Phonon coherence can reflect electron‒phonon coupling information and has been proven to modulate electronic states and charge transport.The manipulation of phonon coherence through spacer cation engineering in organi...Phonon coherence can reflect electron‒phonon coupling information and has been proven to modulate electronic states and charge transport.The manipulation of phonon coherence through spacer cation engineering in organic‒inorganic hybrid perovskites(OIHPs)has been extensively demonstrated;however,the underlying structural origin remains elusive at the molecular level.Herein,we present molecular structure and temperature-dependent coherent phonon studies via a combination of sum frequency generation vibrational spectroscopy(SFG-VS)and transient absorption spectroscopy(TAS).The conformational order of spacer cations dictates the coherent phonon oscillations in 2D OIHPs.Our study further analyzes the static order and dynamic disorder in 2D perovskites.This work provides molecular-level insights into the role of spacer cations in tuning structural order and may provide valuable guidance for advancing emergent optoelecltronics development.展开更多
Determination of molecular structures of organicinorganic hybrid perovskite(OIHP)nanocrystals at the single-nanocrystal and ensemble levels is essential to understanding the mechanisms responsible for their size-depen...Determination of molecular structures of organicinorganic hybrid perovskite(OIHP)nanocrystals at the single-nanocrystal and ensemble levels is essential to understanding the mechanisms responsible for their size-dependent optoelectronic properties and the nanocrystal assembling process,but its detection is still a bit challenging.In this study,we demonstrate that femtosecond sum frequency generation(SFG)vibrational spectroscopy can provide a highly sensitive tool for probing the molecular structures of nanocrystals with a size comparable to the Bohr diameter(∼10 nm)at the single-nanocrystal level.The SFG signals are monitored using the spectral features of the phenyl group in(RMBA)PbBr_(3) and(R-MBA)_(2)PbI_(4) nanocrystals(MBA:methyl-benzyl-ammonium).It is found that the SFG spectra exhibit a strong resonant peak at 3067±3 cm^(−1)(ν2 mode)and a weak shoulder peak at 3045±4 cm^(−1)(ν_(7a) mode)at the ensemble level,whereas a peak of theν2 mode and a peak at 3025±3 cm^(−1)(ν20b mode)at the single-nanocrystal level.The nanocrystals at the single-nanocrystal level tend to lie down on the surface,but stand up as the ensemble number and the averaged sizes increase.This finding may provide valuable information on the structural origins for size-dependent photo-physical properties and photoluminescence blinking dynamics in nanocrystals.展开更多
Ethylene carbonate(EC)is an important electrolyte used in lithium-ion batteries due to its excellent electrochemical performance.However,propylene carbonate(PC)differs from EC by only one methyl substituent and exhibi...Ethylene carbonate(EC)is an important electrolyte used in lithium-ion batteries due to its excellent electrochemical performance.However,propylene carbonate(PC)differs from EC by only one methyl substituent and exhibits markedly poorproperties.The EC-PC disparity is still poorly understood at the molecular level.In this study,we demonstrated that femtosecond broadband sum frequency generation vibrational spectroscopy(SFG-VS)with simultaneous measurement of multiple polarization combinations provides a powerful probe for investigating the physicochemical processes at the electrode-electrolyte interface during the charge-discharge cycles of lithium batteries.Using monolayer graphene as the working electrode,we observed the distinct reaction outcomes of EC and PC on the electrode surface.The interfacial reaction of EC occurred only in the first charge-discharge cycle,while the interfacial reaction of PC was ongoing along with the charge-discharge cycles,which explains why EC is a better electrolyte choice than PC.This study provides direct experimental evidence in elucidating the differences in interfacial performance between EC and PC,facilitating a deeper understanding of battery interface reactions and guiding the design of high-performance lithium-ion batteries.展开更多
