• Transactions of the Korean hydrogen and new energy society
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• v.28 no.4
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• pp.361-368
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• 2017

Alanate-based materials, which were known to have high hydrogen storage capacity, were synthesized by mechanochemically metathesis reaction of metal chloride and sodium alanate without solvent. XRD patterns of synthesized materials showed that metathesis reaction of cations between metal chloride and sodium alanate was progressed favorably without any solvent. Magnesium alanate showed that 3.2 wt.% of hydrogen was evolved by the thermal decomposition. The addition of a small amount of Ti to the magnesium alanate greatly reduced hydrogen evolution temperature. Also, Ti doped magnesium alanate had a good regeneration property. Both the calcium and lithium-magnesium alanate showed the lower starting temperature of the two step hydrogen evolution and fast kinetics for the hydrogen evolution.

• Korean Journal of Materials Research
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• v.28 no.7
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• pp.428-434
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• 2018

Hydrogen evolution on a steel surface and subsequent hydrogen diffusion into the steel matrix are evaluated using an electrochemical permeation test with no applied cathodic current on the hydrogen charging side. In particular, cyclic operation in the permeation test is also conducted to clarify the corrosion-induced hydrogen evolution behavior. In contrast to the conventional perception that the cathodic reduction reaction on the steel in neutral aqueous environments is an oxygen reduction reaction, this study demonstrates that atomic hydrogen may be generated on the steel surface by the corrosion reaction, even in a neutral environment. Although a much lower permeation current density and significant slower diffusion kinetics of hydrogen are observed compared to the results measured in acidic environments, they contribute to the increase in the embrittlement index. This study suggests that the research on hydrogen embrittlement in ultra-strong steels should be approached from the viewpoint of corrosion reactions on the steel surface and subsequent hydrogen evolution/diffusion behavior.

• Journal of Electrochemical Science and Technology
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• v.13 no.4
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• pp.417-423
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• 2022

With the emerging importance of catalysts for water electrolysis, developing efficient and inexpensive electrocatalysts for water electrolysis plays a vital role in renewable hydrogen energy technology. In this study, a 1nm thickness of TiC-supported Ru catalyst for hydrogen evolution reaction (HER) has been successfully fabricated using an electron (E)-beam evaporator and thermal decomposition of gaseous CH₄ in a furnace. The prepared Ru/TiC catalyst exhibited an outstanding performance for alkaline hydrogen evolution reaction with an overpotential of 55 mV at 10 mA cm^-2. Furthermore, we demonstrated that the outstanding HER performance of Ru/TiC was attributed to the high surface area of the support and the metal-support interaction.

• Journal of Electrochemical Science and Technology
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• v.13 no.1
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• pp.120-127
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• 2022

Molybdenum disulfide (MoS₂) has been widely used as a catalyst for the bifunctional activities of hydrogen and oxygen evolution reactions (HER and OER). Here, we investigated size dependent HER and OER performance of MoS₂. The smallest size (90 nm) of MoS₂ exhibits the lowest overpotential of -0.28 V at -10 mAcm^-2 and 1.52 V at 300 mAcm^-2 with the smallest Tafel slopes of 151 and 176 mVdec^-1 for HER and OER, respectively, compared to bigger sizes (2 ㎛ and 6 ㎛) of MoS₂. The better HER and OER performance is attributed to high electrochemical active surface area (6 × 10^-4 cm²) with edge sites and low charge transfer resistance (18.1 Ω), confirming that the smaller MoS₂ nanosheets have the better catalytic behavior.

• Korean Journal of Materials Research
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• v.30 no.12
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• pp.709-714
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• 2020

For zinc-air batteries, there are several limitations associated with zinc anodes. The self-discharge behavior of zinc-air batteries is a critical issue that is induced by corrosion reaction and hydrogen evolution reaction (HER) of zinc anodes. Aluminum and indium are effective additives for controlling the hydrogen evolution reaction as well as the corrosion reaction. To enhance the electrochemical performances of zinc-air batteries, mechanically alloyed Zn-Al and Zn-In materials with different compositions are successfully fabricated at 500rpm and 5h milling time. Investigated materials are characterized by X-ray diffractometer (XRD), field emission scanning electron microscope (FE-SEM), and energy dispersive spectrometer (EDS). Alloys are investigated for the application as novel anodes in zinc-air batteries. Especially, the material with 3 wt% of indium (ZI3) delivers 445.37 mAh/g and 408.52 mAh/g of specific discharge capacity with 1 h and 6 h storage, respectively. Also, it shows 91.72 % capacity retention and has the lowest value of corrosion current density among attempted materials.

