘Direct growth of graphene on insulators is expected to yield significant improvements in performance of graphene-based electronic and spintronic devices. In this study, we successfully reveal the atomic arrangement and electronic properties of a coherent heterostructure of single-layer graphene and α-Al2O3（0001）. The analysis of the atomic arrangement of single-layer graphene on α-Al2O3（0001） revealed an apparentcontradiction. The in-plane analysis shows that single-layer graphene grows not in a single-crystalline epitaxial manner, but rather in polycrystalline form, with two strongly pronounced preferred orientations. This suggests relatively weak interfacial interactions are operative. However, we demonstrate that unusually strong physical interactions between graphene and α-Al2O3（0001） exist, as evidenced by the small separation between the graphene and the α-Al2O3（0001） surface. The interfacial interaction is shown to be dominated by the electrostatic forces involved in the graphene n-system and the unsaturated electrons of the topmost O layer of α-Al2O3（0001）, rather than the van der Waals interactions. Such features causes graphene hole doping and enable the graphene to slide on the α-Al2O3（0001） surface with only a small energy barrier despite the strong interfacial interactions.
