Hydrogen production by water reduction reactions has received considerable attention because hydrogen is considered a clean-energy carrier,key for a sustainable energy future.Computational methods have been widely use...Hydrogen production by water reduction reactions has received considerable attention because hydrogen is considered a clean-energy carrier,key for a sustainable energy future.Computational methods have been widely used to study the reaction mechanism of the hydrogen evolution reaction(HER),but the calculation results need to be supported by experimental results and direct evidence to confirm the mechanistic insights.In this review,we discuss the fundamental principles of the in situ spectroscopic strategy and a theoretical model for a mechanistic understanding of the HER.In addition,we investigate recent studies by in situ Fourier transform infrared(FTIR),Raman spectroscopy,and X-ray absorption spectroscopy(XAS) and cover new findings that occur at the catalyst-electrolyte interface during HER.These spectroscopic strategies provide practical ways to elucidate catalyst phase,reaction intermediate,catalyst-electrolyte interface,intermediate binding energy,metal valency state,and coordination environment during HER.展开更多
The interaction of proteins with salt ions plays an important role in life activities.We used butyramide as a model molecule to investigate the interaction of protein backbones with cations.The experiment was performe...The interaction of proteins with salt ions plays an important role in life activities.We used butyramide as a model molecule to investigate the interaction of protein backbones with cations.The experiment was performed in an aqueous solution of metal chloride using UV Raman spectroscopy.It was found that well-hydrated metal cations(Ca^(2+),Mg^(2+))tend to bind to C=O in the amide bond,resulting in redistribution of the amide I band peaks.Specifically,the peak intensity ratio of 1655 cm^(-1)to 1610 cm^(-1)increases significantly with increasing concentrations.However,this phenomenon is not obviously observed in NaCl solution.Furthermore,we studied the effect of salt ions on the water structures.The addition of Ca^(2+)and Mg^(2+)is beneficial to the enhancement of the water signal at the 3400 cm^(-1)position,while the Na^(+)at the same concentration is not obvious.The results have shown that the interaction between cations and amides satisfies the following order:Ca^(2+)>Mg^(2+)>Na^(+),which conforms to the Hofmeister series.展开更多
Rapid and sensitive detection of dissolved gases in seawater is quite essential for the investigation of the global carbon cycle.Large quantities of in situ optical detection techniques showed restricted measurement e...Rapid and sensitive detection of dissolved gases in seawater is quite essential for the investigation of the global carbon cycle.Large quantities of in situ optical detection techniques showed restricted measurement efficiency,owing to the single gas sensor without the identification ability of multiple gases.In this work,a novel gas-liquid Raman detection method of monitoring the multi-component dissolved gases was proposed based on a continuous gas-liquid separator under a large difference of partial pressure.The limit of detection(LOD)of the gas Raman spectrometer could arrive at about 14 μl·L^(-1)for N_(2)gas.Moreover,based on the continuous gas-liquid separation process,the detection time of the dissolved gases could be largely decreased to about 200 s compared with that of the traditional detection method(30 min).Effect of equilibrium time on gas-liquid separation process indicated that the extracted efficiency and decay time of these dissolved gases was CO_(2)>O_(2)>N_(2).In addition,the analysis of the relationship between equilibrium time and flow speed indicated that the decay time decreased with the increase of the flow speed.The validation and application of the developed system presented its great potential for studying the components and spatiotemporal distribution of dissolved gases in seawater.展开更多
Graphitized carbon foams(GFms)were prepared using mesophase pitch(MP)as a raw material by foaming(450℃),pre-oxidation(320℃),carbonization(1000℃)and graphitization(2800℃).The differences in structure and properties...Graphitized carbon foams(GFms)were prepared using mesophase pitch(MP)as a raw material by foaming(450℃),pre-oxidation(320℃),carbonization(1000℃)and graphitization(2800℃).The differences in structure and properties of GFms prepared from different MP precursors pretreated by ball milling or liquid phase extraction were investigated and compared,and semi-quantitative calculations were conducted on the Raman and FTIR spectra of samples at each preparation stage.Semi-quantitat-ive spectroscopic analysis provided detailed information on the structure and chemical composition changes of the MP and GFm de-rived from it.Combined with microscopic observations,the change from precursor to GFm was analyzed.The results showed that ball milling concentrated the distribution of aromatic molecules in the pitch,which contributed to uniform foaming to give a GFm with a uniform pore distribution and good properties.Liquid phase extraction helped remove light components while retaining large aromatics to form graphitic planes with the largest average size during post-treatment to produce a GFm with the highest degree of graphitization and the fewest open pores,giving the best compression resistance(2.47 MPa),the highest thermal conductivity(64.47 W/(m·K))and the lowest electrical resistance(13.02μΩ·m).Characterization combining semi-quantitative spectroscopic ana-lysis with microscopic observations allowed us to control the preparation of the MP-derived GFms.展开更多
