In situ infrared, Raman and X-ray spectroscopy for the mechanistic understanding of hydrogen evolution reaction

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.

Identifying the effect of photo-generated carriers on the phonons in rutile TiO_(2) through Raman spectroscopy

Investigating lattice vibrations through Raman spectroscopy is a crucial method for studying crystalline materials.Carriers can interact with lattices and influence lattice vibrations;thus,it is feasible to study the effect of photo-generated carriers on phonons by analyzing changes in the Raman spectra of semiconductors.Rutile is one of the predominant crystalline phases of TiO_(2),which is a widely utilized metal oxide semiconductor.In this work,rutile TiO_(2) is coated on a thinned optical fiber to concentrate ultraviolet light energy within the material,thereby enhancing the generation of carriers and amplifying the changes in the Raman spectra.A Raman detection laser with a wavelength of 532 nm is utilized to collect the Raman spectra of rutile TiO_(2) during irradiation.Using this setup,the impact of photo-generated carriers on the phonons corresponding to Raman vibrational modes is researched.The localization and non-radiative recombination of photo-generated carriers contribute to a reduction in both the frequencies and lifetimes of phonons.This work provides a novel approach to researching the effect of carriers on phonons.

Rapid and real-time analysis of multi-component dissolved gas in seawater by Raman spectroscopy combined with continuous gas-liquid separator

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.

Rapid analysis of Chinese steamed bread staling using Raman Spectroscopy

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.

Evaluation on residual stresses of silicon-doped CVD diamond films using X-ray diffraction and Raman spectroscopy

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.

Raman spectroscopy and ionic structure of Na_3AlF_(6-)Al_2O_3 melts

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.

Raman Spectroscopy of Nitrogen Clathrate Hydrates

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.

基于Raman光谱的3,5-二氨基-1,2,4-三唑(DAT)合成反应在线监测与反应机理探究——推荐一个仪器分析综合实验

本实验介绍了一个仪器分析综合性实验——基于Raman光谱的3,5-二氨基-1,2,4-三唑(DAT)合成的在线监测与反应机理探究。该实验是一个科研转化的仪器分析综合实验,内容包括DAT的合成、基于Raman光谱的合成反应过程在线监测以及合成反应机理解析。在实验中,采用化学计量学方法对Raman光谱数据进行处理和分析,以更深入地理解合成反应的机理。通过本实验,可以巩固学生的化学专业知识,提高学生的综合实验操作技能,激发学生对科学研究的兴趣,培养学生的科研探究能力。

基于Raman的复方柳安咖注射液主要成分分析

本文应用拉曼光谱技术对复方柳安咖注射液的主要成分及含量进行了分析。首先测试分析了62个复方柳安咖注射液样品的拉曼光谱,结果表明62个注射液样品的拉曼光谱主要由水杨酸钠、安替比林和咖啡因的水溶液拉曼谱带组成;进一步利用密度泛函理论(DFT)计算了其主要成分的理论拉曼光谱和红外光谱,与实验测定的固体粉末光谱和溶液光谱进行比较分析,进而对复方柳安咖注射液拉曼光谱谱峰的振动模式进行了归属;最后利用水杨酸钠和安替比林浓度梯度溶液拉曼光谱特征峰的峰高和峰面积,分别建立定量分析模型,对62个复方柳安咖注射液样品中主要成分水杨酸钠和安替比林的含量进行预测,并与液相色谱法测试值进行了对比,结果显示预测值与液相色谱法测试值相近,得到了较好的主要成分含量预测结果。研究结果可为复方柳安咖注射液药剂的生产、药品质量的监控、药品光谱分析研究等方面提供参考。

In situ Raman spectroscopic quantification of CH4–CO2 mixture: application to fluid inclusions hosted in quartz veins from the Longmaxi Formation shales in Sichuan Basin, southwestern China

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.

Different angle-resolved polarization configurations of Raman spectroscopy: A case on the basal and edge plane of two-dimensional materials

Angle-resolved polarized Raman（ARPR） spectroscopy can be utilized to assign the Raman modes based on crystal symmetry and Raman selection rules and also to characterize the crystallographic orientation of anisotropic materials.However, polarized Raman measurements can be implemented by several different configurations and thus lead to different results. In this work, we systematically analyze three typical polarization configurations： 1） to change the polarization of the incident laser, 2） to rotate the sample, and 3） to set a half-wave plate in the common optical path of incident laser and scattered Raman signal to simultaneously vary their polarization directions. We provide a general approach of polarization analysis on the Raman intensity under the three polarization configurations and demonstrate that the latter two cases are equivalent to each other. Because the basal plane of highly ordered pyrolytic graphite（HOPG） exhibits isotropic feature and its edge plane is highly anisotropic, HOPG can be treated as a modelling system to study ARPR spectroscopy of twodimensional materials on their basal and edge planes. Therefore, we verify the ARPR behaviors of HOPG on its basal and edge planes at three different polarization configurations. The orientation direction of HOPG edge plane can be accurately determined by the angle-resolved polarization-dependent G mode intensity without rotating sample, which shows potential application for orientation determination of other anisotropic and vertically standing two-dimensional materials and other materials.

