• 제목/요약/키워드: photocatalytic mechanism

검색결과 59건 처리시간 0.025초

PHOTOCATALYTIC SYNTHESIS OF L-PIPECOLINIC ACID FROM $N_{varepsilon}$-CARBAMYL-L-LYSINE BY AQUEOUS SUSPENSION OF PLATINIZED TITANIUM(IV) OXIDE

  • Ohtani, Bunsho;Aoki, Eishiro;Iwai, Kunihiro;Nishimoto, Sei-Ichi
    • Journal of Photoscience
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    • 제1권1호
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    • pp.31-37
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    • 1994
  • Photoirradiation at > 300 nm onto a suspension of platinized TiO$_2$ (TiO$_2$-Pt) particles in an aqueous solution. of N$_{\varepsilon}$-carbamyI-L-lysine (Lys(CONH)$_2$) induced the selective N-cyclization of Lys(CONH$_2$) into almost optically pure L-pipecolinic acid (PCA) under argon atmosphere at ambient temperature. Among various TiO$_2$-Pt catalysts, a P-25 (Degussa) powder platinized via impregnation from chloroplatinic acid followed by hydrogen reduction at 753 K exhibited the highest photocatalytic activity for Lys(CONH$_2$) consumption and L-PCA production. GC-MS analyses of L-PCA obtained photocatalytically from $^{15}$N$\alpha$-Lys(CONH$_2$) revealed the selective formation $^{15}$N-substituted L-PCA. This implies that the mechanism for L-PCA production contains selective cleavage of C$_{\varepsilon}$-N bond and intramolecular alkylation at $\alpha$-amino group. Effect of pH on the rate of this photocatalytic reaction was investigated in detail and compared with the pH-dependent charge distribution in Lys(CONH$_2$) molecule. It is clarified that protonation-deprotonation of $\alpha$-amino group gives marked influence on the rate and selectivity of the photocatalytic reaction. On the basis of these results, it is concluded that the selective production of optically pure L-PCA, especially in an acidic suspension of TiO$_2$-Pt, was attributed to the enhanced protonation of $\alpha$-amino group to prevent undesirable oxidation by photogenerated positive holes and blocking of $\varepsilon$-amino group to yield racemic Schiff base intermediate.

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Photodecomposition Effect of Metal doped $Ti0_2$ System (I)

  • Jin, Eui;Lee, Kang-Hyeob;Kim, Young-Soon;Min, Tae-Jin;Yu, Kook-Hyun
    • Journal of Photoscience
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    • 제9권2호
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    • pp.403-405
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    • 2002
  • To study photocatalytic mechanism of metal doped $Ti0_2$, we investigated photodecomposition effect, photocurrent effect and antibacterial effect. When aluminium content was 2 wt %, photodecomposition effect was better than the others. Silver doped thin films had high photocurrent efficiency and antibacterial effect. This reactions were caused by dissolved oxygen in solution and oxygen adsorbed on surface of thin films.

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Photocatalytic Decompositions of Carboxylic Acid Derivatives by Semiconductors

  • Koon Ha Park;Jung Hae Kim
    • Bulletin of the Korean Chemical Society
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    • 제12권4호
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    • pp.438-440
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    • 1991
  • Each aqueous solution (pH = 1) of acetic acid, acetamide, and acetonitrile produces carbon dioxide and hydrogen at 300 K when irradiated in the presence of semiconductors such as titanium dioxide, platinized titanium dioxide, etc. Similar results were obtained for each of benzoic acid, benzamide, and benzonitrile. Based on the relative amount of carbon dioxide, nitrile is believed to be transformed into carboxylic acid through the intermediacy of amide. A mechanism in which hydrogen atom and hydroxyl radical are involved is presented.

Type-II ZnO/ZnSe 코어/쉘 이종 구조 합성 및 광촉매활성 평가 (Synthesis and Characteristics of Type-II ZnO/ZnSe Core/Shell Heterostructures for High Efficient Photocatalytic Activity)

  • 이우형;최광일;강동천;백수웅;이석호;임철현
    • 한국전기전자재료학회논문지
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    • 제27권3호
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    • pp.178-183
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    • 2014
  • Recently, various type of nanomaterials such as nanorod, nanowire, nanotube and their core/shell nanostructures have attracted much attention in photocatalyst due to their unique properties. Among them, Type-II core/shell heterostructures have extensively studied because it has exhibited improved electrical and optical properties against their single-component nanostructure. Such structures are expected to offer high absorption efficiency and fast charge transport due to their stepwised energetic combination and large internal surface area. Thus, it has been considered as potential candidates for high efficient photocatalytic activity. In this work, we introduce a novel chemical conversion process to synthesize Type-II ZnO/ZnSe core/shell heterostructures. A plausible conversion mechanism to ZnO/ZnSe core/shell heterostructres was proposed based on SEM, XRD, TEM and XPS analysis. The ZnO/ZnSe heterostructures exhibited excellent photocatalytic activity toward the decomposition of RhB dye compared to the ZnO nanorod arrays due to enhanced light absorption and the type-II cascade band structure.

