Anodic and cathodic process of hypophosphite on a Ni-Ag electrode

The reduction and the oxidation of hypophosphite on a Ni-Ag electrode have been studied to provide the information about the phosphorus incorporation mechanisms during the electro-less deposition and the electrodeposition of Ni-P alloys.In the electrooxidation process,an absorbency band around 240nm,which was ascribed to the formation of an intermediate PHO2-,was observed by in situ UV-Vis subtractive reflectance spectroscopy.Accordingly,the electrooxidation of hypophosphite might undergo an H abstraction of hypophosphite from the P-H bond to form the phosphorus-centred radical ' PHO2- ,which was subsequently electrooxidized to the final product,phosphite.In the reduction process Ni-phos-phine compound Ni-(PH3)n was observed by in situ surface Raman spectroscopy.The results from the Raman experiments show that,in the NiSO4-free solution,hypophosphite was reduced only to Ni-phosphine compound,while in the case where NiSO4 coexisted in the solutions,the Ni-phosphine compound,as an intermediate,was oxidise     

The Role of Vanadia for the Selective Oxidation of Benzyl Alcohol over Heteropolymolybdate Supported on Alumina

A series of 12-molybdophosphoric acid (MPA) supported on V2O5 dispersed γ-Al2O3 catalysts with different vanadia loadings were prepared by impregnation and characterized by N2 adsorption-desorption,X-ray diffraction,temperature-programmed reduction,in situ laser Raman spectroscopy,UV-Vis diffused reflectance spectroscopy,scanning electron microscopy,and temperature-programmed desorption of NH3 techniques.Their catalytic activities were evaluated for the vapor phase aerobic oxidation of benzyl alcohol.The catalysts exhibited high catalytic activity and the conversion of benzyl alcohol depended on the vanadia content while the catalyst with 15 wt％ V2O5 content showed optimum activity.The characterization results suggest the presence of well-dispersed V2O5 and partially disintegrated Keggin ions of MPA on the support.In situ Raman studies showed a reduced Mo(IV) species when the catalysts were calcined at high temperatures.The high oxidation activity of the catalysts is related to the synergistic effect between MPA and V2O5.     

一种面向多组分定量的通用谱图解析方法

在一个多组分系统中各组分的定量分析是非常重要的。现代光谱如拉曼光谱(RS)、傅里叶变换红外(FT-IR)光谱、紫外-可见(UV-Vis)光谱、核磁共振(NMR)、质谱(MS)等,可通过获取丰富峰信号的谱图对样品进行各角度的详尽描述。然而,由于谱图的复杂性及其解析工作的繁重,使得仅通过样品谱图来同时量化混合物中的每个组分成为很具挑战性的工作。在这项研究中,我们首次介绍了一个名为定量主成分分析(q PCA)的可靠策略,快速计算混合物中每个成分的比例,而不需要任何手动解谱。通过使用纯组分的谱图作为参考,多组分系统的谱图可以通过PCA自动分辨并解析,然后就可以使用我们的计算方法来计算每个组分的比例。计算机建模实验和RS、FT-IR、UV-Vis、NMR、MS实验都证明了这一策略胜任多组分系统的快速定量工作。     

Origin of negative and dispersive features in anti-Stokes and resonance femtosecond stimulated Raman spectroscopy

Femtosecond stimulated Raman spectroscopy is extended to probe ground state anti-Stokes vibrational features. Off resonance, negative anti-Stokes features are seen that are the mirror image of the positive Stokes side spectra. On resonance, the observed dispersive lineshapes are dramatically dependent on the frequencies of the picosecond pump and femtosecond probe pulses used to generate the stimulated Raman spectra. These observations are explained by the contributions of the inverse Raman and hot luminescence four-wave mixing processes discussed by Sun et al. [J. Chem. Phys. 128, 144114 (2008)], which contribute to the overall femtosecond stimulated Raman signal.     

Pure component spectral analysis of surface adsorbed species measured under real conditions. BTEM-DRIFTS study of CO and NO reaction over a Pd/gamma-Al2O3 catalyst

The adsorption of NO and CO was studied on an alumina-supported palladium catalyst by in situ diffuse reflectance infrared spectroscopy (DRIFTS). The temperature range was 50-160 degrees C and a wide variety of partial pressures was used. The band-target entropy minimization (BTEM) algorithm was applied to the DRIFTS data sets resulting in the pure component spectra of numerous species adsorbed on both the Pd (primarily a variety of Pd-CO and Pd-NO species, in various oxidation states and coordinations) and alumina surface species (i.e. nitrates, nitrites, carbonates, bicarbonates, formates, and isocyanates) as well as gas phase species. Twenty seven previously known species were identified as well as three new and previously unreported or previously unassigned spectra. The present study indicates that BTEM can be meaningfully applied to Pd/Al2O3 DRIFTS in order to provide enhanced spectroscopic analysis. Moreover, the present results are compared in detail with the recent BTEM analysis of CO and NO adsorption on Pt/Al2O3 using DRIFTS (Phys. Chem. Chem. Phys. 2008, 10, 3535).     

