• Journal of Industrial and Engineering Chemistry
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• v.68
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• pp.325-334
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• 2018

Lactose is a reducing disaccharide consisting of two different monosaccharides such as galactose and glucose. The hydrogenation of lactose to lactitol is a formidable challenge because it is a complex process and several side products are formed. In this work, we synthesized Ru-Ni bimetallic nanohybrids as efficient catalysts for selective lactose hydrogenation to give selective lactitol. Ru-Ni bimetallic nanohybrids with $Ru-NiO_x$ (x = 1, 5, and 10 wt%) are prepared by impregnating Ru and Ni salts precursors with $TiO_2$ used as support material. Ru-Ni bimetallic nanohybrids (represented as $5Ru-5NiO/TiO_2$) catalyst is found to exhibit the remarkably high selectivity of lactitol (99.4%) and turnover frequency i.e. ($374h^{-1}$). In contrast, monometallic $Ru/TiO_2$ catalyst shows poor performance with ($TOF=251h^{-1}$). The detailed characterizations confirmed a strong interaction between Ru and NiO species, demonstrating a synergistic effect on the improvement on lactitol selectivity. The impregnation-reduction method for the preparation of bimetallic $Ru-NiO/TiO_2$ catalyst promoted Ru nanoparticles dispersed on NiO and intensified the interaction between Ru and NiO species. $Ru-NiO/TiO_2$ efficiently catalyzed the hydrogenation of lactose to lactitol with high yield/selectivity at almost complete conversion of lactose at $120^{\circ}C$ and 55 bar of hydrogen ($H_2$) pressure. Moreover, $Ru-NiO/TiO_2$ catalyst could also be easily recovered and reused up to four runs without notable change in original activity.

• Journal of Korean Society of Environmental Engineers
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• v.38 no.12
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• pp.667-675
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• 2016

Nanoscale zero-valent iron (nZVI) has been effectively applied for environmental remediation due to its ability to reduce various toxic compounds. However, quantification of nZVI reactivity has not yet been standardized. Here, we adapted colorimetric assays for determining reductive activity of nZVIs. A modified indophenol method was suggested to determine reducing activity of nZVI. The method was originally developed to determine aqueous ammonia concentration, but it was further modified to quantify phenol and aniline. The assay focused on analysis of reduction products rather than its mother compounds, which gave more accurate quantification of reductive activity. The suggested color assay showed superior selectivity toward reduction products, phenol or aniline, in the presence of mother compounds, 4-chlorophenol or nitrobenzene. Reaction conditions, such as reagent concentration and reaction time, were optimized to maximize sensitivity. Additionally, pretreatment step using $Na_2CO_3$ was suggested to eliminate the interference of residual iron ions. Monometallic nZVI and bimetallic Ni/Fe were investigated with the reaction. The substrates showed graduated reactivity, and thus, reduction potency and kinetics of different materials and reaction mechanism was distinguished. The colorimetric assay based on modified indophenol reaction can be promises to be a useful and simple tool in various nZVI related research topics.

• Korean Chemical Engineering Research
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• v.55 no.2
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• pp.270-274
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• 2017

Formic acid has been known as one of key sources of hydrogen. Among various monometallic catalysts, hydrogen can be efficiently produced on Pd catalyst. However, the catalytic activity of Pd is gradually reduced by the blocking of active sites by CO, which is formed from the unwanted indirect oxidation of formic acid. One of promising solutions to overcome such issue is the design of alloy catalyst by adding other metal into Pd since alloying effect (such as ligand and strain effect) can increase the chance to mitigate CO poisoning issue. In this study, we have investigated formic acid deposition on the bimetallic $Pd/Pd_3Fe$ core-shell nanocatalyst using DFT (density functional theory) calculation. In comparison to Pd catalyst, the activation energy of formic acid dehydrogenation is greatly reduced on $Pd/Pd_3Fe$ catalyst. In order to understand the importance of alloying effects in catalysis, we decoupled the strain effect from ligand effect. We found that both strain effect and ligand effect reduced the binding energy of HCOO by 0.03 eV and 0.29 eV, respectively, compared to the pure Pd case. Our DFT analysis of electronic structure suggested that such decrease of HCOO binding energy is related to the dramatic reduction of density of state near the fermi level.

• Journal of the Korean institute of surface engineering
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• v.54 no.1
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• pp.1-11
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• 2021

Porous dendrite structure AuCu alloy was formed using a hydrogen bubble template (HBT) technique by electroplating to improve the catalytic performance of gold, known as an excellent oxygen reduction reaction (ORR) catalyst in alkaline medium. The rich Au surface was maximized by selectively electrochemical etching Cu on the AuCu dendrite surface well formed in a leaf shape. The catalytic activity is mainly due to the synergistic effect of Au and Cu existing on the surface and inside of the particle. Au helps desorption of OH- and Cu contributes to the activation of O2 molecule. Therefore, the porous AuCu dendrite alloy catalyst showed markedly improved catalytic activity compared to the monometallic system. The porous structure AuCu formed by the hydrogen bubble template was able to control the size of the pores according to the formation time and applied current. In addition, the Au-rich surface area increased by selectively removing Cu through electrochemical etching was measured using an electrochemical calculation method (ECSA). The results of this study suggest that the alloying of porous AuCu dendrites and selective Cu dissolution treatment induces an internal alloying effect and a large specific surface area to improve catalyst performance.

• Clean Technology
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• v.27 no.1
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• pp.69-78
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• 2021

Vegetable oils, such as palm oil and cashew nut shell liquid (CNSL), are used as major raw materials for bio-diesel in transportation and bio-heavy oil in power generation in South Korea. However, due to the high unsaturation degree caused by hydrocarbon double bonds and a high content of oxygen originating from the presence of carboxylic acid, the range of applications as fuel oil is limited. In this study, hydrotreating to saturate unsaturated hydrocarbons and remove oxygen in mixed bio-oil containing 1/1 v/v% palm oil and CNSL on monometallic catalysts (Ni and Cu) and bimetallic catalysts (Ni-Zn, Ni-Fe, Ni-Cu Ni-Co, Ni-Pd, and Ni-Pt) was perform under mild conditions (T = 250 ~ 400 ℃, P = 5 ~ 80 bar and LHSV = 1 h-1). The addition of noble metals and transition metals to Ni showed synergistic effects to improve both hydrogenation (HYD) and hydrodeoxygenation (HDO) activities. The most promising catalyst was Ni-Cu/��-Al2O3, and in the wide range of the Ni/Cu atomic ratio of 9/1~1/4, the conversion for HYD and HDO reactions of the catalysts were 90-93% and 95-99%, respectively. The tendency to exhibit almost constant reaction activity in these catalysts of different Ni/Cu atomic ratios implies a typical structure-insensitive reaction. The refined bio-oil produced by hydrotreating (HDY and HDO) had significantly lower iodine value, acid value, and kinetic viscosity than the raw bio-oil and the higher heating value (HHV) was increased by about 10%.