• Title/Summary/Keyword: adsorption free energy

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General picture of co-nonsolvency for linear and ring polymers

  • Park, Gyehyun;Lee, Eunsang;Jung, YounJoon
    • Proceeding of EDISON Challenge
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    • 2016.03a
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    • pp.147-154
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    • 2016
  • Co-nonsolvency is a puzzling phenomenon that a polymer swells in a good solvent individually, but it collapses in a mixture of good solvents. This structural transition with changing solvent environment has been drawing attention due to practical application for stimuli-responsive polymer. The aim of this work is to describe the physical origin of the co-nonsolvency. In this work, we present Monte Carlo simulations for polymer solutions by using simple and general model. We simulate linear and ring polymers to compare their co-nonsolvency behaviors. Calculating Flory exponents and bridging fractions gives a good description for polymer structures. While the polymer structure shows non-monotonous behavior with increasing the cosolvent fraction, the chemical potential decreases monotonously. This indicates that coil-to-globule transition of polymers is purely controlled by free energy and can be regarded as a thermodynamics transition. We also present that ring polymers have higher looping probability than linear polymers, thus the bridging fraction remains higher at high cosolvent fraction. Our study provides a new perspective to understand polymer structure when the polymer "dissolves well" in any solvent.

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Electronic structure of the Au intercalated monolayer graphene on Ni(111)

  • Hwang, H.N.;Jee, H.G.;Han, J.H.;Tai, W.S.;Kim, Y.D.;Hwang, C.C.
    • Proceedings of the Korean Vacuum Society Conference
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    • 2010.02a
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    • pp.342-342
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    • 2010
  • We have investigated an Au intercalated monolayer graphene on Ni(111) using angle-resolved photoemission spectroscopy (ARPES), high resolution photoemission spectroscopy (HRPES), and low energy electron diffraction (LEED) at the 3A2 ARUPS beamline in Pohang Accelerator Laboratory. We find the monolayer graphene is well grown on the Ni(111) surface by the adsorption of acetylene. However, the graphene does not show the characteristic $\pi$ band near the Fermi level due to its strong interaction with the underlying substrate. When Au is adsorbed on the surface and then annealed at high temperature, we observe that Au is intercalated underneath the monolayer graphene. The process of the Au intercalation was monitored by HRPES of corresponding Au 4f and C 1s core levels as well as the electronic structure of the $\sigma$, $\pi$ states at $\Gamma$, K points. The $\sigma$, $\pi$ bands of graphene shift towards the Fermi level and the $\pi$ band is clearly observed at K point after the intercalation of full monolayer Au. The full width at half maximum (FWHM) of the C 1s peak narrows to approximately 0.42 eV after intercalation. These results imply that the interaction between the graphene and substrate is considerably weakened after the Au intercalation. We will discuss the graphene is really closer to ideal free standing graphene suggested recently.

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Effects of Cetyltrimethylammonium bromide on the Corrosion Inhibition of a Lead-free α-Brass by Sodium Gluconate in Sulfuric Acid

  • Jennane, Jamila;Touhami, Mohamed Ebn;Zehra, Saman;Chung, Ill-Min;Lgaz, Hassane
    • Journal of Electrochemical Science and Technology
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    • v.10 no.3
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    • pp.257-270
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    • 2019
  • The inhibition performance of sodium gluconate (SG), cetyltrimethylammonium bromide (CTAB) and their mixture (SG/CTAB) on the corrosion behavior of ${\alpha}$-brass in 0.5 M $H_2SO_4$ solution has been investigated by potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), Scanning Electron Microscope with Energy-Dispersive Spectrometer (SEM-EDS), Inductively Coupled Plasma Spectrometry (ICPS) and molecular dynamics (MD) simulation techniques. The results reveal that SG with 5ppm CTAB, noted SG/CTAB, acts as a good corrosion inhibitor and its inhibition efficiency reached 89% after 24 h immersion in sulfuric acid solution, but slightly decreased at higher temperatures. The polarization curves displayed that SG/CTAB acts as a cathodic-kind inhibitor. Electrochemical impedance spectroscopy (EIS) studies revealed that the addition of 5ppm CTAB to different concentrations of SG considerably increases the corrosion resistance of ${\alpha}$-brass. The SEM-EDS and ICPS analyses support the experimental results. Further, molecular dynamics (MD) simulations were used to understand the adsorption profiles of SG/CTAB on Cu(111) and Zn(111) surfaces.

