• Title/Summary/Keyword: $CH_4$ oxidation

Search Result 184, Processing Time 0.023 seconds

Scanning Tunneling Microscopy (STM)/Atomic Force Microscopy(AFM) Studies of Silicon Surfaces Treated in Alkaline Solutions of Interest to Semiconductor Processing

  • Park, Jin-Goo
    • Journal of the Korean institute of surface engineering
    • /
    • v.28 no.1
    • /
    • pp.55-63
    • /
    • 1995
  • Alkaline solutions such as $NH_4$OH, choline and TMAH (($CH_3$)$_4$NOH) have been introduced in semiconductor wet processing of silicon wafers to control ionic and particulate impurities following etching in acidic solutions. These chemicals usually mixed with hydrogen peroxide and/or surfactants to control the etch rate of silicon. The highest etch rate was observed in $NH_4$OH solutions at a pH in alkaline solutions. It indicates that the etch rate depends on the content of $OH^{-}$ as well as cations of alkaline solutions. STM/AFM techniques were used to characterize the effect of alkaline solutions on silicon surface roughness. In SC1 (mixture of $NH_4$OH : $H_2$$O_2$ : $H_2$O) solutions, the reduction of the ammonium hydroxide proportion from 1 to 0.1 decreased the surface roughness ($R_{rms}$) from 6.4 to $0.8\AA$. The addition of $H_2$$O_2$ and surfactants to choline and TMAH reduced the values of $R_{p-v}$ and $R_{rms}$ significantly. $H_2$$_O2$ and surfactants added in alkaline solutions passivate bare silicon surfaces by the oxidation and adsorption, respectively. The passivation of surfaces in alkaline solutions resulted in lower etch rate of silicon thereby provided smoother surfaces.s.ces.s.

  • PDF

Rates and Mechanism of the Reduction of Vanadium(V) by Benzyl Alcohol in Aqueous Dimethylformamide (DMF 수용매에서 벤질알코올에 의한 바나듐(V)의 환원반응속도와 메카니즘)

  • Chang-Su Kim;Woo-Sik Lee
    • Journal of the Korean Chemical Society
    • /
    • v.32 no.3
    • /
    • pp.179-185
    • /
    • 1988
  • The reaction of VO_2\;^+$ with benzyl alcohol in perchloric acid and aqueous dimethylformamide leads to the formation of $VO^{2+}$ and benzaldehyde. The products, $VO^{2+}$ and benzaldehyde, are identified by infrared spectroscopy and gas chromatography. Kinetic studies on the reaction of VO_2\;^+$ with benzyl alcohol have been carried out using visible spectroscopy. The empirical rate equation can be expressed as $-d[VO_2\;^+]/dt=2\{\\{k_O+k_H[HClO_4]\}\[VO_2\;^+][C_6H_5CH_2OH]$ The rate determining step for the reaction is the process for the formation of $VO^{2+}$ and $C_6H_5CHOH$. The activation parameters are ${\Delta}H^{\neq}=13.32{\pm}1.73\;kcalmol^{-1}$ and ${\Delta}S^{\neq}=-31.02{\pm}0.09\;calmol^{-1}K^{-1}$ for the oxidation of benzyl alcohol in aqueous dimethylformamide.

  • PDF

Partial Oxidation of Methane to $H_2$ Over Pd/Ti-SPK and Pd/Zr-SPK Catalysts and Characterization (Pd/Ti-SPK과 Pd/Zr-SPK 촉매상에서 수소 생산을 위한 메탄의 부분산화반응과 촉매의 특성화)

  • Seo, Ho-Joon;Kang, Ung-Il
    • Applied Chemistry for Engineering
    • /
    • v.21 no.6
    • /
    • pp.648-652
    • /
    • 2010
  • Catalytic activities of the partial oxidation of methane (POM) to hydrogen were investigated over Pd(5)/Ti-SPK and Pd(5)/Zr-SPK in a fixed bed flow reactor (FBFR) under atmosphere, and the catalysts were characterized by BET, XPS, XRD. The BET surface areas, pore volume and pore width of Horvath-Kawaze, micro pore area and volume of t-plot of Pd(5)/Ti-SPK and Pd(5)/Zr-SPK were $284m^2/g$, $0.233cm^3/g$, 3.9 nm, $30m^2/g$, $0.015cm^3/g$ and $396m^2/g$, $0.324cm^3/g$, 3.7nm, $119m^2/g$, $0.055cm^3/g$, repectively. The nitrogen adsorption isotherms were type IV with hysteresis. XPS showed that Si 2p and O 1s core electronlevels of Ti-SPK and Zr-SPK substituted Ti and Zr shifted to slightly lower binding energies than SPK. The oxidation states of Pd on the surface of catalysts were $Pd^0$ and $Pd^{+2}$. XRD patterns showed that crystal structures of fresh catalyst changed amorphous into crystal phase after reaction. The conversion and selectivity of POM to hydrogen over Pd(5)/Ti-SPK and Pd(5)/Zr-SPK were 77, 84% and 78, 72%, respectively, at 973 K, $CH_4/O_2$ = 2, GHSV = $8.4{\times}10^4mL/g_{cat}{\cdot}h$ and were kept constant even after 3 days in stream. These results confirm superior activity, thermal stability, and physicochemical properties of catalyst in POM to hydrogen.