聚乙酰苯胺修饰碳纳米管载铂催化剂对甲醇电催化氧化

以原位化学聚合的聚乙酰苯胺/多壁碳纳米管(PAANI-MWCNTs)复合纳米材料作为载体,采用硼氢化钠还原法将Pt纳米粒子担载到PAANI-MWCNTs复合纳米材料表面,制备了Pt/PAANI-MWCNTs复合纳米催化剂.样品的结构和形貌用紫外-可见(UV-Vis)光谱、拉曼光谱、扫描电镜(SEM)、透射电镜(TEM)和X射线衍射(XRD)进行了表征.结果表明,聚乙酰苯胺与碳纳米管之间存在较强的π-π相互作用,使其能牢固地吸附于多壁碳纳米管表面,对碳纳米管的结构完整性和导电性有一定的改善作用.同时,金属Pt纳米颗粒较为均匀地分散在PAANI-MWCNTs表面,粒径分布范围较窄.采用循环伏安法和计时电流法在酸性溶液中研究了Pt/PAANI-MWCNTs催化剂对甲醇的电催化氧化活性,结果表明Pt/PAANI-MWCNTs复合纳米催化剂比用混酸处理的碳纳米管载铂催化剂对甲醇呈现出更高的电催化氧化活性和更好的抗中毒能力及稳定性.     

On the structure of vanadium oxide supported on aluminas: UV and visible raman spectroscopy, UV-visible diffuse reflectance spectroscopy, and temperature-programmed reduction studies

Vanadia species on aluminas (delta- and gamma-Al2O3) with surface VOx density in the range 0.01-14.2 V/nm2 have been characterized by UV and visible Raman spectroscopy, UV-visible diffuse reflectance spectroscopy (UV-Vis DRS), and temperature-programmed reduction in hydrogen. It is shown that the alumina phase has little influence on the structure and reducibility of surface VOx species under either dehydrated or hydrated conditions. Three similar types of dispersed VOx species, i.e., monovanadates, polyvanadates, and V2O5, are identified on both aluminas under dehydrated conditions. Upon hydration, polymerized VOx species dominate on the surfaces of the two aluminas. The broad Raman band at around 910 cm(-1), observed on dehydrated V/delta-, gamma-Al2O3 at all V loadings (0.01-14.2 V/nm2), is assigned to the interface mode (V-O-Al) instead of the conventionally assigned V-O-V bond. The direct observation of the interface bond is of significance for the understanding of redox catalysis because this bond has been considered to be the key site in oxidation reactions catalyzed by supported vanadia. Two types of frequency shifts of the V=O stretching band (1013-1035 cm(-1)) have been observed in the Raman spectra of V/Al2O3: a shift as a function of surface VOx density and a shift as a function of excitation wavelength. The shift of the V=O band to higher wavenumbers with increasing surface VOx density is due to the change of VOx structure. The V=O stretching band in dispersed vanadia always appears at lower wavenumber in UV Raman spectra than in visible Raman spectra for the same V/Al2O3 sample. This shift is explained by selective resonance enhancement according to the UV-Vis DRS results. It implies that UV Raman has higher sensitivity to isolated and less polymerized VOx species while visible Raman is more sensitive to highly polymerized VOx species and crystalline V2O5. These results show that a multiwavelength excitation approach provides a more complete structural characterization of supported VOx catalysts.     

Quantitative monitoring of yeast fermentation using Raman spectroscopy

Compared to traditional IR methods, Raman spectroscopy has the advantage of only minimal interference from water when measuring aqueous samples, which makes this method potentially useful for in situ monitoring of important industrial bioprocesses. This study demonstrates real-time monitoring of a Saccharomyces cerevisiae fermentation process using a Raman spectroscopy instrument equipped with a robust sapphire ball probe. A method was developed to correct the Raman signal for the attenuation caused by light scattering cell particulate, hence enabling quantification of reaction components and possibly measurement of yeast cell concentrations. Extinction of Raman intensities to more than 50 % during fermentation was normalized with approximated extinction expressions using Raman signal of water around 1,627 cm^?1 as internal standard to correct for the effect of scattering. Complicated standard multi-variant chemometric techniques, such as PLS, were avoided in the quantification model, as an attempt to keep the monitoring method as simple as possible and still get satisfactory estimations. Instead, estimations were made with a two-step approach, where initial scattering correction of attenuated signals was followed by linear regression. In situ quantification measurements of the fermentation resulted in root mean square errors of prediction (RMSEP) of 2.357, 1.611, and 0.633 g/L for glucose, ethanol, and yeast concentrations, respectively.     