Quantitative Comparison of the Photocatalytic Efficiency of TiO2 Nanotube Film and TiO2 Powder

  • Jang, Jun-Won;Park, Sung Jik;Park, Jae-Woo
    • 한국지하수토양환경학회지:지하수토양환경
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    • 제21권2호
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    • pp.8-14
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    • 2016
  • We compared the plausible reaction mechanism and quantitative efficiency of highly self-organized TiO2 nanotube (ntTiO2) film with TiO2 powder. Film was fabricated by electrochemical potentiostatic anodization of titanium thin film in an ethylene-glycol electrolyte solution containing 0.3 wt% NH4F and 2 vol% deionized water. Nanotubes with a pore size of 80-100 nm were formed by anodization at 60 V for 3 h. Humic acid (HA) was degraded through photocatalytic degradation using the ntTiO2 film. Pseudo first-order rate constants for 0.3 g of ntTiO2, 0.3 g TiO2 powder, and 1 g TiO2 powder were 0.081 min−1, 0.003 min−1, and 0.044 min−1, respectively. HA adsorption on the ntTiO2 film was minimal while adsorption on the TiO2 powder was about 20% based on thermogravimetric analysis. Approximately five-fold more normalized OH radicals were generated by the ntTiO2 film than the TiO2 powder. These quantitative findings explain why ntTiO2 film showed superior photocatalytic performance to TiO2 powder.

Preparation of Nanoflake Bi2MoO6 Photocatalyst Using CO(NH2)2 as Structure Orientation and Its Visible Light Degradation of Tetracycline Hydrochloride

  • Hu, Pengwei;Zheng, Dewen;Xian, Yuxi;Hu, Xianhai;Zhang, Qian;Wang, Shanyu;Li, Mingjun;Cheng, Congliang;Liu, Jin;Wang, Ping
    • 한국재료학회지
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    • 제31권6호
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    • pp.325-330
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    • 2021
  • Bi2MoO6 (BMO) via the structure-directing role of CO(NH2)2 is successfully prepared via a facile solvothermal route. The structure, morphology, and photocatalytic performance of the nanoflake BMO are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), fluorescence spectrum analysis (PL), UV-vis spectroscopy (UV-vis) and electrochemical test. SEM images show that the size of nanoflake BMO is about 50 ~ 200 nm. PL and electrochemical analysis show that the nanoflake BMO has a lower recombination rate of photogenerated carriers than particle BMO. The photocatalytic degradation of tetracycline hydrochloride (TC) by nanoflake BMO under visible light is investigated. The results show that the nanoflake BMO-3 has the highest degradation efficiency under visible light, and the degradation efficiency reached 75 % within 120 min, attributed to the unique hierarchical structure, efficient carrier separation and sufficient free radicals to generate active center synergies. The photocatalytic reaction mechanism of TC degradation on the nanoflake BMO is proposed.

The Comparison of Property and Visible Light Activity between Bulk and Surface Doped N-TiO2 Prepared by Sol-gel and N2-plasma Treatment

  • Hu, Shaozheng;Li, Fayun;Fan, Zhiping
    • Bulletin of the Korean Chemical Society
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    • 제33권1호
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    • pp.199-203
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    • 2012
  • A modified sol-gel method and $N_2$-plasma treatment were used to prepare bulk and surface doped N-$TiO_2$, respectively. XRD, TEM, UV-vis spectroscopy, $N_2$ adsorption, Elemental Analyzer, Photoluminescence, and XP spectra were used to characterize the prepared $TiO_2$ samples. The N doping did not change the phase composition and particle sizes of $TiO_2$ samples, but increased the visible light absorption. The photocatalytic activities were tested in the degradation of an aqueous solution of a reactive dyestuff, methylene blue, under visible light. The photocatalytic activity of surface doped N-$TiO_2$ prepared by $N_2$-plasma was much higher than that of bulk doped N-$TiO_2$ prepared by sol-gel method. The possible mechanism for the photocatalysis was proposed.

