Gradient magnetic heterointerfaces have injected infinite vitality in optimizing impedance matching,adjusting dielectric/magnetic resonance and promoting electromagnetic(EM)wave absorption,but still exist a significan...Gradient magnetic heterointerfaces have injected infinite vitality in optimizing impedance matching,adjusting dielectric/magnetic resonance and promoting electromagnetic(EM)wave absorption,but still exist a significant challenging in regulating local phase evolution.Herein,accordion-shaped Co/Co_(3)O_(4)@N-doped carbon nanosheets(Co/Co_(3)O_(4)@NC)with gradient magnetic heterointerfaces have been fabricated via the cooperative high-temperature carbonization and lowtemperature oxidation process.The results indicate that the surface epitaxial growth of crystal Co_(3)O_(4) domains on local Co nanoparticles realizes the adjustment of magnetic-heteroatomic components,which are beneficial for optimizing impedance matching and interfacial polarization.Moreover,gradient magnetic heterointerfaces simultaneously realize magnetic coupling,and long-range magnetic diffraction.Specifically,the synthesized Co/Co_(3)O_(4)@NC absorbents display the strong electromagnetic wave attenuation capability of−53.5 dB at a thickness of 3.0 mm with an effective absorption bandwidth of 5.36 GHz,both are superior to those of single magnetic domains embedded in carbon matrix.This design concept provides us an inspiration in optimizing interfacial polarization,regulating magnetic coupling and promoting electromagnetic wave absorption.展开更多
Manganese-based material is a prospective cathode material for aqueous zinc ion batteries(ZIBs)by virtue of its high theoretical capacity,high operating voltage,and low price.However,the manganese dissolution during t...Manganese-based material is a prospective cathode material for aqueous zinc ion batteries(ZIBs)by virtue of its high theoretical capacity,high operating voltage,and low price.However,the manganese dissolution during the electrochemical reaction causes its electrochemical cycling stability to be undesirable.In this work,heterointerface engineering-induced oxygen defects are introduced into heterostructure MnO_(2)(δa-MnO_(2))by in situ electrochemical activation to inhibit manganese dissolution for aqueous zinc ion batteries.Meanwhile,the heterointerface between the disordered amorphous and the crystalline MnO_(2)ofδa-MnO_(2)is decisive for the formation of oxygen defects.And the experimental results indicate that the manganese dissolution ofδa-MnO_(2)is considerably inhibited during the charge/discharge cycle.Theoretical analysis indicates that the oxygen defect regulates the electronic and band structure and the Mn-O bonding state of the electrode material,thereby promoting electron transport kinetics as well as inhibiting Mn dissolution.Consequently,the capacity ofδa-MnO_(2)does not degrade after 100 cycles at a current density of 0.5 Ag^(-1)and also 91%capacity retention after 500cycles at 1 Ag^(-1).This study provides a promising insight into the development of high-performance manganese-based cathode materials through a facile and low-cost strategy.展开更多
The pervasive adoption of 5th generation mobile communication technology propels electromagnetic wave(EW)absorbents to achieve high-level performance.The heterointerface construction is crucial to the improvement of a...The pervasive adoption of 5th generation mobile communication technology propels electromagnetic wave(EW)absorbents to achieve high-level performance.The heterointerface construction is crucial to the improvement of absorption ability.Herein,a series of ultralight composites with rational heterointerfaces(Co/ZnO@N-doped C/layer-stacked C,MSC)is fabricated by calcination with ration-al construction of sugarcane and CoZn-zeolitic imidazolate framework(ZIF).The components and structures of as-prepared composites were investigated,and their electromagnetic parameters could be adjusted by the content of CoZn-ZIFs.All composites possess excellent EW absorption performance,especially MSC-3.The optimal minimum reflection loss and effective absorption band of MSC-3 can reach−42 dB and 7.28 GHz at the thickness of only 1.6 mm with 20wt%filler loading.This excellent performance is attributed to the syner-gistic effect of dielectric loss stemming from the multiple heterointerfaces and magnetic loss induced by magnetic single Co.The sugar-cane-derived layer-stacked carbon has formed consecutive conductive networks and has further dissipated the electromagnetic energy through multiple reflection and conduction losses.Moreover,the simulated radar cross section(RCS)technology manifests that MSC-3 possesses outstanding EW attenuation capacity under realistic far-field conditions.This study provides a strategy for building efficient ab-sorbents based on biomass.展开更多
Although metallic rhodium(Rh)is regarded as a promising platinum-alternative anode catalyst of direct methanol fuel cell(DMFC),the conventional"particle-to-face"contact model between Rh and matrix largely li...Although metallic rhodium(Rh)is regarded as a promising platinum-alternative anode catalyst of direct methanol fuel cell(DMFC),the conventional"particle-to-face"contact model between Rh and matrix largely limits the overall electrocatalytic performance due to their insufficient cooperative effects.Herein,we report a controllable and robust heterointerface engineering strategy for the bottom-up fabrication of rhombic Rh nanosheets in situ confined on Ti_3C_(2)T_x MXene nanolamellas(Rh NS/MXene)via a convenient stereoassembly process.This unique design concept gives the resulting 2D/2D Rh NS/MXene heterostructure intriguing textural features,including large accessible surface areas,strong"face-toface"interfacial interactions,homogeneous Rh nanosheet distribution,ameliorative electronic structure,and high electronic conductivity.As a consequence,the as-prepared Rh NS/MXene nanoarchitectures exhibit exceptional electrocatalytic methanol oxidation properties in terms of a large electrochemically active surface area of 126.2 m~2 g_(Rh)~(-1),a high mass activity of 1056.9 mA mg_(Rh)-~1,and a long service life,which significantly outperform those of conventional particle-shaped Rh catalysts supported by carbon black,carbon nanotubes,reduced graphene oxide,and MXene matrixes as well as the commercial Pt nanoparticle/carbon black and Pd nanoparticle/carbon black catalysts with the same noble metal loading amount.Density functional theory calculations further demonstrate that the direct electronic interaction at the well-contacted 2D/2D heterointerfaces effectively enhances the adsorption energy of Rh nanosheets and induces a left shift of the d-band center,thereby making the Rh NS/MXene configuration suffer less from CO poisoning.This work highlights the importance of rational heterointerface design in the construction of advanced noble metal/MXene electrocatalysts,which may provide new avenues for developing the next-generation DMFC devices.展开更多
Electrocatalytic CO_(2)-to-formate conversion is considered an economically viable process.In general,Zn-based nanomaterials are well-known to be highly efficient electrocatalysts for the conversion of CO_(2) to CO,bu...Electrocatalytic CO_(2)-to-formate conversion is considered an economically viable process.In general,Zn-based nanomaterials are well-known to be highly efficient electrocatalysts for the conversion of CO_(2) to CO,but seldom do they exhibit excellent selectivity toward formate.In this article,we demonstrate that a heterointerface catalyst ZnO/ZnSnO3 with nanosheet morphology shows enhanced selectivity with a maximum Faradaic efficiency(FE)of 86%at−0.9 V versus reversible hydrogen electrode and larger current density for the conversion of CO_(2) to formate than pristine ZnO and ZnSnO3.In particular,the FEs of the C1 products(CO+HCOO−)exceed 98%over the potential window.The experimental measurements combined with theoretical calculations revealed that the ZnO in ZnO/ZnSnO3 heterojunction delivers the valence electron depletion and accordingly optimizes Zn d-band center,which results in moderate Zn-O hybridization of HCOO*and weakened Zn-C hybridization of competing COOH*,thus greatly boosting the HCOOH generation.Our study highlights the importance of charge redistribution in catalysts on the selectivity of electrochemical CO_(2) reduction.展开更多
