Atmospheric chemistry research and atmospheric measurement techniques have mutually promoted each other and developed rapidly in China in recent years.Cavity-based absorption spectroscopy,which uses a high-finesse cav...Atmospheric chemistry research and atmospheric measurement techniques have mutually promoted each other and developed rapidly in China in recent years.Cavity-based absorption spectroscopy,which uses a high-finesse cavity to achieve very long absorption path-length,thereby achieving ultra-high detection sensitivity,plays an extremely important role in atmospheric chemistry research.Based on the Beer–Lambert law,this technology has the unique advantages of being non-destructive,chemical-free,and highly selective.It does not require any sample preparation and can quantitatively analyze atmospheric trace gases in real time and in situ.In this paper,we review the following:(1)key technological advances in different cavity-based absorption spectroscopy techniques,including cavity ring-down spectroscopy,cavityenhanced absorption spectroscopy,cavity attenuated phase shift spectroscopy,and their extensions;and(2)applications of these techniques in the detection of atmospheric reactive species,such as total peroxy radical,formaldehyde,and reactive nitrogen(e.g.,NOx,HONO,peroxy nitrates,and alkyl nitrates).The review systematically introduces cavity-based absorption spectroscopy techniques and their applications in atmospheric chemistry,which will help promote further communication and cooperation in the fields of laser spectroscopy and atmospheric chemistry.展开更多
Infrared(IR)spectroscopy,a technique within the realm of molecular vibrational spectroscopy,furnishes distinctive chemical signatures pivotal for both structural analysis and compound identification.A notable challeng...Infrared(IR)spectroscopy,a technique within the realm of molecular vibrational spectroscopy,furnishes distinctive chemical signatures pivotal for both structural analysis and compound identification.A notable challenge emerges from the misalignment between the mid-IR light wavelength range and molecular dimensions,culminating in a constrained absorption cross-section and diminished vibrational absorption coefficients(Supplementary data).展开更多
Insight into exciton dynamics of two-dimensional(2D)transition metal dichalcogenides(TMDs)is critical for the optimization of their performance in photonic and optoelectronic devices.Although current researches have p...Insight into exciton dynamics of two-dimensional(2D)transition metal dichalcogenides(TMDs)is critical for the optimization of their performance in photonic and optoelectronic devices.Although current researches have primarily concentrated on the near-resonant excitation scenario in 2D TMDs,the case of excitation energies resonating with highenergy excitons or higher energies has yet to be fully elucidated.Here,a comparative analysis is conducted between highenergy excitation(360 nm)and near-resonant excitation(515 nm)utilizing transient absorption spectroscopy to achieve a comprehensive understanding of the exciton dynamics within monolayer WS_(2).It is observed that the high-energy C-exciton can be generated via an up-conversion process under 515 nm excitation,even the energy of which is less than that of the C-exciton.Furthermore,the capacity to efficiently occupy band-edge A-exciton states leads to longer lifetimes for both the C-excitons and the A-excitons under conditions of near-resonant excitation,accompanied by an augmented rate of radiative recombination.This study provides a paradigm for optimizing the performance of 2D TMDs-based devices by offering valuable insights into their exciton dynamics.展开更多
This review comprehensively explores the theory and applications of attosecond transient absorption spectroscopy(ATAS)in studying ultrafast electronic dynamics across various systems,from atoms to solids.Driven by sig...This review comprehensively explores the theory and applications of attosecond transient absorption spectroscopy(ATAS)in studying ultrafast electronic dynamics across various systems,from atoms to solids.Driven by significant advancements in ultrafast laser technology,such as generating isolated attosecond pulses,ATAS enables detailed investigations of ultrafast electronic processes with unprecedented time resolution.The article introduces the fundamental principles and historical development of ATAS.Applications of ATAS are discussed in three main domains:in atoms,where it has been used to study build-up dynamics of Autler–Townes splitting,Fano resonance,light-induced states,etc.;in molecules,where it has revealed coherent molecular wavepacket dynamics and non-adiabatic dynamics near conical intersections;and in solids,where it has been extended to investigate ultrafast charge carrier dynamics in metals,semiconductors,and insulators.The review highlights the potential of ATAS in developing ultrafast optical switches and petahertz electronics.The ability of ATAS to probe and manipulate electronic dynamics at the attosecond timescale provides a powerful tool for exploring the fundamental limits of electronic and optical processes in materials.展开更多
Nano-scale chemical inhomogeneity in surface oxide films formed on a V-and N-containing martensite stainless steel and tempering heating induced changes are investigated by a combination of synchrotron-based hard X-ra...Nano-scale chemical inhomogeneity in surface oxide films formed on a V-and N-containing martensite stainless steel and tempering heating induced changes are investigated by a combination of synchrotron-based hard X-ray Photoelectron emission spectroscopy(HAXPES)and microscopy(HAXPEEM)as well as microscopic X-ray absorption spectroscopy(μ-XAS)techniques.The results reveal the inhomogeneity in the oxide films on the micron-sized Cr_(2)N-and VN-type particles,while the inhomogeneity on the martensite matrix phase exists due to localised formation of nano-sized tempering nitride particles at 600℃.The oxide film formed on Cr_(2)N-type particles is rich in Cr_(2)O_(3) compared with that on the martensite matrix and VN-type particles.With the increase of tempering temperature,Cr_(2)O_(3) formation is faster for the oxidation of Cr in the martensite matrix than the oxidation of Cr nitride-rich particles.展开更多
