Probing natural gas components with Raman integrating sphere technology.

Raman spectroscopy is a powerful method of probing natural gas components, but higher sensitivity, greater miniaturization, and lower cost techniques are required. Therefore, we designed a Raman integrating sphere-enhanced spectroscopy technology in a volume of 40 × 40 × 20 cm3 based on the principle of integrating sphere reflection. This technology consists of two parts: the first is an integrating sphere model to collect scattered signals, and the second is a right-angle light-boosting system to increase the optical path of the pump light in the sample. Raman integrating sphere technology has a detection limit of 0.5 ppm in the air with an exposure time of 600 s under room temperature and ambient pressure conditions. Experiments of natural gas detection display that the detection limits of ethane, propane, n-butane, isobutane, n-pentane, and isopentane are 28, 28, 95, 28, 189, and 95 ppm, respectively. In addition, there is a linear relationship between the relative Raman intensity and the concentration of each component in natural gas, which can be used as a probe for detecting unknown natural gas components in gas wells.

Trace Analysis of Gases and Liquids with Spontaneous Raman Scattering Based on the Integrating Sphere Principle.

Spontaneous Raman scattering is an attractive optical technique for the analysis of gases and liquids; however, their low densities and notoriously weak scattering cross sections demand an enhancement of the spontaneous Raman scattering signal for detection. Here, we have developed a simple but highly effective and fast technique to enhance the signal of spontaneous Raman scattering from gases and liquids. The technique is developed based on the principle of an integrating sphere, which realizes the multiple pass actions of low-energy pump light and the collection of all Raman scattered light for a sample volume of 2 mL. By measuring the ambient air sample with an exposure time of 180 s, we found the experimental detection limit of our spontaneous Raman scattering setup can reach 3 ppm. CH4 (<2 ppm) in air can be also examined by increasing the exposure time to 300 s. The performance of our setup used for the analysis of trace gases is further illustrated by characterizing ethane, propane, butane, and pentane in methane as well as isotopes of carbon dioxide. The results reveal that the detection limit of our setup for liquids can be improved by nearly 4 orders of magnitude compared to that of confocal Raman scattering spectroscopy with the same experimental conditions.

Raman Spectroscopy for the Competition of Hydrogen Bonds in Ternary (H2O-THF-DMSO) Aqueous Solutions.

The effects of hydrogen bonds on the molecular structure of water-tetrahydrofuran (H2O-THF), water-dimethyl sulfoxide (H2O-DMSO), and water-tetrahydrofuran-dimethyl sulfoxide (H2O-THF-DMSO) in binary aqueous solutions and ternary aqueous solutions were studied using Raman spectroscopy. The results indicate that in the binary aqueous solution, the addition of THF and DMSO will generate hydrogen bonds with water molecules, resulting in changes in the peak positions of S=O bonds and C-O bonds. Compared with the binary aqueous solutions, the hydrogen bonds between DMSO and THF, and the hydrogen bonds between DMSO and H2O in the ternary aqueous solutions are competitive, and the hydrogen bond competition is susceptible to water content. In addition, the formation of hydrogen bonds will destroy the fully hydrogen-bonded water and make it change to the partially hydrogen-bonded water. By fitting the spectra into the three Gaussian components assigned to water molecules with different hydrogen bonding (HB) environments, these spectral features are interpreted by a mechanism that H2O in different solution systems has equal types of water molecules with similar HB degrees-fully hydrogen-bonded H2O (FHW) and partially hydrogen-bonded H2O (PHW). The ratio of the intensity transition from FHW to PHW is determined based on Gaussian fitting. Therefore, the variation of hydrogen bond competition can be supplemented by the intensity ratio of PHW/FHW ((IC2 + IC3)/IC1). This study provides an experimental basis for enriching the hydrogen bonding theory of multivariate aqueous solution systems.

A facile two-step method for fabrication of plate-like WO3 photoanode under mild conditions.