The development of wearable multifunctional electromagnetic protective fabrics with multifunctional,low cost,and high efficiency remains a challenge.Here,inspired by the unique flower branch shape of“Thunberg’s mead...The development of wearable multifunctional electromagnetic protective fabrics with multifunctional,low cost,and high efficiency remains a challenge.Here,inspired by the unique flower branch shape of“Thunberg’s meadowsweet”in nature,a nanofibrous composite membrane with hierarchical structure was constructed.Integrating sophisticated 0D@2D@1D hierarchical structures with multiple heterointerfaces can fully unleash the multifunctional application potential of composite membrane.The targeted induction method was used to precisely regulate the formation site and morphology of the metal–organic framework precursor,and intelligently integrate multiple heterostructures to enhance dielectric polarization,which improves the impedance matching and loss mechanisms of the electromagnetic wave absorbing materials.Due to the synergistic enhancement of electrospinning-derived carbon nanofiber“stems”,MOF-derived carbon nanosheet“petals”and transition metal selenide nano-particle“stamens”,the CoxSey/NiSe@CNSs@CNFs(CNCC)composite membrane obtains a minimum reflection loss value(RL_(min))of-68.40 dB at 2.6 mm and a maximum effective absorption bandwidth(EAB)of 8.88 GHz at a thin thickness of 2.0 mm with a filling amount of only 5 wt%.In addition,the multi-component and hierarchical heterostructure endow the fibrous membrane with excellent flexibility,water resistance,thermal management,and other multifunctional properties.This work provides unique perspectives for the precise design and rational application of multifunctional fabrics.展开更多
Improving the cycling stability of metal sulfide-based anode materials at high rate is of great significance for advanced sodium ion batteries.However,the sluggish reaction kinetics is a big obstacle for the developme...Improving the cycling stability of metal sulfide-based anode materials at high rate is of great significance for advanced sodium ion batteries.However,the sluggish reaction kinetics is a big obstacle for the development of high-performance sodium storage electrodes.Herein,we have rationally engineered the heterointerface by designing the Fe1?xS/MoS2 heterostructure with abundant“ion reservoir”to endow the electrode with excellent cycling stability and rate capability,which is proved by a series of in and ex situ electrochemical investigations.Density functional theory calculations further reveal that the heterointerface greatly decreases sodium ion diffusion barrier and facilitates charge-transfer kinetics.Our present findings not only provide a deep analysis on the correlation between the structure and performance,but also draw inspiration for rational heterointerface engineering toward the next-generation high-performance energy storage devices.展开更多
Zinc-air batteries(ZABs) with high energy density and safety are promising as next-generation energy storage systems, while their applications are severely hindered by the sluggish reaction kinetic of air cathodes. De...Zinc-air batteries(ZABs) with high energy density and safety are promising as next-generation energy storage systems, while their applications are severely hindered by the sluggish reaction kinetic of air cathodes. Developing a bifunctional catalyst with high activity and durability is an effective strategy to address the above challenges. Herein, a Co_(3)O_(4)/Mn_(3)O_(4) nanohybrid with heterointerfaces is designed as advanced cathode catalyst for ZABs. Density functional theory calculations show the heterogeneous interface between Co_(3)O_(4)/Mn_(3)O_(4) can improve the dynamics of carrier transport and thus enhancing the catalytic activity and durability. The Co_(3)O_(4)/Mn_(3)O_(4) catalyst anchored on reduced graphene oxide(rGO)exhibits high oxygen reduction reaction(ORR) activity with a half-wave potential of 0.86 V, and excellent oxygen evolution reaction(OER) activity with the potential of 1.59 V at 10 mA cm^(-2) , which are comparable to the commercial noble metal catalysts. The improved ORR/OER catalytic activity is ascribed to the synergistic effect of heterointerfaces between Co_(3)O_(4) and Mn_(3)O_(4)as well as the improved conductivity and contact area of oxygen/catalysts/electrolytes three-phase interface by r GO. Furthermore, a home-made ZAB based on Co_(3)O_(4)/Mn_(3)O_(4)/r GO shows a high open circuit voltage of 1.54 V, a large power density of 194.6 mW cm^(-2) and good long-term cycling stability of nearly 400 h at 5 mA cm^(-2) , which affords a promising bifunctional oxygen catalyst for rechargeable ZABs.展开更多
Cd1-xZnxS/Cu2ZnSnS4 (CZTS)-based thin film solar cells usually use CdS as a buffer layer, but due to its smaller band gap (2.4 eV), CdS film has been replaced with higher band gap materials. The cadmium zinc sulfi...Cd1-xZnxS/Cu2ZnSnS4 (CZTS)-based thin film solar cells usually use CdS as a buffer layer, but due to its smaller band gap (2.4 eV), CdS film has been replaced with higher band gap materials. The cadmium zinc sulfide (CdZnS) ternary compound has a higher band gap than other compounds, which leads to a decrease in window absorption loss. In this paper, the band offsets at Cd1-xZnxS/CuzZnSnS4 (CZTS) heterointerface are calculated by the first-principles, density- functional and pseudopotential method. The band offsets at Cdl xZnxS/CZTS heterointerface are tuned by controlling the composition of Zn in Cd1-xZnxS alloy, the calculated valence band offsets are small, which is consistent with the commonanion rule. The favorable heterointerface of type-I with a moderate barrier height (〈 0.3 eV) can be obtained by controlling the composition of Zn in Cdl-xZnxS alloy between 0.25 and 0.375.展开更多
Tailoring the electronic states of the Al N/diamond interface is critical to the development of the next-generation semiconductor devices such as the deep-ultraviolet light-emitting diode, photodetector, and high-powe...Tailoring the electronic states of the Al N/diamond interface is critical to the development of the next-generation semiconductor devices such as the deep-ultraviolet light-emitting diode, photodetector, and high-power high-frequency field-effect transistor. In this work, we investigate the electronic properties of the semipolar plane Al N(11^-01)/diamond heterointerfaces by using the first-principles method with regard to different terminated planes of Al N and surface structures of diamond(100) plane. A large number of gap states exist at semi-polar plane Al N(11^-01)/diamond heterointerface, which results from the N 2 p and C 2 s2 p orbital states. Besides, the charge transfer at the interface strongly depends on the surface termination of diamond, on which hydrogen suppresses the charge exchange at the interface. The band alignments of semi-polar plane Al N(11^-01)/diamond show a typical electronic character of the type-Ⅱ staggered band configuration. The hydrogen-termination of diamond markedly increases the band offset with a maximum valence band offset of 2.0 e V and a conduction band offset of 1.3 e V for the semi-polar plane N–Al N(11^-01)/hydrogenated diamond surface. The unique band alignment of this Type-Ⅱ staggered system with the higher CBO and VBO of the semi-polar Al N/HC(100) heterostructure provides an avenue to the development of robust high-power high-frequency power devices.展开更多
The two-dimensional electron gas at SrTiO3-based heterointerfaces has received a great deal of attention in recent years owing to their potential for the exploration of emergent physics and the next generation of elec...The two-dimensional electron gas at SrTiO3-based heterointerfaces has received a great deal of attention in recent years owing to their potential for the exploration of emergent physics and the next generation of electronics. One of the most fascinating aspects in this system is that the light, as a powerful external perturbation, can modify its transport properties. Recent studies have reported that SrTiO3-based heterointerfaces exhibit the persistent photoconductivity and can be tuned by the surface and interface engineering. These researches not only reveal the intrinsic physical mechanisms in the photoresponsive process, but also highlight the ability to be used as a tool for novel all-oxide optical devices. This review mainly contraposes the studies of photoresponse at SrTiO3-based heterointerfaces.展开更多
