• Title/Summary/Keyword: Hydrogen evolution

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Reaction of Lithium Tris(diethylamino)aluminum Hydride in Tetrahydrofuran with Selected Organic Compounds Containing Representative Functional Groups

  • Jin Soon Cha;Jae Cheol Lee
    • Bulletin of the Korean Chemical Society
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    • v.14 no.4
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    • pp.469-475
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    • 1993
  • The approximate rates and stoichiometry of the reaction of excess lithium tris(diethylamino)aluminum hydride (LTDEA) with selected organic compounds containing representative functional groups under standardized condition (tetrahydrofuran, 0$^{\circ}C$) were examined in order to define the characteristics of the reagent for selective reductions. The reducing ability of LTDEA was also compared with those of the parent lithium aluminum hydride (LAH) and lithium tris(dibutylamino)aluminum hydride (LTDBA). In general, the reactivity toward organic functionalities is in order of LAH${\gg}$LTDEA${\geq}$LTDBA. LTDEA shows a unique reducing characteristics. Thus, benzyl alcohol and phenol evolve hydrogen slowly. The rate of hydrogen evolution of primary, secondary, and tertiary alcohols is distinctive: 1-hexanol evolves hydrogen completely in 6 h, whereas 3-hexanol evolves hydrogen very slowly. However, 3-ethyl-3-pentanol does not evolve any hydrogen under these reaction conditions. Primary amine, such as n-hexylamine, evolves only 1 equivalent of hydrogen. On the other hand, thiols examined are absolutely inert to this reagent. LTDEA reduces aldehydes, ketones, esters, acid chlorides, and epoxides readily to the corresponding alcohols. Quinones, such as p-benzoquinone and anthraquinone, are reduced to the corresponding diols without hydrogen evolution. However, carboxylic acids, anhydrides, nitriles, and primary amides are reduced slowly, where as tertiary amides are readily reduced. Finally, sulfides and sulfoxides are reduced to thiols and sulfides, respectively, without evolution of hydrogen. In addition to that, the reagent appears to be an excellent partial reducing agent to convert esters, primary carboxamides, and aromatic nitriles into the corresponding aldehydes. Free carboxylic acids are also converted into aldehydes through treatment of acyloxy-9-BBN with this reagent in excellent yields.

Hydrogen Evolution from Biological Protein Photosystem I and Semiconductor BiVO4 Driven by Z-Schematic Electron Transfer

  • Shin, Seonae;Kim, Younghye;Nam, Ki Tae
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.08a
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    • pp.251.2-251.2
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    • 2013
  • Natural photosynthesis utilizes two proteins, photosystem I and photosystem II, to efficiently oxidize water and reduce NADP+ to NADPH. Artificial photosynthesis which mimics this process achieve water splitting through a two-step Z-schematic water splitting process using man-made synthetic materials for hydrogen fuel production. In this study, Z-scheme system was achieved from the hybrid materials which composed of hydrogen production part as photosystem I protein and water oxidizing part as semiconductor BiVO4. Utilizing photosystem I as the hydrogen evolving part overcomes the problems of existing hydrogen evolving p-type semiconductors such as water instability, expensive cost, few available choices and poor red light (>600 nm) absorbance. Some problems of photosystem II, oxygen evolving part of natural photosynthesis, such as demanding isolation process and D1 photo-damage can also be solved by utilizing BiVO4 as the oxygen evolving part. Preceding research has not suggested any protein-inorganic-hybrid Z-scheme composed of both materials from natural photosynthesis and artificial photosynthesis. In this study, to realize this Z-schematic electron transfer, diffusion step of electron carrier, which usually degrades natural photosynthesis efficiency, was eliminated. Instead, BiVO4 and Pt-photosystem I were all linked together by the mediator gold. Synthesized all-solid-state hybrid materials show enhanced hydrogen evolution ability directly from water when illuminated with visible light.