The Phase-Shift Method for the Langmuir Adsorption Isotherms of Electroadsorbed Hydrogens for the Cathodic H2 Evolution Reactions at the Poly-Pt Electrode Interfaces (다결정 Pt 전극계면에서 음극 H2 발생반응을 위한 전착된 수소의 Langmuir 흡착등온식에 관한 위상이동 방법)

  • Chun, Jang H.;Jeon, Sang K.;Lee, Jae H.
    • Journal of the Korean Electrochemical Society
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    • v.5 no.3
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    • pp.131-142
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    • 2002
  • The Langmuir adsorption isotherms of the under-potentially deposited hydrogen (UPD H) and the over-potentially deposited hydrogen (OPD H) at the poly-Pt/0.5M $H_2SO_4$ and 0.5 M LiOH aqueous electrolyte interfaces have been studied using cyclic voltammetric and ac impedance techniques. The behavior of the phase shift $(0^{\circ}{\leq}{-\phi}{\leq}90^{\circ})$ for the optimum intermediate frequency corresponds well to that of the fractional surface coverage $(1{\geq}{\theta}{\geq}0)$ at the interfaces. The phase-shift method, i.e., the phase-shift profile $({-\phi}\;vs.\;E)$ for the optimum intermediate frequency, can be used as a new electrochemical method to determine the Langmuir adsorption isotherms $({\theta}\;vs.\;E)$ of the UPD H and the OPD H for the cathodic $H_2$ evolution reactions at the interfaces. At the poly-Pt/0.5M $H_2SO_4$ aqueous electrolyte interface, the equilibrium constant (K) and the standard free energy $({\Delta}G_{ads})$ of the OPD H are $2.1\times10^{-4}$ and 21.0kJ/mol, respectively. At the poly-Pt/0.5M LiOH aqueous electrolyte interface, K transits from 2.7(UPD H) to $6.2\times10^{-6}$ (OPD H) depending on the cathode potential (E) and vice versa. Similarly, ${\Delta}G_{ads}$ transits from -2.5kJ/mol (UPD H) to 29.7kJ/mol (OPD H) depending on I and vice versa. The transition of K and ${\Delta}G_{ads}$ is attributed to the two distinct adsorption sites of the UPD H and the OPD H on the poly-Pt surface. The UPD H and the OPD H on the poly-Pt surface are the independent processes depending on the H adsorption sites themselves rather than the sequential processes for the cathodic $H_2$ evolution reactions. The criterion of the UPD H and the OPD H is the H adsorption sites and processes rather than the $H_2$ evolution reactions and potentials. The poly-Pt wire electrode is more efficient and useful than the Pt(100) disc electrode for the cathodic $H_2$ evolution reactions in the aqueous electrolytes. The phase-shift method is well complementary to the thermodynamic method rather than conflicting.

Enhancement of Manganese Removal Ability from Water Phase Using Biochar of Prinus densiflora Bark (소나무 수피 바이오차를 이용한 수중에서 망간의 제거능력 향상)

  • Kim, Min-Ji;Choi, Jung Hoon;Choi, Tae Ryeong;Choi, Suk Soon;Ha, Jeong Hyub;Lee, Young-Seak
    • Applied Chemistry for Engineering
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    • v.31 no.5
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    • pp.526-531
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    • 2020
  • Manganese ions contained in water phase are acting as a toxic substance in the human body and also known to affect the nervous system. In particular, effective treatment technology is required since manganese removal is difficult due to its high solubility in a wide pH range. In this study, Prinus densiflora bark was chemically modified with hydrogen peroxide, and the modified adsorbent was used for removing manganese ions in an aqueous solution. The modified adsorbent showed high removal capacity of 82.1 and 56.2%, respectively, at conditions of 5 and 10 mg/L manganese ions. Also, the adsorption isotherm from the data was applied to the theoretical equation. As a result, the adsorption behavior of manganese ions was better suited to the Langmuir than Freundlich model, and it was also found from kinematics that the pseudo-second order kinetic model was more suitable. In addition, the changes of Gibbs free energy indicated that the adsorption reaction became more spontaneously with increasing temperature. Consequently, these experimental results may be used as a water treatment technology which can efficiently treat manganese ions contained in water.

