Analytical Instrument Documents

High-capacity Li1+x(Ni0.3Mn0.7)1-xO2, (0 < x < 1/3) samples were synthesized by the coprecipitation–calcination method. Both electrochemical cycle and high-rate performances were drastically improved by selecting an N2 atmosphere as final calcination. Scanning transmission electron microscopy—energy dispersive X-ray spectroscopy analysis showed that the sample calcined in an N2 atmosphere had a more homogeneous transition metal distribution into primary particles than that calcined in air. The solid-state 7Li nuclear magnetic resonance data showed that electrochemically inactive domains were only diminished for the sample calcined in an N2 atmosphere after electrochemical activation. X-ray Rietveld analysis revealed that the suitable transition metal distribution and content of the samples were different from those of typical layered rock-salt materials. Only that calcined in an N2 atmosphere had no spinel formation during charging and no oxide ion insertion reaction during discharging. No positive Co substitution effect was observed under the optimized preparation conditions. At the 100th cycle, the discharge capacity was 216 mAh g−1, which corresponds to 87% of the initial capacity (251 mAh g−1) at optimizing synthetic condition.

Polymers can be degraded by the effects of light, oxygen, heat, etc. so it is important to understand how the polymer structures change during degradation. Pyrolysis gas chromatograph quadrupole mass spectrometer (Py-GC-QMS) and matrix-assisted laser desorption/ionization time-of-flight mass spectrometer (MALDI-TOFMS) are powerful tools for analyzing polymeric materials. Py-GC-QMS is a method that instantaneously heats a sample with a pyrolyzer and then analyzes the pyrolysis products by GC-MS. Since most of the pyrolysis products are related to monomers and dimers, this technique allows for easy identification of the polymer substructures which is useful for identifying changes to the polymer when degradation occurs. MALDI-TOFMS involves a soft ionization technique that can directly ionize and analyze the intact polymer molecules and often produces singly-charged ions even for high molecular weight compounds. As a result, the m/z axis of the mass spectrum is equal to the mass of the ions, thus making it easy to interpret polymer distributions. Additionally, when MALDI is used with a high-resolution TOFMS, the accurate mass of each ion in the polymer series can be used to calculate their elemental compositions. Moreover, the molecular weight distribution of polymers can be calculated from the ion intensity distribution. In this work, we used Py-GC-QMS and high-resolution MALDI-TOFMS to evaluate the effects of UV irradiation on polymethyl methacrylate (PMMA).

The recent discovery of Na3LiTi5O12 (NTO), which possesses spinel symmetry (, #227) with the 8a site occupied by Na, has enabled investigations into the effect of the 8a-site cation on the physical properties of spinel titanates. Hence, in this study, the optical and photocatalytic properties of NTO were investigated and compared with those of spinel Li4Ti5O12 (LTO) and rutile TiO2. The bandgaps were estimated theoretically using hybrid density functional theory and experimentally using the ultraviolet–visible spectroscopy, and the obtained results were similar for both methods and spinel titanates. The valence- and conduction-band components of the spinel-type titanates were similar to those of other titanium oxides, and both NTO and LTO exhibited photocatalytic activity for sacrificial H2 evolution from water. However, although they have similar band structures and optical properties, the NTO photocatalytic activity was clearly lower than that of LTO. This can be attributed to the surface roughness and ease of defect formation in the NTO system, which hindered charge separation. These results indicate that the optical properties of spinel-type titanates can be tuned by replacing the cations at the 8a sites.

Analysis of complex mixtures with gas chromatography coupled with high-resolution time-of-flight mass spectrometry (GC-HRTOFMS) can produce a large amount of data. A new software program was recently reported that integrates all of the available mass spectrometric information from GC-HRTOFMS analysis into a concise report. New capabilities have now been added to the software to incorporate retention index data and to identify differences between two samples.

Solid-state NMR is a valuable tool for elucidating the structures and dynamics of materials at an atomic level. Proton multiple-quantum (MQ) /single-quantum (SQ) correlation NMR spectroscopy is widely used to probe spatial proximity among protons. In the triple-quantum (TQ)/SQ correlation experiment, the excitation of triple-quantum (TQ) coherences is traditionally achieved by a 90° pulse in conjugation with double-quantum (DQ) recoupling sequences. Nevertheless, such sequences often suffer from low TQ filtering efficiency and may lead to overlapping spinning sidebands in the indirect TQ dimension, especially at a slow MAS frequency. Herein, we design several supercycled symmetry-based RNnν γ-free TQ recoupling sequences and compare their performance via extensive numerical simulation and experiments. Experimental results further confirm that pulse sequence gives the highest TQ filtering efficiency of around 20% in the slow MAS regime (∼10 kHz). The 2D TQ/SQ spectrum at slow MAS is completely free of spinning sidebands in the TQ dimension due to its γ-free nature. We establish that such a γ-free pulse sequence is a superior candidate for TQ spectroscopy at slow MAS frequency.