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Photochemical hydrogen production from coupled semiconductor systems : CdS-WO3/RuO2, CdS-TiO2 (혼합반도체 시스템에서의 광화학적 수소제조 : CdS-WO3/RuO2, CdS-TiO2)

  • Suh, J.K.;Heo, G.S.
    • Journal of Hydrogen and New Energy
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    • v.4 no.2
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    • pp.5-15
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    • 1993
  • Hydrogen production in visible light with the following semiconductor systems, $CdS-WO_3$, $CdS-TiO_2$, have been investigated in the presence of redox catalyst (Pt, $RuO_2$). MeOH, EtOH, isopropanol, sulfide/sulfite mixture, lactic acid were used as sacrifical reagents. The optimal condition for $H_2$ evolution was found to be in qgueous lactic acid media for $CdS-WO_3/RuO_2$. The photochemical efficiency for this system was 1.05 % and the $H_2$ evolution rate was 26.5ml/min. at $6.07{\times}10^{-5}$ einstein/sec photon rate

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Identification of a Universal Relation between a Thermodynamic Variable and Catalytic Activities of Pyrites toward Hydrogen Evolution Reaction: Density Functional Theory Calculations (수소발생반응에 대한 Pyrites 표면 촉매 성능 예측: 밀도 범함수 이론 계산)

  • Gang, Jun-Hui;Hwang, Ji-Min;Han, Byeong-Chan
    • Proceedings of the Korean Institute of Surface Engineering Conference
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    • 2017.05a
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    • pp.87.1-87.1
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    • 2017
  • High functional catalyst to efficiently produce clean and earth-abundant renewable fuels plays a key role in securing energy sustainability and environmental protection of our society. Hydrogen has been considered as one of the most promising energy carrier as represented by focused research works on developing catalysts for the hydrogen evolution reaction (HER) from the water hydrolysis over the last several decades. So far, however, the major catalysts are expensive transition metals. Here using first principles density functional theory (DFT) calculations we screen various pyrites for HER by identifying fundamental descriptor governing the catalytic activity. We enable to capture a strong linearity between experimentally measured exchange current density in HER and calculated adsorption energy of hydrogen atom in the pyrites. The correlation implies that there is an underlying design principle tuning the catalytic activity of HER.

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Evolution of primary stars in Pop III binary systems

  • Lee, Hunchul;Yoon, Sung-Chul
    • The Bulletin of The Korean Astronomical Society
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    • v.41 no.1
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    • pp.77.4-78
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    • 2016
  • Binary interactions may have significant impact on Pop III stellar evolution. Pop III single star evolution indicates that for primary masses less than $20M_{\odot}$, no significant binary mass transfer would occur before core helium exhaustion. We perform binary system evolution for various primary masses ($20M_{\odot}$ < $M_1$ < $60M_{\odot}$) and initial periods under same mass ratio $M_2/M_1=0.9$, and follow the evolution and mass transfer of the primary star. If binary mass transfer occurs during post main sequence, the primary star does not evolve into naked helium star and still contain significant hydrogen in the envelope. During the post mass transfer phase, the primary star evolves redward, and does not become sufficiently hot to enhance the number of ionizing photons, compared to the case of single star evolution for a given initial mass. This result implies that primary stars of massive Pop III binary systems would have little contribution to the reionization in the early universe. Given the large hydrogen content ($0.326-1.793M_{\odot}$), the primary stars that underwent stable mass transfers would explode as a Type IIb supernova, and it would be difficult for Pop III binary stars to produce Type Ib/c supernovae that look similar to those found in the local universe.

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Hydrogen Evolution Rates of the Aluminum-Air Unit Cell (알루미늄-공기 단위전지의 수소발생속도)

  • Shim Eun-Gi;Doh Chil-Hoon;Moon Seong-In;Hwang Young-Gi
    • Journal of the Korean Electrochemical Society
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    • v.4 no.4
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    • pp.166-171
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    • 2001
  • In an aluminum-air unit cell used alkaline solution, Hydrogen evolution rates were investigated far the observation of the effects of alloy element, inhibitor and its concentration in electrolyte, KOH concentration, solution temperature, and current density loaded to cell. Hydrogen evolution rates were reduced up to $50\%$ by saturating the solution with ZnO, while ZnAc(Zinc Acetate) did not work as inhibitor. The inhibition effect of ZnO increased with increasing the KOH concentration and solution temperature. They were linearly increased with the KOH concentration and current density in first order and exponentially increased with the solution temperature.

