Revisited reaction-diffusion model of thermal desorption spectroscopy experiments on hydrogen retention in material

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guterl, Jerome, E-mail: jguterl@ucsd.edu; Smirnov, R. D.; Krasheninnikov, S. I.

Desorption phase of thermal desorption spectroscopy (TDS) experiments performed on tungsten samples exposed to flux of hydrogen isotopes in fusion relevant conditions is analyzed using a reaction-diffusion model describing hydrogen retention in material bulk. Two regimes of hydrogen desorption are identified depending on whether hydrogen trapping rate is faster than hydrogen diffusion rate in material during TDS experiments. In both regimes, a majority of hydrogen released from material defects is immediately outgassed instead of diffusing deeply in material bulk when the evolution of hydrogen concentration in material is quasi-static, which is the case during TDS experiments performed with tungsten samplesmore » exposed to flux of hydrogen isotopes in fusion related conditions. In this context, analytical expressions of the hydrogen outgassing flux as a function of the material temperature are obtained with sufficient accuracy to describe main features of thermal desorption spectra (TDSP). These expressions are then used to highlight how characteristic temperatures of TDSP depend on hydrogen retention parameters, such as trap concentration or activation energy of detrapping processes. The use of Arrhenius plots to characterize retention processes is then revisited when hydrogen trapping takes place during TDS experiments. Retention processes are also characterized using the shape of desorption peaks in TDSP, and it is shown that diffusion of hydrogen in material during TDS experiment can induce long desorption tails visible aside desorption peaks at high temperature in TDSP. These desorption tails can be used to estimate activation energy of diffusion of hydrogen in material.« less

Drastic reduction of adsorption of CO and H2 on (111)-type Pd layers

NASA Technical Reports Server (NTRS)

Poppa, H.; Soria, F.

1983-01-01

Clean surfaces of (111)-type Pd layers, grown from the vapor phase on Mo(110) at room temperature, were used to study the adsorption of CO and H2 by temperature-programmed desorption, Auger electron spectroscopy, and low-energy electron diffraction. Mild annealing of the as-grown layers during a single desorption cycle (to about 600 K) drastically reduces the adsorption for both adsorbates. Low-dose argon-ion bombardment introduces surface imperfections which restore a high adsorption probability. The results are interpreted in terms of particular (111)-type surface structures that persist tp layer thicknesses of about four monolayers; the results raise questions with respect to the surface structure of supported thin epitaxial islands and particles of Pd and possibly also with respect to conventional methods of preparing bulk surfaces of Pd for adsorption studies.

Elucidation of Active Sites for the Reaction of Ethanol on TiO 2 /Au(111)

DOE PAGES

Boyle, David T.; Wilke, Jeremy A.; Palomino, Robert M.; ...

2017-03-17

Obtaining a molecular-level understanding of the reaction of alcohols with heterogeneous model catalysts is critical for improving industrial catalytic processes, such as the production of H 2 from alcohols. Gold has been shown to be an excellent oxidation catalyst once oxygen is added to it. The use of reducible oxides provides a source of oxygen on Au(111) for the reaction of ethanol, which is easily regenerated in the presence of an oxygen background. In this work, ethanol operates as a probe molecule to investigate the role of Au(111), TiO 2 nanoparticles, and TiO 2/Au interfacial surface sites on the catalyticmore » properties of TiO 2/Au(111). Ultrahigh vacuum temperature-programmed desorption (TPD) studies with ethanol/Au(111) elucidate previously unreported adsorption sites for ethanol. Ethanol molecularly adsorbs to Au terrace sites, step edges, and undercoordinated kink sites with adsorption energies of -51.7, -55.8, and -65.1 kJ/mol, respectively. In a TPD coverage study of ethanol on TiO 2/Au(111) indicates ethanol undergoes dissociative adsorption to form H*(a) and CH 3CH 2O*(a) on the inverse model catalyst surface. The desorption temperature of low coverages of ethanol from TiO2/Au(111) (Tdes ≈ 235 K) is at an intermediate temperature between the desorption temperatures from bulk Au(111) and TiO 2(110), indicating both Au and TiO 2 play a role in the adsorption of ethanol. Both low-temperature adsorption and high-temperature reactions are studied and indicate that ethanol-derived products such as acetaldehyde and ethylene desorb from TiO 2/Au(111) at ~500 K. Here, we report the identification of catalytically active sites on TiO 2/Au(111) as interfacial sites between the oxide and Au(111) surface through the use of temperature-programmed desorption and infrared reflection absorption spectroscopy.« less

Elucidation of Active Sites for the Reaction of Ethanol on TiO 2 /Au(111)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boyle, David T.; Wilke, Jeremy A.; Palomino, Robert M.

Obtaining a molecular-level understanding of the reaction of alcohols with heterogeneous model catalysts is critical for improving industrial catalytic processes, such as the production of H 2 from alcohols. Gold has been shown to be an excellent oxidation catalyst once oxygen is added to it. The use of reducible oxides provides a source of oxygen on Au(111) for the reaction of ethanol, which is easily regenerated in the presence of an oxygen background. In this work, ethanol operates as a probe molecule to investigate the role of Au(111), TiO 2 nanoparticles, and TiO 2/Au interfacial surface sites on the catalyticmore » properties of TiO 2/Au(111). Ultrahigh vacuum temperature-programmed desorption (TPD) studies with ethanol/Au(111) elucidate previously unreported adsorption sites for ethanol. Ethanol molecularly adsorbs to Au terrace sites, step edges, and undercoordinated kink sites with adsorption energies of -51.7, -55.8, and -65.1 kJ/mol, respectively. In a TPD coverage study of ethanol on TiO 2/Au(111) indicates ethanol undergoes dissociative adsorption to form H*(a) and CH 3CH 2O*(a) on the inverse model catalyst surface. The desorption temperature of low coverages of ethanol from TiO2/Au(111) (Tdes ≈ 235 K) is at an intermediate temperature between the desorption temperatures from bulk Au(111) and TiO 2(110), indicating both Au and TiO 2 play a role in the adsorption of ethanol. Both low-temperature adsorption and high-temperature reactions are studied and indicate that ethanol-derived products such as acetaldehyde and ethylene desorb from TiO 2/Au(111) at ~500 K. Here, we report the identification of catalytically active sites on TiO 2/Au(111) as interfacial sites between the oxide and Au(111) surface through the use of temperature-programmed desorption and infrared reflection absorption spectroscopy.« less

The Molecular Volcano Revisited: Determination of Crack Propagation and Distribution During the Crystallization of Nanoscale Amorphous Solid Water Films.

DOE Office of Scientific and Technical Information (OSTI.GOV)

May, Robert A.; Smith, R. Scott; Kay, Bruce D.

2012-02-02

Temperature programmed desorption (TPD) is utilized to determine the length distribution of cracks formed through amorphous solid water (ASW) during crystallization. This distribution is determined by monitoring how the thickness of an ASW overlayer alters desorption of an underlayer of O2. As deposited the ASW overlayer prevents desorption of O2. During crystallization, cracks form through the ASW overlayer and open a path to vacuum which allows O2 to escape in a rapid episodic release known as the 'molecular volcano'. Sufficiently thick ASW overlayers further trap O2 resulting in a second O2 desorption peak commensurate with desorption of the last ofmore » the ASW overlayer. The evolution of this trapping peak with overlayer thickness is the basis for determining the distribution of crystallization induced cracks through the ASW. Reflection adsorption infrared spectroscopy (RAIRS) and TPD of multicomponent parfait structures of ASW, O2 and Kr indicate that a preponderance of these cracks propagate down from the outer surface of the ASW.« less

Variable Temperature Infrared Spectroscopy Investigations of Benzoic Acid Desorption from Sodium and Calcium Montmorillonite Clays.

PubMed

Nickels, Tara M; Ingram, Audrey L; Maraoulaite, Dalia K; White, Robert L

2015-12-01

Processes involved in thermal desorption of benzoic acid from sodium and calcium montmorillonite clays are investigated by using variable temperature diffuse reflection Fourier transform infrared spectroscopy (DRIFTS). By monitoring the temperature dependence of infrared absorbance bands while heating samples, subtle changes in molecular vibrations are detected and employed to characterize specific benzoic acid adsorption sites. Abrupt changes in benzoic acid adsorption site properties occur for both clay samples at about 125 °C. Difference spectra absorbance band frequency variations indicate that adsorbed benzoic acid interacts with interlayer cations through water bridges and that these interactions can be disrupted by the presence of organic anions, in particular, benzoate.

Photodecomposition of Mo(CO)/sub 6/ adsorbed on Si(100)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Creighton, J.R.

1985-01-01

The photochemical decomposition of Mo(CO)/sub 6/ layers physisorbed on Si(100) was investigated to determine the feasibility of molybdenum deposition and also to examine the photochemical reaction mechanism and efficiency. Temperature programmed desorption (TPD) was used to investigate the interaction of Mo(CO)/sub 6/ with the silicon surface before and after irradiation. Auger spectroscopy was used to determine surface elemental composition before Mo(CO)/sub 6/ adsorption and after photodecomposition.

Laser Infrared Desorption Spectroscopy to Detect Complex Organic Molecules on Icy Planetary Surfaces

NASA Technical Reports Server (NTRS)

Sollit, Luke S.; Beegle, Luther W.

2008-01-01

Laser Desorption-Infrared Spectroscopy (LD-IR) uses an IR laser pulse to desorb surface materials while a spectrometer measures the emission spectrum of the desorbed materials (Figure 1). In this example, laser desorption operates by having the incident laser energy absorbed by near surface material (10 microns in depth). This desorption produces a plume that exists in an excited state at elevated temperatures. A natural analog for this phenomenon can be observed when comets approach the sun and become active and individual molecular emission spectra can be observed in the IR [1,2,3,4,5]. When this occurs in comets, the same species that initially emit radiation down to the ground state are free to absorb it, reducing the amount of detectable emission features. The nature of our technique results in absorption not occurring, because the laser pulse could easily be moved away form the initial desorption plume, and still have better spatial resolution then reflectance spectroscopy. In reflectance spectroscopy, trace components have a relatively weak signal when compared to the entire active nature of the surface. With LDIR, the emission spectrum is used to identify and analyze surface materials.

Deuterium sputtering of Li and Li-O films

NASA Astrophysics Data System (ADS)

Nelson, Andrew; Buzi, Luxherta; Kaita, Robert; Koel, Bruce

2017-10-01

Lithium wall coatings have been shown to enhance the operational plasma performance of many fusion devices, including NSTX and other tokamaks, by reducing the global wall recycling coefficient. However, pure lithium surfaces are extremely difficult to maintain in experimental fusion devices due to both inevitable oxidation and codeposition from sputtering of hot plasma facing components. Sputtering of thin lithium and lithium oxide films on a molybdenum target by energetic deuterium ion bombardment was studied in laboratory experiments conducted in a surface science apparatus. A Colutron ion source was used to produce a monoenergetic, mass-selected ion beam. Measurements were made under ultrahigh vacuum conditions as a function of surface temperature (90-520 K) using x-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and temperature programmed desorption (TPD). Results are compared with computer simulations conducted on a temperature-dependent data-calibrated (TRIM) model.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schulberg, M.T.; Allendorf, M.D.; Outka, D.A.

NH{sub 3} is an important component of many chemical vapor deposition (CVD) processes for TiN films, which are used for diffusion barriers and other applications in microelectronic circuits. In this study, the interaction of NH{sub 3} with TiN surfaces is examined with temperature programmed desorption (TPD) and Auger electron spectroscopy. NH{sub 3} has two adsorption states on TiN: a chemisorbed state and a multilayer state. A new method for analyzing TPD spectra in systems with slow pumping speeds yields activation energies for desorption for the two states of 24 kcal/mol and 7.3 kcal/mol, respectively. The sticking probability into the chemisorptionmore » state is {approximately}0.06. These results are discussed in the context of TiN CVD. In addition, the high temperature stability of TiN is investigated. TiN decomposes to its elements only after heating to 1300 K, showing that decomposition is unlikely to occur under CVD conditions.« less

Evaluation of GeO desorption behavior in the metalGeO(2)Ge structure and its improvement of the electrical characteristics.

PubMed

Oniki, Yusuke; Koumo, Hideo; Iwazaki, Yoshitaka; Ueno, Tomo

2010-06-15

The relation between germanium monoxide (GeO) desorption and either improvement or deterioration in electrical characteristics of metalGeO(2)Ge capacitors fabricated by thermal oxidation has been investigated. In the metalGeO(2)Ge stack, two processes of GeO desorption at different sites and at different temperatures were observed by thermal desorption spectroscopy measurements. The electrical characteristics of as-oxidized metalGeO(2)Ge capacitors shows a large flat-band voltage shift and minority carrier generation due to the GeO desorption from the GeO(2)Ge interface during oxidation of Ge substrates. On the other hand, the electrical properties were drastically improved by a postmetallization annealing at low temperature resulting in a metal catalyzed GeO desorption from the top interface.

Adsorption, polymerization and decomposition of acetaldehyde on clean and carbon-covered Rh(111) surfaces

NASA Astrophysics Data System (ADS)

Kovács, Imre; Farkas, Arnold Péter; Szitás, Ádám; Kónya, Zoltán; Kiss, János

2017-10-01

The adsorption and dissociation of acetaldehyde were investigated on clean and carbon-covered Rh(111) single crystal surfaces by electron energy loss spectroscopy (EELS), temperature programmed desorption (TPD), high-resolution electron energy loss spectroscopy (HREELS) and work function (Δφ) measurements. Acetaldehyde is a starting material for the catalytic production of many important chemicals and investigation of its reactions motivated by environmental purposes too. The adsorption of acetaldehyde on clean Rh(111) surface produced various types of adsorption forms. η1-(O)-CH3CHOa and η2-(O,C)-CH3CHOa are developing and characterized by HREELS. η1-CH3CHOa partly desorbed at Tp = 150 K, another part of these species are incorporated in trimer and linear 2D polimer species. The desorption of trimers (at amu 132) were observed in TPD with a peak maximum at Tp = 225 K. Above this temperature acetaldehyde either desorbed or bonded as a stable surface intermediate (η2-CH3CHOa) on the rhodium surface. The molecules decomposed to adsorbed products, and only hydrogen and carbon monoxide were analyzed in TPD. Surface carbon decreased the uptake of adsorbed acetaldehyde, inhibited the formation of polymers, nevertheless, it induced the Csbnd O bond scission and CO formation with 40-50 K lower temperature after higher acetaldehyde exposure.

Defect annealing and thermal desorption of deuterium in low dose HFIR neutron-irradiated tungsten

DOE Office of Scientific and Technical Information (OSTI.GOV)

Masashi Shimada; M. Hara; T. Otsuka

2014-05-01

Accurately estimating tritium retention in plasma facing components (PFCs) and minimizing its uncertainty are key safety issues for licensing future fusion power reactors. D-T fusion reactions produce 14.1 MeV neutrons that activate PFCs and create radiation defects throughout the bulk of the material of these components. Recent studies show that tritium migrates and is trapped in bulk (>> 10 µm) tungsten beyond the detection range of nuclear reaction analysis technique [1-2], and thermal desorption spectroscopy (TDS) technique becomes the only established diagnostic that can reveal hydrogen isotope behavior in in bulk (>> 10 µm) tungsten. Radiation damage and its recoverymore » mechanisms in neutron-irradiated tungsten are still poorly understood, and neutron-irradiation data of tungsten is very limited. In this paper, systematic investigations with repeated plasma exposures and thermal desorption are performed to study defect annealing and thermal desorption of deuterium in low dose neutron-irradiated tungsten. Three tungsten samples (99.99 at. % purity from A.L.M.T. Co., Japan) irradiated at High Flux Isotope Reactor at Oak Ridge National Laboratory were exposed to high flux (ion flux of (0.5-1.0)x1022 m-2s-1 and ion fluence of 1x1026 m-2) deuterium plasma at three different temperatures (100, 200, and 500 °C) in Tritium Plasma Experiment at Idaho National Laboratory. Subsequently, thermal desorption spectroscopy (TDS) was performed with a ramp rate of 10 °C/min up to 900 °C, and the samples were annealed at 900 °C for 0.5 hour. These procedures were repeated three (for 100 and 200 °C samples) and four (for 500 °C sample) times to uncover damage recovery mechanisms and its effects on deuterium behavior. The results show that deuterium retention decreases approximately 90, 75, and 66 % for 100, 200, and 500 °C, respectively after each annealing. When subjected to the same TDS recipe, the desorption temperature shifts from 800 °C to 600 °C after 1st annealing for the sample exposed to TPE at 500 °C. Tritium Migration Analysis Program (TMAP) analysis reveals that the detrapping energy decreases from 1.8 eV to 1.4 eV, indicating the changes in trapping mechanisms. This paper also summarizes deuterium behavior studies in HFIR neutron-irradiated tungsten under US-Japan TITAN program.« less

Adsorption and Dissociation of CO2 on Ru(0001)

PubMed Central

2017-01-01

The adsorption and dissociation of carbon dioxide on a Ru(0001) single crystal surface was investigated by reflection–absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD) spectroscopy for CO2 adsorbed at 85 K. RAIRS spectroscopy shows that the adsorption of CO2 on a Ru(0001) single crystal is partially dissociative, resulting in CO2 and CO. The CO vibrational mode was also observed to split into two distinct modes, indicating two general populations of CO present at the surface. Furthermore, a time-dependent blue-shift is observed, which is characteristic of increasing CO surface coverage. TPD showed that coverages of up to 0.3 ML were obtained, and no evidence for chemisorption of oxygen on ruthenium was found. PMID:28413569

Adsorption and reaction of propene on Ni(100)

NASA Astrophysics Data System (ADS)

Kleyna, R.; Borgmann, D.; Wedler, G.

1998-05-01

Photoelectron spectroscopy (UPS, XPS) and thermal desorption techniques were used to study the chemisorption and decomposition reactions of propene on Ni(100). Propene is molecularly adsorbed at temperatures below 150 K. At saturation coverage the TD spectrum shows two propene desorption peaks at 155 and 225 K and three hydrogen desorption peaks at 300, 330 and 380 K with a shoulder at 420 K. No other desorbing species could be detected. The amount of desorption of propene was determined by XPS to be 20% of the saturation coverage. The electronic structure of adsorbed propene and the chemical nature of its decomposition products were deduced from UP and XP spectra taken at saturation coverage. Adsorption at low temperatures results in a π-bonded species which is stable up to 150 K. At temperatures above 150 K the UP spectra point to a σ-bonded species which decomposes further at temperatures above 260 K.

Adsorption and Desorption of Nickel(II) Ions from Aqueous Solution by a Lignocellulose/Montmorillonite Nanocomposite

PubMed Central

Zhang, Xiaotao; Wang, Ximing

2015-01-01

A new and inexpensive lignocellulose/montmorillonite (LNC/MMT) nanocomposite was prepared by a chemical intercalation of LNC into MMT and was subsequently investigated as an adsorbent in batch systems for the adsorption-desorption of Ni(II) ions in an aqueous solution. The optimum conditions for the Ni(II) ion adsorption capacity of the LNC/MMT nanocomposite were studied in detail by varying parameters such as the initial Ni(II) concentration, the solution pH value, the adsorption temperature and time. The results indicated that the maximum adsorption capacity of Ni(II) reached 94.86 mg/g at an initial Ni(II) concentration of 0.0032 mol/L, a solution pH of 6.8, an adsorption temperature of 70°C, and adsorption time of 40 min. The represented adsorption kinetics model exhibited good agreement between the experimental data and the pseudo-second-order kinetic model. The Langmuir isotherm equation best fit the experimental data. The structure of the LNC/MMT nanocomposite was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM), whereas the adsorption mechanism was discussed in combination with the results obtained from scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and Fourier-transform infrared spectroscopy analyses (FTIR). The desorption capacity of the LNC/MMT nanocomposite depended on parameters such as HNO3 concentration, desorption temperature, and desorption time. The satisfactory desorption capacity of 81.34 mg/g was obtained at a HNO3 concentration, desorption temperature, and desorption time of 0.2 mol/L, 60 ºC, and 30 min, respectively. The regeneration studies showed that the adsorption capacity of the LNC/MMT nanocomposite was consistent for five cycles without any appreciable loss in the batch process and confirmed that the LNC/MMT nanocomposite was reusable. The overall study revealed that the LNC/MMT nanocomposite functioned as an effective adsorbent in the detoxification of Ni(II)-contaminated wastewater. PMID:25647398

Evaluation of GeO desorption behavior in the metal∕GeO2∕Ge structure and its improvement of the electrical characteristics

PubMed Central

Oniki, Yusuke; Koumo, Hideo; Iwazaki, Yoshitaka; Ueno, Tomo

2010-01-01

The relation between germanium monoxide (GeO) desorption and either improvement or deterioration in electrical characteristics of metal∕GeO2∕Ge capacitors fabricated by thermal oxidation has been investigated. In the metal∕GeO2∕Ge stack, two processes of GeO desorption at different sites and at different temperatures were observed by thermal desorption spectroscopy measurements. The electrical characteristics of as-oxidized metal∕GeO2∕Ge capacitors shows a large flat-band voltage shift and minority carrier generation due to the GeO desorption from the GeO2∕Ge interface during oxidation of Ge substrates. On the other hand, the electrical properties were drastically improved by a postmetallization annealing at low temperature resulting in a metal catalyzed GeO desorption from the top interface. PMID:20644659

Mechanisms of deep benzene oxidation on the Pt(1 1 1) surface using temperature-programmed reaction methods

NASA Astrophysics Data System (ADS)

Marsh, Anderson L.; Gland, John L.

2003-06-01

The catalytic oxidation of benzene on the Pt(1 1 1) surface has been characterized using temperature-programmed reaction spectroscopy (TPRS) over a wide range of benzene and oxygen coverages. Coadsorbed atomic oxygen and benzene are the primary reactants on the surface during the initial oxidation step. Benzene is oxidized over the 300-500 K range to produce carbon dioxide and water. Carbon-hydrogen and carbon-carbon bond activation are clearly rate-limiting steps for these reactions. Preferential oxidation causes depletion of bridge-bonded benzene, suggesting enhanced reactivity in this bonding configuration. When oxygen is in excess on the surface, all of the surface carbon and hydrogen is oxidized. When benzene is in excess on the surface, hydrogen produced by dehydrogenation is desorbed after all of the surface oxygen has been consumed. Repulsive interactions between benzene and molecular oxygen dominate at low temperatures. Preadsorption of oxygen inhibits adsorption of less reactive benzene in threefold hollow sites. The desorption temperature of this non-reactive chemisorbed benzene decreases and overlaps with the multilayer desorption peak with increasing oxygen exposure. The results presented here provide a clear picture of rate-limiting steps during deep oxidation of benzene on the Pt(1 1 1) surface.

Changes induced on the surfaces of small Pd clusters by the thermal desorption of CO

NASA Technical Reports Server (NTRS)

Doering, D. L.; Poppa, H.; Dickinson, J. T.

1980-01-01

The stability and adsorption/desorption properties of supported Pd crystallites less than 5 nm in size were studied by Auger electron spectroscopy and repeated flash thermal desorption of CO. The Pd particles were grown epitaxially on heat-treated, UHV-cleaved mica at a substrate temperature of 300 C and a Pd impingement flux of 10 to the 13th atoms/sq cm s. Auger analysis allowed in situ measurement of relative particle dispersion and contamination, while FTD monitored the CO desorption properties. The results show that significant changes in the adsorption properties can be detected. Changes in the Pd Auger signal and the desorption spectrum during the first few thermal cycles are due to particle coalescence and facetting and the rate of this change is dependent on the temperature and duration of the desorption. Significant reductions in the amplitude of the desorptions peak occur during successive CO desorptions which are attributed to increases of surface carbon, induced by the desorption of CO. The contamination process could be reversed by heat treatment in oxygen or hydrogen

Growth of an Ultrathin Zirconia Film on Pt3Zr Examined by High-Resolution X-ray Photoelectron Spectroscopy, Temperature-Programmed Desorption, Scanning Tunneling Microscopy, and Density Functional Theory.

PubMed

Li, Hao; Choi, Joong-Il Jake; Mayr-Schmölzer, Wernfried; Weilach, Christian; Rameshan, Christoph; Mittendorfer, Florian; Redinger, Josef; Schmid, Michael; Rupprechter, Günther

2015-02-05

Ultrathin (∼3 Å) zirconium oxide films were grown on a single-crystalline Pt 3 Zr(0001) substrate by oxidation in 1 × 10 -7 mbar of O 2 at 673 K, followed by annealing at temperatures up to 1023 K. The ZrO 2 films are intended to serve as model supports for reforming catalysts and fuel cell anodes. The atomic and electronic structure and composition of the ZrO 2 films were determined by synchrotron-based high-resolution X-ray photoelectron spectroscopy (HR-XPS) (including depth profiling), low-energy electron diffraction (LEED), scanning tunneling microscopy (STM), and density functional theory (DFT) calculations. Oxidation mainly leads to ultrathin trilayer (O-Zr-O) films on the alloy; only a small area fraction (10-15%) is covered by ZrO 2 clusters (thickness ∼0.5-10 nm). The amount of clusters decreases with increasing annealing temperature. Temperature-programmed desorption (TPD) of CO was utilized to confirm complete coverage of the Pt 3 Zr substrate by ZrO 2 , that is, formation of a closed oxide overlayer. Experiments and DFT calculations show that the core level shifts of Zr in the trilayer ZrO 2 films are between those of metallic Zr and thick (bulklike) ZrO 2 . Therefore, the assignment of such XPS core level shifts to substoichiometric ZrO x is not necessarily correct, because these XPS signals may equally well arise from ultrathin ZrO 2 films or metal/ZrO 2 interfaces. Furthermore, our results indicate that the common approach of calculating core level shifts by DFT including final-state effects should be taken with care for thicker insulating films, clusters, and bulk insulators.

Low-Temperature Reduction of Graphene Oxide: Electrical Conductance and Scanning Kelvin Probe Force Microscopy

NASA Astrophysics Data System (ADS)

Slobodian, Oleksandr M.; Lytvyn, Peter M.; Nikolenko, Andrii S.; Naseka, Victor M.; Khyzhun, Oleg Yu.; Vasin, Andrey V.; Sevostianov, Stanislav V.; Nazarov, Alexei N.

2018-05-01

Graphene oxide (GO) films were formed by drop-casting method and were studied by FTIR spectroscopy, micro-Raman spectroscopy (mRS), X-ray photoelectron spectroscopy (XPS), four-points probe method, atomic force microscopy (AFM), and scanning Kelvin probe force (SKPFM) microscopy after low-temperature annealing at ambient conditions. It was shown that in temperature range from 50 to 250 °C the electrical resistivity of the GO films decreases by seven orders of magnitude and is governed by two processes with activation energies of 6.22 and 1.65 eV, respectively. It was shown that the first process is mainly associated with water and OH groups desorption reducing the thickness of the film by 35% and causing the resistivity decrease by five orders of magnitude. The corresponding activation energy is the effective value determined by desorption and electrical connection of GO flakes from different layers. The second process is mainly associated with desorption of oxygen epoxy and alkoxy groups connected with carbon located in the basal plane of GO. AFM and SKPFM methods showed that during the second process, first, the surface of GO plane is destroyed forming nanostructured surface with low work function and then at higher temperature a flat carbon plane is formed that results in an increase of the work function of reduced GO.

Desorption dynamics of deuterium in CuCrZr alloy

NASA Astrophysics Data System (ADS)

Thi Nguyen, Lan Anh; Lee, Sanghwa; Noh, S. J.; Lee, S. K.; Park, M. C.; Shu, Wataru; Pitcher, Spencer; Torcy, David; Guillermain, David; Kim, Jaeyong

2017-12-01

Desorption behavior of deuterium (D2) in CuCrZr alloy was investigated considering sample thickness, loading and baking temperature of deuterium followed by the ITER scopes. Cylindrical specimens of 1, 3, 5 mm thick with 4 mm diameter were exposed to deuterium at a pressure of 25 bar at 120, 240 and 350 °C for 24 h, then baked at 800 °C in a vacuum chamber maintained at a pressure lower than 10-7 Torr. Deuterium desorption characteristics such as desorption rate and amount of deuterium in the sample were estimated by analyzing the desorption peaks monitored with a residual gas analyzer (RGA), and the trapping energy of deuterium was calculated using thermal desorption spectroscopy (TDS). Secondary ion mass spectroscopy (SIMS) results showed that deuterium atoms embedded in the sample at a depth of less than 15 μm and desorbed as low as 400 °C. All absorbed deuterium atoms in the specimen were completely retrieved by dynamic pumping at 800 °C in 15 min. The desorption rate of deuterium per unit area was inversely proportional to the increment of the thickness of the sample, and was proportional to the loading temperature. Based on the assumption that a uniform distribution of interstitial sites for deuterium follows the Femi-Dirac statistics, the result of TDS demonstrated that the CuCrZr alloy has two types of trapping energies, which were estimated to be 62 and 79 kJ/mol.

Scanning tunnelling microscope for boron surface studies

NASA Astrophysics Data System (ADS)

Trenary, Michael

1990-10-01

The equipment purchased is to be used in an experimental study of the relationship between atomic structure and chemical reactivity for boron and carbon surfaces. This research is currently being supported by grant AFOSR-88-0111. A renewal proposal is currently pending with AFOSR to continue these studies. Carbon and boron are exceptionally stable, covalently bonded solids with highly unique crystal structures. The specific reactions to be studied are loosely related to the problems of oxidation and oxidation inhibition of carbon/carbon composites. The main experimental instrument to be used is a scanning tunneling microscope (STM) purchased under grant number AFSOR-89-0146. Other techniques to be used include Auger electron spectroscopy, X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), low energy electron diffraction (LEED), temperature programmed desorption (TPD) and scanning tunneling microscopy (STM).

The Effect of Platinum-coatings on Hydrogen- and Water-absorption and Desorption Characteristics of Lithium Zirconate

NASA Astrophysics Data System (ADS)

Tsuchiya, B.; Bandow, S.; Nagata, S.; Saito, K.; Tokunaga, K.; Morita, K.

Hydrogen (H)- and water (H2O)-storage and desorption characteristics of 25 nm thick Pt films onLi2ZrO3composite materials, exposed to normal air at room temperature, have been investigated by means of elastic recoil detection (ERD), Rutherford backscattering spectrometry (RBS), weight gain measurement (WGM), and thermal desorption spectroscopy (TDS) techniques. It was found by the ERD and TDS that H and H2O were absorbed into the Pt-coated Li2ZrO3 in air at room temperature and desorbed from it in vacuum at much low temperatures of approximately 317 and 309 K, respectively. In addition, the WGM and TDS spectra revealed that the absorption and desorption characters ofsome gases such as CH4, CO, and CO2including H as well as H2Ointo the Li2ZrO3 bulk were improved by Pt deposition.

Deuterium trapping in the carbon-silicon co-deposition layers prepared by RF sputtering in D2 atmosphere

NASA Astrophysics Data System (ADS)

Zhang, Hongliang; Zhang, Weiyuan; Su, Ranran; Tu, Hanjun; Shi, Liqun; Hu, Jiansheng

2018-04-01

Deuterated carbon-silicon layers co-deposited on graphite and silicon substrates by radio frequency magnetron sputtering in pure D2 plasma were produced to study deuterium trapping and characteristics of the C-Si layers. The C-Si co-deposited layers were examined by ion beam analysis (IBA), Raman spectroscopy (RS), infrared absorption (IR) spectroscopy, thermal desorption spectroscopy (TDS) and scanning electron microscopy (SEM). It was found that the growth rate of the C-Si co-deposition layer decreased with increasing temperature from 350 K to 800 K, the D concentration and C/Si ratios increased differently on graphite and silicon substrates. TDS shows that D desorption is mainly as D2, HD, HDO, CD4, and C2D4 and release peaks occurred at temperatures of less than 900 K. RS and IR analysis reveal that the structure of the C-Si layers became more disordered with increasing temperatures. Rounded areas of peeling with 1-2 μm diameters were observed on the surface.

The influence of calcination temperatures on the acid-based properties and catalytic activity for the 1,3-butadiene synthesis from ethanol/acetaldehyde mixture

NASA Astrophysics Data System (ADS)

Gao, Meixiang; Jiang, Haoxi; Zhang, Minhua

2018-05-01

The influences of the calcination temperature on the catalysts' acid-based properties and catalytic activity for the 1,3-butadiene synthesis from ethanol are investigated. The results show that the 2 wt% ZrO2/Nano-SiO2 calcined at 773 K shows the best performance with the selectivity of 93.18% and conversion of 58.52% when reacted at 593 K, a WHSV of 1.8 h-1 and 3.5:1 volume ratio ethanol-to-acetaldehyde in an atmospheric fixed-bed reactor. Prepared catalysts were characterized by N2 adsorption-desorption, XRD, temperature-programmed desorption of NH3 and CO2, FTIR spectroscopy of adsorbed pyridine and CO2. Based on the relationship between the catalyst activity and its properties, the fact can be presumed that the formation and strength of Zrsbnd Osbnd Si bond determines the acid-based properties of the catalyst. In addition, moderate-intensity weak acid-basic sites are more suitable for ethanol conversion to BD with the amount of acid and basic sites as close as possible.

Interactions between glycine and amorphous solid water nanoscale films

NASA Astrophysics Data System (ADS)

Tzvetkov, George; Koller, Georg; Netzer, Falko P.

2012-12-01

The interactions of glycine (Gly) with amorphous solid water (ASW) nanolayers (≤ 100 ML), vapor-deposited on single crystalline AlOx surfaces at 100 K, have been investigated by near-edge X-ray absorption fine structure spectroscopy (NEXAFS) at the oxygen K-edge, temperature-programmed thermal desorption (TPD), X-ray photoelectron spectroscopy (XPS), and temperature-dependent work function measurements. Gly-on-ASW, ASW-on-Gly, and Gly on top of ASW-on-Gly ultrathin films have been fabricated. In contrast to the uniform ASW films grown directly on the hydrophilic AlOx, water molecules adsorb on the hydrophobic Gly films in the form of 3D ASW clusters. This leads to significant differences in the NEXAFS and work function data obtained from ASW-on-AlOx and ASW-on-Gly films, respectively. Furthermore, these structural differences influence the chemical state of Gly molecules (neutral vs. zwitterionic) adsorbed on top of ASW films. N1s XPS measurements revealed an increased amount of neutral Gly molecules in the film top-deposited on the ASW-on-Gly structure in comparison to the neutral Gly in the films directly condensed on AlOx or grown on the ASW substrate. H2O TPD spectra demonstrate that the crystallization and desorption processes of ASW are affected in a different way by the Gly layers, top-deposited on to ASW-on-AlOx and ASW-on-Gly films. At the same time, Gly adlayers sink into the ASW film during crystallization/desorption of the latter and land softly on the alumina surface in the form of zwitterionic clusters.