• Bulletin of the Korean Chemical Society
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• v.13 no.5
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• pp.531-537
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• 1992

The approximate rates and stoichiometry of the reaction of excess potassium 2-thexyl-1,3,2-dioxaborinane hydride(KTDBNH) with 55 selected compounds containing representative functional groups under standardized conditions (tetrahydrofuran, TEX>$0^{\circ}C$, reagent : compound=4 : 1) was examined in order to define the characteristics of the reagent for selective reductions. Benzyl alcohol and phenol evolve hydrogen immediately. However, primary, secondary and tertiary alcohols evolve hydrogen slowly, and the rate of hydrogen evolution is in order of $1^{\circ}$> $2^{\circ}$> $3^{\circ}$. n-Hexylamine is inert toward the reagent, whereas the thiols examined evolve hydrogen rapidly. Aldehydes and ketones are reduced rapidly and quantitatively to give the corresponding alcohols. Cinnamaldehyde is rapidly reduced to cinnamyl alcohol, and further reduction is slow under these conditions. The reaction with p-benzoquinone dose not show a clean reduction, but anthraquinone is cleanly reduced to 9,10-dihydro-9,10-anthracenediol. Carboxylic acids liberate hydrogen immediately, further reduction is very slow. Cyclic anhydrides slowly consume 2 equiv of hydride, corresponding to reduction to the caboxylic acid and alcohol stages. Acid chlorides, esters, and lactones are rapidly and quantitatively reduced to the corresponding carbinols. Epoxides consume 1 equiv hydride slowly. Primary amides evolve 1 equiv of hydrogen readily, but further reduction is slow. Tertiary amides are also reduced slowly. Both aliphatic and aromatic nitriles consume 1 equiv of hydride rapidly, but further hydride uptake is slow. Analysis of the reaction mixture with 2,4-dinitrophenylhydrazine yields 64% of caproaldehyde and 87% of benzaldehyde, respectively. 1-Nitropropane utilizes 2 equiv of hydride, one for hydrogen evolution and the other for reduction. Other nitrogen compounds examined are also reduced slowly. Cyclohexanone oxime undergoes slow reduction to N-cyclohexylhydroxyamine. Pyridine ring is slowly attacked. Disulfides examined are reduced readily to the correponding thiols with rapid evolution of 1 equiv hydrogen. Dimethyl sulfoxide is reduced slowly to dimethyl sulfide, whereas the reduction of diphenyl sulfone is very slow. Sulfonic acids only liberate hydrogen quantitatively without any reduction. Finally, cyclohexyl tosylate is inert to this reagent. Consequently, potassium 2-thexyl-1,3,2-dioxaborinane hydride, a monoalkyldialkoxyborohydride, shows a unique reducing characteristics. The reducing power of this reagent exists somewhere between trialkylborohydrides and trialkoxyborohydride. Therefore, the reagent should find a useful application in organic synthesis, especially in the field of selective reduction.

• Journal of the Korean institute of surface engineering
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• v.54 no.4
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• pp.164-170
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• 2021

Vanadium redox flow batteries (VRFB) have emerged as large-scale energy storage systems (ESS) due to their advantages such as low cross-contamination, long life, and flexible design. However, Hydrogen evolution reaction (HER) in the negative half-cell causes a harmful influence on the performance of the VRFB by consuming current. Moreover, HER hinders V²⁺/V³⁺ redox reaction between electrode and electrolyte by forming a bubble. To address the HER problem, carbon nanotube/graphite felt electrode (CNT/GF) with oxygen functional groups was synthesized through the hydrothermal method in the H₂SO₄ + HNO₃ (3:1) mixed acid solution. These oxygen functional groups on the CNT/GF succeed in suppressing the HER and improving charge transfer for V²⁺/V³⁺ redox reaction. As a result, the oxygen functional group applied electrode exhibited a low overpotential of 0.395 V for V²⁺/V³⁺ redox reaction. Hence, this work could offer a new strategy to design and synthesize effective electrodes for HER suppression and improving the energy density of VRFB.

