Polarization spectroscopy of the D lines of rubidium atoms is investigated experimentally,especially with different pump powers and cell temperatures.We find that there are four candidate transitions suitable for freq...Polarization spectroscopy of the D lines of rubidium atoms is investigated experimentally,especially with different pump powers and cell temperatures.We find that there are four candidate transitions suitable for frequency stabilization,and optimal pump powers and cell temperatures are also presented to obtain a perfect signal with maximal amplitude and slope.The optimal signal is insensitive to the fluctuations of laser power and the temperature,which can enhance the performance of frequency locking.展开更多
Angle-resolved polarized Raman（ARPR） spectroscopy can be utilized to assign the Raman modes based on crystal symmetry and Raman selection rules and also to characterize the crystallographic orientation of anisotropi...Angle-resolved polarized Raman（ARPR） spectroscopy can be utilized to assign the Raman modes based on crystal symmetry and Raman selection rules and also to characterize the crystallographic orientation of anisotropic materials.However, polarized Raman measurements can be implemented by several different configurations and thus lead to different results. In this work, we systematically analyze three typical polarization configurations： 1） to change the polarization of the incident laser, 2） to rotate the sample, and 3） to set a half-wave plate in the common optical path of incident laser and scattered Raman signal to simultaneously vary their polarization directions. We provide a general approach of polarization analysis on the Raman intensity under the three polarization configurations and demonstrate that the latter two cases are equivalent to each other. Because the basal plane of highly ordered pyrolytic graphite（HOPG） exhibits isotropic feature and its edge plane is highly anisotropic, HOPG can be treated as a modelling system to study ARPR spectroscopy of twodimensional materials on their basal and edge planes. Therefore, we verify the ARPR behaviors of HOPG on its basal and edge planes at three different polarization configurations. The orientation direction of HOPG edge plane can be accurately determined by the angle-resolved polarization-dependent G mode intensity without rotating sample, which shows potential application for orientation determination of other anisotropic and vertically standing two-dimensional materials and other materials.展开更多
Edge structures are ubiquitous in the processing and fabrication of various optoelectronic devices.Novel physical properties and enhanced light–matter interactions are anticipated to occur at crystal edges due to the...Edge structures are ubiquitous in the processing and fabrication of various optoelectronic devices.Novel physical properties and enhanced light–matter interactions are anticipated to occur at crystal edges due to the broken spatial translational symmetry.However,the intensity of first-order Raman scattering at crystal edges has been rarely explored,although the mechanical stress and edge characteristics have been thoroughly studied by the Raman peak shift and the spectral features of the edge-related Raman modes.Here,by taking Ga As crystal with a well-defined edge as an example,we reveal the intensity enhancement of Raman-active modes and the emergence of Raman-forbidden modes under specific polarization configurations at the edge.This is attributed to the presence of a hot spot at the edge due to the redistributed electromagnetic fields and electromagnetic wave propagations of incident laser and Raman signal near the edge,which are confirmed by the finite-difference time-domain simulations.Spatially-resolved Raman intensities of both Raman-active and Raman-forbidden modes near the edge are calculated based on the redistributed electromagnetic fields,which quantitatively reproduce the corresponding experimental results.These findings offer new insights into the intensity enhancement of Raman scattering at crystal edges and present a new avenue to manipulate light–matter interactions of crystal by manufacturing various types of edges and to characterize the edge structures in photonic and optoelectronic devices.展开更多
This feature article illustrates the potential of polarization modulation infrared reflection absorption spectroscopy(PM IRRAS)to provide molecular-level information about the structure,orientation and conformation of...This feature article illustrates the potential of polarization modulation infrared reflection absorption spectroscopy(PM IRRAS)to provide molecular-level information about the structure,orientation and conformation of constituents of thin films at electrode surfaces.PM IRRAS relies on the surface selection rules stating that the p-polarized IR beam is enhanced,while the s-polarized beam is attenuated at the metal surface.The difference between p-and s-polarized beams eliminates the background of the solvent and provides IR spectra at a single electrode potential.In contrast,two other popular in situ IR spectroscopic techniques,namely,subtractively normalized interfacial Fourier transform infrared spectroscopy(SNIFTIRS)and surface-enhanced infrared reflection absorption spectroscopy(SEIRAS),provide potential difference spectra to remove the signal from the bulk solution.In this feature article,we provide a brief tutorial on how to run the PM IRRAS experiment and describe the methods used for background elimination first.The application of the PM IRRAS in the biomimetic research is then illustrated by three examples:construction of a tethered bilayer,reconstitution of colicin into a phospholipid bilayer and determination of the orientation of nucleolipids in a monolayer assembled at a gold electrode surface.Finally,the structural changes of graphene oxide during its electrochemical reduction are described to highlight the promising application of PM IRRAS in materials science.展开更多