By combination of the transient Raman spectroscopic measurement and the density functional theoretical calculations,the structural evolution and stability of TATB under shock compression was investigated.Due to the im...By combination of the transient Raman spectroscopic measurement and the density functional theoretical calculations,the structural evolution and stability of TATB under shock compression was investigated.Due to the improvement in synchronization control between two-stage light gas gun and the transient Raman spectra acquisition,as well as the sample preparation,the Raman peak of the N-O mode of TATB was firstly observed under shock pressure up to 13.6 GPa,noticeably higher than the upper limit of 8.5 GPa reported in available literatures.By taking into account of the continuous shift of the main peak and other observed Raman peaks,we did not distinguish any structural transition or any new species.Moreover,both the present Raman spectra and the time-resolved radiation of TATB during shock loading showed that TATB exhibits higher chemical stability than previous declaration.To reveal the detailed structural response and evolution of TATB under compression,the density functional theoretical calculations were conducted,and it was found that the pressure make N-O bond lengths shorter,nitro bond angles larger,and intermolecular and intra-molecular hydrogen bond interactions enhanced.The observed red shift of Raman peak was ascribed to the abnormal enhancement of H-bound effect on the scissor vibration mode of the nitro group.展开更多
Au-Ag alloy nanostars based flexible paper surface enhanced Raman spectroscopy sensors were fabricated through simple nanostar coating on regular office paper,and the surface enhanced Raman spectroscopy detection perf...Au-Ag alloy nanostars based flexible paper surface enhanced Raman spectroscopy sensors were fabricated through simple nanostar coating on regular office paper,and the surface enhanced Raman spectroscopy detection performances were investigated using crystal violet dye analyte.Au-Ag nanostars with sharp tips were synthesized via metal ions reduction method.Transmission electron microscope images,X-Ray diffraction pattern and energy dispersive spectroscopy elemental mapping confirmed the nanostar geometry and Au/Ag components of the nanostructure.UV-Vis-NIR absorption spectrum shows wide local surface plasmon resonance induced optical extinction.In addition,finite-difference time-domain simulation shows much stronger electromagnetic field from nanostars than from sphere nanoparticle.The effect of coating layer on Raman signal intensities was discussed,and optimized 5-layer coating with best Raman signal was obtained.The Au-Ag nanostatrs homogeneously distribute on paper fiber surface.The detection limit is 10-10 M,and the relationship between analyte concentrations and Raman signal intensities shows well linear,for potential quantitative analysis.The calculated enhancement factor is 4.795×10^(6).The flexible paper surface enhanced Raman spectroscopy sensors could be applied for trace chemical and biology molecule detection.展开更多
Interfacial water molecules are the most important participants in the hydrogen evolution reaction(HER).Hence,understanding the behavior and role that interfacial water plays will ultimately reveal the HER mechanism.U...Interfacial water molecules are the most important participants in the hydrogen evolution reaction(HER).Hence,understanding the behavior and role that interfacial water plays will ultimately reveal the HER mechanism.Unfortunately,investigating interfacial water is extremely challenging owing to the interference caused by bulk water molecules and complexity of the interfacial environment.Here,the behaviors of interfacial water in different cationic electrolytes on Pd surfaces were investigated by the electrochemistry,in situ core-shell nanostructure enhanced Raman spectroscopy and theoretical simulation techniques.Direct spectral evidence reveals a red shift in the frequency and a decrease in the intensity of interfacial water as the potential is shifted in the positively direction.When comparing the different cation electrolyte systems at a given potential,the frequency of the interfacial water peak increases in the specified order:Li+<Na^(+)<K^(+)<Ca^(2+)<Sr^(2+).The structure of interfacial water was optimized by adjusting the radius,valence,and concentration of cation to form the two-H down structure.This unique interfacial water structure will improve the charge transfer efficiency between the water and electrode further enhancing the HER performance.Therefore,local cation tuning strategies can be used to improve the HER performance by optimizing the interfacial water structure.展开更多
The Marplex Convention was established to prevent the manufacture of unmarked plastic explosives and stipulates that a volatile detection agent must be added at the time of manufacture.However,to-date,laboratory testi...The Marplex Convention was established to prevent the manufacture of unmarked plastic explosives and stipulates that a volatile detection agent must be added at the time of manufacture.However,to-date,laboratory testing remains the internationally accepted practice for identifying and quantifying the taggants stipulated in the Convention.In this project,portable FTIR and Raman instruments were tested for their ability to detect 2,3-dimethyl-2,3-dinitrobutane(DMDNB),the chemical marker incorporated in plastic explosives that are manufactured within Australia.While both FTIR and Raman instruments detected solid DMDNB(98%purity),field analysis of plastic explosives at an Australian Defence establishment showed that both FTIR and Raman spectra were matched the relevant explosive(RDX or PETN),rather than the DMDNB taggant.For all three plastic explosives tested,the concentration of DMDNB was measured by SPME-GC-MS to be between 1.8 and 2%,greater than the minimum 1%concentration stipulated by the Marplex Convention.Additional testing with a plastic explosive analogue confirmed that the minor absorption peaks that would characterize low concentrations of DMDNB were masked by absorption bands from other compounds within the solid.Thus,while both FTIR and Raman spectroscopy are suitable for detection of plastic explosives,neither rely on the presence of DMDNB for detection.It is likely that similar results would be found for other taggants stipulated by the Marplex Convention,given they are also present in concentrations less than 1%.展开更多