Sum frequency generation vibrational spectroscopy(SFG-VS)is a powerful technique for determining molecular structures at both buried interface and air surface.Distinguishing the contribution of SFG signals from buried...Sum frequency generation vibrational spectroscopy(SFG-VS)is a powerful technique for determining molecular structures at both buried interface and air surface.Distinguishing the contribution of SFG signals from buried interface and air surface is crucial to the applications in devices such as microelectronics and bio-tips.Here we demonstrate that the SFG spectra from buried interface and air surface can be differentiated by controlling the film thickness and employment of surface-plasmon enhancement.Using substrate-supported PMMA(poly(methyl methacrylate))films as a model,we have visualized the variations in the contribution of SFG signals from buried interface and air surface.By monitoring carbonyl and C-H stretching groups,we found that SFG signals are dominated by the moieties(-CH2,-CH3,-OCH3 and C=O)segregated at the PMMA/air surface for the thin films while they are mainly contributed by the groups(-OCH3 and C=O)at the substrate/PMMA buried interface for the thick films.At the buried interface,the tilt angle of C=O decreases from65°to 43°as the film preparation concentration increases;in contrast,the angles at the air surface fall in the range from 38°to 21°.Surface plasmon generated by gold nanorods can largely enhance SFG signals,particularly the signals from the buried interface.展开更多
Layered inorganic materials provide an essential platform for constructing new structural configurations of materials with exceptional properties.However,precise control over the interlayer molecular arrangement remai...Layered inorganic materials provide an essential platform for constructing new structural configurations of materials with exceptional properties.However,precise control over the interlayer molecular arrangement remains a significant challenge,impeding in-depth exploration in physics and chemistry realm.Herein,we demonstrated a new layered organic-inorganic superlattice composed of a S-Ta-S inorganic lattice and bilayer linear molecules,providing superhigh heat insulation.A series of interlayer-confined intercalations of alkylamines with increasing chain length in the layered inorganic materials were achieved through precisely ordered molecule design(TaS_(2)-Cn,n=3,6,8,12).Systematic spectral analysis reveals that as the length of the intercalated alkyl chain increases,the alkyl chain between layers becomes more ordered and linear,and the gauche conformation decreases.Furthermore,the more linear and ordered alkyl chain conformation results in lower thermal conductivity.The thermal conductivity of TaS_(2)-C12 is 0.426 W m^(−1) K^(−1),which is only one-third that of the pristine TaS_(2) crystal.We anticipate that this layered organic-inorganic superlattice design will pave a new avenue for developing new organic-inorganic functional materials and probing the limits of ultralow thermal conductivity materials.展开更多
Dehydration of a surface is the first step for the interaction between biomolecules and the surface. In this study, we systemati- cally investigated the influence of cholesterol analog 6-ketocholestanol （6-KC） on th...Dehydration of a surface is the first step for the interaction between biomolecules and the surface. In this study, we systemati- cally investigated the influence of cholesterol analog 6-ketocholestanol （6-KC） on the dehydration of model cell membrane, using sum frequency generation vibrational spectroscopy. In pure DI water environment, two separate dehydration dynamic components were observed in neutrally charged and isotopically labeled 1,2-dimyristoyl-sn-glycero-3-phosphocholine （DMPC） and positively charged 1,2-dimyristoyl-sn-glycero-3-ethylphosphocholine（chloride salt） （DMEPC） bilayer： a large-amplitude fast component and a small-amplitude slow component, which originated from the water molecules with a weak and a strong water-membrane bound strengths, respectively. Dehydration of a negatively charged mixed DMPC/DMPG bilayer lead to the membrane-bound water being reorganized to ordered structures quickly. It is evident that the water-membrane bound strengths depend largely on the charge status of the lipid and has an order of neutrally charged membrane〈〈positively charged mem- brane〈〈negatively charged membrane. In an ionic environment, KC1 solution can not only dehydrate DMPC bilayer, but also prevent the 6-KC fiom further dehydrating this model cell membrane. We observed that the dehydration dynamics behavior of DMPC bilayer in the presence of the chaotropic anions is similar to that of the negatively charged DMPG bilayer because of the penetration of chaotropic anions into the DMPC bilayer. The degree of dehydration difficulty in kosmotropic anions fol- lows a Hofmeister series and linearly correlates with the hydration Gibbs free energy of the anions. Our results provide a molecular basis for the interpretation of the Hofmeister effect of kosmotropic anions on ion transport proteins.展开更多
基金supported by the National Natural Science Foundation of China(Nos.21925302,92250306)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0450202)+1 种基金the Innovation Program for Quantum Science and Technology(2021ZD0303303)the National Key Research and Development Program of China(2018YFA0208702).