MOF-74 as an Efficient Catalyst for the Low-Temperature Selective Catalytic Reduction of NOx with NH3.

PubMed

Jiang, Haoxi; Wang, Qianyun; Wang, Huiqin; Chen, Yifei; Zhang, Minhua

2016-10-12

In this work, Mn-MOF-74 with hollow spherical structure and Co-MOF-74 with petal-like shape have been prepared successfully via the hydrothermal method. The catalysts were characterized using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetry-mass spectrum analysis (TG-MS), N 2 adsorption/desorption, scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). It is found that MOF-74(Mn, Co) exhibits the capability for selective catalytic reduction (SCR) of NO x at low temperatures. Both experimental (temperature-programmed desorption, TPD) and computational methods have shown that Co-MOF-74 and Mn-MOF-74 owned high adsorption and activation abilities for NO and NH 3 . The catalytic activities of Mn-MOF-74 and Co-MOF-74 for low-temperature denitrification (deNO x ) in the presence of NH 3 were 99% at 220 °C and 70% at 210 °C, respectively. It is found that the coordinatively unsaturated metal sites (CUSs) in M-MOF-74 (M = Mn and Co) played important roles in SCR reaction. M-MOF-74 (M = Mn and Co), especially Mn-MOF-74, showed excellent catalytic performance for low-temperature SCR. In addition, in the reaction process, NO conversion on Mn-MOF-74 decreased with the introduction of H 2 O and SO 2 and almost recovered when gas was cut off. However, for Co-MOF-74, SO 2 almost has no effect on the catalytic activity. This work showed that MOF-74 could be used prospectively as deNO x catalyst.

New insights into proton surface mobility processes in PEMFC catalysts using isotopic exchange methods.

PubMed

Ferreira-Aparicio, Paloma

2009-09-01

The surface chemistry and the adsorption/desorption/exchange behavior of a proton-exchange membrane fuel cell catalyst are analyzed as a case study for the development of tailor-made support materials of enhanced performance and stability. By using H2, D2, and CO as probe molecules, the relevance of some surface functional groups of the catalyst support on several diffusion processes taking place during the adsorption is shown. Sulfonic groups associated with the vulcanized carbon black surface have been detected by means of spectroscopic techniques (X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy) and by analysis of the desorbed products during temperature-programmed desorption tests by mass spectrometry. Such hydrophilic species have been observed to favor proton surface mobility and exchange with Pt-adsorbed deuterium even in the presence of adsorbed CO. This behavior is relevant both for the proper characterization of these kinds of catalysts using adsorption probes and for the design of new surface-modified carbon supports, enabling alternative proton-transfer pathways throughout the catalytic layers toward the membrane.

Acidic Zeolite L as a Highly Efficient Catalyst for Dehydration of Fructose to 5-Hydroxymethylfurfural in Ionic Liquid.

PubMed

Ma, Zhongsen; Hu, Hualei; Sun, Zhongqiang; Fang, Wenting; Zhang, Jian; Yang, Longfei; Zhang, Yajie; Wang, Lei

2017-04-22

Zeolite L was synthesized by the hydrothermal method and post-treated by NH 4 exchange to adjust its acidity. The samples were systematic characterized by various techniques including XRD, X-ray fluorescence spectroscopy, N 2 adsorption-desorption, scanning electron microscopy, pyridine IR spectroscopy, and NH 3 temperature-programmed desorption. The results demonstrated that the NH 4 -exchange post-treatment increased the surface area, micropore volume, and acidity of zeolite L. The catalytic performance of the samples was tested in the dehydration of fructose to 5-hydroxymethylfurfural (HMF) in ionic liquid (1-butyl-3-methylimidazolium bromide, [bmim]Br). 99.1 % yield of HMF was obtained when the KL-80 °C-1 h sample (KL zeolite treated with 1 m NH 4 NO 3 solution at 80 °C for 1 h) was used. The high efficiency could be attributed to the appropriate acid properties of the catalyst. The zeolite catalyst could be reused four times without significant decrease in activity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spontaneous desorption and phase transitions of self-assembled alkanethiol and alicyclic thiol monolayers chemisorbed on Au(111) in ultrahigh vacuum at room temperature.

PubMed

Ito, Eisuke; Kang, Hungu; Lee, Dongjin; Park, Joon B; Hara, Masahiko; Noh, Jaegeun

2013-03-15

Scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) were used to examine the surface structure and adsorption conditions of hexanethiol (HT) and cyclohexanethiol (CHT) self-assembled monolayers (SAMs) on Au(111) as a function of storage period in ultrahigh vacuum (UHV) conditions of 3×10(-7) Pa at room temperature (RT). STM imaging revealed that after storage for 7 days, HT SAMs underwent phase transitions from c(4×2) phase to low coverage 4×√3 phase. This transition is due to a structural rearrangement of hexanethiolates that results from the spontaneous desorption of chemisorbed HT molecules on Au(111) surface. XPS measurements showed approximately 28% reduction in sulfur coverage, which indicates desorption of hexanethiolates from the surfaces. Contrary to HT SAMs, the structural order of CHT SAMs with (5×2√3)R35° phase completely disappeared after storage for 3 or 7 days. XPS results show desorption of more than 80% of the cyclohexanethiolates, even after storage for 3 days. We found that spontaneous desorption of CHT molecules on Au(111) in UHV at RT occurred quickly, whereas spontaneous desorption of HT molecules was much slower. Thermal desorption spectroscopy (TDS) results suggest CHT SAMs in UHV at RT can desorb more efficiently than HT SAMs due to formation of thiol desorption fragments that result from chemical reactions between surface hydrogen atoms and thiolates on Au(111) surfaces. This study clearly demonstrated that organic thiols chemisorbed on gold surfaces are desorbed spontaneously in UHV at RT and van der Waals interactions play an important role in determining the structural stability of thiolate SAMs in UHV. Copyright © 2012 Elsevier Inc. All rights reserved.

Alcohol Dehydration on Monooxo W=O and Dioxo O=W=O Species

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Zhenjun; Smid, Bretislav; Kim, Yu Kwon

2012-08-16

The dehydration of 1-propanol on nanoporous WO3 films prepared via ballistic deposition at ~20 K has been investigated using temperature programmed desorption, infrared reflection absorption spectroscopy and density functional theory. The as deposited films are extremely efficient in 1-propanol dehydration to propene. This activity is correlated with the presence of dioxo O=W=O groups while monooxo W=O species are shown to be inactive. Annealing of the film induces densification that results in the loss of catalytic activity due to annihilation O=W=O species.

Desorption of Hg(II) and Sb(V) on extracellular polymeric substances: effects of pH, EDTA, Ca(II) and temperature shocks.

PubMed

Zhang, Daoyong; Lee, Duu-Jong; Pan, Xiangliang

2013-01-01

Extracellular polymeric substances (EPS) existed ubiquitously in biological systems affect the mobility and availability of heavy metals in the environments. The adsorption-desorption behaviors of Hg(II) and Sb(V) on EPS were investigated. The sorption rates follow Sb(V) > Hg(II), and the desorption rates follow reverse order. Applications of ethylene diamine tetraacetic acid (EDTA), Ca(II) and pH shocks affect desorption rates and desorbed quantities of Hg(II) from EPS-Hg complex. Temperature shock minimally affects the desorption rate of Hg(II). Conversely, the EPS-Sb complex is stable subjected to EDTA, Ca(II), temperature or pH shocks. The excitation-emission matrix (EEM) fluorescence spectroscopy and fast-Fourier (FT-IR) analysis showed that Hg(II) and Sb(V) principally interacted with polysaccharides and protein-like compounds in the EPS, respectively. The EPS-Hg complex presents a time bomb that may release high levels of Hg(II) in short time period under environmental shocks. Copyright © 2012 Elsevier Ltd. All rights reserved.

Interaction of dimethylamine with clean and partially oxidized copper surfaces

NASA Astrophysics Data System (ADS)

Kelber, J. A.; Rogers, J. W.; Banse, B. A.; Koel, B. E.

1990-05-01

The interaction of dimethylamine (DMA) with partially oxidized polycrystalline copper [Cu(poly)] and clean and partially oxidized Cu(110) between 110 and 500 K has been examined using electron stimulated desorption (ESD), high resolution electron energy loss spectroscopy (HREELS) and temperature programmed desorption (TPD). ESD mass spectra of the DMA adsorbed on O/Cu(poly) between 112 and 230 K consistently display peaks at 44 amu [(CH 3) 2N] + and 46 amu [(CH 3) 2NH-H] +, but no significant parent peak at 45 amu [(CH 3) 2NH] +, even though this last feature is prominent in the gas-phase mass spectrum. OH - is not observed at temperatures below 184 K and the yield at higher temperatures is much less than that of O +. HREELS of DMA on clean and oxygen covered Cu(110) obtained at temperatures between 100 and 320 K show characteristic vibrational spectra for molecular DMA and no OH(a) vibrational modes. TPD results show that the desorption profiles of all the major peaks in the DMA mass spectrum follow that of the parent peak with no evidence for production of H 2O. The ESD, HREELS and TPD results all indicate that DMA is molecularly and reversibly adsorbed, with no significant formation of surface hydroxyl species. The results indicate that preferential adsorption of amines from amine/epoxy mixtures onto metal oxide surfaces could passivate the surface and prevent subsequent bonding to the epoxy resin.

Heterogeneous catalytic ozonation of hydroquinone using sewage sludge-derived carbonaceous catalysts.

PubMed

Xu, Jinglu; Yu, Yang; Ding, Kang; Liu, Zhiying; Wang, Lei; Xu, Yanhua

2018-03-01

This study converted sewage sludge into a carbonaceous catalyst via pyrolysis and employed it in the ozonation of hydroquinone. The catalyst was characterized by Mössbauer spectroscopy, X-ray photoelectron spectroscopy, temperature programmed desorption, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy and X-ray diffraction. Intermediate products were detected by gas chromatography-mass spectrometry, and a pathway for hydroquinone degradation was proposed. The results showed that sludge pyrolyzed at 700 °C promoted hydroquinone degradation, compared with commercial activated carbon derived from coal. When the catalyst dose was 0.5 g/L, the hydroquinone (200 mg/L) removal rate reached 97.86% after exposure to ozone (the ozone concentration was 17 mg/L and the flow rate was 50 mL/min) for 60 min. The results indicated that basic groups contributed to the catalysis.

The temperature and ion energy dependence of deuterium retention in lithium films

NASA Astrophysics Data System (ADS)

Buzi, Luxherta; Koel, Bruce E.; Skinner, Charles H.

2016-10-01

Lithium conditioning of plasma facing components in magnetic fusion devices has improved plasma performance and lowered hydrogen recycling. For applications of lithium in future high heat flux and long pulse duration machines it is important to understand and parameterize deuterium retention in lithium. This work presents surface science studies of deuterium retention in lithium films as a function of surface temperature, incident deuterium ion energy and flux. Initial experiments are performed on thin (3-30 ML) lithium films deposited on a single crystal molybdenum substrate to avoid effects due to grain boundaries, intrinsic defects and impurities. A monoenergetic and mass-filtered deuterium ion beam was generated in a differentially pumped Colutron ion gun. Auger electron spectroscopy and X-ray photoelectron spectroscopy were used to identify the elemental composition and temperature programmed desorption was used to measure the deuterium retention under the different conditions. Support was provided through DOE Contract Number DE-AC02-09CH11466.

Annealing effect reversal by water sorption-desorption and heating above the glass transition temperature-comparison of properties.

PubMed

Saxena, A; Jean, Y C; Suryanarayanan, R

2013-08-05

Our objective is to compare the physical properties of materials obtained from two different methods of annealing reversal, that is, water sorption-desorption (WSD) and heating above glass transition temperature (HAT). Trehalose was annealed by storing at 100 °C for 120 h. The annealing effect was reversed either by WSD or HAT, and the resulting materials were characterized by differential scanning calorimetry (DSC), water sorption studies, and positron annihilation spectroscopy (PAS). While the products obtained by the two methods of annealing reversal appeared to be identical by conventional characterization methods, they exhibited pronounced differences in their water sorption behavior. Positron annihilation spectroscopy (PAS), by measuring the fractional free volume changes in the processed samples, provided a mechanistic explanation for the differences in the observed behavior.

Dynamic Moisture Sorption and Desorption in Fumed Silica-filled Silicone Foam

DOE Office of Scientific and Technical Information (OSTI.GOV)

Trautschold, Olivia Carol

Characterizing dynamic moisture sorption and desorption in fumed silica-filled silicone foam is necessary for determining material compatibilities and life predictions, particularly in sealed environments that may be exposed to a range of environmental conditions. Thermogravimetric analysis (TGA) and near infrared spectroscopy (NIR) were performed on S5470 fumed silica-filled silicone foam to determine the weight percent of moisture at saturation. Additionally, TGA was used to determine the time, temperature, and relative humidity levels required for sorption and desorption of physisorbed moisture in S5470.

Growth kinetics of indium metal atoms on Si(1 1 2) surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Raj, Vidur; Chauhan, Amit Kumar Singh; Gupta, Govind, E-mail: govind@nplindia.org

Graphical abstract: Controlled growth of indium atoms on Si(1 1 2) surface has been carried out systematically and the influence of substrate temperature on the kinetics is analysed under various growth conditions. Temperature induced anomalous layer-to-clusters transformation during thermal desorption has also been reported. - Highlights: • Controlled growth of indium atoms on Si(1 1 2) surface & their thermal stability. • Influence of substrate temperature on the kinetics under various growth conditions. • Temperature induced layer-to-clusters transformation during thermal desorption. - Abstract: The growth kinetics and desorption behavior of indium (In) atoms grown on high index Si(1 1 2)more » surface at different substrate temperatures has been studied. Auger electron spectroscopy analysis revealed that In growth at room temperature (RT) and high substrate temperature (HT) ∼250 °C follows Frank–van der Merve growth mode whereas at temperatures ≥450 °C, In growth evolves through Volmer–Weber growth mode. Thermal desorption studies of RT and 250 °C grown In/Si(1 1 2) systems show temperature induced rearrangement of In atoms over Si(1 1 2) surface leading to clusters to layer transformation. The monolayer and bilayer desorption energies for RT grown In/Si(1 1 2) system are calculated to be 2.5 eV and 1.52 eV, while for HT-250 °C the values are found to be 1.6 eV and 1.3 eV, respectively. This study demonstrates the effect of temperature on growth kinetics as well as on the multilayer/monolayer desorption pathway of In on Si(1 1 2) surface.« less

Low-temperature CO oxidation on Ni(111) and on a Au/Ni(111) surface alloy.

PubMed

Knudsen, Jan; Merte, Lindsay R; Peng, Guowen; Vang, Ronnie T; Resta, Andrea; Laegsgaard, Erik; Andersen, Jesper N; Mavrikakis, Manos; Besenbacher, Flemming

2010-08-24

From an interplay between scanning tunneling microscopy, temperature programmed desorption, X-ray photoelectron spectroscopy, and density functional theory calculations we have studied low-temperature CO oxidation on Au/Ni(111) surface alloys and on Ni(111). We show that an oxide is formed on both the Ni(111) and the Au/Ni(111) surfaces when oxygen is dosed at 100 K, and that CO can be oxidized at 100 K on both of these surfaces in the presence of weakly bound oxygen. We suggest that low-temperature CO oxidation can be rationalized by CO oxidation on O(2)-saturated NiO(111) surfaces, and show that the main effect of Au in the Au/Ni(111) surface alloy is to block the formation of carbonate and thereby increase the low-temperature CO(2) production.

A temperature-programmed X-ray photoelectron spectroscopy (TPXPS) study of chlorine adsorption and diffusion on Ag(1 1 1)

NASA Astrophysics Data System (ADS)

Piao, H.; Adib, K.; Barteau, Mark A.

2004-05-01

Synchrotron-based temperature programmed X-ray photoelectron spectroscopy (TPXPS) has been used to investigate the surface chloridation of Ag(1 1 1) to monolayer coverages. At 100 K both atomic and molecular chlorine species are present on the surface; adsorption at 300 K or annealing the adlayer at 100 K to this temperature generates adsorbed Cl atoms. As the surface is heated from 300 to 600 K, chlorine atoms diffuse below the surface, as demonstrated by attenuation of the Cl2p signals in TPXPS experiments. Quantitative analysis of the extent of attenuation is consistent with chlorine diffusion below the topmost silver layer. For coverages in the monolayer and sub-monolayer regime, chlorine diffusion to and from the bulk appears not to be significant, in contrast to previous results obtained at higher chlorine loadings. Chlorine is removed from the surface at 650-780 K by desorption as AgCl. These results demonstrate that chlorine diffusion beneath the surface does occur at coverages and temperatures relevant to olefin epoxidation processes carried out on silver catalysts with chlorine promoters. The surface sensitivity advantages of synchrotron-based XPS experiments were critical to observing Cl diffusion to the sub-surface at low coverages.

Fast hydrogen sorption from MgH2-VO2(B) composite materials

NASA Astrophysics Data System (ADS)

Milošević, Sanja; Kurko, Sandra; Pasquini, Luca; Matović, Ljiljana; Vujasin, Radojka; Novaković, Nikola; Novaković, Jasmina Grbović

2016-03-01

The hydrogen sorption kinetics of MgH2‒VO2(B) composites synthesised by mechanical milling have been studied. The microstructural properties of composites were characterized by means of X-ray diffraction (XRD), Raman spectroscopy, Scanning electron microscopy (SEM), Particle size analysis (PSD), while sorption behaviour was followed by differential scanning calorimetry (DSC) and Sievert measurements. Results have shown that although desorption temperature reduction is moderate; there is a substantial improvement in hydrogen sorption kinetics. The complete desorption of pure MgH2 at elevated temperature takes place in more than 30 min while the composite fully desorbs in less than 2 min even at lower temperatures. It has been shown that the metastable γ-MgH2 phase and the point defects have a decisive role in desorption process only in the first sorption cycle, while the second and the subsequent sorption cycles are affected by microstructural and morphological characteristics of the composite.

Thermal and FTIR spectroscopic analysis of the interactions of aniline adsorbed on to MCM-41 mesoporous material.

PubMed

Eimer, Griselda A; Gómez Costa, Marcos B; Pierella, Liliana B; Anunziata, Oscar A

2003-07-15

The adsorption of aniline on Na-AlMCM-41 synthesized by us has been characterized by infrared spectroscopy, temperature programmed desorption (TPD), and differential thermal analysis methods. Aniline would be mostly bound to the mesostructure through weak pi interactions. On the mesostructure containing adsorbed water, the co-adsorption of aniline could occur by weak hydrogen bonding through surface water molecules. For water, two possible modes of adsorption have been identified. Different associations between aniline and hydrated and nonhydrated mesostructures have been evaluated in order to favor the posterior in situ polymerization of adsorbed aniline.

Desorption Kinetics of Methanol, Ethanol, and Water from Graphene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, R. Scott; Matthiesen, Jesper; Kay, Bruce D.

2014-09-18

The desorption kinetics of methanol, ethanol, and water from graphene covered Pt(111) are investigated. The temperature programmed desorption (TPD) spectra for both methanol and ethanol have well-resolved first, second, third, and multilayer layer desorption peaks. The alignment of the leading edges is consistent with zero-order desorption kinetics from all layers. In contrast, for water the first and second layers are not resolved. At low water coverages (< 1 ML) the initial desorption leading edges are aligned but then fall out of alignment at higher temperatures. For thicker water layers (10 to 100 ML), the desorption leading edges are in alignmentmore » throughout the desorption of the film. The coverage dependence of the desorption behavoir suggests that at low water coverages the non-alignment of the desorption leading edges is due to water dewetting from the graphene substrate. Kinetic simulations reveal that the experimental results are consistent with zero-order desorption. The simulations also show that fractional order desorption kinetics would be readily apparent in the experimental TPD spectra.« less

Desorption kinetics of methanol, ethanol, and water from graphene.

PubMed

Smith, R Scott; Matthiesen, Jesper; Kay, Bruce D

2014-09-18

The desorption kinetics of methanol, ethanol, and water from graphene covered Pt(111) are investigated. The temperature programmed desorption (TPD) spectra for both methanol and ethanol have well-resolved first, second, third, and multilayer layer desorption peaks. The alignment of the leading edges is consistent with zero-order desorption kinetics from all layers. In contrast, for water, the first and second layers are not resolved. At low water coverages (<1 monolayer (ML)) the initial desorption leading edges are aligned but then fall out of alignment at higher temperatures. For thicker water layers (10-100 ML), the desorption leading edges are in alignment throughout the desorption of the film. The coverage dependence of the desorption behavoir suggests that at low water coverages the nonalignment of the desorption leading edges is due to water dewetting from the graphene substrate. Kinetic simulations reveal that the experimental results are consistent with zero-order desorption. The simulations also show that fractional order desorption kinetics would be readily apparent in the experimental TPD spectra.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, R. Scott; Kay, Bruce D.

The desorption kinetics for benzene and cyclohexane from a graphene covered Pt(111) surface were investigated using temperature programmed desorption (TPD). The benzene desorption spectra show well-resolved monolayer and multilayer desorption peaks. The benzene monolayer TPD spectra have the same desorption peak temperature and have line shapes which are consistent with first-order desorption kinetics. For benzene coverages greater than 1 ML, the TPD spectra align on a common leading edge which is consistent with zero-order desorption. An inversion analysis of the monolayer benzene TPD spectra yielded a desorption activation energy of 54 ± 3 kJ/mol with a prefactor of 1017 ±more » 1 s-1. The TPD spectra for cyclohexane also have well-resolved monolayer and multilayer desorption features. The desorption leading edges for the monolayer and the multilayer TPD spectra are aligned indicating zero-order desorption kinetics in both cases. An Arrhenius analysis of the monolayer cyclohexane TPD spectra yielded a desorption activation energy of 53.5 ± 2 kJ/mol with a prefactor of 1016 ± 1 ML s-1.« less

Thermal desorption spectroscopy of high fluence irradiated ultrafine and nanocrystalline tungsten: helium trapping and desorption correlated with morphology

NASA Astrophysics Data System (ADS)

El-Atwani, O.; Taylor, C. N.; Frishkoff, J.; Harlow, W.; Esquivel, E.; Maloy, S. A.; Taheri, M. L.

2018-01-01

Microstructural changes due to displacement damage and helium desorption are two phenomena that occur in tungsten plasma facing materials in fusion reactors. Nanocrystalline metals are being investigated as radiation tolerant materials that can mitigate these microstructural changes and better trap helium along their grain boundaries. Here, we investigate the performance of three tungsten grades (nanocrystalline, ultrafine and ITER grade tungsten), exposed to a high fluence of 4 keV helium at both RT and 773 K, during a thermal desorption spectroscopy (TDS) experiment. An investigation of the microstructure in pre-and post-TDS sample sets was performed. The amount of desorbed helium was shown to be highest in the ITER grade tungsten and lowest in the nanocrystalline tungsten. Correlating the desorption spectra and the microstructure (grain boundaries decorated with nanopores and crack formation) and comparing with previous literature on coarse grained tungsten samples at similar irradiation and TDS conditions, revealed the importance of grain boundaries in trapping helium and limiting helium desorption up to a high temperature of 1350 K in agreement with transmission electron microscopy studies on helium irradiated tungsten which showed preferential and large facetted bubble formation along the grain boundaries in the nanocrystalline tungsten grade.

Thermal desorption spectroscopy of high fluence irradiated ultrafine and nanocrystalline tungsten: helium trapping and desorption correlated with morphology

DOE PAGES

El-Atwani, Osman; Taylor, Chase N.; Frishkoff, James; ...

2017-11-09

Here, microstructural changes due to displacement damage and helium desorption are two phenomena that occur in tungsten plasma facing materials in fusion reactors. Nanocrystalline metals are being investigated as radiation tolerant materials that can mitigate these microstructural changes and better trap helium along their grain boundaries. Here, we investigate the performance of three tungsten grades (nanocrystalline, ultrafine and ITER grade tungsten), exposed to a high fluence of 4 keV helium at both RT and 773 K, during a thermal desorption spectroscopy (TDS) experiment. An investigation of the microstructure in pre-and post-TDS sample sets was performed. The amount of desorbed heliummore » was shown to be highest in the ITER grade tungsten and lowest in the nanocrystalline tungsten. Correlating the desorption spectra and the microstructure (grain boundaries decorated with nanopores and crack formation) and comparing with previous literature on coarse grained tungsten samples at similar irradiation and TDS conditions, revealed the importance of grain boundaries in trapping helium and limiting helium desorption up to a high temperature of 1350 K in agreement with transmission electron microscopy studies on helium irradiated tungsten which showed preferential and large facetted bubble formation along the grain boundaries in the nanocrystalline tungsten grade.« less

Low-energy electron-induced reactions in condensed matter

NASA Astrophysics Data System (ADS)

Arumainayagam, Christopher R.; Lee, Hsiao-Lu; Nelson, Rachel B.; Haines, David R.; Gunawardane, Richard P.

2010-01-01

The goal of this review is to discuss post-irradiation analysis of low-energy (≤50 eV) electron-induced processes in nanoscale thin films. Because electron-induced surface reactions in monolayer adsorbates have been extensively reviewed, we will instead focus on low-energy electron-induced reactions in multilayer adsorbates. The latter studies, involving nanoscale thin films, serve to elucidate the pivotal role that the low-energy electron-induced reactions play in high-energy radiation-induced chemical reactions in condensed matter. Although electron-stimulated desorption (ESD) experiments conducted during irradiation have yielded vital information relevant to primary or initial electron-induced processes, we wish to demonstrate in this review that analyzing the products following low-energy electron irradiation can provide new insights into radiation chemistry. This review presents studies of electron-induced reactions in nanoscale films of molecular species such as oxygen, nitrogen trifluoride, water, alkanes, alcohols, aldehydes, ketones, carboxylic acids, nitriles, halocarbons, alkane and phenyl thiols, thiophenes, ferrocene, amino acids, nucleotides, and DNA using post-irradiation techniques such as temperature-programmed desorption (TPD), reflection-absorption infrared spectroscopy (RAIRS), X-ray photoelectron spectroscopy (XPS), high-resolution electron energy loss spectroscopy (HREELS), gel electrophoresis, and microarray fluorescence. Post-irradiation temperature-programmed desorption, in particular, has been shown to be useful in identifying labile radiolysis products as demonstrated by the first identification of methoxymethanol as a reaction product of methanol radiolysis. Results of post-irradiation studies have been used not only to identify radiolysis products, but also to determine the dynamics of electron-induced reactions. For example, studies of the radiolysis yield as a function of incident electron energy have shown that dissociative electron attachment plays an important role in the electron-induced single strand breaks in DNA leading to mutagenic damage. Studies such as these not only provide insight into the fundamentals of electron-molecule interactions in the condensed phase but also may provide information valuable to (a) furthering cost-efficient destruction of hazardous chemicals, (b) understanding the electron-induced decomposition of feed gases used in the plasma processing of semiconductor devices, (c) clarifying the role, if any, of low-energy electrons, produced by cosmic rays, contributing to the formation of the ozone hole by interacting with halocarbons and producing Cl atoms, (d) illuminating the dynamics of electron-induced oligomerization and/or polymerization, and (e) explicating the astrochemistry of icy grains.

Synthesis of Ternary Borocarbonitrides by High Temperature Pyrolysis of Ethane 1,2-Diamineborane

PubMed Central

Leardini, Fabrice; Massimi, Lorenzo; Flores-Cuevas, Eduardo; Fernández, Jose Francisco; Ares, Jose Ramon; Betti, Maria Grazia; Mariani, Carlo

2015-01-01

Ethane 1,2-diamineborane (EDAB) is an alkyl-containing amine-borane adduct with improved hydrogen desorption properties as compared to ammonia borane. In this work, it is reported the high temperature thermolytic decomposition of EDAB. Thermolysis of EDAB has been investigated by concomitant thermogravimetry-differential thermal analysis-mass spectrometry experiments. EDAB shows up to four H2 desorption events below 1000 °C. Small fractions of CH4, C2H4 and CO/CO2 are also observed at moderate-high temperatures. The solid-state thermolysis product has been characterized by means of different structural and chemical methods, such as X-ray diffraction, Raman spectroscopy, Scanning electron microscopy, Elemental analysis, and X-ray photoelectron spectroscopy (XPS). The obtained results indicate the formation of a ternary borocarbonitride compound with a poorly-crystalline graphitic-like structure. By contrast, XPS measurements show that the surface is rich in carbon and nitrogen oxides, which is quite different to the bulk of the material. PMID:28793545

Ellipsometry-based combination of isothermal sorption-desorption measurement and temperature programmed desorption technique: A probe for interaction of thin polymer films with solvent vapor.

PubMed

Efremov, Mikhail Yu; Nealey, Paul F

2018-05-01

An environmental chamber equipped with an in situ spectroscopic ellipsometer, programmatic vapor pressure control, and variable temperature substrate holder has been designed for studying polymer coating behavior during an exposure to a solvent vapor and also for probing the residual solvent in the film afterwards. Both sorption-desorption cycle at a constant temperature and temperature programmed desorption (TPD) of the residual solvent manifest themselves as a change of the film thickness. Monitoring of ellipsometric angles of the coating allows us to determine the thickness as a function of the vapor pressure or sample temperature. The solvent vapor pressure is precisely regulated by a computer-controlled pneumatics. TPD spectra are recorded during heating of the film in an oil-free vacuum. The vapor pressure control system is described in detail. The system has been tested on 6-170 nm thick polystyrene, poly(methyl methacrylate), and poly(2-vinyl pyridine) films deposited on silicon substrates. Liquid toluene, water, ethanol, isopropanol, cyclohexane, 1,2-dichloroethane, and chlorobenzene were used to create a vapor atmosphere. Typical sorption-desorption and TPD curves are shown. The instrument achieves sub-monolayer sensitivity for adsorption studies on flat surfaces. Polymer-solvent vapor systems with strong interaction demonstrate characteristic absorption-desorption hysteresis spanning from vacuum to the glass transition pressure. Features on the TPD curves can be classified as either glass transition related film contraction or low temperature broad contraction peak. Typical absorption-desorption and TPD dependencies recorded for the 6 nm thick polystyrene film demonstrate the possibility to apply the presented technique for probing size effects in extremely thin coatings.

Ellipsometry-based combination of isothermal sorption-desorption measurement and temperature programmed desorption technique: A probe for interaction of thin polymer films with solvent vapor

NASA Astrophysics Data System (ADS)

Efremov, Mikhail Yu.; Nealey, Paul F.

2018-05-01

An environmental chamber equipped with an in situ spectroscopic ellipsometer, programmatic vapor pressure control, and variable temperature substrate holder has been designed for studying polymer coating behavior during an exposure to a solvent vapor and also for probing the residual solvent in the film afterwards. Both sorption-desorption cycle at a constant temperature and temperature programmed desorption (TPD) of the residual solvent manifest themselves as a change of the film thickness. Monitoring of ellipsometric angles of the coating allows us to determine the thickness as a function of the vapor pressure or sample temperature. The solvent vapor pressure is precisely regulated by a computer-controlled pneumatics. TPD spectra are recorded during heating of the film in an oil-free vacuum. The vapor pressure control system is described in detail. The system has been tested on 6-170 nm thick polystyrene, poly(methyl methacrylate), and poly(2-vinyl pyridine) films deposited on silicon substrates. Liquid toluene, water, ethanol, isopropanol, cyclohexane, 1,2-dichloroethane, and chlorobenzene were used to create a vapor atmosphere. Typical sorption-desorption and TPD curves are shown. The instrument achieves sub-monolayer sensitivity for adsorption studies on flat surfaces. Polymer-solvent vapor systems with strong interaction demonstrate characteristic absorption-desorption hysteresis spanning from vacuum to the glass transition pressure. Features on the TPD curves can be classified as either glass transition related film contraction or low temperature broad contraction peak. Typical absorption-desorption and TPD dependencies recorded for the 6 nm thick polystyrene film demonstrate the possibility to apply the presented technique for probing size effects in extremely thin coatings.

Synthesis of core-shell structured FAU/SBA-15 composite molecular sieves and their performance in catalytic cracking of polystyrene

NASA Astrophysics Data System (ADS)

Du, Jinlong; Shi, Chunwei; Wu, Wenyuan; Bian, Xue; Chen, Ping; Cui, Qingzhu; Cui, Zhixuan

2017-12-01

Composite molecular sieves, FAU/SBA-15, having core-shell structure were synthesized. The synthesized composite sieves were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS), pyrolysis fourier transform infrared (Py-FTIR) spectroscopy, temperature programmed desorption spectra (NH3-TPD), UV Raman spectroscopy, nuclear magnetic resonance (NMR) and other techniques. XRD, SEM, TEM, N2 adsorption-desorption, mass spectrometry, NMR and EDS results showed that the composite molecular sieve contained two pore channels. Py-FTIR results showed that the addition of HY molecular sieves improved the acidity of the composite zeolite. The crystallization mechanism during the growth of FAU/SBA-15 shell was deduced from the influence of crystallization time on the synthesis of FAU/SBA-15 core-shell structured composite molecular sieve. HY dissociated partially in H2SO4 solution, and consisted of secondary structural units. This framework structure was more stable than its presence in the isolated form on the same ring or in the absence of Al. Thus it played a guiding role and connected with SBA-15 closely through the Si-O bond. This resulted in the gradual covering of the exterior surface of FAU phase by SBA-15 molecular sieves. The presence of SBA-15 restricted the formation of the other high mass components and increased the selectivity towards ethylbenzene.

Reactivity and reaction intermediates for acetic acid adsorbed on CeO 2(111)

DOE PAGES

Calaza, Florencia C.; Chen, Tsung -Liang; Mullins, David R.; ...