The measurement of the combustion characteristics of a single biomass particle is essential for studying massive biofuel energy conversion process;however,it is challenging due to the small physical scale of the bioma...The measurement of the combustion characteristics of a single biomass particle is essential for studying massive biofuel energy conversion process;however,it is challenging due to the small physical scale of the biomass particle flame.In this work,we report an investigation of the combustion behavior of single lignin and single cellulose particle through CO_(2)absorption spectroscopy and high-speed photography.The biomass samples are prepared with an initial diameter of about 1.0 mm and are ignited on a heating plate placed inside a multi-pass absorption cell.The shape and size transformation of single biomass particle are recorded through high-speed photography,and the combustion temperature and CO_(2)column densities are measured through laser absorption spectroscopy at 4.172µm.We find that the maximum combustion temperatures are 1662±38 K and 1569±26 K for lignin and cellulose particle,respectively.Besides,we find that CO_(2)generation precedes the generation of visible volatile flame for cellulose particle.While for lignin particle,the CO_(2)generation is found to be almost at the same time as its volatile combustion stage begins.The measurement technique and results presented in this work are of practical interest for biomass combustion studies and arc meaningful for the development of biomass thermal conversion mode.展开更多
Chlorine dioxide （OC10） is an important indicator for Cl-activation. The monitoring of OC10 appears to be crucial for understanding the chemistry of Cl-initialed oxidation and its impact on air quality in polluted c...Chlorine dioxide （OC10） is an important indicator for Cl-activation. The monitoring of OC10 appears to be crucial for understanding the chemistry of Cl-initialed oxidation and its impact on air quality in polluted coastal regions and industrialized areas. We report the development of a Xe arc lamp based near-ultraviolet （335-375 nm） incoherent broad- band cavity enhanced absorption spectroscopy （IBBCEAS） spectrometer for quantitative assessment of OC10 in an atmospheric simulation chamber. The important intermediate compound CH20, and other key atmospheric trace species （NO2） were also simultaneously measured. The instrumental performance shows a strong potential of this kind of IBBCEAS instrument for field and laboratory studies of atmospheric halogen chemistry.展开更多
The mixture of graphene oxide （GO） and dye molecules may provide some new applications due to unique electronic, optical, and structural properties. Methylene blue （MB）, a typ- ical anionic dye, can attach on GO v...The mixture of graphene oxide （GO） and dye molecules may provide some new applications due to unique electronic, optical, and structural properties. Methylene blue （MB）, a typ- ical anionic dye, can attach on GO via π-π stacking and electrostatic interaction, and the molecule removal process on GO has been observed. However, it remains unclear about the ultrafast carrier dynamics and the internal energy transfer pathways of the system which is composed of GO and MB. We have employed ultrafast optical pump-probe spectroscopy to investigate the excited dynamics of the GO-MB system dispersed in water by exciting the samples at 400 nm pump pulse. The pristine MB and GO dynamics are also analyzed in tandem for a direct comparison. Utilizing the global analysis to fit the measured signal via a sequential model, five lifetimes are acquired：（0.61±0.01） ps, （3.52±0.04） ps, （14.1±0.3） ps, （84±2） ps, and （3.66±0.08） ns. The ultrafast dynamics corresponding to these lifetimes was analyzed and the new relaxation processes were found in the GO-MB system, compared with the pristine MB. The results reveal that the functionalization of GO can alter the known decay pathways of MB via the energy transfer from GO to MB in system, the increased intermediate state, and the promoted energy transfer from triplet state MB to ground state oxygen molecules dissolved in aqueous sample.展开更多
The long-path differential optical absorption spectroscopy （LP-DOAS） technique was developed to mea- sure nighttime atmospheric nitrate radical （NO3） concentrations. An optimized retrieval method, resulting in a s...The long-path differential optical absorption spectroscopy （LP-DOAS） technique was developed to mea- sure nighttime atmospheric nitrate radical （NO3） concentrations. An optimized retrieval method, resulting in a small residual structure and low detection limits, was developed to retrieve NO3. The time series of the NO3 concentration were collected from 17 to 24 March, 2006, where a nighttime average value of 15.8 ppt was observed. The interfering factors and errors are also discussed. These results indicate that the DOAS technique provides an essential tool for the quantification of NO3 concentration and in the study of its effects upon nighttime chemistry.展开更多
Electrochemical energy conversion technologies involving processes such as water splitting and O_(2)/CO_(2) reduction,provide promising solutions for addressing global energy scarcity and minimizing adverse environmen...Electrochemical energy conversion technologies involving processes such as water splitting and O_(2)/CO_(2) reduction,provide promising solutions for addressing global energy scarcity and minimizing adverse environmental impact.However,due to a lack of an in-depth understanding of the reaction mechanisms and the nature of the active sites,further advancement of these techniques has been limited by the development of efficient and robust catalysts.Therefore,in situ characterization of these electrocatalytic processes under working conditions is essential.In this review,recent applications of in situ Raman spectroscopy and X-ray absorption spectroscopy for various nano-and single-atom catalysts in energy-related reactions are summarized.Notable cases are highlighted,including the capture of oxygen-containing intermediate species formed during the reduction of oxygen and oxidation of hydrogen,and the detection of catalyst structural transformations occurring with the change in potential during the evolution of oxygen and reduction of CO_(2).Finally,the challenges and outlook for advancing in situ spectroscopic technologies to gain a deeper fundamental understanding of these energy-related electrocatalytic processes are discussed.展开更多
An accurate and reasonable technique combining direct absorption spectroscopy and laser-induced fluorescence（LIF）methods is developed to quantitatively measure the concentrations of hydroxyl in CH;/air flat laminar ...An accurate and reasonable technique combining direct absorption spectroscopy and laser-induced fluorescence（LIF）methods is developed to quantitatively measure the concentrations of hydroxyl in CH;/air flat laminar flame. In our approach, particular attention is paid to the linear laser-induced fluorescence and absorption processes, and experimental details as well. Through measuring the temperature, LIF signal distribution and integrated absorption, spatially absolute OH concentrations profiles are successfully resolved. These experimental results are then compared with the numerical simulation. It is proved that the good quality of the results implies that this method is suitable for calibrating the OH-PLIF measurement in a practical combustor.展开更多