Staling is an important issue that Chinese steamed bread(CSB)may encounter during storage,which significantly affects their taste,flavor,and nutritional value.The monitoring technology for rapid aging is particularly ...Staling is an important issue that Chinese steamed bread(CSB)may encounter during storage,which significantly affects their taste,flavor,and nutritional value.The monitoring technology for rapid aging is particularly important to effectively control the aging process of CSB,reduce quality deterioration,and promote the industrial production of CSB.Raman spectroscopy has been widely used in the study of food structure and properties due to its non-destructive and high-sensitivity characteristics,particularly demonstrating unique advantages in the analysis of starch structure.This study explored the possibility of analyzing the staling of CSB using Raman spectroscopy based on hardness and moisture content.Analysis of the correlation between the hardness of CSB and the full width at half maximum(FWHM)at 480 cm^(−1)during storage was conducted,and a significant positive correlation between them was found,with R^(2)above 0.8.Besides,nine characteristic peaks of CSB samples related to starch were selected for analysis.As the moisture content of CSB decreased,the peak intensities and areas of showed an upward trend during storage,with the best correlation coefficient above 0.8 revealed by linear regression analysis.Therefore,Raman spectra could be used as a potential method for the fast prediction of CSB staling.展开更多
The effect of silicon doping on the residual stress of CVD diamond films is examined using both X-ray diffraction (XRD) analysis and Raman spectroscopy measurements. The examined Si-doped diamond films are deposited o...The effect of silicon doping on the residual stress of CVD diamond films is examined using both X-ray diffraction (XRD) analysis and Raman spectroscopy measurements. The examined Si-doped diamond films are deposited on WC-Co substrates in a home-made bias-enhanced HFCVD apparatus. Ethyl silicate (Si(OC2H5)4) is dissolved in acetone to obtain various Si/C mole ratio ranging from 0.1% to 1.4% in the reaction gas. Characterizations with SEM and XRD indicate increasing silicon concentration may result in grain size decreasing and diamond [110] texture becoming dominant. The residual stress values of as-deposited Si-doped diamond films are evaluated by both sin2ψ method, which measures the (220) diamond Bragg diffraction peaks using XRD, with ψ-values ranging from 0° to 45°, and Raman spectroscopy, which detects the diamond Raman peak shift from the natural diamond line at 1332 cm-1. The residual stress evolution on the silicon doping level estimated from the above two methods presents rather good agreements, exhibiting that all deposited Si-doped diamond films present compressive stress and the sample with Si/C mole ratio of 0.1% possesses the largest residual stress of ~1.75 GPa (Raman) or ~2.3 GPa (XRD). As the silicon doping level is up further, the residual stress reduces to a relative stable value around 1.3 GPa.展开更多
Raman spectrum of molten cryolite was recorded. Based on the new understanding of the scattering coefficients, contents of various structural entities in acidic NaF-AlF3 melts at 942-1 024 ℃ in previous research were...Raman spectrum of molten cryolite was recorded. Based on the new understanding of the scattering coefficients, contents of various structural entities in acidic NaF-AlF3 melts at 942-1 024 ℃ in previous research were reanalyzed. The new quantitative analysis results show that when cryolite ratio（CR） is less than 2, AlF4- is the dominant anion in the melts, and its mole fraction is about 0.70 for melts with CR=1.5 and 0.50 for melts with CR=2. When CR is more than 2.5, the mole fraction of AlF6^3- is relatively large, which is around 0.45 for melts with CR=2.5. Ionic structure of Na3AlF6-Al2O3 melts was investigated by UV-Raman spectroscopy. Octahedral AlF6^3- and tetrahedral AlF4- are proved to exist with possible partial replacement of F- by O^2-. Al2O2F4^2- with a large scattering coefficient also exists in the melts in which alumina concentration is more than 4% （mass fraction）. The increase of temperature causes blue-shift of the bands in the Raman spectra.展开更多
Nitrogen hydrate samples were synthesized using liquid nitrogen and powder ice at 16 MPa and 253 K. Confocal laser Raman spectroscopy was used to investigate the characteristics of nitrogen clathrate hydrates. The res...Nitrogen hydrate samples were synthesized using liquid nitrogen and powder ice at 16 MPa and 253 K. Confocal laser Raman spectroscopy was used to investigate the characteristics of nitrogen clathrate hydrates. The results show that the Raman peaks of N-N and O-H stretching vibration in nitrogen hydrates are observed at 2322.4 and 3092.1 cm^-1, respectively, which are very similar to those in natural air clathrate hydrates. For comparison, we measured the Raman peaks of N-N stretching vibration both in liquid nitrogen and nitrogen molecules saturated water, which appear at 2326.6 and 2325.0 cm^-1, respectively. The Raman spectroscopic observations on the dissociation process suggest that nitrogen molecules occupy both the large and small cages in nitrogen clathrate hydrates. However, only one Raman peak is observed for N N stretching vibration because the difference of the environment of nitrogen molecules between large and small cages is too small to be differentiated by Raman spectroscopy.展开更多