Voltammetric Studies of Diazocalix[4]crown-6 for Metal Ion Sensing

  • Dong, Yun-Yan;Kim, Tae-Hyun;Lee, Chang-Seuk;Kim, Hyun-Jung;Lee, Jae-Hong;Lee, Joung-Hae;Kim, Ha-Suck;Kim, Jong-Seung
    • Bulletin of the Korean Chemical Society
    • /
    • v.31 no.12
    • /
    • pp.3549-3552
    • /
    • 2010
  • The complex formation between diazocalix[4]dipropyl (1) and diazocalix[4]crown-6 ether (2) with alkali, alkaline earth and transition metal ions was investigated by voltammetry. Electrochemical properties of compounds 1 and 2 and their selectivity toward metal ions were evaluated in $CH_3CN$ solution by comparison of voltammetric behaviors of two phenols in each compound. Compounds 1 and 2 showed almost same voltammetric behavior which is two irreversible oxidation peaks caused by intramolecular hydrogen bonding between two phenols in 1 and 2. While, however, upon interacting with various metal ions, 1 with two propyl ether groups showed no significant changes in voltammetry, 2 with crown ether group caused significant voltammetric changes upon the addition of $Ba^{2+}$ to 2. Their behavior is closely related to the complex formation by entrapment of metal ion into crown ether cavity, and ion-dipole interaction between metal ion and two phenolic groups in calix[4]crown-6.

Synthesis Gas Production via Partial Oxidation, CO2 Reforming, and Oxidative CO2 Reforming of CH4 over a Ni/Mg-Al Hydrotalcite-type Catalyst

  • Song, Hoon Sub;Kwon, Soon Jin;Epling, William S.;Croiset, Eric;Nam, Sung Chan;Yi, Kwang Bok
    • Clean Technology
    • /
    • v.20 no.2
    • /
    • pp.189-201
    • /
    • 2014
  • Partial oxidation, $CO_2$ reforming and the oxidative $CO_2$ reforming of $CH_4$ to produce synthesis gas over supported Ni hydrotalcite-type ($Ni_{0.5}Ca_{2.5}Al$ catalyst) catalysts were carried out and the effects of metal supports (i.e.; Mg and Ca) on the formation of a stable double-layer structure on the catalysts were evaluated. The $CH_4$ reforming stability was determined to be affected by the differences in the interaction strength between the active Ni ions and support metal ions. Only a Ni-Mg-Al composition produced a highly stable hydrotalcite-type double-layered structure; while the Ni-Ca-Al-type composition did not. Such structure provides excellent stability for the catalyst (-80% efficiency) as confirmed by the long-term $CO_2$ reforming test (-100 h), while the Ni-Ca-Al catalyst exhibited deactivation phases starting at the beginning of the reaction. The interaction strength between the active metal (Ni) and the supporting components (Mg and Al) was determined by temperature-programed reduction (TPR) analyses. The affinity was also confirmed by the TPR temperature because the Ni-Mg-Al catalyst required a higher temperature to reduce the Ni relative to the Ni-Ca-Al catalyst. The highest initial activity for synthesis gas production was observed for the $Ni_{0.5}Ca_{2.5}Al$ catalyst; however, this activity decreased quickly due to coke formation. The $Ni_{0.5}Ca_{2.5}Al$ catalyst exhibited a high reactivity and was more stable than the other catalysts because it had a higher resistance to coke formation.