The on-surface synthesis method allows the fabrication of atomically precise narrow graphene nanoribbons(GNRs),which bears great potential in electronic applications.Here,we synthesize armchair graphene nanoribbons(AG...The on-surface synthesis method allows the fabrication of atomically precise narrow graphene nanoribbons(GNRs),which bears great potential in electronic applications.Here,we synthesize armchair graphene nanoribbons(AGNRs)and chevron-type graphene nanoribbons(CGNRs)array on a vicinal Au(111112)surface using 10,10′-dibromo-9,9′-bianthracene(DBBA)and 6,12-dibromochrysene(DBCh)as precursors,respectively.This process creates spatially wellaligned GNRs,as characterized by scanning tunneling microscopy.AGNRs show strong Raman linear polarizability for application in optical modulation devices.Different from the distinct polarization of AGNRs,only weak polarization exists in CGNRs polarized Raman spectrum,which suggests that the presence of the zigzag boundary in the nanoribbon attenuates the polarization rate as an important factor affecting the polarization.We analyze the Raman activation mode of CGNRs using the peak polarization to expand the application of the polarization Raman spectroscopy in nanoarray analysis.展开更多
We present a systematic angle-resolved polarized Raman spectroscopy(ARPRS)study of black phosphorus(BP)nanostructures formed via electrochemical sodium-and lithium-ion intercalation.Sodium intercalation leads to bundl...We present a systematic angle-resolved polarized Raman spectroscopy(ARPRS)study of black phosphorus(BP)nanostructures formed via electrochemical sodium-and lithium-ion intercalation.Sodium intercalation leads to bundles of densely packed,highly uniform phosphorene nanoribbons(PNRs)separated by parallel amorphous channels,whereas lithium intercalation results in shorter,irregular nanoribbon-like segments with lower aspect ratios.In both cases,six additional Raman peaks(P1-P6)appear alongside the three primary Raman-active modes of BP(A_(g)^(1),B_(2g),and A_(g)^(2)).These peaks are attributed to the amorphous regions,as confirmed by their isotropic angular dependence in ARPRS measurements.The three BP modes show pronounced angular variations that differ significantly between the two intercalated samples.In sodium-intercalated BP,A_(g)^(1)and A_(g)^(2)modes retain a dumbbell-like angular dependence under parallel polarization with enhanced anisotropy and reduced symmetry under crossed polarization.At the same time,the B_(2g)mode transitions from four-lobed(cloverleaf)polar plot to a butterfly-like one.In contrast,lithium-intercalated BP exhibits weaker anisotropy and less anisotropic features in the angular polar plots for all three modes.These differences reflect the sensitivity of phonon behavior to underlying nanostructure morphology.The vibrational frequencies density of states(FDOS)calculations attribute the B_(2g)mode change to phonon band folding and mode mixing in PNRs.This study demonstrates the power of ARPRS in probing phonon-structure relationships and highlights the influence of edge geometry and quantum confinement on phonon dispersion in PNRs.展开更多
Molecular self-assembly is extremely important in many fields, but the characterization of their corresponding intermolecular interactions is still lacking. The C-H stretching Raman band can reflect the hydrophobic in...Molecular self-assembly is extremely important in many fields, but the characterization of their corresponding intermolecular interactions is still lacking. The C-H stretching Raman band can reflect the hydrophobic interactions during the self-assembly process of sodium dodecyl sulfate （SDS） in aqueous solutions. However, the Raman spectra in this region are seriously overlapped by the OH stretching band of water. In this work, vertically polarized Raman spectra were used to improve the detection sensitivity of spectra of C-H region for the first time. The spectral results showed that the first critical micelle concentration and the second critical micelle concentration of SDS in water were 8.5 and 69 mmol/L, respectively, which were consistent with the results given by surface tension measurements. Because of the high sensitivity of vertically polarized Raman spectra, the critical micelle concentration of SDS in a relatively high concentration of salt solution could be obtained in our experiment. The two critical concentrations of SDS in 100 mmol/L NaCl solution were recorded to be 1.8 and 16.5 mmol/L, respectively. Through comparing the spectra and surface tension of SDS in water and in NaCl solution, the self-assembly process in bulk phase and at interface were discussed. The interactions among salt ions, SDS and water molecules were also analyzed. These results demonstrated the vertically polarized Raman spectra could be employed to study the self-assembly process of SDS in water.展开更多
The corrosion behavior of 907 steel under thin electrolyte layer(TEL) has been investigated by means of cathodic polarization curve measurement, electrochemical impedance spectroscopy(EIS) and scanning electron micros...The corrosion behavior of 907 steel under thin electrolyte layer(TEL) has been investigated by means of cathodic polarization curve measurement, electrochemical impedance spectroscopy(EIS) and scanning electron microscopy(SEM). The results show that the cathodic diffusion current density presents the variation trend of initial increase and subsequent decrease with the decrease of TEL thickness, and the maximum deposits at 58 μm. The cotangent-hyperbolic impedance(O) is rationally first introduced to study the diffusion process of the reactants through the corrosion products layer with many permeable holes. The initial corrosion rate of 907 steel under different TEL thickness increases with the decrease of TEL thickness except that of 104 μm,whereas the corrosion rate after long time corrosion can be ranked as 104 μm﹥402 μm﹥198 μm﹥301 μm﹥bulk solution.展开更多