Herein, a novel non-planar 2D COF with a stair-stepped structure was constructed from a Z-shaped building block for the first time. Compared with its similar planar COF, the unique stair-stepped non-planar COF possesses larger surface area and stronger fluorescence, which was further applied for specific explosive detection through a fluorescence quenching mechanism. This work not only extends the traditional planar 2D COF structures to unique non-planar structures based on the bottom-up design principle, but also expands the potential applications of COF materials.

Diffusion-ordered NMR spectroscopy (DOSY) constructs multidimensional spectra displaying signal strength as a function of Larmor frequency and of diffusion coefficient from experimental measurements using pulsed field gradient spin or stimulated echoes. Peak positions in the diffusion domain are determined by diffusion coefficients estimated by fitting experimental data to some variant of the Stejskal–Tanner equation, with the peak widths determined by the standard error estimated in the fitting process. The accuracy and reliability of the diffusion domain in DOSY spectra are therefore determined by the uncertainties in the experimental data and thus in part by the signal-to-noise ratio of the experimental spectra measured. Here the Cramér–Rao lower bound, Monte Carlo methods, and experimental data are used to investigate the relationship between signal-to-noise ratio, experimental parameters, and diffusion domain accuracy in 2D DOSY experiments. Experimental results confirm that sources of error other than noise put an upper limit on the improvement in diffusion domain accuracy obtainable by time averaging.

The conversion of CO2 into functional materials under ambient conditions is a major challenge to realize a carbon-neutral society. Metal–organic frameworks (MOFs) have been extensively studied as designable porous materials. Despite the fact that CO2 is an attractive renewable resource, the synthesis of MOFs from CO2 remains unexplored. Chemical inertness of CO2 has hampered its conversion into typical MOF linkers such as carboxylates without high energy reactants and/or harsh conditions. Here, we present a one-pot conversion of CO2 into highly porous crystalline MOFs at ambient temperature and pressure. Cubic [Zn4O(piperazine dicarbamate)3] is synthesized via in situ formation of bridging dicarbamate linkers from piperazines and CO2 and shows high surface areas (∼2366 m2 g–1) and CO2 contents (>30 wt %). Whereas the dicarbamate linkers are thermodynamically unstable by themselves and readily release CO2, the formation of an extended coordination network in the MOF lattices stabilizes the linker enough to demonstrate stable permanent porosity.

Structural analysis by NMR can provide not only a planar molecular structure but also three-dimensional structural information. In this Note, we describe a method for obtaining information on dihedral angles by using 1H-1H coupling constants (JHH values). For example, hydrogen atoms attached to a cyclohexane ring are either located in axial or equatorial positions in respect to the cyclohexane ring (Fig. 1). The dihedral angles between vicinal protons are known to be ∠Hax-C-C-Hax ≈ 180°, ∠Hax-C-Heq ≈ 60°, and ∠Heq-C-C-Heq ≈ 60°. If we look at the Karplus curve shown in Fig. 2, we can see that 3JHH of around 4 Hz can be expected in the case of the dihedral angle of 60°, while 3JHH of around 13 Hz corresponds to the dihedral angle of 180°. In reality, 3JHH values depend on substituents attached to the cyclohexane ring in substituted cyclohexanes, so the analysis is not straightforward, but the basic trend of having a larger J-value for a 180° dihedral angle compared to a 60° dihedral angle remains unchanged. Therefore, from the value of 3JHH of the methylene protons, it is possible to differentiate between the dihedral angle of 60° or 180°.

The new generation diffusion probe is specially designed for diffusion applications that requires a large magnetic field gradient. By improving the design around the coil, the recovery time after field gradient pulse has been significantly shortened compared to the conventional model. Using a newly developed 50A bipolar magnetic field gradient power supply, a magnetic field gradient of 20 T/m (2000 G/cm) can be applied, making it possible to measure diffusion coefficients on the order of 10-14 m2/s. This system is ideal for measuring the diffusion of ions in solid electrolytes.