The development of non-platinum group metal(non-PGM)and efficient multifunctional electrocatalysts for oxygen reduction reaction(ORR),oxygen evolution reaction(OER),and hydrogen evolution reaction(HER)with high activi...The development of non-platinum group metal(non-PGM)and efficient multifunctional electrocatalysts for oxygen reduction reaction(ORR),oxygen evolution reaction(OER),and hydrogen evolution reaction(HER)with high activity and stability remains a great challenge.Herein,by in-situ transforming silver manganese composite oxide heterointerface into boosted Mott-Schottky heterointerface through a facile carbon reduction strategy,a nanorod-like silver/manganese oxide with superior multifunctional catalytic activities for ORR,OER and HER and stability was obtained.The nanorod-like silver/manganese oxide with Mott-Schottky heterointerface(designated as Ag/Mn_(3)O_(4))exhibits an ORR half-wave potential of 0.831 V(vs.RHE)in 0.1 M KOH,an OER overpotential of 338 mV and a HER overpotential of 177 mV at the current density of 10 mA·cm^(-2)in 1 M KOH,contributing to its noble-metal benchmarks comparable performance in aqueous aluminum-air(Al-air)battery and laboratorial overall water splitting electrolytic cell.Moreover,in-situ electrochemical Raman and synchrotron radiation spectroscopic measurements were conducted to further illustrate the catalytic mechanism of Ag/Mn_(3)O_(4)Mott-Schottky heterointerface towards various electrocatalytic reactions.At the heterointerface,the Ag phase serves as the electron donor and the active phase for ORR and HER,while the Mn_(3)O_(4)phase serves as the electron acceptor and the active phase for OER,respectively.This work deepens the understanding of the Mott-Schottky effect on electrocatalysis and fills in the gap in fundamental physical principles that are behind measured electrocatalytic activity,which offers substantial implications for the rational design of cost-effective multifunctional electrocatalysts with Mott-Schottky effect.展开更多
To promote the practices of perovskite photovoltaics,it requires to develop efficient perovskite solar cells(PVSCs)standing long-time operation under the adverse environments.Herein,we demonstrate that the tailor-made...To promote the practices of perovskite photovoltaics,it requires to develop efficient perovskite solar cells(PVSCs)standing long-time operation under the adverse environments.Herein,we demonstrate that the tailor-made conjugated polymers as conductive adhesives stabilized the originally redox-reactive heterointerface between perovskite and metal oxide,facilitating the access of efficient and stable inverted PVSCs.It was revealed that bithiophene and phenyl alternating conjugated polymers with partial glycol chains atop of the metal oxide layer has resulted in effective organic-inorganic hybrid hole transporting bilayers,which allow maintaining efficient hole extraction and transport,meanwhile preventing halide migration to directly contact with the nickel oxide(NiO_(x))layer.As a result,the corresponding inverted PVSCs with the organic-inorganic hole transporting bilayers have achieved an excellent power conversion efficiency of 23.22%,outperforming 20.65% of bare NiO_(x)-based devices.Moreover,the encapsulated PVSCs with organic-inorganic bilayers exhibited the excellent photostability with 91% of the initial efficiency after 1000-h one-sun equivalent illumination in ambient conditions.Overall,this work provides new insights into stabilizing the vulnerable heterointerface for perovskite solar cells.展开更多
To improve the synergistic effect between dielectric and magnetic loss is a practical and effective way in optimizing electromagnetic wave absorbing materials.The composites of metal particles and carbon ligands deriv...To improve the synergistic effect between dielectric and magnetic loss is a practical and effective way in optimizing electromagnetic wave absorbing materials.The composites of metal particles and carbon ligands derived from metal organic frameworks have gained wide attention.In this study,Co particles and multiwalled carbon nanotubes(CNT)were successfully synthesized covering the surface of silicon carbide(SiC)fibers,and the morphology,interfaces and electromagnetic wave absorption performance were explored.For sample SiC@Co/CNT,the minimum reflection loss value can reach-70.22 dB at 11.21 GHz with the thickness of 2.12 mm.The effective absorbing bandwidth can reach up to 6.03 GHz with the thickness of 1.71 mm,which covers the entire Ku band.It brings more interfaces between Co particles and CNTs as well as SiC fibers and Co/C nanosheets.The interfacial polarization has been hugely enhanced,and the microwave absorbing properties have been improved.This article reports on the impedance matching of magnetic and non-magnetic components and the heterointerface engineering,which can be effective strategy and inspiration to illustrate the relationship between components,structures and functions of electromagnetic wave absorbing materials.展开更多
The heterointerface engineering involving different components or phases represents a desirable strategy for enhancing the sluggish kinetics of hydrogen evolution reaction(HER).However,constructing desired heterointer...The heterointerface engineering involving different components or phases represents a desirable strategy for enhancing the sluggish kinetics of hydrogen evolution reaction(HER).However,constructing desired heterointerfaces and elucidating the reaction mechanisms on the interface remains a considerable challenge.In this work,we propose a straightforward electrochemical synthesis strategy to prepare the nickel sulfide-based heterointerfaces for HER.The mechanism of electrochemical synthesis is revealed,wherein metal-thiourea species can be formed at the cathode potential and subsequently oxidized to nickel sulfides at the anode potentials.Leveraging this mechanism,a range of nickel sulfides,including NiS,Ni_(3)S_(2)/NiS,Ni/Ni_(3)S_(2)and Ni_(3)S_(2),have been successfully synthesized by tuning the potential range of cyclic voltammetry.Among these,the obtained Ni_(3)S_(2)/NiS@CC(CC:carbon cloth)exhibits the smallest overpotential of84 mV at 10 mA·cm^(-2)and high stability.Theoretical calculations further reveal that the combination of NiS and Ni_(3)S_(2)induces electron redistribution at the interface,and thus the Volmer process is effectively promoted with faster water dissociation and OH desorption kinetics.Significantly,the simplicity method coupled with a clear synthesis mechanism and outstanding HER performance highlights its promising potential for practical applications.展开更多
Catalyst–support interaction plays a crucial role in improving the catalytic activity of oxygen evolution reaction(OER).Here we modulate the catalyst–support interaction in polyaniline-supported Ni_(3)Fe oxide(Ni_(3...Catalyst–support interaction plays a crucial role in improving the catalytic activity of oxygen evolution reaction(OER).Here we modulate the catalyst–support interaction in polyaniline-supported Ni_(3)Fe oxide(Ni_(3)Fe oxide/PANI)with a robust hetero-interface,which significantly improves oxygen evolution activities with an overpotential of 270 mV at 10 mA cm^(-2)and specific activity of 2.08 mA cm_(ECSA)^(-2)at overpotential of 300 mV,3.84-fold that of Ni_(3)Fe oxide.It is revealed that the catalyst–support interaction between Ni_(3)Fe oxide and PANI support enhances the Ni–O covalency via the interfacial Ni–N bond,thus promoting the charge and mass transfer on Ni_(3)Fe oxide.Considering the excellent activity and stability,rechargeable Zn-air batteries with optimum Ni_(3)Fe oxide/PANI are assembled,delivering a low charge voltage of 1.95 V to cycle for 400 h at 10 mA cm^(-2).The regulation of the effect of catalyst–support interaction on catalytic activity provides new possibilities for the future design of highly efficient OER catalysts.展开更多