Degradation of oxytetracycline by nano zero valent iron under UV-A irradiation: Chemical mechanism and kinetic

  • Hassanzadeh, Parisa;Ganjidoust, Hossein;Ayati, Bita
    • Advances in environmental research
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    • 제3권1호
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    • pp.29-43
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    • 2014
  • Pharmaceutical wastewater effluents are well known for their difficult elimination by traditional biotreatment methods and their important contribution to environmental pollution due to its fluctuating and recalcitrant nature. OTC is one of the nonbiodegradable antibiotics that makes antibiotic-resistant, so it can make be high risk for environment. NZVI can be a good choice for removal of OTC in aqueous solution. Response surface methodology (RSM) was used to optimize the amounts of NZVI and OTC to be used at pH 3 and under 200 W, UV-A irradiation. The responses were removal percent of absorption at 290 and 348 nm, TOC and COD of OTC. In the optimum condition, Linear model was performed 155 ppm of OTC were removed by 1000 ppm NZVI after 6.5 hours and the removal efficiency of absorption at 290 and 348 nm, TOC and COD were 87, 95, 85 and 89 percent, respectively. In the similar process, there is no organic compound after 14 hours. The parameters ORP, DO and pH were investigated for 6:30 hours to study the type of NZVI reaction in process. In the beginning of reaction, oxidation was the dominant reaction after 3 hours, photocatalytic reaction was remarkable. The mechanism of OTC degradation is proposed by HPLC/ESI-MS and four by products were found. Also the rate constants (first order kinetic chain reaction model) were 0.0099, 0.0021, 0.0010, 0.0049 and $0.0074min^{-1}$, respectively.

광합성을 모사한 광촉매 물분해 수소 제조 (The photocatalytic water splitting into $H_2$ and $O_2$ mimicking a Z-scheme mechanism)

  • 전명석;홍준기;전영갑;최호석
    • 한국태양에너지학회 논문집
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    • 제23권4호
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    • pp.29-35
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    • 2003
  • We studied the water splitting into $H_2$ and $O_2$ using two different semiconductor photo catalysts and redox mediator, mimicking the Z-scheme mechanism of the photosynthesis, $H_2$ evolution took place on a Pt-$SrTiO_2$ (Cr-Ta doped) photocatalyst using $I^-$ electron donor under the visible light irradiation. The Pt-$WO_3$ photocatalyst showed an excellent activity of the $O_2$ evolution using $IO_3^-$ electron acceptor under visible light. $H_2$ and $O_2$ gases evolved in the stoichiometric ratio($H_2/O_2$=2) under visible light using a mixture of the Pt-$WO_3$ and Pt-$SrTiO_3$ (Cr-Ta doped) suspended in NaI aqueous solution. We proposed a two-step photo-excitation mechanism using redox mediator under the visible irradiation.

TiO2 나노입자 광촉매 반응에 의한 비스페놀 A의 분해 제거 및 독성 저감 (Photocatalytic Degradation and Detoxification of Bisphenol A Using TiO2 Nanoparticles)

  • 조아영;정진호
    • Ecology and Resilient Infrastructure
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    • 제2권4호
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    • pp.330-336
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    • 2015
  • 본 논문은 수용액에서 $TiO_2$ 나노입자 (Degussa P25) 광촉매 반응에 의한 비스페놀 A (BPA)의 분해 제거를 연구하였다. 3시간의 광촉매 반응 (자외선 파장 = 365 nm, 자외선 강도 = $3mW\;cm^{-2}$, $TiO_2$ 농도 = $2.0g\;L^{-1}$)에 의하여 98%의 BPA ($1.0{\times}10^{-5}M$)와 89%의 총유기탄소가 제거되었다. 그리고 광분해, 가수분해와 흡착반응에 의한 BPA의 분해 제거는 각각 2%, 5%와 13%로 나타났다. 광촉매 반응에 의한 BPA의 분해 제거는 수산화 라디칼의 소광제인 메탄올의 농도가 증가 할수록 감소하였다. 이것은 BPA와 수산화 라디칼의 반응이 BPA 분해 제거의 주요한 기작이라는 것을 나타낸다. 이 반응의 초기 유사 1차 속도 상수는 $7.94{\times}10^{-4}min^{-1}$로 계산되었으며, BPA 90%를 분해 제거하는 시간은 25분으로 나타났다. 그리고 광촉매 반응에 의한 BPA의 독성 저감을 평가하기 위하여 물벼룩 (Daphnia magna, 생후 24시간 미만)을 이용한 급성독성 시험을 실시하였다. 물벼룩에 대한 BPA의 급성독성 (48시간)은 초기 2.93 TU (독성 단위)였으며, 3시간의 광촉매 반응 후에는 무독성으로 나타났다. 이것은 BPA의 광촉매 반응에서 독성 분해산물이 생성되지 않는 다는 것을 제시한다.