Removal of Basic Dye from Aqueous Solution using Coal-based Granular Activated Carbon (석탄계 입상활성탄을 이용한 수용액으로부터 염기성 염료의 제거)

  • Choi, Han Ah;Park, Ha Neul;Moon, Hye Woon;Kim, Eun Bin;Jang, Yeon Woo;Won, Sung Wook
    • Clean Technology
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    • v.23 no.2
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    • pp.188-195
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    • 2017
  • This research studied the adsorption of basic dye, Basic Blue 3 (BB3) by using coal-based granular activated carbon (C-GAC) from aqueous solution. All experiments were performed in batch processes, and adsorption parameters such as C-GAC dosage, contact time, initial dye concentration and temperature were evaluated. The removal efficiency of BB3 was increased with increasing the C-GAC dosage and 100% of initial concentration, $50mg\;L^{-1}$ was removed above 0.2 g of C-GAC. Also, the time to reach equilibrium depended on the initial dye concentration. According to the Langmuir model, the maximum uptakes of C-GAC were calculated to be 66.45, 84.97 and $87.19mg\;g^{-1}$ at 25, 35 and $45^{\circ}C$, respectively. In addition, thermodynamic parameters such as Gibbs free energy change, enthalpy change and entropy change were investigated.

Ammonia Decomposition over Ni Catalysts Supported on Zeolites for Clean Hydrogen Production (청정수소 생산을 위한 암모니아 분해 반응에서 Ni/Zeolite 촉매의 반응활성에 관한 연구)

  • Jiyu Kim;Kyoung Deok Kim;Unho Jung;Yongha Park;Ki Bong Lee;Kee Young Koo
    • Journal of the Korean Institute of Gas
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    • v.27 no.3
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    • pp.19-26
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    • 2023
  • Hydrogen, a clean energy source free of COx emissions, is poised to replace fossil fuels, with its usage on the rise. Despite its high energy content per unit mass, hydrogen faces limitations in storage and transportation due to its low storage density and challenges in long-term storage. In contrast, ammonia offers a high storage capacity per unit volume and is relatively easy to liquefy, making it an attractive option for storing and transporting large volumes of hydrogen. While NH3 decomposition is an endothermic reaction, achieving excellent low-temperature catalytic activity is essential for process efficiency and cost-effectiveness. The study examined the effects of different zeolite types (5A, NaY, ZSM5) on NH3 decomposition activity, considering differences in pore structure, cations, and Si/Al-ratio. Notably, the 5A zeolite facilitated the high dispersion of Ni across the surface, inside pores, and within the structure. Its low Si/Al ratio contributed to abundant acidity, enhancing ammonia adsorption. Additionally, the presence of Na and Ca cations in the support created medium basic sites that improved N2 desorption rates. As a result, among the prepared catalysts, the 15 wt%Ni/5A catalyst exhibited the highest NH3 conversion and a high H2 formation rate of 23.5 mmol/gcat·min (30,000 mL/gcat·h, 600 ℃). This performance was attributed to the strong metal-support interaction and the enhancement of N2 desorption rates through the presence of medium basic sites.