Defects-rich heterointerfaces integrated with adjustable crystalline phases and atom vacancies,as well as veiled dielectric-responsive character,are instrumental in electromagnetic dissipation.Conventional methods,how...Defects-rich heterointerfaces integrated with adjustable crystalline phases and atom vacancies,as well as veiled dielectric-responsive character,are instrumental in electromagnetic dissipation.Conventional methods,however,constrain their delicate constructions.Herein,an innovative alternative is proposed:carrageenan-assistant cations-regulated(CACR)strategy,which induces a series of sulfides nanoparticles rooted in situ on the surface of carbon matrix.This unique configuration originates from strategic vacancy formation energy of sulfides and strong sulfides-carbon support interaction,benefiting the delicate construction of defects-rich heterostructures in M_(x)S_(y)/carbon composites(M-CAs).Impressively,these generated sulfur vacancies are firstly found to strengthen electron accumulation/consumption ability at heterointerfaces and,simultaneously,induct local asymmetry of electronic structure to evoke large dipole moment,ultimately leading to polarization coupling,i.e.,defect-type interfacial polarization.Such“Janus effect”(Janus effect means versatility,as in the Greek two-headed Janus)of interfacial sulfur vacancies is intuitively confirmed by both theoretical and experimental investigations for the first time.Consequently,the sulfur vacancies-rich heterostructured Co/Ni-CAs displays broad absorption bandwidth of 6.76 GHz at only 1.8 mm,compared to sulfur vacancies-free CAs without any dielectric response.Harnessing defects-rich heterostructures,this one-pot CACR strategy may steer the design and development of advanced nanomaterials,boosting functionality across diverse application domains beyond electromagnetic response.展开更多
The synthesis of carbon supporter/nanoscale high-entropy alloys(HEAs)electromagnetic response composites by carbothermal shock method has been identified as an advanced strategy for the collaborative competition engin...The synthesis of carbon supporter/nanoscale high-entropy alloys(HEAs)electromagnetic response composites by carbothermal shock method has been identified as an advanced strategy for the collaborative competition engineering of conductive/dielectric genes.Electron migration modes within HEAs as manipulated by the electronegativity,valence electron configurations and molar proportions of constituent elements determine the steady state and efficiency of equivalent dipoles.Herein,enlightened by skin-like effect,a reformative carbothermal shock method using carbonized cellulose paper(CCP)as carbon supporter is used to preserve the oxygencontaining functional groups(O·)of carbonized cellulose fibers(CCF).Nucleation of HEAs and construction of emblematic shell-core CCF/HEAs heterointerfaces are inextricably linked to carbon metabolism induced by O·.Meanwhile,the electron migration mode of switchable electronrich sites promotes the orientation polarization of anisotropic equivalent dipoles.By virtue of the reinforcement strategy,CCP/HEAs composite prepared by 35%molar ratio of Mn element(CCP/HEAs-Mn_(2.15))achieves efficient electromagnetic wave(EMW)absorption of−51.35 dB at an ultra-thin thickness of 1.03 mm.The mechanisms of the resulting dielectric properties of HEAs-based EMW absorbing materials are elucidated by combining theoretical calculations with experimental characterizations,which provide theoretical bases and feasible strategies for the simulation and practical application of electromagnetic functional devices(e.g.,ultra-wideband bandpass filter).展开更多
Constructing heterointerface engineering has becoming an effective and general strategy for developing highly efficient and durable nonnoble electrocatalysts for catalyzing both hydrogen evolution reaction(HER)and oxy...Constructing heterointerface engineering has becoming an effective and general strategy for developing highly efficient and durable nonnoble electrocatalysts for catalyzing both hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).In this work,we synthesized a self-supporting heterogeneous NiSe@Co_(0.85)Se/NF electrocatalyst using a facile in situ selenization of transition metal precursors that coated on the nickel foam(NF)in polyol solution.The NF was used as both conductive substrate and nickel source,ensuring superior electronic conductivity for catalyzing.The NiSe@-Co_(0.85)Se/NF exhibited remarkable bifunctional electrocatalytic activities with HER overpotential of 168 mV and OER overpotential of 258 mV to achieve 10 mA·cm-2.The water splitting system using NiSe@Co_(0.85)Se/NF as both anode and cathode electrodes achieved a current density of 10 mA·cm^(-2) at 1.61 V with nearly 100% faradaic efficiency and impressively long-term stability.The efficient bifunctional catalytic performance of NiSe@-Co_(0.85)Se/NF should be attributed to the electronic modulation and synergistic effect between NiSe and Co_(0.85)Se,the intrinsic metallic conductivity and the enlarged active sites exposure.This work provides a facile method for developing heterogeneous bifunctional catalysts for advanced electrochemical energy conversion technologies.展开更多
The fabrication of heterointerface materials with hierarchical morphologies more than two levels is a challenging yet promising approach to achieve optimal electrocatalyst for hydrogen evolution reaction(HER).Here,usi...The fabrication of heterointerface materials with hierarchical morphologies more than two levels is a challenging yet promising approach to achieve optimal electrocatalyst for hydrogen evolution reaction(HER).Here,using a facile two-step method,we are able to prepare the Ni_(2)P/(Co,Ni)OOH heterointerface with a three-level hierarchy morphology.The multiple levels of hierarchy structures not only offer considerable area for active sites loading,but also facilitate the substance transportation,both beneficial for HER.Meanwhile,the strong charge transfer at the Ni_(2)P/(Co,Ni)OOH heterointerface eliminates the spin asymmetry and achieves the thermos-neutral adsorption of active H species.Moreover,the resulted Coulomb attraction stacks the two materials firmly,facilitating the stability.Density functional theory(DFT)and in-situ Raman measurements reveal the sufficient Ni atoms acting as the active sites.With these merits,the Ni_(2)P/(Co,Ni)OOH exhibits much better HER activity than the separate Ni_(2)P or(Co,Ni)OOH,affording a current density of 100 mA/cm^(2)at an overpotential of 169 mV and a Tafel slope of 41 mV/dec,when tested in alkaline electrolyte.This work provides inspiration for optimizing the intrinsic HER activity utilizing multiple-level hierarchy structures.展开更多
基金financially supported by the National Natural Science Foundation of China(52373271)Science,Technology and Innovation Commission of Shenzhen Municipality under Grant(KCXFZ20201221173004012)+1 种基金National Key Research and Development Program of Shaanxi Province(No.2023-YBNY-271)Open Testing Foundation of the Analytical&Testing Center of Northwestern Polytechnical University(2023T019).
文摘Gradient magnetic heterointerfaces have injected infinite vitality in optimizing impedance matching,adjusting dielectric/magnetic resonance and promoting electromagnetic(EM)wave absorption,but still exist a significant challenging in regulating local phase evolution.Herein,accordion-shaped Co/Co_(3)O_(4)@N-doped carbon nanosheets(Co/Co_(3)O_(4)@NC)with gradient magnetic heterointerfaces have been fabricated via the cooperative high-temperature carbonization and lowtemperature oxidation process.The results indicate that the surface epitaxial growth of crystal Co_(3)O_(4) domains on local Co nanoparticles realizes the adjustment of magnetic-heteroatomic components,which are beneficial for optimizing impedance matching and interfacial polarization.Moreover,gradient magnetic heterointerfaces simultaneously realize magnetic coupling,and long-range magnetic diffraction.Specifically,the synthesized Co/Co_(3)O_(4)@NC absorbents display the strong electromagnetic wave attenuation capability of−53.5 dB at a thickness of 3.0 mm with an effective absorption bandwidth of 5.36 GHz,both are superior to those of single magnetic domains embedded in carbon matrix.This design concept provides us an inspiration in optimizing interfacial polarization,regulating magnetic coupling and promoting electromagnetic wave absorption.
