• Journal of Electrochemical Science and Technology
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• v.14 no.2
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• pp.105-119
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• 2023

The electrochemical chlorine evolution reaction (CER) is an important electrochemical reaction and has been widely used in chlor-alkali electrolysis, on-site generation of ClO^-, and Cl₂-mediated electrosynthesis. Although precious metal-based mixed metal oxides (MMOs) have been used as CER catalysts for more than half a century, they intrinsically suffer from a selectivity problem between the CER and parasitic oxygen evolution reaction (OER). Hence, the design of selective CER electrocatalysts is critically important. In this review, we provide an overview of the fundamental issues related to the electrocatalysis of the CER and design strategies for selective CER electrocatalysts. We present experimental and theoretical methods for assessing the active sites of MMO catalysts and the origin of the scaling relationship between the CER and the OER. We discuss kinetic analysis methods to understand the kinetics and mechanisms of CER. Next, we summarize the design strategies for new CER electrocatalysts that can enhance the reactivity of MMO-based catalysts and overcome their scaling relationship, which include the doping of MMO catalysts with foreign metals and the development of non-precious metal-based catalysts and atomically dispersed metal catalysts.

• Journal of the Korean Chemical Society
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• v.32 no.5
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• pp.501-506
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• 1988

The effects of alkali promoters on the activity and selectivity of Co/NaY catalyst have been investigated. The catalysts were prepared by impregnating NaY with aqueous solutions of alkali compounds and a benzene solution of $Co_2(CO)_8$. Hydrocarbon synthesis was studied in a flow reactor under the reaction conditions : temperature = 200∼250$^{\circ}C$, space velocity = 120∼$160hr^{-1}$, pressure = 1 atm, $H_2$/CO = 1. As the basicity of alkali promoter increases, the olefin selectivity, probability of chain growth, and CO$_2$ formation increase and methane formation decreases. The activity of CO hydrogenation increases with the pH of alkali solutions.

• Clean Technology
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• v.30 no.1
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• pp.62-67
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• 2024

In this study, an alkali metal Na was introduced into iron-based catalysts used in the carbon dioxide-based Fischer-Tropsch process by wet impregnation and physical mixing methods to compare their performance. The as-prepared catalysts were evaluated for reactivity at 3.5 MPa, 330 ℃, feed ratio of H₂/CO₂ = 3 with a space velocity of 4,000 mL h^-1 g_cat^-1. Comparing the two catalysts, it was found that Na was uniformly distributed throughout the catalyst when wet-impregnated, but Na for physically mixed catalyst was relatively located on the surface of the catalyst. In addition, the wet-impregnated catalyst showed higher liquid hydrocarbon (C₅₊) yield and lower CO selectivity. In conclusion, the effect of Na distribution in the catalyst on the reaction was identified and can be controlled by the introduction method.

• Journal of the Korean Applied Science and Technology
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• v.23 no.4
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• pp.300-306
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• 2006

The esterification of palmitic acid in rapeseed oil and methanol emulsified by propylene glycol with PTSA(p-toluene sulfonic acid) was followed by the transesterification of rapeseed oil into biodiesel with 1(w/v)% GMS(glycerol monostearate) as an emulsifier using TMAH(tetramethyl ammonium hydroxide) catalysts at $60^{\circ}C$. The former reaction was optimized at the 1:20 of molar ratio of oil to methanol and 5wt% PTSA, and the latter was optimized at the 1:8 of molar ratio of oil to methanol and 0.8wt% TMAH. The overall conversion into biodiesel was 98% after 60min of reaction time at the 1:8 of molar ratio, 0.8wt% TMAH and $60^{\circ}C$. TMAH was a good catalyst to control the viscosity of biodiesel mixture.

• Journal of the Korean Applied Science and Technology
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• v.24 no.2
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• pp.190-195
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• 2007

The transesterifications of beef tallow and the mixture of beef tallow and rapeseed oil were conducted at $65^{\circ}C$ respectively using TMAH, NaOH and their mixed catalysts. The reactants were emulsified with 1vol% emulsifier and propylene glycol. The overall conversion of beef tallow was 95% at such optimum conditions as the 1:8 of molar ratio and 0.8 wt% TMAH. The overall conversion of mixed fat at the 1:8 of molar ratio and mixed catalyst of 70 wt% TMAH 30 wt% NaOH was close to 97% which appeared at 0.8 wt% TMAH in 80min. And the kinematic viscosity of biodiesel mixture using the mixed catalyst was $6.5mm^2/s$ at $40^{\circ}C$.

• Journal of Powder Materials
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• v.18 no.6
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• pp.510-516
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• 2011

In the present study, potassium and caesium doped Ag/$Al_2O_3$ catalysts were synthesized by simple wet impregnation method and evaluated for selective catalytic reduction (SCR) of NOx using methane. TEM analysis and diffraction patterns demonstrated the finely dispersed Ag particles. BET surface measurements reveal that the prepared materials have moderate to high surface area and the metal amount found from ICP analysis was well matching with the theoretical loadings. The synthesized K-Ag/$Al_2O_3$ and Cs-Ag/$Al_2O_3$ catalysts exhibited a promotional effect on deNOx activity in the presence of $SO_2$ and $H_2O$. The long-term isothermal studies at $550^{\circ}C$ under oxygen rich condition showed the superior catalytic properties of the both alkali promoted samples. The crucial catalytic properties of materials are attributed to NO adsorption properties detected by the NO TPD.