Herein,a novel interference-free surface-enhanced Raman spectroscopy(SERS)strategy based on magnetic nanoparticles(MNPs)and aptamer-driven assemblies was proposed for the ultrasensitive detection of histamine.A core-s...Herein,a novel interference-free surface-enhanced Raman spectroscopy(SERS)strategy based on magnetic nanoparticles(MNPs)and aptamer-driven assemblies was proposed for the ultrasensitive detection of histamine.A core-satellite SERS aptasensor was constructed by combining aptamer-decorated Fe_(3)O_(4)@Au MNPs(as the recognize probe for histamine)and complementary DNA-modified silver nanoparticles carrying 4-mercaptobenzonitrile(4-MBN)(Ag@4-MBN@Ag-c-DNA)as the SERS signal probe for the indirect detection of histamine.Under an applied magnetic field in the absence of histamine,the assembly gave an intense Raman signal at“Raman biological-silent”region due to 4-MBN.In the presence of histamine,the Ag@4-MBN@Ag-c-DNA SERS-tag was released from the Fe_(3)O_(4)@Au MNPs,thus decreasing the SERS signal.Under optimal conditions,an ultra-low limit of detection of 0.65×10^(-3)ng/mL and a linear range 10^(-2)-10^5 ng/mL on the SERS aptasensor were obtained.The histamine content in four food samples were analyzed using the SERS aptasensor,with the results consistent with those determined by high performance liquid chromatography.The present work highlights the merits of indirect strategies for the ultrasensitive and highly selective SERS detection of small biological molecules in complex matrices.展开更多
The potential （E）-dependent vibrational behavior of a saturated CO adlayer on Au-core Pd-shell nanoparticle film electrodes was investigated over a wide potential range, in acidic, neutral, and basic solutions, usin...The potential （E）-dependent vibrational behavior of a saturated CO adlayer on Au-core Pd-shell nanoparticle film electrodes was investigated over a wide potential range, in acidic, neutral, and basic solutions, using in situ surface-enhanced Raman spectroscopy （SERS）. Over the whole of the examined potential region （-1.5 to 0.55 V vs. NHE）, the peak frequencies of both the C-OM and the Pd-COM band （here, M denotes the multiply-bonded configuration） displayed three distinct linear regions： dvc oM/dE decreased from -185-207 （from -1.5 to -1.2 V） to -83-84 cm-1/V （-1.2 to -0.15 V）, and then to 43 cm-1/V （-0.2 to 0.55 V）; on the other hand, dvpd coM/dE changed from -10 to -8 cm I/V （from -1.5 to -1.2 V） to ^-31 to -30 cm-1/V （-1.2 to -0.15 V）, and then to -15 cm-1/V （-0.2 to 0.55 V）. The simultaneously recorded cyclic voltammograms revealed that at E 〈 -1.2 V, a hydro- gen evolution reaction （HER） occurred. With the help of periodic density functional theory calcula- tions using two different （2 × 2）-3CO slab models with Pd（111）, the unusually high dvc-oM/dE and the small dVPd-CoM/dE in the HER region were explained as being due to the conversion of COad from bridge to hollow sites, which was induced by the co-adsorbed hydrogen atoms formed from dissociated water at negative potentials.展开更多
We re-evaluate the Raman spectroscopic quantification of the molar ratio and pressure for CH4–CO2 mixtures.Firstly,the Raman quantification factors of CH4 and CO2 increase with rising pressure at room temperature,ind...We re-evaluate the Raman spectroscopic quantification of the molar ratio and pressure for CH4–CO2 mixtures.Firstly,the Raman quantification factors of CH4 and CO2 increase with rising pressure at room temperature,indicating that Raman quantification of CH4/CO2 molar ratio can be applied to those fluid inclusions(FIs)with high internal pressure(i.e.,>15 MPa).Secondly,the v1(CH4)peak position shifts to lower wavenumber with increasing pressure at constant temperature,confirming that the v1(CH4)peak position can be used to calculate the fluid pressure.However,this method should be carefully calibrated before applying to FI analyses because large discrepancies exist among the reported v1(CH4)-P curves,especially in the highpressure range.These calibrations are applied to CH4-rich FIs in quartz veins of the Silurian Longmaxi black shales in southern Sichuan Basin.The vapor phases of these FIs are mainly composed of CH4 and minor CO2,with CO2 molar fractions from4.4%to 7.4%.The pressure of single-phase gas FI ranges from 103.65 to 128.35 MPa at room temperature,which is higher than previously reported.Thermodynamic calculations supported the presence of extremely high-pressure CH4-saturated fluid(218.03–256.82 MPa at 200°C),which may be responsible for the expulsion of CH4 to adjacent reservoirs.展开更多
基金the immense support provided by the National Research Foundation of Korea(NRF)Grant funded by the Korean Government(MSIT)(RS-2023–00210114)the National R&D Program through the National Research Foundation of Korea(NRF)funded by Ministry of Science and ICT(2021M3D1A2051636)。
文摘Hydrogen production by water reduction reactions has received considerable attention because hydrogen is considered a clean-energy carrier,key for a sustainable energy future.Computational methods have been widely used to study the reaction mechanism of the hydrogen evolution reaction(HER),but the calculation results need to be supported by experimental results and direct evidence to confirm the mechanistic insights.In this review,we discuss the fundamental principles of the in situ spectroscopic strategy and a theoretical model for a mechanistic understanding of the HER.In addition,we investigate recent studies by in situ Fourier transform infrared(FTIR),Raman spectroscopy,and X-ray absorption spectroscopy(XAS) and cover new findings that occur at the catalyst-electrolyte interface during HER.These spectroscopic strategies provide practical ways to elucidate catalyst phase,reaction intermediate,catalyst-electrolyte interface,intermediate binding energy,metal valency state,and coordination environment during HER.