The through-thickness corrosion inhomogeneity of 7050-T7451 Al alloy thick plate was studied using immersion tests, potentiodynamic polarization, electrochemical impedance spectroscopy(EIS), slow strain rate testing(S...The through-thickness corrosion inhomogeneity of 7050-T7451 Al alloy thick plate was studied using immersion tests, potentiodynamic polarization, electrochemical impedance spectroscopy(EIS), slow strain rate testing(SSRT) technique combined with optical microscopy(OM), scanning electron microscopy(SEM) and transmission electron microscopy(TEM). The results show that the through-thickness corrosion resistance is ranked in the order of T/2>surface>T/4. And the 75 mm-thick 7050 alloy plate presents better corrosion resistance than the 35 mm-thick plate. The results are discussed in terms of the combined effect of recrystallization and cooling rate in quenching. Alloy with lower volume fraction of recrystallization and smaller grain aspect ratio displays better corrosion resistance. The lower corrosion resistance caused by the slower cooling rate results from the higher coverage rate of grain boundary precipitates and larger width of precipitate free zone.展开更多
In this study,ceramic coatings were deposited on 6061 Al alloy using a plasma electrolytic oxidation（PEO）technique,and the effect of concentrations of KOH and Na_2SiO_3 as electrolytes for PEO process was studied on...In this study,ceramic coatings were deposited on 6061 Al alloy using a plasma electrolytic oxidation（PEO）technique,and the effect of concentrations of KOH and Na_2SiO_3 as electrolytes for PEO process was studied on microstructure,chemical composition,and electrochemical behavior of PEO coatings formed on the 6061 Al alloy.The results indicated that the increase in concentration of KOH led to rise in electrical conductivity of electrolyte.Consequently,the breakdown voltage reduced,which in turn improved the surface quality and the corrosion behavior.Moreover,the increase in concentration of Na_2SiO_3 resulted in the increase in incorporation of Si in the coating,which led to a higher corrosion potential in the concentration of 4 g L^（-1）.According to this investigation,the best protection behavior of coatings can be obtained when the KOH and Na_2SiO_3 concentrations in PEO electrolyte are equal to 4 g L^（-1）.展开更多
The effect of solution pH,Cl;concentration and temperature on the electrochemical corrosion behavior of PH13-8Mo steel in acidic solution was investigated by using the electrochemical tests,scanning electron microscop...The effect of solution pH,Cl;concentration and temperature on the electrochemical corrosion behavior of PH13-8Mo steel in acidic solution was investigated by using the electrochemical tests,scanning electron microscopy and X-ray photoelectron spectroscopy.The PH13-8Mo martensitic precipitation hardened stainless steel is in the passivity state when the pH value is above 3.0,below which the anodic polarization curves of the steel are actively dissolved.The corrosion current density gradually decreases with increasing the solution pH and decreasing Cl;concentration and solution temperature.Pits are initiated on the sample surface in the presence of the Cl;and gradually developed into uniform corrosion with increasing the Cl;concentrations.Moreover,the corrosion is more serious with an increase in solution temperature.展开更多
Corrosion evolution during immersion tests （up to 43 days） of NiCu steel in deaerated 0.1 mol/L bicarbonate solutions was investigated by electrochemical measurements, scanning electron microscopy （SEM） and X-ray ...Corrosion evolution during immersion tests （up to 43 days） of NiCu steel in deaerated 0.1 mol/L bicarbonate solutions was investigated by electrochemical measurements, scanning electron microscopy （SEM） and X-ray diffraction （XRD）. Results show that NiCu steel transformed from the anodic dissolution in the early stage of immersion to a metastable passive state in the final stage as the open-circuit potential value shifted positively, which was aroused by the precipitation of corrosion products. This process was mainly promoted by the trace amount of oxygen. Simultaneously, dominant cathodic reaction transformed from the hydrogen evolution in early stage to reduction processes of corrosion products in later stages. Possible corrosion processes were discussed with the assistance of a corresponding Pourbaix diagram.展开更多
Unlocking of the extremely inert C=O bond during electrochemical CO_(2) reduction demands subtle regulation on a key“resource”,protons,necessary for intermediate conversion but also readily trapped in water splittin...Unlocking of the extremely inert C=O bond during electrochemical CO_(2) reduction demands subtle regulation on a key“resource”,protons,necessary for intermediate conversion but also readily trapped in water splitting,which is still challenging for developing efficient single-atom catalysts limited by their structural simplicity usually incompetent to handle this task.Incorporation of extra functional units should be viable.Herein,a proton deployment strategy is demonstrated via“atomic and nanostructured iron(A/N-Fe)pairs”,comprising atomically dispersed iron active centers spin-polarized by nanostructured iron carbide ferromagnets,to boost the critical protonation steps.The as-designed catalyst displays a broad window(300 mV)for CO selectivity>90%(98%maximum),even outperforming numerous cutting-edge M–N–C systems.The well-placed control of proton dynamics by A/N-Fe can promote*COOH/*CO formation and simultaneously suppress H2 evolution,benefiting from the magnetic-proximity-induced exchange splitting(spin polarization)that properly adjusts energy levels of the Fe sites’d-shells,and further those of the adsorbed intermediates’antibonding molecular orbitals.展开更多
