• 한국수소및신에너지학회논문집
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• 제25권5호
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• pp.475-481
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• 2014

Ammonia borane ($NH_3BH_3$), as a source material for energy generation and hydrogen storage, has attracted growing interest due to its high hydrogen content. We have investigated the synthesis of ammonia borane from sodium borohydride ($NaBH_4$) and ammonium chloride ($NH_4Cl$) utilizing a low-temperature process. From our results, we obtained a maximum synthetic yield of 98.2% of ammonia borane complex. The diammoniate diborane (DADB) was detected in about 5~10mol% with in the solid ammonia borane by solid-state $^{11}B$-NMR analysis. The synthesized solid ammonia borane products were studied to characterize hydrogen release upon thermal dehydrogenation.

• Bulletin of the Korean Chemical Society
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• 제13권5호
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• pp.565-570
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• 1992

The 1,5-sigmatropic rearrangements involving group (X) migration in ${\omega}$(X)-substituted 1,3-pentadiene, $C^1H_2=C^2H-C^3H=C^4H-C^5H_2-X$, where X = H, $CH_3$, $BH_2$, $NH_2$, OH or F, are investigated MO theoretically using the AM1 method. For the migrating groups without lone pair electrons, X = H, $CH_3$, or $BH_2$, the suprafacial pathway is favored, whereas for the migrating groups with lone pair electrons participating in the TS, $X=NH_2$, OH, or F, the antarafacial pathway is favored electronically. However excessive steric inhibition in the antarafacial TS for $X=NH_2$ leads to subjacent orbital controlled suprafacial process. The antarafacial shift of F is relatively disfavored compared to that of OH due to smaller orbital overlap and larger interfrontier energy gap in the TS.

• 대한화학회지
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• 제22권2호
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• pp.62-66
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• 1978

변분법을 이용하여 $NH_3,\;BH_3,\;HCN,\;C_2H_4,\;PO,\;PO^-$, 및 CO 분자에 대한 편극율을 계산하였다. $\alpha$ 값은 CNDO/2, MINDO/1, MINDO/2 보다 실험치에 가까운 값을 얻었지만 ${\alpha}_{\perp}$은 좋은 값을 얻지 못했다.

• 한국자기공명학회논문지
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• 제14권1호
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• pp.38-44
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• 2010

In liquids NMR, $^{1}H$ is the most widely observed nucleus, which is not the case in solids NMR. The reason is due to the strong homo-dipolar interactions between the hydrogen atoms which mask the useful chemical shift information. Therefore we must remove the strong homo-dipolar interactions in order to get structural information, which can be investigated by the isotropic chemical shift. There are two ways of obtaining it. One is the ultra-fast MAS of ca. 70 kHz spinning speed, which has become available only recently. The other way is devising a pulse sequence which can remove the strong homo-dipolar interaction. In the latter way, MAS with a moderate spinning rate of a few kHz, is enough to remove the chemical shift anisotropy. In this report, 1D-CRAMPS and 2D MASFSLG techniques are utilized and their results will be compared. This kind of highresolution $^{1}H$ NMR for solids, should become a valuable analytical tool in the understanding and the developing of a new class of hydrogen storage materials. Here ammonium borane $-NH_{3}BH_{3}$, whose hydrogen content is high, is used as a sample.

• 대한화학회지
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• 제16권5호
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• pp.261-264
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• 1972

LiH, BeH, BH, CH, NH 및 OH 등의 heteronuclear diatomic molecules의 quadratic force constants를 Bishop등의 일점전개함수에 의하여 계산하였다. 계산의 master formula는 본 저자들 중의 한 사람에 의하여 이미 제안된 바 있다. 계산 결과는 실험치와 잘 일치하였다. 일점전개함수의 전개중심에 가까이 위치하고 있는 원자핵의 주위에서의 전자분포는 실제에서 비교적 벗어나며, $P_2(cos{\theta})/r^3$의 전개 중심을 이 원자핵에 잡으면 제안된 식으로부터 그릇된 결과가 얻어지는 것을 발견하였다

• Advances in Energy Research
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• 제4권2호
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• pp.177-187
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• 2016

Ammonia borane $NH_3BH_3$ solubilized in organic solvent is a potential liquid-state chemical hydrogen storage material. In this study, metal acetylacetonates like $Fe(O_2C_5H_7)_3$, $Co(O_2C_5H_7)_2$, $Ni(O_2C_5H_7)_2$, $Pd(O_2C_5H_7)_2$, $Pt(O_2C_5H_7)_2$ and $Ru(O_2C_5H_7)_3$ are considered for assisting dehydrocoupling of ammonia borane in diglyme (0.135 M) at $50^{\circ}C$. The molar ratio between ammonia borane and metal acetylacetonate is fixed at 100. A protocol for the separation of the soluble and insoluble fractions present in the slurry is proposed; it consists in using acetonitrile to make the precipitation of metal-based compounds easier and to solubilize boron-based intermediates/products. The nature of the metal does not affect the dehydrocoupling mechanisms, the $^{11}B\{^1H\}$ NMR spectra showing the formation of the same reaction intermediates. The aforementioned metal acetylacetonates do mainly have effect on the kinetics of dehydrocoupling. Dehydrocoupling takes place heterogeneously and dehydrogenation of ammonia borane in these conditions leads to the formation of polyborazylene via intermediates like e.g., B-(cyclodiborazanyl) amine-borane and borazine. Our main results are reported and discussed herein.

