Operando FTIR study on water additive in lithium-sulfur batteries to mitigate shuttle effect

Additives in the electrolytes of Li-S batteries aim to increase overall capacity,improve Li ion conductivity,enhance cyclability,and mitigate the shuttle effect,which is one of the major issues of this system.Here,the use of water as an additive in the commonly used electrolyte,1.0 M LiTFSI/1.0%(w/w) LiNO_(3) and a 1:1 mixture of 1,3-dioxolane(DOL) and 1,2-dimethoxyethane(DME) was investigated.We used Co_(2)Mn_(0.5)Al_(0.5)O_(4)(CMA) as an electrocatalyst anchored on an activated carbon(AC) electrode with added sulfur via a melt-diffusion process.The structural analysis of CMA via Rietveld refinement showed interatomic spaces that can promote ionic conductivity,facilitating Li^(+) ion migration.Electrochemical tests determined 1600 ppm as the optimal water concentration,significantly reducing the shuttle effect.Post-mortem XPS analysis focused on the lithium metal anode revealed the formation of Li_(2)O layers in dry samples and LiOH in wet samples.Better capacity was observed in wet samples,which can be attributed to the superior ionic conductivity of LiOH at the electrode/electrolyte interface,surpassing that of Li_(2)O by 12 times.Finally,Operando FTIR experiments provided real-time insights into electrolyte degradation and SEI formation,elucidating the activity mechanisms of water and Li_(2)CO_(3) over the cycles.This work presents results that could aid future advancements in Li-S battery technology,offering possibilities to mitigate its challenges with inexpensive and scalable additives.

Semi-quantitative analysis of the structural evolution of mesophase pitch-based carbon foams by Raman and FTIR spectroscopy

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.

Studies of XRD and FTIR on Synthesized Novel Hybrid Thin Film Made of Hydroxyapatite, Poly Vinyl Alcohol and Gelatin for Biomedical Application

With the modern advancement of treatment approaches in medical science, the application of biomaterials in tissue engineering provides a remarkable opportunity to overcome graft rejection as well as proper wound healing. In this study, novel hybrid films have been synthesized by incorporation of polyvinyl alcohol (PVA), gelatin, and gelatin with glycerin along with different concentrations of pre-prepared hydroxyapatite (HAP) by solution casting method at room temperature in a biosafety cabinet. Glutaraldehyde has been added as a crosslinker in this whole procedure. Fourier-transform infrared spectroscopy (FTIR), X-Ray Diffraction (XRD) have been conducted to observe and compare the structural and chemical stability of the synthesized hybrid film properties. The FTIR results and X-Ray Diffraction analyses confirmed the chemical interactions between HAP, PVA, gelatin, and glycerin have occurred. The crystallinity of HAP also remains in all the prepared hybrid film samples that are observed in XRD. It is expected that these newly synthesized hybrid films could be a better opportunity for various sectors of tissue engineering such as skin, bone, tendon, and cartilage. These synthesized hybrid films can be suitable for wound healing covering. These studies could be a new scope for long-term drug delivery directly on wound sites in diabetic gangrene foot or burn patients as well as cartilage or joint replacement therapy.

Assessment of portable FTIR and Raman spectroscopy for the detection of 2,3-dimethyl-2,3-dinitrobutane(DMDNB)in plastic explosives

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%.

Molecular structure characterization of middle-high rank coal via^(13)C NMR,XPS,and FTIR spectroscopy

Elemental analysis,nuclear magnetic resonance carbon spectroscopy(^(13)C-NMR),X-ray photoelectron spectroscopy(XPS)and Fourier transform infrared spectroscopy(FTIR)experiments were carried out to determine the existence of aromatic structure,heteroatom structure and fat structure in coal.MS(materials studio)software was used to optimize and construct a 3D molecular structure model of coal.A method for establishing a coal molecular structure model was formed,which was“determination of key structures in coal,construction of planar molecular structure model,and optimization of three-dimensional molecular structure model”.The structural differences were compared and analyzed.The results show that with the increase of coal rank,the dehydrogenation of cycloalkanes in coal is continuously enhanced,and the content of heteroatoms in the aromatic ring decreases.The heteroatoms and branch chains in the coal are reduced,and the structure is more orderly and tight.The stability of the structure is determined by theπ-πinteraction between the aromatic rings in the nonbonding energy EN.Key Stretching Energy The size of EB determines how tight the structure is.The research results provide a method and reference for the study of the molecular structure of medium and high coal ranks.