2015-05-02

Adsorption and reaction of acetic acid on a CeO 2(1 1 1) surface was studied by a combination of ultra-highvacuum based methods including temperature desorption spectroscopy (TPD), soft X-ray photoelectronspectroscopy (sXPS), near edge X-ray absorption spectroscopy (NEXAFS) and reflection absorption IRspectroscopy (RAIRS), together with density functional theory (DFT) calculations. TPD shows that thedesorption products are strongly dependent upon the initial oxidation state of the CeO 2 surface, includingselectivity between acetone and acetaldehyde products. The combination of sXPS and NEXAFS demon-strate that acetate forms upon adsorption at low temperature and is stable to above 500 K, above whichpoint ketene, acetone andmore » acetic acid desorb. Furthermore, DFT and RAIRS show that below 500 K, bridge bondedacetate coexists with a moiety formed by adsorption of an acetate at an oxygen vacancy, formed bywater desorption.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

King, Sean W., E-mail: sean.king@intel.com; Davis, Robert F.; Carter, Richard J.

The desorption kinetics of molecular hydrogen (H{sub 2}) from silicon (001) surfaces exposed to aqueous hydrogen fluoride and remote hydrogen plasmas were examined using temperature programmed desorption. Multiple H{sub 2} desorption states were observed and attributed to surface monohydride (SiH), di/trihydride (SiH{sub 2/3}), and hydroxide (SiOH) species, subsurface hydrogen trapped at defects, and hydrogen evolved during the desorption of surface oxides. The observed surface hydride species were dependent on the surface temperature during hydrogen plasma exposure with mono, di, and trihydride species being observed after low temperature exposure (150 °C), while predominantly monohydride species were observed after higher temperature exposure (450 °C).more » The ratio of surface versus subsurface H{sub 2} desorption was also found to be dependent on the substrate temperature with 150 °C remote hydrogen plasma exposure generally leading to more H{sub 2} evolved from subsurface states and 450 °C exposure leading to more H{sub 2} desorption from surface SiH{sub x} species. Additional surface desorption states were observed, which were attributed to H{sub 2} desorption from Si (111) facets formed as a result of surface etching by the remote hydrogen plasma or aqueous hydrogen fluoride treatment. The kinetics of surface H{sub 2} desorption were found to be in excellent agreement with prior investigations of silicon surfaces exposed to thermally generated atomic hydrogen.« less

Desorption and sublimation kinetics for fluorinated aluminum nitride surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

King, Sean W., E-mail: sean.king@intel.com; Davis, Robert F.; Nemanich, Robert J.

2014-09-01

The adsorption and desorption of halogen and other gaseous species from surfaces is a key fundamental process for both wet chemical and dry plasma etch and clean processes utilized in nanoelectronic fabrication processes. Therefore, to increase the fundamental understanding of these processes with regard to aluminum nitride (AlN) surfaces, temperature programmed desorption (TPD) and x-ray photoelectron spectroscopy (XPS) have been utilized to investigate the desorption kinetics of water (H{sub 2}O), fluorine (F{sub 2}), hydrogen (H{sub 2}), hydrogen fluoride (HF), and other related species from aluminum nitride thin film surfaces treated with an aqueous solution of buffered hydrogen fluoride (BHF) dilutedmore » in methanol (CH{sub 3}OH). Pre-TPD XPS measurements of the CH{sub 3}OH:BHF treated AlN surfaces showed the presence of a variety of Al-F, N-F, Al-O, Al-OH, C-H, and C-O surfaces species in addition to Al-N bonding from the AlN thin film. The primary species observed desorbing from these same surfaces during TPD measurements included H{sub 2}, H{sub 2}O, HF, F{sub 2}, and CH{sub 3}OH with some evidence for nitrogen (N{sub 2}) and ammonia (NH{sub 3}) desorption as well. For H{sub 2}O, two desorption peaks with second order kinetics were observed at 195 and 460 °C with activation energies (E{sub d}) of 51 ± 3 and 87 ± 5 kJ/mol, respectively. Desorption of HF similarly exhibited second order kinetics with a peak temperature of 475 °C and E{sub d} of 110 ± 5 kJ/mol. The TPD spectra for F{sub 2} exhibited two peaks at 485 and 585 °C with second order kinetics and E{sub d} of 62 ± 3 and 270 ± 10 kJ/mol, respectively. These values are in excellent agreement with previous E{sub d} measurements for desorption of H{sub 2}O from SiO{sub 2} and AlF{sub x} from AlN surfaces, respectively. The F{sub 2} desorption is therefore attributed to fragmentation of AlF{sub x} species in the mass spectrometer ionizer. H{sub 2} desorption exhibited an additional high temperature peak at 910 °C with E{sub d} = 370 ± 10 kJ/mol that is consistent with both the dehydrogenation of surface AlOH species and H{sub 2} assisted sublimation of AlN. Similarly, N{sub 2} exhibited a similar higher temperature desorption peak with E{sub d} = 535 ± 40 kJ/mol that is consistent with the activation energy for direct sublimation of AlN.« less

Adsorption of acrolein, propanal, and allyl alcohol on Pd(111): a combined infrared reflection–absorption spectroscopy and temperature programmed desorption study

PubMed Central

Dostert, Karl-Heinz; O'Brien, Casey P.; Mirabella, Francesca; Ivars-Barceló, Francisco

2016-01-01

Atomistic-level understanding of the interaction of α,β-unsaturated aldehydes and their derivatives with late transition metals is of fundamental importance for the rational design of new catalytic materials with the desired selectivity towards C 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 C vs. CO bond partial hydrogenation. In this study, we investigate the interaction of acrolein, and its partial hydrogenation products propanal and allyl alcohol, with Pd(111) as a prototypical system. A combination of infrared reflection–absorption spectroscopy (IRAS) and temperature programmed desorption (TPD) experiments was applied under well-defined ultrahigh vacuum (UHV) conditions to obtain detailed information on the adsorption geometries of acrolein, propanal, and allyl alcohol as a function of coverage. We compare the IR spectra obtained for multilayer coverages, reflecting the molecular structure of unperturbed molecules, with the spectra acquired for sub-monolayer coverages, at which the chemical bonds of the molecules are strongly distorted. Coverage-dependent IR spectra of acrolein on Pd(111) point to the strong changes in the adsorption geometry with increasing acrolein coverage. Acrolein adsorbs with the CC and CO bonds lying parallel to the surface in the low coverage regime and changes its geometry to a more upright orientation with increasing coverage. TPD studies indicate decomposition of the species adsorbed in the sub-monolayer regime upon heating. Similar strong coverage dependence of the IR spectra were found for propanal and allyl alcohol. For all investigated molecules a detailed assignment of vibrational bands is reported. PMID:27149902

Deuterium desorption from ion-irradiated tantalum and effects on surface morphology

NASA Astrophysics Data System (ADS)

Novakowski, T. J.; Sundaram, A.; Tripathi, J. K.; Gonderman, S.; Hassanein, A.

2018-06-01

Compared to tungsten (W), tantalum (Ta) has shown superior resistance to helium (He)-induced surface morphology changes under fusion-relevant irradiation conditions. However, Ta is also expected to have a stronger interaction with hydrogen isotopes, potentially limiting its use as a plasma-facing material. Despite these concerns, detailed investigations on hydrogen irradiation effects on Ta are scarce. In this study, pristine and fuzzy (He+ ion-irradiated) Ta samples are irradiated with 120 eV deuterium (D) ions at various temperatures and examined with a combination of thermal desorption spectroscopy (TDS), scanning electron microscopy (SEM), and optical reflectivity. TDS reveals discrete D desorption temperatures at 660 and 760 K, corresponding to trapping energies of 1.82 and 2.11 eV, respectively. Although D is retained in Ta both in higher quantities and at higher temperatures compared to W, extreme surface temperatures expected in tokamak divertors may exceed these desorption temperatures and counteract retention. Furthermore, this study indicates that Ta is relatively resistant to adverse surface structuring under D+ ion irradiation. In fact, D+ is shown to prevent and suppress Ta fuzz formation in sequential D+/He+ ion irradiation experiments. While further investigations are needed to elucidate this behavior, these initial investigations show a strong potential for the use of Ta as a PFC material.

Coadsorbed species explain the mechanism of methanol temperature-desorption on CeO 2(111)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sutton, Jonathan E.; Steven H. Overbury; Beste, Ariana

2016-03-24

Here, we have used density functional theory calculations to investigate the temperature-programmed desorption (TPD) of methanol from CeO 2(111). For the first time, low-temperature water formation and high-temperature methanol desorption are explained by our calculations. High coverages of methanol, which correspond to experimental conditions, are required to properly describe these features of the TPD spectrum. We identify a mechanism for the low-temperature formation of water involving the dissociation of two methanol molecules on the same surface O atom and filling of the resulting surface vacancy with one of the methoxy products. After water desorption, methoxy groups are stabilized on themore » surface and react at higher temperatures to form methanol and formaldehyde by a disproportionation mechanism. Alternatively, the stabilized methoxy groups undergo sequential C–H scission reactions to produce formaldehyde. Calculated energy requirements and methanol/formaldehyde selectivity agree with the experimental data.« less

Helium self-trapping and diffusion behaviors in deformed 316L stainless steel exposed to high flux and low energy helium plasma

NASA Astrophysics Data System (ADS)

Gong, Yihao; Jin, Shuoxue; Zhu, Te; Cheng, Long; Cao, Xingzhong; You, Li; Lu, Guanghong; Guo, Liping; Wang, Baoyi

2018-04-01

A large number of dislocation networks were introduced in to 316L stainless steel by cold rolling. Subsequently, low energy (40 eV) helium ions were implanted by exposing the steel to helium plasma. Thermal desorption and positron annihilation spectroscopy were used to study the behavior of helium in the presence of dislocations, with emphasis on helium self-trapping and migration behaviors. Helium desorption behaviour from different helium trapping states was measured by the thermal desorption spectroscopy. Most of the helium desorbed from the He m V n clusters, and the corresponding desorption peak is located at ~650 K. The desorption peak from helium-dislocation clusters (He m D) is at approximately 805 K. The effect of annealing on the defect evolution was investigated by positron annihilation spectroscopy. For the specimen exposed to helium plasma without displacement damage, the increment of S parameter meant the existence of helium self-trapping behavior (He m V n ). Helium atoms could diffuse two to three orders of magnitude deeper than the implantation depth calculated by SRIM. The diffusing helium atoms were gradually trapped by dislocation lines and formed He m D. Elevated temperatures enhance the self-trapping behavior and cause helium atoms to dissociate/desorb from the He m V n clusters, increasing the S parameters at 473-673 K. The gradual recovery of vacancies in the He m V n clusters decreased the S parameter above 673 K.

Thermal desorption of CO and H2 from degassed 304 and 347 stainless steel

NASA Technical Reports Server (NTRS)

Rezaie-Serej, S.; Outlaw, R. A.

1994-01-01

Thermal desorption spectroscopy (TDS), along with Auger electron spectroscopy, was used to study the desorption of H2 and CO from baked 304 and 347 stainless-steel samples exposed only to residual gases. Both 347 and 304 samples gave identical TDS spectra. The spectra for CO contained a sharp leading peak centered in the temperature range 410-440C and an exponentially increasing part for temperatures higher than 500C, with a small peak around 600C appearing as a shoulder. The leading peak followed a second-order desorption behavior with an activation energy of 28+/-2 kcal/mol, suggesting that the rate-limiting step for this peak is most likely a surface reaction that produces the CO molecules in the surface layer. The amount of desorbed CO corresponding to this peak was approximately 0.5X10(exp 14) molecules/cm(exp 2) . The exponentially rising part of the CO spectrum appeared to originate from a bulk diffusion process. The TDS spectrum for H2 consisted of a main peak centered also in the temperature range 410-440C, with two small peaks appearing as shoulders at approximately 500 and 650C. The main peak in this case also displayed a second-order behavior with an activation energy of 14+/-2 kcal/mol. The amount of desorbed H2, approximately 1.9X 10(exp 15) molecules/cm(exp 2) , appeared to be independent of the concentration of hydrogen in the bulk, indicating that the majority of the desorbed H2 originated from the surface layer.

Thermal and adsorbate effects on the activity and morphology of size-selected Pdn/TiO2 model catalysts

NASA Astrophysics Data System (ADS)

Kaden, William E.; Kunkel, William A.; Roberts, F. Sloan; Kane, Matthew; Anderson, Scott L.

2014-03-01

Model catalysts containing size-selected Pdn (n = 1,2,4,7,10,16,20,25) deposited on rutile TiO2(110) deactivate during repeated CO oxidation temperature-programmed reaction (TPR) cycles, and the deactivation process has been probed using a combination of X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), low-energy ion scattering (ISS), temperature-dependent ion scattering (TD-ISS), annealing experiments, and temperature-programmed desorption following exposure to CO and O2 reactants. Results from such experiments suggest the cluster deactivation proceeds via an alloy-like, strong metal-support interaction (SMSI) effect that chemically modifies the clusters via electronic interactions between the supported metal atoms and Ti from the support. Threshold measurements show that this effect detrimentally affects CO-oxidation activity prior to the formation of an encapsulating overlayer by severely weakening the COPd bond strengths for binding configurations on top of the clusters. Oxidation appears to provide means of partially restoring the clusters to their initial state, but after sufficient exposure to reducing environments and elevated temperatures, all Pdn become covered by an overlayer and begin to electronically and chemically resemble freshly deposited atoms, which are completely inactive towards the probe reaction. In addition, we find evidence of oxygen spillover induced by co-adsorbed CO during TPRs for all active Pdn clusters.

Decomposition of multilayer benzene and n-hexane films on vanadium.

PubMed

Souda, Ryutaro

2015-09-21

Reactions of multilayer hydrocarbon films with a polycrystalline V substrate have been investigated using temperature-programmed desorption and time-of-flight secondary ion mass spectrometry. Most of the benzene molecules were dissociated on V, as evidenced by the strong depression in the thermal desorption yields of physisorbed species at 150 K. The reaction products dehydrogenated gradually after the multilayer film disappeared from the surface. Large amount of oxygen was needed to passivate the benzene decomposition on V. These behaviors indicate that the subsurface sites of V play a role in multilayer benzene decomposition. Decomposition of the n-hexane multilayer films is manifested by the desorption of methane at 105 K and gradual hydrogen desorption starting at this temperature, indicating that C-C bond scission precedes C-H bond cleavage. The n-hexane dissociation temperature is considerably lower than the thermal desorption temperature of the physisorbed species (140 K). The n-hexane multilayer morphology changes at the decomposition temperature, suggesting that a liquid-like phase formed after crystallization plays a role in the low-temperature decomposition of n-hexane.

Film growth, adsorption and desorption kinetics of indigo on SiO{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scherwitzl, Boris, E-mail: b.scherwitzl@tugraz.at; Resel, Roland; Winkler, Adolf

2014-05-14

Organic dyes have recently been discovered as promising semiconducting materials, attributable to the formation of hydrogen bonds. In this work, the adsorption and desorption behavior, as well as thin film growth was studied in detail for indigo molecules on silicon dioxide with different substrate treatments. The material was evaporated onto the substrate by means of physical vapor deposition under ultra-high vacuum conditions and was subsequently studied by Thermal Desorption Spectroscopy (TDS), Auger Electron Spectroscopy, X-Ray Diffraction, and Atomic Force Microscopy. TDS revealed initially adsorbed molecules to be strongly bonded on a sputter cleaned surface. After further deposition a formation ofmore » dimers is suggested, which de-stabilizes the bonding mechanism to the substrate and leads to a weakly bonded adsorbate. The dimers are highly mobile on the surface until they get incorporated into energetically favourable three-dimensional islands in a dewetting process. The stronger bonding of molecules within those islands could be shown by a higher desorption temperature. On a carbon contaminated surface no strongly bonded molecules appeared initially, weakly bonded monomers rather rearrange into islands at a surface coverage that is equivalent to one third of a monolayer of flat-lying molecules. The sticking coefficient was found to be unity on both substrates. The desorption energies from carbon covered silicon dioxide calculated to 1.67 ± 0.05 eV for multilayer desorption from the islands and 0.84 ± 0.05 eV for monolayer desorption. Corresponding values for desorption from a sputter cleaned surface are 1.53 ± 0.05 eV for multilayer and 0.83 ± 0.05 eV for monolayer desorption.« less

Film growth, adsorption and desorption kinetics of indigo on SiO2.

PubMed

Scherwitzl, Boris; Resel, Roland; Winkler, Adolf

2014-05-14

Organic dyes have recently been discovered as promising semiconducting materials, attributable to the formation of hydrogen bonds. In this work, the adsorption and desorption behavior, as well as thin film growth was studied in detail for indigo molecules on silicon dioxide with different substrate treatments. The material was evaporated onto the substrate by means of physical vapor deposition under ultra-high vacuum conditions and was subsequently studied by Thermal Desorption Spectroscopy (TDS), Auger Electron Spectroscopy, X-Ray Diffraction, and Atomic Force Microscopy. TDS revealed initially adsorbed molecules to be strongly bonded on a sputter cleaned surface. After further deposition a formation of dimers is suggested, which de-stabilizes the bonding mechanism to the substrate and leads to a weakly bonded adsorbate. The dimers are highly mobile on the surface until they get incorporated into energetically favourable three-dimensional islands in a dewetting process. The stronger bonding of molecules within those islands could be shown by a higher desorption temperature. On a carbon contaminated surface no strongly bonded molecules appeared initially, weakly bonded monomers rather rearrange into islands at a surface coverage that is equivalent to one third of a monolayer of flat-lying molecules. The sticking coefficient was found to be unity on both substrates. The desorption energies from carbon covered silicon dioxide calculated to 1.67 ± 0.05 eV for multilayer desorption from the islands and 0.84 ± 0.05 eV for monolayer desorption. Corresponding values for desorption from a sputter cleaned surface are 1.53 ± 0.05 eV for multilayer and 0.83 ± 0.05 eV for monolayer desorption.

Ion scattering and electron spectroscopy of the chemical species at a HF-prepared Si(211) surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jaime-Vasquez, M.; Martinka, M.; Groenert, M.

2006-01-16

The species and the nature of their chemical bonds at the surface of a hydrogen-terminated Si(211) wafer were characterized using temperature desorption spectroscopy, ion scattering spectroscopy, and electron spectroscopy. The surface region is dominated by monohydride species with dihydrides present in small amounts. Fluorine is distributed across the top layer as largely a physisorbed species to the Si substrate. Low-energy {sup 3}He{sup +} ions remove the H and F species with only minimal damage to the underlying region.

Surface science studies of ethene containing model interstellar ices

NASA Astrophysics Data System (ADS)

Puletti, F.; Whelan, M.; Brown, W. A.

2011-05-01

The formation of saturated hydrocarbons in the interstellar medium (ISM) is difficult to explain only by taking into account gas phase reactions. This is mostly due to the fact that carbonium ions only react with H_2 to make unsaturated hydrocarbons, and hence no viable route to saturated hydrocarbons has been postulated to date. It is therefore likely that saturation processes occur via surface reactions that take place on interstellar dust grains. One of the species of interest in this family of reactions is C_2H_4 (ethene) which is an intermediate in several molecular formation routes (e.g. C_2H_2 → C_2H_6). To help to understand some of the surface processes involving ethene, a study of ethene deposited on a dust grain analogue surface (highly oriented pyrolytic graphite) held under ultra-high vacuum at 20 K has been performed. The adsorption and desorption of ethene has been studied both in water-free and water-dominated model interstellar ices. A combination of temperature programmed desorption (TPD) and reflection absorption infrared spectroscopy (RAIRS) have been used to identify the adsorbed and trapped species and to determine the kinetics of the desorption processes. In all cases, ethene is found to physisorb on the carbonaceous surface. As expected water has a very strong influence on the desorption of ethene, as previously observed for other model interstellar ice systems.

Hydrocracking of Jatropha Oil over non-sulfided PTA-NiMo/ZSM-5 Catalyst

PubMed Central

Yang, Xiaosong; Liu, Jing; Fan, Kai; Rong, Long

2017-01-01

The PTA-NiMo/ZSM-5 catalyst impregnated with phosphotungstic acid (PTA) was designed for the transformation of Jatropha oil into benzene, toluene, and xylenes (BTX) aromatics. The produced catalyst was characterized by N2 adsorption-desorption, powder X-ray diffraction (XRD), Fourier transform infrared (FT-IR), X-ray photoelectron spectroscopy (XPS), and the temperature-programmed desorption of ammonia (NH3-TPD). The catalytic performance was evaluated by gas chromatography (GC). The liquid products were 70 wt% of the feed oil, and the majority of the liquid products were BTX. The aromatization activity of the catalyst was improved by the addition of PTA and the hierarchical process. The favorable PTA amount was 20 wt% and the yield of BTX was 59 wt% at 380 °C, 3 MPa, H2/oil (v/v) = 1000 and LHSV = 1 h−1 over the PTA20-NiMo/HZ0.5 catalyst (PTA 20 wt%) without sulfurization. PMID:28134313

New insight into the promoting role of process on the CeO₂-WO₃/TiO₂ catalyst for NO reduction with NH₃ at low-temperature.

PubMed

Zhang, Shule; Zhong, Qin; Shen, Yuge; Zhu, Li; Ding, Jie

2015-06-15

This study aimed at investigating the reason of high catalytic activity for CeO2-WO3/TiO2 catalyst from the aspects of WO3 interaction with other species and the NO oxidation process. Analysis by X-ray diffractometry, photoluminescence spectra, diffuse reflectance UV-visible, X-ray photoelectron spectroscopy, density functional theory calculations, electron paramagnetic resonance spectroscopy, temperature-programmed-desorption of NO and in situ diffuse reflectance infrared transform spectroscopy showed that WO3 could interact with CeO2 to improve the electron gaining capability of CeO2 species. In addition, WO3 species acted as electron donating groups to transfer the electrons to CeO2 species. The two aspects enhanced the formation of reduced CeO2 species to improve the formation of superoxide ions. Furthermore, the Ce species were the active sites for the NO adsorption and the superoxide ions over the catalyst needed oxidizing the adsorbed NO to improve the NO oxidation. This process was responsible for the high catalytic activity of CeO2-WO3/TiO2 catalyst. Copyright © 2015 Elsevier Inc. All rights reserved.

Coverage-dependent adsorption and desorption of oxygen on Pd(100)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dunnen, Angela den; Jacobse, Leon; Wiegman, Sandra

2016-06-28

We have studied the adsorption and desorption of O{sub 2} on Pd(100) by supersonic molecular beam techniques and thermal desorption spectroscopy. Adsorption measurements on the bare surface confirm that O{sub 2} initially dissociates for all kinetic energies between 56 and 380 meV and surface temperatures between 100 and 600 K via a direct mechanism. At and below 150 K, continued adsorption leads to a combined O/O{sub 2} overlayer. Dissociation of molecularly bound O{sub 2} during a subsequent temperature ramp leads to unexpected high atomic oxygen coverages, which are also obtained at high incident energy and high surface temperature. At intermediatemore » temperatures and energies, these high final coverages are not obtained. Our results show that kinetic energy of the gas phase reactant and reaction energy dissipated during O{sub 2} dissociation on the cold surface both enable activated nucleation of high-coverage surface structures. We suggest that excitation of local substrate phonons may play a crucial role in oxygen dissociation at any coverage.« less

Inclusion of Ti and Zr species on clay surfaces and their effect on the interaction with organic molecules

NASA Astrophysics Data System (ADS)

Rangel-Rivera, Pedro; Bachiller-Baeza, María Belén; Galindo-Esquivel, Ignacio; Rangel-Porras, Gustavo

2018-07-01

The interactions between the clay surface and the organic molecules play an important role in the efficient of these materials in adsorption and catalytic processes. These materials are often modified with the inclusion of other catalytic particles for the purpose of enhancing the activity. In this study, commercial clay K10 was modified with the particles inclusion of titanium and zirconium. The solid surfaces were examined by infrared spectroscopy, scanning electron microscopy (SEM) coupled to an energy-dispersive X-ray spectroscopy device (EDS), and X-ray photoelectron spectroscopy (XPS). Temperature programmed desorption of ammonia (TPD-NH3) and propan-2-ol decomposition test reaction were performed to probe the acid properties. The adsorption of acetic acid, ethanol, and propan-2-ol on the surface of each solid and their thermal stability were studied by diffuse reflectance infrared Fourier transform spectroscopy (DRIFT). Finally, these materials were used in the esterification of acetic acid with penta-1-ol. The real effect over the incorporation of titanium species and zirconium species on clay surface for interacting with the organic molecules was discussed.

Synthesis of core–shell structured FAU/SBA-15 composite molecular sieves and their performance in catalytic cracking of polystyrene

PubMed Central

Du, Jinlong; Shi, Chunwei; Wu, Wenyuan; Bian, Xue; Chen, Ping; Cui, Qingzhu; Cui, Zhixuan

2017-01-01

Abstract Composite molecular sieves, FAU/SBA-15, having core-shell structure were synthesized. The synthesized composite sieves were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS), pyrolysis fourier transform infrared (Py-FTIR) spectroscopy, temperature programmed desorption spectra (NH3-TPD), UV Raman spectroscopy, nuclear magnetic resonance (NMR) and other techniques. XRD, SEM, TEM, N2 adsorption-desorption, mass spectrometry, NMR and EDS results showed that the composite molecular sieve contained two pore channels. Py-FTIR results showed that the addition of HY molecular sieves improved the acidity of the composite zeolite. The crystallization mechanism during the growth of FAU/SBA-15 shell was deduced from the influence of crystallization time on the synthesis of FAU/SBA-15 core-shell structured composite molecular sieve. HY dissociated partially in H2SO4 solution, and consisted of secondary structural units. This framework structure was more stable than its presence in the isolated form on the same ring or in the absence of Al. Thus it played a guiding role and connected with SBA-15 closely through the Si-O bond. This resulted in the gradual covering of the exterior surface of FAU phase by SBA-15 molecular sieves. The presence of SBA-15 restricted the formation of the other high mass components and increased the selectivity towards ethylbenzene. PMID:29383044

Desorption Kinetics of Benzene and Cyclohexane from a Graphene Surface.

PubMed

Smith, R Scott; Kay, Bruce D

2018-01-18

The desorption kinetics for benzene and cyclohexane from a graphene covered Pt(111) surface were investigated using temperature-programmed desorption (TPD). The benzene desorption spectra show well-resolved monolayer and multilayer desorption peaks. The benzene monolayer and submonolayer TPD spectra for coverages greater than ∼0.1 ML have nearly the same desorption peak temperature and have line shapes which are consistent with first-order desorption kinetics. For benzene coverages greater than 1 ML, the TPD spectra align on a common leading edge which is consistent with zero-order desorption. An "inversion" procedure in which the prefactor is varied to find the value that best reproduces the entire set of experimental desorption spectra was used to analyze the benzene data. The inversion analysis of the benzene TPD spectra yielded a desorption activation energy of 54 ± 3 kJ/mol with a prefactor of 10 17±1 s -1 . The TPD spectra for cyclohexane also have well-resolved monolayer and multilayer desorption features. The desorption leading edges for the monolayer and the multilayer TPD spectra are aligned indicating zero-order desorption kinetics in both cases. An Arrhenius analysis of the monolayer cyclohexane TPD spectra yielded a desorption activation energy of 53.5 ± 2 kJ/mol with a prefactor of 10 16±1 ML s -1 .

Adsorption of hydrogen on stable and metastable Ir(100) surfaces

NASA Astrophysics Data System (ADS)

Arman, Mohammad Alif; Klein, Andreas; Ferstl, Pascal; Valookaran, Abhilash; Gustafson, Johan; Schulte, Karina; Lundgren, Edvin; Heinz, Klaus; Schneider, Alexander; Mittendorfer, Florian; Hammer, Lutz; Knudsen, Jan

2017-02-01

Using the combination of high resolution core level spectroscopy and density functional theory we present a detailed spectroscopic study for all clean and hydrogen covered phases of Ir(100). The results are complemented by an investigation of the hydrogen desorption process from various phases using temperature programmed desorption spectroscopy and scanning tunneling microscopy. In total, all experimentally determined core level shifts match very well with those predicted by density functional theory based on established structural models. In particular, we find for the (bridge site) adsorption on the unreconstructed 1×1 phase that the initial core level shift of surface Ir atoms is altered by +0.17 eV for each Ir-H bond formed. In the submonolayer regime we find evidence for island formation at low temperatures. For the H-induced deconstructed 5×1-H phase we identify four different surface core level shifts with two of them being degenerate. Finally, for the reconstructed 5×1-hex phase also four surface components are identified, which undergo a rather rigid core level shift of +0.15 eV upon hydrogen adsorption suggesting a similarly homogeneous charge transfer to all Ir surface atoms. Thermodesorption experiments for the 5×1-H phase reveal two different binding states for hydrogen independent of the total coverage. We conclude that the surface always separates into patches of fully covered deconstructed and uncovered reconstructed phases. We could also show by tunneling microscopy that with the desorption of the last hydrogen atom from the deconstructed unit cell the surface instantaneously reverts into the reconstructed state. Eventually, we could determine the saturation coverage upon molecular adsorption for all phases to be θmax1 × 1 - H = 1.0 ML , θmax5 × 1 - H = 0.8 ML , and θmax5 × 1 - hex - H ≥ 1.0 ML .

Film growth, adsorption and desorption kinetics of indigo on SiO2

PubMed Central

Scherwitzl, Boris; Resel, Roland; Winkler, Adolf

2015-01-01

Organic dyes have recently been discovered as promising semiconducting materials, attributable to the formation of hydrogen bonds. In this work, the adsorption and desorption behavior, as well as thin film growth was studied in detail for indigo molecules on silicon dioxide with different substrate treatments. The material was evaporated onto the substrate by means of physical vapor deposition under ultra-high vacuum conditions and was subsequently studied by Thermal Desorption Spectroscopy (TDS), Auger Electron Spectroscopy, X-Ray Diffraction, and Atomic Force Microscopy. TDS revealed initially adsorbed molecules to be strongly bonded on a sputter cleaned surface. After further deposition a formation of dimers is suggested, which de-stabilizes the bonding mechanism to the substrate and leads to a weakly bonded adsorbate. The dimers are highly mobile on the surface until they get incorporated into energetically favourable three-dimensional islands in a dewetting process. The stronger bonding of molecules within those islands could be shown by a higher desorption temperature. On a carbon contaminated surface no strongly bonded molecules appeared initially, weakly bonded monomers rather rearrange into islands at a surface coverage that is equivalent to one third of a monolayer of flat-lying molecules. The sticking coefficient was found to be unity on both substrates. The desorption energies from carbon covered silicon dioxide calculated to 1.67 ± 0.05 eV for multilayer desorption from the islands and 0.84 ± 0.05 eV for monolayer des orption. Corresponding values for desorption from a sputter cleaned surface are 1.53 ± 0.05 eV for multilayer and 0.83 ± 0.05 eV for monolayer desorption. PMID:24832297

Methanol ice co-desorption as a mechanism to explain cold methanol in the gas-phase

NASA Astrophysics Data System (ADS)

Ligterink, N. F. W.; Walsh, C.; Bhuin, R. G.; Vissapragada, S.; van Scheltinga, J. Terwisscha; Linnartz, H.

2018-05-01

Context. Methanol is formed via surface reactions on icy dust grains. Methanol is also detected in the gas-phase at temperatures below its thermal desorption temperature and at levels higher than can be explained by pure gas-phase chemistry. The process that controls the transition from solid state to gas-phase methanol in cold environments is not understood. Aims: The goal of this work is to investigate whether thermal CO desorption provides an indirect pathway for methanol to co-desorb at low temperatures. Methods: Mixed CH3OH:CO/CH4 ices were heated under ultra-high vacuum conditions and ice contents are traced using RAIRS (reflection absorption IR spectroscopy), while desorbing species were detected mass spectrometrically. An updated gas-grain chemical network was used to test the impact of the results of these experiments. The physical model used is applicable for TW Hya, a protoplanetary disk in which cold gas-phase methanol has recently been detected. Results: Methanol release together with thermal CO desorption is found to be an ineffective process in the experiments, resulting in an upper limit of ≤ 7.3 × 10-7 CH3OH molecules per CO molecule over all ice mixtures considered. Chemical modelling based on the upper limits shows that co-desorption rates as low as 10-6 CH3OH molecules per CO molecule are high enough to release substantial amounts of methanol to the gas-phase at and around the location of the CO thermal desorption front in a protoplanetary disk. The impact of thermal co-desorption of CH3OH with CO as a grain-gas bridge mechanism is compared with that of UV induced photodesorption and chemisorption.

Adsorption and Reaction of Acetaldehyde on Shape-Controlled CeO2 Nanocrystals: Elucidation of Structure-function Relationships

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mann, Amanda K; Wu, Zili; Calaza, Florencia

2014-01-01

CeO2 cubes with {100} facets, octahedra with {111} facets, and wires with highly defective structures were utilized to probe the structure-dependent reactivity of acetaldehyde. Using temperature-programmed desorption (TPD), temperature-programmed surface reactions (TPSR), and in situ infrared spectroscopy it was found that acetaldehyde desorbs unreacted or undergoes reduction, coupling, or C-C bond scission reactions depending on the surface structure of CeO2. Room temperature FTIR indicates that acetaldehyde binds primarily as 1-acetaldehyde on the octahedra, in a variety of conformations on the cubes, including coupling products and acetate and enolate species, and primarily as coupling products on the wires. The percent consumptionmore » of acetaldehyde follows the order of wires > cubes > octahedra. All the nanoshapes produce the coupling product crotonaldehyde; however, the selectivity to produce ethanol follows the order wires cubes >> octahedra. The selectivity and other differences can be attributed to the variation in the basicity of the surfaces, defects densities, coordination numbers of surface atoms, and the reducibility of the nanoshapes.« less

The Release of Trapped Gases from Amorphous Solid Water Films: II. “Bottom-Up” Induced Desorption Pathways

DOE Office of Scientific and Technical Information (OSTI.GOV)

May, Robert A.; Smith, R. Scott; Kay, Bruce D.