Hierarchically porous carbon aerogels with high specific surface area prepared from ionic liquids via salt templating method

  • Zhang, Zhen;Feng, Junzong;Jiang, Yonggang;Feng, Jian
    • Carbon letters
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    • v.28
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    • pp.47-54
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    • 2018
  • High surface carbon aerogels with hierarchical and tunable pore structure were prepared using ionic liquid as carbon precursor via a simple salt templating method. The as-prepared carbon aerogels were characterized by nitrogen sorption measurement and scanning electron microscopy. Through instant visual observation experiments, it was found that salt eutectics not only serve as solvents, porogens, and templates, but also play an important role of foaming agents in the preparation of carbon aerogels. When the pyrolyzing temperature rises from 800 to $1000^{\circ}C$, the higher temperature deepens the carbonization reaction further to form a nanoporous interconnected fractal structure and increase the contribution of super-micropores and small mesopores and improve the specific surface area and pore volume, while having few effects on the macropores. As the mass ratio of ionic liquid to salt eutectics drops from 55% to 15%, that is, the content of salt eutectics increases, the salt eutectics gradually aggregate from ion pairs, to clusters with minimal free energy, and finally to a continuous salt phase, leading to the formation of micropores, uniform mesopores, and macropores, respectively; these processes cause BET specific surface area initially to increase but subsequently to decrease. With the mass ratio of ionic liquids to salts at 35% and carbonization temperature at $900^{\circ}C$, the specific surface area of the resultant carbon aerogels reached $2309m^2g^{-1}$. By controlling the carbonization temperature and mass ratio of the raw materials, the hierarchically porous architecture of carbon aerogels can be tuned; this advantage will promote their use in the fields of electrodes and adsorption.

A Convenient Method on the Methyl-Ethyl-Ketone Extraction of $^{99m}TcO^-{_4}$ ($^{99m}TcO^-{_4}$의 메틸-에틸-케톤-간편 추출법)

  • Lee, Jong-Du;Lee, Byung-Hyn
    • Journal of Radiation Protection and Research
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    • v.9 no.2
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    • pp.103-111
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    • 1984
  • A convenient method of $^{99m}Tc$-methyl-ethyl-ketone (MEK) extraction technique was developed and a mobile $^{99m}Tc$-extraction generator was designed. The MEK extraction and the phase separation of $^{99m}TcO^-{_4}$ were carried out with a simple procedure in the same container. The shielding of $^{99}Mo$ radioactivity was made with one lead container. The system was simplified by shielding $^{99m}TcO_4{^-}({\gamma}_e=0.14\;MeV)$ separately. $^{99m}TcO^-{_4}\;in\;^{99m}Tc-MEK$ extract was recovered by adsorption and elution only, and therefore, the possibility of volatilization was reduced. The volume of $^{99m}TcO^{-}{_4}$-saline product was reduced to 1 ml by using a small alumina column and the column operation time was shortened. The separation time of $^{99m}Tc$ was reduced to 30 minutes, and the operation was carried out at the outside of the shielding. The system was designed to operate under the condition of bacteria-free.

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Wet Foam Stability from Colloidal Suspension to Porous Ceramics: A Review

  • Kim, Ik Jin;Park, Jung Gyu;Han, Young Han;Kim, Suk Young;Shackelford, James F.
    • Journal of the Korean Ceramic Society
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    • v.56 no.3
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    • pp.211-232
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    • 2019
  • Porous ceramics are promising materials for a number of functional and structural applications that include thermal insulation, filters, bio-scaffolds for tissue engineering, and preforms for composite fabrication. These applications take advantage of the special characteristics of porous ceramics, such as low thermal mass, low thermal conductivity, high surface area, controlled permeability, and low density. In this review, we emphasize the direct foaming method, a simple and versatile approach that allows the fabrication of porous ceramics with tailored microstructure, along with distinctive properties. The wet foam stability is achieved under the controlled addition of amphiphiles to the colloidal suspension, which induce in situ hydrophobization, allowing the wet foam to resist coarsening and Ostwald ripening upon drying and sintering. Different components, like contact angle, adsorption free energy, air content, bubble size, and Laplace pressure, play vital roles in the stabilization of the particle stabilized wet foam to the porous ceramics. The mechanical behavior of the load-displacements curves of sintered samples was investigated using Herzian indentations testes. From the collected results, we found that microporous structures with pore sizes from 30 ㎛ to 570 ㎛ and the porosity within the range from 70% to 85%.