• Bulletin of the Korean Chemical Society
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• 제18권8호
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• pp.806-810
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• 1997

A series of new hydridocarbonyl osmium(Ⅱ) complexes, OsHCl(CO)(PPh3)(L-L)[L-L=Ph2P(CH2)nPPh2 (n=1 (1), 2 (2), 3 (3), cis-Ph2PCH=CHPPh2 (4), and Fe(η5-C5H4PPh2)2 (5)] has been synthesized from OsHCl(CO)(PPh3)3 and chelating diphosphines. These complexes have been characterized by IR, 1H NMR and elemental analysis. The catalytic activities of these complexes both for the transfer hydrogenation of trans-cinnamaldehyde with 2-propanol as the hydrogen donor, and for the selective hydrogenation of trans-cinnamaldehyde with H2, have been examined. Complexes (1)-(5) were shown to have higher selectivities for the transfer hydrogenation of the C=O bond of aldehyde than for the transfer hydrogenation of the C=C bond of aldehyde. The selectivities for the transfer hydrogenation with 2-propanol as well as for the hydrogenation with H2 have been found to decrease in the order 3 > 5 > 2 > 4 > 1. Complex (3) has shown to possess almost 90% of the selectivity to cinnamyl alcohol for transfer hydrogenation. It is also found that there is a correlation between the ν(CO) of each complex and the hydrogenation, of the C=O bond of trans-cinnamaldehyde. Overall, the selectivities with the complexes (1)-(5) are greater for the transfer hydrogenation with 2-propanol than for the hydrogenation with H2.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2014년도 제46회 동계 정기학술대회 초록집
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• pp.191.2-191.2
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• 2014

Cu/ZnO/$Al_2O_3$ is widely used methanol synthesis catalyst at elevated pressures P (50 to 100 bar) and temperatures T (473 to 573 K) using $CO_2$, CO, $H_2$ syngas mixture. Although Cu step and planar defects have been regarded as active sites in this catalyst, detailed $CO_2$ hydrogenation procedure has been still unknown and debated as well as initial intermediate. In this study, we investigated the mechanism of $CO_2$ hydrogenation on Cu(111) model surface at P (1 bar) and T (298 to 450 K) using reflection absorption infrared spectroscopy (RAIRS). Two distinct formates by hydrogenation of $CO_2$, on step and on terrace, show different behavior with elevating temperature. The peak intensity of on step formate was continuously decreased above 360 K up to 450K in contrast to the increase of on terrace formate. These phenomena are strong possibilities that the formate is initial intermediate and is desorbed by hydrogenation reaction because thermal desorption temperature of formate (~470 K) is much higher than desorption of on step formate. And the formate production peak of on step site was weakly correlated with CO formation.

• Bulletin of the Korean Chemical Society
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• 제4권4호
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• pp.169-171
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• 1983

It has been found that the acrylonitrile solution of trans-$RhCl(CO)(Ph_3P)_2$ produces propionitrile catalytically at $90^{\circ}C$ under $P_{H_2}$=3 atm. This catalytic hydrogenation proceeds only for a certain period of time producing ca. 50 moles of propionitrile per mole of the rhodium complex. The hydrogenation with trans-$RhCl(CO)(Ph_3P)_2$ in the presence of formaldehyde is much faster than in the absence of formaldehyde, and continues without a decrease in the rate for a prolonged period of time. It is suggested that the hydrogenation with trans-$RhCl(CO)(Ph_3P)_2$ proceeds through the unsaturated route initiated by the dissociation of CO from trans- $RhCl(CO)(Ph_3P)_2$ to give coordinatively unsaturated $RhCl(Ph_3P)_2$.

• Bulletin of the Korean Chemical Society
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• 제23권12호
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• pp.1785-1789
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• 2002

2,2'-Dichlorohydroazobenzene was prepared by selective hydrogenation of o-nitrochlorobenzene with hydrogen in the presence of 0.8% and 5% Pd/C catalyst. O-Chloroaniline was a minor product in the catalytic hydrogenation of o-nitrochlorobenzene. The effects of base, Pd/C catalyst, and co-catalyst were discussed on catalytic hydrogenation. 2,2'-Dichlorohydroazobenzene, as an intermediate, was rearranged to 3,3'-dichlorobenzidine after reacting with HCl. It was shown that selectivity of catalytic hydrogenation of o-nitro-chlorobenzene is affected strongly by concentration of base, Pd/C catalyst, and co-catalyst. $^1Hand^{13}C$NMR spectroscopy confirmed the chemical structures of 2,2'-dichlorohydrazobenzene and 3,3'-dichlorobenzidine.

