• 제목/요약/키워드: Reaction mechanisms

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Electrocatalysis of Selective Chlorine Evolution Reaction: Fundamental Understanding and Catalyst Design

  • Taejung Lim;Jinjong Kim;Sang Hoon Joo
    • Journal of Electrochemical Science and Technology
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    • 제14권2호
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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.

지방족 탄화수소의 할로겐 유도체 수용액의 광촉매-광분해 (Photodegradation of Halogen Derivatives of Aliphatic Hydrocarbon in Aqueous Photocatalytic Suspensions)

  • 전진;정학진;김해진;김삼혁
    • 한국환경과학회지
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    • 제6권1호
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    • pp.75-88
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    • 1997
  • The rates of photodegradation, reactivities, and mechanisms of photooxidation for the aqueous solution containing with halogen derivatives of aliphatic hydrocarbons have been discussed with respect to the kinds of photocatalysts, concentration of photocatalytlc suspensions, strength of radiant power, time of illumination, changes of pH of substrate solution, wavelength of radiation, and pressure of oxygen gas saturated In the solution. These aqueous solutions suspended with 0.5 $gL^{-1}$ $TiO_2$ powder have been photodecomposed in the range of 100 and 93.8% per 1 hour if it is illuminated with wavelength (λ $\geq$ 300nm) produced from Xe-lamp(450W). The photocatalytic abilities have been increased In the order of $Fe_2O_3$ < CdS < $CeO_2$ < Y_2O_3$ <$TiO_2$, and rates of photodegradation for the solution have maldmum values in the condition of pH 6 ~ 8 and 3 psi-$O_2$ gL^{-1}$. These rates for the Photoolddation Per 1 hour were dependent on the size of molecular weight and chemical bonding for organic halogen compounds and the rates of photodegadation were increased in the order of $C_2H_5Br$ < CH_2Br_2$ < C_5H_11Cl C_2H_4Cl_2$ < tracts-$C_2H_2Cl_2$ < cis-C_2H_2Cl_2$ The T_{1/2}$ and t99% for these solutions were 5~21 and 40~90 minutes. respectively, and these values were coincided with Initial reaction kinetics(ro). It was found that reaction of photodegradation has the pseudo first-order kinetics controlled by the amount of $h^+_{VB}$ diffused from a surface of photocatalysts.

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실리콘 산화막의 플라즈마 식각에 대한 표면반응 모델링 (Surface Reaction Modeling for Plasma Etching of SiO2 Thin Film)

  • 임연호
    • Korean Chemical Engineering Research
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    • 제44권5호
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    • pp.520-527
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    • 2006
  • 본 연구에서는 FC(fluorocarbon) 플라즈마 반응기에서 입사하는 이온에너지에 따른 고분자 증착, 식각과 증착의 경쟁반응 및 물리적 스퍼터링 등의 여러 표면 현상들을 모델링하였다. $SiO_2$ 식각에 대한 표면반응은 식각반응 영역을 잘 혼합된 CSTR(continuous stirred tank reactor) 가정을 도입하여 이온 도움에 의한 식각으로 모사되었다. 정상상태 고분자층을 통한 식각과 증착의 경쟁반응의 모델링은 이온 도움에 의한 고분자 생성 및 분해 메커니즘을 제안하여 수행하였다. 이러한 메커니즘은 최근 발표된 실험 및 분자동력학적 전산모사 결과에 기초하였으며,모델 계수들은 빔실험 결과 및 플라즈마 실험결과들을 이용하여 구하였다. 최종 개발된 모델의 결과들은 타당성을 검증하기 위해 문헌에 보고된 실험결과들과 비교하였다.

열 원자층 식각법을 이용한 박막 재료 식각 연구 (Thermal Atomic Layer Etching of the Thin Films: A Review )

  • 조현희;이서현;윤은서;서지은;이진우;한동훈;남서아;한정환
    • 한국분말재료학회지
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    • 제30권1호
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    • pp.53-64
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    • 2023
  • Atomic layer etching (ALE) is a promising technique with atomic-level thickness controllability and high selectivity based on self-limiting surface reactions. ALE is performed by sequential exposure of the film surface to reactants, which results in surface modification and release of volatile species. Among the various ALE methods, thermal ALE involves a thermally activated reaction by employing gas species to release the modified surface without using energetic species, such as accelerated ions and neutral beams. In this study, the basic principle and surface reaction mechanisms of thermal ALE?processes, including "fluorination-ligand exchange reaction", "conversion-etch reaction", "conversion-fluorination reaction", "oxidation-fluorination reaction", "oxidation-ligand exchange reaction", and "oxidation-conversion-fluorination reaction" are described. In addition, the reported thermal ALE processes for the removal of various oxides, metals, and nitrides are presented.