二维傅里叶变换红外(2D FTIR)相关光谱技术研究聚羟基丁酸酯(PHB)的熔融与结晶

应用新型二维傅里叶变换红外 (2 D FTIR)相关光谱研究细菌合成聚羟基丁酸酯 (PHB)在升温时的预熔行为以及降温后的重结晶过程 .在 2 5～ 2 2 0℃的变温过程中测得动态红外光谱 .着重讨论了在热力学干扰导致红外谱图中羰基峰 (1 70 0～ 1 770 cm- 1 )和醚键 (1 2 3 0～ 1 3 1 0 cm- 1 )吸收强度的波动 .结果表明 ,这种影响来自样品中 PHB的结晶态和非晶态之间的相态变化 .二维谱图分析表明 ,在热熔过程中 ,结晶态的消失并不同时引起完全非晶态的出现 ,暗示在分子排列高度有序的晶态和非晶态之间存在某种中间态 ,PHB晶体向非晶态转变时必须经过一个预熔过程 .在红外谱图上这个中间态很可能对应着由二维分析显示出来的位于 1 73 0 cm- 1 的吸收峰 .同时 ,在

In situ FTIR and ex situ XPS/HS-LEIS study of supported Cu/Al_(2)O_(3)and Cu/ZnO catalysts for CO_(2)hydrogenation

Cu-based catalysts are commonly used in industry for methanol synthesis.In this study,supported catalysts of 5 wt%Cu/Al_(2)O_(3)and 5 wt%Cu/ZnO were prepared,and their surface characteristics during H_(2) reduction and CO_(2)hydrogenation were investigated using in situ Fourier transform infrared spectroscopy(FTIR),ex situ X-ray photoelectron spectroscopy,and high sensitivity low energy ion scattering spectroscopy.During the H2 reduction and CO_(2)hydrogenation processes,it was found that Al_(2)O_(3)can stabilize Cu^(+).In situ FTIR spectra indicated that the 5 wt%Cu/Al_(2)O_(3)can adsorb large amounts of bicarbonate and carbonate species,which then convert into formate during CO_(2)hydrogenation.For the 5 wt%Cu/ZnO,it was found that Cu nanoparticles were gradually covered by a highly defective ZnOx overlayer during H2 reduction,which can effectively dissociate H2.During CO_(2)hydrogenation,the adsorbed bicarbonate or carbonate species can convert into formate and then into a methoxy species.Using these surface sensitive methods,a more in-depth understanding of the synergistic effect among the Cu,Al_(2)O_(3),and ZnO components of Cu-based catalysts was achieved.