2013-03-14

In this (Paper II) and the preceding companion paper (Paper I) we investigate the mechanisms for the release of trapped gases from underneath of amorphous solid water (ASW) films. In Paper I, we focused on the low coverage (pressure) regime where the release mechanism is controlled by crystallization-induced cracks formed in the ASW overlayer. In that regime the results were largely independent of the particular gas underlayer. Here in Paper II, we focus on the high coverage (pressure) regime where new desorption pathways become accessible prior to ASW crystallization. In contrast to the results for the low coverage regime (Papermore » I), the release mechanism is a function of the multilayer thickness and composition, displaying dramatically different behavior between Ar, Kr, Xe, CH4, N2, O2, and CO. Two primary desorption pathways are observed. The first occurs between 100 and 150 K and manifests itself as sharp, extremely narrow desorption peaks. Temperature programmed desorption is utilized to show that abrupt desorption bursts are due to pressure induced structural failure of the ASW overlyaer. The second pathway occurs at low temperature (typically <100 K) where broad desorption peaks are observed. Desorption through this pathway is attributed to diffusion through pores and connected pathways formed during ASW deposition. The extent of desorption and the lineshape of the low temperature desorption peak are dependent on the substrate on which the gas underlayer is deposited. Angle dependent ballistic deposition of the ASW is used vary the porosity of overlayer and confirm that the low temperature desorption pathway is due to porosity that is inherent in the ASW overlayer during deposition.« less

Metal-phthalocyanine ordered layers on Au(110): Metal-dependent adsorption energy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Massimi, Lorenzo, E-mail: lorenzo.massimi@uniroma1.it; Angelucci, Marco; Gargiani, Pierluigi

2014-06-28

Iron-phthalocyanine and cobalt-phthalocyanine chains, assembled along the Au(110)-(1×2) reconstructed channels, present a strong interaction with the Au metallic states, via the central metal ion. X-ray photoemission spectroscopy from the metal-2p core-levels and valence band high-resolution ultraviolet photoelectron spectroscopy bring to light signatures of the interaction of the metal-phthalocyanine single-layer with gold. The charge transfer from Au to the molecule causes the emerging of a metal-2p core level component at lower binding energy with respect to that measured in the molecular thin films, while the core-levels associated to the organic macrocycle (C and N 1s) are less influenced by the adsorption,more » and the macrocycles stabilize the interaction, inducing a strong interface dipole. Temperature Programmed Desorption experiments and photoemission as a function of temperature allow to estimate the adsorption energy for the thin-films, mainly due to the molecule-molecule van der Waals interaction, while the FePc and CoPc single-layers remain adsorbed on the Au surface up to at least 820 K.« less

Distinct water activation on polar/non-polar facets of ZnO nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, He; Sun, Junming; Liu, Changjun

2015-11-01

ZnO nanoparticles with differing dominant facets were prepared and characterized by a complimentary of techniques such as X-ray diffraction, electron microscopy, temperature programmed desorption of H2O, and Fourier transform infrared spectroscopy analysis of adsorbed D2O. For the first time, water interaction/activation is compared on ZnO polar and non-polar facets. We report that non-polar facets exhibit high activity in water activation, which favors reactions such as ketonization and steam reforming in which dissociated water is involved. The distinct water dissociation on ZnO non-polar facets could be related to its facile formation of oxygen vacancies under realistic reaction conditions.

Chemical surface modification of polycrystalline platinum thin-films to promote preferential chemisorption of n-hexane, piperidine, and cyclohexane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thomas, V.; Schwank, J.; Gland, J.

In this study, hard/soft Lewis acid-base (HSAB) principles are used to modify a thin-polycrystalline platinum film to promote preferential chemisorption of molecules such as piperidine, n-hexane, and cyclohexane. Specifically, the particle size and electron density distribution of the platinum surface is modified using thermal treatment and co-adsorption of electro-positive and negative species. These studies are conducted in an ultra-high vacuum chamber. The platinum surface is characterized, before and after modification protocols, using a variety of in-situ and ex-situ techniques. These include temperature programmed desorption (TPD), both resistance change and work function measurements, and both X-ray photoelectron spectroscopy and diffraction.

Temperature Programmed Desorption of Quench-condensed Krypton and Acetone in Air; Selective Concentration of Ultra-trace Gas Components.

PubMed

Suzuki, Taku T; Sakaguchi, Isao

2016-01-01

Selective concentration of ultra-trace components in air-like gases has an important application in analyzing volatile organic compounds in the gas. In the present study, we examined quench-condensation of the sample gas on a ZnO substrate below 50 K followed by temperature programmed desorption (TPD) (low temperature TPD) as a selective gas concentration technique. We studied two specific gases in the normal air; krypton as an inert gas and acetone as a reactive gas. We evaluated the relationship between the operating condition of low temperature TPD and the lowest detection limit. In the case of krypton, we observed the selective concentration by exposing at 6 K followed by thermal desorption at about 60 K. On the other hand, no selectivity appeared for acetone although trace acetone was successfully concentrated. This is likely due to the solvent effect by a major component in the air, which is suggested to be water. We suggest that pre-condensation to remove the water component may improve the selectivity in the trace acetone analysis by low temperature TPD.

Lignin-derived oxygenate reforming on a bimetallic surface: The reaction of benzaldehyde on Zn/Pt(111)

NASA Astrophysics Data System (ADS)

Shi, Daming; Vohs, John M.

2016-08-01

Temperature programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS) were used to characterize the adsorption and reaction of benzaldehyde (C6H5CHO) on hydrogen-covered Pt(111) and Zn-modified Pt(111) surfaces. Benzaldehyde was found to interact with Pt(111) via both the phenyl ring and carbonyl of the aldehyde group. This bonding configuration facilitates unselective decomposition of the benzaldehyde to produce CO, H2, and small hydrocarbon fragments at relatively low temperatures. On the other hand, benzaldehyde was found to bond to Zn-decorated Pt(111) surface exclusively via the carbonyl group in an η2(C, O) configuration, with the phenyl ring tilted away from the surface. This configuration weakens Csbnd O bond in the carbonyl facilitating its cleavage and helps prevent hydrogenation of the phenyl ring.

Effect of Temperature on the Desorption of Lithium from Molybdenum(110) Surfaces: Implications for Fusion Reactor First Wall Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Mohan; Roszell, John; Scoullos, Emanuel V.

2016-03-30

Determining the strength of Li binding to Mo is critical to assessing the survivability of Li as a potential first wall material in fusion reactors. Here, we present the results of a joint experimental and theoretical investigation into how Li desorbs from Mo(110) surfaces, based on what can be deduced from temperature-programmed desorption measurements and density functional theory (DFT). Li desorption peaks measured at temperatures ranging from 711 K (1 monolayer, ML) to 1030 K (0.04 ML), with corresponding desorption onsets from 489 to 878 K, follow a trend similar to predicted Gibbs free energies for Li adsorption. Bader chargemore » analysis of DFT densities reveals that repulsive forces between neighboring positively charged Li atoms increase with coverage and thus reduce the bond strength between Mo and Li, thereby lowering the desorption temperature as the coverage increases. In addition, DFT predicts that Li desorbs at higher temperatures from a surface with vacancies than from a perfect surface, offering an explanation for the anomalously high desorption temperatures for the last Li to desorb from Mo(110). Analysis of simulated local densities of states indicates that the stronger binding to the defective surface is correlated with enhanced interaction between Li and Mo, involving the Li 2s electrons and not only the Mo 4d electrons as in the case of the pristine surface, but also the Mo 5s electrons in the case with surface vacancies. We suggest that steps and kinks present on the Mo(110) surface behave similarly and contribute to the high desorption temperatures. These findings imply that roughened Mo surfaces may strengthen Li film adhesion at higher temperatures.« less

Breaking through the glass ceiling: The correlation between the self-diffusivity in and krypton permeation through deeply supercooled liquid nanoscale methanol films

NASA Astrophysics Data System (ADS)

Smith, R. Scott; Matthiesen, Jesper; Kay, Bruce D.

2010-03-01

Molecular beam techniques, temperature-programmed desorption (TPD), and reflection absorption infrared spectroscopy (RAIRS) are used to explore the relationship between krypton permeation through and the self-diffusivity of supercooled liquid methanol at temperatures (100-115 K) near the glass transition temperature, Tg (103 K). Layered films, consisting of CH3OH and CD3OH, are deposited on top of a monolayer of Kr on a graphene covered Pt(111) substrate at 25 K. Concurrent Kr TPD and RAIRS spectra are acquired during the heating of the composite film to temperatures above Tg. The CO vibrational stretch is sensitive to the local molecular environment and is used to determine the supercooled liquid diffusivity from the intermixing of the isotopic layers. We find that the Kr permeation and the diffusivity of the supercooled liquid are directly and quantitatively correlated. These results validate the rare-gas permeation technique as a tool for probing the diffusivity of supercooled liquids.

Breaking through the glass ceiling: the correlation between the self-diffusivity in and krypton permeation through deeply supercooled liquid nanoscale methanol films.

PubMed

Smith, R Scott; Matthiesen, Jesper; Kay, Bruce D

2010-03-28

Molecular beam techniques, temperature-programmed desorption (TPD), and reflection absorption infrared spectroscopy (RAIRS) are used to explore the relationship between krypton permeation through and the self-diffusivity of supercooled liquid methanol at temperatures (100-115 K) near the glass transition temperature, T(g) (103 K). Layered films, consisting of CH(3)OH and CD(3)OH, are deposited on top of a monolayer of Kr on a graphene covered Pt(111) substrate at 25 K. Concurrent Kr TPD and RAIRS spectra are acquired during the heating of the composite film to temperatures above T(g). The CO vibrational stretch is sensitive to the local molecular environment and is used to determine the supercooled liquid diffusivity from the intermixing of the isotopic layers. We find that the Kr permeation and the diffusivity of the supercooled liquid are directly and quantitatively correlated. These results validate the rare-gas permeation technique as a tool for probing the diffusivity of supercooled liquids.

CCl 4 chemistry on the magnetite selvedge of single-crystal hematite: competitive surface reactions

NASA Astrophysics Data System (ADS)

Adib, K.; Camillone, N., III; Fitts, J. P.; Rim, K. T.; Flynn, G. W.; Joyce, S. A.; Osgood, R. M., Jr.

2002-01-01

Temperature programmed reaction/desorption (TPR/D) studies were undertaken to characterize the surface chemistry which occurs between CCl 4 and the Fe 3O 4 (1 1 1) selvedge of single crystal α-Fe 2O 3 (0 0 0 1). Six separate desorption events are clearly observed and four desorbing species are identified: CCl 4, OCCl 2, C 2Cl 4 and FeCl 2. It is proposed that OCCl 2, CCl 4 and C 2Cl 4 are produced in reactions involving the same precursor, CCl 2. Three reaction paths compete for the CCl 2 precursor: oxygen atom abstraction (for OCCl 2), molecular recombinative desorption (for CCl 4) and associative desorption (for C 2Cl 4). During the TPR/D temperature ramp, the branching ratio is observed to depend upon temperature and the availability of reactive sites. The data are consistent with a rich site-dependent chemistry.

X-ray photoelectron spectroscopy study of the stability of Fomblin Z25 on the native oxide of aluminum

NASA Technical Reports Server (NTRS)

Herrera-Fierro, Pilar; Pepper, Stephen V.; Jones, William R.

1992-01-01

Thin films of Fomblin Z25, a perfluoropolyalkylether lubricant, were vapor deposited onto clean, oxidized aluminum, and onto sapphire surfaces, and their behavior at different temperatures was studied using X-ray photoelectron spectroscopy and temperature desorption spectroscopy (TDS). The interfacial fluid molecules decompose on the native oxide at room temperature, and continue to decompose at elevated temperatures, as previous studies had shown to occur on the clean metal. TDS indicated that different degradation mechanisms were operative for clean and oxidized aluminum. On sapphire substrates, no reaction was observed at room temperature. The native oxide of aluminum is neither passive nor protective towards Fomblin Z25. At higher temperatures (150 C), degradation of the polymer on sapphire produced a debris layer at the interface with a chemical composition similar to the one formed on aluminum oxide. Rubbing a Fomblin film on a single crystal sapphire also induced the decomposition of the lubricant in contact with the interface and the formation of a debris layer.

Sodium-promoted Pd/TiO2 for catalytic oxidation of formaldehyde at ambient temperature.

PubMed

Zhang, Changbin; Li, Yaobin; Wang, Yafei; He, Hong

2014-05-20

Catalytic oxidation of formaldehyde (HCHO) to CO2 at ambient conditions is of great interest for indoor HCHO purification. Here, we report that sodium-doped Pd/TiO2 is a highly effective catalyst for the catalytic oxidation of HCHO at room temperature. It was observed that Na doping has a dramatic promotion effect on the Pd/TiO2 catalyst and that nearly 100% HCHO conversion could be achieved over the 2Na-Pd/TiO2 catalyst at a GHSV of 95000 h(-1) and HCHO inlet concentration of 140 ppm at 25 °C. The mechanism of the Na-promotion effect was investigated by using Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), CO chemisorption, Temperature-programmed reduction by H2 (H2-TPR), X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption of O2 (O2-TPD) methods. The results showed that Na species addition can induce and further stabilize a negatively charged and well-dispersed Pd species, which then facilitates the activation of H2O and chemisorbed oxygen, therefore resulting in the high performance of the 2Na-Pd/TiO2 catalyst for the ambient HCHO destruction.

Methanol Adsorption and Reaction on Samaria Thin Films on Pt(111).

PubMed

Jhang, Jin-Hao; Schaefer, Andreas; Zielasek, Volkmar; Weaver, Jason F; Bäumer, Marcus

2015-09-17

We investigated the adsorption and reaction of methanol on continuous and discontinuous films of samarium oxide (SmO x ) grown on Pt(111) in ultrahigh vacuum. The methanol decomposition was studied by temperature programmed desorption (TPD) and infrared reflection absorption spectroscopy (IRRAS), while structural changes of the oxide surface were monitored by low-energy electron diffraction (LEED). Methanol dehydrogenates to adsorbed methoxy species on both the continuous and discontinuous SmO x films, eventually leading to the desorption of CO and H₂ which desorbs at temperatures in the range 400-600 K. Small quantities of CO₂ are also detected mainly on as-prepared Sm₂O₃ thin films, but the production of CO₂ is limited during repeated TPD runs. The discontinuous film exhibits the highest reactivity compared to the continuous film and the Pt(111) substrate. The reactivity of methanol on reduced and reoxidized films was also investigated, revealing how SmO x structures influence the chemical behavior. Over repeated TPD experiments, a SmO x structural/chemical equilibrium condition is found which can be approached either from oxidized or reduced films. We also observed hydrogen absence in TPD which indicates that hydrogen is stored either in SmO x films or as OH groups on the SmO x surfaces.

Methanol Adsorption and Reaction on Samaria Thin Films on Pt(111)

PubMed Central

Jhang, Jin-Hao; Schaefer, Andreas; Zielasek, Volkmar; Weaver, Jason F.; Bäumer, Marcus

2015-01-01

We investigated the adsorption and reaction of methanol on continuous and discontinuous films of samarium oxide (SmOx) grown on Pt(111) in ultrahigh vacuum. The methanol decomposition was studied by temperature programmed desorption (TPD) and infrared reflection absorption spectroscopy (IRRAS), while structural changes of the oxide surface were monitored by low-energy electron diffraction (LEED). Methanol dehydrogenates to adsorbed methoxy species on both the continuous and discontinuous SmOx films, eventually leading to the desorption of CO and H2 which desorbs at temperatures in the range 400–600 K. Small quantities of CO2 are also detected mainly on as-prepared Sm2O3 thin films, but the production of CO2 is limited during repeated TPD runs. The discontinuous film exhibits the highest reactivity compared to the continuous film and the Pt(111) substrate. The reactivity of methanol on reduced and reoxidized films was also investigated, revealing how SmOx structures influence the chemical behavior. Over repeated TPD experiments, a SmOx structural/chemical equilibrium condition is found which can be approached either from oxidized or reduced films. We also observed hydrogen absence in TPD which indicates that hydrogen is stored either in SmOx films or as OH groups on the SmOx surfaces. PMID:28793562

Turning things downside up: Adsorbate induced water flipping on Pt(111)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kimmel, Gregory A.; Zubkov, Tykhon; Smith, R. Scott

2014-11-14

We have examined the adsorption of the weakly bound species N2, O2, CO and Kr on the water monolayer on Pt(111) using a combination of molecular beam dosing, infrared reflection absorption spectroscopy (IRAS), and temperature programmed desorption (TPD). In contrast to multilayer crystalline ice, the adsorbate-free water monolayer is characterized by a lack of dangling OH bonds protruding into the vacuum (H-up). Instead, the non-hydrogen-bonded OH groups are oriented downward (H-down) to maximize their interaction with the underlying Pt(111) substrate. Adsorption of Kr and O2 have little effect on the structure and vibrational spectrum of the “ ” water monolayermore » while adsorption of both N2, and CO are effective in “flipping” H-down water molecules into an H-up configuration. This “flipping” occurs readily upon adsorption at temperatures as low as 20 K and the water monolayer transforms back to the H-down, “ ” structure upon adsorbate desorption above 35 K, indicating small energy differences and barriers between the H-down and H-up configurations. The results suggest that converting water in the first layer from H-down to H-up is mediated by the electrostatic interactions between the water and the adsorbates.« less

Promising SiC support for Pd catalyst in selective hydrogenation of acetylene to ethylene

NASA Astrophysics Data System (ADS)

Guo, Zhanglong; Liu, Yuefeng; Liu, Yan; Chu, Wei

2018-06-01

In this study, SiC supported Pd nanoparticles were found to be an efficient catalyst in acetylene selective hydrogenation reaction. The ethylene selectivity can be about 20% higher than that on Pd/TiO2 catalyst at the same acetylene conversion at 90%. Moreover, Pd/SiC catalyst showed a stable catalytic life at 65 °C with 80% ethylene selectivity. With the detailed characterization using temperature-programmed reduction (H2-TPR), powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N2 adsorption/desorption analysis, CO-chemisorption and thermo-gravimetric analysis (TGA), it was found that SiC owns a lower surface area (22.9 m2/g) and a broad distribution of meso-/macro-porosity (from 5 to 65 nm), which enhanced the mass transfer during the chemical process at high reaction rate and decreased the residence time of ethylene on catalyst surface. Importantly, SiC support has the high thermal conductivity, which favored the rapid temperature homogenization through the catalyst bed and inhabited the over-hydrogenation of acetylene. The surface electronic density of Pd on Pd/SiC catalyst was higher than that on Pd/TiO2, which could promote desorption of ethylene from surface of the catalyst. TGA results confirmed a much less coke deposition on Pd/SiC catalyst.

Surface cleaning and pure nitridation of GaSb by in-situ plasma processing

NASA Astrophysics Data System (ADS)

Gotow, Takahiro; Fujikawa, Sachie; Fujishiro, Hiroki I.; Ogura, Mutsuo; Chang, Wen Hsin; Yasuda, Tetsuji; Maeda, Tatsuro

2017-10-01

A clean and flat GaSb surface without native oxides has been attained by H2 plasma cleaning and subsequent in-situ N2 plasma nitridation process at 300 oC. The mechanisms of thermal desorption behavior of native oxides on GaSb have been studied by thermal desorption spectroscopy (TDS) analysis. The suitable heat treatment process window for preparing a clean GaSb surface is given. Auger electron spectroscopy (AES) analysis indicates that native oxides were completely removed on the GaSb surface after H2 plasma exposure and the pure nitridation of the clean GaSb surface was obtained at a relatively low temperature of 300 °C. This pure nitridation of GaSb have a possibility to be used as a passivation layer for high quality GaSb MOS devices.

Oxygen sorption and desorption properties of selected lanthanum manganites and lanthanum ferrite manganites.

PubMed

Nielsen, Jimmi; Skou, Eivind M; Jacobsen, Torben

2015-06-08

Temperature-programmed desorption (TPD) with a carrier gas was used to study the oxygen sorption and desorption properties of oxidation catalysts and solid-oxide fuel cell (SOFC) cathode materials (La(0.85) Sr(0.15)0.95 MnO(3+δ) (LSM) and La(0.60) Sr(0.40) Fe(0.80) Mn(0.20) O(3-δ) (LSFM). The powders were characterized by X-ray diffractometry, atomic force microscopy (AFM), and BET surface adsorption. Sorbed oxygen could be distinguished from oxygen originating from stoichiometry changes. The results indicated that there is one main site for oxygen sorption/desorption. The amount of sorbed oxygen was monitored over time at different temperatures. Furthermore, through data analysis it was shown that the desorption peak associated with oxygen sorption is described well by second-order desorption kinetics. This indicates that oxygen molecules dissociate upon adsorption and that the rate-determining step for the desorption reaction is a recombination of monatomic oxygen. Typical problems with re-adsorption in this kind of TPD setup were revealed to be insignificant by using simulations. Finally, different key parameters of sorption and desorption were determined, such as desorption activation energies, density of sorption sites, and adsorption and desorption reaction order. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ordered hexagonal mesoporous aluminosilicates with low Si/Al ratio: synthesis, characterization, and catalytic application.

PubMed

Liu, Aifeng; Che, Hongwei; Liu, Chuanzhi; Fu, Quanrong; Jiang, Ruijiao; Wang, Cheng; Wang, Liang

2014-06-01

Ordered hexagonal mesoporous aluminosilicates with lower Si/Al ratio below 5 have been successfully synthesized via the co-assembly of preformed aluminosilicate precursors with Gemini surfactant [C12H25N+(CH3)2(CH2)6N+(CH3)2C12H25] x 2Br(-) as the template. Powder X-ray diffraction, transmission electron microscopy, scanning electron microscopy, N2 adsorption-desorption isotherm measurements, Fourier transform infrared spectroscopy, 27Al nuclear magnetic resonance, thermogravimetric analysis, and temperature-programmed desorption of cyclohexylamine are employed to characterize the resulting samples. The phenol alkylation reaction is carried out to evaluate their catalytic performances. These studies indicate that the sample with a low Si/Al ratio of 3 still retains a highly ordered hexagonal mesoporous structure. And it also possesses the highest acidity of 0.96 mmol among the samples with lower Si/Al ratios below 5 due to its higher specific surface area together with more content of tetrahedrally coordinated Al in the framework. The catalytic tests confirm that the acidity of the samples plays a key role in determining their catalytic performances.

Interaction of Ester-Functionalized Ionic Liquids with Atomically-Defined Cobalt Oxides Surfaces: Adsorption, Reaction and Thermal Stability.

PubMed

Xu, Tao; Waehler, Tobias; Vecchietti, Julia; Bonivardi, Adrian; Bauer, Tanja; Schwegler, Johannes; Schulz, Peter S; Wasserscheid, Peter; Libuda, Joerg

2017-12-06

Hybrid materials consisting of ionic liquid (ILs) films on supported oxides hold a great potential for applications in electronic and energy materials. In this work, we have performed surface science model studies scrutinizing the interaction of ester-functionalized ILs with atomically defined Co 3 O 4 (111) and CoO(100) surfaces. Both supports are prepared under ultra-high vacuum (UHV) conditions in form of thin films on Ir(100) single crystals. Subsequently, thin films of three ILs, 3-butyl-1-methyl imidazolium bis(trifluoromethyl-sulfonyl) imide ([BMIM][NTf 2 ]), 3-(4-methoxyl-4-oxobutyl)-1-methylimidazolium bis(trifluoromethyl-sulfonyl) imide ([MBMIM][NTf 2 ]), and 3-(4-isopropoxy-4-oxobutyl)-1-methylimidazolium bis(trifluoromethyl-sulfonyl) imide ([IPBMIM][NTf 2 ]), were deposited on these surfaces by physical vapor deposition (PVD). Time-resolved and temperature-programmed infrared reflection absorption spectroscopy (TR-IRAS, TP-IRAS) were applied to monitor in situ the adsorption, film growth, and thermally induced desorption. By TP-IRAS, we determined the multilayer desorption temperature of [BMIM][NTf 2 ] (360±5 K), [MBMIM][NTf 2 ] (380 K) and [IPBMIM][NTf 2 ] (380 K). Upon deposition below the multilayer desorption temperature, all three ILs physisorb on both cobalt oxide surfaces. However, strong orientation effects are observed in the first monolayer, where the [NTf 2 ] - ion interacts with the surface through the SO 2 groups and the CF 3 groups point towards the vacuum. For the two functionalized ILs, the [MBMIM] + and [IPBMIM] + interact with the surface Co 2+ ions of both surfaces via the CO group of their ester function. A very different behavior is found, if the ILs are deposited above the multilayer desorption temperature (400 K). While for [BMIM][NTf 2 ] and [MBMIM][NTf 2 ] a molecularly adsorbed monolayer film is formed, [IPBMIM][NTf 2 ] undergoes a chemical transformation on the CoO(100) surface. Here, the ester group is cleaved and the cation is chemically linked to the surface by formation of a surface carboxylate. The IL-derived species in the monolayer desorb at temperatures around 500 to 550 K. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Water adsorption on the Fe3O4(111) surface: dissociation and network formation.

PubMed

Zaki, Eman; Mirabella, Francesca; Ivars-Barceló, Francisco; Seifert, Jan; Carey, Spencer; Shaikhutdinov, Shamil; Freund, Hans-Joachim; Li, Xiaoke; Paier, Joachim; Sauer, Joachim

2018-06-13

We monitored adsorption of water on a well-defined Fe3O4(111) film surface at different temperatures as a function of coverage using infrared reflection-absorption spectroscopy, temperature programmed desorption, and single crystal adsorption calorimetry. Additionally, density functional theory was employed using a Fe3O4(111)-(2 × 2) slab model to generate 15 energy minimum structures for various coverages. Corresponding vibrational properties of the adsorbed water species were also computed. The results show that water molecules readily dissociate on regular surface Fetet1-O ion pairs to form "monomers", i.e., terminal Fe-OH and surface OH groups. Further water molecules adsorb on the hydroxyl covered surface non-dissociatively and form "dimers" and larger oligomers, which ultimately assemble into an ordered (2 × 2) hydrogen-bonded network structure with increasing coverage prior to the formation of a solid water film.

Desorption Kinetics of Ar, Kr, Xe, N2, O2, CO, Methane, Ethane, and Propane from Graphene and Amorphous Solid Water Surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, R. Scott; May, Robert A.; Kay, Bruce D.

2016-03-03

The desorption kinetics for Ar, Kr, Xe, N2, O2, CO, methane, ethane, and propane from grapheme covered Pt(111) and amorphous solid water (ASW) surfaces are investigated using temperature programmed desorption (TPD). The TPD spectra for all of the adsorbates from graphene have well-resolved first, second, third, and multi- layer desorption peaks. The alignment of the leading edges is consistent the zero-order desorption for all of the adsorbates. An Arrhenius analysis is used to obtain desorption energies and prefactors for desorption from graphene for all of the adsorbates. In contrast, the leading desorption edges for the adsorbates from ASW do notmore » align (for coverages < 2 ML). The non-alignment of TPD leading edges suggests that there are multiple desorption binding sites on the ASW surface. Inversion analysis is used to obtain the coverage dependent desorption energies and prefactors for desorption from ASW for all of the adsorbates.« less

Desorption Kinetics of Ar, Kr, Xe, N2, O2, CO, Methane, Ethane, and Propane from Graphene and Amorphous Solid Water Surfaces.

PubMed

Smith, R Scott; May, R Alan; Kay, Bruce D

2016-03-03

The desorption kinetics for Ar, Kr, Xe, N2, O2, CO, methane, ethane, and propane from graphene-covered Pt(111) and amorphous solid water (ASW) surfaces are investigated using temperature-programmed desorption (TPD). The TPD spectra for all of the adsorbates from graphene have well-resolved first, second, third, and multilayer desorption peaks. The alignment of the leading edges is consistent the zero-order desorption for all of the adsorbates. An Arrhenius analysis is used to obtain desorption energies and prefactors for desorption from graphene for all of the adsorbates. In contrast, the leading desorption edges for the adsorbates from ASW do not align (for coverages < 2 ML). The nonalignment of TPD leading edges suggests that there are multiple desorption binding sites on the ASW surface. Inversion analysis is used to obtain the coverage dependent desorption energies and prefactors for desorption from ASW for all of the adsorbates.

Formation of nanocarbon spheres by thermal treatment of woody char from fast pyrolysis process

Treesearch

Qiangu Yan; Hossein Toghiani; Zhiyong Cai; Jilei Zhang

2014-01-01

Influences of thermal treatment conditions of temperature, reaction cycle and time, and purge gas type on nanocarbon formation over bio-chars from fast pyrolysis and effects of thermal reaction cycle and purge gas type on bio-char surface functional groups were investigated by temperature-programmed desorption (TPD) and temperature programmed reduction methods....

Metal-support interactions during the adsorption of CO on thin layers and islands of epitaxial palladium

NASA Technical Reports Server (NTRS)

Park, C.; Poppa, H.; Soria, F.

1984-01-01

Islands and continuous layers of palladium were grown in an ultrahigh vacuum on substrates of Mo(110)c(14 x 7)-O, designated MoO(x), and of clean Mo(110). It was found that as-deposited islands and layers exhibited bulk palladium adsorption properties for CO when deposited at room temperature and for palladium thicknesses in excess of about 3 monolayers. CO adsorption was drastically reduced, however, on annealing. For islands, annealing temperatures of as low as 400 K led to some reduction in CO adsorption whereas more severe reductions were found to occur at 600 K for islands and at 800 K for continuous multilayers. The deactivation depended on the palladium thickness, the substrate species and the extent of thermal treatments. Auger electron spectroscopy, temperature-programmed desorption and Delta-Phi measurements were combined to interpret the deactivation behavior in terms of substrate-support interactions involving the diffusion of substrate species towards the palladium surface.

Initial stages of organic film growth characterized by thermal desorption spectroscopy

PubMed Central

Winkler, Adolf

2015-01-01

In the wake of the increasing importance of organic electronics, a more in-depth understanding of the early stages of organic film growth is indispensable. In this review a survey of several rod-like and plate-like organic molecules (p-quaterphenyl, p-sexiphenyl, hexaazatriphenylene-hexacarbonitrile (HATCN), rubicene, indigo) deposited on various application relevant substrates (gold, silver, mica, silicon dioxide) is given. The focus is particularly put on the application of thermal desorption spectroscopy to shed light on the kinetics and energetics of the molecule-substrate interaction. While each adsorption system reveals a manifold of features that are specific for the individual system, one can draw some general statements on the early stages of organic film formation from the available datasets. Among the important issues in this context is the formation of wetting layers and the dewetting as a function of the substrate surface conditions, organic film thickness and temperature. PMID:26778860

Conformational reduction of DOPA in the gas phase studied by laser desorption supersonic jet laser spectroscopy.

PubMed

Ishiuchi, Shun-ichi; Mitsuda, Haruhiko; Asakawa, Toshiro; Miyazaki, Mitsuhiko; Fujii, Masaaki

2011-05-07

The conformational reduction in catecholamine neurotransmitters was studied by resonance enhanced multi photon ionization (REMPI), ultraviolet-ultraviolet (UV-UV) hole burning and infrared (IR) dip spectroscopy with applying a laser desorption supersonic jet technique to DOPA, which is one of the catecholamine neurotransmitters and has one more phenolic OH group than tyrosine. It is concluded that DOPA has a single observable conformer in the gas phase at low temperature. Quantum chemical calculations at several levels with or without the dispersion correction were also carried out to study stable conformations. From the comparison between the computational IR spectra and the experimental ones, the most stable structure was determined. It is strongly suggested that the conformational reduction is caused by electrostatic interactions, such as a dipole-dipole interaction, between the chain and OH groups. This journal is © the Owner Societies 2011

Temperature-programmed desorption study of NO reactions on rutile TiO2(110)-1×1

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Boseong; Dohnálek, Zdenek; Szanyi, János

2016-10-01

Systematic temperature-programmed desorption (TPD) studies of NO adsorption and reactions on rutile TiO2(110)-1×1 surface reveal several distinct reaction channels in a temperature range of 50 – 500 K. NO readily reacts on TiO2(110) to form N2O which desorbs between 50 and 200 K (LT N2O channels), which leaves the TiO2 surface populated with adsorbed oxygen atoms (Oa) as a byproduct of N2O formation. In addition, we observe simultaneous desorption peaks of NO and N2O at 270 K (HT1 N2O) and 400 K (HT2 N2O), respectively, both of which are attributed to reaction-limited processes. No N-derived reaction product desorbs from TiO2(110)more » surface above 500 K or higher, while the surface may be populated with Oa’s and oxidized products such as NO2 and NO3. The adsorbate-free TiO2 surface with oxygen vacancies can be regenerated by prolonged annealing at 850 K or higher. Detailed analysis of the three N2O desorption yields reveals that the surface species for the HT channels are likely to be various forms of NO dimers.« less

Temperature-programmed desorption study of NO reactions on rutile TiO 2(110)-1×1

DOE PAGES

Kim, Boseong; Dohnalek, Zdenek; Szanyi, Janos; ...