Importance of Sperm Capacitation, Removal of Cumulus Matrix, Acrosome Reaction, and Sperm-egg Fusion in the Process of In Vitro Fertilization

  • Kim, Ki-Sun;Hwang, Kyung-A;Kim, Hyoung-Chin;Nam, Ki-Hoan;Choi, Kyung-Chul
    • 한국수정란이식학회지
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    • 제26권4호
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    • pp.287-296
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    • 2011
  • Mammalian fertilization is a complex cascade process consisting of sperm migration through the female reproductive tract, physiological changes to sperm such as sperm capacitation and acrosome reaction, and sperm-egg interaction in the oviduct in vivo. On the other hand, in vitro fertilization (IVF) is a process by which egg cells are fertilized by sperm outside the body: in vitro. IVF has been used for a variety of purposes in reproductive biotechnology for human and animals. The discovery of sperm capacitation in 1951 promoted the development of IVF technology. In the initial stage of IVF, sperm capacitation in preincubation medium was shown to be essential to fuse with eggs. Besides, sperms should detour some of the in vivo regulations for IVF. This review introduces a general mammalian fertilization process, including sperm capacitation, removal of cumulus matrix, acrosome reaction, and sperm-egg fusion and focuses on the roles of key biochemical molecules, signal mechanisms, and genes involved during IVF and novel results of sperm-oocyte interaction elucidated in various gene-knockout mice models.

제올라이트 촉매상에서의 알킬 방향족 화합물 전환 반응기구에 대한 최근 연구 동향 (Recent Advances in the Mechanistic Studies of Alkylaromatic Conversions over Zeolite Catalysts)

  • 민형기;홍석봉
    • Korean Chemical Engineering Research
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    • 제51권1호
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    • pp.1-9
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    • 2013
  • 제올라이트 촉매를 이용한 알킬 방향족 화합물의 전환은 현대 석유화학 산업에서 큰 비중을 차지한다. 본 총설에서는 제올라이트의 구조적 물리화학적 특성에 따른 알킬 방향족 화합물 전환 반응의 기구에 대해 고찰하였다. 제올라이트의 형상선택성은 알킬 방향족 화합물 전환에 있어서 반응중간체의 생성을 조절함으로써 반응 기구 및 생성물 분포에 직접적인 영향을 미친다. 다양한 알킬 방향족 화합물의 전환 반응에 대하여 반응 중간체의 구조 및 역할에 대한 고찰을 통해 지금까지 알려진 반응기구들을 정리하였다. 아울러 제올라이트 촉매를 기초로 하는 향후 석유화학 공정 개발에 대한 전망을 기술하였다.

일산화탄소가 포함된 에탄올 수용액의 광화학 반응 (Photochemical Reaction of Aqueous Ethanol in the Presence of CO)

  • 김희정;이형철;박형련
    • 대한화학회지
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    • 제38권4호
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    • pp.271-275
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    • 1994
  • 아르곤과 일산화탄소가 포화된 에탄올 수용액의 광화학 반응을 184.9 nm의 자외선을 이용 연구하였다. 아르곤이 포화된 $1{\times}10^{-2}$M의 에탄올 수용액에서는 acetaldehyde와 2,3-butanediol만이 얻어졌으나, 일산화탄소가 포화된 용액의 광반응에서는 이들 두 가지 생성물 이외에 carboxylation 및 carboxylation반응이 진행되어 ${\alpha}$-hydroxypropionaldehyde, formaldehyde, glyoxal, formic acid, oxalic acid and glyoxylic acid등이 생성되었다. 그러나 에탄올의 농도가 증가한 용액의 광반응에서는 일산화탄소의 존재유무에 관계없이 carboxylation과 carboxylation반응은 관찰되지 않았다. 반응의 결과 얻어진 각 생성물들에 대한 initial quantum yield의 값들을 결정하였으며, 산소가 제거된 에탄올 수용액의 광반응에서 얻은 결과와 비교하여 가능한 반응메카니즘을 제시하였다.

