• Bulletin of the Korean Chemical Society
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• 제15권10호
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• pp.873-881
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• 1994

The approximate rate and stoichiometry of the reaction of excess diisobutylaluminum hydride-dimethyl sulfide complex($DIBAH-SMe_2$) with organic compounds containing representative functional group under standardized conditions (toluene, $0{\circ}C$) were examined in order to define the reducing characterstics of the reagent and to compare the reducing power with DIBAH itself. In general, the reducing action of the complex is similar to that of DIBAH. However, the reducing power of the complex is weaker than that of DIBAH. All of the active hydrogen compounds including alcohols, amines, and thiols evolve hydrogen slowly. Aldehydes and ketones are reduced readily and quantitatively to give the corresponding alcohols. However, $DIBAH-SMe_2$ reduces carboxylic acids at a faster rate than DIBAH alone to the corresponding alcohols with a partial evolution of hydrogen. Similarly, acid chlorides, esters, and epoxides are readily reduced to the corresponding alcohols, but the reduction rate is much slower than that of DIBAH alone. Both primary aliphatic and aromatic amides examined evolve 1 equiv of hydrogen rapidly and are reduced slowly to the amines. Tertiary amides readily utilize 2 equiv of hydride for reduction. Nitriles consume 1 equiv of hydride rapidly but further hydride uptake is quite slow. Nitro compounds, azobenzene, and azoxybenzene are reduced moderately. Cyclohexanone oxime liberates ca. 0.8 equiv of hydrogen rapidly and is reduced to the N-hydroxylamine stage. Phenyl isocyanate is rapidly reduced to the imine stage, but further hydride uptake is quite sluggish. Pyridine reacts at a moderate rate with an uptake of one hydride in 48 h, while pyridine N-oxide reacts rapidly with consumption of 2 equiv of hydride for reduction in 6h. Similarly, disulfides and sulfoxide are readily reduced, whereas sulfide, sulfone, and sulfonic acid are inert to this reagent under these reaction conditions.

• 한국수소및신에너지학회논문집
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• 제27권6호
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• pp.677-684
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• 2016

Various commercially available gas diffusion layers (GDLs) from different manufacturers were used to prepare an air electrode using $La_{0.8}Sr_{0.2}CoO_3$ perovskite (LSCP) as the catalyst for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in an alkaline solution. Various GDLs have different physical properties, such as porosity, conductivity, hydrophobicity, etc. The ORR and OER of the resulting cathode were electrochemically evaluated in an alkaline solution. The electrochemical properties of the resulting cathodes were slightly different when compared to the physical properties of GDLs. Pore structure and conductivity of GDLs had a prominent effect and their hydrophobicities had a minor effect on the electrochemical performances of cathodes for ORR and OER.

• 한국수소및신에너지학회논문집
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• 제27권3호
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• pp.276-282
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• 2016

The effects of conductive additives in a $La_{0.8}Sr_{0.2}MnO_3$ perovskite bifunctional electrode for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) were investigated in an alkaline solution. Highly porous carbon black (CB) and Ni powder were added to the bifunctional electrodes as conductive additives. The surface morphologies of electrodes containing CB and Ni were observed by scanning electron microscopy (SEM). The current densities for both ORR and OER were changed by the addition of CB. The conductive additive changed physical properties of bifunctional electrodes such as the sheet conductance, gas permeability and contact angle. It was observed that the air permeability of electrode was most effective to enhance the currents for ORR and OER.

• 한국수소및신에너지학회논문집
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• 제27권6호
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• pp.636-641
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• 2016

Alkaline water electrolysis is commercial hydrogen production technology. It is possible to operate MW scale plant. Because It used non-precious metal for electrode. But It has relatively low current density and low efficiency. In this study, research objective is development of anode for alkaline water electrolysis with low cost, high corrosion resistance and high efficiency. Stainless steel 316L (SUS 316L) was selected for a substrate of electrode. To improve corrosion resistance of substrate, Nickel (Ni) layer was electrodeposited on SUS 316L. Ni-Fe alloy was electrodeposited on the passivated Ni layer as active catalyst for oxygen evolution reaction(OER). We optimized preparation condition of Ni-Fe alloy electrodeposition by changing current density, electrodeposition time and composition ratio of Ni-Fe electrodeposition bath. This electrodes were electrochemically evaluated by using Linear sweep voltammetry (LSV) and Cyclic voltammetry (CV). The Ni-Fe alloy (Ni : Fe = 1 : 1) showed best activity of OER. The optimized electrode decreased overpotential about 40% at $100mA/cm^2$ compared with Ni anode.