基金funds from the National Natural Science Foundation of China(51772082 and 51804106)the Natural Science Foundation of Hunan Province(2023JJ10005)
文摘Manganese-based material is a prospective cathode material for aqueous zinc ion batteries(ZIBs)by virtue of its high theoretical capacity,high operating voltage,and low price.However,the manganese dissolution during the electrochemical reaction causes its electrochemical cycling stability to be undesirable.In this work,heterointerface engineering-induced oxygen defects are introduced into heterostructure MnO_(2)(δa-MnO_(2))by in situ electrochemical activation to inhibit manganese dissolution for aqueous zinc ion batteries.Meanwhile,the heterointerface between the disordered amorphous and the crystalline MnO_(2)ofδa-MnO_(2)is decisive for the formation of oxygen defects.And the experimental results indicate that the manganese dissolution ofδa-MnO_(2)is considerably inhibited during the charge/discharge cycle.Theoretical analysis indicates that the oxygen defect regulates the electronic and band structure and the Mn-O bonding state of the electrode material,thereby promoting electron transport kinetics as well as inhibiting Mn dissolution.Consequently,the capacity ofδa-MnO_(2)does not degrade after 100 cycles at a current density of 0.5 Ag^(-1)and also 91%capacity retention after 500cycles at 1 Ag^(-1).This study provides a promising insight into the development of high-performance manganese-based cathode materials through a facile and low-cost strategy.
基金supported by the National-Natural Science Foundation of China(Nos.52302362,52377026,and 52301192)Doctorial Foundation of Henan University of Technology,China(Nos.2021BS030 and 2020BS030)+3 种基金Key Scientific and Technological Research Projects in Henan Province,China(Nos.222102240091 and 232102240038)Natural Science Foundation from the Department of Science and Technology of Henan Province,China(No.232300420309)Taishan Scholars and Young Experts Program of Shandong Province,China(No.tsqn202103057)“Sanqin Scholars”Innovation Teams Project of Shaanxi Province,China(Clean Energy Materials and High-Performance Devices Innovation Team of Shaanxi Dongling Smelting Co.,Ltd.).
文摘The pervasive adoption of 5th generation mobile communication technology propels electromagnetic wave(EW)absorbents to achieve high-level performance.The heterointerface construction is crucial to the improvement of absorption ability.Herein,a series of ultralight composites with rational heterointerfaces(Co/ZnO@N-doped C/layer-stacked C,MSC)is fabricated by calcination with ration-al construction of sugarcane and CoZn-zeolitic imidazolate framework(ZIF).The components and structures of as-prepared composites were investigated,and their electromagnetic parameters could be adjusted by the content of CoZn-ZIFs.All composites possess excellent EW absorption performance,especially MSC-3.The optimal minimum reflection loss and effective absorption band of MSC-3 can reach−42 dB and 7.28 GHz at the thickness of only 1.6 mm with 20wt%filler loading.This excellent performance is attributed to the syner-gistic effect of dielectric loss stemming from the multiple heterointerfaces and magnetic loss induced by magnetic single Co.The sugar-cane-derived layer-stacked carbon has formed consecutive conductive networks and has further dissipated the electromagnetic energy through multiple reflection and conduction losses.Moreover,the simulated radar cross section(RCS)technology manifests that MSC-3 possesses outstanding EW attenuation capacity under realistic far-field conditions.This study provides a strategy for building efficient ab-sorbents based on biomass.
基金supported by the National Natural Science Foundation of China(11872171 and 22209037)the Project on Excellent Post-graduate Dissertation of Hohai University。
文摘Although metallic rhodium(Rh)is regarded as a promising platinum-alternative anode catalyst of direct methanol fuel cell(DMFC),the conventional"particle-to-face"contact model between Rh and matrix largely limits the overall electrocatalytic performance due to their insufficient cooperative effects.Herein,we report a controllable and robust heterointerface engineering strategy for the bottom-up fabrication of rhombic Rh nanosheets in situ confined on Ti_3C_(2)T_x MXene nanolamellas(Rh NS/MXene)via a convenient stereoassembly process.This unique design concept gives the resulting 2D/2D Rh NS/MXene heterostructure intriguing textural features,including large accessible surface areas,strong"face-toface"interfacial interactions,homogeneous Rh nanosheet distribution,ameliorative electronic structure,and high electronic conductivity.As a consequence,the as-prepared Rh NS/MXene nanoarchitectures exhibit exceptional electrocatalytic methanol oxidation properties in terms of a large electrochemically active surface area of 126.2 m~2 g_(Rh)~(-1),a high mass activity of 1056.9 mA mg_(Rh)-~1,and a long service life,which significantly outperform those of conventional particle-shaped Rh catalysts supported by carbon black,carbon nanotubes,reduced graphene oxide,and MXene matrixes as well as the commercial Pt nanoparticle/carbon black and Pd nanoparticle/carbon black catalysts with the same noble metal loading amount.Density functional theory calculations further demonstrate that the direct electronic interaction at the well-contacted 2D/2D heterointerfaces effectively enhances the adsorption energy of Rh nanosheets and induces a left shift of the d-band center,thereby making the Rh NS/MXene configuration suffer less from CO poisoning.This work highlights the importance of rational heterointerface design in the construction of advanced noble metal/MXene electrocatalysts,which may provide new avenues for developing the next-generation DMFC devices.
基金National Natural Science Foundation of China,Grant/Award Number:22102079Taishan Scholar Program of Shandong Province,China,Grant/Award Number:tsqn202211162Natural Science Foundation of Shandong Province of China,Grant/Award Numbers:ZR2021YQ10,ZR2022QB163。
文摘Electrocatalytic CO_(2)-to-formate conversion is considered an economically viable process.In general,Zn-based nanomaterials are well-known to be highly efficient electrocatalysts for the conversion of CO_(2) to CO,but seldom do they exhibit excellent selectivity toward formate.In this article,we demonstrate that a heterointerface catalyst ZnO/ZnSnO3 with nanosheet morphology shows enhanced selectivity with a maximum Faradaic efficiency(FE)of 86%at−0.9 V versus reversible hydrogen electrode and larger current density for the conversion of CO_(2) to formate than pristine ZnO and ZnSnO3.In particular,the FEs of the C1 products(CO+HCOO−)exceed 98%over the potential window.The experimental measurements combined with theoretical calculations revealed that the ZnO in ZnO/ZnSnO3 heterojunction delivers the valence electron depletion and accordingly optimizes Zn d-band center,which results in moderate Zn-O hybridization of HCOO*and weakened Zn-C hybridization of competing COOH*,thus greatly boosting the HCOOH generation.Our study highlights the importance of charge redistribution in catalysts on the selectivity of electrochemical CO_(2) reduction.
基金supported by the National Natural Science Foundation of China(No.51407134,No.52002196)Natural Science Foundation of Shandong Province(No.ZR2019YQ24,No.ZR2020QF084)+2 种基金Taishan Scholars and Young Experts Program of Shandong Province(No.tsqn202103057)the Qingchuang Talents Induction Program of Shandong Higher Education Institution(Research and Innovation Team of Structural-Functional Polymer Composites)Special Financial of Shandong Province(Structural Design of Highefficiency Electromagnetic Wave-absorbing Composite Materials and Construction of Shandong Provincial Talent Teams(No.37000022P990304116449)).