2016-02-24

In this study, systematic temperature-programmed desorption (TPD) studies of NO adsorption and reactions on rutile TiO 2(110)-1 × 1 surface reveal several distinct reaction channels in a temperature range of 50–500 K. NO readily reacts on TiO 2(110) to form N 2O, which desorbs between 50 and 200 K (LT N 2O channels), which leaves the TiO 2 surface populated with adsorbed oxygen atoms (O a) as a by-product of N 2O formation. In addition, we observe simultaneous desorption peaks of NO and N 2O at 270 K (HT1 N 2O) and 400 K (HT2 N 2O), respectively, both ofmore » which are attributed to reaction-limited processes. No N-derived reaction product desorbs from TiO 2(110) surface above 500 K or higher, while the surface may be populated with Oa's and oxidized products such as NO 2 and NO 3. The adsorbate-free TiO 2 surface with oxygen vacancies can be regenerated by prolonged annealing at 850 K or higher. Detailed analysis of the three N 2O desorption yields reveals that the surface species for the HT channels are likely to be various forms of NO dimers.« less

Deuterium trapping in tungsten

NASA Astrophysics Data System (ADS)

Poon, Michael

Tungsten is one of the primary material candidates being investigated for use in the first-wall of a magnetic confinement fusion reactor. An ion accelerator was used to simulate the type of ion interaction that may occur at a plasma-facing material. Thermal desorption spectroscopy (TDS) was the primary tool used to analyze the effects of the irradiation. Secondary ion mass spectroscopy (SIMS) was used to determine the distribution of trapped D in the tungsten specimen. The tritium migration analysis program (TMAP) was used to simulate thermal desorption profiles from the D depth distributions. Fitting of the simulated thermal desorption profiles with the measured TDS results provided values of the D trap energies. Deuterium trapping in single crystal tungsten was studied as a function of the incident ion fluence, ion flux, irradiation temperature, irradiation history, and surface impurity levels during irradiation. The results show that deuterium was trapped at vacancies and voids. Two deuterium atoms could be trapped at a tungsten vacancy, with trapping energies of 1.4 eV and 1.2 eV for the first and second D atoms, respectively. In a tungsten void, D is trapped as atoms adsorbed on the inner walls of the void with a trap energy of 2.1 eV, or as D2 molecules inside the void with a trap energy of 1.2 eV. Deuterium trapping in polycrystalline tungsten was also studied as a function of the incident fluence, irradiation temperature, and irradiation history. Deuterium trapping in polycrystalline tungsten also occurs primarily at vacancies and voids with the same trap energies as in single crystal tungsten; however, the presence of grain boundaries promotes the formation of large surface blisters with high fluence irradiations at 500 K. In general, D trapping is greater in polycrystalline tungsten than in single crystal tungsten. To simulate mixed materials comprising of carbon (C) and tungsten, tungsten specimens were pre-irradiated with carbon ions prior to D irradiation. Deuterium trapping could be characterized by three regimes: (i) enhanced D retention in a graphitic film formed by the C+ irradiation; (ii) decreased D retention in a modified tungsten-carbon layer; and (iii) D retention in pure tungsten.

Formation of Germa-ketenimine on the Ge(100) Surface by Adsorption of tert-Butyl Isocyanide.

PubMed

Shong, Bonggeun; Yoo, Jong Suk; Sandoval, Tania E; Bent, Stacey F

2017-06-28

Reactions of the (100) surfaces of Ge and Si with organic molecules have been generally understood within the concept of "dimers" formed by the 2 × 1 surface reconstruction. In this work, the adsorption of tert-butyl isocyanide on the Ge(100)-2 × 1 surface at large exposures is investigated under ultrahigh vacuum conditions. A combination of infrared spectroscopy, X-ray photoelectron spectroscopy, and temperature-programmed desorption experiments along with dispersion-corrected density functional theory calculations is used to determine the surface products. Upon adsorption of a dense monolayer of tert-butyl isocyanide, a product whose structure resembles a germa-ketenimine (N=C=Ge) with σ donation toward and π back-donation from the Ge(100) surface appears. Formation of this structure involves divalent-type surface Ge atoms that arise from cleavage of the Ge(100)-2 × 1 surface dimers. Our results reveal an unprecedented class of reactions of organic molecules at the Ge(100) surface.

Desorption of Benzene, 1,3,5-Trifluorobenzene, and Hexafluorobenzene from a Graphene Surface: The Effect of Lateral Interactions on the Desorption Kinetics.

PubMed

Smith, R Scott; Kay, Bruce D

2018-05-17

The desorption of benzene, 1,3,5-trifluorobenzene (TFB), and hexafluorobenzene (HFB) from a graphene covered Pt(111) substrate was investigated using temperature-programmed desorption (TPD). All three species have well-resolved monolayer and second-layer desorption peaks. The desorption spectra for submonolayer coverages of benzene and HFB are consistent with first-order desorption kinetics. In contrast, the submonolayer TPD spectra for TFB align on a common leading-edge, which is indicative of zero-order desorption kinetics. The desorption behavior of the three molecules can be correlated with the strength of the quadrupole moments. Calculations (second-order Møller-Plesset perturbation and density functional theory) show that the potential minimum for coplanar TFB dimers is more than a factor of 2 greater than that for either benzene or HFB dimers. The calculations support the interpretation that benzene and HFB are less likely to form the two-dimensional islands that are needed for submonolayer zero-order desorption kinetics.

Interaction of D2 with H2O amorphous ice studied by temperature-programmed desorption experiments.

PubMed

Amiaud, L; Fillion, J H; Baouche, S; Dulieu, F; Momeni, A; Lemaire, J L

2006-03-07

The gas-surface interaction of molecular hydrogen D2 with a thin film of porous amorphous solid water (ASW) grown at 10 K by slow vapor deposition has been studied by temperature-programmed-desorption (TPD) experiments. Molecular hydrogen diffuses rapidly into the porous network of the ice. The D2 desorption occurring between 10 and 30 K is considered here as a good probe of the effective surface of ASW interacting with the gas. The desorption kinetics have been systematically measured at various coverages. A careful analysis based on the Arrhenius plot method has provided the D2 binding energies as a function of the coverage. Asymmetric and broad distributions of binding energies were found, with a maximum population peaking at low energy. We propose a model for the desorption kinetics that assumes a complete thermal equilibrium of the molecules with the ice film. The sample is characterized by a distribution of adsorption sites that are filled according to a Fermi-Dirac statistic law. The TPD curves can be simulated and fitted to provide the parameters describing the distribution of the molecules as a function of their binding energy. This approach contributes to a correct description of the interaction of molecular hydrogen with the surface of possibly porous grain mantles in the interstellar medium.

Facile Dehydrogenation of Ethane on the IrO2(110) Surface.

PubMed

Bian, Yingxue; Kim, Minkyu; Li, Tao; Asthagiri, Aravind; Weaver, Jason F

2018-02-21

Realizing the efficient and selective conversion of ethane to ethylene is important for improving the utilization of hydrocarbon resources, yet remains a major challenge in catalysis. Herein, ethane dehydrogenation on the IrO 2 (110) surface is investigated using temperature-programmed reaction spectroscopy (TPRS) and density functional theory (DFT) calculations. The results show that ethane forms strongly bound σ-complexes on IrO 2 (110) and that a large fraction of the complexes undergo C-H bond cleavage during TPRS at temperatures below 200 K. Continued heating causes as much as 40% of the dissociated ethane to dehydrogenate and desorb as ethylene near 350 K, with the remainder oxidizing to CO x species. Both TPRS and DFT show that ethylene desorption is the rate-controlling step in the conversion of ethane to ethylene on IrO 2 (110) during TPRS. Partial hydrogenation of the IrO 2 (110) surface is found to enhance ethylene production from ethane while suppressing oxidation to CO x species. DFT predicts that hydrogenation of reactive oxygen atoms of the IrO 2 (110) surface effectively deactivates these sites as H atom acceptors, and causes ethylene desorption to become favored over further dehydrogenation and oxidation of ethane-derived species. The study reveals that IrO 2 (110) exhibits an exceptional ability to promote ethane dehydrogenation to ethylene near room temperature, and provides molecular-level insights for understanding how surface properties influence selectivity toward ethylene production.

Phase transitions of amorphous solid acetone in confined geometry investigated by reflection absorption infrared spectroscopy.

PubMed

Shin, Sunghwan; Kang, Hani; Kim, Jun Soo; Kang, Heon

2014-11-26

We investigated the phase transformations of amorphous solid acetone under confined geometry by preparing acetone films trapped in amorphous solid water (ASW) or CCl4. Reflection absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD) were used to monitor the phase changes of the acetone sample with increasing temperature. An acetone film trapped in ASW shows an abrupt change in the RAIRS features of the acetone vibrational bands during heating from 80 to 100 K, which indicates the transformation of amorphous solid acetone to a molecularly aligned crystalline phase. Further heating of the sample to 140 K produces an isotropic solid phase, and eventually a fluid phase near 157 K, at which the acetone sample is probably trapped in a pressurized, superheated condition inside the ASW matrix. Inside a CCl4 matrix, amorphous solid acetone crystallizes into a different, isotropic structure at ca. 90 K. We propose that the molecularly aligned crystalline phase formed in ASW is created by heterogeneous nucleation at the acetone-water interface, with resultant crystal growth, whereas the isotropic crystalline phase in CCl4 is formed by homogeneous crystal growth starting from the bulk region of the acetone sample.

A Novel Nanocomposite as an Efficient Adsorbent for the Rapid Adsorption of Ni(II) from Aqueous Solution

PubMed Central

Wang, Ximing; Chen, Zhangjing

2017-01-01

A sulfhydryl-lignocellulose/montmorillonite (SLT) nanocomposite was prepared using a chemical intercalation reaction. The SLT nanocomposite was characterized by Fourier Transform Infrared Spectroscopy (FTIR), X-Ray Diffraction (XRD), Scanning Electron Microscope (SEM), and Transmission Electron Microscopy (TEM), the results demonstrated that an intercalated-exfoliated nanostructure was formed in the SLT nanocomposite. Batch experiments were conducted to optimize parameters such as SLT nanocomposite dosage, the initial concentration of Ni(II), solution pH, temperature, and time. The results indicated that the attractive adsorption capacity reached 1134.08 mg/g with 0.05 g of SLT at an initial concentration of Ni(II) of 700 mg/L, solution pH of 5.5, adsorption temperature of 50 °C, and adsorption time of 40 min, meanwhile, the Ni(II) adsorption capacity significantly decreased with the increase in ionic strength. The pseudo-second order kinetic model could describe the whole adsorption process well, and the isotherm adsorption equilibrium conformed to the Freundlich model. The adsorption mechanism of SLT was also discussed by means of FTIR and Energy-Dispersive X-Ray (EDX). Dramatically, the introduction of sulfhydryl achieves the increased activated functional groups content of SLT nanocomposite, leading to remarkably higher adsorption amount on Ni(II). The desorption capacity of SLT was dependent on parameters such as HNO3 concentration, desorption temperature, and ultrasonic desorption time. The satisfactory desorption capacity and desorption efficiency of 458.21 mg/g and 40.40% were obtained at an HNO3 concentration, desorption temperature, and ultrasonic desorption time of 0.4 mol/L, 40 °C, and 30 min, respectively. The regeneration studies showed that the adsorption capacity of SLT was consistent for four cycles without any appreciable loss and confirmed that the SLT was reusable. Owing to such outstanding features, the novel SLT nanocomposite proved the great potential in adsorption for Ni(II) removal from aqueous solution, and exhibited an extremely significant amount of Ni(II), compared to pristine lignocellulose/montmorillonite and the conventional spent adsorbents. PMID:28937606

Desorption of oxygen from alloyed Ag/Pt(111)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jankowski, Maciej; Wormeester, Herbert, E-mail: h.wormeester@utwente.nl; Zandvliet, Harold J. W.

2014-06-21

We have investigated the interaction of oxygen with the Ag/Pt(111) surface alloy by thermal desorption spectroscopy (TDS). The surface alloy was formed during the deposition of sub-monolayer amounts of silver on Pt(111) at 800 K and subsequent cooling to 300 K. The low-temperature phase of the surface alloy is composed of nanometer-sized silver rich stripes, embedded within platinum-rich domains, which were characterized with spot profile analysis low energy electron diffraction. The TDS measurements show that oxygen adsorption is blocked on Ag sites: the saturation coverage of oxygen decreases with increasing Ag coverage. Also, the activation energy for desorption (E{sub des})more » decreases with Ag coverage. The analysis of the desorption spectra from clean Pt(111) shows a linear decay of E{sub des} with oxygen coverage, which indicates repulsive interactions between the adsorbed oxygen atoms. In contrast, adsorption on alloyed Ag/Pt(111) leads to an attractive interaction between adsorbed oxygen atoms.« less

(100) facets of γ-Al2O3: the active surfaces for alcohol dehydration reactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kwak, Ja Hun; Mei, Donghai; Peden, Charles HF

2011-05-01

Temperature programmed desorption (TPD) of ethanol, and methanol dehydration reaction were studied on γ-Al2O3 in order to identify the catalytic active sites for alcohol dehydration reactions. Two high temperature (> 473 K) desorption features were observed following ethanol adsorption. Samples calcined at T≤473 K displayed a desorption feature in the 523-533 K temperature range, while those calcined at T ≥ 673 K showed a single desorption feature at 498 K. The switch from the high to low temperature ethanol desorption correlated well with the dehydroxylation of the (100) facets of γ-Al2O3 that was predicted at 550 K DFT calculations. Theoreticalmore » DFT simulations of the mechanism of dehydration. on clean and hydroxylated γ-Al2O3(100) surfaces, find that a concerted elimination of ethylene from an ethanol molecule chemisorbed at an Al3+ pentacoordinated site is the rate limiting step for catalytic cycle on both surfaces. Furthermore, titration of the pentacoordinate Al3+ sites on the (100) facets of γ-Al2O3 by BaO completely turned off the methanol dehydration reaction activity. These results unambiguously demonstrate that only the (100) facets on γ-Al2O3 are the catalytic active surfaces for alcohol dehydration.« less

CO Diffusion and Desorption Kinetics in CO2 Ices

NASA Astrophysics Data System (ADS)

Cooke, Ilsa R.; Öberg, Karin I.; Fayolle, Edith C.; Peeler, Zoe; Bergner, Jennifer B.

2018-01-01

The diffusion of species in icy dust grain mantles is a fundamental process that shapes the chemistry of interstellar regions; yet, measurements of diffusion in interstellar ice analogs are scarce. Here we present measurements of CO diffusion into CO2 ice at low temperatures (T = 11–23 K) using CO2 longitudinal optical phonon modes to monitor the level of mixing of initially layered ices. We model the diffusion kinetics using Fick’s second law and find that the temperature-dependent diffusion coefficients are well fit by an Arrhenius equation, giving a diffusion barrier of 300 ± 40 K. The low barrier along with the diffusion kinetics through isotopically labeled layers suggest that CO diffuses through CO2 along pore surfaces rather than through bulk diffusion. In complementary experiments, we measure the desorption energy of CO from CO2 ices deposited at 11–50 K by temperature programmed desorption and find that the desorption barrier ranges from 1240 ± 90 K to 1410 ± 70 K depending on the CO2 deposition temperature and resultant ice porosity. The measured CO–CO2 desorption barriers demonstrate that CO binds equally well to CO2 and H2O ices when both are compact. The CO–CO2 diffusion–desorption barrier ratio ranges from 0.21 to 0.24 dependent on the binding environment during diffusion. The diffusion–desorption ratio is consistent with the above hypothesis that the observed diffusion is a surface process and adds to previous experimental evidence on diffusion in water ice that suggests surface diffusion is important to the mobility of molecules within interstellar ices.

Water as probe molecule for midgap states in nanocrystalline strontium titanate by conventional and synchronous luminescence spectroscopy under ambient conditions

NASA Astrophysics Data System (ADS)

Taylor, Sean; Samokhvalov, Alexander

2017-03-01

Alkaline earth metal titanates are broad bandgap semiconductors with applications in electronic devices, as catalysts, photocatalysts, sorbents, and sensors. Strontium titanate SrTiO3 is of interest in electronic devices, sensors, in the photocatalytic hydrogen generation, as catalyst and sorbent. Both photocatalysis and operation of electronic devices rely upon the pathways of relaxation of excited charge in the semiconductor, including relaxation through the midgap states. We report characterization of nanocrystalline SrTiO3 at room temperature by "conventional" vs. synchronous luminescence spectroscopy and complementary methods. We determined energies of radiative transitions in the visible range through the two midgap states in the nanocrystalline SrTiO3. Further, adsorption and desorption of vapor of water as "probe molecule" for midgap states in the nanocrystalline SrTiO3 was studied, for the first time, by luminescence spectroscopy under ambient conditions. Emission of visible light from the nanocrystalline SrTiO3 is significantly increased upon desorption of water and decreased (quenched) upon adsorption of water vapor, due to interactions with the surface midgap states.

In situ supported MnOx-CeOx on carbon nanotubes for the low-temperature selective catalytic reduction of NO with NH3

NASA Astrophysics Data System (ADS)

Zhang, Dengsong; Zhang, Lei; Shi, Liyi; Fang, Cheng; Li, Hongrui; Gao, Ruihua; Huang, Lei; Zhang, Jianping

2013-01-01

The MnOx and CeOx were in situ supported on carbon nanotubes (CNTs) by a poly(sodium 4-styrenesulfonate) assisted reflux route for the low-temperature selective catalytic reduction (SCR) of NO with NH3. X-Ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), X-ray photoelectron spectroscopy (XPS), H2 temperature-programmed reduction (H2-TPR) and NH3 temperature-programmed desorption (NH3-TPD) have been used to elucidate the structure and surface properties of the obtained catalysts. It was found that the in situ prepared catalyst exhibited the highest activity and the most extensive operating-temperature window, compared to the catalysts prepared by impregnation or mechanically mixed methods. The XRD and TEM results indicated that the manganese oxide and cerium oxide species had a good dispersion on the CNT surface. The XPS results demonstrated that the higher atomic concentration of Mn existed on the surface of CNTs and the more chemisorbed oxygen species exist. The H2-TPR results suggested that there was a strong interaction between the manganese oxide and cerium oxide on the surface of CNTs. The NH3-TPD results demonstrated that the catalysts presented a larger acid amount and stronger acid strength. In addition, the obtained catalysts exhibited much higher SO2-tolerance and improved the water-resistance as compared to that prepared by impregnation or mechanically mixed methods.The MnOx and CeOx were in situ supported on carbon nanotubes (CNTs) by a poly(sodium 4-styrenesulfonate) assisted reflux route for the low-temperature selective catalytic reduction (SCR) of NO with NH3. X-Ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), X-ray photoelectron spectroscopy (XPS), H2 temperature-programmed reduction (H2-TPR) and NH3 temperature-programmed desorption (NH3-TPD) have been used to elucidate the structure and surface properties of the obtained catalysts. It was found that the in situ prepared catalyst exhibited the highest activity and the most extensive operating-temperature window, compared to the catalysts prepared by impregnation or mechanically mixed methods. The XRD and TEM results indicated that the manganese oxide and cerium oxide species had a good dispersion on the CNT surface. The XPS results demonstrated that the higher atomic concentration of Mn existed on the surface of CNTs and the more chemisorbed oxygen species exist. The H2-TPR results suggested that there was a strong interaction between the manganese oxide and cerium oxide on the surface of CNTs. The NH3-TPD results demonstrated that the catalysts presented a larger acid amount and stronger acid strength. In addition, the obtained catalysts exhibited much higher SO2-tolerance and improved the water-resistance as compared to that prepared by impregnation or mechanically mixed methods. Electronic supplementary information (ESI) available: SEM images and EDS analysis, TEM images, and XPS spectrum of samples. See DOI: 10.1039/c2nr33006g

Interaction of acetonitrile with the surfaces of amorphous and crystalline ice

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schaff, J.E.; Roberts, J.T.

1999-10-12

The adsorption of acetonitrile (CH{sub 3}CN) on ultrathin films of ice under ultrahigh vacuum was investigated with temperature-programmed desorption ass spectrometry (TPD) and Fourier transform infrared reflection absorption spectroscopy (FTIRAS). Two types of film were studied, amorphous and crystalline. On the amorphous films, two sates of adsorbed acetonitrile were observed by TPD and FTIRAS. One of the states is attributed to acetonitrile that is hydrogen bonded to agree OH group at the ice surface; the other state is assigned to acetonitrile that is purely physiorbed. Evidence for the hydrogen-bonded state is two-fold. First, there is a large kinetic isotope effectmore » for desorption from H{sub 2}O-and D{sub 2}O-ice: the desorption temperatures from ice-h{sub 2} and ice-d{sub 2} are {approximately}161 and {approximately}176 K, respectively. Second, the C{triple{underscore}bond}N stretching frequency (2,265 cm{sup {minus}1}) is 16 cm{sup {minus}1} is greater than that of physisorbed acetonitrile, and it is roughly equal to that of acetonitrile which is hydrogen bonded to an OH group at the air-liquid water interface. On the crystalline films, there is no evidence for a hydrogen-bonded state in the TPD spectra. The FTIRAS spectra do show that some hydrogen-bonded acetonitrile is present but at a maximum coverage that is roughly one-sixth of that on the amorphous surface. The difference between the amorphous and crystalline surfaces cannot be attributed to a difference n surface areas. Rather, this work provides additional evidence that the surface chemical properties of amorphous ice are different from those of crystalline ice.« less

Promotion of redox and stability features of doped Ce-W-Ti for NH3-SCR reaction over a wide temperature range

NASA Astrophysics Data System (ADS)

Zhao, Kun; Han, Weiliang; Lu, Gongxuan; Lu, Jiangyin; Tang, Zhicheng; Zhen, Xinping

2016-08-01

In this study, transition metals Co, Mn, and Cu were introduced into a Ce-W-Ti catalyst to promote low-temperature catalytic activity. Among these metal-modified M/Ce-W-Ti catalysts (M represents Co, Mn, or Cu), the Cu/Ce-W-Ti catalyst with an optimized Cu content of 5 wt.% exhibited more than 90% conversion of nitrogen oxide (NOx) in the selective catalytic reduction by NH3 over a wide temperature range (260-400 °C). This catalyst likewise exhibited higher resistance to SO2 gas and water vapor under severe test conditions. On the basis of the characterization results by powder X-ray diffraction and X-ray photoelectron spectroscopy, we concluded that the superior catalytic properties of the Cu/Ce-W-Ti catalyst could be attributed to the highly dispersed Cu species, which increased the contents of Ce3+ species and adsorbed oxygen species in the catalysts. In addition, the NH3 temperature-programmed desorption results demonstrated that the Cu species doped into the Ce-W-Ti catalysts optimized surface acid content.

Note: A versatile mass spectrometer chamber for molecular beam and temperature programmed desorption experiments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tonks, James P., E-mail: james.tonks@awe.co.uk; AWE Plc, Aldermaston, Reading, Berkshire RG7 4PR; Galloway, Ewan C., E-mail: ewan.galloway@awe.co.uk

2016-08-15

A dual purpose mass spectrometer chamber capable of performing molecular beam scattering (MBS) and temperature programmed desorption (TPD) is detailed. Two simple features of this design allow it to perform these techniques. First, the diameter of entrance aperture to the mass spectrometer can be varied to maximize signal for TPD or to maximize angular resolution for MBS. Second, the mass spectrometer chamber can be radially translated so that it can be positioned close to the sample to maximize signal or far from the sample to maximize angular resolution. The performance of this system is described and compares well with systemsmore » designed for only one of these techniques.« less

Enhanced room-temperature catalytic decomposition of formaldehyde on magnesium-aluminum hydrotalcite/boehmite supported platinum nanoparticles catalyst.

PubMed

Yan, Zhaoxiong; Yang, Zhihua; Xu, Zhihua; An, Liang; Xie, Fang; Liu, Jiyan

2018-08-15

Magnesium-aluminum hydrotalcite (Mg-Al HT)/boehmite (AlOOH) composite supported Pt catalysts were obtained via one-pot microemulsion synthesis of Mg-Al HT/AlOOH composite and NaBH 4 -reduction of Pt precursor processes. The catalytic performances of the catalysts were evaluated for formaldehyde (HCHO) removal at room temperature. The performance tests showed that the catalyst obtained by immobilizing Pt nanoparticles (NPs) on Mg-Al HT/AlOOH support with Al/Mg molar ratio equivalent to 9:1 (Pt/Al 9 Mg 1 ) displayed a superior catalytic activity and stability for HCHO removal. In order to find out the causes of its higher activity, X-ray diffraction, transmission electron microscopy, N 2 adsorption/desorption, X-ray photoelectron spectroscopy, temperature programmed desorption of CO 2 and reduction of H 2 were used to analyze the physicochemical properties of Pt/Al 9 Mg 1 and Pt/AlOOH. The remarkable catalytic performance of Pt/Al 9 Mg 1 is mainly attributed to the relatively larger amount of surface oxygen species, and more reactive oxygen species led by the interaction of Mg-Al HT and AlOOH/Pt, and relatively larger number of weak base sites caused by Mg-Al HT. The formate species are the main reaction intermediate over Pt/Al 9 Mg 1 during HCHO oxidation at room temperature, which could be further oxidized into CO 2 and H 2 O in the presence of O 2 . This study might shed some light on further improving the catalytic performance of the catalyst for indoor air purification at room temperature. Copyright © 2018 Elsevier Inc. All rights reserved.

Adsorption, desorption, and displacement kinetics of H2O and CO2 on TiO2(110).

PubMed

Smith, R Scott; Li, Zhenjun; Chen, Long; Dohnálek, Zdenek; Kay, Bruce D

2014-07-17

The adsorption, desorption, and displacement kinetics of H2O and CO2 on TiO2(110) are investigated using temperature programmed desorption (TPD) and molecular beam techniques. The TPD spectra for both H2O and CO2 have well-resolved peaks corresponding to desorption from bridge-bonded oxygen (Ob), Ti5c, and defect sites in order of increasing peak temperature. Analysis of the saturated surface spectrum for both species reveals that the corresponding adsorption energies on all sites are greater for H2O than for CO2. Sequential dosing of H2O and CO2 reveals that, independent of the dose order, H2O molecules will displace CO2 in order to occupy the highest energy binding sites available. Isothermal experiments show that the displacement of CO2 by H2O occurs between 75 and 80 K.

Irradiation effect on deuterium behaviour in low-dose HFIR neutron-irradiated tungsten

DOE PAGES

Shimada, Masashi; Cao, G.; Otsuka, T.; ...

2014-12-01

Tungsten samples were irradiated by neutrons in the High Flux Isotope Reactor, Oak Ridge National Laboratory at reactor coolant temperatures of 50-70°C to low displacement damage of 0.025 and 0.3 dpa under the framework of the US-Japan TITAN program (2007-2013). After cooling down, the HFIR neutron-irradiated tungsten samples were exposed to deuterium plasmas in the Tritium Plasma Experiment, Idaho National Laboratory at 100, 200 and 500 °C twice at the ion fluence of 5×10²⁵ m⁻² to reach a total ion fluence of 1×10²⁶ m⁻² in order to investigate the near surface deuterium retention and saturation via nuclear reaction analysis. Finalmore » thermal desorption spectroscopy was performed to elucidate irradiation effect on total deuterium retention. Nuclear reaction analysis results showed that the maximum near surface (<5 µm depth) deuterium concentration increased from 0.5 at % D/W in 0.025 dpa samples to 0.8 at. % D/W in 0.3 dpa samples. The large discrepancy between the total retention via thermal desorption spectroscopy and the near surface retention via nuclear reaction analysis indicated the deuterium was migrated and trapped in bulk (at least 50 µm depth for 0.025 dpa and 35 µm depth for 0.025 dpa) at 500 °C case even in the relatively low ion fluence of 10²⁶ m⁻².« less

Laboratory Studies of Alkali Components in Tenuous Planetary Atmospheres

NASA Astrophysics Data System (ADS)

Yakshinskiy, B. V.

2004-05-01

We report on studies performed at the Laboratory for Surface Modification of Rutgers University and focused on the origin of alkali vapors (Na, K) in the tenuous atmospheres of the planet Mercury, the Moon, and Jupiter's icy satellite Europa [1, 2]; we also address the question why alkaline-earth metals (Mg, Ca) are less abundant in the atmospheres. A variety of ultrahigh-vacuum surface science techniques are used, including X-ray Photoelectron Spectroscopy (XPS), Low-Energy Ion Scattering (LEIS), Thermal Programmed Desorption (TPD), Electron- and Photon-Stimulated Desorption (ESD and PSD), Surface Ionization (SI). Measurements have been made on different samples, including the model mineral binary oxide SiO2 that simulates lunar silicates, and a lunar sample obtained from NASA. Desorption induced by electronic excitations (mainly PSD) rather than by thermal processes is found to be the dominant source process on the lunar surface. The flux at the lunar surface of ultraviolet photons from the Sun is adequate to insure that PSD of sodium contributes substantially to the Moon's atmosphere. A model based on irradiation-induced charge-transfer is proposed to explain the desorption process. There is a strong temperature-dependence of Na ESD and PSD signals from a lunar sample, under conditions where the Na surface coverage is constant and thermal desorption is negligible [3]. On Mercury solar heating of the surface is high enough that thermal desorption will also be a potential source of atmospheric sodium. Ion bombardment of the lunar sample causes both the sputtering of alkali atoms into vacuum and implantation into the sample bulk. In the future we outline the use a novel method, Nuclear Resonance Profiling (NRP) to study the diffusion of alkalis through model minerals, ices, and lunar samples; these measurements would provide additional information to understand the replenishment of Na at the surface of the Moon, Mercury and Europa. We also describe a new detector that we will use to search for desorption of alkaline-earth atoms. [1] T.E. Madey, R.E. Johnson, T.M. Orlando, Surf. Sci. 500 (2002) 838. [2] B.V. Yakshinskiy, T.E. Madey, Surf. Sci. 528 (2003) 54. [3] B.V. Yakshinskiy, T.E. Madey, Icarus 168 (2004) 53.

Turning things downside up: Adsorbate induced water flipping on Pt(111)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kimmel, Greg A., E-mail: gregory.kimmel@pnnl.gov, E-mail: bruce.kay@pnnl.gov; Zubkov, Tykhon; Smith, R. Scott

2014-11-14

We have examined the adsorption of the weakly bound species N{sub 2}, O{sub 2}, CO, and Kr on the (√(37)×√(37))R25.3{sup ∘} water monolayer on Pt(111) using a combination of molecular beam dosing, infrared reflection absorption spectroscopy, and temperature programmed desorption. In contrast to multilayer crystalline ice, the adsorbate-free water monolayer is characterized by a lack of dangling OH bonds protruding into the vacuum (H-up). Instead, the non-hydrogen-bonded OH groups are oriented downward (H-down) to maximize their interaction with the underlying Pt(111) substrate. Adsorption of Kr and O{sub 2} have little effect on the structure and vibrational spectrum of the “√(37)”more » water monolayer while adsorption of both N{sub 2}, and CO are effective in “flipping” H-down water molecules into an H-up configuration. This “flipping” occurs readily upon adsorption at temperatures as low as 20 K and the water monolayer transforms back to the H-down, “√(37)” structure upon adsorbate desorption above 35 K, indicating small energy differences and barriers between the H-down and H-up configurations. The results suggest that converting water in the first layer from H-down to H-up is mediated by the electrostatic interactions between the water and the adsorbates.« less

Porous Ni-Mn oxide nanosheets in situ formed on nickel foam as 3D hierarchical monolith de-NOx catalysts

NASA Astrophysics Data System (ADS)

Cai, Sixiang; Zhang, Dengsong; Shi, Liyi; Xu, Jing; Zhang, Lei; Huang, Lei; Li, Hongrui; Zhang, Jianping

2014-06-01

In this work, we successfully in situ decorated nickel foam with porous Ni-Mn oxide nanosheets (3DH-NM/NF) as 3D hierarchical monolith de-NOx catalysts via a simple hydrothermal reaction and calcination process. The catalysts were carefully examined by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, elemental mapping, X-ray photoelectron spectroscopy, H2 temperature-programmed reduction and NH3 temperature-programmed desorption measurements. The results indicated that the nanosheets are composed of a Ni6Mn1O8 spinel and the metal species are uniformly dispersed in bi-metal oxides. As a result, the strong synergistic effects between the Mn and Ni species have been observed. The active oxygen species, reducible species and acidity are enhanced by the in situ formation of the nanosheets on the surface of nickel foam. These desirable features of 3DH-NM/NF catalysts bring about the excellent de-NOx performance. Moreover, the 3DH-NM/NF catalysts also present good stability and H2O resistance. Based on these favorable properties, 3DH-NM/NF could be considered as a promising candidate for the monolith de-NOx catalysts.In this work, we successfully in situ decorated nickel foam with porous Ni-Mn oxide nanosheets (3DH-NM/NF) as 3D hierarchical monolith de-NOx catalysts via a simple hydrothermal reaction and calcination process. The catalysts were carefully examined by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, elemental mapping, X-ray photoelectron spectroscopy, H2 temperature-programmed reduction and NH3 temperature-programmed desorption measurements. The results indicated that the nanosheets are composed of a Ni6Mn1O8 spinel and the metal species are uniformly dispersed in bi-metal oxides. As a result, the strong synergistic effects between the Mn and Ni species have been observed. The active oxygen species, reducible species and acidity are enhanced by the in situ formation of the nanosheets on the surface of nickel foam. These desirable features of 3DH-NM/NF catalysts bring about the excellent de-NOx performance. Moreover, the 3DH-NM/NF catalysts also present good stability and H2O resistance. Based on these favorable properties, 3DH-NM/NF could be considered as a promising candidate for the monolith de-NOx catalysts. Electronic supplementary information (ESI) available: Experimental details and catalytic performance of the NM/cordierite catalysts, SEM image and EDX analysis of the NF and 3DH-N/NF catalysts, N2 selectivity and catalytic performance under different gas hourly space velocities of the 3DH-NM/NF catalysts. See DOI: 10.1039/c4nr00475b

Chemical structural analysis of diamondlike carbon films: II. Raman analysis

NASA Astrophysics Data System (ADS)

Takabayashi, Susumu; Ješko, Radek; Shinohara, Masanori; Hayashi, Hiroyuki; Sugimoto, Rintaro; Ogawa, Shuichi; Takakuwa, Yuji

2018-02-01

The chemical structure of diamondlike carbon (DLC) films, synthesized by photoemission-assisted glow discharge, has been analyzed by Raman spectroscopy. Raman analysis in conjunction with the sp2 cluster model clarified the film structure. The sp2 clusters in DLC films synthesized at low temperature preferred various aliphatic structures. Sufficient argon-ion assist allowed for formation of less strained DLC films containing large amounts of hydrogen. As the synthesis temperature was increased, thermal desorption of hydrogen left carbon dangling bonds with active unpaired electrons in the films, and the reactions that followed created strained films containing aromatic sp2 clusters. In parallel, the desorption of methane molecules from the growing surface by chemisorption of hydrogen radicals prevented the action of argon ions, promoting internal strain of the films. However, in synthesis at very high temperature, where sp2 clusters are sufficiently dominant, the strain was dissolved gradually. In contrast, the DLC films synthesized at low temperature were more stable than other films synthesized at the same temperature because of stable hydrogen-carbon bonds in the films.

An XPS study of the stability of Fomblin Z25 on the native oxide of aluminum. [x ray photoelectron spectroscopy

NASA Technical Reports Server (NTRS)

Herrera-Fierro, Pilar; Pepper, Stephen V.; Jones, William R.