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A TISSUE RESPONSE TO THE TITANIUM ALLOY (Ti-13Zr-6Nb) IN VIVO

  • Kim Chang-Su;Lee Seok-Hyung;Shin Sang-Wan;Suh Kyu-Won;Ryu Jae-Jun
    • 대한치과보철학회지
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    • 제42권6호
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    • pp.619-627
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    • 2004
  • Statement of problem. Mechanisms of tissue-implant interaction and the effect of the implant surface on the behavior of cells has not yet been clarified. Purpose. This study was performed to investigate the tissue reaction to the titanium alloy submerged into rat peritoneum in vivo. Materials and methods. Titanium alloys (titanium-13Zirconium-6Niobium) were inserted inside the peritoneal cavity of Sprague Dawley rats. After 3 months, the tissue formed around the inserted titanium alloys were examined with a light-microscope. Tissue reaction around the material was analyzed by confocal microscopy to evaluate their biocompatibility in a living body. Results. In in vivo study, foreign body type multinucleated giant cells were found in the fibrous tissue formed as a reaction to the foreign material (4 in 20 cases), but the inflammatory reaction was very weak. After experiment, the contaminants of biomaterials was removed from living tissue. In confocal microscopy, we observed that the staining of vinculin and actin showed mixed appearance. In a few cases, we found that the staining of vinculin and beta-catenin showed the prominent appearance. Conclusion. We found that titanium-13Zirconium-6Niobium alloy was an excellent biomaterial.

Furfurylidene acetophenone유도체에 대한 Thiourea의 친핵성 첨가반응 메카니즘과 그 반응속도론적 연구 (The Kinetics and Mechanism of the Nucleophilic Addition of Thiourea for Furfurylidene Acetophenone derivatives)

  • 이기창;목갑영;오세영;류정욱
    • 한국응용과학기술학회지
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    • 제14권1호
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    • pp.27-32
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    • 1997
  • Furfurylidene acetophenone derivatives were synthesis, it was measured that nucleophilic addition made use of UV at a wide pH 1.0${\sim}$13.0 range in 30% dioxane-$H_2O$ solution, 25$^{\circ}C$. On the basis of general base catalysis, substitutent effect, confirmation of nucleophilic addition products, it was measured the reaction rate of furfurylidene acetophenone derivatives for the pH change. It may be concluded that a part was unrelated to pH and another part was in proportion to concentration of hydroxide ion: Above pH 10.0. sulfide anion adds to the double bond (Michael type addition), a part having no concern with pH, addition reaction to double bond is initiated by addition of neutral thiourea molecule. From the result of measurement the reaction rate, nucleophilic addition of furfurylidene acetophenone derivatives confirmed to the irreversible first order. Through measurement the substituent effect. It found that reaction rate was accelerated by electron attracting group. On the basis of these findings, nucleophilic addition of thiourea for the furfurylidene acetophenone derivative was proposed a fitting mechanisms.

Formation Mechanism of Intermediate Phase in $Ba(Mg_{1/3}Ta_{2/3})O_3$ Microwave Dielectrics

  • Fang, Yonghan;Oh, Young-Jei
    • 한국세라믹학회지
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    • 제38권10호
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    • pp.881-885
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    • 2001
  • Kinetics and mechanisms of intermediate phases formation in $Ba(Mg_{1/3}Ta_{2/3})O_3$, obtained by a solid state reaction were studied. $Ba{Ta_2}{O_6}$ and ${Ba_4}{Ta_2}{O_9}$ as intermediate products were first formed at $700^{\circ}C$. $Ba(Mg_{1/3}Ta_{2/3})O_3$ was appeared at $800^{\circ}C$. Several reactions take place on heating process. $Ba{Ta_2}{O_6}$ is found at the first stage of the reaction, and then $Ba{Ta_2}{O_6}$ or ${Ba_4}{Ta_2}{O_9}$ react with MgO to form $Ba(Mg_{1/3}Ta_{2/3})O_3$. The reaction of $Ba(Mg_{1/3}Ta_{2/3})O_3$ formation does not complete until fired at $1350^{\circ}C$ for 60 min. The kinetics of solid-state reaction between powdered reactants was controlled by diffusion mechanism, and can be explained by the Jander's model for three-dimensional diffusion.

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