• 전기화학회지
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• 제26권4호
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• pp.64-70
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• 2023

급격한 온실가스 배출량 증가로 인해 지구 온난화가 심화되고 있다. 이로 인해 탄소중립의 필요성과 이행이 더욱 절실해졌다. 이를 위해 여러 가지 신재생에너지 중 수소에 대한 관심이 부각되고 있다. 수소는 지구 상에 풍부한 자원이며 무탄소 전원으로 친환경적이다. 궁극적으로 물의 전기분해에 의해 친환경 수소를 얻을 수 있다. 하지만 산소 발생 반응에 사용되는 촉매는 고가이며 희귀하고 촉매의 내구성에 문제가 있어 어려움을 겪고 있기 때문에 비귀금속 촉매의 개발이 필요하다. 본 총설에서는 최근 발표된 산소 발생 촉매 중 비귀금속 촉매인 Co와 Mo 기반의 촉매를 정리, 요약하여 소개하고 있다. 이를 통해 비귀금속 촉매의 활성과 내구성을 증가시키기 위한 촉매의 특성 설계를 이해하는 데 도움이 될 것이다.

• 한국전기화학회:학술대회논문집
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• 한국전기화학회 2005년도 수소연료전지공동심포지움 2005논문집
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• pp.373-378
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• 2005

[ $Zn(BH_4)_2$ ] ($8.4\;wt\%$ theoretical hydrogen storage capacity) powders have been successfully synthesized by mechanochemical reaction from mixtures of $ZnCl_2$ and $NaBH_4$ powders in a 1:2 molar ratio in different times. $$ZnCl_2\;+\;2NaBH_4\rightarrow\;Zn(BH_4)_2\;+\;2NaCl\;(1)$$ $Zn(BH_4)_2$ powders were characterized by X-ray diffractometry(XRD), and Furier Transform Infrared spectrometry(FT-IR). The thermal stabilities of $Zn(BH_4)_2$ powders were studied by Differential scanning calorimetry(DSC), Thermogravimetry analysis(TGA), and Mass spectrometry(MS). $Zn(BH_4)_2$ can be tested for hydrogen evolution without further purification. The reaction to yield hydrogen is irreversible, the other products being compounds of Zn, and borane. $Zn(BH_4)_2$ thermally decomposes to release borane and hydrogen gas between about 85 and $150^{\circ}C$.

• 한국재료학회지
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• 제32권10호
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• pp.408-413
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• 2022

The oxygen evolution reaction (OER) is very sluggish compared to the hydrogen evolution reaction (HER). Considering this difference is essential when designing and developing a cost-effective and facile synthesis method for a catalyst that can effectively perform OER activity. The material should possess a high surface area and more active sites. Considering these points, in this work we successfully synthesized sheets of cobalt phosphate hydrate (CP) and sulphurated cobalt phosphate hydrate (CPS) material, using simple successive ionic layered adsorption and reaction (SILAR) methods followed by sulfurization. The CP and CPS electrodes exhibited overpotentials of 279 mV with a Tafel slope of 212 mV dec^-1 and 381 mV with a Tafel slope of 212 mV dec^-1, respectively. The superior performance after sulfurization is attributed to the intrinsic activity of the deposited well-aligned nanosheet structures, which provided a substantial number of electrochemically active surface sites, speeded electron transfer, and at the same time improved the diffusion of the electrolyte.

• 한국수소및신에너지학회논문집
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• 제26권4호
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• pp.308-317
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• 2015

To investigate the effect of microstructure on the formation of the desorption peak, the volumetric thermal analysis technique (VTA) was applied to the Mg-13.5 wt% Ni hydride system. The sample made by the HCS (hydriding combustion synthesis) process had two kinds of Mg microstructures. Linear heating was started with various constant heating rates. Only one peak was appeared in the case of the small initial hydrogen wt% (0.83 wt%). Yet, two peaks were appeared with increasing initial hydrogen wt% (1.85 and 3.73 wt%) when only Mg was hydrogenated. The first peak was formed through the evolution of hydrogen from $MgH_2$, made by eutectic Mg. The second peak was formed through the evolution of hydrogen from $MgH_2$, made by primary Mg. Therefore, this result shows that the microstructure also has a considerable effect on forming the desorption peak. We have also derived the hydrogen desorption equations by VTA to get apparent activation energy when the rate-controlling step for the desorption of the hydrided system is the diffusion of hydrogen through the ${\alpha}$ phase and the chemical reaction ${\beta}{\rightarrow}{\alpha}$.