文摘The development of wearable multifunctional electromagnetic protective fabrics with multifunctional,low cost,and high efficiency remains a challenge.Here,inspired by the unique flower branch shape of“Thunberg’s meadowsweet”in nature,a nanofibrous composite membrane with hierarchical structure was constructed.Integrating sophisticated 0D@2D@1D hierarchical structures with multiple heterointerfaces can fully unleash the multifunctional application potential of composite membrane.The targeted induction method was used to precisely regulate the formation site and morphology of the metal–organic framework precursor,and intelligently integrate multiple heterostructures to enhance dielectric polarization,which improves the impedance matching and loss mechanisms of the electromagnetic wave absorbing materials.Due to the synergistic enhancement of electrospinning-derived carbon nanofiber“stems”,MOF-derived carbon nanosheet“petals”and transition metal selenide nano-particle“stamens”,the CoxSey/NiSe@CNSs@CNFs(CNCC)composite membrane obtains a minimum reflection loss value(RL_(min))of-68.40 dB at 2.6 mm and a maximum effective absorption bandwidth(EAB)of 8.88 GHz at a thin thickness of 2.0 mm with a filling amount of only 5 wt%.In addition,the multi-component and hierarchical heterostructure endow the fibrous membrane with excellent flexibility,water resistance,thermal management,and other multifunctional properties.This work provides unique perspectives for the precise design and rational application of multifunctional fabrics.
基金the support from the Thousand Young Talents Program of Chinathe National Natural Science Foundation of China(Nos.51602200,61874074,21603192)+3 种基金Science and Technology Project of Shenzhen(JCYJ20170817101100705,JCYJ20170817100111548,ZDSYS201707271014468)the(Key)Project of Department of Education of Guangdong Province(No.2016KZDXM008)supported by Shenzhen Peacock Plan(No.KQTD2016053112042971)Singapore Ministry of Education Academic Research Fund Tier 2(MOE2018-T2-2-178).
文摘Improving the cycling stability of metal sulfide-based anode materials at high rate is of great significance for advanced sodium ion batteries.However,the sluggish reaction kinetics is a big obstacle for the development of high-performance sodium storage electrodes.Herein,we have rationally engineered the heterointerface by designing the Fe1?xS/MoS2 heterostructure with abundant“ion reservoir”to endow the electrode with excellent cycling stability and rate capability,which is proved by a series of in and ex situ electrochemical investigations.Density functional theory calculations further reveal that the heterointerface greatly decreases sodium ion diffusion barrier and facilitates charge-transfer kinetics.Our present findings not only provide a deep analysis on the correlation between the structure and performance,but also draw inspiration for rational heterointerface engineering toward the next-generation high-performance energy storage devices.
基金support from the National Key Research and Development Program of China (2019YFA0705700)the National Natural Science Foundation of China (52072205)+1 种基金the start-up funds of Tsinghua Shenzhen International Graduate Schoosupported by the China Postdoctoral Science Foundation(2020M680542)。
文摘Zinc-air batteries(ZABs) with high energy density and safety are promising as next-generation energy storage systems, while their applications are severely hindered by the sluggish reaction kinetic of air cathodes. Developing a bifunctional catalyst with high activity and durability is an effective strategy to address the above challenges. Herein, a Co_(3)O_(4)/Mn_(3)O_(4) nanohybrid with heterointerfaces is designed as advanced cathode catalyst for ZABs. Density functional theory calculations show the heterogeneous interface between Co_(3)O_(4)/Mn_(3)O_(4) can improve the dynamics of carrier transport and thus enhancing the catalytic activity and durability. The Co_(3)O_(4)/Mn_(3)O_(4) catalyst anchored on reduced graphene oxide(rGO)exhibits high oxygen reduction reaction(ORR) activity with a half-wave potential of 0.86 V, and excellent oxygen evolution reaction(OER) activity with the potential of 1.59 V at 10 mA cm^(-2) , which are comparable to the commercial noble metal catalysts. The improved ORR/OER catalytic activity is ascribed to the synergistic effect of heterointerfaces between Co_(3)O_(4) and Mn_(3)O_(4)as well as the improved conductivity and contact area of oxygen/catalysts/electrolytes three-phase interface by r GO. Furthermore, a home-made ZAB based on Co_(3)O_(4)/Mn_(3)O_(4)/r GO shows a high open circuit voltage of 1.54 V, a large power density of 194.6 mW cm^(-2) and good long-term cycling stability of nearly 400 h at 5 mA cm^(-2) , which affords a promising bifunctional oxygen catalyst for rechargeable ZABs.
基金Project supported by the Special Funds of the National Natural Science Foundation of China(Grant Nos.11547226 and 11547180)
文摘Cd1-xZnxS/Cu2ZnSnS4 (CZTS)-based thin film solar cells usually use CdS as a buffer layer, but due to its smaller band gap (2.4 eV), CdS film has been replaced with higher band gap materials. The cadmium zinc sulfide (CdZnS) ternary compound has a higher band gap than other compounds, which leads to a decrease in window absorption loss. In this paper, the band offsets at Cd1-xZnxS/CuzZnSnS4 (CZTS) heterointerface are calculated by the first-principles, density- functional and pseudopotential method. The band offsets at Cdl xZnxS/CZTS heterointerface are tuned by controlling the composition of Zn in Cd1-xZnxS alloy, the calculated valence band offsets are small, which is consistent with the commonanion rule. The favorable heterointerface of type-I with a moderate barrier height (〈 0.3 eV) can be obtained by controlling the composition of Zn in Cdl-xZnxS alloy between 0.25 and 0.375.
基金Project supported by the Scholarship Council of China(Grant No.201508340047)the Postdoctoral Science Foundation of China(Grant No.2016M601993)+1 种基金the Postdoctoral Science Foundation of Anhui Province,China(Grant No.2017B215)the Anhui Province University Outstanding Talent Cultivation Program,China(Grant No.gxfx ZD2016077)
文摘Tailoring the electronic states of the Al N/diamond interface is critical to the development of the next-generation semiconductor devices such as the deep-ultraviolet light-emitting diode, photodetector, and high-power high-frequency field-effect transistor. In this work, we investigate the electronic properties of the semipolar plane Al N(11^-01)/diamond heterointerfaces by using the first-principles method with regard to different terminated planes of Al N and surface structures of diamond(100) plane. A large number of gap states exist at semi-polar plane Al N(11^-01)/diamond heterointerface, which results from the N 2 p and C 2 s2 p orbital states. Besides, the charge transfer at the interface strongly depends on the surface termination of diamond, on which hydrogen suppresses the charge exchange at the interface. The band alignments of semi-polar plane Al N(11^-01)/diamond show a typical electronic character of the type-Ⅱ staggered band configuration. The hydrogen-termination of diamond markedly increases the band offset with a maximum valence band offset of 2.0 e V and a conduction band offset of 1.3 e V for the semi-polar plane N–Al N(11^-01)/hydrogenated diamond surface. The unique band alignment of this Type-Ⅱ staggered system with the higher CBO and VBO of the semi-polar Al N/HC(100) heterostructure provides an avenue to the development of robust high-power high-frequency power devices.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.51572222 and 11604265)Innovation Foundation for Doctor Dissertation of Northwestern Polytechnical University,China(Grant No.CX201836)
文摘The two-dimensional electron gas at SrTiO3-based heterointerfaces has received a great deal of attention in recent years owing to their potential for the exploration of emergent physics and the next generation of electronics. One of the most fascinating aspects in this system is that the light, as a powerful external perturbation, can modify its transport properties. Recent studies have reported that SrTiO3-based heterointerfaces exhibit the persistent photoconductivity and can be tuned by the surface and interface engineering. These researches not only reveal the intrinsic physical mechanisms in the photoresponsive process, but also highlight the ability to be used as a tool for novel all-oxide optical devices. This review mainly contraposes the studies of photoresponse at SrTiO3-based heterointerfaces.