Developing an understanding of the physics underlying vibrational phonon modes,which are strongly related to thermal transport,has attracted significant research interest.Herein,we report the successful synthesis of b...Developing an understanding of the physics underlying vibrational phonon modes,which are strongly related to thermal transport,has attracted significant research interest.Herein,we report the successful synthesis of bulk SbCrSe_(3)single crystal and its thermal transport property over the temperature range from 2 to 300 K.Using angle-resolved polarized Raman spectroscopy(ARPRS)and group theory calculation,the vibrational symmetry of each observed Raman mode in the cleaved(001)crystal plane of SbCrSe_(3)is identified for the first time,and then further verified through firstprinciples calculations.The ARPRS results of some Raman modes(e.g.,Ag2~64 cm-1 and Ag 7~185 cm-1)can be adopted to determine the crystalline orientation.More importantly,the temperature dependence of the lattice thermal conductivity(κL)is revealed to be more accurately depicted by the three-phonon scattering processes throughout the measured temperature range,substantiated by in-situ Raman spectroscopy analysis and the model-predictedκL.These results reveal the fundamental physics of thermal transport for SbCrSe_(3)from a completely new perspective and should thus ignite research interest in the thermal properties of other lowdimensional materials using the same strategy.展开更多
Layered trihalides exhibit distinctive band structures and physical properties due to the sixfold coordinated 3d or 4d transition metal site and partially occupied d orbitals,holding great potential in condensed matte...Layered trihalides exhibit distinctive band structures and physical properties due to the sixfold coordinated 3d or 4d transition metal site and partially occupied d orbitals,holding great potential in condensed matter physics and advanced electronic applications.Prior research focused on trihalides with highly symmetric honeycomb-like structures,such as CrI3 andα-RuCl_(3),while the role of crystal anisotropy in trihalides remains elusive.In particular,the trihalide MoCl_(3) manifests strong in-plane crystal anisotropy with the largest difference in Mo–Mo interatomic distances.Research on such material is imperative to address the lack of investigations on the effect of anisotropy on the properties of trihalides.Herein,we demonstrated the anisotropy of MoCl_(3) through polarized Raman spectroscopy and further tuned the phonon frequency via strain engineering.We showed the Raman intensity exhibits twofold symmetry under parallel configuration and fourfold symmetry under perpendicular configuration with changing the polarization angle of incident light.Furthermore,we found that the phonon frequencies of MoCl_(3) decrease gradually and linearly with applying uniaxial tensile strain along the axis of symmetry in the MoCl_(3) crystal,while those frequencies increase with uniaxial tensile strain applied perpendicularly.Our results shed light on the manipulation of anisotropic light-matter interactions via strain engineering,and lay a foundation for further exploration of the anisotropy of trihalides and the modulation of their electronic,optical,and magnetic properties.展开更多
Two-dimensional （2D） layered materials, transition-metal dichalcogenides, and black phosphorus have attracted considerable interest from the viewpoints of fundamental physics and device applications. The establishme...Two-dimensional （2D） layered materials, transition-metal dichalcogenides, and black phosphorus have attracted considerable interest from the viewpoints of fundamental physics and device applications. The establishment of new functionalities in anisotropic layered 2D materials is a challenging but rewarding frontier, owing to the remarkable optical properties of these materials and their prospects for new devices. Herein, we report the anisotropic and thickness- dependent optical properties of a 2D layered monochalcogenide of germanium sulfide （GeS）. Three Raman-scattering peaks corresponding to the B3g,, A1g, and A2g modes with a strong polarization dependence are demonstrated in the GeS flakes, which validates polarized Raman spectroscopy as an effective method for identifying the crystal orientation of anisotropic layered GeS. Photoluminescence （PL） is observed with a peak at -1.66 eV that originates from the direct optical transition in GeS at room temperature. The polarization-dependent characteristics of the PL, which are revealed for the first time, along with the demonstration of anisotropic absorption, indicate an obvious anisotropic optical transition near the band edge of GeS, which is supported by density functional theory calculations. The significantly thickness-dependent PL is observed and discussed. This anisotropic layered GeS presents opportunities for the discovery of new physical phenomena and will find applications that exploit its anisotropic properties, such as polarization-sensitive photodetectors.展开更多
基金Project supported by the Research Project of Shanghai Science and Technology Commission (Grant No. 09DJ1400700)the National 973 Program of China(Grant No. 2011CB921504)the National Natural Science Foundation of China (Grant No. 10974211)
文摘Polarization spectroscopy of the D lines of rubidium atoms is investigated experimentally,especially with different pump powers and cell temperatures.We find that there are four candidate transitions suitable for frequency stabilization,and optimal pump powers and cell temperatures are also presented to obtain a perfect signal with maximal amplitude and slope.The optimal signal is insensitive to the fluctuations of laser power and the temperature,which can enhance the performance of frequency locking.