• 한국수소및신에너지학회논문집
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• 제23권5호
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• pp.448-454
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• 2012

In this paper, a three-dimensional hydrogen absorption model is applied to a thin double-layered annulus ZrCo hydride bed and validated against the temperature evolution data measured by Kang et al. The present model reasonably captures the bed temperature evolution behavior and the 99% hydrogen charging time. The equilibrium pressure expression for hydrogen absorption on ZrCo is derived as a function of temperature and the H/M atomic ratio based on the pressure-composition isotherm data given by Konishi et al. In addition, this present model provides multi-dimensional contours such as temperature and H/M atomic ratio in the thin doublelayered annulus metal hydride region. This numerical study provides fundamental understanding during hydrogen absorption process and indicates that efficient design of the metal hydride bed is critical to achieve rapid hydrogen charging performance. The present three-dimensional hydrogen absorption model is a useful tool for the optimization of bed design and operating conditions.

• Bulletin of the Korean Chemical Society
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• 제15권10호
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• pp.881-888
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• 1994

The approximate rates and stoichiometry of the reaction of excess sodium tris(diethylamino)aluminum hydride (ST-DEA) with selected organic compounds containing representative functional groups under standardized conditions(tetrahydrofuran, $0{\circ}$) were studied in order to characterize the reducing characteristics of the reagent for selective reductions. The reducing ability of STDEA was also compared with those of the parent sodium aluminum hydride (SAH) and lithium tris(diethylamino)aluminum hydride (LTDEA). The reagent appears to be milder than LTDEA. Nevertheless, the reducing action of STDEA is very similar to that observed previously for LTDEA, as is the case of the corresponding parent sodium and lithium aluminum hydrides. STDEA shows a unique reducing characteristics. Thus, benzyl alcohol, phenol and 1-hexanol evolved hydrogen slowly, whereas 3-hexanol and 3-ethyl-3-pentanol, secondary and tertiary alcohols, were essentially inert to STDEA. Primary amine, such as n-hexylamine, evolved only 1 equivalent of hydrogen slowly. On the other hand, thiols examined were absolutely stable. STDEA reduced aidehydes and ketones rapidly to the corresponding alcohols. The stereoselectivity in the reduction of cyclic ketones by STDEA was similar to that by LTDEA. Quinones, such as p-benzoquinone and anthraquinone, were reduced to the corresponding 1,4-dihydroxycyclohexadienes without evolution of hydrogen. Carboxylic acids and anhydrides were reduced very slowly, whereas acid chlorides were reduced to the corresponding alcohols readily. Esters and epoxides were also reduced readily. Primary carboxamides consumed hydrides for reduction slowly with concurrent hydrogen evolution, but tertiary amides were readily reduced to the corresponding tertiary amines. The rate of reduction of aromatic nitriles was much faster than that of aliphatic nitriles. Nitrogen compounds examined were also reduced slowly. Finally, disulfide, sulfoxide, sulfone, and cyclohexyl tosylate were readily reduced without evolution of hydrogen. In addition to that, the reagent appears to be an excellent partial reducing agent: like LTDEA, STDEA converted ester and primary carboxamides to the corresponding aldehydes in good yields. Furthermore, the reagent reduced aromatic nitriles to the corresponding aldehydes chemoselectively in the presence of aliphatic nitriles. Consequently, STDEA can replace LTDEA effectively, with a higher selectivity, in most organic reductions.