基金supported by the National Natural Science Foundation of China(No.52274302)Natural Science Foundation of Shanghai(Nos.21ZR1429400,22ZR1429700).
文摘The development of non-platinum group metal(non-PGM)and efficient multifunctional electrocatalysts for oxygen reduction reaction(ORR),oxygen evolution reaction(OER),and hydrogen evolution reaction(HER)with high activity and stability remains a great challenge.Herein,by in-situ transforming silver manganese composite oxide heterointerface into boosted Mott-Schottky heterointerface through a facile carbon reduction strategy,a nanorod-like silver/manganese oxide with superior multifunctional catalytic activities for ORR,OER and HER and stability was obtained.The nanorod-like silver/manganese oxide with Mott-Schottky heterointerface(designated as Ag/Mn_(3)O_(4))exhibits an ORR half-wave potential of 0.831 V(vs.RHE)in 0.1 M KOH,an OER overpotential of 338 mV and a HER overpotential of 177 mV at the current density of 10 mA·cm^(-2)in 1 M KOH,contributing to its noble-metal benchmarks comparable performance in aqueous aluminum-air(Al-air)battery and laboratorial overall water splitting electrolytic cell.Moreover,in-situ electrochemical Raman and synchrotron radiation spectroscopic measurements were conducted to further illustrate the catalytic mechanism of Ag/Mn_(3)O_(4)Mott-Schottky heterointerface towards various electrocatalytic reactions.At the heterointerface,the Ag phase serves as the electron donor and the active phase for ORR and HER,while the Mn_(3)O_(4)phase serves as the electron acceptor and the active phase for OER,respectively.This work deepens the understanding of the Mott-Schottky effect on electrocatalysis and fills in the gap in fundamental physical principles that are behind measured electrocatalytic activity,which offers substantial implications for the rational design of cost-effective multifunctional electrocatalysts with Mott-Schottky effect.
基金funded by the National Natural Science Foundation of China(No.22125901)the National Key Research and Development Program of China(No.2019YFA0705900)the Fundamental Research Funds for the Central Universities(No.226-2023-00113)。
文摘To promote the practices of perovskite photovoltaics,it requires to develop efficient perovskite solar cells(PVSCs)standing long-time operation under the adverse environments.Herein,we demonstrate that the tailor-made conjugated polymers as conductive adhesives stabilized the originally redox-reactive heterointerface between perovskite and metal oxide,facilitating the access of efficient and stable inverted PVSCs.It was revealed that bithiophene and phenyl alternating conjugated polymers with partial glycol chains atop of the metal oxide layer has resulted in effective organic-inorganic hybrid hole transporting bilayers,which allow maintaining efficient hole extraction and transport,meanwhile preventing halide migration to directly contact with the nickel oxide(NiO_(x))layer.As a result,the corresponding inverted PVSCs with the organic-inorganic hole transporting bilayers have achieved an excellent power conversion efficiency of 23.22%,outperforming 20.65% of bare NiO_(x)-based devices.Moreover,the encapsulated PVSCs with organic-inorganic bilayers exhibited the excellent photostability with 91% of the initial efficiency after 1000-h one-sun equivalent illumination in ambient conditions.Overall,this work provides new insights into stabilizing the vulnerable heterointerface for perovskite solar cells.
基金supported by the Hunan Science and Technology Innovation Talents Program(No.2021RC3003)the Basic Strengthening Research Sub-project(No.2022-JCJQ-ZD-01-1).
文摘To improve the synergistic effect between dielectric and magnetic loss is a practical and effective way in optimizing electromagnetic wave absorbing materials.The composites of metal particles and carbon ligands derived from metal organic frameworks have gained wide attention.In this study,Co particles and multiwalled carbon nanotubes(CNT)were successfully synthesized covering the surface of silicon carbide(SiC)fibers,and the morphology,interfaces and electromagnetic wave absorption performance were explored.For sample SiC@Co/CNT,the minimum reflection loss value can reach-70.22 dB at 11.21 GHz with the thickness of 2.12 mm.The effective absorbing bandwidth can reach up to 6.03 GHz with the thickness of 1.71 mm,which covers the entire Ku band.It brings more interfaces between Co particles and CNTs as well as SiC fibers and Co/C nanosheets.The interfacial polarization has been hugely enhanced,and the microwave absorbing properties have been improved.This article reports on the impedance matching of magnetic and non-magnetic components and the heterointerface engineering,which can be effective strategy and inspiration to illustrate the relationship between components,structures and functions of electromagnetic wave absorbing materials.
基金financially supported by the National Natural Science Foundation of China(No.22202042)Guangdong Basic and Applied Basic Research Foundation(No.2022A1515140012)Yunnan Fundamental Research Projects(grant No.202401CF070036)。
文摘The heterointerface engineering involving different components or phases represents a desirable strategy for enhancing the sluggish kinetics of hydrogen evolution reaction(HER).However,constructing desired heterointerfaces and elucidating the reaction mechanisms on the interface remains a considerable challenge.In this work,we propose a straightforward electrochemical synthesis strategy to prepare the nickel sulfide-based heterointerfaces for HER.The mechanism of electrochemical synthesis is revealed,wherein metal-thiourea species can be formed at the cathode potential and subsequently oxidized to nickel sulfides at the anode potentials.Leveraging this mechanism,a range of nickel sulfides,including NiS,Ni_(3)S_(2)/NiS,Ni/Ni_(3)S_(2)and Ni_(3)S_(2),have been successfully synthesized by tuning the potential range of cyclic voltammetry.Among these,the obtained Ni_(3)S_(2)/NiS@CC(CC:carbon cloth)exhibits the smallest overpotential of84 mV at 10 mA·cm^(-2)and high stability.Theoretical calculations further reveal that the combination of NiS and Ni_(3)S_(2)induces electron redistribution at the interface,and thus the Volmer process is effectively promoted with faster water dissociation and OH desorption kinetics.Significantly,the simplicity method coupled with a clear synthesis mechanism and outstanding HER performance highlights its promising potential for practical applications.
基金Research Institute for Smart Energy(CDB2)the grant from the Research Institute for Advanced Manufacturing(CD8Z)+4 种基金the grant from the Carbon Neutrality Funding Scheme(WZ2R)at The Hong Kong Polytechnic Universitysupport from the Hong Kong Polytechnic University(CD9B,CDBZ and WZ4Q)the National Natural Science Foundation of China(22205187)Shenzhen Municipal Science and Technology Innovation Commission(JCYJ20230807140402006)Start-up Foundation for Introducing Talent of NUIST and Natural Science Foundation of Jiangsu Province of China(BK20230426).