Antioxidative Protective Effect of Icariin on the FeSO_4/H_2O_2-damaged Human Sperm Based on Confocal Raman Micro-spectroscopy

Oxidative stress is implicated in male infertility and significantly higher reactive oxygen species are detected in 25% of infertile males. Although different agents of various alternative medicines, including traditional Chinese medicine, have been tried with varying success, evidence remains limited on whether and how much herbs or supplements might help increase the anti-oxidant ability of the sperm. This study examined the anti-oxidative effects of icariin, a flavonoid isolated from Herba Epimedii, on the human sperm. We prepared the FeSO4/H202-damaged human sperms, which were co-cultured with icariin in vitro, and then observed the changes of the sperm by employing Raman mi- cro-spectroscopy. The results showed that Raman mapping with a 514 nm excitation laser allowed clear differentiation of the nucleus, neck, and, in particular, the mitochondria-rich middle piece of a human sperm cell. The effect oficariin on different organelles of the sperm was quantified by localized spectral Raman signatures obtained within milli-seconds, and icariin could keep the ＂Raman fingerprint＂ of the human sperm the same as the control groups, suggesting that icariin could protect the human sperm from being damaged by FeSO4/H202. Icariin may serve as a tonifying and replenishing agent of herbal origin for enhancing reproductive fimctions.

Existence of Al2F-7^- in molten MF–AlF3(M = K, Cs) systems as determined by Raman spectroscopy and structural simulation

The molten mixtures of alkali metal fluorides and aluminum fluoride are applied as aluminum electrolytes or brazing fluxes.However,the presence of Al2F-7^-in such molten systems is disputed.In the present study,MF-AlF3(M=K,Cs)systems with molar ratios<1 were studied by in-situ Raman spectroscopy and molecular simulation.The results show that,in addition to AlF6^(3-),AlF5^(2-),and AlF4^-,the systems also contained Al2F-7^-.The characteristic bands in the Raman spectra belonging to Al2F-7^-were located at about 225 cm^-1,315 cm^-1,479 cm^-1,and 720 cm^-1.There are two possible structures of Al2F-7^-,which belong to the D3d and D3hpoint groups.Both of these structures are linear,and their single-point energies were found to differ by only 0.31 kcal/mol.

Optical penetration of surface-enhanced micro-scale spatial offset Raman spectroscopy in turbid gel and biological tissue

The limited penetration of photons in biological tissue restricts the deep-tissue detection and imaging application.The micro-scale spatially offset Raman spectroscopy(micro-SORS)with an optical fiber probe,colleting photons from deeper regions by offsetting the position of laser excitation from the collection optics in a range of hundreds of microns,shows great potential to be integrated with endoscopy for inside-body noninvasive detection by circumventing this restric-tion,particularly with the combination of surface-enhanced Raman spectroscopy(SERS).However,a detailed tissue penetration study of micro-SORS in combination with SERS is still lacking.Herein,we compared the signal decay of enhanced Raman nanotags through the tissue phantom of agarose gel and the biological tissue of porcine muscle in the near-infrared(NIR)region using a portable Raman spectrometer with a micro-SORS probe(2.1 mm in diameter)and a conventional hand-held probe(9.7mm in diameter).Two kinds of Raman nanotags were prepared from gold nanorods decorated with the nonresonant(4-nitrobenzenethiol)or resonant Raman reporter molecules(IR-780 iodide).The SERS measurements show that the penetration depths of two Raman nanotags are both over 2 cm in agarose gel and 3 mm in porcine muscle.The depth could be improved to over 4 cm in agarose gel and 5 mm in porcine tissue when using the micro-SORS system.This demonstrates the superiority of optical-fiber micro-SORS system over the conventional Raman detection for the detection of nanotags in deeper layers in the turbid medium and biological tissue,offering the possibility of combining the micro-SORS technique with SERS for noninvasive in vivo endoscopy-integrated clinical application.