Various experimental conditions were described for the vanadium determinationby graphite furnace atomic absorption spectroscopy (GFAAS). The experiments showed that whenatomization took place under the conditions wher...Various experimental conditions were described for the vanadium determinationby graphite furnace atomic absorption spectroscopy (GFAAS). The experiments showed that whenatomization took place under the conditions where the combination of a pyrolytic coating graphitetube and fast raising temperature were used and the temperature was stable, the signal peak shapescould be improved, the sensitivity was enhanced, and the memory effect was removed. The vanadium infood and traditional Chinese medicinal herbs can be accurately determined using the standard curvemethod.展开更多
Based on the synchrotron soft X-ray absorption spectroscopy experiments,the fundamental electronic structures of layered Li NixCoyMnzO_(2)(NCM)are investigated systematically and the data of transitionmetal(TM)L-and O...Based on the synchrotron soft X-ray absorption spectroscopy experiments,the fundamental electronic structures of layered Li NixCoyMnzO_(2)(NCM)are investigated systematically and the data of transitionmetal(TM)L-and O K-edges spectra are collected.Distribution of Ni ions under different oxidation states is evaluated according to linear combination fit.It is found that the ratio of Ni^(4+)expands with the increase of Ni since it dominates in charge compensation during charging,and that the existence of Ni^(3+)is nearly negligible in delithiated NCM.The valence state of Co also strongly depends on Ni content,the perceptible position shift of Co L_(3)-edge absorption peak towards higher energy in Ni-rich material agrees well with the small voltage plateau at around 4.2 V.The stability of Mn is verified as no obvious spectral change with the Mn L-edge is observed.Moreover,as Ni content rises,the O 2p holes near the Femi level increases with higher oxidation state of Ni,indicating the enhanced hybridization of O 2p-TM 3 d.Delithiated NCMs with higher Ni content are prior to lose electron existing in highly hybridized Ni3 dO 2 p bands upon heating,which accounts for the pronounced O_(2)release in phase transitions and the deterioration in thermal stability.These detailed observation of the electronic structure evolution is one of the key ingredients to improving the electrochemical and thermal performance of NCM.展开更多
Exhaust gas temperature is an important factor in NOx, THC and PM emissions of engines. Especially 2D temperature and concentration distribution plays an important role for the engine efficiency. A thermocouple is int...Exhaust gas temperature is an important factor in NOx, THC and PM emissions of engines. Especially 2D temperature and concentration distribution plays an important role for the engine efficiency. A thermocouple is intrinsically a point temperature measurement method and noncontact 2D temperature distribution cannot be attained by thermocouples. Recently, as a measurement technique with high sensitivity and high response, laser diagnostics has been developed and applied to the actual engine combustions. With these engineering developments, transient phenomena such as start-ups and load changes in engines have been gradually elucidated in various conditions. In this study, the theoretical and experimental research has been conducted in order to develop the noncontact and fast response 2D temperature and concentration distribution measurement method. The method is based on a Computed Tomography （CT） method using absorption spectra of water vapor at 1388 nm. It has been demonstrated that the method has been successfully applied to engine exhausts to measure 2D temperature distributions.展开更多
Nitric oxide(NO)is one of the most crucial products in the plasma-based nitrogen fixation process.In this work,in situ measurements were performed for quantifying the NO synthesis spatially in a warm air glow discharg...Nitric oxide(NO)is one of the most crucial products in the plasma-based nitrogen fixation process.In this work,in situ measurements were performed for quantifying the NO synthesis spatially in a warm air glow discharge,through the method of Mid-infrared quantum cascade laser absorption spectroscopy(QCL-AS).Two ro-vibrational transitions at 1900.076 cm^(-1) and 1900.517 cm^(-1) of the ground-state NO(X)were probed sensitively by the help of the wavelength modulation spectroscopy(WMS)approach to increase the signal/noise(S/N)level.The results show a decline trend of NO synthesis rate along the discharge channel from the cathode to the anode.However,from the point of energy efficiency,the cathode region is of significantly low energy efficiency of NO production.Severe disproportionality was found for the high energy consumption but low NO production in the region of cathode area,compared to that in the positive column zone.Further analysis demonstrates the high energy cost of NO production in the cathode region,is ascribed to the extremely high reduced electric field E/N therein not selectively preferable for the processes of vibrational excitation or dissociation of N_(2) and O_(2) molecules.This drags down the overall energy efficiency of NO synthesis by this typical warm air glow discharge,particularly for the ones with short electrode gaps.Limitations of further improving the energy cost of NO synthesis by variations of the discharge operation conditions,such as discharge current or airflow rate,imply other effective manners able to tune the energy delivery selectively to the NO formation process,are sorely needed.展开更多