文摘Catalyst–support interaction plays a crucial role in improving the catalytic activity of oxygen evolution reaction(OER).Here we modulate the catalyst–support interaction in polyaniline-supported Ni_(3)Fe oxide(Ni_(3)Fe oxide/PANI)with a robust hetero-interface,which significantly improves oxygen evolution activities with an overpotential of 270 mV at 10 mA cm^(-2)and specific activity of 2.08 mA cm_(ECSA)^(-2)at overpotential of 300 mV,3.84-fold that of Ni_(3)Fe oxide.It is revealed that the catalyst–support interaction between Ni_(3)Fe oxide and PANI support enhances the Ni–O covalency via the interfacial Ni–N bond,thus promoting the charge and mass transfer on Ni_(3)Fe oxide.Considering the excellent activity and stability,rechargeable Zn-air batteries with optimum Ni_(3)Fe oxide/PANI are assembled,delivering a low charge voltage of 1.95 V to cycle for 400 h at 10 mA cm^(-2).The regulation of the effect of catalyst–support interaction on catalytic activity provides new possibilities for the future design of highly efficient OER catalysts.
基金financially supported by the National Natural Science Foundation of China(Grants nos.62201411,62371378,22205168,52302150 and 62304171)the China Postdoctoral Science Foundation(2022M722500)+1 种基金the Fundamental Research Funds for the Central Universities(Grants nos.ZYTS2308 and 20103237929)Startup Foundation of Xidian University(10251220001).
文摘Defects-rich heterointerfaces integrated with adjustable crystalline phases and atom vacancies,as well as veiled dielectric-responsive character,are instrumental in electromagnetic dissipation.Conventional methods,however,constrain their delicate constructions.Herein,an innovative alternative is proposed:carrageenan-assistant cations-regulated(CACR)strategy,which induces a series of sulfides nanoparticles rooted in situ on the surface of carbon matrix.This unique configuration originates from strategic vacancy formation energy of sulfides and strong sulfides-carbon support interaction,benefiting the delicate construction of defects-rich heterostructures in M_(x)S_(y)/carbon composites(M-CAs).Impressively,these generated sulfur vacancies are firstly found to strengthen electron accumulation/consumption ability at heterointerfaces and,simultaneously,induct local asymmetry of electronic structure to evoke large dipole moment,ultimately leading to polarization coupling,i.e.,defect-type interfacial polarization.Such“Janus effect”(Janus effect means versatility,as in the Greek two-headed Janus)of interfacial sulfur vacancies is intuitively confirmed by both theoretical and experimental investigations for the first time.Consequently,the sulfur vacancies-rich heterostructured Co/Ni-CAs displays broad absorption bandwidth of 6.76 GHz at only 1.8 mm,compared to sulfur vacancies-free CAs without any dielectric response.Harnessing defects-rich heterostructures,this one-pot CACR strategy may steer the design and development of advanced nanomaterials,boosting functionality across diverse application domains beyond electromagnetic response.
基金Financial support from the National Natural Science Foundation of China(52372289,52102368,52231007,12327804,T2321003,22088101,22178037 and U22A20424)Regional Joint Fund for Basic Research and Applied Basic Research of Guangdong Province(No.2020A1515110905)+1 种基金Guangdong Special Fund for key Areas(20237DZX3042)Shenzhen Stable Support Project,Liaoning Revitalization Talents Program(XLYC2002114)are highly appreciated.
文摘The synthesis of carbon supporter/nanoscale high-entropy alloys(HEAs)electromagnetic response composites by carbothermal shock method has been identified as an advanced strategy for the collaborative competition engineering of conductive/dielectric genes.Electron migration modes within HEAs as manipulated by the electronegativity,valence electron configurations and molar proportions of constituent elements determine the steady state and efficiency of equivalent dipoles.Herein,enlightened by skin-like effect,a reformative carbothermal shock method using carbonized cellulose paper(CCP)as carbon supporter is used to preserve the oxygencontaining functional groups(O·)of carbonized cellulose fibers(CCF).Nucleation of HEAs and construction of emblematic shell-core CCF/HEAs heterointerfaces are inextricably linked to carbon metabolism induced by O·.Meanwhile,the electron migration mode of switchable electronrich sites promotes the orientation polarization of anisotropic equivalent dipoles.By virtue of the reinforcement strategy,CCP/HEAs composite prepared by 35%molar ratio of Mn element(CCP/HEAs-Mn_(2.15))achieves efficient electromagnetic wave(EMW)absorption of−51.35 dB at an ultra-thin thickness of 1.03 mm.The mechanisms of the resulting dielectric properties of HEAs-based EMW absorbing materials are elucidated by combining theoretical calculations with experimental characterizations,which provide theoretical bases and feasible strategies for the simulation and practical application of electromagnetic functional devices(e.g.,ultra-wideband bandpass filter).
基金financially supported by the National Natural Science Foundation of China(No.51804216)。
文摘Constructing heterointerface engineering has becoming an effective and general strategy for developing highly efficient and durable nonnoble electrocatalysts for catalyzing both hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).In this work,we synthesized a self-supporting heterogeneous NiSe@Co_(0.85)Se/NF electrocatalyst using a facile in situ selenization of transition metal precursors that coated on the nickel foam(NF)in polyol solution.The NF was used as both conductive substrate and nickel source,ensuring superior electronic conductivity for catalyzing.The NiSe@-Co_(0.85)Se/NF exhibited remarkable bifunctional electrocatalytic activities with HER overpotential of 168 mV and OER overpotential of 258 mV to achieve 10 mA·cm-2.The water splitting system using NiSe@Co_(0.85)Se/NF as both anode and cathode electrodes achieved a current density of 10 mA·cm^(-2) at 1.61 V with nearly 100% faradaic efficiency and impressively long-term stability.The efficient bifunctional catalytic performance of NiSe@-Co_(0.85)Se/NF should be attributed to the electronic modulation and synergistic effect between NiSe and Co_(0.85)Se,the intrinsic metallic conductivity and the enlarged active sites exposure.This work provides a facile method for developing heterogeneous bifunctional catalysts for advanced electrochemical energy conversion technologies.
基金the Major Research plan of the National Natural Science Foundation of China(No.92163115)the National Natural Science Foundation(No.52072255)+1 种基金the Science Fund for Distinguished Young Scholars of Zhejiang Province(No.LR22E020003)the Natural Science Foundation of Zhejiang Province(Nos.LY21E020001 and LTY20E020001).
文摘The fabrication of heterointerface materials with hierarchical morphologies more than two levels is a challenging yet promising approach to achieve optimal electrocatalyst for hydrogen evolution reaction(HER).Here,using a facile two-step method,we are able to prepare the Ni_(2)P/(Co,Ni)OOH heterointerface with a three-level hierarchy morphology.The multiple levels of hierarchy structures not only offer considerable area for active sites loading,but also facilitate the substance transportation,both beneficial for HER.Meanwhile,the strong charge transfer at the Ni_(2)P/(Co,Ni)OOH heterointerface eliminates the spin asymmetry and achieves the thermos-neutral adsorption of active H species.Moreover,the resulted Coulomb attraction stacks the two materials firmly,facilitating the stability.Density functional theory(DFT)and in-situ Raman measurements reveal the sufficient Ni atoms acting as the active sites.With these merits,the Ni_(2)P/(Co,Ni)OOH exhibits much better HER activity than the separate Ni_(2)P or(Co,Ni)OOH,affording a current density of 100 mA/cm^(2)at an overpotential of 169 mV and a Tafel slope of 41 mV/dec,when tested in alkaline electrolyte.This work provides inspiration for optimizing the intrinsic HER activity utilizing multiple-level hierarchy structures.