基金supported by the National Natural Science Foundation of China(No.62005108,No.62205134)the Natural Science Foundation of the Higher Education Institutions of Jiangsu Province(No.21KJB140008)the Graduate Research and Practice Innovation Program of Jiangsu Normal University(No.2021XKT1201,No.2021XKT1204).
文摘The interaction of proteins with salt ions plays an important role in life activities.We used butyramide as a model molecule to investigate the interaction of protein backbones with cations.The experiment was performed in an aqueous solution of metal chloride using UV Raman spectroscopy.It was found that well-hydrated metal cations(Ca^(2+),Mg^(2+))tend to bind to C=O in the amide bond,resulting in redistribution of the amide I band peaks.Specifically,the peak intensity ratio of 1655 cm^(-1)to 1610 cm^(-1)increases significantly with increasing concentrations.However,this phenomenon is not obviously observed in NaCl solution.Furthermore,we studied the effect of salt ions on the water structures.The addition of Ca^(2+)and Mg^(2+)is beneficial to the enhancement of the water signal at the 3400 cm^(-1)position,while the Na^(+)at the same concentration is not obvious.The results have shown that the interaction between cations and amides satisfies the following order:Ca^(2+)>Mg^(2+)>Na^(+),which conforms to the Hofmeister series.
基金the National Natural Science Foundation of China(52304236)the Natural Science Foundation of Shandong Province(ZR2021QE076)for the financial support to this research extracted from the project.
文摘Rapid and sensitive detection of dissolved gases in seawater is quite essential for the investigation of the global carbon cycle.Large quantities of in situ optical detection techniques showed restricted measurement efficiency,owing to the single gas sensor without the identification ability of multiple gases.In this work,a novel gas-liquid Raman detection method of monitoring the multi-component dissolved gases was proposed based on a continuous gas-liquid separator under a large difference of partial pressure.The limit of detection(LOD)of the gas Raman spectrometer could arrive at about 14 μl·L^(-1)for N_(2)gas.Moreover,based on the continuous gas-liquid separation process,the detection time of the dissolved gases could be largely decreased to about 200 s compared with that of the traditional detection method(30 min).Effect of equilibrium time on gas-liquid separation process indicated that the extracted efficiency and decay time of these dissolved gases was CO_(2)>O_(2)>N_(2).In addition,the analysis of the relationship between equilibrium time and flow speed indicated that the decay time decreased with the increase of the flow speed.The validation and application of the developed system presented its great potential for studying the components and spatiotemporal distribution of dissolved gases in seawater.
文摘Graphitized carbon foams(GFms)were prepared using mesophase pitch(MP)as a raw material by foaming(450℃),pre-oxidation(320℃),carbonization(1000℃)and graphitization(2800℃).The differences in structure and properties of GFms prepared from different MP precursors pretreated by ball milling or liquid phase extraction were investigated and compared,and semi-quantitative calculations were conducted on the Raman and FTIR spectra of samples at each preparation stage.Semi-quantitat-ive spectroscopic analysis provided detailed information on the structure and chemical composition changes of the MP and GFm de-rived from it.Combined with microscopic observations,the change from precursor to GFm was analyzed.The results showed that ball milling concentrated the distribution of aromatic molecules in the pitch,which contributed to uniform foaming to give a GFm with a uniform pore distribution and good properties.Liquid phase extraction helped remove light components while retaining large aromatics to form graphitic planes with the largest average size during post-treatment to produce a GFm with the highest degree of graphitization and the fewest open pores,giving the best compression resistance(2.47 MPa),the highest thermal conductivity(64.47 W/(m·K))and the lowest electrical resistance(13.02μΩ·m).Characterization combining semi-quantitative spectroscopic ana-lysis with microscopic observations allowed us to control the preparation of the MP-derived GFms.