基金supported by the National Key Research and Development Program of China(Grant No.2016YFA0301204)the National Natural Science Foundation of China(Grant Nos.11604326,11434010,11474277,and 11225421)
文摘Angle-resolved polarized Raman（ARPR） spectroscopy can be utilized to assign the Raman modes based on crystal symmetry and Raman selection rules and also to characterize the crystallographic orientation of anisotropic materials.However, polarized Raman measurements can be implemented by several different configurations and thus lead to different results. In this work, we systematically analyze three typical polarization configurations： 1） to change the polarization of the incident laser, 2） to rotate the sample, and 3） to set a half-wave plate in the common optical path of incident laser and scattered Raman signal to simultaneously vary their polarization directions. We provide a general approach of polarization analysis on the Raman intensity under the three polarization configurations and demonstrate that the latter two cases are equivalent to each other. Because the basal plane of highly ordered pyrolytic graphite（HOPG） exhibits isotropic feature and its edge plane is highly anisotropic, HOPG can be treated as a modelling system to study ARPR spectroscopy of twodimensional materials on their basal and edge planes. Therefore, we verify the ARPR behaviors of HOPG on its basal and edge planes at three different polarization configurations. The orientation direction of HOPG edge plane can be accurately determined by the angle-resolved polarization-dependent G mode intensity without rotating sample, which shows potential application for orientation determination of other anisotropic and vertically standing two-dimensional materials and other materials.
基金Project supported by the National Key Research and Development Program of China(Grant No.2023YFA1407000)the Strategic Priority Research Program of Chinese Academy of Sciences(Grant No.XDB0460000)+4 种基金the National Natural Science Foundation of China(Grant Nos.12322401,12127807,and 12393832)CAS Key Research Program of Frontier Sciences(Grant No.ZDBS-LY-SLH004)Beijing Nova Program(Grant No.20230484301)Youth Innovation Promotion Association,Chinese Academy of Sciences(Grant No.2023125)CAS Project for Young Scientists in Basic Research(Grant No.YSBR-026)。
文摘Edge structures are ubiquitous in the processing and fabrication of various optoelectronic devices.Novel physical properties and enhanced light–matter interactions are anticipated to occur at crystal edges due to the broken spatial translational symmetry.However,the intensity of first-order Raman scattering at crystal edges has been rarely explored,although the mechanical stress and edge characteristics have been thoroughly studied by the Raman peak shift and the spectral features of the edge-related Raman modes.Here,by taking Ga As crystal with a well-defined edge as an example,we reveal the intensity enhancement of Raman-active modes and the emergence of Raman-forbidden modes under specific polarization configurations at the edge.This is attributed to the presence of a hot spot at the edge due to the redistributed electromagnetic fields and electromagnetic wave propagations of incident laser and Raman signal near the edge,which are confirmed by the finite-difference time-domain simulations.Spatially-resolved Raman intensities of both Raman-active and Raman-forbidden modes near the edge are calculated based on the redistributed electromagnetic fields,which quantitatively reproduce the corresponding experimental results.These findings offer new insights into the intensity enhancement of Raman scattering at crystal edges and present a new avenue to manipulate light–matter interactions of crystal by manufacturing various types of edges and to characterize the edge structures in photonic and optoelectronic devices.
基金This research was funded by Discovery Grants from the Natural Sciences and Engineering Research Council of Canada(JL:RGPIN-2022-03958AC:RGPIN-2022-04238).
文摘This feature article illustrates the potential of polarization modulation infrared reflection absorption spectroscopy(PM IRRAS)to provide molecular-level information about the structure,orientation and conformation of constituents of thin films at electrode surfaces.PM IRRAS relies on the surface selection rules stating that the p-polarized IR beam is enhanced,while the s-polarized beam is attenuated at the metal surface.The difference between p-and s-polarized beams eliminates the background of the solvent and provides IR spectra at a single electrode potential.In contrast,two other popular in situ IR spectroscopic techniques,namely,subtractively normalized interfacial Fourier transform infrared spectroscopy(SNIFTIRS)and surface-enhanced infrared reflection absorption spectroscopy(SEIRAS),provide potential difference spectra to remove the signal from the bulk solution.In this feature article,we provide a brief tutorial on how to run the PM IRRAS experiment and describe the methods used for background elimination first.The application of the PM IRRAS in the biomimetic research is then illustrated by three examples:construction of a tethered bilayer,reconstitution of colicin into a phospholipid bilayer and determination of the orientation of nucleolipids in a monolayer assembled at a gold electrode surface.Finally,the structural changes of graphene oxide during its electrochemical reduction are described to highlight the promising application of PM IRRAS in materials science.