• Bulletin of the Korean Chemical Society
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• 제4권4호
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• pp.180-183
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• 1983

The reaction of $IrClH_2(CO)(Ph_3P)_2$ ($Ph_3P$=triphenylphosphine) with acrylonitrile (AN) produces a stoichiometric amount of propionitrile (PN) at $100^{\circ}C$ under nitrogen, which suggests that the catalytic hydrogenation of AN to PN with $IrCl(CO)(Ph_3P)_2$ proceeds through the hydride route where the formation of the dihydrido complex, $IrClH_2(CO)(Ph_3P)_2$ is the initial step. The rate of the hydrogenation of AN to PN with $IrCl(CO)(Ph_3P)_2$ is decreased by the presence of excess $Cl^-$ in the reaction system, which suggests that $Cl^-$ is the dissociating ligand in the catalytic cycle. It has been also found that the rate of the hydrogenation increases with inercase both in hydrogen pressure and in concentration of free $Ph_3P$, and with decrease in AN concentration in the reaction system.

• Bulletin of the Korean Chemical Society
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• 제35권9호
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• pp.2726-2732
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• 2014

The promoting effect of rhodium on the structure and activity of the supported Cu-Co based catalysts for CO hydrogenation was investigated in detail. The samples were characterized by DRIFTS, $N_2$-adsorption, XRD, $H_2$-TPR, $H_2$-TPD and XPS. The results indicated that the introduction of rhodium to Cu-Co catalysts resulted in modification of metal dispersion, reducibility and crystal structure. DRIFTS results of CO hydrogenation at reaction condition (P=2 MPa, $T=260^{\circ}C$) indicated the addition of 1 wt % rhodium improved hydrogenation ability of Cu-Co catalysts. The ethanol selectivity and CO conversion were both improved by 1 wt % Rh promoted Cu-Co based catalysts. The alcohol distribution over un-promoted and rhodium promoted Cu-Co based catalysts obeys A-S-F rule and higher chain growth probability was got on rhodium promoted catalyst.

• 한국분말재료학회지
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• 제26권4호
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• pp.290-298
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• 2019

$TiO_2$-particles containing Co grains are fabricated via thermal hydrogenation and selective oxidation of TiCo alloy. For comparison, $TiO_2$-Co composite powders are prepared by two kinds of methods which were the mechanical carbonization and oxidation process, and the conventional mixing process. The microstructural characteristics of the prepared composites are analyzed by X-ray diffraction, field-emission scattering electron microscopy, and transmission electron microscopy. In addition, the composite powders are sintered at $800^{\circ}C$ by spark plasma sintering. The flexural strength and fracture toughness of the sintered samples prepared by thermal hydrogenation and mechanical carbonization are found to be higher than those of the samples prepared by the conventional mixing process. Moreover, the microstructures of sintered samples prepared by thermal hydrogenation and mechanical carbonization processes are found to be similar. The difference in the mechanical properties of sintered samples prepared by thermal hydrogenation and mechanical carbonization processes is attributed to the different sizes of metallic Co particles in the samples.

• 한국산학기술학회논문지
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• 제7권4호
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• pp.715-720
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• 2006

CO와 유사한 분자궤도함수를 갖는 isocyanide 리간드가 포함된$Cp(CO)_{2}(L)MH$ (L = t-butylisocyanide and 2,6-dimethylphenylisocyanide M = Mo and W)를 합성하고, 이 착물과 triflic acid를 사용하여 카르보닐기를 알코올로 전환시키는 실험을 하였다. 또한, 이들 착물을 촉매 전구체로 이용하여 3-pentanone의 수소화 반응을 온화한 조건 ($23^{\circ}C,\;<4.1\;atm H_{2}$)에서 수행하였다. 촉매 활성은 매우 낮았으며, [$Cp(CO)_{2}(ArNC)Mo][BA_{r}^{F}_{4}$]의 경우에 2 turnovers/day의 결과를 나타내었다.

• Bulletin of the Korean Chemical Society
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• 제5권5호
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• pp.199-201
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• 1984

It has been found that $Rh(ClO_4)(CO)(P(C_6H_5)_3)_2$ catalyzes the hydrogenation and isomerization of soybean oil at room temperature under the atmospheric pressure of hydrogen. The hydrogenation occurs at the olefinic groups to produce saturated groups leaving the ester groups intact, and the isomerization converts $-CH = CH- CH_2-CH = CH-$ units to conjugated dienes and the dienes separated by more than two $-CH_2-$ groups. The rate of the hydrogenation is faster than that of the isomerization.

• Journal of Industrial and Engineering Chemistry
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• 제67권
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• pp.486-496
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• 2018

Bimetallic Pd@Ni nanostructure exhibited enhanced co-catalytic activity for the selective hydrogenation of benzaldehyde compare to their monometallic counterparts. Impregnation of these mono/bimetallic nanostructures on mesoporous $TiO_2$ leads to several surface modifications. The bimetallic PNT-3 ($Pd_3@Ni_1/mTiO_2$) exhibited large surface area ($212m^2g^{-1}$), and low recombination rate of the charge carriers ($e^--h^+$). The hydrogenation reaction was analyzed under controlled experiments. It was observed that under UV-light irradiations and saturated hydrogen atmosphere the bimetallic PNT-3 photocatalyst display higher rate constant $k=5.31{\times}10^{-1}h^{-1}$ owing to reduction in the barrier height which leads to efficiently transfer of electron at bimetallic/$mTiO_2$ interface.