基金supported by the National Natural Science Foundation of China(Grant Nos.12072299,11902276)the Natural Science Foundation of Sichuan Province(Grant No.2022NSFSC1802)+1 种基金the Basic Research Project of Southwest Jiaotong University(Grant No.2682023ZTPY009)the National Key Laboratory for Shock Wave and Detonation Physics of China(Grant No.JCKYS2019212007)。
文摘By combination of the transient Raman spectroscopic measurement and the density functional theoretical calculations,the structural evolution and stability of TATB under shock compression was investigated.Due to the improvement in synchronization control between two-stage light gas gun and the transient Raman spectra acquisition,as well as the sample preparation,the Raman peak of the N-O mode of TATB was firstly observed under shock pressure up to 13.6 GPa,noticeably higher than the upper limit of 8.5 GPa reported in available literatures.By taking into account of the continuous shift of the main peak and other observed Raman peaks,we did not distinguish any structural transition or any new species.Moreover,both the present Raman spectra and the time-resolved radiation of TATB during shock loading showed that TATB exhibits higher chemical stability than previous declaration.To reveal the detailed structural response and evolution of TATB under compression,the density functional theoretical calculations were conducted,and it was found that the pressure make N-O bond lengths shorter,nitro bond angles larger,and intermolecular and intra-molecular hydrogen bond interactions enhanced.The observed red shift of Raman peak was ascribed to the abnormal enhancement of H-bound effect on the scissor vibration mode of the nitro group.
基金Funded by the Project of Sanya Yazhou Bay Science and Technology City(No.SCKJ-JYRC-2022-44)the Fundamental Research Funds for the Central Universities(WUT:2023Ⅲ007XXH)。
文摘Au-Ag alloy nanostars based flexible paper surface enhanced Raman spectroscopy sensors were fabricated through simple nanostar coating on regular office paper,and the surface enhanced Raman spectroscopy detection performances were investigated using crystal violet dye analyte.Au-Ag nanostars with sharp tips were synthesized via metal ions reduction method.Transmission electron microscope images,X-Ray diffraction pattern and energy dispersive spectroscopy elemental mapping confirmed the nanostar geometry and Au/Ag components of the nanostructure.UV-Vis-NIR absorption spectrum shows wide local surface plasmon resonance induced optical extinction.In addition,finite-difference time-domain simulation shows much stronger electromagnetic field from nanostars than from sphere nanoparticle.The effect of coating layer on Raman signal intensities was discussed,and optimized 5-layer coating with best Raman signal was obtained.The Au-Ag nanostatrs homogeneously distribute on paper fiber surface.The detection limit is 10-10 M,and the relationship between analyte concentrations and Raman signal intensities shows well linear,for potential quantitative analysis.The calculated enhancement factor is 4.795×10^(6).The flexible paper surface enhanced Raman spectroscopy sensors could be applied for trace chemical and biology molecule detection.
基金the National Key Research and Development Program of China(2019YFA0705400)the National Natural Science Foundation of China(T2293692,21925404,22021001,21991151,and 22002036)+1 种基金the Natural Science Foundation of Fujian Province of China(2021J06001)the National Natural Science Foundation of Henan province(232300421081).
文摘Interfacial water molecules are the most important participants in the hydrogen evolution reaction(HER).Hence,understanding the behavior and role that interfacial water plays will ultimately reveal the HER mechanism.Unfortunately,investigating interfacial water is extremely challenging owing to the interference caused by bulk water molecules and complexity of the interfacial environment.Here,the behaviors of interfacial water in different cationic electrolytes on Pd surfaces were investigated by the electrochemistry,in situ core-shell nanostructure enhanced Raman spectroscopy and theoretical simulation techniques.Direct spectral evidence reveals a red shift in the frequency and a decrease in the intensity of interfacial water as the potential is shifted in the positively direction.When comparing the different cation electrolyte systems at a given potential,the frequency of the interfacial water peak increases in the specified order:Li+<Na^(+)<K^(+)<Ca^(2+)<Sr^(2+).The structure of interfacial water was optimized by adjusting the radius,valence,and concentration of cation to form the two-H down structure.This unique interfacial water structure will improve the charge transfer efficiency between the water and electrode further enhancing the HER performance.Therefore,local cation tuning strategies can be used to improve the HER performance by optimizing the interfacial water structure.