• 한국수소및신에너지학회논문집
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• 제16권3호
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• pp.262-268
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• 2005

[ $Zn(BH_4)_2$ ](8.4 wt% theoretical hydrogen storage capacity powders have been successfully synthesized by mechanochemical reaction from mixtures of $ZnCl_2$ and $NaBH_4$ powders in a 1:2 molar ratio in different times. $$ZnCl_2+2NaBH_4{\rightarrow}Zn(BH_4)_2+2NaCl$$ (1) $Zn(BH_4)_2$ powders were characterized by X-ray diffractometry(XRD), and Furier Transform Infrared spectrometry(FT-IR). The thermal stabilities of $Zn(BH_4)_2$ powders were studied by Differential scanning calorimetry(DSC), Thermogravimetry analysis(TGA), and Mass spectrometry(MS). $Zn(BH_4)_2$ can be tested for hydrogen evolution without further purification. The reaction to yield hydrogen is irreversible, the other products being compounds of Zn, and borane. $Zn(BH_4)_2$ thermally decomposes to release borane and hydrogen gas between about 85 and 150$^{\circ}C$.

• Bulletin of the Korean Chemical Society
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• 제14권6호
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• pp.743-749
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• 1993

The approximate rates and stoichiometry of the reaction of excess lithium tris(dihexylamino)aluminum hydride(LTDHA) with selected organic compounds containing representative functional groups under the standardized conditions (tetrahydrofuran, 0$^{\circ}$C) were studied in order to define the reducing characteristics of the reagent for selective reductions. The reducing ability of LTDHA was also compared with those of the parent lithium aluminum hydride(LAH), lithium tris(diethylamino)aluminum hydride(LTDEA), and lithium tris(dibutylamino)aluminum hydride(LTDBA). In general, the reactivity toward organic functionalities is in order of $LAH{\gg}LTDEA{\geq}LTDBA>LTDHA$. LTDHA shows a unique reducing characteristics. Thus, the reagent reduces aldehydes, ketones, esters, epoxides, and tertiary amides readily. Anthraquinone is cleanly reduced to 9,10-dihydro-9,10-anthracenediol without hydrogen evolution, whereas p-benzoquinone in inert to LTDHA. In addition to that, disulfides are also readily reduced to thiols without hydrogen evolution. However, carboxylic acids, anhydrides, nitriles, and primary amides are reduced slowly. Especially, this reagent reduces aromatic nitriles to the corresponding aldehydes in good yields.

• Bulletin of the Korean Chemical Society
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• 제12권6호
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• pp.644-649
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• 1991

The approximate rates and stoichiometry of the reaction of excess lithium tris(dibutylamino)aluminum hydride (LT-DBA) with selected organic compounds containing representative functional groups under standardized conditions (tetrahydrofuran, $0^{\circ}C$) were studied in order to characterize the reducing characteristics of the reagent for selective reductions. The reducing ability of LTDBA was also compared with those of the parent lithium aluminum hydride and the alkoxy derivatives. The reagent appears to be much milder than the parent reagent, but stronger than lithium tri-t-butoxyaluminohydride in reducing strength. LTDBA shows a unique reducing characteristics. Thus, the reagent reduces aldehydes, ketones, esters, acid chlorides, epoxides, and amides readily. In addition to that, ${\alpha},{\beta}$-unsaturated aldehyde is reduced to ${\alpha},{\beta}$-unsaturated alcohol. Quinones are reduced to the corresponding diols without evolution of hydrogen. Tertiary amides and aromatic nitriles are converted to aldehydes with a limiting amount of LTDBA. Finally, disulfides and sulfoxides are readily reduced to thiols and sulfides, respectively, without hydrogen evolution.

• 한국미생물·생명공학회지
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• 제11권3호
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• pp.211-216
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• 1983

R. sphaeroides K- 7에 의한 수소생성과 질소고정효소(nitrogenase)와의 연관성을 조사한 결과 수소생성은 질소고정효소에 의해 이루어지는 것으로 나타났다. 또한 수소생성은 수소효소(hydrogenase)와 무관하며 박테리오클로로필의 농도와도 무관한 것으로 나타났다. 글루타민산이 in vivo에서 질소고정효소의 활성도를 조절하는데 중요한 역할을 할 수 있는 것으로 나타났으며 질소개스를 이용해 키운 세균을 글루타민산 존재하로 옮겼을때 보다 큰 정도의 수소생성능 및 질소고정효소 활성도가 나타났다.