1991-01-01

Thin films of Fomblin Z25, a perfluoropolyalkylether lubricant, were vapor deposited onto clean, oxidized aluminum and sapphire surfaces, and their behavior at different temperatures was studied using x ray photoelectron spectroscopy (XPS) and thermal desorption spectroscopy (TDS). It was found that the interfacial fluid molecules decompose on the native oxide at room temperature, and continue to decompose at elevated temperatures, as previous studies had shown to occur on clean metal. TDS indicated that different degradation mechanisms were operative for clean and oxidized aluminum. On sapphire substrates, no reaction was observed at room temperature. Our conclusion is that the native oxide of aluminum is neither passive nor protective towards Fomblin Z25. At high temperatures (150 C) degradation of the polymer on sapphire produced a debris layer at the interface with a chemical composition similar to the one formed on aluminum oxide. Rubbing a Fomblin film on a single crystal sapphire also induced the decomposition of the lubricant in contact with the interface and the formulation of a debris layer.

ISS and TPD study of the adsorption and interaction of CO and H2 on polycrystalline Pt

NASA Technical Reports Server (NTRS)

Melendez, Orlando; Hoflund, Gar B.; Schryer, David R.

1990-01-01

The adsorption and interaction of CO and H2 on polycrystalline Pt has been studied using ion scattering spectroscopy (ISS) and temperature programmed desorption (TPD). The ISS results indicate that the initial CO adsorption on Pt takes place very rapidly and saturates the Pt surface with coverage close to a monolayer. ISS also shows that the CO molecules adsorb at an angular orientation from the surface normal and perhaps parallel to the surface. A TPD spectrum obtained after coadsorbing C-12 O-16 and C-13 O-18 on Pt shows no isotopic mixing, which is indicative of molecular CO adsorption. TPD spectra obtained after coadsorbing H2 and CO on polycrystalline Pt provides evidence for the formation of a CO-H surface species.

ON THE FORMATION OF BENZOIC ACID AND HIGHER-ORDER BENZENE CARBOXYLIC ACIDS IN INTERSTELLAR MODEL ICE GRAINS

DOE Office of Scientific and Technical Information (OSTI.GOV)

McMurtry, Brandon M.; Saito, Sean E. J.; Turner, A

With a binary ice mixture of benzene (C{sub 6}H{sub 6}) and carbon dioxide (CO{sub 2}) at 10 K under contamination-free ultrahigh vacuum conditions, the formation of benzene carboxylic acids in interstellar ice grains was studied. Fourier transform infrared spectroscopy was used to probe for the formation of new species during the chemical processing of the ice mixture and during the following temperature-programmed desorption. Newly formed benzene carboxylic acid species, i.e., benzoic acid, as well as meta - and para -benzene dicarboxylic acid, were assigned using newly emerging bands in the infrared spectrum; a reaction mechanism, along with rate constants, wasmore » proposed utilizing the kinetic fitting of the coupled differential equations.« less

Facile and Low-cost Synthesis of Mesoporous Ti-Mo Bi-metal Oxide Catalysts for Biodiesel Production from Esterification of Free Fatty Acids in Jatropha curcas Crude Oil.

PubMed

Zhang, Qiuyun; Li, Hu; Yang, Song

2018-05-01

Mesoporous Ti-Mo bi-metal oxides with various titanium-molybdenum ratios were successfully fabricated via a facile approach by using stearic acid as a low-cost template agent. thermal gravity (TG) /differential scanning calorimetry (DSC) analysis, X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, nitrogen adsorption-desorption isotherm, NH 3 temperature-programmed desorption (NH 3 -TPD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) measurements indicated these materials possessing mesoporous structure, sufficient pore size and high acid intensity. The catalytic performance of prepared catalysts was evaluated by esterification of free fatty acids in Jatropha curcas crude oil (JCCO) with methanol. The effects of various parameters on FFA conversion were investigated. The esterification conversion of 87.8% was achieved under the condition of 180°C, 2 h, methanol to JCCO molar ratio of 20:1 and 3.0 wt.% catalyst (relative to the weight of JCCO). The mesoporous catalysts were found to exhibit high activities toward the simultaneous esterification and transesterification of JCCO. Furthermore, the catalyst could be recovered with a good reusability.

Oxidation of MnO(100) and NaMnO2 formation: Characterization of Mn2+ and Mn3+ surfaces via XPS and water TPD

NASA Astrophysics Data System (ADS)

Feng, Xu; Cox, David F.

2018-09-01

The oxidation of clean and Na precovered MnO(100) has been investigated by X-ray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED) and temperature programmed desorption (TPD) of adsorbed water. XPS results indicate that Mn3O4-like and Mn2O3-like surfaces can be formed by various oxidation treatments of clean and nearly-stoichiometric MnO(100), while a NaMnO2-like surface can be produced by the oxidation of MnO(100) pre-covered with multilayers of metallic Na. Water TPD results indicate that water adsorption/desorption is sensitive to the available oxidation states of surface Mn cations, and can be used to distinguish between surfaces exposing Mn2+and Mn3+ cations, or a combination of these oxidation states. Carbon dioxide and water TPD results from the NaMnO2-like surface indicate that pre-adsorbed water blocks the uptake of CO2, while water displaces pre-adsorbed CO2. No indication of a strong reactive interaction is observed between CO2, water and the NaMnO2-like surface under the conditions of our study.

Weak interactions between water and clathrate-forming gases at low pressures

DOE PAGES

Thürmer, Konrad; Yuan, Chunqing; Kimmel, Greg A.; ...

2015-07-17

Using scanning probe microscopy and temperature programed desorption we examined the interaction between water and two common clathrate-forming gases, methane and isobutane, at low temperature and low pressure. Water co-deposited with up to 10 –1 mbar methane or 10 –5 mbar isobutane at 140 K onto a Pt(111) substrate yielded pure crystalline ice, i.e., the exposure to up to ~ 10 7 gas molecules for each deposited water molecule did not have any detectable effect on the growing films. Exposing metastable, less than 2 molecular layers thick, water films to 10 –5 mbar methane does not alter their morphology, suggestingmore » that the presence of the Pt(111) surface is not a strong driver for hydrate formation. This weak water–gas interaction at low pressures is supported by our thermal desorption measurements from amorphous solid water and crystalline ice where 1 ML of methane desorbs near ~ 43 K and isobutane desorbs near ~ 100 K. As a result, similar desorption temperatures were observed for desorption from amorphous solid water.« less

Helium retention behavior in simultaneously He+-H2+ irradiated tungsten

NASA Astrophysics Data System (ADS)

Zhou, Qilai; Azuma, Keisuke; Togari, Akihiro; Yajima, Miyuki; Tokitani, Masayuki; Masuzaki, Suguru; Yoshida, Naoaki; Hara, Masanori; Hatano, Yuji; Oya, Yasuhisa

2018-04-01

The purpose of this study is to elucidate helium (He) retention behavior in tungsten (W) under simultaneous He and hydrogen (H) irradiation. Polycrystalline-W was irradiated by He+ and H2+ simultaneously with the energy of 1.0 keV and 3.0 keV. He+ fluences were (0.5, 1.0, 10) × 1021 He+ m-2 and H2+ fluence was 1.0 × 1022 H+ m-2,respectively. After irradiation, He desorption behavior was investigated by high temperature thermal desorption spectroscopy (HT-TDS) in the temperature range of R.T.-1773 K. Micro-structure changes of W after irradiation were observed by TEM. It was found that simultaneous irradiation with different H2+ energy significantly changed He retention behavior. 1.0 keV H2+ suppressed the He bubble growth and no bubbles can be observed at room temperature. On the other hand, 3.0 keV H2+ facilitated the formation of He bubbles and increased the He retention due to the additional damage introduction by energetic H2+.

A hot implantation study on the evolution of defects in He ion implanted MgO(1 0 0)

NASA Astrophysics Data System (ADS)

Fedorov, A. V.; van Huis, M. A.; van Veen, A.

2002-05-01

Ion implantation at elevated temperature, so-called hot implantation, was used to study nucleation and thermal stability of the defects. In this work, MgO(1 0 0) single crystal samples were implanted with 30 keV He ions at various implantation temperatures. The implantation doses ranged from 10 14 to 10 16 cm -2. The implantation introduced defects were subsequently studied by thermal helium desorption spectroscopy (THDS) and Doppler broadening positron beam analysis (PBA). The THDS study provides vital information on the kinetics of He release from the sample. PBA technique, being sensitive to the open volume defects, provides complementary information on cavity evolution. The THD study has shown that in most cases helium release is characterised by the activation energy of Q=4.7±0.5 eV with the maximum release temperature of Tmax=1830 K. By applying first order desorption model the pre-exponent factor is estimated as ν=4.3×10 11 s -1.

The structural and electronic properties of cleaved silicon (111) surfaces following adsorption of silver

NASA Astrophysics Data System (ADS)

Le Lay, G.; Chauvet, A.; Manneville, M.; Kern, R.

Silver overlayers for coverages ranging from zero to several monolayers are evaporated on vacuum-cleaved (111) silicon surfaces and carefully examined using low-energy electron diffraction (diffraction patterns and I(v) curves), and Auger electron spectroscopy (condensation/desorption curves), with the aim of establishing a closer correlation between the adsorption process, the different superlattices observed (i.e. 7 × 7-R(±19°1), 3 × 3-R(30° ), 3 × 1 and 6 × 1), the growth mechanism of the deposit on the one hand and the electronic properties of the system recently probed using photoemission yield spectroscopy on the other hand. These new results basically confirm the direct relations we had previously shown between the growth mode as monitored with electron diffraction LEED, RHEED, TED and Auger spectroscopy, and the electronic structures as investigated by low energy electron spectroscopy, but permit a deeper insight into the adsorption process at low coverage. At room temperature on the 2 × 1 cleavage structure where the silver-silicon interaction is weak, the adsorbed phase is completed at about 6/7 of a monolayer (θ ≃ 6/7) and a local arrangement of vacancies in the adlayer yields the 7 superstructure, while little effect on the silicon dangling bonds is noticed, but when silver two-dimensional islands (θ > 6/7) growing in a quasi layer fashion have covered the substrate surface. At higher temperatures three-dimensional growth of crystallites occurs after completion of the 3 phase whose saturation coverage increases with condensation temperatures, maxima ranging from θ ˜ 0.7 to θ ˜ 1.0 ( T ˜ 500°C) for different cleaves. This Si(111) 3-Ag surface exhibits again the same dangling bond peak as a clean 2 × 1 Si surface, despite the fact that the interaction between Ag and Si is now rather strong, as is confirmed by desorption experiments ( T ˜ 600°C). We thus critically discuss the geometrical models of this 3 phase previously devised and tentatively propose a new one which accounts better for these recent results, along with models of the 3 × 1 and 6 × 1 structures observed in the course of the desorption process.

N2 and CO Desorption Energies from Water Ice

NASA Astrophysics Data System (ADS)

Fayolle, Edith C.; Balfe, Jodi; Loomis, Ryan; Bergner, Jennifer; Graninger, Dawn; Rajappan, Mahesh; Öberg, Karin I.

2016-01-01

The relative desorption energies of CO and N2 are key to interpretations of observed interstellar CO and N2 abundance patterns, including the well-documented CO and N2H+ anti-correlations in disks, protostars, and molecular cloud cores. Based on laboratory experiments on pure CO and N2 ice desorption, the difference between CO and N2 desorption energies is small; the N2-to-CO desorption energy ratio is 0.93 ± 0.03. Interstellar ices are not pure, however, and in this study we explore the effect of water ice on the desorption energy ratio of the two molecules. We present temperature programmed desorption experiments of different coverages of 13CO and 15N2 on porous and compact amorphous water ices and, for reference, of pure ices. In all experiments, 15N2 desorption begins a few degrees before the onset of 13CO desorption. The 15N2 and 13CO energy barriers are 770 and 866 K for the pure ices, 1034-1143 K and 1155-1298 K for different submonolayer coverages on compact water ice, and 1435 and 1575 K for ˜1 ML of ice on top of porous water ice. For all equivalent experiments, the N2-to-CO desorption energy ratio is consistently 0.9. Whenever CO and N2 ice reside in similar ice environments (e.g., experience a similar degree of interaction with water ice) their desorption temperatures should thus be within a few degrees of one another. A smaller N2-to-CO desorption energy ratio may be present in interstellar and circumstellar environments if the average CO ice molecules interacts more with water ice compared to the average N2 molecules.

Modifying surface properties of KIT-6 zeolite with Ni and V for enhancing catalytic CO methanation

NASA Astrophysics Data System (ADS)

Cao, Hong-Xia; Zhang, Jun; Guo, Cheng-Long; Chen, Jingguang G.; Ren, Xiang-Kun

2017-12-01

The surface of the KIT-6 zeolite was modified with different amounts of Ni and V to promote the catalytic properties for CO methanation. A series of xNi-yV/KIT-6 with various Ni and V contents were prepared by the incipient-wetness impregnation method. The modified surfaces were characterized using N2 adsorption-desorption, Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), hydrogen temperature-programmed reduction (H2-TPR), Fourier transformed infrared spectroscopy (FT-IR), Raman, X-ray photoelectron spectroscopy (XPS), transmission electron microscope (TEM), and energy-dispersive X-ray spectroscopy (EDX), respectively. The characterization results illustrated that the modification of V species was able to significantly promote low-temperature catalytic performance below 350 °C compared to that of unmodified Ni/KIT-6, which was likely due to an increase in the H2 uptake accompanied by enhanced CO dissociation derived from stronger electron transfer from V species to Ni0. Correspondingly, the xNi-yV/KIT-6 catalysts exhibited a distinct enhancement in CO conversion, CH4 selectivity and CH4 yield over unmodified Ni/KIT-6. Among all catalysts, 20Ni-2V/KIT-6 showed the best catalytic performance, corresponding to nearly 100% CO conversion and 85% CH4 yield at a low temperature of 300 °C. Furthermore, 20Ni-2V/KIT-6 presented enhanced coking-resistant and anti-sintering properties during a 60h-lifetime test at 500 °C and 1 atm with a high weight hourly space velocity (WHSV) of 60000 ml/g/h.

Infrared Spectra and Binding Energies of Chemical Warfare Nerve Agent Simulants on the Surface of Amorphous Silica

DTIC Science & Technology

2013-06-24

Limited TPD of Water from Zeolite Linde 4A. Thermochim. Acta 1998, 319 (1), 177−184. (43) Palermo, A.; Löffler, D. G. Kinetics of Water Desorption...from Pelletized 4A and 5A Zeolites . Thermochim. Acta 1990, 159, 171−176. (44) Gorte, R. J. Design Parameters for Temperature Programmed Desorption from

Femtogram-scale photothermal spectroscopy of explosive molecules on nanostrings.

PubMed

Biswas, T S; Miriyala, N; Doolin, C; Liu, X; Thundat, T; Davis, J P

2014-11-18

We demonstrate detection of femtogram-scale quantities of the explosive molecule 1,3,5-trinitroperhydro-1,3,5-triazine (RDX) via combined nanomechanical photothermal spectroscopy and mass desorption. Photothermal spectroscopy provides a spectroscopic fingerprint of the molecule, which is unavailable using mass adsorption/desorption alone. Our measurement, based on thermomechanical measurement of silicon nitride nanostrings, represents the highest mass resolution ever demonstrated via nanomechanical photothermal spectroscopy. This detection scheme is quick, label-free, and is compatible with parallelized molecular analysis of multicomponent targets.

The Influence of Microstructure on Deuterium Retention in Polycrystalline Tungsten

DOE PAGES

Garrison, Lauren M.; Meyer, Fred W.; Bannister, Mark E.

2017-09-18

The retention of hydrogen isotopes in the plasma-facing materials of a fusion reactor is dependent on the density of trapping sites in the material. One factor that can influence the trapping defects is the surface state of the material before exposure. Mechanically polished, electropolished, and recrystallized tungsten samples were compared by exposing them to 350 eV D + beams with peak fluences of ~1 × 10 24 D +/m 2 at 500 and 740 K at the Multicharged Ion Research Facility (MIRF). At the exposure temperature of 740 K, no significant retention was detected. For material exposed at 500 K,more » significant differences in retention were observed, and the order of increasing retention was recrystallized, electropolished, and mechanically polished. Lastly, the other variable besides surface treatment was the time delay between ion exposure and thermal desorption spectroscopy which also may have impacted the retention measurements if there was out-gassing of the D while samples were in storage before thermal desorption spectroscopy (TDS).« less

The Influence of Microstructure on Deuterium Retention in Polycrystalline Tungsten

DOE Office of Scientific and Technical Information (OSTI.GOV)

Garrison, Lauren M.; Meyer, Fred W.; Bannister, Mark E.

The retention of hydrogen isotopes in the plasma-facing materials of a fusion reactor is dependent on the density of trapping sites in the material. One factor that can influence the trapping defects is the surface state of the material before exposure. Mechanically polished, electropolished, and recrystallized tungsten samples were compared by exposing them to 350 eV D + beams with peak fluences of ~1 × 10 24 D +/m 2 at 500 and 740 K at the Multicharged Ion Research Facility (MIRF). At the exposure temperature of 740 K, no significant retention was detected. For material exposed at 500 K,more » significant differences in retention were observed, and the order of increasing retention was recrystallized, electropolished, and mechanically polished. Lastly, the other variable besides surface treatment was the time delay between ion exposure and thermal desorption spectroscopy which also may have impacted the retention measurements if there was out-gassing of the D while samples were in storage before thermal desorption spectroscopy (TDS).« less

An X-ray photoelectron spectroscopy study of BF3 adsorption on positively and negatively poled LiNbO3 (0001)

NASA Astrophysics Data System (ADS)

Herdiech, M. W.; Mönig, H.; Altman, E. I.

2014-08-01

Adsorption of the strong Lewis acid BF3 was investigated to probe the sensitivity of the Lewis basicity of surface oxygens on LiNbO3 (0001) to the ferroelectric polarization direction. Adsorption and desorption were characterized by using X-ray photoelectron spectroscopy (XPS) to monitor the intensity and binding energy of the F 1s core level as a function of BF3 exposure and temperature. The results indicate that both BF3 uptake and desorption are very similar on the positively and negatively poled surfaces. In particular, BF3 only weakly adsorbs with the majority of the adsorbed BF3 desorbing below 200 K. Despite the similarities in the uptake and desorption behavior, the binding energy of the F 1s peak relative to the substrate Nb 3d5/2 peak was sensitive to the polarization direction, with the F 1s peak occurring at a binding energy up to 0.3 eV lower on positively poled than negatively poled LiNbO3 for equivalent BF3 exposures. Rather than reflecting a difference in bonding to the surface, however, this shift could be associated with oppositely oriented dipoles at the positively and negatively poled surfaces creating opposite band offsets between the adsorbate and the substrate. A similar effect was observed with lead zirconate titanate thin films where the Pb 4f XPS peak position changes as a function of temperature as a result of the pyroelectric effect which changes the magnitude of the surface and interface dipoles.

Iron phthalocyanine on Cu(111): Coverage-dependent assembly and symmetry breaking, temperature-induced homocoupling, and modification of the adsorbate-surface interaction by annealing.

PubMed

Snezhkova, Olesia; Bischoff, Felix; He, Yuanqin; Wiengarten, Alissa; Chaudhary, Shilpi; Johansson, Niclas; Schulte, Karina; Knudsen, Jan; Barth, Johannes V; Seufert, Knud; Auwärter, Willi; Schnadt, Joachim

2016-03-07

We have examined the geometric and electronic structures of iron phthalocyanine assemblies on a Cu(111) surface at different sub- to mono-layer coverages and the changes induced by thermal annealing at temperatures between 250 and 320 °C by scanning tunneling microscopy, x-ray photoelectron spectroscopy, and x-ray absorption spectroscopy. The symmetry breaking observed in scanning tunneling microscopy images is found to be coverage dependent and to persist upon annealing. Further, we find that annealing to temperatures between 300 and 320 °C leads to both desorption of iron phthalocyanine molecules from the surface and their agglomeration. We see clear evidence of temperature-induced homocoupling reactions of the iron phthalocyanine molecules following dehydrogenation of their isoindole rings, similar to what has been observed for related tetrapyrroles on transition metal surfaces. Finally, spectroscopy indicates a modified substrate-adsorbate interaction upon annealing with a shortened bond distance. This finding could potentially explain a changed reactivity of Cu-supported iron phthalocyanine in comparison to that of the pristine compound.

Surface Characterization of Mesoporous CoOx/SBA-15 Catalyst upon 1,2-Dichloropropane Oxidation.

PubMed

Finocchio, Elisabetta; Gonzalez-Prior, Jonatan; Gutierrez-Ortiz, Jose Ignacio; Lopez-Fonseca, Ruben; Busca, Guido; de Rivas, Beatriz

2018-05-29

The active combustion catalyst that is based on 30 wt % cobalt oxide on mesoporous SBA-15 has been tested in 1,2-dichloropropane oxidation and is characterized by means of FT-IR (Fourier transform infrared spectroscopy) and ammonia-TPD (temperature-programmed desorption). In this work, we report the spectroscopic evidence for the role of surface acidity in chloroalkane conversion. Both Lewis acidity and weakly acidic silanol groups from SBA support are involved in the adsorption and initial conversion steps. Moreover, total oxidation reaction results in the formation of new Bronsted acidic sites, which are likely associated with the generation of HCl at high temperature and its adsorption at the catalyst surface. Highly dispersed Co oxide on the mesoporous support and Co-chloride or oxychloride particles, together with the presence of several families of acidic sites originated from the conditioning effect of reaction products may explain the good activity of this catalyst in the oxidation of Chlorinated Volatile Organic Compounds.

Enhanced capture of elemental mercury by bamboo-based sorbents.

PubMed

Tan, Zengqiang; Xiang, Jun; Su, Sheng; Zeng, Hancai; Zhou, Changsong; Sun, Lushi; Hu, Song; Qiu, Jianrong

2012-11-15

To develop cost-effective sorbent for gas-phase elemental mercury removal, the bamboo charcoal (BC) produced from renewable bamboo and KI modified BC (BC-I) were used for elemental mercury removal. The effect of NO, SO2 on gas-phase Hg0 adsorption by KI modified BC was evaluated on a fixed bed reactor using an online mercury analyzer. BET surface area analysis, temperature programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS) were used to determine the pore structure and surface chemistry of the sorbents. The results show that KI impregnation reduced the sorbents' BET surface area and total pore volume compared with that of the original BC. But the BC-I has excellent adsorption capacity for elemental mercury at a relatively higher temperature of 140 °C and 180 °C. The presence of NO or SO2 could inhibit Hg0 capture, but BC-I has strong anti-poisoning ability. The specific reaction mechanism has been further analyzed. Copyright © 2012 Elsevier B.V. All rights reserved.

Interaction of acetone with single wall carbon nanotubes at cryogenic temperatures: a combined temperature programmed desorption and theoretical study.

PubMed

Kazachkin, Dmitry; Nishimura, Yoshifumi; Irle, Stephan; Morokuma, Keiji; Vidic, Radisav D; Borguet, Eric

2008-08-05

The interaction of acetone with single wall carbon nanotubes (SWCNTs) at low temperatures was studied by a combination of temperature programmed desorption (TPD) and dispersion-augmented density-functional-based tight binding (DFTB-D) theoretical simulations. On the basis of the results of the TPD study and theoretical simulations, the desorption peaks of acetone can be assigned to the following adsorption sites: (i) sites with energy of approximately 75 kJ mol (-1) ( T des approximately 300 K)endohedral sites of small diameter nanotubes ( approximately 7.7 A); (ii) sites with energy 40-68 kJ mol (-1) ( T des approximately 240 K)acetone adsorption on accessible interstitial, groove sites, and endohedral sites of larger nanotubes ( approximately 14 A); (iii) sites with energy 25-42 kJ mol (-1) ( T des approximately 140 K)acetone adsorption on external walls of SWCNTs and multilayer adsorption. Oxidatively purified SWCNTs have limited access to endohedral sites due to the presence of oxygen functionalities. Oxygen functionalities can be removed by annealing to elevated temperature (900 K) opening access to endohedral sites of nanotubes. Nonpurified, as-received SWCNTs are characterized by limited access for acetone to endohedral sites even after annealing to elevated temperatures (900 K). Annealing of both purified and as-produced SWCNTs to high temperatures (1400 K) leads to reduction of access for acetone molecules to endohedral sites of small nanotubes, probably due to defect self-healing and cap formation at the ends of SWCNTs. No chemical interaction between acetone and SWCNTs was detected for low temperature adsorption experiments. Theoretical simulations of acetone adsorption on finite pristine SWCNTs of different diameters suggest a clear relationship of the adsorption energy with tube sidewall curvature. Adsorption of acetone is due to dispersion forces, with its C-O bond either parallel to the surface or O pointing away from it. No significant charge transfer or polarization was found. Carbon black was used to model amorphous carbonaceous impurities present in as-produced SWCNTs. Desorption of acetone from carbon black revealed two peaks at approximately 140 and approximately 180-230 K, similar to two acetone desorption peaks from SWCNTs. The characteristic feature of acetone desorption from SWCNTs was peak at approximately 300 K that was not observed for carbon black. Care should be taken when assigning TPD peaks for molecules desorbing from carbon nanotubes as amorphous carbon can interfere.

Multicharged Ion Promoted Desorption (MIPD) of Reaction Co-Products

DTIC Science & Technology

2015-02-13

measurements of surface modifications using mass spectrometry, Raman spectroscopy and XPS were made to 1. REPORT DATE (DD-MM-YYYY) 4. TITLE AND...desorption and ex-situ measurements of surface modifications using mass spectrometry, Raman spectroscopy and XPS were made to determine ion-induced...irradiations were made with the samples at normal incidence to the incoming beams and post-analysis of these samples was achieved using Raman spectroscopy. It

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scherwitzl, Boris; Lassnig, Roman; Truger, Magdalena

The evaporation of quinacridone from a stainless steel Knudsen cell leads to the partial decomposition of this molecule in the cell, due to its comparably high sublimation temperature. At least one additional type of molecules, namely indigo, could be detected in the effusion flux. Thermal desorption spectroscopy and atomic force microscopy have been used to study the co-deposition of these molecules on sputter-cleaned and carbon-covered silicon dioxide surfaces. Desorption of indigo appears at temperatures of about 400 K, while quinacridone desorbs at around 510 K. For quinacridone, a desorption energy of 2.1 eV and a frequency factor for desorption ofmore » 1 × 10{sup 19} s{sup −1} were calculated, which in this magnitude is typical for large organic molecules. A fraction of the adsorbed quinacridone molecules (∼5%) decomposes during heating, nearly independent of the adsorbed amount, resulting in a surface composed of small carbon islands. The sticking coefficients of indigo and quinacridone were found to be close to unity on a carbon covered SiO{sub 2} surface but significantly smaller on a sputter-cleaned substrate. The reason for the latter can be attributed to insufficient energy dissipation for unfavorably oriented impinging molecules. However, due to adsorption via a hot-precursor state, the sticking probability is increased on the surface covered with carbon islands, which act as accommodation centers.« less

Impedance spectroscopy of reduced monoclinic zirconia.

PubMed

Eder, Dominik; Kramer, Reinhard

2006-10-14

Zirconia doped with low-valent cations (e.g. Y3+ or Ca2+) exhibits an exceptionally high ionic conductivity, making them ideal candidates for various electrochemical applications including solid oxide fuel cells (SOFC) and oxygen sensors. It is nevertheless important to study the undoped, monoclinic ZrO2 as a model system to construct a comprehensive picture of the electrical behaviour. In pure zirconia a residual number of anion vacancies remains because of contaminants in the material as well as the thermodynamic disorder equilibrium, but electronic conduction may also contribute to the observed conductivity. Reduction of zirconia in hydrogen leads to the adsorption of hydrogen and to the formation of oxygen vacancies, with their concentration affected by various parameters (e.g. reduction temperature and time, surface area, and water vapour pressure). However, there is still little known about the reactivities of defect species and their effect on the ionic and electronic conduction. Thus, we applied electrochemical impedance spectroscopy to investigate the electric performance of pure monoclinic zirconia with different surface areas in both oxidizing and reducing atmospheres. A novel equivalent circuit model including parallel ionic and electronic conduction has previously been developed for titania and is used herein to decouple the conduction processes. The concentration of defects and their formation energies were measured using volumetric oxygen titration and temperature programmed oxidation/desorption.

Design of Zeolitic Imidazolate Framework Derived Nitrogen-Doped Nanoporous Carbons Containing Metal Species for Carbon Dioxide Fixation Reactions.

PubMed

Toyao, Takashi; Fujiwaki, Mika; Miyahara, Kenta; Kim, Tae-Ho; Horiuchi, Yu; Matsuoka, Masaya

2015-11-01

Various N-doped nanoporous carbons containing metal species were prepared by direct thermal conversion of zeolitic imidazolate frameworks (ZIFs; ZIF-7, -8, -9, and -67) at different temperatures (600, 800, and 1000 °C). These materials were utilized as bifunctional acid-base catalysts to promote the reaction of CO2 with epoxides to form cyclic carbonates under 0.6 MPa of CO2 at 80 °C. The catalyst generated by thermal conversion of ZIF-9 at 600 °C (C600-ZIF-9) was found to exhibit a higher catalytic activity than the other ZIFs, other conventional catalysts, and other metal-organic framework catalysts. The results of various characterization techniques including elemental analysis, X-ray diffraction, X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and transmission electron microscopy show that C600-ZIF-9 contains partly oxidized Co nanoparticles and N species. Temperature-programmed desorption measurements by using CO2 and NH3 as probe molecules revealed that C600-ZIF-9 has both Lewis acid and Lewis base catalytic sites. Finally, the substrate scope was extended to seven other kinds of epoxides. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reaction of methyl formate with VC(1 0 0) and TiC(1 0 0) surfaces

NASA Astrophysics Data System (ADS)

Frantz, Peter; Kim, Hyun I.; Didziulis, Stephen V.; Li, Shuang; Chen, Zhiying; Perry, Scott S.

2005-12-01

The chemistry of the (1 0 0) surface of the tribologically important materials vanadium carbide (VC) and titanium carbide (TiC) with methyl formate (CH 3OCHO) has been studied with X-ray photoelectron spectroscopy (XPS), high resolution electron energy loss spectroscopy (HREELS), and temperature programmed desorption (TPD). The molecule reacts with each surface at temperatures below 150 K, although the extent of reaction is greater on the TiC surface. XPS and HREELS results indicate that the first step in this chemistry is the cleavage of the CH 3O-CHO bond, generating surface methoxy groups (CH 3O-) and either carbon monoxide on VC or a formyl (CHO) group on TiC. The methoxy group reacts further on both surfaces via pathways expected based on previous methanol adsorption studies, primarily decomposing through a formyl intermediate on VC to generate formaldehyde and evolving methanol on TiC. The formyl group formed directly from methyl formate on TiC enables the production and evolution of formaldehyde, and also appears to break down further to the elements. These results indicate a propensity for these carbides to react with esters, leading potentially to the beneficial formation of friction lowering surface films or the deleterious degradation of ester-based lubricants.

Determination of residual solvents in pharmaceuticals by thermal desorption-GC/MS.

PubMed

Hashimoto, K; Urakami, K; Fujiwara, Y; Terada, S; Watanabe, C

2001-05-01

A novel method for the determination of residual solvents in pharmaceuticals by thermal desorption (TD)-GC/MS has been established. A programmed temperature pyrolyzer (double shot pyrolyzer) is applied for the TD. This method does not require any sample pretreatment and allows very small amounts of the sample. Directly desorbed solvents from intact pharmaceuticals (ca. 1 mg) in the desorption cup (5 mm x 3.8 mm i.d.) were cryofocused at the head of a capillary column prior to a GC/MS analysis. The desorption temperature was set at a point about 20 degrees C higher than the melting point of each sample individually, and held for 3 min. The analytical results using 7 different pharmaceuticals were in agreement with those obtained by direct injection (DI) of the solution, followed by USP XXIII. This proposed TD-GC/MS method was demonstrated to be very useful for the identification and quantification of residual solvents. Furthermore, this method was simple, allowed rapid analysis and gave good repeatability.

Laser heating of scanning probe tips for thermal near-field spectroscopy and imaging

NASA Astrophysics Data System (ADS)

O'Callahan, Brian T.; Raschke, Markus B.

2017-02-01

Spectroscopy and microscopy of the thermal near-field yield valuable insight into the mechanisms of resonant near-field heat transfer and Casimir and Casimir-Polder forces, as well as providing nanoscale spatial resolution for infrared vibrational spectroscopy. A heated scanning probe tip brought close to a sample surface can excite and probe the thermal near-field. Typically, tip temperature control is provided by resistive heating of the tip cantilever. However, this requires specialized tips with limited temperature range and temporal response. By focusing laser radiation onto AFM cantilevers, we achieve heating up to ˜1800 K, with millisecond thermal response time. We demonstrate application to thermal infrared near-field spectroscopy (TINS) by acquiring near-field spectra of the vibrational resonances of silicon carbide, hexagonal boron nitride, and polytetrafluoroethylene. We discuss the thermal response as a function of the incident excitation laser power and model the dominant cooling contributions. Our results provide a basis for laser heating as a viable approach for TINS, nanoscale thermal transport measurements, and thermal desorption nano-spectroscopy.

Solid-phase microextraction with temperature-programmed desorption for the analysis of iodination disinfection byproducts.

PubMed

Frazey, P A; Barkley, R M; Sievers, R E

1998-02-01

An analytical approach for the determination of chlorination and iodination disinfection byproducts based on solid-phase microextraction (SPME) was developed. Solid-phase microextraction presents a simple, rapid, sensitive, and solvent-free approach to sample preparation in which analytes in either air or water matrixes are extracted into the polymeric coating of an optical fiber. Analytes are subsequently thermally desorbed in the injection port of a gas chromatograph for separation, detection, and quantitation. Thermal degradation of iodoform was observed during desorption from a polyacrylate fiber in initial GC/MS and GC/ECD experiments. Experiments were designed to determine SPME conditions that would allow quantification without significant degradation of analytes. Isothermal and temperature-programmed thermal desorptions were evaluated for efficacy in transferring analytes with wide-ranging volatilities and thermal stabilities into chromatographic analysis columns. A temperature-programmed desorption (TPD) (120-200 degrees C at 5 degrees C/min with an on-column injection port or 150-200 degrees C at 25 degrees C/min with a split/splitless injection port) was able to efficiently remove analytes with wide-ranging volatilities without causing thermal degradation. The SPME-TPD method was linear over 2-3 orders of magnitude with an electron capture detector and detection limits were in the submicrogram per liter range. Precision and detection limits for selected trihalomethanes were comparable to those of EPA method 551. Extraction efficiencies were not affected by the presence of 10 mg/L soap, 15 mg/L sodium iodide, and 6000 mg/L sodium thiosulfate. The SPME-TPD technique was applied to the determination of iodination disinfection byproducts from individual precursor compounds using GC/MS and to the quantitation of iodoform at trace levels in a water recycle system using GC/ECD.