Densities of Ar metastable states 1s5 and 1s3 are measured by using the tunable diode laser absorption spectroscopy（TDLAS） in Ar and Ar/O2 mixture dual-frequency capacitively coupled plasma（DF-CCP）. We investigate...Densities of Ar metastable states 1s5 and 1s3 are measured by using the tunable diode laser absorption spectroscopy（TDLAS） in Ar and Ar/O2 mixture dual-frequency capacitively coupled plasma（DF-CCP）. We investigate the effects of high-frequency（HF, 60 MHz） power, low-frequency（LF, 2 MHz） power, and working pressure on the density of Ar metastable states for three different gas components（0%, 5%, and 10% oxygen mixed in argon）. The dependence of Ar metastable state density on the oxygen content is also studied at different working pressures. It is found that densities of Ar metastable states in discharges with different gas components exhibit different behaviors as HF power increases. With the increase of HF power, the metastable density increases rapidly at the initial stage, and then tends to be saturated at a higher HF power. With a small fraction（5% or 10%） of oxygen added in argon plasma, a similar change of the Ar metastable density with HF power can be observed, but the metastable density is saturated at a higher HF power than in the pure argon discharge. In the DF-CCP, the metastable density is found to be higher than in a single frequency discharge, and has weak dependence on LF power. As working pressure increases, the metastable state density first increases and then decreases,and the pressure value, at which the density maximum occurs, decreases with oxygen content increasing. Besides, adding a small fraction of oxygen into argon plasma will significantly dwindle the metastable state density as a result of quenching loss by oxygen molecules.展开更多
The ultrafast photoisomerization and excited-state dynamics of trans-4-methoxyazobenzene (trans-4-MAB) in solutions were investigated by femtosecond transient absorption spectroscopy and quantum chemistry calculations...The ultrafast photoisomerization and excited-state dynamics of trans-4-methoxyazobenzene (trans-4-MAB) in solutions were investigated by femtosecond transient absorption spectroscopy and quantum chemistry calculations. After being excited to the S2 state, the two-dimensional transient absorptions spectra show that cis-4-MAB is produced and witnessed by the permanent positive absorption in 400-480 nm. Three decay components are determined to be 0.11, 1.4 and 2.9 ps in ethanol, and 0.16, 1.5 and 7.5 ps in ethylene glycol, respectively. The fast component is assigned to the internal conversion from the S2 to S1 state. The other relaxation pathways are correlated with the decay of the S1 state via internal conversion and isomerization, and the vibrational cooling of the hot S0 state of the cis-isomer. Comparing of the dynamics in different solvents, it is demonstrated that the photoisomerization pathway undergoes the inversion mechanism rather than the rotation mechanism.展开更多
A dual-gas sensor system is developed for CO and CO_2 detection using a single broadband light source, pyroelectric detectors and time-division multiplexing(TDM) technique. A stepper motor based rotating system and a ...A dual-gas sensor system is developed for CO and CO_2 detection using a single broadband light source, pyroelectric detectors and time-division multiplexing(TDM) technique. A stepper motor based rotating system and a single-reflection spherical optical mirror are designed and adopted for realizing and enhancing dual-gas detection. Detailed measurements under static detection mode(without rotation) and dynamic mode(with rotation) are performed to study the performance of the sensor system for the two gas samples. The detection period is 7.9 s in one round of detection by scanning the two detectors. Based on an Allan deviation analysis, the 1σ detection limits under static operation are 3.0 parts per million(ppm) in volume and 2.6 ppm for CO and CO_2, respectively, and those under dynamic operation are 9.4 ppm and 10.8 ppm for CO and CO_2, respectively. The reported sensor has potential applications in various fields requiring CO and CO_2 detection such as in the coal mine.展开更多
Elucidation of a reaction mechanism is the most critical aspect for designing electrodes for highperformance secondary batteries.Herein,we investigate the sodium insertion/extraction into an iron fluoride hydrate(FeF_...Elucidation of a reaction mechanism is the most critical aspect for designing electrodes for highperformance secondary batteries.Herein,we investigate the sodium insertion/extraction into an iron fluoride hydrate(FeF_(3)·0.5H_(2)O)electrode for sodium-ion batteries(SIBs).The electrode material is prepared by employing an ionic liquid 1-butyl-3-methylimidazolium-tetrafluoroborate,which serves as a reaction medium and precursor for F^(-)ions.The crystal structure of FeF_(3)·0.5H_(2)O is observed as pyrochlore type with large open 3-D tunnels and a unit cell volume of 1129A^(3).The morphology of FeF_(3)·0.5H_(2)O is spherical shape with a mesoporous structure.The microstructure analysis reveals primary particle size of around 10 nm.The FeF_(3)·0.5H_(2)O cathode exhibits stable discharge capacities of 158,210,and 284 mA h g^(-1) in three different potential ranges of 1.5-4.5,1.2-4.5,and 1.0-4.5 V,respectively at 0.05 C rate.The specific capacities remained stable in over 50 cycles in all three potential ranges,while the rate capability was best in the potential range of 1.5-4.5 V.The electrochemical sodium storage mechanism is studied using X-ray absorption spectroscopy,indicating higher conversion at a more discharged state.Ex-situ M?ssbauer spectroscopy strengthens the results for reversible reduction/oxidation of Fe.These results will be favorable to establish high-performance cathode materials with selective voltage window for SIBs.展开更多
The local structure of an alternative Pb（Zn1/3Nb2/3）O3-based perovskite ceramic is investigated. The 0.07BaTiO33-0.93Pb（Zn1/3Nb2/3）O3 ceramic is synthesized using a combination of Zn3Nb2O8 B-site precursor and BaT...The local structure of an alternative Pb（Zn1/3Nb2/3）O3-based perovskite ceramic is investigated. The 0.07BaTiO33-0.93Pb（Zn1/3Nb2/3）O3 ceramic is synthesized using a combination of Zn3Nb2O8 B-site precursor and BaTiO33 perovskite phase stabilizer. Then, x-ray absorption spectroscopy and density functional theory are employed to calculate the local structure configuration and formation energy of the prepared samples. Ba2＋ is found to replace Pb2＋ in AA-site with Zn2＋ occupying BB-site in Pb（Zn1/3Nb2/3）O3, while in the neighboring structure, Ti4＋4＋ replaces Nb5＋5＋ in BB-site with Pb2＋2＋ occupying AA-site. With the substitution of BaTiO33 in Pb（Zn1/3Nb2/3）O3, the bond length between Zn2＋ and Pb2＋ is longer than that of the typical perovskite phase of Pb（Zn1/3Nb2/3）O3. This indicates the key role of BaTiO33 in decreasing the steric hindrance of Pb2＋ lone pair, and the mutual interactions between Pb2＋ lone pair and Zn2＋ and the formation energy is seen to decrease. This finding of the formation energy and local structure configuration relationship can further extend a fundamental understanding of the role of BaTiO33 in stabilizing the perovskite phase in PbZn13Nb23O3-based materials, which in turn will lead to an improved preparation technique for desired electrical properties.展开更多
基金supported by the National Natural Science Foundation of China(Grant Nos.U21A2028,42022051,62275250,42030609,41627810,91644107,and 91544228).