• Korean Journal of Materials Research
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• v.26 no.5
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• pp.241-245
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• 2016

Hydrogen is considered a potential future energy source. Among other applications of hydrogen, hydrogen-rich water is emerging as a new health care product in industrial areas. Water electrolysis is typically used to generate a hydrogen rich water system. We annealed 10AA carbon paper in air to use it as an electrode of a hydrogen rich water generator. Driven by annealing, structural changes of the carbon paper were identified by secondary electron microscope analysis. Depending on the various annealing temperatures, changes of the hydrophilic characteristics were demonstrated. The crystal structures of pristine and heat-treated carbon paper were characterized by X-ray diffraction. Improvement of the efficiency of the electrochemical oxygen evolution reaction was measured via linear voltammetry. The optimized annealing temperature of 10AA carbon paper showed the possibility of using this material as an effective hydrogen rich water generator.

• Applied Chemistry for Engineering
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• v.34 no.6
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• pp.567-575
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• 2023

Water electrolysis is undergoing active research as one of the promising technologies for producing effective green hydrogen. Using seawater directly as a raw material for a water electrolysis system can solve the problem of the limitations of existing freshwater raw materials, as seawater accounts for approximately 97% of the water on Earth. At the same time, abundant by-product materials can be obtained, representative examples of which are Cl₂, ClO^-, Br₂, and Mg(OH)₂ produced during electrolysis, depending on their composition and pH environment. In order to develop a successful seawater electrolysis system and oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) catalysts, it is necessary to understand the causes and consequences of reactions that occur in the seawater environment. Therefore, in this paper, we will investigate the reaction mechanism and characteristics of the seawater electrolysis system as well as the research and development trends of electrochemical catalysts used in anode and cathode electrodes.

• Bulletin of the Korean Chemical Society
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• v.14 no.4
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• pp.469-475
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• 1993

The approximate rates and stoichiometry of the reaction of excess lithium tris(diethylamino)aluminum hydride (LTDEA) with selected organic compounds containing representative functional groups under standardized condition (tetrahydrofuran, 0$^{\circ}C$) were examined in order to define the characteristics of the reagent for selective reductions. The reducing ability of LTDEA was also compared with those of the parent lithium aluminum hydride (LAH) and lithium tris(dibutylamino)aluminum hydride (LTDBA). In general, the reactivity toward organic functionalities is in order of LAH${\gg}$LTDEA${\geq}$LTDBA. LTDEA shows a unique reducing characteristics. Thus, benzyl alcohol and phenol evolve hydrogen slowly. The rate of hydrogen evolution of primary, secondary, and tertiary alcohols is distinctive: 1-hexanol evolves hydrogen completely in 6 h, whereas 3-hexanol evolves hydrogen very slowly. However, 3-ethyl-3-pentanol does not evolve any hydrogen under these reaction conditions. Primary amine, such as n-hexylamine, evolves only 1 equivalent of hydrogen. On the other hand, thiols examined are absolutely inert to this reagent. LTDEA reduces aldehydes, ketones, esters, acid chlorides, and epoxides readily to the corresponding alcohols. Quinones, such as p-benzoquinone and anthraquinone, are reduced to the corresponding diols without hydrogen evolution. However, carboxylic acids, anhydrides, nitriles, and primary amides are reduced slowly, where as tertiary amides are readily reduced. Finally, sulfides and sulfoxides are reduced to thiols and sulfides, respectively, without evolution of hydrogen. In addition to that, the reagent appears to be an excellent partial reducing agent to convert esters, primary carboxamides, and aromatic nitriles into the corresponding aldehydes. Free carboxylic acids are also converted into aldehydes through treatment of acyloxy-9-BBN with this reagent in excellent yields.