Fabrication of photoelectrodes on a large-scale, with low-cost and high efficiency is a challenge for their practical application in photoelectrochemical (PEC) water splitting. In this work, a typical plate-like WO(3) photoanode was fabricated with chemical etching of the as-prepared mixed tungsten-metal oxides (W-M-O, M = Cu, Zn or Al) by a reactive magnetron co-sputtering technique, which results in a greatly enhanced PEC performance for water oxidation in comparison with that obtained from a conventional magnetron sputtering method. The current approach is applicable for the fabrication of some other semiconductor photoelectrodes and is promising for the scaling up of applications for highly efficient solar energy conversion systems.

In-situ analysis of trace components in proportioning distilled spirits using Raman integrating sphere spectroscopy.

In situ and on-site analysis of trace components, such as methanol and ethyl acetate, in distilled spirits poses significant challenges. In this study, we have proposed a simple, yet effective and rapid approach that combines Raman spectroscopy with Raman integrating sphere technology to accurately detect trace constituents in distilled spirits. An external standard method to effectively separate overlapping Raman peaks from different substances are developed. Experimental results demonstrate that with an exposure time of 180 s under normal temperature and pressure, the detection limits for methanol, acetic acid, and ethyl acetate in proportioned distilled spirits are below 0.1 g/L. Importantly, the detection limit of methanol and acetic acid remains unaffected by the concentration of distilled spirits and the types of trace substances. Notably, the concentration of trace solute exhibits a highly linear relationship with its corresponding Raman intensity, offering a reliable probe for identifying unknown components in distilled spirits.

Chiral sulfur compounds studied by Raman optical activity: tert-butanesulfinamide and its precursor tert-butyl tert-butanethiosulfinate.

Two chiral sulfur compounds, tert-butyl tert-butanethiosulfinate (1) and tert-butanesulfinamide (2), with inversion of configuration, have been studied by Raman optical activity (ROA) and electronic circular dichroism combined with density functional theory calculation. With the S-S linkage in 1, the couplings between the two tertiary carbon atoms often generate large ROA signals, whereas the tertiary carbon atom itself generally makes a large contribution to ROA signals in 2 for similar vibrational modes. The conformational dependence of ROA parameters provides probing conformation around the S-S bond from a new perspective. The simultaneous use of electronic circular dichroism and ROA is warranted to extract reliable conformational information. ROA provides a suitable candidate for the stereochemical study of chiral sulfur compounds, especially its capability of sensing the conformation around the S-S bond.

Investigation on the Influence of Microstructure Based on Hydrogen Bonding on Surface Tension by Raman Spectroscopy.

Surface tension and Raman spectra containing hydrogen bonding in acetonitrile aqueous solutions with different mole ratios were obtained. Varied surface tension and hydrogen bonding in the mixed solution were discussed. For this purpose, the OH stretching bands were fitted into three Gaussian components to which different hydrogen-bonded water samples were assigned. Furthermore, the microstructures of binary solution were analyzed. The results indicated that the surface tension decreases dramatically with the enhancement of hydrogen bonds in the mixture. A spectroscopic method for studying the macroscopic properties of aqueous solutions was employed. The direct experiment results provided the relationship between surface tension and microstructure in aqueous solutions.

[Explanation of C=O of acetone changing in solvents by some models].

Raman spectra of acetone's carbonyl stretching in 16 solvents were measured, and were also calculated by self-consistent reaction field (SCRF) method in Gaussian03. The frequency shift in experiment was analyzed by donor-acceptor model, Kirkwood model and SCRF model respectively. Among them, the donor-acceptor model can explain the shift very well. The SCRF method can do it also, while not as well as the donor-acceptor model, but is better than Kirkwood model. Correlating the mechanisms of the 3 methods, it was found that the donor-acceptor model is powerful in explaining the vibrational spectra of molecular bond, which is nucleophilic reagent. The SCRF model considers not only the influence of dielectric constant epsilon, but also the influence of the bulk and the structure of molecule etc. Although the model is complex and difficult to calculate, but it takes many factors into account, so the calculated results accord with experiment better than the Kirkwood model. The main parameter of the Kirkwood model is epsilon, so it is very simple and easy to calculate, nonetheless the trend of frequency shift can still be reflected, indicating that the dielectric constant epsilon is a main character affecting the frequency shift.

CoO x nanoparticle anchored on sulfonated-graphite as efficient water oxidation catalyst.