文摘Atmospheric chemistry research and atmospheric measurement techniques have mutually promoted each other and developed rapidly in China in recent years.Cavity-based absorption spectroscopy,which uses a high-finesse cavity to achieve very long absorption path-length,thereby achieving ultra-high detection sensitivity,plays an extremely important role in atmospheric chemistry research.Based on the Beer–Lambert law,this technology has the unique advantages of being non-destructive,chemical-free,and highly selective.It does not require any sample preparation and can quantitatively analyze atmospheric trace gases in real time and in situ.In this paper,we review the following:(1)key technological advances in different cavity-based absorption spectroscopy techniques,including cavity ring-down spectroscopy,cavityenhanced absorption spectroscopy,cavity attenuated phase shift spectroscopy,and their extensions;and(2)applications of these techniques in the detection of atmospheric reactive species,such as total peroxy radical,formaldehyde,and reactive nitrogen(e.g.,NOx,HONO,peroxy nitrates,and alkyl nitrates).The review systematically introduces cavity-based absorption spectroscopy techniques and their applications in atmospheric chemistry,which will help promote further communication and cooperation in the fields of laser spectroscopy and atmospheric chemistry.
基金supported by National Natural Science Foundation of China(Grant No.:32301161)the Natural Scientific Foundation of Hunan Province,China(Grant No.:2023JJ60052)+3 种基金the Scientific Research Project of Hunan Provincial Health Commission,China(Grant No.:202112062218,20190161)the Scientific Research Project of Hunan Provincial Department of Education,China(Grant No.:22B0455)the Clinical“4310”Project of the University of South China,China(Grant No.:20224310NHYCG02)the Doctoral Scientific Research Foundation of University of South China,China(Grant No.:200XQD042).
文摘Infrared(IR)spectroscopy,a technique within the realm of molecular vibrational spectroscopy,furnishes distinctive chemical signatures pivotal for both structural analysis and compound identification.A notable challenge emerges from the misalignment between the mid-IR light wavelength range and molecular dimensions,culminating in a constrained absorption cross-section and diminished vibrational absorption coefficients(Supplementary data).
基金supported by the National Natural Science Foundation of China(Grant Nos.12474421 and 12104066)the Fund from Education Department of Jilin Province(Grant Nos.JJKH20250473KJ and JJKH20241413KJ)the Fund from Department of Science and Technology of Jilin Province(Grant No.YDZJ202101ZYTS041)。
文摘Insight into exciton dynamics of two-dimensional(2D)transition metal dichalcogenides(TMDs)is critical for the optimization of their performance in photonic and optoelectronic devices.Although current researches have primarily concentrated on the near-resonant excitation scenario in 2D TMDs,the case of excitation energies resonating with highenergy excitons or higher energies has yet to be fully elucidated.Here,a comparative analysis is conducted between highenergy excitation(360 nm)and near-resonant excitation(515 nm)utilizing transient absorption spectroscopy to achieve a comprehensive understanding of the exciton dynamics within monolayer WS_(2).It is observed that the high-energy C-exciton can be generated via an up-conversion process under 515 nm excitation,even the energy of which is less than that of the C-exciton.Furthermore,the capacity to efficiently occupy band-edge A-exciton states leads to longer lifetimes for both the C-excitons and the A-excitons under conditions of near-resonant excitation,accompanied by an augmented rate of radiative recombination.This study provides a paradigm for optimizing the performance of 2D TMDs-based devices by offering valuable insights into their exciton dynamics.
基金Project supported by the National Natural Science Foundation of China(Grant No.12174034)。
文摘This review comprehensively explores the theory and applications of attosecond transient absorption spectroscopy(ATAS)in studying ultrafast electronic dynamics across various systems,from atoms to solids.Driven by significant advancements in ultrafast laser technology,such as generating isolated attosecond pulses,ATAS enables detailed investigations of ultrafast electronic processes with unprecedented time resolution.The article introduces the fundamental principles and historical development of ATAS.Applications of ATAS are discussed in three main domains:in atoms,where it has been used to study build-up dynamics of Autler–Townes splitting,Fano resonance,light-induced states,etc.;in molecules,where it has revealed coherent molecular wavepacket dynamics and non-adiabatic dynamics near conical intersections;and in solids,where it has been extended to investigate ultrafast charge carrier dynamics in metals,semiconductors,and insulators.The review highlights the potential of ATAS in developing ultrafast optical switches and petahertz electronics.The ability of ATAS to probe and manipulate electronic dynamics at the attosecond timescale provides a powerful tool for exploring the fundamental limits of electronic and optical processes in materials.
基金supported by the Vinnova(project number 2020-03778)supported by the Swedish Research Council(Vetenskapsradet,project number 2021-04157).
文摘Nano-scale chemical inhomogeneity in surface oxide films formed on a V-and N-containing martensite stainless steel and tempering heating induced changes are investigated by a combination of synchrotron-based hard X-ray Photoelectron emission spectroscopy(HAXPES)and microscopy(HAXPEEM)as well as microscopic X-ray absorption spectroscopy(μ-XAS)techniques.The results reveal the inhomogeneity in the oxide films on the micron-sized Cr_(2)N-and VN-type particles,while the inhomogeneity on the martensite matrix phase exists due to localised formation of nano-sized tempering nitride particles at 600℃.The oxide film formed on Cr_(2)N-type particles is rich in Cr_(2)O_(3) compared with that on the martensite matrix and VN-type particles.With the increase of tempering temperature,Cr_(2)O_(3) formation is faster for the oxidation of Cr in the martensite matrix than the oxidation of Cr nitride-rich particles.
基金surpported by the National Natural Science Foundation of China(No.52206222,No.22227901)Aero Engine and Gas Turbine Basic Science Centre Project(P2023-B-V-002-001).