• Bulletin of the Korean Chemical Society
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• 제15권2호
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• pp.132-138
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• 1994

Bis(diethylamino)aluminum hydride was utilized in a systematic study of the approximate rates and stoichiometry of the reaction of excess reagent with 55 selected organic compounds containing representative functional groups under standardized conditions (THF, $0^{\circ}C$, reagent to compound=4 : 1) in order to define the characteristics of the reagent for selective reductions. The reducing action of BEAH was also compared with that of the parent aluminum hydride. The reducing action of the reagent is quite similar to that of aluminum hydride, but the reducing power is much weaker. Aldehydes and ketones were readily reduced in 1-3 h to the corresponding alcohols. However, unexpectedly, a ready involvement of the double bond in cinnamaldehyde was realized to afford hydrocinnamyl alcohol. The introduction of diethylamino group to the parent aluminum hydride appears not to be appreciably influential in stereoselectivity on the reduction of cyclic ketones. Both p-benzoquinone and anthraquinone utilized 2 equiv of hydride readily without evolution of hydrogen, proceeded cleanly to the 1,4-reduction products. Carboxylic acids and acid chlorides underwent reduction to alcohols slowly, whereas cyclic anhydrides utilized only 2 equiv of hydride slowly to the corresponding hydroxylacids. Especially, benzoic acid with a limiting amount of hydride was reduced to benzaldehyde in a yield of 80%. Esters and lactones were also readily reduced to alcohols. Epoxides examined all reacted slowly to give the ring-opened products. Primary and tertiary amides utilized 1 equiv of hydride fast and further hydride utilization was quite slow. The examination for possibility of achieving a partial reduction to aldehydes was also performed. Among them, benzamide and N,N-dimethylbenzamide gave ca, 90% yields of benzaldehyde. Both the nitriles examined were also slowly reduced to the amines. Unexpectedly, both aliphatic and aromatic nitro compounds proved to be relatively reactive to the reagent. On the other hand, azo- and azoxybenzenes were quite inert to BEAH. Cyclohexanone oxime liberated 1 equiv of hydrogen and utilized 1 equiv of hydride for reduction, corresponding to N-hydroxycyclohexylamine. Pyridine ring compounds were also slowly attacked. Disulfides were readily reduced with hydrogen evolution to the thiols, and dimethyl sulfoxide and diphenyl sulfone were also rapidly reduced to the sulfides.

• 전기화학회지
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• 제25권2호
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• pp.69-80
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• 2022

고순도 수소생산을 위한 음이온 교환막 수전해는 양성자 교환막 수전해 시스템에서 사용되는 기존 귀금속 촉매 대신 저렴한 비귀금속 기반 촉매를 사용하여 차세대 녹색 수소 생산 기술로 많은 관심을 받고 있다. 하지만 음이온 교환막 수전해 기술은 개발 초기 단계이기 때문에 음이온 교환막 수전해의 핵심 요소인 음이온 교환막, 이오노머, 전극지지체 및 촉매에 관한 연구 수행이 필요하다. 그 중, 현재 촉매 분야에서 진행되고 있는 연구들은 기개발된 알칼리용 반쪽전지 촉매를 음이온 교환막 시스템에 적용하는 방향의 연구가 진행되고 있으며 적용된 촉매는 낮은 활성도와 내구성의 문제점을 가진다. 이에 본 총설은 알칼리성 매질에서 비귀금속 기반 촉매를 사용하여 산소발생반응 및 수소발생반응을 촉진시킨 촉매 합성 기술을 제시하였다.