Solid‐state thermal stability and degradation of a family of poly(N‐isopropylacrylamide‐co‐hydroxymethylacrylamide) copolymers

There is widespread interest in responsive polymers that show cloud point behavior, but little attention is paid to their solid state thermal properties. To manufacture products based on such polymers, it may be necessary to subject them to high temperatures; hence, it is important to investigate their thermal behavior. In this study, we characterized a family of poly(N‐isopropylacrylamide‐co‐hydroxymethylacrylamide) copolymers. Although poly(N‐isopropylacrylamide) shows very high thermal stability (up to 360 °C), introduction of hydroxy side chains leads to a significant reduction in stability and new degradation processes become apparent. Thermogravimetric analysis and fourier transform infrared spectroscopy (FT‐IR) indicate that the first degradation process involves a chemical dehydration step (110–240 °C), supported by the nonreversing heat flow response in modulated temperature differential scanning calorimetry. Water loss scales with the fraction of hydroxy monomer in the copolymer. Glass transition temperatures (T_g) are higher than the temperatures causing dehydration; hence, these values relate to newly‐formed copolymer structures produced by controlled heating under nitrogen. Fourier transform‐Raman (FT‐Raman) spectra suggest that this transition involves imine formation. The T_g increases as the fraction of hydroxy groups in the original copolymer increases. Further heating leads to degradation and mass loss, and more complex changes in the FT‐IR spectra, consistent with formation of unsaturated species. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Infrared and electronic spectroscopy of a model system for the nucleophilic substitution intermediate in the gas phase: the C-N valence bond formation in the benzene-ammonia cluster cation

Infrared and electronic spectroscopy was applied to the benzene-ammonia cluster cation in the gas phase, and the observed spectra revealed the formation of a new C-N valence bond between the benzene and ammonia moieties, which has been predicted by the quantum chemical calculations (Tachikawa, H. Phys. Chem. Chem.Phys. 2002, 4, 6018). This cluster cation is regarded as a model for the cyclohexadienyl type intermediate in nucleophilic substitution reactions.     

Graphitization of Carbon Particles in a Non-thermal Plasma Reactor

The production of nanomaterials using non-thermal plasmas remains the focus of ongoing investigations due to advantageous properties of this class of processes, most notably the intense plasma-induced heating arising from energetic recombination events occurring at the surface of nanoparticles, which allows for the tailored synthesis of crystalline nanoparticles. In this work, the authors discuss an in situ, in-flight Fourier Transform Infrared absorption spectroscopy technique to investigate the temperature variation of carbon nanoparticles during their synthesis in an acetylene–argon–hydrogen non-thermal RF plasma. Based on the FTIR measurements, decreasing hydrogenation levels and the progressive onset of an incandescence signal were observed at increasing RF input power. In the high RF power region, the carbon particle temperature, derived by fitting the corresponding FTIR spectra with a modified Planck’s law, shows values above 2000 K. The corresponding ex situ characterization of the synthesized materials by Transmission Electron Microscopy and Raman Spectroscopy displays the production of highly graphitic particles and loss of bonded hydrogen from the material, hence supporting the substantial nanoparticle heating derived from the FTIR measurements.     