Electron-Scavenging Chemistry of Benzoquinone on TiO2(110)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Henderson, Michael A.; Shen, Mingmin

The chemistry of benzoquinone (BQ) on TiO2(110) was examined using temperature programmed desorption (TPD), electron energy loss spectroscopy (EELS) and Auger electron spectroscopy (AES). BQ adsorbs mostly molecularly on the clean surface, although EELS demonstrates that electrons from surface Ti3+ sites at oxygen vacancy sites (VO) are readily oxidized by the high electron scavenging ability of the molecule. In contrast, when the surface is covered with water, subsequently adsorbed BQ molecules that scavenge surface electrons also abstract H from surface OHbr groups to form hydroquinone (HQ), which desorbs at ~450 K. This work was supported by the US Department ofmore » Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. The research was performed using the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory.« less

CO adsorption on W(100) during temperature-programmed desorption: A combined density functional theory and kinetic Monte Carlo study

NASA Astrophysics Data System (ADS)

Albao, Marvin A.; Padama, Allan Abraham B.

2017-02-01

Using a combined density functional theory (DFT) and kinetic Monte Carlo (KMC) simulations, we study the adsorption at 800 K and subsequent desorption of CO on W(100) at higher temperatures. The resulting TPD profiles are known experimentally to exhibit three desorption peaks β1, β2, and β3 at 930 K, 1070 K, and 1375 K, respectively. Unlike more recent theoretical studies that propose that all three aforementioned peaks are molecularly rather than associatively desorbed, our KMC analyses are in support of the latter, since at 800 K dissociation is facile and that CO exists as dissociation fragments C and O. We show that these peaks arise from desorption from the same adsorption site but whose binding energy varies depending on local environment, that is, the presence of CO as well as dissociation fragments C and O nearby. Furthermore we show that several key parameters, such as desorption, dissociation and recombination barriers all play a key role in the TPD spectra-these parameter effectively controls not only the location of the TPD peaks but the shape and width of the desorption peaks as well. Moreover, our KMC simulations reveal that varying the heating rate shifts the peaks but leaves their shape intact.

Effect of the Mn oxidation state and lattice oxygen in Mn-based TiO2 catalysts on the low-temperature selective catalytic reduction of NO by NH3.

PubMed

Lee, Sang Moon; Park, Kwang Hee; Kim, Sung Su; Kwon, Dong Wook; Hong, Sung Chang

2012-09-01

TiO2-supported manganese oxide catalysts formed using different calcination temperatures were prepared by using the wet-impregnation method and were investigated for their activity in the low-temperature selective catalytic reduction (SCR) of NO by NH3 with respect to the Mn valence and lattice oxygen behavior. The surface and bulk properties of these catalysts were examined using Brunauer-Emmett-Teller (BET) surface area, X-ray diffraction (XRD), temperature-programmed reduction (TPR), and temperature-programmed desorption (TPD). Catalysts prepared using lower calcination temperatures, which contained Mn4+ displayed high SCR activity at low temperatures and possessed several acid sites and active oxygen. The TPD analysis determined that the Brönsted and Lewis acid sites in the Mn/TiO2 catalysts were important for the low-temperature SCR at 80-160 and 200-350 degrees C, respectively. In addition, the available lattice oxygen was important for attaining high NO to NO2 oxidation at low temperatures. Recently, various Mn catalysts have been evaluated as SCR catalysts. However, there have been no studies on the relationship of adsorption and desorption properties and behavior of lattice oxygen according to the valence state for manganese oxides (MnO(x)). Therefore, in this study, the catalysts were prepared by the wet-impregnation method at different calcination temperatures in order to show the difference of manganese oxidation state. These catalysts were then characterized using various physicochemical techniques, including BET, XRD, TPR, and TPD, to understand the structure, oxidation state, redox properties, and adsorption and desorption properties of the Mn/TiO2 catalysts.

Relationship between Intensity of Fullerene-Mass Spectrum and Carbon Vibrational Temperature in Microwave-Helium Plasmas

NASA Astrophysics Data System (ADS)

Ueda, Kengo; Kuwahara, Kiyoshi; Fujiyama, Hiroshi

1999-07-01

Soot containing fullerenes, such as C60 and C70, was synthesized with He plasmas generated in a quartz tube by microwave-glow discharge. A reticulated vitreous carbon (RVC) heated by the microwave He plasmas with an electric field of TE10 mode was used as the carbon source. Swan bands of C2 molecules were observed during the synthesis by optical emission spectroscopy (OES) in order to investigate the effect of the vibrational temperature of C2 molecules on the formation of the fullerenes. The soot deposited on the quartz tube was analyzed by laser desorption time-of-flight mass-spectroscopy (LD-TOF-MS). The intensities of the mass spectra of fullerenes were confirmed to be maximum for the conditions as follows: the absorbed microwave power Pab=200 W and the He gas pressure P=100 Torr, while the C2 vibrational temperature was approximately 7000 K.

Mobility of Supercooled liquid Toluene, Ethylbenzene, and Benzene near their Glass Transition Temperatures Investigated using Inert Gas Permeation

DOE Office of Scientific and Technical Information (OSTI.GOV)

May, Robert A.; Smith, R. Scott; Kay, Bruce D.

We investigate the mobility of supercooled liquid toluene, ethylbenzene, and benzene near their respective glass transition temperatures (Tg). The permeation rate of Ar, Kr, and Xe through the supercooled liquid created when initially amorphous overlayers heated above their glass transition temperature is used to determine the diffusivity. Amorphous benzene crystallizes at temperatures well below its Tg and as a result the inert gas underlayer remains trapped until the onset of benzene desorption. In contrast, for toluene and ethylbenzene the onset of inert gas permeation is observed at temperatues near Tg. The inert gas desorption peak temperature as a function ofmore » the heating rate and overlayer thickness is used to quantify the diffusivity of supercooled liquid toluene and ethylbenzene from 115 K to 135 K. In this temperature range, diffusivities are found to vary across five orders of magnitude (~10-14 to 10-9 cm2/s). These data are compared to viscosity measurements and used to determine the low temperature fractional Stokes-Einstein exponent. Efforts to determine the diffusivity of a mixture of benzene and ethylbenzene are detailed, and the effect of mixing these materials on benzene crystallization is explored using infrared spectroscopy.« less

Surface modification of a low cost bentonite for post-combustion CO2 capture

NASA Astrophysics Data System (ADS)

Chen, Chao; Park, Dong-Wha; Ahn, Wha-Seung

2013-10-01

A low cost bentonite was modified with PEI (polyethylenimine) through a physical impregnation method. Bentonite in its natural state and after amine modification were characterized by scanning electron microscopy-energy dispersive X-ray spectroscopy, X-ray diffraction, N2 adsorption-desorption isotherms, and investigated for CO2 capture using a thermogravimetric analysis unit connected to a flow panel. The effect of adsorption temperature, PEI loading and CO2 partial pressure on the CO2 capture performance of the PEI-modified bentonite was examined. A cyclic CO2 adsorption-desorption test was also carried out to assess the stability of PEI-modified bentonite as a CO2 adsorbent. Bentonite in its natural state showed negligible CO2 uptake. After amine modification, the CO2 uptake increased significantly due to CO2 capture by amine species introduced via chemisorption. The PEI-modified bentonites showed high CO2 capture selectivity over N2, and exhibited excellent stability in cyclic CO2 adsorption-desorption runs.

Infrared and reflectron time-of-flight mass spectroscopic study on the synthesis of glycolaldehyde in methanol (CH3OH) and methanol-carbon monoxide (CH3OH-CO) ices exposed to ionization radiation.

PubMed

Maity, Surajit; Kaiser, Ralf I; Jones, Brant M

2014-01-01

We present conclusive evidence on the formation of glycolaldehyde (HOCH2CHO) synthesized within astrophysically relevant ices of methanol (CH3OH) and methanol-carbon monoxide (CH3OH-CO) upon exposure to ionizing radiation at 5.5 K. The radiation induced chemical processes of the ices were monitored on line and in situ via infrared spectroscopy which was complimented by temperature programmed desorption studies post irradiation, utilizing highly sensitive reflectron time-of-flight mass spectrometry coupled with single photon fragment free photoionization (ReTOF-PI) at 10.49 eV. Specifically, glycolaldehyde was observed via the v14 band and further enhanced with the associated frequency shifts of the carbonyl stretching mode observed in irradiated isotopologue ice mixtures. Furthermore, experiments conducted with mixed isotopic ices of methanol-carbon monoxide (13CH3OH-CO, CH3(18)OH-CO, CD3OD-13CO and CH3OH-C18O) provide solid evidence of at least three competing reaction pathways involved in the formation of glycolaldehyde via non-equilibrium chemistry, which were identified as follows: (i) radical-radical recombination of HCO and CH2OH formed via decomposition of methanol--the "two methanol pathway"; (ii) via the reaction of one methanol unit (CH2OH from the decomposition of CH3OH) with one carbon monoxide unit (HCO from the hydrogenation of CO)--the "one methanol, one carbon monoxide pathway"; and (iii) formation via hydrogenation of carbon monoxide resulting in radicals of HCO and CH2OH--the "two carbon monoxide pathway". In addition, temperature programmed desorption studies revealed an increase in the amount of glycolaldehyde formed, suggesting further thermal chemistry of trapped radicals within the ice matrix. Sublimation of glycolaldehyde during the warm up was also monitored via ReTOF-PI and validated via the mutual agreement of the associated isotopic frequency shifts within the infrared band positions and the identical sublimation profiles obtained from the ReTOF spectra and infrared spectroscopy of the corresponding isotopes. In addition, an isomer of glycolaldehyde (ethene-1,2-diol) was tentatively assigned. Confirmation of the identified pathways based on infrared spectroscopy was also obtained from the observed ion signals corresponding to isotopomers of glycolaldehyde. These coupled techniques provide clear, concise evidence of the formation of a complex and astrobiologically important organic, glycolaldehyde, relevant to the icy mantles observed in the interstellar medium.

Methanol Oxidation Using Ozone on Titania-Supported Vanadium Catalyst

EPA Science Inventory

Ozone-enhanced catalytic oxidation of methanol has been conducted at mild temperatures of 100 to 250NC using V2O5/TiO2 catalyst prepared by the sol-gel method. The catalyst was characterized using XRD, surface area measurements, and temperature-programmed desorption of methanol. ...

Hydrogenation at low temperatures does not always lead to saturation: the case of HNCO

NASA Astrophysics Data System (ADS)

Noble, J. A.; Theule, P.; Congiu, E.; Dulieu, F.; Bonnin, M.; Bassas, A.; Duvernay, F.; Danger, G.; Chiavassa, T.

2015-04-01

Context. It is generally agreed that hydrogenation reactions dominate chemistry on grain surfaces in cold, dense molecular cores, saturating the molecules present in ice mantles. Aims: We present a study of the low temperature reactivity of solid phase isocyanic acid (HNCO) with hydrogen atoms, with the aim of elucidating its reaction network. Methods: Fourier transform infrared spectroscopy and mass spectrometry were employed to follow the evolution of pure HNCO ice during bombardment with H atoms. Both multilayer and monolayer regimes were investigated. Results: The hydrogenation of HNCO does not produce detectable amounts of formamide (NH2CHO) as the major product. Experiments using deuterium reveal that deuteration of solid HNCO occurs rapidly, probably via cyclic reaction paths regenerating HNCO. Chemical desorption during these reaction cycles leads to loss of HNCO from the surface. Conclusions: It is unlikely that significant quantities of NH2CHO form from HNCO. In dense regions, however, deuteration of HNCO will occur. HNCO and DNCO will be introduced into the gas phase, even at low temperatures, as a result of chemical desorption.

Radiolytic stability of gibbsite and boehmite with adsorbed water

NASA Astrophysics Data System (ADS)

Huestis, Patricia; Pearce, Carolyn I.; Zhang, X.; N'Diaye, Alpha T.; Rosso, Kevin M.; LaVerne, Jay A.

2018-04-01

Aluminum oxyhydroxide (boehmite, AlOOH) and aluminum hydroxide (gibbsite, Al(OH)3) powders with adsorbed water were irradiated with γ-rays and 5 MeV He ions (α-particles) in order to determine overall radiation stability and chemical modification to the surface. No variation in overall phase or crystallinity due to radiolysis was observed with X-ray diffraction (XRD) and Raman spectroscopy for doses up to 2 MGy with γ-rays and 175 MGy with α-particles. Temperature programed desorption (TPD) of the water from the surface to the gas phase indicated that the water was chemisorbed and strongly bound. Water adsorption sites are of similar energy for both gibbsite and boehmite. Observation of the water adsorbed on the surface of gibbsite and boehmite with diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) showed broad peaks at 3100-3600 cm-1 due to OH stretching that slowly decreased on heating to 500 °C, which corresponds well with the water vapor evolution observed with TPD. Both materials were found to be amorphous following heating to 500 °C. X-ray photoelectron spectroscopy (XPS) indicated surface reduction of Al(III) to Al metal on radiolysis with α-particles. Complete loss of chemisorbed water and the formation of bulk O atoms was observed following radiolysis with α-particles.

Radiolytic stability of gibbsite and boehmite with adsorbed water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huestis, Patricia; Pearce, Carolyn I.; Zhang, X.

Aluminum oxyhydroxide (boehmite, AlOOH) and aluminum hydroxide (gibbsite, Al(OH)3) powders with adsorbed water were irradiated with -rays and 5 MeV He ions (α-particles) in order to determine overall radiation stability and chemical modification to the surface. No variation in overall phase or crystallinity due to radiolysis was observed with X-ray diffraction (XRD) and Raman spectroscopy for doses up to 2 MGy with -rays and 175 MGy with α-particles. Temperature programed desorption (TPD) of the water from the surface to the gas phase indicated that the water was chemisorbed and strongly bound. Water adsorption sites are of similar energy for bothmore » gibbsite and boehmite. Observation of the water adsorbed on the surface of gibbsite and boehmite with diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) showed broad peaks at 3100-3600 cm-1 due to OH stretching that slowly decreased on heating to 500oC, which corresponds well with the water vapor evolution observed with TPD. Both materials were found to be amorphous following heating to 500oC. X-ray photoelectron spectroscopy (XPS) indicated surface reduction of Al(III) to Al metal on radiolysis with α-particles. Complete loss of chemisorbed water and the formation of bulk O atoms was observed following radiolysis with α-particles.« less

Insights into Acetone Photochemistry on Rutile TiO2(110). 1. Off-Normal CH3 Ejection from Acetone Diolate.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petrik, Nikolay G.; Henderson, Michael A.; Kimmel, Gregory A.

2015-06-04

Thermal- and photon-stimulated reactions of acetone co-adsorbed with oxygen on rutile TiO2(110) surface are studied with infrared reflection-adsorption spectroscopy (IRAS) combined with temperature programmed desorption and angle-resolved photon stimulated desorption. IRAS results show that n2-acetone diolate ((CH3)2COO) is produced via thermally-activated reactions between the chemisorbed oxygen with co-adsorbed acetone. Formation of acetone diolate is also consistent with 18O / 16O isotopic exchange experiments. During UV irradiation at 30 K, CH3 radicals are ejected from the acetone diolate with a distribution that is peaked at .-. +- 66 degrees from the surface normal along the azimuth (i.e. perpendicular to the rowsmore » of bridging oxygen and Ti5c ions). This distribution is also consistent with the orientation of the C–CH3 bonds in the n2-acetone diolate on TiO2(110). The acetone diolate peaks disappear from the IRAS spectra after UV irradiation and new peaks are observed and associated with n2-acetate. The data presented here demonstrate direct signatures of the proposed earlier 2-step mechanism for acetone photooxidation on TiO2(110)« less

Adsorption and desorption of SO2, NO and chlorobenzene on activated carbon.

PubMed

Li, Yuran; Guo, Yangyang; Zhu, Tingyu; Ding, Song

2016-05-01

Activated carbon (AC) is very effective for multi-pollutant removal; however, the complicated components in flue gas can influence each other's adsorption. A series of adsorption experiments for multicomponents, including SO2, NO, chlorobenzene and H2O, on AC were performed in a fixed-bed reactor. For single-component adsorption, the adsorption amount for chlorobenzene was larger than for SO2 and NO on the AC. In the multi-component atmosphere, the adsorption amount decreased by 27.6% for chlorobenzene and decreased by 95.6% for NO, whereas it increased by a factor of two for SO2, demonstrating that a complex atmosphere is unfavorable for chlorobenzene adsorption and inhibits NO adsorption. In contrast, it is very beneficial for SO2 adsorption. The temperature-programmed desorption (TPD) results indicated that the binding strength between the gas adsorbates and the AC follows the order of SO2>chlorobenzene > NO. The adsorption amount is independent of the binding strength. The presence of H2O enhanced the component effects, while it weakened the binding force between the gas adsorbates and the AC. AC oxygen functional groups were analyzed using TPD and X-ray photoelectron spectroscopy (XPS) measurements. The results reveal the reason why the chlorobenzene adsorption is less affected by the presence of other components. Lactone groups partly transform into carbonyl and quinone groups after chlorobenzene desorption. The chlorobenzene adsorption increases the number of C=O groups, which explains the positive effect of chlorobenzene on SO2 adsorption and the strong NO adsorption. Copyright © 2015. Published by Elsevier B.V.

Surface Characterization.

ERIC Educational Resources Information Center

Fulghum, J. E.; And Others

1989-01-01

This review is divided into the following analytical methods: ion spectroscopy, electron spectroscopy, scanning tunneling microscopy, atomic force microscopy, optical spectroscopy, desorption techniques, and X-ray techniques. (MVL)

Catalytic dehydration of fructose to 5-hydroxymethylfurfural over Nb2O5 catalyst in organic solvent.

PubMed

Wang, Fenfen; Wu, Hai-Zhen; Liu, Chun-Ling; Yang, Rong-Zhen; Dong, Wen-Sheng

2013-03-07

The catalytic dehydration of fructose to 5-hydroxymethylfurfural (HMF) in DMSO was performed over Nb2O5 derived from calcination of niobic acid at various temperatures (300-700 °C). The catalysts were characterized by powder X-ray diffraction, N2 physical adsorption, temperature-programed desorption of NH3, n-butylamine titration using Hammett indicators, infrared spectroscopy of adsorbed pyridine, and X-ray photoelectron spectroscopy. It was found that both catalytic activity and surface acid sites decrease with increasing calcination temperatures. The Nb2O5 derived from calcination of niobic acid at 400 °C reveals the maximum yield of HMF among all the catalysts, although the amount of acid sites on the catalyst is lower than that on the sample calcined at 300 °C. The results suggest that the presence of larger amounts of strong acid sites on the surface of the Nb2O5 calcined at 300 °C may promote side reactions. The Nb2O5 prepared at 400 °C shows 100% fructose conversion with 86.2% HMF yield in DMSO at 120 °C after 2 h. The activity of the catalyst decreases gradually during recycle because of coke deposition; however, it can be fully recovered by calcination at 400 °C for 2 h, suggesting that this catalyst is of significance for practical applications. Copyright © 2012 Elsevier Ltd. All rights reserved.

Theoretical and experimental studies of hydrogen adsorption and desorption on Ir surfaces

DOE PAGES

Kaghazchi, Payam; Jacob, Timo; Chen, Wenhua; ...

2013-06-03

Here, we report adsorption and desorption of hydrogen on planar Ir(210) and faceted Ir(210), consisting of nanoscale {311} and (110) facets, by means of temperature programmed desorption (TPD) and density functional theory (DFT) in combination with the ab initio atomistic thermodynamics approach. TPD spectra show that only one H 2 peak is seen from planar Ir(210) at all coverages whereas a single H 2 peak is observed at around 440 K (F1) at fractional monolayer (ML) coverage and an additional H 2 peak appears at around 360 K (F2) at 1 ML coverage on faceted Ir(210), implying structure sensitivity inmore » recombination and desorption of hydrogen on faceted Ir(210) versus planar Ir(210), but no evidence is found for size effects in recombination and desorption of hydrogen on faceted Ir(210) for average facet sizes of 5-14 nm. Calculations indicate that H prefers to bind at the two-fold short-bridge sites of the Ir surfaces. In addition, we studied the stability of the Ir surfaces in the presence of hydrogen at different H coverages through surface free energy plots as a function of the chemical potential, which is also converted to a temperature scale. Moreover, the calculations revealed the origin of the two TPD peaks of H 2 from faceted Ir(210): F1 from desorption of H 2 on {311} facets while F2 from desorption of H 2 on (110) facets.« less

Hierarchically porous LaFeO3 perovskite prepared from the pomelo peel bio-template for catalytic oxidation of NO

NASA Astrophysics Data System (ADS)

Zhao, Shaojun; Wang, Li; Wang, Ying; Li, Xing

2018-05-01

In this paper, pomelo peel was used as biological template to obtain hierarchically porous LaFeO3 perovskite for the catalytic oxidation of NO to NO2. In addition, X-ray diffraction (XRD), scanning electron microscopy (SEM), N2 adsorption-desorption analyses, X-ray photoelectron spectra (XPS), NO temperature-programmed desorption (NO-TPD), oxygen temperature-programmed desorption (O2-TPD) and hydrogen temperature-programmed reduction (H2-TPR) were used to investigate the micro-structure and the redox properties of the hierarchically porous LaFeO3 perovskite prepared from pomelo peel biological template and the LaFeO3 perovskite without the biological template. The results indicated that the hierarchically porous LaFeO3 perovskite successfully replicated the porous structure of pomelo peel with high specific surface area. Compared to the LaFeO3 perovskite prepared without the pomelo peel template, the hierarchically porous LaFeO3 perovskite showed better catalytic oxidization of NO to NO2 under the same conditions. The maximum NO conversions for LaFeO3 prepared with and without template were 90% at 305 °C and 76% at 313 °C, respectively. This is mainly attributed to the higher ratio of Fe4+/Fe3+, the hierarchically porous structure with more adsorbed oxygen species and higher surface area for the hierarchically porous LaFeO3 perovskite compared with the sample prepared without the pomelo peel template.

Isosteric heat of water adsorption and desorption in homoionic alkaline-earth montmorillonites

NASA Astrophysics Data System (ADS)

Belhocine, M.; Haouzi, A.; Bassou, G.; Phou, T.; Maurin, D.; Bantignies, J. L.; Henn, F.

2018-02-01

The aim of the present work is to study by means of thermodynamic measurements and Infrared spectroscopy, the effect of the interlayer cations on the adsorption-desorption of water in the case of a montmorillonite exchanged with alkaline-earth metals. For the first time, the net isosteric heat of water adsorption and desorption is determined from isotherms recorded at three temperatures. The net isosteric heat is a very useful parameter for getting more insights into the sorption mechanism since it provides information about the sorption energy evolution which can be complementary to that obtained from structural or gravimetric measurements. The homoionic montmorillonite samples are prepared from purification and cationic exchanged in aqueous solution of the raw material, i.e. the reference SWy-2 Wyoming material. XRD at the dry state and elemental chemical analysis confirm that the treatment does not deteriorate the clay structure and yield the expected homoionic composition. The sorption isotherms measured at various temperatures show that the nature of the interlayer, i.e. exchangeable, cation changes the adsorbed/desorbed amount of water molecules for a given water relative pressure. The total amount of water adsorbed at P/P∘ = 0.5 follows the cation sequence Ca ∼ Mg>Ba while the sorption isosteric heats follow a slightly different sequence, i.e. Ca > Mg>Ba. This discrepancy between the adsorption and desorption heat is due to the higher irreversibility of water sorption process in the Ca exchanged montmorillonite. Finally, analysis of the IR spectra recorded at room temperature and under a primary vacuum reveals that the amount of adsorbed water follows the same sequence as that of the isosteric heat of adsorption and shows the coexistence of liquid-like and solid-like water confined in the interlayer space.

DOE Office of Scientific and Technical Information (OSTI.GOV)

El-Atwani, Osman; Taylor, Chase N.; Frishkoff, James

Here, microstructural changes due to displacement damage and helium desorption are two phenomena that occur in tungsten plasma facing materials in fusion reactors. Nanocrystalline metals are being investigated as radiation tolerant materials that can mitigate these microstructural changes and better trap helium along their grain boundaries. Here, we investigate the performance of three tungsten grades (nanocrystalline, ultrafine and ITER grade tungsten), exposed to a high fluence of 4 keV helium at both RT and 773 K, during a thermal desorption spectroscopy (TDS) experiment. An investigation of the microstructure in pre-and post-TDS sample sets was performed. The amount of desorbed heliummore » was shown to be highest in the ITER grade tungsten and lowest in the nanocrystalline tungsten. Correlating the desorption spectra and the microstructure (grain boundaries decorated with nanopores and crack formation) and comparing with previous literature on coarse grained tungsten samples at similar irradiation and TDS conditions, revealed the importance of grain boundaries in trapping helium and limiting helium desorption up to a high temperature of 1350 K in agreement with transmission electron microscopy studies on helium irradiated tungsten which showed preferential and large facetted bubble formation along the grain boundaries in the nanocrystalline tungsten grade.« less

A kinetic Monte Carlo approach to diffusion-controlled thermal desorption spectroscopy

NASA Astrophysics Data System (ADS)

Schablitzki, T.; Rogal, J.; Drautz, R.

2017-06-01

Atomistic simulations of thermal desorption spectra for effusion from bulk materials to characterize binding or trapping sites are a challenging task as large system sizes as well as extended time scales are required. Here, we introduce an approach where we combine kinetic Monte Carlo with an analytic approximation of the superbasins within the framework of absorbing Markov chains. We apply our approach to the effusion of hydrogen from BCC iron, where the diffusion within bulk grains is coarse grained using absorbing Markov chains, which provide an exact solution of the dynamics within a superbasin. Our analytic approximation to the superbasin is transferable with respect to grain size and elliptical shapes and can be applied in simulations with constant temperature as well as constant heating rate. The resulting thermal desorption spectra are in close agreement with direct kinetic Monte Carlo simulations, but the calculations are computationally much more efficient. Our approach is thus applicable to much larger system sizes and provides a first step towards an atomistic understanding of the influence of structural features on the position and shape of peaks in thermal desorption spectra. This article is part of the themed issue 'The challenges of hydrogen and metals'.

Analysis of the volatile organic matter of engine piston deposits by direct sample introduction thermal desorption gas chromatography/mass spectrometry.

PubMed

Diaby, M; Kinani, S; Genty, C; Bouchonnet, S; Sablier, M; Le Negrate, A; El Fassi, M

2009-12-01

This article establishes an alternative method for the characterization of volatiles organic matter (VOM) contained in deposits of the piston first ring grooves of diesel engines using a ChromatoProbe direct sample introduction (DSI) device coupled to gas chromatography/mass spectrometry (GC/MS) analysis. The addition of an organic solvent during thermal desorption leads to an efficient extraction and a good chromatographic separation of extracted products. The method was optimized investigating the effects of several solvents, the volume added to the solid sample, and temperature programming of the ChromatoProbe DSI device. The best results for thermal desorption were found using toluene as an extraction solvent and heating the programmable temperature injector from room temperature to 300 degrees C with a temperature step of 105 degrees C. With the use of the optimized thermal desorption conditions, several components have been positively identified in the volatile fraction of the deposits: aromatics, antioxidants, and antioxidant degradation products. Moreover, this work highlighted the presence of diesel fuel in the VOM of the piston deposits and gave new facts on the absence of the role of diesel fuel in the deposit formation process. Most importantly, it opens the possibility of quickly performing the analysis of deposits with small amounts of samples while having a good separation of the volatiles.

Adsorption, Desorption, and Displacement Kinetics of H2O and CO2 on TiO2(110)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, R. Scott; Li, Zhenjun; Chen, Long

The adsorption, desorption, and displacement kinetics of H2O and CO2 on TiO2(110) are investigated using temperature programmed desorption (TPD) and molecular beam techniques. The TPD spectra for both H2O and CO2 have well-resolved peaks corresponding to desorption from bridge-bonded oxygen (BBO), Ti, and oxygen vacancies (VO) sites in order of increasing peak temperature. Analysis of the saturated monolayer peak for both species reveals that the corresponding adsorption energies on all sites are greater for H2O and for CO2. Sequential dosing of H2O and CO2 reveals that, independent of the dose order, H2O molecules will displace CO2 in order to occupymore » the highest energy binding sites available. Isothermal experiments show that the displacement of CO2 by H2O occurs between 75 and 80 K. Further analysis shows that a ratio of 4 H2O to 3 CO2 molecules is needed to displace CO2 from the TiO2(110) surface.« less

Preparation, IR spectroscopy, and time-of-flight mass spectrometry of halogenated and methylated Si(111)

NASA Astrophysics Data System (ADS)

Salingue, Nils; Hess, Peter

2011-09-01

The preparation of chlorine-, bromine-, and iodine-terminated silicon surfaces (Si(111):Cl, Br, and I) using atomically flat Si(111)-(1×1):H is described. The halogenated surfaces were obtained by photochemically induced radical substitution reactions with the corresponding dihalogen in a Schlenk tube by conventional inert gas chemistry. The nucleophilic substitution of the Si-Cl functionality with the Grignard reagent (CH3MgCl) resulted in the unreconstructed methylated Si(111)-(1×1):CH3 surface. The halogenated and methylated silicon surfaces were characterized by Fourier transform infrared (FTIR) spectroscopy and laser-induced desorption of monolayers (LIDOM). Calibration of the desorption temperature via analysis of time-of-flight (TOF) distributions as a function of laser fluence allowed the determination of the originally emitted neutral fragments by TOF mass spectrometry using electron-impact ionization. The halogens were desorbed atomically and as SiX n (X = Cl, Br) clusters. The methyl groups mainly desorbed as methyl and ethyl fragments and a small amount of +SiCH3.

Reactive Desorption of CO Hydrogenation Products under Cold Pre-stellar Core Conditions

NASA Astrophysics Data System (ADS)

Chuang, K.-J.; Fedoseev, G.; Qasim, D.; Ioppolo, S.; van Dishoeck, E. F.; Linnartz, H.

2018-02-01

The astronomical gas-phase detection of simple species and small organic molecules in cold pre-stellar cores, with abundances as high as ∼10‑8–10‑9 n H, contradicts the generally accepted idea that at 10 K, such species should be fully frozen out on grain surfaces. A physical or chemical mechanism that results in a net transfer from solid-state species into the gas phase offers a possible explanation. Reactive desorption, i.e., desorption following the exothermic formation of a species, is one of the options that has been proposed. In astronomical models, the fraction of molecules desorbed through this process is handled as a free parameter, as experimental studies quantifying the impact of exothermicity on desorption efficiencies are largely lacking. In this work, we present a detailed laboratory study with the goal of deriving an upper limit for the reactive desorption efficiency of species involved in the CO–H2CO–CH3OH solid-state hydrogenation reaction chain. The limit for the overall reactive desorption fraction is derived by precisely investigating the solid-state elemental carbon budget, using reflection absorption infrared spectroscopy and the calibrated solid-state band-strength values for CO, H2CO and CH3OH. We find that for temperatures in the range of 10 to 14 K, an upper limit of 0.24 ± 0.02 for the overall elemental carbon loss upon CO conversion into CH3OH. This corresponds with an effective reaction desorption fraction of ≤0.07 per hydrogenation step, or ≤0.02 per H-atom induced reaction, assuming that H-atom addition and abstraction reactions equally contribute to the overall reactive desorption fraction along the hydrogenation sequence. The astronomical relevance of this finding is discussed.

Change in desorption mechanism from pore blocking to cavitation with temperature for nitrogen in ordered silica with cagelike pores.

PubMed

Morishige, Kunimitsu; Tateishi, Masayoshi; Hirose, Fumi; Aramaki, Kenji

2006-10-24

To verify pore blocking controlled desorption in ink-bottle pores, we measured the temperature dependence of the adsorption-desorption isotherms of nitrogen on four kinds of KIT-5 samples with expanded cavities hydrothermally treated for different periods of time at 393 K. In the samples, almost spherical cavities are arranged in a face-centered cubic array and the cavities are connected through small channels. The pore size of the channels increased with an increase in the hydrothermal treatment time. At lower temperatures a steep desorption branch changed to a gradual one as the hydrothermal treatment was prolonged. For the sample hydrothermally treated only for 1 day, the rectangular hysteresis loop shrank gradually with increasing temperature while keeping its shape. The temperature dependence of the evaporation pressure observed was identical with that expected for cavitation-controlled desorption. On the other hand, for the samples hydrothermally treated for long times, the gradual desorption branch became a sharp one with increasing temperature. This strongly suggests that the desorption mechanism is altered from pore blocking to cavitation with temperature. Application of percolation theory to the pore blocking controlled desorption observed here is discussed.

PET-modified red mud as catalysts for oxidative desulfurization reactions.

PubMed

do Prado, Nayara T; Heitmann, Ana P; Mansur, Herman S; Mansur, Alexandra A; Oliveira, Luiz C A; de Castro, Cinthia S

2017-07-01

This work describes the synthesis of catalysts based on red mud/polyethylene terephthalate (PET) composites and their subsequent heat treatment under N 2 atmosphere. The materials were characterized by scanning electron microscopy (SEM), temperature programmed reduction (TPR), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric (TG) analysis and N 2 adsorption/desorption. The catalysts were evaluated in the oxidative desulfurization reaction of dibenzothiophene (DBT) in a biphasic system. The results indicated that the PET impregnation on red mud increased the affinity of the catalyst with the nonpolar phase (fuel), in which the contaminant was dissolved, allowing a higher conversion (up to 80%) and selectivity to the corresponding dibenzothiophene sulfone. The sulfone compound is more polar than DBT and diffused into the polar solvent as indicated by the data obtained via gas chromatography-mass spectrometry (GC-MS). Copyright © 2017. Published by Elsevier B.V.