文摘The measurement of the combustion characteristics of a single biomass particle is essential for studying massive biofuel energy conversion process;however,it is challenging due to the small physical scale of the biomass particle flame.In this work,we report an investigation of the combustion behavior of single lignin and single cellulose particle through CO_(2)absorption spectroscopy and high-speed photography.The biomass samples are prepared with an initial diameter of about 1.0 mm and are ignited on a heating plate placed inside a multi-pass absorption cell.The shape and size transformation of single biomass particle are recorded through high-speed photography,and the combustion temperature and CO_(2)column densities are measured through laser absorption spectroscopy at 4.172µm.We find that the maximum combustion temperatures are 1662±38 K and 1569±26 K for lignin and cellulose particle,respectively.Besides,we find that CO_(2)generation precedes the generation of visible volatile flame for cellulose particle.While for lignin particle,the CO_(2)generation is found to be almost at the same time as its volatile combustion stage begins.The measurement technique and results presented in this work are of practical interest for biomass combustion studies and arc meaningful for the development of biomass thermal conversion mode.
基金This work was supported by the National Natural Science Foundation of China （No.41005017）, the Instrument Developing Project of the Chinese Academy of Sciences （No.YZ201121）, Jiangsu Provincial Natural Science Foundation of China （No.BK2011829）, and the Open Research Fund of Key Laboratory of Atmospheric Composition and Optical Radiation. The support of the Groupement de Recherche International SAMIA between CNRS （National Center for Scientific Research, France）, RFBR （Russian Foundation for Basic Research, Russia）, and CAS （Chinese Academy of Sciences, China） is acknowledged. We thank Dr. Albert A. Ruth at university college cork for the helpful discussion on the Xe lamp source based IBBCEAS.
文摘Chlorine dioxide （OC10） is an important indicator for Cl-activation. The monitoring of OC10 appears to be crucial for understanding the chemistry of Cl-initialed oxidation and its impact on air quality in polluted coastal regions and industrialized areas. We report the development of a Xe arc lamp based near-ultraviolet （335-375 nm） incoherent broad- band cavity enhanced absorption spectroscopy （IBBCEAS） spectrometer for quantitative assessment of OC10 in an atmospheric simulation chamber. The important intermediate compound CH20, and other key atmospheric trace species （NO2） were also simultaneously measured. The instrumental performance shows a strong potential of this kind of IBBCEAS instrument for field and laboratory studies of atmospheric halogen chemistry.
基金This work was supported by the National Natural Basic Research Program of China （No.2013CB922200）,the National Natural Science Foundation of China （No.11674128, No.11474129, and No.11504129）, Jilin Province Scientific and Technological Development Program, China （No.20170101063JC）, the Thirteenth Five- Year Scientific and Technological Research Project of the Education Department of Jilin Province, China （No.n00）.
文摘The mixture of graphene oxide （GO） and dye molecules may provide some new applications due to unique electronic, optical, and structural properties. Methylene blue （MB）, a typ- ical anionic dye, can attach on GO via π-π stacking and electrostatic interaction, and the molecule removal process on GO has been observed. However, it remains unclear about the ultrafast carrier dynamics and the internal energy transfer pathways of the system which is composed of GO and MB. We have employed ultrafast optical pump-probe spectroscopy to investigate the excited dynamics of the GO-MB system dispersed in water by exciting the samples at 400 nm pump pulse. The pristine MB and GO dynamics are also analyzed in tandem for a direct comparison. Utilizing the global analysis to fit the measured signal via a sequential model, five lifetimes are acquired：（0.61±0.01） ps, （3.52±0.04） ps, （14.1±0.3） ps, （84±2） ps, and （3.66±0.08） ns. The ultrafast dynamics corresponding to these lifetimes was analyzed and the new relaxation processes were found in the GO-MB system, compared with the pristine MB. The results reveal that the functionalization of GO can alter the known decay pathways of MB via the energy transfer from GO to MB in system, the increased intermediate state, and the promoted energy transfer from triplet state MB to ground state oxygen molecules dissolved in aqueous sample.
文摘The long-path differential optical absorption spectroscopy （LP-DOAS） technique was developed to mea- sure nighttime atmospheric nitrate radical （NO3） concentrations. An optimized retrieval method, resulting in a small residual structure and low detection limits, was developed to retrieve NO3. The time series of the NO3 concentration were collected from 17 to 24 March, 2006, where a nighttime average value of 15.8 ppt was observed. The interfering factors and errors are also discussed. These results indicate that the DOAS technique provides an essential tool for the quantification of NO3 concentration and in the study of its effects upon nighttime chemistry.
文摘Electrochemical energy conversion technologies involving processes such as water splitting and O_(2)/CO_(2) reduction,provide promising solutions for addressing global energy scarcity and minimizing adverse environmental impact.However,due to a lack of an in-depth understanding of the reaction mechanisms and the nature of the active sites,further advancement of these techniques has been limited by the development of efficient and robust catalysts.Therefore,in situ characterization of these electrocatalytic processes under working conditions is essential.In this review,recent applications of in situ Raman spectroscopy and X-ray absorption spectroscopy for various nano-and single-atom catalysts in energy-related reactions are summarized.Notable cases are highlighted,including the capture of oxygen-containing intermediate species formed during the reduction of oxygen and oxidation of hydrogen,and the detection of catalyst structural transformations occurring with the change in potential during the evolution of oxygen and reduction of CO_(2).Finally,the challenges and outlook for advancing in situ spectroscopic technologies to gain a deeper fundamental understanding of these energy-related electrocatalytic processes are discussed.
基金supported by the National Natural Science Foundation of China(Grant No.11272338)the Science and Technology on Scramjet Key Laboratory Funding,China(Grant No.STSKFKT 2013004)the China Scholarship Council
文摘An accurate and reasonable technique combining direct absorption spectroscopy and laser-induced fluorescence（LIF）methods is developed to quantitatively measure the concentrations of hydroxyl in CH;/air flat laminar flame. In our approach, particular attention is paid to the linear laser-induced fluorescence and absorption processes, and experimental details as well. Through measuring the temperature, LIF signal distribution and integrated absorption, spatially absolute OH concentrations profiles are successfully resolved. These experimental results are then compared with the numerical simulation. It is proved that the good quality of the results implies that this method is suitable for calibrating the OH-PLIF measurement in a practical combustor.