Luminescence and Raman spectra of acetylacetone at low temperatures

Raman spectra of acetylacetone were recorded for molecules isolated in an argon matrix at 10 K and for a polycrystalline sample. In the solid sample, broad bands appear superimposed on a much weaker Raman spectrum corresponding mainly to the stable enol form. The position of these bands depends on the excitation wavelength (514.5 and 488.8 nm argon ion laser lines were used), sample temperature, and cooling history. They are attributed to transitions from an excited electronic state to various isomer states in the ground electronic state. Laser photons have energies comparable to energies of a number of excited triplet states predicted for a free acetylacetone molecule (Chen, X.-B.; Fang, W.-H.; Phillips, D. L. J. Phys. Chem. A 2006, 110, 4434). Since singlet-to-triplet photon absorption transitions are forbidden, states existing in the solid have mixed singlet/triplet character. Their decay results in population of different isomer states, which except for the lowest isomers SYN enol, TS2 enol (described in Matanovi? I.; Dosli?, N. J. Phys. Chem. A 2005, 109, 4185), and the keto form, which can be detected in the Raman spectra of the solid, are not vibrationally resolved. Differential scanning calorimetry detected two signals upon cooling of acetylacetone, one at 229 K and one at 217 K, while upon heating, they appear at 254 and 225 K. The phase change at higher temperature is attributed to a freezing/melting transition, while the one at lower temperature seems to correspond to freezing/melting of keto domains, as suggested by Johnson et al. (Johnson, M. R.; Jones, N. H.; Geis, A; Horsewill. A. J.; Trommsdorff, H. P. J. Chem. Phys. 2002, 116, 5694). Using matrix isolation in argon, the vibrational spectrum of acetylacetone at 10 K was recorded. Strong bands at 1602 and 1629 cm(-1) are assigned as the SYN enol bands, while a weaker underlying band at 1687 cm(-1) and a medium shoulder at 1617 cm(-1) are assigned as TS2 enol bands.     

Isobaric annealing of high-density amorphous ice between 0.3 and 1.9 GPa: in situ density values and structural changes

We report in situ density values of amorphous ice obtained between 0.3 and 1.9 GPa and 144 to 183 K. Starting from high-density amorphous ice made by pressure-amorphizing hexagonal ice at 77 K, samples were heated at a constant pressure until crystallization to high-pressure ices occurred. Densities of amorphous ice were calculated from those of high-pressure ice mixtures and the volume change on crystallization. In the density versus pressure plot a pronounced change of slope occurs at approximately 0.8 GPa, with a slope of 0.21 g cm(-3) GPa(-1) below 0.8 GPa and a slope of 0.10 g cm(-3) GPa(-1) above 0.8 GPa. Both X-ray diffractograms and Raman spectra of recovered samples show that major structural changes occur up to approximately 0.8 GPa, developing towards those of very high-density amorphous ice reported by (T. Loerting, C. Salzmann, I. Kohl, E. Mayer and A. Hallbrucker, Phys. Chem. Chem. Phys., 2001, 3, 5355) and that further increase of pressure has only a minor effect. In addition, the effect of annealing temperature (T(A)) at a given pressure on the structural changes was studied by Raman spectra of recovered samples in the coupled O-H and decoupled O-D stretching band region: at 0.5 GPa structural changes are observed between approximately 100-116 K, at 1.17 GPa between approximately 121-130 K. Further increase of T(A) or of annealing time has no effect, thus indicating that the samples are fully relaxed. We conclude that mainly irreversible structural changes between 0.3 to approximately 0.8 GPa lead to the pronounced increase in density, whereas above approximately 0.8 GPa the density increase is dominated to a large extent by reversible elastic compression. These results seem consistent with simulation studies by (R. Martonàk, D. Donadio and M. Parrinello, J. Chem. Phys., 2005, 122, 134501) where substantial reconstruction of the topology of the hydrogen bonded network and changes in the ring statistics from e.g. mainly six-membered to mainly nine-membered rings were observed on pressure increase up to 0.9 GPa and further pressure increase had little effect.     

Observation of a transition in the water-nanoparticle formation process at 167 K

Rapid-scan Fourier transform infrared spectroscopy of the vapor/solid formation process of water nanoparticles in the 180-140 K temperature range at thermal-equilibrium conditions is reported. At 167 K a transition in the formation process was observed: the particle volume quintuples and the particle formation time triples within a temperature interval of +/-0.4 K caused by the temperature control. The authors interpret this behavior by an abrupt change in the nucleation rate of the H2O monomers in He buffer gas kept at 167 K and 200 mbar. A size and shape analysis of the particles during the formation process was carried out by application of the discrete dipole approximation method which delivers excellent accordance between experimental and calculated mid-IR spectra. Compared to other compact shapes (cube, prolate ellipsoid, and hexagonal prism) the ideal spherical shape fits the experimental spectra best. A distinct change in shape by particle conversion or agglomeration could be excluded to be involved in the formation process. As a possible explanation of the observed phenomenon, a transition from vapor/liquid/solid to vapor/solid nucleation with decreasing temperature is considered which was recently theoretically predicted by van Dongen and co-workers [J. Chem. Phys. 117, 5647 (2002); private communication; J. Chem. Phys. 120, 6314 (2004)].     