基金Project supported by the National Natural Science Foundation of China(Grant No.61901200)the Yunnan Fundamental Research Projects(Grant Nos.2019FD041,202101AU070043,202101AV070008+2 种基金202101AW070010)the Strategic Priority Research Program of Chinese Academy of Sciences(Grant No.NXDB30010000)the Dongguan Innovation Research Team Program。
文摘The on-surface synthesis method allows the fabrication of atomically precise narrow graphene nanoribbons(GNRs),which bears great potential in electronic applications.Here,we synthesize armchair graphene nanoribbons(AGNRs)and chevron-type graphene nanoribbons(CGNRs)array on a vicinal Au(111112)surface using 10,10′-dibromo-9,9′-bianthracene(DBBA)and 6,12-dibromochrysene(DBCh)as precursors,respectively.This process creates spatially wellaligned GNRs,as characterized by scanning tunneling microscopy.AGNRs show strong Raman linear polarizability for application in optical modulation devices.Different from the distinct polarization of AGNRs,only weak polarization exists in CGNRs polarized Raman spectrum,which suggests that the presence of the zigzag boundary in the nanoribbon attenuates the polarization rate as an important factor affecting the polarization.We analyze the Raman activation mode of CGNRs using the peak polarization to expand the application of the polarization Raman spectroscopy in nanoarray analysis.
基金supported by the U.S.Department of Energy,Office of Science,Basic Energy Sciences,under Award#DE-SC0024131.
文摘We present a systematic angle-resolved polarized Raman spectroscopy(ARPRS)study of black phosphorus(BP)nanostructures formed via electrochemical sodium-and lithium-ion intercalation.Sodium intercalation leads to bundles of densely packed,highly uniform phosphorene nanoribbons(PNRs)separated by parallel amorphous channels,whereas lithium intercalation results in shorter,irregular nanoribbon-like segments with lower aspect ratios.In both cases,six additional Raman peaks(P1-P6)appear alongside the three primary Raman-active modes of BP(A_(g)^(1),B_(2g),and A_(g)^(2)).These peaks are attributed to the amorphous regions,as confirmed by their isotropic angular dependence in ARPRS measurements.The three BP modes show pronounced angular variations that differ significantly between the two intercalated samples.In sodium-intercalated BP,A_(g)^(1)and A_(g)^(2)modes retain a dumbbell-like angular dependence under parallel polarization with enhanced anisotropy and reduced symmetry under crossed polarization.At the same time,the B_(2g)mode transitions from four-lobed(cloverleaf)polar plot to a butterfly-like one.In contrast,lithium-intercalated BP exhibits weaker anisotropy and less anisotropic features in the angular polar plots for all three modes.These differences reflect the sensitivity of phonon behavior to underlying nanostructure morphology.The vibrational frequencies density of states(FDOS)calculations attribute the B_(2g)mode change to phonon band folding and mode mixing in PNRs.This study demonstrates the power of ARPRS in probing phonon-structure relationships and highlights the influence of edge geometry and quantum confinement on phonon dispersion in PNRs.
基金This work is supported by the National Natural Science Foundation of China （No.21473171 and No.21573208）, the Pundamental Research Funds for the Central Universities （No.JB160508）, and the Huashan Mountain Scholar Program.
文摘Molecular self-assembly is extremely important in many fields, but the characterization of their corresponding intermolecular interactions is still lacking. The C-H stretching Raman band can reflect the hydrophobic interactions during the self-assembly process of sodium dodecyl sulfate （SDS） in aqueous solutions. However, the Raman spectra in this region are seriously overlapped by the OH stretching band of water. In this work, vertically polarized Raman spectra were used to improve the detection sensitivity of spectra of C-H region for the first time. The spectral results showed that the first critical micelle concentration and the second critical micelle concentration of SDS in water were 8.5 and 69 mmol/L, respectively, which were consistent with the results given by surface tension measurements. Because of the high sensitivity of vertically polarized Raman spectra, the critical micelle concentration of SDS in a relatively high concentration of salt solution could be obtained in our experiment. The two critical concentrations of SDS in 100 mmol/L NaCl solution were recorded to be 1.8 and 16.5 mmol/L, respectively. Through comparing the spectra and surface tension of SDS in water and in NaCl solution, the self-assembly process in bulk phase and at interface were discussed. The interactions among salt ions, SDS and water molecules were also analyzed. These results demonstrated the vertically polarized Raman spectra could be employed to study the self-assembly process of SDS in water.