文摘Various experimental conditions were described for the vanadium determinationby graphite furnace atomic absorption spectroscopy (GFAAS). The experiments showed that whenatomization took place under the conditions where the combination of a pyrolytic coating graphitetube and fast raising temperature were used and the temperature was stable, the signal peak shapescould be improved, the sensitivity was enhanced, and the memory effect was removed. The vanadium infood and traditional Chinese medicinal herbs can be accurately determined using the standard curvemethod.
基金supported by the National Natural Science Foundation of China(No.51976209)the Fundamental Research Funds for the Central Universities(No.WK2320000040)supported by the Youth Innovation Promotion Association CAS(No.Y201768)。
文摘Based on the synchrotron soft X-ray absorption spectroscopy experiments,the fundamental electronic structures of layered Li NixCoyMnzO_(2)(NCM)are investigated systematically and the data of transitionmetal(TM)L-and O K-edges spectra are collected.Distribution of Ni ions under different oxidation states is evaluated according to linear combination fit.It is found that the ratio of Ni^(4+)expands with the increase of Ni since it dominates in charge compensation during charging,and that the existence of Ni^(3+)is nearly negligible in delithiated NCM.The valence state of Co also strongly depends on Ni content,the perceptible position shift of Co L_(3)-edge absorption peak towards higher energy in Ni-rich material agrees well with the small voltage plateau at around 4.2 V.The stability of Mn is verified as no obvious spectral change with the Mn L-edge is observed.Moreover,as Ni content rises,the O 2p holes near the Femi level increases with higher oxidation state of Ni,indicating the enhanced hybridization of O 2p-TM 3 d.Delithiated NCMs with higher Ni content are prior to lose electron existing in highly hybridized Ni3 dO 2 p bands upon heating,which accounts for the pronounced O_(2)release in phase transitions and the deterioration in thermal stability.These detailed observation of the electronic structure evolution is one of the key ingredients to improving the electrochemical and thermal performance of NCM.
文摘Exhaust gas temperature is an important factor in NOx, THC and PM emissions of engines. Especially 2D temperature and concentration distribution plays an important role for the engine efficiency. A thermocouple is intrinsically a point temperature measurement method and noncontact 2D temperature distribution cannot be attained by thermocouples. Recently, as a measurement technique with high sensitivity and high response, laser diagnostics has been developed and applied to the actual engine combustions. With these engineering developments, transient phenomena such as start-ups and load changes in engines have been gradually elucidated in various conditions. In this study, the theoretical and experimental research has been conducted in order to develop the noncontact and fast response 2D temperature and concentration distribution measurement method. The method is based on a Computed Tomography （CT） method using absorption spectra of water vapor at 1388 nm. It has been demonstrated that the method has been successfully applied to engine exhausts to measure 2D temperature distributions.
基金partly supported by National Natural Science Foundation of China(Nos.11975061,52111530088)the Technology Innovation and Application Development Project of Chongqing(No.cstc2019jscx-msxm X0041)+1 种基金the Construction Committee Project of Chongqing(No.2018-1-3-6)the Fundamental Research Funds for the Central Universities(No.2019CDQYDQ034)。
文摘Nitric oxide(NO)is one of the most crucial products in the plasma-based nitrogen fixation process.In this work,in situ measurements were performed for quantifying the NO synthesis spatially in a warm air glow discharge,through the method of Mid-infrared quantum cascade laser absorption spectroscopy(QCL-AS).Two ro-vibrational transitions at 1900.076 cm^(-1) and 1900.517 cm^(-1) of the ground-state NO(X)were probed sensitively by the help of the wavelength modulation spectroscopy(WMS)approach to increase the signal/noise(S/N)level.The results show a decline trend of NO synthesis rate along the discharge channel from the cathode to the anode.However,from the point of energy efficiency,the cathode region is of significantly low energy efficiency of NO production.Severe disproportionality was found for the high energy consumption but low NO production in the region of cathode area,compared to that in the positive column zone.Further analysis demonstrates the high energy cost of NO production in the cathode region,is ascribed to the extremely high reduced electric field E/N therein not selectively preferable for the processes of vibrational excitation or dissociation of N_(2) and O_(2) molecules.This drags down the overall energy efficiency of NO synthesis by this typical warm air glow discharge,particularly for the ones with short electrode gaps.Limitations of further improving the energy cost of NO synthesis by variations of the discharge operation conditions,such as discharge current or airflow rate,imply other effective manners able to tune the energy delivery selectively to the NO formation process,are sorely needed.
基金supported by the National Natural Science Foundation of China(Grant Nos.11335004,11722541,11675039,and 11747153)the Important National Science and Technology Specific Project,China(Grant No.2011ZX02403-001)
文摘Densities of Ar metastable states 1s5 and 1s3 are measured by using the tunable diode laser absorption spectroscopy（TDLAS） in Ar and Ar/O2 mixture dual-frequency capacitively coupled plasma（DF-CCP）. We investigate the effects of high-frequency（HF, 60 MHz） power, low-frequency（LF, 2 MHz） power, and working pressure on the density of Ar metastable states for three different gas components（0%, 5%, and 10% oxygen mixed in argon）. The dependence of Ar metastable state density on the oxygen content is also studied at different working pressures. It is found that densities of Ar metastable states in discharges with different gas components exhibit different behaviors as HF power increases. With the increase of HF power, the metastable density increases rapidly at the initial stage, and then tends to be saturated at a higher HF power. With a small fraction（5% or 10%） of oxygen added in argon plasma, a similar change of the Ar metastable density with HF power can be observed, but the metastable density is saturated at a higher HF power than in the pure argon discharge. In the DF-CCP, the metastable density is found to be higher than in a single frequency discharge, and has weak dependence on LF power. As working pressure increases, the metastable state density first increases and then decreases,and the pressure value, at which the density maximum occurs, decreases with oxygen content increasing. Besides, adding a small fraction of oxygen into argon plasma will significantly dwindle the metastable state density as a result of quenching loss by oxygen molecules.