六氰合铁酸铜钴薄膜修饰电极的in-situ FTIR研究

本文用循环伏安法在铂电极的表面电沉积了六氰合铁酸铜钴薄膜 ,结合电化学方法 ,研究了修饰膜氧化过程中的现场红外光谱。

草酸在铅电极上电催化还原过程的in situ FTIRS研究

采用电化学原位傅里叶变换红外反射光谱(electrochemical in situ fourier transform infrared reflec-tion spectroscopy,in situFTIRS)研究了草酸在铅电极上电催化还原过程。多步电位阶跃FTIRS(MSFTIRS)和时间分辨FTIRS(TRFTIRS)的结果表明:当研究电位为-0·70V(vs·SCE)时,即可明显检测到乙醛酸生成;研究电位为-0·85V时,电极表面累积生成乙醛酸的量达到最大值。随着电位的负移,生成的乙醛酸的量减少。同时在-0·95V时即可明显检测到乙醛酸进一步被还原,生成的乙醇酸在1093cm-1附近为—CH2OH的CO伸缩振动吸收。当研究电位为-1·50V时,电极表面的乙醛酸几乎都被还原成乙醇酸。另外,随着电位的负移,并没有检测到其他新物种的出现,表明乙醇酸在电极表面不会进一步发生还原反应。研究电位为-0·75V的原位时间分辨红外反射光谱显示反应产物乙醛酸在1750cm-1左右CO的伸缩振动吸收谱峰的左右积分强度随时间线性增加;而研究电位在-1·60V原位时间分辨红外反射光谱还观察到乙醇酸在1093cm-1附近—CH2OH的C—O伸缩振动吸收。电化学原位红外反射光谱技术有利于对反应中各物种官能团振动吸收的检测,为草酸电催化还原反应机理提供直接实验依据。

用 X 射线衍射和 FTIR 光谱研究突出区煤的结构

用 Ｘ射线衍射和 Ｆ Ｔ Ｉ Ｒ 光谱法对突出区煤的大分子结构进行了研究，并采用 Ｆｒａｎｋｌｉｎ 公式计算微晶参数 Ｌａ结果表明，用 Ｆｒａｎｋｌｉｎ 公式得到的 Ｌａ 比 Ｗａｒｒｅｎ 方程计算值更接近煤大分子实际结构；突出区煤面间距非常接近， Ｌａ 随ｘｃ的升高而增大， Ｌｃ 则刚好相反；突出区煤中具有脂肪族 Ｃ Ｈ２ 、 Ｃ Ｈ３ 的２９２０ ｃｍ － １ 吸收带，平均多核芳环数为５ ～６ 个，平均原子数为２０ ～２３ 个。

In Situ FTIR Spectroscopic Study of Electrochemical Adsorption of Phosphate Ions on Gold

Infrared reflection-absorption spectra for primary, secondary and tertiary orthophosphate anions on a gold electrode in aqueous solution were studied by in situ FTIR spectroscopy. The spectra show that H2PO4- , HPO ions do not interact with the electrode surface as strong as PO do. According to the surface selection rule, we deduce the modes of adsorption of these anions on the electrode from these spectra. The experiment also confirms the affection to adsorption of ion on the electrode due to ion-migration into thin-layer cavity.

In situ FTIR Investigation of Magnetic Field Effect on Heterogeneous Photocatalytic Degradation of Benzene over Pt/TiO_(2)

In situ FTIR spectroscopy was utilized to investigate the magnetic field effect on the heterogeneous photocatalytic degradation of benzene over platinized titania （Pt/TiO2）. The results revealed that the employment of magnetic field may not change the mechanism of photocatalytic degradation of benzene, however, it greatly facilitate the conversion of benzene to phenol and quinone, as well as the transformation from phenol to quinone, resulting in opening the benzene ring easily and promoting the production of CO2.

In-situ FTIR Spectroelectrochemical and Electrochemical Studies of Ferrocene and Derivatives at a Platinum Electrode

Redox mechanism of ferrocene, acetylferrocene, ferrocenyl cinnamenyl ketone at a platinum electrode was studied with cyclic voltammetry (CV) and in-situ Fourier transform infrared (FTIR) spectroelectrochemistry. The IR bands in the range of 2000-1000 cm-1 attributed to the stretching and ring vibrations of these materials show the main spectral changes in the processes.

IN-SITU REFLECTION MICROSCOPIC FTIR SPECTROELECTROCHEMISTRY AT MICRO-/ULTRAMICROELECTRODE

An in-situ reflection ultramicroelectrode microscopic FTIR spectroelectrochemical cell was constructed and demonstrated by using hexacyanoferrate redox couple in aqueous sulphate solution.An excellent microscopic SNIFTIRS reflection spectra had been obtained with no difficulty of IR beam focusing.The cell is simple in construction and convenient for use,And it will have most of all advantages of micro-/ultramicroelectrode.