Development of efficient, robust and earth-abundant water oxidation catalysts (WOCs) is extremely desirable for water splitting by electrolysis or photocatalysis. Herein, we report cobalt oxide nanoparticles anchored on the surface of sulfonated graphite (denoted as "CoO x @G-Ph-SN") to exhibit unexpectedly efficient water oxidation activity with a turnover frequency (TOF) of 1.2 s-1; two or three orders of magnitude higher than most cobalt-based oxide WOCs reported so far. The CoO x @G-Ph-SN nanocomposite can be easily prepared by a soft hydrothermal route to have an average CoO x size below 2 nm. Additionally, the loading of CoO x @G-Ph-SN catalyst on the surface of a BiVO4 or Fe2O3 photoanode can boost remarkably the photoanode currents for robust photocatalytic water oxidation under visible light irradiation. Its excellent activity and photochemical stability for water oxidation suggest that this ultrasmall cobalt-based composite is a promising candidate for solar fuel production.

Directly Probing Charge Separation at Interface of TiO2 Phase Junction.

Phase junction is often recognized as an effective strategy to achieve efficient charge separation in photocatalysis and photochemistry. As a crucial factor to determine the photogenerated charges dynamics, there is an increasingly hot debate about the energy band alignment across the interface of phase junction. Herein, we reported the direct measurement of the surface potential profile over the interface of TiO2 phase junction. A built-in electric field up to 1 kV/cm from rutile to anatase nanoparticle was detected by Kelvin Probe Force Microscopy (KPFM). Home-built spatially resolved surface photovoltage spectroscopy (SRSPS) supplies a direct evidence for the vectorial charge transfer of photogenerated electrons from rutile to anatase. Moreover, the tunable anatase nanoparticle sizes in TiO2 phase junction leads to high surface photovoltage (SPV) by creating completely depleted space charge region (SCR) and enhancing the charge separation efficiency. The results provide a strong basis for understanding the impact of built-in electric field on the charge transfer across the interface of artificial photocatalysts.

Substrate-Electrode Interface Engineering by an Electron-Transport Layer in Hematite Photoanode.

The photoelectrochemical water oxidation efficiency of photoanodes is largely limited by interfacial charge-transfer processes. Herein, a metal oxide electron-transport layer (ETL) was introduced at the substrate-electrode interface. Hematite photoanodes prepared on Li(+)- or WO3-modified substrates deliver higher photocurrent. It is inferred that a Li-doped Fe2O3 (Li:Fe2O3) layer with lower flat band potential than the bulk is formed. Li:Fe2O3 and WO3 are proved to function as an expressway for electron extraction. Via introducing ETL, both the charge separation and injection efficiencies are improved. The lifetime of photogenerated electrons is prolonged by 3 times, and the ratio of surface charge transfer and recombination rate is enhanced by 5 times with Li:Fe2O3 and 125 times with WO3 ETL at 1.23 V versus reversible hydrogen electrode. This result indicates the expedited electron extraction from photoanode to the substrate can suppress not only the recombination at the back contact interface but also those at the surface, which results in higher water oxidation efficiency.

Understanding the anatase-rutile phase junction in charge separation and transfer in a TiO2 electrode for photoelectrochemical water splitting.

New insight into junction-based designs for efficient charge separation is vitally important for current solar energy conversion research. Herein, an anatase-rutile phase junction is elaborately introduced into TiO2 films by rapid thermal annealing treatment and the roles of phase junction on charge separation and transfer are studied in detail. A combined study of transient absorption spectroscopy, electrochemical and photoelectrochemical (PEC) measurements reveals that appropriate phase alignment is essential for unidirectional charge transfer, and a junction interface with minimized trap states is crucial to liberate the charge separation potential of the phase junction. By tailored control of phase alignment and interface structure, an optimized TiO2 film with an appropriately introduced phase junction shows superior performance in charge separation and transfer, hence achieving ca. 3 and 9 times photocurrent density enhancement compared to pristine anatase and rutile phase TiO2 electrodes, respectively. This work demonstrates the great potential of phase junctions for efficient charge separation and transfer in solar energy conversion applications.