Characteristic of Partial Oxidation of Methane and Ni Catalyst Reforming using GlidArc Plasma (GlidArc 플라즈마를 이용한 메탄 부분산화 및 Ni 촉매 개질 특성)

  • Kim, Seong-Cheon;Chun, Young-Nam
    • Journal of Korean Society of Environmental Engineers
    • /
    • v.30 no.12
    • /
    • pp.1268-1272
    • /
    • 2008
  • Low temperature plasma applied with partial oxidation is a technique to produce synthesis gas from methane. Low temperature plasma reformer has superior miniaturization and start-up characteristics to reformers using steam reforming or CO$_2$ reforming. In this research, a low temperature plasma reformer using GlidArc discharge was proposed. Reforming characteristics for each of the following variables were studied: gas components ratio (O$_2$/CH$_4$), the amount of steam, comparison of reaction on nickle and iron catalysts and the amount of CO$_2$. The optimum conditions for hydrogen production from methane was found. The maximum Hydrogen concentration of 41.1% was obtained under the following in this condition: O$_2$/C ratio of 0.64, total gas flow of 14.2 L/min, catalyst reactor temperature of 672$^{\circ}C$, the amount of steam was 0.8, reformer energy density of 1.1 kJ/L with Ni catalyst in the catalyst reactor. At this point, the methane conversion rate, hydrogen selectivity and reformer thermal efficiency were 66%, 93% and 35.2%, respectively.

Determination of the NDR and Electron Transport Properties of Self-Assembled Nitro-Benzene Monolayers Using UHV-STM

  • Lee Nam-Suk;Chang Jeong-Soo;Kwon Young-Soo
    • Journal of Electrical Engineering and Technology
    • /
    • v.1 no.3
    • /
    • pp.366-370
    • /
    • 2006
  • We investigated the negative differential resistance (NDR) property of self-assembled 4,4-di(ethynylphenyl)-2'-nitro-l-(thioacetyl)benzene ('nitro-benzene'), which has been well known as a conducting molecule [1], Self-assembly monolayers (SAMs) were prepared on Au (111), which had been thermally deposited onto pre-treated $(H_2SO_4: H_2O_2=3:1)$ Si, The Au substrate was exposed to a 1mM solution of 1-dodecanethiol in ethanol for 24 hours to form a monolayer. After thorough rinsing of the sample, it was exposed to a $0.1{\mu}M$ solution of nitro-benzene in dimethylformamide (DMF) for 30 min and kept in the dark during immersion to avoid photo-oxidation. Following the assembly, the samples were removed from the solutions, rinsed thoroughly with methanol, acetone, and $CH_2Cl_2$, and finally blown dry with $N_2$. Under these conditions, we measured the electrical properties of SAMs using ultra high vacuum scanning tunneling microscopy (UHV-STM) and scanning tunneling spectroscopy (STS) [2]. As a result, we confirmed the properties of NDR in between the positive and negative region.

Electrochemical Polymerization of Ruthenium(II) Complex and Application to Acetaminophen Analysis

  • Kannan, Sethuraman;Son, Jung-Ik;Yang, Jee-Eun;Shim, Yoon-Bo
    • Bulletin of the Korean Chemical Society
    • /
    • v.32 no.4
    • /
    • pp.1341-1345
    • /
    • 2011
  • A novel ruthenium(II) complex, [$RuCl_2(DMSO)_2$(PhenTPy)] has been synthesized by the condensation of $RuCl_2(DMSO)_4$ with (1-(1,10-phenanthrolinyl)-2,5-di(2-thienyl)-1H-pyrrole)[PhenTPy] in $CHCl_3$ solution. The [$RuCl_2(DMSO)_2$(PhenTPy)] complex modified electrode was fabricated through the electropolymerization of the monomer in a 0.1 M tetrabutylammonium perchlorate (TBAP)/$CH_2Cl_2$ solution, to take advantage of the electronic communication between metal ion center by the conjugated backbone. The UV-visible spectroscopy (UV), mass spectrometry (MS), and cyclic voltammetry (CV) were employed to characterize the [$RuCl_2(DMSO)_2$(PhenTPy)] complex and its polymer (poly-Ru(II)Phen complex). The poly-Ru(II)Phen complex modified electrode exhibited an electrocatalytic activity to the oxidation of acetaminophen and the catalytic property was used for the analysis of acetaminophen at the concentration range between 0.09 and 0.01 mM in a phosphate buffer solution (pH 7.0).

Biodegradation of Kraft Lignins by White-Rot Fungi(I) -Lignin from Pitch Pine- (백색부후균에 의한 크라프트 리그닌의 분해(I) -리기다소나무 리그닌-)