PrOy-ZrO2固溶体的结构表征和CO氧化性能

采用共沉淀法制备了不同Pr/Zr比的PrOy-ZrO2固溶体,用激光拉曼光谱(Raman)、X-射线粉末衍射(XRD)、紫外可见吸收光谱(UV-Vis)等技术对固溶体进行了物相结构表征并选择CO氧化作为模型反应考察了固溶体的催化性能。结果表明,随着Pr含量的增加,无定形ZrO2转化为晶相ZrO2的温度提高、热效应下降,而PrOy-ZrO2固溶体的物相结构从单斜相逐步向四方和立方相转变。XRD和Raman光谱得到的物相结构的差别是PrOy-ZrO2固溶体的表层和体相结构不一致造成的,PrOy-ZrO2固溶体表层更易生成低对称性的物相,而且也容易生成非晶相的物相。CO氧化实验表明PrOy-ZrO2固溶体的催化活性与样品的组成有很大关系,其中高温区和低温区分别是PZ-30和PZ-50的CO氧化活性最高。     

基于高斯函数卷积的色散型拉曼光谱仪温度校正

色散型拉曼光谱仪易受到温度影响,使测得的光谱重复性变差。针对这个问题,本研究提出了基于高斯函数卷积的温度校正方法。利用标准物质获得光谱仪在不同温度下的仪器响应函数,并以此构造高斯函数,通过卷积运算对温度造成的波数漂移以及分辨率变化进行校正。本方法直接基于拉曼谱分析,机理性强,且无需测量大量样本。利用苯作标准物质,对间二甲苯与汽油样本的拉曼光谱进行温度校正。结果表明,本方法能有效去除温度对色散型拉曼光谱仪的影响,使得不同温度下测得的光谱一致性显著提高。     

Monitoring Silica Supported Molybdenum Oxide Catalysts at Work: A Raman Spectroscopic Study

The structure of silica SBA‐15‐supported molybdenum oxide catalysts is investigated during selective oxidation of propylene at 500 °C using operando Raman spectroscopy. The active catalysts contain mixtures of dispersed molybdenum oxide species exhibiting monooxo and dioxo structure. An increase in molybdenum oxide loading results in a decrease of the ratio of dioxo and monooxo species from 3.8 to 1.9, as determined by quantitative analysis of Raman spectra. Additional in situ Raman studies at 500 °C reveal that the dioxo/monooxo ratio increases in the presence of steam at higher molybdenum oxide loadings. The observed structural changes are assigned to shifts in the equilibrium between dioxo and monooxo species resulting from hydration/dehydration of the catalyst. This study demonstrates that the detailed structure of nanostructured molybdenum oxide catalysts depends on temperature, gas‐phase composition, and molybdenum oxide loading.     

DFT vibrational calculations of rhodamine 6G adsorbed on silver: analysis of tip-enhanced Raman spectroscopy

The tip-enhanced near-field Raman (TERS) bands of Rhodamine 6G (R6G), that we reported earlier [Chem. Phys. Lett. 2001, 335, 369.], are assigned on the basis of density-functional theory (DFT) calculations at the 6-311++G(d,p) level. The Raman and infrared intensities as well as frequencies of the vibrational modes are used for band assignments. These vibrational modes, in combination with characterization of resonant electronic transitions using time-dependent DFT calculations, predict spectral changes in resonant Raman and surface-enhanced resonant Raman scatterings of R6G. Moreover, the TERS spectra of R6G are analyzed in detail, where interactions between the tip and R6G molecules and their enhancement mechanisms are discussed. Finally, we propose a novel Raman spectroscopy technique capable of detecting molecular vibrations at sub-nanometer scale.     

Interpreting DNA vibrational circular dichroism spectra using a coupling model from two-dimensional infrared spectroscopy

Two-dimensional infrared spectroscopy was recently used to measure the vibrational couplings between carbonyl bonds located on DNA nucleobases (Krummel, A. T.; Mukherjee, P.; Zanni, M. T. J. Phys. Chem. B 2003, 107, 9165 and Krummel, A. T.; Zanni, M. T. J. Phys. Chem. B 2006, 110, 13991). Here, we extend the coupling model derived from these 2D IR experiments to simulate the vibrational absorption and vibrational circular dichroism (VCD) spectra of three double-stranded DNA oligomers: poly(dG)-poly(dC), poly(dG-dC), and dGGCC. Using this model, we determine that the VCD spectrum of A-form poly(dG)-poly(dC) is dominated by interactions between stacked bases, whereas the coupling between base pairs and stacked bases carries equal importance in the VCD spectrum of B-form poly(dG-dC). We also simulate the absorption and VCD spectra of dGGCC, which is a combination of A- and B-form configurations. These simulations give insight into the structural interpretation of VCD and absorption spectroscopies that have long been used to monitor DNA secondary structure and kinetics.