Effect of Electrolyte-Additives on the Performance of Al-Air Cells (전해질 첨가제가 알루미늄-공기전지의 성능에 미치는 영향)

  • Park, Gwun Pil;Chun, Hai Soo
    • Applied Chemistry for Engineering
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    • v.9 no.1
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    • pp.52-57
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    • 1998
  • The effects of additives such as zinc compounds in 4M KOH electrolyte of Al-air cell have been studied. Zinc compounds in electrolyte increased hydrogen evolution overpotential and TPC(tripotasium citrate)/CaO formed fine film on aluminum surface, and these additives decreased hydrogen evolution rate and corrosion rate of aluminum. These additives shifted the OCP in the positive direction on high purity aluminum(purity, 99.999%) and in the negative direction on Al No 1050(purity,99.5%). Addition of two or more additives resulted in the prevention or the reduction of corrosion rate and hydrogen evolution at OCP. As the overpotential on Al electrode increased, the hydrogen evolution rate decreased and the utilization of aluminum increased. At high current density$(>100mA/cm^2)$, TPC/CaO/ZnO additives increased the utilization of high purity aluminum up to that of aluminum alloys containing indium, gallium and thallium.

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Research and Development Trends in Seawater Electrolysis Systems and Catalysts (해수 수전해 시스템 및 촉매 연구 개발 동향)

  • Yoonseong Jung;Tuan Linh Doan;Ta Nam Nguyen;Taekeun Kim
    • Applied Chemistry for Engineering
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    • v.34 no.6
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    • pp.567-575
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    • 2023
  • Water electrolysis is undergoing active research as one of the promising technologies for producing effective green hydrogen. Using seawater directly as a raw material for a water electrolysis system can solve the problem of the limitations of existing freshwater raw materials, as seawater accounts for approximately 97% of the water on Earth. At the same time, abundant by-product materials can be obtained, representative examples of which are Cl2, ClO-, Br2, and Mg(OH)2 produced during electrolysis, depending on their composition and pH environment. In order to develop a successful seawater electrolysis system and oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) catalysts, it is necessary to understand the causes and consequences of reactions that occur in the seawater environment. Therefore, in this paper, we will investigate the reaction mechanism and characteristics of the seawater electrolysis system as well as the research and development trends of electrochemical catalysts used in anode and cathode electrodes.

A Numerical Investigation of Hydrogen Desorption Reaction for Tritium Delivery from Tritium Storage Based on ZrCo (ZrCo 기반 저장용기로부터 삼중수소 공급을 위한 수소 방출에 대한 수치해석적 연구 (II))

  • Yoo, Haneul;Jo, Arae;Gwak, Geonhui;Yun, Seihun;Chang, Minho;Kang, Hyungoo;Ju, Hyunchul
    • Journal of Hydrogen and New Energy
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    • v.24 no.1
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    • pp.36-43
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    • 2013
  • In this paper, a three-dimensional hydrogen desorption model is applied to a thin double-layered annulus ZrCo hydride bed and validated against the temperature evolution data measured by Kang et al. The present model reasonably captures the bed temperature evolution behavior and the 90% hydrogen discharging time. In addition, the performance of thin double-layered annulus bed is evaluated by comparing with a simple cylindrical bed using hydrogen desorption model. This study provides multi-dimensional contours such as temperature and H/M atomic ratio in the metal hydride region. This numerical study provides fundamental understanding during hydrogen desorption process and indicates that efficient design of the metal hydride bed is critical to achieve rapid hydrogen discharging performance. The present three-dimensional hydrogen desorption model is a useful tool for the optimization of bed design and operating conditions.

Synthesis and characterization of NiFe2O4 nanoparticle electrocatalyst for urea and water oxidation (요소 산화반응을 위한 NiFe2O4 나노파티클 촉매 합성 및 특성 분석 )

  • Ki-Yong Yoon;Kyung-Bok Lee;Dohyung Kim;Hee Yoon Roh;Sung Mook Choi;Ji-hoon Lee;Jaehoon Jeong;Juchan Yang
    • Journal of the Korean institute of surface engineering
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    • v.56 no.4
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    • pp.243-249
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    • 2023
  • Urea oxidation reaction (UOR) via electrochemical oxidation process can replace oxygen evolution reaction (OER) for green hydrogen production since UOR has lower thermodynamic potential (0.37 VRHE) than that of OER (1.23 VRHE). However, in the case of UOR, 6 electrons are required for the entire UOR. For this reason, the reaction rate is slower than OER, which requires 4 electrons. In addition, it is an important challenge to develop catalysts in which both oxidation reactions (UOR and OER) are active since the active sites of OER and UOR are opposite to each other. We prove that among the NiFe2O4 nanoparticles synthesized by the hydrothermal method at various synthesis temperatures, NiFe2O4 nanoparticle with properly controlled particle size and crystallinity can actively operate OER and UOR at the same time.