IN-SITU DISTANCE RESOLVED OPTICALLY TRANSPARENT THIN-LAYER MICROSCOPIC FTIR SPECTROELECTROCEMISTRY.ESTIMATION OF THE ELECTROCHEMICAL CONCENTRATION-DISTANCE PROFILE

An in-situ optically transparent thin-layer microscopic FTIR spectroelectro- chemical cell was constructed.Using this cell,we characterize a concentration-distance profile in the electrochemical diffusion thin-layer by in-situ adjusting the focal point at different distances to the electrode surface.

Analysis of the Secondary Structure of the Transmembrane Domain of SARS CoV E Protein Using FTIR Spectroscopy

One of the major obstacles facing the field of structural biology in the post genomic era is the inherent difficulty of analyzing the structure of membrane proteins under native conditions. The method of choice for studying such proteins is FTIR spectroscopy. Following the outbreaking of the severe acute respiratory syndrome （SARS） virus, in 2003, extensive work has been directed at elucidating the structure of the E transmembrane proteins of the SARS coronavirus. In this study, the secondary structure of the transmembrane a-helical bundles was analysised using the biophysical method site specific infrared dichroism （SSID）. Sixteen amino acids were isotopically labeled with （~3C=180） at different positions of the primary structure of the synthesized E protein CoV. The secondary structure was studied using Attenuated Total Internal Reflection （ATR） FTIR spectroscopy. Based on our findings, the presence of two possible H-bonding interactions between the carbonyl oxygen of two residues 26 and 31 （Phe and Leu） respectively with water molecules which may be trapped within the helix structure were postulatesed. These interactions may cause a change in this structure.

吴茱萸碱与脂质体模拟生物膜的相互作用: FTIR和DSC研究

药物与生物膜相互作用的研究对于了解药物药效和改善其生物性能具有重要的意义。但生物膜的组成复杂,直接研究药物活性成分与生物膜的相互作用比较困难。以脂质体作为生物膜模型,研究了吴茱萸碱与脂质体的相互作用,分析了吴茱萸碱分子在脂质体中的包封位置,探讨了吴茱萸碱抗炎作用可能的作用机制。以二棕榈酰磷脂酰胆碱(DPPC)为膜材,应用薄膜分散法制备含有不同摩尔百分比(x)的吴茱萸碱脂质体,应用傅立叶变换红外光谱(FTIR)和差示扫描量热(DSC)技术分析随着脂质体中药物摩尔百分比的增大,DPPC分子各红外特征吸收峰频率、峰形及量热参数的变化情况,从而探讨药物在脂质体中的包封位置及吴茱萸碱分子对脂质体膜流动性的影响。实验数据表明,在0<x<10mol%的浓度范围内,DPPC头部区域磷酸基团的不对称伸缩振动频率没有明显变化,脂质体相变温度和相变焓均随药物摩尔百分比的增大而减小。在0<x<5mol%浓度范围内,DPPC界面区域的水化的羰基峰的吸收波数由1726.0cm-1增加到1731.8cm-1,当x=10mol%时,该波数又减小到1728.0cm^-1。在10mol%≤x<20mol%浓度范围内,磷酸基团的不对称伸缩振动的波数由1242.0cm^-1减小为1236.3cm^-1,水化的羰基峰的吸收频率没有明显变化,脂质体相变温度和相变焓均随药物摩尔百分比的增大而增大。纯DPPC脂质体中亚甲基的对称伸缩振动波数为2848.4cm^-1,载药后该波数都增大到2850.3cm^-1。这些结果表明吴茱萸碱在脂质体中的包封位置具有浓度依赖性:在0<x<10mol%浓度范围内,吴茱萸碱主要作用于DPPC分子的疏水尾链区域,少部分药物分子作用于DPPC分子的界面区域。在10mol%≤x<20mol%浓度范围内,吴茱萸碱分子则主要作用于DPPC分子的头部区域,少部分药物分子作用于DPPC分子的疏水尾链区。所有载药脂质体的相变温度均低于纯DPPC脂质体的相变温度,即不同浓度的吴茱萸碱均可以使脂质体的膜流动性增加,并且,当药物摩尔百分比为10mol%时,吴茱萸碱对生物膜流动性的增加效应最为明显。研究工作对于进一步揭示吴茱萸碱与生物膜的相互作用机制具有重要意义。