• Advances in Energy Research
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• 제1권1호
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• pp.1-12
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• 2013

In this work, we present the catalytic dehydrogenation of hydrazine borane $N_2H_4BH_3$ (HB) using supported nickel catalysts at $50^{\circ}C$. In the presence of monometallic nickel catalysts, the dehydrogenation of HB is a one-step reaction consisting of the hydrolysis of the $BH_3$ group only. The challenge is to activate nickel to make it reactive towards the $N_2H_4$ moiety of HB. A set of 52 catalysts were prepared by using 2 supports ($Al_2O_3$ and $TiO_2$), 5 nickel precursors and 3 preparation methods. For the first time, we show that the supported nickel catalysts are able to dehydrogenate the $NH_3$ moiety of HB. In our experimental conditions, the best results were obtained with 20 wt% Ni-$Al_2O_3$ and 20 wt% Ni-$TiO_2$, with ca. 190 mL $H_2+N_2$ generated over a total theoretical volume of 283 mL, suggesting $H_2$ selectivity of 37 and 32%, respectively. Both catalysts were then characterized by EDX, XPS, and XRD. Our achievement is the first step forward and opens new perspectives for developing catalysts for the total dehydrogenation of HB.

• Bulletin of the Korean Chemical Society
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• 제34권4호
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• pp.1030-1034
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• 2013

Elimination reactions of $(E)-2,4-(NO_2)_2C_6H_2CH=NOC_6H_3-2-X-4-NO_2$ (1a-e) promoted by $R_3N/R_3NH^+$ in 70 mol % MeCN(aq) have been studied kinetically. The reactions are second-order and exhibit Br$\ddot{o}$nsted ${\beta}$ = 0.80-0.84 and ${\mid}{\beta}_{lg}{\mid}$ = 0.39-0.42, respectively. For all leaving groups and bases employed in this study, the ${\beta}$ and ${\mid}{\beta}_{lg}{\mid}$ values remained almost the same. The results can be described by a negligible $p_{xy}$ interaction coefficient, $p_{xy}={\partial}{\beta}/pK_{lg}={\partial}{\beta}_{lg}/pK_{BH}{\approx}0$, which describes the interaction between the base catalyst and the leaving group. The negligible pxy interaction coefficient is consistent with the $(E1cb)_{irr}$ mechanism. Change of the base-solvent system from $R_3N$/MeCN to $R_3N/R_3NH^+$-70 mol % MeCN(aq) changed the reaction mechanism from E2 to $(E1cb)_{irr}$. Noteworthy was the relative insensitivity of the transition state structure to the reaction mechanism change.

• 폴리머
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• 제36권5호
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• pp.656-661
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• 2012

케이지 구조의 POSS-$NH_3{^+}$를 이용하여 팔라듐 입자들의 자기 조직화로 인한 구조가 제어된 Pd-POSS 나노입자를 제조하였다. 또한 흑연을 강산과 산화제를 이용하여 산화된 그래핀 옥사이드(GO)를 합성한 후 얻어진 GO와 NaBH4와의 반응을 통하여 그래핀을 제조하였다. 합성된 그래핀과 acrylic acid와 라디칼 중합 반응을 통하여 그래핀 표면에 poly(acrylic acid)(PAA)가 결합된 PAA-grafted graphene을 얻었다. Pd-POSS와 PAA-grafted graphene을 이용한 나노복합체는 POSS-$NH_3{^+}$로 인하여 양전하를 띠는 Pd-POSS 나노입자와 PAA로 인하여 음전하를 띠는 PAA-grafted graphene와의 정전기적 인력을 이용하여 제조하였다. Pd-POSS 나노입자가 PAA로 치환된 그래핀 표면에 정전기적 인력으로 결합되어 있고, 나노복합체의 열적 안정성은 PAA와 PAA-grafted graphene 보다 우수한 것을 확인할 수 있었다. 제조된 Pd-POSS/PAA-grafted graphene 나노복합체의 구조 및 형태와 열적 안정성은 FE-SEM, AFM, TEM, EDX, FTIR과 TGA를 통하여 분석하였다.

• Bulletin of the Korean Chemical Society
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• 제19권2호
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• pp.222-226
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• 1998

Borazine (B3N3H6) as an inorganic analogue of benzene was synthesized by reaction of cheap raw materials (NaBH4 and (NH4)2SO4), and by using simple glass reaction apparatus in a scale up to 20 g per run with highly improved yield over 50%. It appears that synthesis of borazine is competing with formation of poly(aminoborane) as an inorganic analogue of polyethylene. The synthesized borazine and its polymerized product were characterized by comparison with products obtained from a commercial one. Bulk pyrolysis of the borazine polymer to 1500 ℃ produced a pure boron nitride (BN) with 75% ceramic yield, which displayed good oxidation resistance under dry air.