基金Projects(21073162,21273199) supported by the National Natural Science Foundation of ChinaProject(GCTKF2012013) supported by the Science and Technology Bureau of Jiaxing Municipality and the State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology,China
文摘The corrosion behavior of 907 steel under thin electrolyte layer(TEL) has been investigated by means of cathodic polarization curve measurement, electrochemical impedance spectroscopy(EIS) and scanning electron microscopy(SEM). The results show that the cathodic diffusion current density presents the variation trend of initial increase and subsequent decrease with the decrease of TEL thickness, and the maximum deposits at 58 μm. The cotangent-hyperbolic impedance(O) is rationally first introduced to study the diffusion process of the reactants through the corrosion products layer with many permeable holes. The initial corrosion rate of 907 steel under different TEL thickness increases with the decrease of TEL thickness except that of 104 μm,whereas the corrosion rate after long time corrosion can be ranked as 104 μm﹥402 μm﹥198 μm﹥301 μm﹥bulk solution.
基金Project(2012CB619503)supported by the National Basic Research Program of ChinaProject(2013AH100055)supported by the Foshan Civic Technological Innovation Foundation,China
文摘The through-thickness corrosion inhomogeneity of 7050-T7451 Al alloy thick plate was studied using immersion tests, potentiodynamic polarization, electrochemical impedance spectroscopy(EIS), slow strain rate testing(SSRT) technique combined with optical microscopy(OM), scanning electron microscopy(SEM) and transmission electron microscopy(TEM). The results show that the through-thickness corrosion resistance is ranked in the order of T/2>surface>T/4. And the 75 mm-thick 7050 alloy plate presents better corrosion resistance than the 35 mm-thick plate. The results are discussed in terms of the combined effect of recrystallization and cooling rate in quenching. Alloy with lower volume fraction of recrystallization and smaller grain aspect ratio displays better corrosion resistance. The lower corrosion resistance caused by the slower cooling rate results from the higher coverage rate of grain boundary precipitates and larger width of precipitate free zone.
文摘In this study,ceramic coatings were deposited on 6061 Al alloy using a plasma electrolytic oxidation（PEO）technique,and the effect of concentrations of KOH and Na_2SiO_3 as electrolytes for PEO process was studied on microstructure,chemical composition,and electrochemical behavior of PEO coatings formed on the 6061 Al alloy.The results indicated that the increase in concentration of KOH led to rise in electrical conductivity of electrolyte.Consequently,the breakdown voltage reduced,which in turn improved the surface quality and the corrosion behavior.Moreover,the increase in concentration of Na_2SiO_3 resulted in the increase in incorporation of Si in the coating,which led to a higher corrosion potential in the concentration of 4 g L^（-1）.According to this investigation,the best protection behavior of coatings can be obtained when the KOH and Na_2SiO_3 concentrations in PEO electrolyte are equal to 4 g L^（-1）.
基金financially sponsored by the National Basic Research Program of China(2014CB643306)
文摘The effect of solution pH,Cl;concentration and temperature on the electrochemical corrosion behavior of PH13-8Mo steel in acidic solution was investigated by using the electrochemical tests,scanning electron microscopy and X-ray photoelectron spectroscopy.The PH13-8Mo martensitic precipitation hardened stainless steel is in the passivity state when the pH value is above 3.0,below which the anodic polarization curves of the steel are actively dissolved.The corrosion current density gradually decreases with increasing the solution pH and decreasing Cl;concentration and solution temperature.Pits are initiated on the sample surface in the presence of the Cl;and gradually developed into uniform corrosion with increasing the Cl;concentrations.Moreover,the corrosion is more serious with an increase in solution temperature.
基金supported by the National Natural Science Foundation of China (No. 51471175)
文摘Corrosion evolution during immersion tests （up to 43 days） of NiCu steel in deaerated 0.1 mol/L bicarbonate solutions was investigated by electrochemical measurements, scanning electron microscopy （SEM） and X-ray diffraction （XRD）. Results show that NiCu steel transformed from the anodic dissolution in the early stage of immersion to a metastable passive state in the final stage as the open-circuit potential value shifted positively, which was aroused by the precipitation of corrosion products. This process was mainly promoted by the trace amount of oxygen. Simultaneously, dominant cathodic reaction transformed from the hydrogen evolution in early stage to reduction processes of corrosion products in later stages. Possible corrosion processes were discussed with the assistance of a corresponding Pourbaix diagram.
基金This work was financially supported by National Natural Science Foundation of China(Grant Nos.22075245,21922811,21878270,and 21961160742)Zhejiang Provincial Natural Science Foundation of China(Grant No.LR19B060002)+2 种基金Fundamental Research Funds for the Central Universities(Grant No.2020XZZX002-09)Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(Grant No.2019R01006)Startup Foundation for Hundred-Talent Program of Zhejiang University,Key Laboratory of Marine Materials and Related Technologies,Chinese Academy of Science,and Zhejiang Key Laboratory of Marine Materials and Protective Technologies(2020K10).