文摘Phonon coherence can reflect electron‒phonon coupling information and has been proven to modulate electronic states and charge transport.The manipulation of phonon coherence through spacer cation engineering in organic‒inorganic hybrid perovskites(OIHPs)has been extensively demonstrated;however,the underlying structural origin remains elusive at the molecular level.Herein,we present molecular structure and temperature-dependent coherent phonon studies via a combination of sum frequency generation vibrational spectroscopy(SFG-VS)and transient absorption spectroscopy(TAS).The conformational order of spacer cations dictates the coherent phonon oscillations in 2D OIHPs.Our study further analyzes the static order and dynamic disorder in 2D perovskites.This work provides molecular-level insights into the role of spacer cations in tuning structural order and may provide valuable guidance for advancing emergent optoelecltronics development.
基金supported by the National Key Research and Development Program of China(No.2017YFA0303500,No.2018YFA0208702)the National Natural Science Foundation of China(No.21925302,No.21873090,and No.21633007)Anhui Initiative in Quantum Information Technologies(No.AHY090000)。
文摘Determination of molecular structures of organicinorganic hybrid perovskite(OIHP)nanocrystals at the single-nanocrystal and ensemble levels is essential to understanding the mechanisms responsible for their size-dependent optoelectronic properties and the nanocrystal assembling process,but its detection is still a bit challenging.In this study,we demonstrate that femtosecond sum frequency generation(SFG)vibrational spectroscopy can provide a highly sensitive tool for probing the molecular structures of nanocrystals with a size comparable to the Bohr diameter(∼10 nm)at the single-nanocrystal level.The SFG signals are monitored using the spectral features of the phenyl group in(RMBA)PbBr_(3) and(R-MBA)_(2)PbI_(4) nanocrystals(MBA:methyl-benzyl-ammonium).It is found that the SFG spectra exhibit a strong resonant peak at 3067±3 cm^(−1)(ν2 mode)and a weak shoulder peak at 3045±4 cm^(−1)(ν_(7a) mode)at the ensemble level,whereas a peak of theν2 mode and a peak at 3025±3 cm^(−1)(ν20b mode)at the single-nanocrystal level.The nanocrystals at the single-nanocrystal level tend to lie down on the surface,but stand up as the ensemble number and the averaged sizes increase.This finding may provide valuable information on the structural origins for size-dependent photo-physical properties and photoluminescence blinking dynamics in nanocrystals.
基金supported by the National Natural Science Foundation of China(No.21925302)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0450202).
文摘Ethylene carbonate(EC)is an important electrolyte used in lithium-ion batteries due to its excellent electrochemical performance.However,propylene carbonate(PC)differs from EC by only one methyl substituent and exhibits markedly poorproperties.The EC-PC disparity is still poorly understood at the molecular level.In this study,we demonstrated that femtosecond broadband sum frequency generation vibrational spectroscopy(SFG-VS)with simultaneous measurement of multiple polarization combinations provides a powerful probe for investigating the physicochemical processes at the electrode-electrolyte interface during the charge-discharge cycles of lithium batteries.Using monolayer graphene as the working electrode,we observed the distinct reaction outcomes of EC and PC on the electrode surface.The interfacial reaction of EC occurred only in the first charge-discharge cycle,while the interfacial reaction of PC was ongoing along with the charge-discharge cycles,which explains why EC is a better electrolyte choice than PC.This study provides direct experimental evidence in elucidating the differences in interfacial performance between EC and PC,facilitating a deeper understanding of battery interface reactions and guiding the design of high-performance lithium-ion batteries.
基金supported by the National Key Research and Development Program of China(No.2018YFA0208700 and No.2017YFA0303500)the National Natural Science Foundation of China(No.21925302,No.21633007,and No.21873090)Anhui Initiative in Quantum Information Technologies(AHY090000)。
文摘Sum frequency generation vibrational spectroscopy(SFG-VS)is a powerful technique for determining molecular structures at both buried interface and air surface.Distinguishing the contribution of SFG signals from buried interface and air surface is crucial to the applications in devices such as microelectronics and bio-tips.Here we demonstrate that the SFG spectra from buried interface and air surface can be differentiated by controlling the film thickness and employment of surface-plasmon enhancement.Using substrate-supported PMMA(poly(methyl methacrylate))films as a model,we have visualized the variations in the contribution of SFG signals from buried interface and air surface.By monitoring carbonyl and C-H stretching groups,we found that SFG signals are dominated by the moieties(-CH2,-CH3,-OCH3 and C=O)segregated at the PMMA/air surface for the thin films while they are mainly contributed by the groups(-OCH3 and C=O)at the substrate/PMMA buried interface for the thick films.At the buried interface,the tilt angle of C=O decreases from65°to 43°as the film preparation concentration increases;in contrast,the angles at the air surface fall in the range from 38°to 21°.Surface plasmon generated by gold nanorods can largely enhance SFG signals,particularly the signals from the buried interface.