基金funded by the Defence Science Technology Group(DSTG)。
文摘The Marplex Convention was established to prevent the manufacture of unmarked plastic explosives and stipulates that a volatile detection agent must be added at the time of manufacture.However,to-date,laboratory testing remains the internationally accepted practice for identifying and quantifying the taggants stipulated in the Convention.In this project,portable FTIR and Raman instruments were tested for their ability to detect 2,3-dimethyl-2,3-dinitrobutane(DMDNB),the chemical marker incorporated in plastic explosives that are manufactured within Australia.While both FTIR and Raman instruments detected solid DMDNB(98%purity),field analysis of plastic explosives at an Australian Defence establishment showed that both FTIR and Raman spectra were matched the relevant explosive(RDX or PETN),rather than the DMDNB taggant.For all three plastic explosives tested,the concentration of DMDNB was measured by SPME-GC-MS to be between 1.8 and 2%,greater than the minimum 1%concentration stipulated by the Marplex Convention.Additional testing with a plastic explosive analogue confirmed that the minor absorption peaks that would characterize low concentrations of DMDNB were masked by absorption bands from other compounds within the solid.Thus,while both FTIR and Raman spectroscopy are suitable for detection of plastic explosives,neither rely on the presence of DMDNB for detection.It is likely that similar results would be found for other taggants stipulated by the Marplex Convention,given they are also present in concentrations less than 1%.
基金the support from Scientific Research Project of Wuhan Polytechnic University(532100308).
文摘Staling is an important issue that Chinese steamed bread(CSB)may encounter during storage,which significantly affects their taste,flavor,and nutritional value.The monitoring technology for rapid aging is particularly important to effectively control the aging process of CSB,reduce quality deterioration,and promote the industrial production of CSB.Raman spectroscopy has been widely used in the study of food structure and properties due to its non-destructive and high-sensitivity characteristics,particularly demonstrating unique advantages in the analysis of starch structure.This study explored the possibility of analyzing the staling of CSB using Raman spectroscopy based on hardness and moisture content.Analysis of the correlation between the hardness of CSB and the full width at half maximum(FWHM)at 480 cm^(−1)during storage was conducted,and a significant positive correlation between them was found,with R^(2)above 0.8.Besides,nine characteristic peaks of CSB samples related to starch were selected for analysis.As the moisture content of CSB decreased,the peak intensities and areas of showed an upward trend during storage,with the best correlation coefficient above 0.8 revealed by linear regression analysis.Therefore,Raman spectra could be used as a potential method for the fast prediction of CSB staling.
基金Project (51005154) supported by the National Natural Science Foundation of ChinaProject (12CG11) supported by the Chenguang Program of Shanghai Municipal Education Commission, ChinaProject (201104271) supported by the China Postdoctoral Science Foundation
文摘The effect of silicon doping on the residual stress of CVD diamond films is examined using both X-ray diffraction (XRD) analysis and Raman spectroscopy measurements. The examined Si-doped diamond films are deposited on WC-Co substrates in a home-made bias-enhanced HFCVD apparatus. Ethyl silicate (Si(OC2H5)4) is dissolved in acetone to obtain various Si/C mole ratio ranging from 0.1% to 1.4% in the reaction gas. Characterizations with SEM and XRD indicate increasing silicon concentration may result in grain size decreasing and diamond [110] texture becoming dominant. The residual stress values of as-deposited Si-doped diamond films are evaluated by both sin2ψ method, which measures the (220) diamond Bragg diffraction peaks using XRD, with ψ-values ranging from 0° to 45°, and Raman spectroscopy, which detects the diamond Raman peak shift from the natural diamond line at 1332 cm-1. The residual stress evolution on the silicon doping level estimated from the above two methods presents rather good agreements, exhibiting that all deposited Si-doped diamond films present compressive stress and the sample with Si/C mole ratio of 0.1% possesses the largest residual stress of ~1.75 GPa (Raman) or ~2.3 GPa (XRD). As the silicon doping level is up further, the residual stress reduces to a relative stable value around 1.3 GPa.
基金Project (51004034) supported by the National Natural Science, ChinaProject(N090302009) supported by the Fundamental Research Funds for the Central Universities, China
文摘Raman spectrum of molten cryolite was recorded. Based on the new understanding of the scattering coefficients, contents of various structural entities in acidic NaF-AlF3 melts at 942-1 024 ℃ in previous research were reanalyzed. The new quantitative analysis results show that when cryolite ratio（CR） is less than 2, AlF4- is the dominant anion in the melts, and its mole fraction is about 0.70 for melts with CR=1.5 and 0.50 for melts with CR=2. When CR is more than 2.5, the mole fraction of AlF6^3- is relatively large, which is around 0.45 for melts with CR=2.5. Ionic structure of Na3AlF6-Al2O3 melts was investigated by UV-Raman spectroscopy. Octahedral AlF6^3- and tetrahedral AlF4- are proved to exist with possible partial replacement of F- by O^2-. Al2O2F4^2- with a large scattering coefficient also exists in the melts in which alumina concentration is more than 4% （mass fraction）. The increase of temperature causes blue-shift of the bands in the Raman spectra.
文摘Nitrogen hydrate samples were synthesized using liquid nitrogen and powder ice at 16 MPa and 253 K. Confocal laser Raman spectroscopy was used to investigate the characteristics of nitrogen clathrate hydrates. The results show that the Raman peaks of N-N and O-H stretching vibration in nitrogen hydrates are observed at 2322.4 and 3092.1 cm^-1, respectively, which are very similar to those in natural air clathrate hydrates. For comparison, we measured the Raman peaks of N-N stretching vibration both in liquid nitrogen and nitrogen molecules saturated water, which appear at 2326.6 and 2325.0 cm^-1, respectively. The Raman spectroscopic observations on the dissociation process suggest that nitrogen molecules occupy both the large and small cages in nitrogen clathrate hydrates. However, only one Raman peak is observed for N N stretching vibration because the difference of the environment of nitrogen molecules between large and small cages is too small to be differentiated by Raman spectroscopy.