文摘Unlocking of the extremely inert C=O bond during electrochemical CO_(2) reduction demands subtle regulation on a key“resource”,protons,necessary for intermediate conversion but also readily trapped in water splitting,which is still challenging for developing efficient single-atom catalysts limited by their structural simplicity usually incompetent to handle this task.Incorporation of extra functional units should be viable.Herein,a proton deployment strategy is demonstrated via“atomic and nanostructured iron(A/N-Fe)pairs”,comprising atomically dispersed iron active centers spin-polarized by nanostructured iron carbide ferromagnets,to boost the critical protonation steps.The as-designed catalyst displays a broad window(300 mV)for CO selectivity>90%(98%maximum),even outperforming numerous cutting-edge M–N–C systems.The well-placed control of proton dynamics by A/N-Fe can promote*COOH/*CO formation and simultaneously suppress H2 evolution,benefiting from the magnetic-proximity-induced exchange splitting(spin polarization)that properly adjusts energy levels of the Fe sites’d-shells,and further those of the adsorbed intermediates’antibonding molecular orbitals.
基金the National Natural Science Foundation of China(11904348,11604032,51772035,51672270 and 52071041)the Fundamental Research Funds for the Central Universities(106112016CDJZR308808)。
文摘Developing an understanding of the physics underlying vibrational phonon modes,which are strongly related to thermal transport,has attracted significant research interest.Herein,we report the successful synthesis of bulk SbCrSe_(3)single crystal and its thermal transport property over the temperature range from 2 to 300 K.Using angle-resolved polarized Raman spectroscopy(ARPRS)and group theory calculation,the vibrational symmetry of each observed Raman mode in the cleaved(001)crystal plane of SbCrSe_(3)is identified for the first time,and then further verified through firstprinciples calculations.The ARPRS results of some Raman modes(e.g.,Ag2~64 cm-1 and Ag 7~185 cm-1)can be adopted to determine the crystalline orientation.More importantly,the temperature dependence of the lattice thermal conductivity(κL)is revealed to be more accurately depicted by the three-phonon scattering processes throughout the measured temperature range,substantiated by in-situ Raman spectroscopy analysis and the model-predictedκL.These results reveal the fundamental physics of thermal transport for SbCrSe_(3)from a completely new perspective and should thus ignite research interest in the thermal properties of other lowdimensional materials using the same strategy.
基金supported by the National Natural Science Foundation of China(Nos.92365203,52072168,51861145201,and 523B1010)the National Key Basic Research Program of the Ministry of Science and Technology of China(No.2021YFA1202901)the Natural Science Foundation of Jiangsu Province(No.BK20200341).
文摘Layered trihalides exhibit distinctive band structures and physical properties due to the sixfold coordinated 3d or 4d transition metal site and partially occupied d orbitals,holding great potential in condensed matter physics and advanced electronic applications.Prior research focused on trihalides with highly symmetric honeycomb-like structures,such as CrI3 andα-RuCl_(3),while the role of crystal anisotropy in trihalides remains elusive.In particular,the trihalide MoCl_(3) manifests strong in-plane crystal anisotropy with the largest difference in Mo–Mo interatomic distances.Research on such material is imperative to address the lack of investigations on the effect of anisotropy on the properties of trihalides.Herein,we demonstrated the anisotropy of MoCl_(3) through polarized Raman spectroscopy and further tuned the phonon frequency via strain engineering.We showed the Raman intensity exhibits twofold symmetry under parallel configuration and fourfold symmetry under perpendicular configuration with changing the polarization angle of incident light.Furthermore,we found that the phonon frequencies of MoCl_(3) decrease gradually and linearly with applying uniaxial tensile strain along the axis of symmetry in the MoCl_(3) crystal,while those frequencies increase with uniaxial tensile strain applied perpendicularly.Our results shed light on the manipulation of anisotropic light-matter interactions via strain engineering,and lay a foundation for further exploration of the anisotropy of trihalides and the modulation of their electronic,optical,and magnetic properties.
文摘Two-dimensional （2D） layered materials, transition-metal dichalcogenides, and black phosphorus have attracted considerable interest from the viewpoints of fundamental physics and device applications. The establishment of new functionalities in anisotropic layered 2D materials is a challenging but rewarding frontier, owing to the remarkable optical properties of these materials and their prospects for new devices. Herein, we report the anisotropic and thickness- dependent optical properties of a 2D layered monochalcogenide of germanium sulfide （GeS）. Three Raman-scattering peaks corresponding to the B3g,, A1g, and A2g modes with a strong polarization dependence are demonstrated in the GeS flakes, which validates polarized Raman spectroscopy as an effective method for identifying the crystal orientation of anisotropic layered GeS. Photoluminescence （PL） is observed with a peak at -1.66 eV that originates from the direct optical transition in GeS at room temperature. The polarization-dependent characteristics of the PL, which are revealed for the first time, along with the demonstration of anisotropic absorption, indicate an obvious anisotropic optical transition near the band edge of GeS, which is supported by density functional theory calculations. The significantly thickness-dependent PL is observed and discussed. This anisotropic layered GeS presents opportunities for the discovery of new physical phenomena and will find applications that exploit its anisotropic properties, such as polarization-sensitive photodetectors.