Direct observation of the CO_(2) formation and C–H consumption of carbon electrode in an aqueous neutral electrolyte supercapacitor by in-situ FTIR and Raman

Electrical double-layer capacitors(EDLCs)consist of energy storage devices that present high-power and moderate energy density.The electrolyte and electrode physicochemical properties are crucial for improving their overall energy storage capabilities.Therefore,the stability of the EDLCs’materials is the primary focus of this study.Since energy storage depends on the specific capacitance,and also on the square of the maximum capacitive cell voltage(UMCV).Thus,electrodes with high specific surface area(SSA)and electrolytes with excellent electrochemical stability are commonly reported in the literature.Aqueous electrolytes are safer and green devices compared to other organic-based solutions.On the other hand,their UMCVis reduced compared to other electrolytes(e.g.,organic-based and ionic liquids).In this sense,spanning the UMCVfor aqueous-based electrolytes is a’hot topic’research.Unfortunately,the lack of protocols to establish reliable UMCVvalues has culminated in the publishing of several conflicting results.Herein,we confirm that multiwalled carbon nanotubes(MWCNTs)housed in cells degrade and produce CO_(2) under abusive polarisation conditions.It is probed by employing electrochemical techniques,in-situ FTIR and in-situ Raman spectroscopies.From these considerations,the current study uses spectro-electrochemical techniques to support the correct determination of the electrode and electrolyte stability conditions as a function of the operating electrochemical parameters.

减肥保健品非法添加3种化学药物的TLC-Micro FTIR检测

利用薄层色谱(TLC)与显微傅里叶变换红外光谱(Micro FTIR)联用技术检测减肥保健品中非法添加酚酞、西布曲明、芬氟拉明3种组分。供试品用甲醇超声提取,以硅胶GF254铝合金薄层板为固定相,以氯仿-甲醇-氨水(11∶1∶0.12)为展开剂,在紫外灯254 nm下检视,薄层色谱法(TLC)快速初筛,显微傅里叶变换红外光谱(Micro FTIR)进行定性检测。结果显示在随机抽取的9批供试品中,5批检测到酚酞,7批含有西布曲明,2批含有芬氟拉明。所建立的方法专属性强、灵敏度高,可以作为该类保健品非法添加酚酞、西布曲明、芬氟拉明的检测方法。

吸附态和溶液相CO在Pt(110)电极上氧化过程的CV和in situ FTIRS 研究

应用电化学原位傅里叶变换红外反射光谱(in situ FTIRS)研究了酸性介质中Pt(110)单晶电极上吸附态CO(COad)和溶液相CO(COsol)的氧化过程.循环伏安测试表明,COsol氧化的峰电位比COad氧化的正移了168mV,其峰电流密度为后者的6.7倍.电化学原位红外光谱检测到CO主要生成线型的吸附态物种(COL),均匀分布在Pt(110)表面上.当溶液中不存在CO时,COL仅在电位高于0.15V才发生氧化.而且,该谱峰在其稳定吸附的电位区间内随电位增加蓝移,Stark系数为30cm-1·V-1;在COL发生氧化的电位区间,其谱峰强度随电位增加减小、峰位红移,线性变化率为-56cm-1·V-1.溶液中饱和CO时,原位红外光谱在-0.05V即可检测到CO2的存在,显示COL起始氧化的电位提前了200mV;电位高于-0.05V,该谱峰即发生红移,对应的线性变化率为-26.5cm-1·V-1.