• Title/Summary/Keyword: Physisorbed water

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Dimerization of tert-Butylmercaptan over the Surface of Aerosil? Impregnated with Copper and Manganese

  • Park, Dong Geon;Park, Seon Hui;Lee, Su Jin
    • Bulletin of the Korean Chemical Society
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    • v.21 no.7
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    • pp.715-719
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    • 2000
  • A ceramic powder of destructive adsorbent was synthesized by impregnating copper and manganese on the surface of silica aerosil@. In-site FTIR measurements on pulses of malodorant tert-butylmercaptan injected over the powder showed that rert-butylmercaptan dimerized into di-tert-hutyldisulfide on the surface of the adsorbent in an ambient condition. GC/MS measurement on the gas over the adsorbent showed no tert-butylmercaptan remaining, and showed only the dimerization product of di-tert-butyldisulfide. Most of the dimerization product, di-tert-butyldisulfide,remained on the surface of the adsorbent as physisorbed condense, and apparently Iowered the destruction efficiency by blocking the surface from the access by tert-butylmercaptan. Upon being heated above $100^{\circ}C$ it was observed that the physisorbed di-tert-butyldisulfide dissociated back into tert-butylmercaptan. tert-butylmercaptan physisorbed on the activated carbon, thereby no dimerization was occurring on the surface of the activated carbon. In an argn environment, the dimerization reaction was practically not occurring even on the surface of the adsorbent, indicating the free oxygen in air was also participating in the dimerization reaction. Water was identified as a by-product of the dimerization reaction. Possible reactions on the surface of the adsorbent were proposed.

1H Solid-state NMR Methodology Study for the Quantification of Water Content of Amorphous Silica Nanoparticles Depending on Relative Humidity (상대습도에 따른 비정질 규산염 나노입자의 함수량 정량 분석을 위한 1H 고상 핵자기 공명 분광분석 방법론 연구)

  • Oh, Sol Bi;Kim, Hyun Na
    • Korean Journal of Mineralogy and Petrology
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    • v.34 no.1
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    • pp.31-40
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    • 2021
  • The hydrogen in nominally anhydrous mineral is known to be associated with lattice defects, but it also can exist in the form of water and hydroxyl groups on the large surface of the nanoscale particles. In this study, we investigate the effectiveness of 1H solid-state nuclear magnetic resonance (NMR) spectroscopy as a robust experimental method to quantify the hydrogen atomic environments of amorphous silica nanoparticles with varying relative humidity. Amorphous silica nanoparticles were packed into NMR rotors in a temperature-humidity controlled glove box, then stored in different atmospheric conditions with 25% and 70% relative humidity for 2~10 days until 1H NMR experiments, and a slight difference was observed in 1H NMR spectra. These results indicate that amount of hydrous species in the sample packed in the NMR rotor is rarely changed by the external atmosphere. The amount of hydrogen atom, especially the amount of physisorbed water may vary in the range of ~10% due to the temporal and spatial inhomogeneity of relative humidity in the glove box. The quantitative analysis of 1H NMR spectra shows that the amount of hydrogen atom in amorphous silica nanoparticles linearly increases as the relative humidity increases. These results imply that the sample sealing capability of the NMR rotor is sufficient to preserve the hydrous environments of samples, and is suitable for the quantitative measurement of water content of ultrafine nominally anhydrous minerals depending on the atmospheric relative humidity. We expect that 1H solid-state NMR method is suitable to investigate systematically the effect of surface area and crystallinity on the water content of diverse nano-sized nominally anhydrous minerals with varying relative humidity.

Effect of Particle Size on the Atomic Structure of Amorphous Silica Nanoparticles: Solid-state NMR and Quantum Chemical Calculations (비정질 규산염 나노입자의 입자 크기에 따른 원자 구조 변화 : 고상 핵자기공명 분석 및 양자화학계산 연구)

  • Kim, Hyun-Na;Lee, Sung-Keun
    • Journal of the Mineralogical Society of Korea
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    • v.21 no.3
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    • pp.321-329
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    • 2008
  • Amorphous silica nanoparticles are among the most fundamental $SiO_2$ compounds, having implications in diverse geological processes and technological applications. Here, we explore structural details of amorphous silica nanoparticles with varying particle sizes (7 and 14 nm) using $^{29}Si$ and $^{1}H$ MAS NMR spectroscopy together with quantum chemical calculations to have better prospect for their size-dependent atomic structures. $^{29}Si$ MAS NMR spectra at 9.4 T resolve $Q^2,\;Q^3$ and $Q^4$ species at -93 ppm, -101 ppm, -110 ppm, respectively. The fractions of $Q^2,\;Q^3,\;O^4$ species are $7{\pm}1%,\;27{\pm}2%$, and $66{\pm}2%$ for 7 nm amorphous silica nanoparticles and $6{\pm}1%,\;21{\pm}2%$, and $73{\pm}2%$ for 14 nm amorphous silica nanoparticles. Whereas it has been suggested that $Q^2$ and $Q^3$ species exist on particles surfaces, the difference in $Q^{2}\;+\;Q^{3}$ fraction in both 7 and 14 nm particles is not significant, suggesting that $Q^2$ and $Q^3$ species could exist inside particles. $^{1}H$ MAS NMR spectra at 11.7 T shows diverse hydrogen environments, including physisorbed water, hydrogen bonded silanol, and non-hydrogen bonded silanol with varying hydrogen bond strength. The hydrogen contents in the 7nm silica nanoparticles (including water and hydroxyl groups) are about 3 times of that of 14 nm particles. The larger chemical shills for proton environments in the former suggest stronger hydrogen bond strength. The fractions of non-hydrogen bonded silanols in the 14 nm amorphous silica nanoparticles are larger than those in 7 nm amorphous silica nanoparticles. This observation suggests closer proximity among hydrogen atoms in the nanoparticles with smaller diameter. The current results with high-resolution solid-state NMR reveal previously unknown structural details in amorphous silica nanoparticles with particle size.

Long-term Air Stability of Small Molecules passivated-Graphene Field Effect Transistors

  • Shin, Dong Heon;Kim, Yoon Jeong;Kim, Sang Jin;Moon, Byung Joon;Oh, Yelin;Ahn, Seokhoon;Bae, Sukang
    • Proceedings of the Korean Vacuum Society Conference
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    • 2016.02a
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    • pp.237.1-237.1
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    • 2016
  • Electrical properties of graphene-based field effect transistors (G-FETs) can be degraded in ambient conditions owing to physisorbed oxygen or water molecules on the graphene surface. Passivation technique is one of a fascinating strategy for fabrication of G-FETs, which allows to sustain electrical properties of graphene in the long term without disrupting its inherent properties: transparency, flexibility and thinness. Ironically, despite its importance in producing high performance graphene devices, this method has been much less studied compared to patterning or device fabrication processes. Here we report a novel surface passivation method by using atomically thin self-assembled alkane layers such as C18- NH2, C18-Br and C36 to prevent unintentional doping effects that can suppress the degradation of electrical properties. In each passivated device, we observe a shift in charge neutral point to near zero gate voltage and it maintains the device performance for 1 year. In addition, the fabricated PG-FETs on a plastic substrate with ion-gel gate dielectrics exhibit not only mechanical flexibility but also long-term stability in ambient conditions. Therefore, we believe that these highly transparent and ultra-thin passivation layers can become a promising candidate in a wide range of graphene based electronic applications.

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