基金the National Natural Science Foundation of China，the Fundamental Research Funds for the Central Universities，the Key Research Program of Chinese Academy of Sciences
基金financially supported by the Chinese Academy of Sciences (CAS) Project for Young Scientists in Basic Research (YSBR-070)the National Natural Science Foundation of China (21925110, 21890750, U2032161, 12147105, 22201273, 22205226 and 21925302)+6 种基金the National Key Research and Development Program of China (2022YFA1203601, 2022YFA1203601 and 2022YFA1203602)the National Natural Science Fund for Young Scholars (22205226)the Open Foundation of the Key Laboratory Center of Engineering Research Center of Building Energy Efficiency Control and Evaluation, Ministry of Education (AHJZNX2023-04)the Fellowship of China Postdoctoral Science Foundation (2022M710141)the Fellowship of China National Postdoctoral Program for Innovative Talents (BX2021280)the University Synergy Innovation Program of Anhui Province (GXXT-2022-006)the Users with Excellence Project of Hefei Science Center CAS (2021HSC-UE004)。
文摘Layered inorganic materials provide an essential platform for constructing new structural configurations of materials with exceptional properties.However,precise control over the interlayer molecular arrangement remains a significant challenge,impeding in-depth exploration in physics and chemistry realm.Herein,we demonstrated a new layered organic-inorganic superlattice composed of a S-Ta-S inorganic lattice and bilayer linear molecules,providing superhigh heat insulation.A series of interlayer-confined intercalations of alkylamines with increasing chain length in the layered inorganic materials were achieved through precisely ordered molecule design(TaS_(2)-Cn,n=3,6,8,12).Systematic spectral analysis reveals that as the length of the intercalated alkyl chain increases,the alkyl chain between layers becomes more ordered and linear,and the gauche conformation decreases.Furthermore,the more linear and ordered alkyl chain conformation results in lower thermal conductivity.The thermal conductivity of TaS_(2)-C12 is 0.426 W m^(−1) K^(−1),which is only one-third that of the pristine TaS_(2) crystal.We anticipate that this layered organic-inorganic superlattice design will pave a new avenue for developing new organic-inorganic functional materials and probing the limits of ultralow thermal conductivity materials.
基金supported by the National Natural Science Foundation of China(21273217,91127042,21161160557)the National Basic Research Program of China(2010CB923300)+2 种基金the Key Research Program of the Chinese Academy of Sciencesthe Scientific Research Foundation for the Returned Overseas Chinese Scholars(State Education Ministry)the Fundamental Research Funds for the Central Universities
文摘Dehydration of a surface is the first step for the interaction between biomolecules and the surface. In this study, we systemati- cally investigated the influence of cholesterol analog 6-ketocholestanol （6-KC） on the dehydration of model cell membrane, using sum frequency generation vibrational spectroscopy. In pure DI water environment, two separate dehydration dynamic components were observed in neutrally charged and isotopically labeled 1,2-dimyristoyl-sn-glycero-3-phosphocholine （DMPC） and positively charged 1,2-dimyristoyl-sn-glycero-3-ethylphosphocholine（chloride salt） （DMEPC） bilayer： a large-amplitude fast component and a small-amplitude slow component, which originated from the water molecules with a weak and a strong water-membrane bound strengths, respectively. Dehydration of a negatively charged mixed DMPC/DMPG bilayer lead to the membrane-bound water being reorganized to ordered structures quickly. It is evident that the water-membrane bound strengths depend largely on the charge status of the lipid and has an order of neutrally charged membrane〈〈positively charged mem- brane〈〈negatively charged membrane. In an ionic environment, KC1 solution can not only dehydrate DMPC bilayer, but also prevent the 6-KC fiom further dehydrating this model cell membrane. We observed that the dehydration dynamics behavior of DMPC bilayer in the presence of the chaotropic anions is similar to that of the negatively charged DMPG bilayer because of the penetration of chaotropic anions into the DMPC bilayer. The degree of dehydration difficulty in kosmotropic anions fol- lows a Hofmeister series and linearly correlates with the hydration Gibbs free energy of the anions. Our results provide a molecular basis for the interpretation of the Hofmeister effect of kosmotropic anions on ion transport proteins.