Determination of inner pressure for fluid inclusions by Raman spectroscopy and its application

Using a Diamond Anvil Cell combined with micro Raman spectroscopy, the quantitative relations among Raman shifts, pressure and temperature were obtained for the vibration of O-H in H2O-NaCl, C-O in CO3^2-, S-O in SO4^2- and C-H in n-heptane-cyclohexane. Based on the quantitative relationships obtained, it is possible to determine the inner pressure for single fluid inclusions and to further determine the isochore of the systems. It is not only helpful to obtain the forming temperatures and pressures of the enclosing minerals, but also to be able to provide information concerning the chemical compositions of the fluid inclusions.

In situ studies of energy-related electrochemical reactions using Raman and X-ray absorption spectroscopy

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.

Sensitive and Label-Free Detection of Protein Secondary Structure by Amide Ⅲ Spectral Signals using Surface-Enhanced Raman Spectroscopy

Proteins and peptides perform a vital role in living systems, however it remains a challenge for accurate description of proteins at the molecular level. Despite that surface-enhanced Raman spectroscopy (SERS) can provide the intrinsic fingerprint information of samples with ultrahigh sensitivity, it suffers from the poor reproducibility and reliability. Herein, we demonstrate that the silver nanorod array fabricated by an oblique angle deposition method is a powerful substrate for SERS to probe the protein secondary structures without exogenous labels. With this method, the SERS signals of two typical proteins (lysozyme and cytochrome c) are successfully obtained. Additionally, by analyzing the spectral signals of the amide Ⅲ of protein backbone, the influence of concentration on the folding status of proteins has been elucidated. With the concentration increasing, the components of α-helix and β-sheet structures of lysozyme increase while the secondary structures of cytochrome c almost keep constant. The SERS method in this work offers an effective optical marker to characterize the structures of proteins.

Application of confocal laser Raman spectroscopy on marine sediment microplastics

Marine sediment is the primary sink of microplastics and is an indicator of pollution levels.However,although there are well-developed detection methods,detection is rarely focused on lowmicrometer-sized particles,mainly due to technique limitations.In this study,a simplifi ed process omitting digestion procedures was developed to pretreat microplastics obtained from marine sediment and was coupled with micro-Raman spectroscopy to identify microplastics.Based on the overall analysis of the characteristic peak assignments,a Raman spectral reference library was constructed for 18 types of plastic.In addition,the eff ects of the measurement parameters were systematically described.Field research was then conducted to validate the developed process and investigate microplastic contamination in Huiquan Bay,Qingdao,China.This simplifi ed process could retain the original appearance of microparticles and accomplish the detection of<500μm-sized microplastics in environmental samples.Microplastics in the size range of 10-150μm accounted for 76%of all microplastics,and 56%of the total particles was particles smaller than 50μm.Polypropylene(42%)and polyethylene(20%)were predominant components of the particles.In particular,polypropylene particles smaller than 10μm were identifi ed in marine sediment.This work demonstrates that Raman spectroscopy is not only an eff ective tool for detecting environmental particles but also highly applicable for identifying particles extracted from marine sediment.

Classification and Quantitative Analysis of Azithromycin Tablets by Raman Spectroscopy and Chemometrics

Raman spectroscopy has been proven a noninvasive technique with high potential in pharmaceutical industry. In this study, micro Raman technique and chemometric tools were used for identification of azithromycin (AZM) tablets by different manufacturers and quantitative analysis of the active pharmaceutical ingredient (API) in the samples. Support vector machine (SVM), Bayes classifier and K-nearest neighbour (KNN) were employed for identification, partial least squares (PLS) regression was used for quantitative determination, and interval partial least squares (iPLS) and Monte Carlo based uninformative variable elimination (MC-UVE) methods were used to select informative variables for improving the models. The results show that all the samples can be classified into groups by manufacturers with high accuracy, and the correlation coefficient between the predicted API concentrations and reference values is as high as 0.96. Therefore, micro Raman spectroscopy coupled with chemometrics may be a fast and powerful tool for identification and quantitative determination of pharmaceutical tablets.

Surface-enhanced resonance Raman scattering spectroscopy of single R6G molecules

Surface-enhanced resonance Raman scattering （SERRS） of Rhodamine 6G （R6G） adsorbed on colloidal silver clusters has been studied. Based on the great enhancement of the Raman signal and the quench of the fluorescence, the SERRS spectra of R6G were recorded for the samples of dye colloidal solution with different concentrations. Spectral inhomogeneity behaviours from single molecules in the dried sample films were observed with complementary evidences, such as spectral polarization, spectral diffusion, intensity fluctuation of vibrational lines and even ＂breathing＂ of the molecules. Sequential spectra observed from a liquid sample with an average of 0.3 dye molecules in the probed volume exhibited the expected Poisson distribution for actually measuring 0, 1 or 2 molecules. Difference between the SERRS spectra of R6G excited by linearly and circularly polarized light were experimentally measured.