基金supported by the National Natural Science Foundation of China(No.21603049,No.11674355,No.11705043,No.21327804,No.11364043)the Fundamental Research Funds for the Central Universities(No.JZ2015HGBZ0532)+1 种基金the Industry-UniversityResearch Fund of Hefei University of Technology Xuancheng Campus(No.XC2016JZBZ11)the Natural Science Foundation of Xinjiang Uygur Autonomous Region(No.2016D01A058)
文摘The ultrafast photoisomerization and excited-state dynamics of trans-4-methoxyazobenzene (trans-4-MAB) in solutions were investigated by femtosecond transient absorption spectroscopy and quantum chemistry calculations. After being excited to the S2 state, the two-dimensional transient absorptions spectra show that cis-4-MAB is produced and witnessed by the permanent positive absorption in 400-480 nm. Three decay components are determined to be 0.11, 1.4 and 2.9 ps in ethanol, and 0.16, 1.5 and 7.5 ps in ethylene glycol, respectively. The fast component is assigned to the internal conversion from the S2 to S1 state. The other relaxation pathways are correlated with the decay of the S1 state via internal conversion and isomerization, and the vibrational cooling of the hot S0 state of the cis-isomer. Comparing of the dynamics in different solvents, it is demonstrated that the photoisomerization pathway undergoes the inversion mechanism rather than the rotation mechanism.
基金supported by the National Key R&D Program of China(Nos.2016YFD0700101 and 2016YFC0303902)the National Natural Science Foundation of China(Nos.61775079,61627823 and 61307124)+3 种基金the Science and Technology Planning Project of Guangdong Province,China(No.2017A020216011)the Science and Technology Development Program of Jilin Province,China(No.20140307014SF)the Industrial Innovation Program of Jilin Province,China(No.2017C027)Changchun Municipal Science and Technology Bureau,China(No.14KG022)
文摘A dual-gas sensor system is developed for CO and CO_2 detection using a single broadband light source, pyroelectric detectors and time-division multiplexing(TDM) technique. A stepper motor based rotating system and a single-reflection spherical optical mirror are designed and adopted for realizing and enhancing dual-gas detection. Detailed measurements under static detection mode(without rotation) and dynamic mode(with rotation) are performed to study the performance of the sensor system for the two gas samples. The detection period is 7.9 s in one round of detection by scanning the two detectors. Based on an Allan deviation analysis, the 1σ detection limits under static operation are 3.0 parts per million(ppm) in volume and 2.6 ppm for CO and CO_2, respectively, and those under dynamic operation are 9.4 ppm and 10.8 ppm for CO and CO_2, respectively. The reported sensor has potential applications in various fields requiring CO and CO_2 detection such as in the coal mine.
基金supported by the Basic Science Research Program of the National Research Foundation(NRF)of South Koreafunded by the Ministry of Science&ICT and Future Planning(NRF-2020M3H4A3081889)KIST Institutional Program of South Korea(Project Nos.2E31860)。
文摘Elucidation of a reaction mechanism is the most critical aspect for designing electrodes for highperformance secondary batteries.Herein,we investigate the sodium insertion/extraction into an iron fluoride hydrate(FeF_(3)·0.5H_(2)O)electrode for sodium-ion batteries(SIBs).The electrode material is prepared by employing an ionic liquid 1-butyl-3-methylimidazolium-tetrafluoroborate,which serves as a reaction medium and precursor for F^(-)ions.The crystal structure of FeF_(3)·0.5H_(2)O is observed as pyrochlore type with large open 3-D tunnels and a unit cell volume of 1129A^(3).The morphology of FeF_(3)·0.5H_(2)O is spherical shape with a mesoporous structure.The microstructure analysis reveals primary particle size of around 10 nm.The FeF_(3)·0.5H_(2)O cathode exhibits stable discharge capacities of 158,210,and 284 mA h g^(-1) in three different potential ranges of 1.5-4.5,1.2-4.5,and 1.0-4.5 V,respectively at 0.05 C rate.The specific capacities remained stable in over 50 cycles in all three potential ranges,while the rate capability was best in the potential range of 1.5-4.5 V.The electrochemical sodium storage mechanism is studied using X-ray absorption spectroscopy,indicating higher conversion at a more discharged state.Ex-situ M?ssbauer spectroscopy strengthens the results for reversible reduction/oxidation of Fe.These results will be favorable to establish high-performance cathode materials with selective voltage window for SIBs.
基金Supported by the Thailand Research Fund under Grant No TRG5880097
文摘The local structure of an alternative Pb（Zn1/3Nb2/3）O3-based perovskite ceramic is investigated. The 0.07BaTiO33-0.93Pb（Zn1/3Nb2/3）O3 ceramic is synthesized using a combination of Zn3Nb2O8 B-site precursor and BaTiO33 perovskite phase stabilizer. Then, x-ray absorption spectroscopy and density functional theory are employed to calculate the local structure configuration and formation energy of the prepared samples. Ba2＋ is found to replace Pb2＋ in AA-site with Zn2＋ occupying BB-site in Pb（Zn1/3Nb2/3）O3, while in the neighboring structure, Ti4＋4＋ replaces Nb5＋5＋ in BB-site with Pb2＋2＋ occupying AA-site. With the substitution of BaTiO33 in Pb（Zn1/3Nb2/3）O3, the bond length between Zn2＋ and Pb2＋ is longer than that of the typical perovskite phase of Pb（Zn1/3Nb2/3）O3. This indicates the key role of BaTiO33 in decreasing the steric hindrance of Pb2＋ lone pair, and the mutual interactions between Pb2＋ lone pair and Zn2＋ and the formation energy is seen to decrease. This finding of the formation energy and local structure configuration relationship can further extend a fundamental understanding of the role of BaTiO33 in stabilizing the perovskite phase in PbZn13Nb23O3-based materials, which in turn will lead to an improved preparation technique for desired electrical properties.