基金financially supported by the National Natural Science Foundation of China(31972149)funding support from the MacDiarmid Institute for Advanced Materials and Nanotechnologythe Dodd-Walls Centre for Photonic and Quantum Technologies。
文摘Herein,a novel interference-free surface-enhanced Raman spectroscopy(SERS)strategy based on magnetic nanoparticles(MNPs)and aptamer-driven assemblies was proposed for the ultrasensitive detection of histamine.A core-satellite SERS aptasensor was constructed by combining aptamer-decorated Fe_(3)O_(4)@Au MNPs(as the recognize probe for histamine)and complementary DNA-modified silver nanoparticles carrying 4-mercaptobenzonitrile(4-MBN)(Ag@4-MBN@Ag-c-DNA)as the SERS signal probe for the indirect detection of histamine.Under an applied magnetic field in the absence of histamine,the assembly gave an intense Raman signal at“Raman biological-silent”region due to 4-MBN.In the presence of histamine,the Ag@4-MBN@Ag-c-DNA SERS-tag was released from the Fe_(3)O_(4)@Au MNPs,thus decreasing the SERS signal.Under optimal conditions,an ultra-low limit of detection of 0.65×10^(-3)ng/mL and a linear range 10^(-2)-10^5 ng/mL on the SERS aptasensor were obtained.The histamine content in four food samples were analyzed using the SERS aptasensor,with the results consistent with those determined by high performance liquid chromatography.The present work highlights the merits of indirect strategies for the ultrasensitive and highly selective SERS detection of small biological molecules in complex matrices.
基金supported by the National Natural Science Foundation of China(21473175)the National Instrumentation Program(2011YQ03012416)the National Basic Reserarch Program of China(973 Program,2015CB932301)
文摘The potential （E）-dependent vibrational behavior of a saturated CO adlayer on Au-core Pd-shell nanoparticle film electrodes was investigated over a wide potential range, in acidic, neutral, and basic solutions, using in situ surface-enhanced Raman spectroscopy （SERS）. Over the whole of the examined potential region （-1.5 to 0.55 V vs. NHE）, the peak frequencies of both the C-OM and the Pd-COM band （here, M denotes the multiply-bonded configuration） displayed three distinct linear regions： dvc oM/dE decreased from -185-207 （from -1.5 to -1.2 V） to -83-84 cm-1/V （-1.2 to -0.15 V）, and then to 43 cm-1/V （-0.2 to 0.55 V）; on the other hand, dvpd coM/dE changed from -10 to -8 cm I/V （from -1.5 to -1.2 V） to ^-31 to -30 cm-1/V （-1.2 to -0.15 V）, and then to -15 cm-1/V （-0.2 to 0.55 V）. The simultaneously recorded cyclic voltammograms revealed that at E 〈 -1.2 V, a hydro- gen evolution reaction （HER） occurred. With the help of periodic density functional theory calcula- tions using two different （2 × 2）-3CO slab models with Pd（111）, the unusually high dvc-oM/dE and the small dVPd-CoM/dE in the HER region were explained as being due to the conversion of COad from bridge to hollow sites, which was induced by the co-adsorbed hydrogen atoms formed from dissociated water at negative potentials.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.41922023 and 41830425)the Fundamental Research Funds for the Central Universities(Grant Nos.020614380056 and 020614380078).
文摘We re-evaluate the Raman spectroscopic quantification of the molar ratio and pressure for CH4–CO2 mixtures.Firstly,the Raman quantification factors of CH4 and CO2 increase with rising pressure at room temperature,indicating that Raman quantification of CH4/CO2 molar ratio can be applied to those fluid inclusions(FIs)with high internal pressure(i.e.,>15 MPa).Secondly,the v1(CH4)peak position shifts to lower wavenumber with increasing pressure at constant temperature,confirming that the v1(CH4)peak position can be used to calculate the fluid pressure.However,this method should be carefully calibrated before applying to FI analyses because large discrepancies exist among the reported v1(CH4)-P curves,especially in the highpressure range.These calibrations are applied to CH4-rich FIs in quartz veins of the Silurian Longmaxi black shales in southern Sichuan Basin.The vapor phases of these FIs are mainly composed of CH4 and minor CO2,with CO2 molar fractions from4.4%to 7.4%.The pressure of single-phase gas FI ranges from 103.65 to 128.35 MPa at room temperature,which is higher than previously reported.Thermodynamic calculations supported the presence of extremely high-pressure CH4-saturated fluid(218.03–256.82 MPa at 200°C),which may be responsible for the expulsion of CH4 to adjacent reservoirs.