  • 김명길;안원영
    • Journal of Korea Foresty Energy
    • /
    • v.17 no.1
    • /
    • pp.56-70
    • /
    • 1998
  • This study was carried out to investigate the structural characteristics of kraft lignin and the wood degrading characteristics, the productivity of ligninolytic enzymes and the enzymatic degradation of kraft lignin by white-rot fungi. To purify kraft lignin, precipitation of kraft pulping black liquors of pitch pine meal was done by titration with lN $H_{2}SO_{4}$ reaching to pH 2, and isolation of the precipitates done by centrifugation. The isolated precipitates from pitch pine were redissloved in lN NaOH, reprecipitated by titration with lN $H_{2}SO_{4}$, washed with deionized water, and kept ofr analysis after freeze drying. Fractionation of the precipitates in solution by successive extraction with $CH_{2}Cl_{2}$ and MeOH, and the fractionates were named SwKL, SwKL I, SwKL II, and SwKL III for pitch pine kraft lignin. The more molecular weights of kraft lignin increased, the less phenolic hydroxyl groups and the more aliphatic hydroxyl groups. Because as the molecular weights increased, the ratio of etherified guaiayl/syringyl(G/S ratio) and the percentage were increased. The spectra obtained by 13C NMR and FTIR assigned by comparing the chemical shifts of various signals with shifts of signals from autherized ones reported. The optimal growth temperature and pH of white-rot fungi in medium were $28^{\circ}C$ and 4.5-5.0, respectively. Especially, in temperature and pH range, and mycelial growth, the best white-rot fungus selected was Phanerochaete chrysosporium for biodegradation. For the degradation pathways, the ligninolytic fungus jcultivated with stationary culture using medium of 1% kraft lignin as a substrate for 3 weeks at $28^{\circ}C$. The weight loss of pitch pine kraft lignin was 15.8%. The degraded products extracted successively methoanol, 90% dioxane and diethyl ether. The ether solubles were analyzed by HPLC. Kraft lignin degradation was initiated in $\beta$-O-4 bonds of lignin by the laccase from Phanerochaete chrysosporium and the degraded compounds were produced from the cleavage of $C\alpha$-$C\beta$ linkages at the side chains by oxidation process. After $C\alpha$-$C\beta$ cleavage, $C\alpha$-Carbon was oxidized and changed into aldehyde and acidic compounds such as syringic acid, syringic aldehyde and vanilline. And the other compound as quinonemethide, coumarin, was analyzed. The structural characteristics of kraft lignin were composed of guaiacyl group substituted functional OHs, methoxyl, and carbonyl at C-3, -4, and -5 and these groups were combinated with $\alpha$ aryl ether, $\beta$ aryl ether and biphenyl. Kraft lignin degradation pathways by Phanerochaete chrysosporium were initially accomplished cleavage of $C\alpha$-$C\beta$ linkages and $C\alpha$ oxidation at the propyl side chains and finally cleavage of aromatic ring and oxidation of OHs.

  • PDF

Characteristics of Methanol Production Derived from Methane Oxidation by Inhibiting Methanol Dehydrogenase (메탄올탈수소효소 저해시 메탄산화에 의한 메탄올 전환생성 특성)

  • Yoo, Yeon-Sun;Han, Ji-Sun;Ahn, Chang-Min;Min, Dong-Hee;Mo, Woo-Jong;Yoon, Soon-Uk;Lee, Jong-Gyu;Lee, Jong-Yeon;Kim, Chang-Gyun
    • Journal of Korean Society of Environmental Engineers
    • /
    • v.33 no.9
    • /
    • pp.662-669
    • /
    • 2011
  • This study was conducted to biologically convert methane into methanol. Methane contained in biogas was bio-catalytically oxidized by methane monooxygenase (MMO) of methanotrophs, while methanol conversion was observed by inhibiting methanol dehydrogenase (MDH) using MDH activity inhibitors such as phosphate, NaCl, $NH_4Cl$, and EDTA. The degree of methane oxidation by methanotrophs was the most highly accomplished as 0.56 mmol for the condition at $35^{\circ}C$ and pH 7 under 0.4 (v/v%) of biogas ($CH_4$ 50%, $CO_2$ 50%) / Air ratio. By the inhibition of 40 mM of phosphate, 50 mM of NaCl, 40 mM of $NH_4Cl$ and $150{\mu}m$ of EDTA, methane oxidation rate could achieve more than 80% regardless of type of inhibitors. In the meantime, addition of 40 mM of phosphate, 100 mM of NaCl, 40 mM of $NH_4Cl$ and $50{\mu}m$ of EDTA each led to generating the highest amount of methanol, i.e, 0.71, 0.60, 0.66, and 0.66 mmol when 1.3, 0.67, 0.74, and 1.3 mmol of methane was each concurrently consumed. At that time, methanol conversion rate was 54.7, 89.9, 89.6, and 47.8% respectively, and maximum methanol production rate was $7.4{\mu}mol/mg{\cdot}h$. From this, it was decided that the methanol production could be maximized as 89.9% when MDH activity was specifically inhibited into the typical level of 35% for the inhibitor of concern.