• Korean Chemical Engineering Research
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• 제49권5호
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• pp.516-520
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• 2011

휴대용 고분자전해질 연료전지의 수소발생용으로써 $NaBH_4$는 많은 장점을 갖고 있다. 본 연구에서는 $NaBH_4$ 가수분해 반응의 수소 수율에 대해 연구하였다. $NaBH_4$ 가수분해 반응의 수소 수율에 미치는 촉매 형태, 온도, $NaBH_4$ 농도, NaOH 농도 등의 영향에 대해 실험하였다. 촉매는 Co-P/Cu, Co-B/Cu와 Co-P-B/Cu를 사용하였는데 이들 촉매 종류에 따라 $NaBH_4$ 가수분해 반응의 수소 수율에 미치는 영향은 거의 없었다. $60^{\circ}C$ 이하의 온도에서 $NaBH_4$ 농도가 증가하면 부산물과 $NaBH_4$에 의해 겔이 형성되면서 가수분해 반응의 수소 수율이 감소였다. 겔 형성에 의해서 $NaBH_4$ 가수분해 반응 속도와 수소 총 발생량이 감소하였다. 안정화제인 NaOH를 첨가하면 겔 형성을 촉진해 수소 수율을 감소시켰다.

• Bulletin of the Korean Chemical Society
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• 제18권3호
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• pp.274-280
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• 1997

The rates and stoichiometry of the reaction of gallane-trimethylamine with selected organic compounds containing representative functional groups were examined in tetrahydrofuran solution under standardized conditions (THF, 0 ℃). And its reducing characteristics were compared with those of aluminum hydride-triethylamine(AHTEA). The rate of hydrogen evolution from active hydrogen compounds varied considerably with the nature of the functional group and the structure of the hydrocarbon moiety. Alcohols, phenol, amines, thiols evolved hydrogen rapidly and quantitatively. Aldehydes and ketones were reduced moderately to the corresponding alcohols. Cinnamaldehyde was reduced to cinnamyl alcohol, which means that the conjugated double bond was not attacked by gallane-trimethylamine. Carboxylic acids, esters, and lactones were stable to the reagent under standard conditions. Acid chlorides also were rapidly reduced to the corresponding alcohols. Epoxides and halides were inert to the reagent. Caproamide and nitrile were stable to the reagent, whereas benzamide was rapidly reduced to benzylamine. Nitropropane, nitrobenzene and azoxybenzene were stable to the reagent, whereas azobenzene was reduced to 1,2-diphenylhydrazine. Oximes and pyridine N-oxide were reduced rapidly. Di-n-butyl disulfide and dimethyl sulfoxide were reduced only slowly, but diphenyl disulfide was reduced rapidly. Finally, sulfones and sulfonic acids were inert to the reagent under the reaction.

• Bulletin of the Korean Chemical Society
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• 제32권12호
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• pp.4392-4396
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• 2011

Porous silicon with a complex network of nanopores is utilized for photoelectrochemical energy conversion. A novel electroless Pt deposition onto porous silicon is investigated in the context of photoelectrochemical hydrogen generation. The electroless Pt deposition is shown to improve the characteristics of the PS photoelectrode toward photoelectrochemical $H^+$ reduction, though excessive Pt deposition leads to decrease of photocurrent. Furthermore, it is found that a thin layer (< 10 ${\mu}m$) of porous silicon can serve as anti-reflection layer for the underlying Si substrate, improving photocurrent by reducing photon reflection at the Si/liquid interface. However, as the thickness of the porous silicon increases, the surface recombination on the dramatically increased interface area of the porous silicon begins to dominate, diminishing the photocurrent.

• 한국수소및신에너지학회논문집
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• 제30권3호
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• pp.193-200
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• 2019

$RuO_2$, $PtO_2$, and various $(Ru,Pt)O_2$ colloidal solution were prepared using modified Watanabe method. Electrodes were manufactured by dipping of Ni mesh into the colloidal solution. Manufactured electrodes were characterized by XRD, SEM, and EDS. $(Ru,Pt)O_2$ electrodes showed $RuO_2$ crystal structure and high roughness. The hydrogen evolution reaction (HER) activities were evaluated by Linear Sweep Voltammetry. 1Ru2Pt electrode showed similar activity with commercial electrode, HER potentials are -0.9 V for both.