• Journal of Environmental Science International
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• v.13 no.1
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• pp.79-87
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• 2004

Esterification of soybean oil with methanol was investigated. First of all, liquid-liquid equilibriums for systems of soybean oil and methanol were measured at temperatures ranging from 40 to 65$^{\circ}C$. Profiles of conversion of soybean oil with time were determined from the glycerine content in reaction mixtures for the different kinds of catalysts, such as NaOH, CaO, Ca(OH)$_2$, MgO, Mg(OH)$_2$, and Ba(OH)$_2$. The effects of dose of catalyst, cosolvent and reaction temperature on final conversion were examined. Esterification of waste vegetable oil with methanol was investigated and compared to the case of soybean oil. Solubility of methanol in soybean oil was substantially greater than that of soybean oil in methanol. When the esterification reaction of soybean oil was catalyzed by solid catalyst, final conversion was strongly dependent on the alkalinity of the solid catalyst, and increased with the alkalinity of the metal. Hydroxides from the alkali metals were more effective than oxides. When Ca(OH)$_2$ was used for the esterification catalyst, maximum value of final conversion was measured at dose of 4％. When CHCl$_3$ as a cosolvent, was added into the reaction mixture of soybean oil which catalyzed by Ba(OH)$_2$, maximum value of final conversion was appeared at dose of 3％. When waste vegetable oil was catalyzed by NaOH and solid catalysts, high final conversion, over 90％, and fast reaction rate were obtained.

• Applied Chemistry for Engineering
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• v.7 no.4
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• pp.698-706
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• 1996

Dehydrogenation of methanol to produce formaldehyde was carried out over various silica-alumina catalysts doped with alkali metals in a continuous flow system. The reaction was rather dependent on Lewis acid than Br${\ddot{o}}$nsted acid suggesting that dehydrogenation of methanol was an electronic reaction. The Br${\ddot{o}}$nsted acid sites on silica-alumina were neutralized by doping with alkali metals, and the neutralization effect of Br${\ddot{o}}$nsted acid was dependent on the electron-donating capacity of the dopant metals. Activation energy for dehydrogenation of methanol decreased when Br${\ddot{o}}$nsted acid was neutralized by doping with K.

• Applied Chemistry for Engineering
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• v.31 no.5
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• pp.560-567
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• 2020

In this study, we investigated that the effect of alkali metals [Na(Sodium) and K(Potassium)], known as representative deactivating substances among exhaust gases of various industrial processes, on the NH₃-SCR (selective catalytic reduction) reaction of V/W/TiO₂ catalysts. NO, NH₃-TPD (temperature programmed desorption), DRIFT (diffuse reflectance infrared fourier transform spectroscopy analysis), and H₂-TPR analysis were performed to determine the cause of the decrease in activity. As a result, each alkali metal acts as a catalyst poisoning, reducing the amount of NH₃ adsorption, and Na and K reduce the SCR reaction by reducing the L and B acid points that contribute to the reaction activity of the catalyst. Through the H₂-TPR analysis, the alkali metal is considered to be the cause of the decrease in activity because the reduction temperature rises to a high temperature by affecting the reduction temperature of V-O-V (bridge oxygen bond) and V=O (terminal bond).

• Journal of the Korean Institute of Gas
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• v.9 no.4 s.29
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• pp.17-25
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• 2005

The dealuminated and alkali/alkaline-earth metal exchanged Y-zeolites were prepared as a catalyst. Elemental compositions and structures of the prepared catalysts were analyzed by the various spectroscopic techniques such as inductively coupled plasma-atomic emission spectroscopy(ICP-AES), X-ray fluorescence(XRF) and X-ray diffraction(XRD), and the desorption behaviors of adsorbed species on the catalyst surfaces were investigated via NO-TPD experiment. Comparing with the composition of the starting material of NaY zeolite, the magnitudes of Si/Al ratio in catalytic materials were increased after dealumination. The Si/Al ratio of catalytic materials after dealumination followed by Cs and Ba cation exchange were additionally decreased. Dealumination to catalysts induced a destruction of basic frame due to a detachment of aluminum, which results in reducing framework structure, while increasing non-framework structure. This phenomenon becomes more serious with increasing time of steam treatment and even more significant for the cation exchanged catalysts. In NO-TPD experiments, the desorption peaks of NO which indicates an activity point of catalysts shifted to the low temperature region after dealumination and cation exchange. The desorption peaks of the NO-TPD profiles taken after steam treatment also shifted to the low temperature region as the steam treatment time increased. In dealuminated and cation exchanged Y-zeolites, the catalytic activities were more influenced by exchanged cation and the formation of non-framework structure.