• Journal of the Korean Chemical Society
• /
• v.39 no.8
• /
• pp.657-665
• /
• 1995

The oxidation of various benzyl ethers and benzyl alkyl ethers to benzoates has been studied in two-phase system of $CH_3CO_2Et$ and aqueous NaOCl (6.6 mol eq.). The oxidant N-oxo-4-methoxy-2,2,6,6-tetramethylpiperidium bromide (N-oxoammonium salt) was prepared in situ and recycled by addition of 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (0.03 mol eq., 4-methoxy-TEMPO), co-catalyst KBr (0.03mol eq.) and second oxidant NaOCl. Thus the catalytic amount of 4-methoxy-TEMPO was used. An adjustment of the pH value of below 8.0 was also required for this reaction with 2.5 hr of reaction time at 0∼5$^{\circ}C$. Under these conditions benzyl ethers were oxidized to benzoates. The selectivity of oxidation of benzyl alkyl ethers is dependent on the acidity of hydrogen and steric effect of alkyl group.

• Journal of the Korean Magnetic Resonance Society
• /
• v.22 no.2
• /
• pp.34-39
• /
• 2018

The Nuclear Magnetic Resonance (NMR) technique using Dynamic Nuclear Polarization (DNP) procedures is one of the promising techniques that enable overcoming low sensitivity problems in NMR spectroscopy. We constructed an ODNP-NMR system using a commercial benchtop EPR spectrometer. The $^1H$ NMR peak area of water in aqueous solutions of 4-hydroxy-TEMPO was enhanced more than 95 times in the ODNP-NMR experiments. Our signal enhancement results were about 55% of the previously reported result. This could be due to non-uniform microwave power over a sample and unwanted sample heating by microwave. However, this portable ODNP-NMR spectrometer will be eventually useful for site-specific detection with nano-scale spatial resolutions and molecular dynamics studies with significantly improved signal sensitivity.

• Journal of the Korean Chemical Society
• /
• v.66 no.3
• /
• pp.209-217
• /
• 2022

We have developed photosensitive electrochromic smart windows that does not require any transparent conducting oxide (TCO) substrate. In our previous study, we demonstrated that a flexible film-type device made with a low temperature curing WO₃ sol and TiO₂ sol could show a reversible and rapid switching between colored and bleached state via incorporation of platinum catalysts on the surface of WO₃ layer. However, when these devices were exposed to sunlight over 4 hour, it was confirmed that they did not return to fully bleached state in the darkened state due to their overcoloring process. In this study, we added 4-hydroxy-(2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPOL) as an additive to the electrolyte of photosensitive electrochromic device to effectively prevent the undesired overcoloring process. The resulting device with TEMPOL indeed did not undergo excessive coloration and showed great reversibility even after being exposed to sunlight for over 4 hours. Various concentrations of TEMPOL were applied to compare changes in the visible transmittance and coloring/bleaching kinetics of devices. In terms of energetic point of view, we proposed a plausible mechanism of TEMPOL to prevent excessive coloration.

• Korean Chemical Engineering Research
• /
• v.57 no.6
• /
• pp.868-873
• /
• 2019

In this study, the evaluation of performance of AORFB using methyl viologen and TEMPOL as organic active materials in neutral supporting electrolyte (NaCl) with various membrane types was performed. Using methyl viologen and TEMPOL as active materials in neutral electrolyte solution, the cell voltage is 1.37V which is relatively high value for AORFB. Two types of membranes were examined for performance comparison. First, when using Nafion 117 membrane which is commercial cation exchange membrane, only the charge process occurred in the first cycle and the single cell couldn't work because of its high resistance. However, when using Fumasep anion exchange membrane (FAA-3-50) instead of Nafion 117 membrane, the result was obtained as the totally different charge-discharge graphs. When current density was $40mA{\cdot}cm^{-2}$ and cut off voltage range was from 0.55 V to 1.7 V, the charge efficiency (CE) was 97% and voltage efficiency (VE) was 78%. In addition, the discharge capacity was $1.44Ah{\cdot}L^{-1}$ which was 54% of theoretical capacity ($2.68Ah{\cdot}L^{-1}$) at $10^{th}$ cycle and the capacity loss rate was $0.0015Ah{\cdot}L^{-1}$ per cycle during 50 cycles. Through cyclic voltammetry test, it seems that this difference in the performance between the full cell using Nafion 117 membrane and Fumasep anion exchange membrane came from increasing resistance due to chemical reaction between membrane and active material, not the capacity loss due to cross-over of active material through membrane.