Preparation and surface functionalization of MWCNTs: study of the composite materials produced by the interaction with an iron phthalocyanine complex

PubMed Central

2011-01-01

Carbon nanotubes [CNTs] were synthesized by the catalytic vapor decomposition method. Thereafter, they were functionalized in order to incorporate the oxygen groups (OCNT) and subsequently the amine groups (ACNT). All three CNTs (the as-synthesized and functionalized) underwent reaction with an iron organometallic complex (FePcS), iron(III) phthalocyanine-4,4",4",4""-tetrasulfonic acid, in order to study the nature of the interaction between this complex and the CNTs and the potential formation of nanocomposite materials. Transmission electronic microscopy, N2 adsorption at 77 K, thermogravimetric analysis, temperature-programmed desorption, and X-ray photoelectron spectroscopy were the characterization techniques employed to confirm the successful functionalization of CNTs as well as the type of interaction existing with the FePcS. All results obtained led to the same conclusion: There were no specific chemical interactions between CNTs and the fixed FePcS. PMID:21711881

Preparation and surface functionalization of MWCNTs: study of the composite materials produced by the interaction with an iron phthalocyanine complex

NASA Astrophysics Data System (ADS)

Asedegbega-Nieto, Esther; Pérez-Cadenas, María; Carter, Jonathan; Anderson, James A.; Guerrero-Ruiz, Antonio

2011-04-01

Carbon nanotubes [CNTs] were synthesized by the catalytic vapor decomposition method. Thereafter, they were functionalized in order to incorporate the oxygen groups (OCNT) and subsequently the amine groups (ACNT). All three CNTs (the as-synthesized and functionalized) underwent reaction with an iron organometallic complex (FePcS), iron(III) phthalocyanine-4,4",4",4""-tetrasulfonic acid, in order to study the nature of the interaction between this complex and the CNTs and the potential formation of nanocomposite materials. Transmission electronic microscopy, N2 adsorption at 77 K, thermogravimetric analysis, temperature-programmed desorption, and X-ray photoelectron spectroscopy were the characterization techniques employed to confirm the successful functionalization of CNTs as well as the type of interaction existing with the FePcS. All results obtained led to the same conclusion: There were no specific chemical interactions between CNTs and the fixed FePcS.

Photodecomposition of Mo(CO)/sub 6/ adsorbed on Si(100)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Creighton, J.R.

1986-01-15

The photochemical properties of Mo(CO)/sub 6/ adsorbed on Si(100) were investigated using temperature programmed desorption (TPD) and Auger spectroscopy. TPD experiments indicate that Mo(CO)/sub 6/ physisorbs on silicon and desorbs at 210--230 K. At 150 K, KrF laser radiation (248 nm) partially decomposes the adsorbed Mo(CO)/sub 6/ releasing gas-phase CO in the process and TPD experiments after irradiation show that additional CO desorbs at 335 K. However, Auger analysis indicates that one CO molecule per molybdenum atom dissociates, leaving the molybdenum overlayer heavily contaminated with carbon and oxygen. The cross section for photodecomposition was measured to be 5 +- 3more » x 10/sup -17/ cm/sup 2/. Decomposition of the excited molecule must compete strongly with energy relaxation to account for the magnitude of this cross section.« less

Key factor affecting the structural and textural properties of ZSM-5/MCM-41 composite

NASA Astrophysics Data System (ADS)

Boukoussa, Bouhadjar; Aouad, Nafissa; Hamacha, Rachida; Bengueddach, Abdelkader

2015-03-01

ZSM-5/MCM-41 micro/mesoporous composite materials were synthesized by the hydrothermal technique with alkali-treated ZSM-5 zeolite as source of silica and aluminum and characterized by various physico-chemical techniques such as X-ray diffraction (XRD), nitrogen sorption at 77 K, transmission electronic microscopy (TEM), FTIR spectroscopy and NH3 temperature programmed desorption (TPD) techniques. The effect of concentration of CTAB in the synthesis of these solids has been investigated, the mesopore volume, surface area and surface acidity decrease with increasing the concentration of CTAB. Increasing the CTAB concentration causes the recrystallization of zeolite ZSM-5 and it disadvantage the formation of mesoporous materials MCM-41. The catalytic activity of ZSM-5/MCM-41 materials has been evaluated in the Friedel-Crafts acylation of anisole with benzoyl chloride as alkylating agent. The results revealed the reaction to be influenced by surface area, pore volume and surface acidity.

Hydroisomerization of n-dodecane over Pt/Al-MCM-48 catalysts.

PubMed

Yun, Soyoung; Park, Young-Kwon; Jeong, Soon-Yong; Han, Jeongsik; Jeon, Jong-Ki

2014-04-01

The objective of this study is to evaluate the catalytic potential of Pt/Al-MCM-48 catalysts in hydroisomerization of n-dodecane. The effects of the Si/Al ratio and platinum loading on the acid characteristics of Al-MCM-48 and the catalytic performance in n-dodecane hydroisomerization were analyzed. The catalysts were characterized by X-ray diffraction, nitrogen adsorption, infrared spectroscopy of pyridine adsorption, and temperature programmed desorption of ammonia. The number of weak strength acid sites on Al-MCM-48 increased with 0.5 wt% platinum loading. The weak strength acid sites of Pt/Al-MCM-48 catalysts were ascribed to Lewis acid sites, which can be confirmed by NH3-TPD and FTIR spectra of pyridine adsorption. Iso-dodecane can be produced with high selectivity in n-dodecane hydrosisomerization over Pt/Al-MCM-48 catalysts. This is attributed to the mild acidic properties of Pt/Al-MCM-48 catalysts.

Desorption of oxygen from YBa2Cu3O6+x films studied by Raman spectroscopy

NASA Astrophysics Data System (ADS)

Bock, A.; Kürsten, R.; Brühl, M.; Dieckmann, N.; Merkt, U.

1996-08-01

Phonons of laser-deposited YBa2Cu3O6+x films on MgO(100) substrates are investigated in a Raman setup as a function of laser power density. Investigations of YBa2Cu3O7 films allow us to study oxygen out-diffusion, where the onset of out-diffusion is indicated by the appearance of disorder-induced modes in the Raman spectra. At a pressure of 5×10-6 mbar the temperature threshold of the out-diffusion is (490+/-15) K. With increasing oxygen pressure the observed temperature thresholds rise only moderately in contrast to the behavior expected from the pox-T phase diagram of YBa2Cu3O6+x. Even at 1 bar oxygen partial pressure out-diffusion is observed and tetragonal sites with x=0 develop. These observations can be explained by photon-stimulated desorption of oxygen. Investigations of YBa2Cu3O6 films allow us to study oxygen in-diffusion. In 1 bar oxygen we observe competing oxygen fluxes due to thermally activated diffusion and photon-stimulated desorption. From these measurements we determine an upper bound of the thermal activation energy of the oxygen in-diffusion into YBa2Cu3O6 films of (0.19+/-0.01) eV.

Manganese oxide nanoparticle-assisted laser desorption/ionization mass spectrometry for medical applications

NASA Astrophysics Data System (ADS)

Taira, Shu; Kitajima, Kenji; Katayanagi, Hikaru; Ichiishi, Eiichiro; Ichiyanagi, Yuko

2009-06-01

We prepared and characterized manganese oxide magnetic nanoparticles (d =5.6 nm) and developed nanoparticle-assited laser desorption/ionization (nano-PALDI) mass spectrometry. The nanoparticles had MnO2 and Mn2O3 cores conjugated with hydroxyl and amino groups, and showed paramagnetism at room temperature. The nanoparticles worked as an ionization assisting reagent in mass spectroscopy. The mass spectra showed no background in the low m/z. The nanoparticles could ionize samples of peptide, drug and proteins (approx. 5000 Da) without using matrix, i.e., 2,5-dihydroxybenzoic acid (DHB), 4-hydroxy-α-cinnamic acid (CHCA) and liquid matrix, as conventional ionization assisting reagents. Post source decay spectra by nano-PALDI mass spectrometry will yield information of the chemical structure of analytes.

Experimental study on desorption characteristics of SAPO-34 and ZSM-5 zeolite

NASA Astrophysics Data System (ADS)

Yuan, Z. X.; Zhang, X.; Wang, W. C.; Du, C. X.; Liu, Z. B.; Chen, Y. C.

2018-03-01

The dynamic characteristics of SAPO-34 and ZSM-5 zeolite in the desorption process have been experimentally studied with the gravimetric method. The weight change of the test sample was recorded continually for different conditions of temperature and pressure. The curve of the desorption degree with the temperature and the pressure was obtained and discussed. With the intrinsic different micro-structure, the two zeolites showed distinguished characteristics of the desorption. In contrast to an S-shaped desorption curve of the SAPO-34, the ZSM-5 showed an exponential desorption curve. In comparison, the desorption characteristics of the ZSM-5 were better than that of the SAPO-34 in the temperature range of 40 °C 90 °C. Nevertheless, the effect of the pressure on the desorption degree was stronger for the SAPO-34 than for the ZSM-5. Further analysis revealed that the desorption speed was affected more strongly by the temperature than by the pressure.

Water desorption from a confined biopolymer.

PubMed

Pradipkanti, L; Satapathy, Dillip K

2018-03-14

We study desorption of water from a confined biopolymer (chitosan thin films) by employing temperature dependent specular X-ray reflectivity and spectroscopic ellipsometry. The water desorption is found to occur via three distinct stages with significantly different desorption rates. The distinct rates of water desorption are attributed to the presence of different kinds of water with disparate mobilities inside the biopolymer film. We identify two characteristic temperatures (T c1 and T c2 ) at which the water desorption rate changes abruptly. Interestingly, the characteristic temperatures decrease with decreasing the film thickness. The thickness dependence of the characteristic temperature is interpreted in the context of a higher mobility of polymer chains at the free surface for polymers under one-dimensional confinement.

Synthesis of waste cooking oil based biodiesel via ferric-manganese promoted molybdenum oxide / zirconia nanoparticle solid acid catalyst: influence of ferric and manganese dopants.

PubMed

Alhassan, Fatah H; Rashid, Umer; Taufiq-Yap, Yun Hin

2015-01-01

The utilization of ferric-manganese promoted molybdenum oxide/zirconia (Fe-Mn- MoO3/ZrO2) (FMMZ) solid acid catalyst for production of biodiesel was demonstrated. FMMZ is produced through impregnation reaction followed by calcination at 600°C for 3 h. The characterization of FMMZ had been done using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis (TGA), temperature programmed desorption of NH3 (TPD-NH3), transmission electron microscopy(TEM) and Brunner-Emmett-Teller (BET) surface area measurement. The effect of waste cooking oil methyl esters (WCOME's) yield on the reactions variables such as reaction temperature, catalyst loading, molar ratio of methanol/oil and reusability were also assessed. The catalyst was used to convert the waste cooking oil into corresponding methyl esters (95.6%±0.15) within 5 h at 200℃ reaction temperature, 600 rpm stirring speed, 1:25 molar ratio of oil to alcohol and 4% w/w catalyst loading. The reported catalyst was successfully recycled in six connective experiments without loss in activity. Moreover, the fuel properties of WCOME's were also reported using ASTM D 6751 methods.

Chemistry of CCl 4 on Fe 3O 4(1 1 1)-(2 × 2) surfaces in the presence of adsorbed D 2O studied by temperature programmed desorption

NASA Astrophysics Data System (ADS)

Adib, K.; Totir, G. G.; Fitts, J. P.; Rim, K. T.; Mueller, T.; Flynn, G. W.; Joyce, S. A.; Osgood, R. M.

2003-07-01

Temperature programmed desorption (TPD) was used to study surface reactions of Fe 3O 4(1 1 1)-(2 × 2) sequentially exposed, at ˜100 K, to vapor-phase D 2O and CCl 4. Previous TPD and XPS results have indicated that in the absence of D 2O, CCl 4 dissociatively adsorbs on Fe 3O 4(1 1 1) producing chemisorbed Cl and CCl 2. Subsequent heating of the surface results in abstraction of lattice iron and oxygen atoms and causes them to desorb as FeCl 2 and OCCl 2, respectively. This study shows that when this Fe 3O 4 surface is exposed only to D 2O, TPD measures a rich surface chemistry with multiple desorption events extending as high as ˜800 K, indicating dissociative adsorption of D 2O on the Fe 3O 4(1 1 1) surface. After sequential exposure to D 2O and then CCl 4, the production of FeCl 2 and OCCl 2 from adsorbed CCl 4 is suppressed, indicating that D 2O fragments block the surface reactive sites.

Surface Response of Brominated Carbon Media on Laser and Thermal Excitation: Optical and Thermal Analysis Study.

PubMed

Multian, Volodymyr V; Kinzerskyi, Fillip E; Vakaliuk, Anna V; Grishchenko, Liudmyla M; Diyuk, Vitaliy E; Boldyrieva, Olga Yu; Kozhanov, Vadim O; Mischanchuk, Oleksandr V; Lisnyak, Vladyslav V; Gayvoronsky, Volodymyr Ya

2017-12-01

The present study is objected to develop an analytical remote optical diagnostics of the functionalized carbons surface. Carbon composites with up to 1 mmol g -1 of irreversibly adsorbed bromine were produced by the room temperature plasma treatment of an activated carbon fabric (ACF) derived from polyacrylonitrile textile. The brominated ACF (BrACF) was studied by elastic optical scattering indicatrix analysis at wavelength 532 nm. The obtained data were interpreted within results of the thermogravimetric analysis, X-ray photoelectron spectroscopy and temperature programmed desorption mass spectrometry. The bromination dramatically reduces the microporosity producing practically non-porous material, while the incorporated into the micropores bromine induces the dielectric and structural impact on surface polarizability and conductivity due to the charging effect. We have found that the elastic optical scattering in proper solid angles in the forward and the backward hemispheres is sensitive to the kind of the bromine bonding, e.g., physical adsorption or chemisorption, and the bromination level, respectively, that can be utilized for the express remote fabrication control of the nanoscale carbons with given interfaces.

Adsorption and electron-induced polymerization of methyl methacrylate on Ru(101xAF0)

NASA Astrophysics Data System (ADS)

Hedhili, M. N.; Yakshinskiy, B. V.; Wasielewski, R.; Ciszewski, A.; Madey, T. E.

2008-05-01

The adsorption and electron irradiation of methyl methacrylate (MMA) on a Ru(101¯0) surface have been studied using x-ray photoelectron spectroscopy (XPS), temperature programmed desorption (TPD), and low energy ion scattering. TPD analysis indicates that a monolayer of MMA chemisorbs and dissociates on the Ru(101¯0) surface. The reaction products observed upon heating include H2, CO, CO2, and a small amount of MMA. Physisorbed multilayers of MMA desorb at temperatures around 170K. Electron irradiation of physisorbed MMA at 140K leads to a modification of the MMA film: The XPS spectra show an increase in thermal stability of the film with retention of the MMA structure, and indicate that electron irradiation induces polymerization. An increase in the electron bombardment fluence induces a degradation of the formed polymerized species and leads to the accumulation of carbon on the Ru surface. These results are relevant to the accumulation of carbon on surfaces of Ru films that serve as capping layers on Mo /Si multilayer mirrors used in extreme ultraviolet lithography.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gouder, T.; Colmenares, C.

This report summarizes the experimental work carried out at the Lawrence Livermore National Laboratory on the electronic structure and reactivity of uranium thin films on Pd, Pt, Si, graphite, Cu, and Au substrates from 1990 to 1993. The U-Pd system was studied in the most detail because it was the first to be chosen right after the completion of the experimental equipment. We first studied and characterized clean U overlayers and the possible surface reactions between this metal and the substrates studied. We then subjected these systems to reactive conditions such as heating and adsorbing corrosive gases (O{sub 2}, CO,more » CO{sub 2}, and C{sub 2}H{sub 4}). Finally we investigated the diffusion of U metal and some of its compounds into the substrates. A new technique was developed, based on Auger Electron Spectroscopy, to follow in real time the diffusion of U overlayers into the substrate. The temperature of the sample is ramped linearly up to 900{degrees}C while following the Auger peak intensities of the two components for a given system. Diffusion rates are obtained by differentiating the measured intensity curves, then peaks result corresponding to diffusion processes with different activation energies. This technique bears a strong similarity to thermal desorption spectroscopy (TDS), where the sample is heated linearly and the rate of desorption is measured as a function of temperature and heating rate.« less

Spreading of lithium on a stainless steel surface at room temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Skinner, C. H.; Capece, A. M.; Roszell, J. P.

Lithium conditioned plasma facing surfaces have lowered recycling and enhanced plasma performance on many fusion devices and liquid lithium plasma facing components are under consideration for future machines. A key factor in the performance of liquid lithium components is the wetting by lithium of its container. We have observed the surface spreading of lithium from a mm-scale particle to adjacent stainless steel surfaces using a scanning Auger microprobe that has elemental discrimination. Here, the spreading of lithium occurred at room temperature (when lithium is a solid) from one location at a speed of 0.62 μm/day under ultrahigh vacuum conditions. Separatemore » experiments using temperature programmed desorption (TPD) investigated bonding energetics between monolayer-scale films of lithium and stainless steel. While multilayer lithium desorption from stainless steel begins to occur just above 500 K (E des = 1.54 eV), sub-monolayer Li desorption occurred in a TPD peak at 942 K (E des = 2.52 eV) indicating more energetically favorable lithium-stainless steel bonding (in the absence of an oxidation layer) than lithium lithium bonding.« less

Spreading of lithium on a stainless steel surface at room temperature

DOE PAGES

Skinner, C. H.; Capece, A. M.; Roszell, J. P.; ...

2015-11-10

Lithium conditioned plasma facing surfaces have lowered recycling and enhanced plasma performance on many fusion devices and liquid lithium plasma facing components are under consideration for future machines. A key factor in the performance of liquid lithium components is the wetting by lithium of its container. We have observed the surface spreading of lithium from a mm-scale particle to adjacent stainless steel surfaces using a scanning Auger microprobe that has elemental discrimination. Here, the spreading of lithium occurred at room temperature (when lithium is a solid) from one location at a speed of 0.62 μm/day under ultrahigh vacuum conditions. Separatemore » experiments using temperature programmed desorption (TPD) investigated bonding energetics between monolayer-scale films of lithium and stainless steel. While multilayer lithium desorption from stainless steel begins to occur just above 500 K (E des = 1.54 eV), sub-monolayer Li desorption occurred in a TPD peak at 942 K (E des = 2.52 eV) indicating more energetically favorable lithium-stainless steel bonding (in the absence of an oxidation layer) than lithium lithium bonding.« less

Spreading of lithium on a stainless steel surface at room temperature

NASA Astrophysics Data System (ADS)

Skinner, C. H.; Capece, A. M.; Roszell, J. P.; Koel, B. E.

2016-01-01

Lithium conditioned plasma facing surfaces have lowered recycling and enhanced plasma performance on many fusion devices and liquid lithium plasma facing components are under consideration for future machines. A key factor in the performance of liquid lithium components is the wetting by lithium of its container. We have observed the surface spreading of lithium from a mm-scale particle to adjacent stainless steel surfaces using a scanning Auger microprobe that has elemental discrimination. The spreading of lithium occurred at room temperature (when lithium is a solid) from one location at a speed of 0.62 μm/day under ultrahigh vacuum conditions. Separate experiments using temperature programmed desorption (TPD) investigated bonding energetics between monolayer-scale films of lithium and stainless steel. While multilayer lithium desorption from stainless steel begins to occur just above 500 K (Edes = 1.54 eV), sub-monolayer Li desorption occurred in a TPD peak at 942 K (Edes = 2.52 eV) indicating more energetically favorable lithium-stainless steel bonding (in the absence of an oxidation layer) than lithium-lithium bonding.

Adsorption, Desorption, and Displacement Kinetics of H2O and CO2 on Forsterite, Mg2SiO4(011)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, R. Scott; Li, Zhenjun; Dohnalek, Zdenek

We have examined the adsorbate-substrate interaction kinetics of CO2 and H2O on a natural forsterite crystal surface, Mg2SiO4(011), with 10-15% of substitutional Fe2+. We use temperature programmed desorption (TPD) and molecular beam techniques to determine the adsorption, desorption, and displacement kinetics for H2O and CO2. Neither CO2 nor H2O has distinct sub-monolayer desorption peaks but instead both have a broad continuous desorption feature that evolve smoothly into multilayer desorption. Inversion of the monolayer coverage spectra for both molecules reveals that the corresponding binding energies for H2O are greater than that for CO2 on all sites. The relative strength of thesemore » interactions is the dominant factor in the competitive adsorption/displacement kinetics. In experiments where the two adsorbates are co-dosed, H2O always binds to the highest energy binding sites available and displaces CO2. The onset of CO2 displacement by H2O occurs between 65 and 75 K.« less

Radical-induced chemistry from VUV photolysis of interstellar ice analogues containing formaldehyde

NASA Astrophysics Data System (ADS)

Butscher, Teddy; Duvernay, Fabrice; Danger, Grégoire; Chiavassa, Thierry

2016-09-01

Surface processes and radical chemistry within interstellar ices are increasingly suspected to play an important role in the formation of complex organic molecules (COMs) observed in several astrophysical regions and cometary environments. We present new laboratory experiments on the low-temperature solid state formation of complex organic molecules - glycolaldehyde, ethylene glycol, and polyoxymethylene - through radical-induced reactivity from VUV photolysis of formaldehyde in water-free and water-dominated ices. Radical reactivity and endogenous formation of COMs were monitored in situ via infrared spectroscopy in the solid state and post photolysis with temperature programmed desorption (TPD) using a quadripole mass spectrometer. We show the ability of free radicals to be stored when formed at low temperature in water-dominated ices, and to react with other radicals or on double bonds of unsaturated molecules when the temperature increases. It experimentally confirms the role of thermal diffusion in radical reactivity. We propose a new pathway for formaldehyde polymerisation induced by HCO radicals that might explain some observations made by the Ptolemy instrument on board the Rosetta lander Philae. In addition, our results seem to indicate that H-atom additions on H2CO proceed preferentially through CH2OH intermediate radicals rather than the CH3O radical.

Evaluation of biochars by temperature programmed oxidation/mass spectroscopy

USDA-ARS?s Scientific Manuscript database

Biochar from the thermochemical conversion of biomass was evaluated by Temperature Programmed Oxidation (TPO) coupled with mass spectroscopy. This technique can be used to assess the oxidative reactivity of carbonaceous solids where higher temperature reactivity indicates greater structural order. ...

Photon-Induced Thermal Desorption of CO from Small Metal-Carbonyl Clusters

NASA Astrophysics Data System (ADS)

Lüttgens, G.; Pontius, N.; Bechthold, P. S.; Neeb, M.; Eberhardt, W.

2002-02-01

Thermal CO desorption from photoexcited free metal-carbonyl clusters has been resolved in real time using two-color pump-probe photoelectron spectroscopy. Sequential energy dissipation steps between the initial photoexcitation and the final desorption event, e.g., electron relaxation and thermalization, have been resolved for Au2(CO)- and Pt2(CO)-5. The desorption rates for the two clusters differ considerably due to the different numbers of vibrational degrees of freedom. The unimolecular CO-desorption thresholds of Au2(CO)- and Pt2(CO)-5 have been approximated by means of a statistical Rice-Ramsperger-Kassel calculation using the experimentally derived desorption rate constants.

Adsorption of methanol, ethanol and water on well-characterized PtSn surface alloys

NASA Astrophysics Data System (ADS)

Panja, Chameli; Saliba, Najat; Koel, Bruce E.

1998-01-01

Adsorption and desorption of methanol (CH 3OH), ethanol (C 2H 5OH) and water on Pt(111) and two, ordered, PtSn alloys has been studied primarily using temperature-programmed desorption (TPD) mass spectroscopy. The two alloys studied were the {p(2 × 2) Sn}/{Pt(111) } and (√3 × √3) R30° {Sn}/{Pt(111) } surface alloys prepared by vapor deposition of Sn on Pt(111), with θSn = 0.25 and 0.33, respectively. All three molecules are weakly bonded and reversibly adsorbed under UHV conditions on all three surfaces, molecularly desorbing during TPD without any decomposition. The two PtSn surface alloys were found to chemisorb both methanol and ethanol slightly more weakly than on the Pt(111) surface. The desorption activation energies measured by TPD, and hence the adsorption energies, of both methanol and ethanol progressively decrease as the surface concentration of Sn increases, compared with Pt(111). The decreased binding energy leads one to expect a lower reactivity for these alcohols on the two alloys. The sticking coefficients and the monolayer coverages of these alcohols on the two alloys were identical to that on Pt(111) at 100 K, independent of the amount of Sn present in the surface layer. Alloying Sn in Pt(111) also slightly weakens the adsorption energy of water. Water clusters are formed even at low coverages on all three surfaces, eventually forming a water bilayer prior to the formation of a condensed ice phase. These results are relevant to a molecular-level explanation for the reactivity of Sn-promoted Pt surfaces that have been used in the electro-oxidation of simple organic molecules.

Importance of the structure and nanoporosity of organic matter on the desorption kinetics of benzo[a]pyrene in sediments.

PubMed

Huang, Youda; Zhang, Dainan; Duan, Dandan; Yang, Yu; Xiong, Yongqiang; Ran, Yong

2017-06-01

The desorption kinetics and mechanism were investigated using a Tenax extraction technique on different sediments spiked with radiocarbon-labeled benzo[a]pyrene (BaP). Five sedimentary fractions were sequentially fractionated, and the only nonhydrolyzable organic carbon fractions (NHC) were characterized using advanced solid-state 13 C nuclear magnetic resonance spectroscopy (NMR), improved six end-member model, and a CO 2 gas adsorption technique. The sediments contained high percentages of algaenan and/or sporopollenin but low percentages of black carbon and lignin. A first-order, two-compartment kinetics model described the desorption process very well (R 2  > 0.990). Although some of the organic carbon fractions were significantly related to the desorption kinetics parameters, the NHC fractions showed the highly significant correlation. Moreover, the nanoporosity or specific surface area (SSA) of the NHC fractions was highly related to their OC contents and aliphatic C (R 2  = 0.960, p < 0.01). The multiple regression equations among the desorption kinetics parameters, structural parameters, and nanoporosity were well established (R 2 =>0.999). Nanoporosity and aromatic C were the dominant contributors. Furthermore, the enhanced percentages of desorbed BaP at elevated temperatures significantly showed a linear regression with the structure and nanoporosity. To our knowledge, the above evidence demonstrates for the first time that the transfer (or diffusion) of BaP in the nanopores of condensed aromatic components is the dominant mechanism of the desorption kinetics of BaP at organic matter particle scale. Copyright © 2017 Elsevier Ltd. All rights reserved.

Rotational state modification and fast ortho-para conversion of H2 trapped within the highly anisotropic potential of Pd(210)

NASA Astrophysics Data System (ADS)

Ohno, S.; Ivanov, D.; Ogura, S.; Wilde, M.; Arguelles, E. F.; Diño, W. A.; Kasai, H.; Fukutani, K.

2018-02-01

The rotational state and ortho-para conversion of H2 on a Pd(210) surface is investigated with rotational-state-selective temperature-programmed desorption (RS-TPD) and theoretical calculations. The isotope dependence of TPD shows a higher desorption energy for D2 than that for H2, which is ascribed to the rotational and zero-point vibrational energies. The RS-TPD data show that the desorption energy of H2(J =1 ) (J : rotational quantum number) is higher than that of H2(J =0 ). This is due to the orientationally anisotropic potential confining the adsorbed H2, which is in agreement with theoretical calculations. Furthermore, the H2 desorption intensity ratio in J =1 and J =0 indicates fast ortho-para conversion in the adsorption state, which we estimate to be of the order of 1 s.

Rapid screening of pharmaceutical drugs using thermal desorption - SALDI mass spectrometry

NASA Astrophysics Data System (ADS)

Grechnikov, A. A.; Kubasov, A. E.; Georgieva, V. B.; Borodkov, A. S.; Nikiforov, S. M.; Simanovsky, Ya O.; Alimpiev, S. S.

2012-12-01

A novel approach to the rapid screening of pharmaceutical drugs by surface assisted laser desorption-ionization (SALDI) mass spectrometry with the rotating ball interface coupled with temperature programmed thermal desorption has been developed. Analytes were thermally desorbed and deposited onto the surface of amorphous silicon substrate attached to the rotating ball. The ball was rotated and the deposited analytes were analyzed using SALDI. The effectiveness of coupling SALDI mass spectrometry with thermal desorption was evaluated by the direct and rapid analysis of tablets containing lidocaine, diphenhydramine and propranolol without any sample pretreatment. The overall duration of the screening procedure was 30÷40 sec. Real urine samples were studied for drug analysis. It is shown that with simple preparation steps, urine samples can be quantitatively analyzed using the proposed technique with the detection limits in the range of 0.2÷0.5 ng/ml.

PAES study of the positron thermal desorption from a Ge(100) surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Soininen, E.; Schwab, A.; Lynn, K.G.

1991-02-01

Positron induced Auger electron spectroscopy (PAES) from a clean Ge(100) surface was studied as a function of temperature. Three low-energy Auger peaks were detected at 50 eV, 90 eV and 100--150 eV, attributed to M{sub 2,3}M{sub 4}M{sub 4}, M{sub 2,3}M{sub 4}V and M{sub 1}M{sub 4}M{sub 4} Auger transitions, respectively. An estimated 4({plus minus}1)% of the surface trapped positrons annihilate with Ge 3p level electrons. The PAES yield from a Ge(100) surface is reduced at elevated temperatures, in accordance with an activation process found earlier in several Ps fraction experiments. A desorption model adopted from these studies does not accurately describemore » the PAES intensity at higher temperatures ({gt}500 {degree}C), which levels off at 5% of the room temperature value. Possible sources for the discrepancy are discussed. On a Ge(100) surface, an upper limit for the Ps emission near the melting point is 97%. The error in calibration parameters due to the earlier assumption of 100% Ps emission from Ge surfaces seems to induce only small errors to the Ps fraction measurements.« less

A multifunctional setup to record FTIR and UV-vis spectra of organic molecules and their photoproducts in astronomical ices.

PubMed

Kofman, V; Witlox, M J A; Bouwman, J; Ten Kate, I L; Linnartz, H

2018-05-01

This article describes a new, multi-functional, high-vacuum ice setup that allows to record the in situ and real-time spectra of vacuum UV (VUV)-irradiated non-volatile molecules embedded in a low-temperature (10 K) amorphous solid water environment. Three complementary diagnostic tools-UV-visible (UV-vis) and Fourier Transform Infrared (FTIR) spectroscopy and temperature-programmed desorption quadrupole mass spectrometry-can be used to simultaneously study the physical and chemical behavior of the organic molecules in the ice upon VUV irradiation. The setup is equipped with a temperature-controlled sublimation oven that enables the controlled homogeneous deposition of solid species such as amino acids, nucleobases, and polycyclic aromatic hydrocarbons (PAHs) in ice mixtures prepared from precursor gases and/or liquids. The resulting ice is photo-processed with a microwave discharge hydrogen lamp, generating VUV radiation with a spectral energy distribution representative for the interstellar medium. The characteristics, performance, and future potential of the system are discussed by describing three different applications. First, a new method is introduced, which uses broadband interference transmission fringes recorded during ice deposition, to determine the wavelength-dependent refractive index, n λ , of amorphous solid water. This approach is also applicable to other solids, pure and mixed. Second, the UV-vis and FTIR spectroscopy of an VUV-irradiated triphenylene:water ice mixture is discussed, monitoring the ionization efficiency of PAHs in interstellar ice environments. The third and final example investigates the stability of solid glycine upon VUV irradiation by monitoring the formation of dissociation products in real time.

Carbon nanotube materials for hydrogen storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dillon, A.C.; Parilla, P.A.; Jones, K.M.

1998-08-01

Carbon single-wall nanotubes (SWNTs) are essentially elongated pores of molecular dimensions and are capable of adsorbing hydrogen at relatively high temperatures and low pressures. This behavior is unique to these materials and indicates that SWNTs are the ideal building block for constructing safe, efficient, and high energy density adsorbents for hydrogen storage applications. In past work the authors developed methods for preparing and opening SWNTs, discovered the unique adsorption properties of these new materials, confirmed that hydrogen is stabilized by physical rather than chemical interactions, measured the strength of interaction to be {approximately} 5 times higher than for adsorption onmore » planar graphite, and performed infrared absorption spectroscopy to determine the chemical nature of the surface terminations before, during, and after oxidation. This year the authors have made significant advances in synthesis and characterization of SWNT materials so that they can now prepare gram quantities of high-purity SWNT samples and measure and control the diameter distribution of the tubes by varying key parameters during synthesis. They have also developed methods which purify nanotubes and cut nanotubes into shorter segments. These capabilities provide a means for opening the tubes which were unreactive to the oxidation methods that successfully opened tubes, and offer a path towards organizing nanotube segments to enable high volumetric hydrogen storage densities. They also performed temperature programmed desorption spectroscopy on high purity carbon nanotube material obtained from collaborator Prof. Patrick Bernier and finished construction of a high precision Seivert`s apparatus which will allow the hydrogen pressure-temperature-composition phase diagrams to be evaluated for SWNT materials.« less

A multifunctional setup to record FTIR and UV-vis spectra of organic molecules and their photoproducts in astronomical ices

NASA Astrophysics Data System (ADS)

Kofman, V.; Witlox, M. J. A.; Bouwman, J.; ten Kate, I. L.; Linnartz, H.

2018-05-01

This article describes a new, multi-functional, high-vacuum ice setup that allows to record the in situ and real-time spectra of vacuum UV (VUV)-irradiated non-volatile molecules embedded in a low-temperature (10 K) amorphous solid water environment. Three complementary diagnostic tools—UV-visible (UV-vis) and Fourier Transform Infrared (FTIR) spectroscopy and temperature-programmed desorption quadrupole mass spectrometry—can be used to simultaneously study the physical and chemical behavior of the organic molecules in the ice upon VUV irradiation. The setup is equipped with a temperature-controlled sublimation oven that enables the controlled homogeneous deposition of solid species such as amino acids, nucleobases, and polycyclic aromatic hydrocarbons (PAHs) in ice mixtures prepared from precursor gases and/or liquids. The resulting ice is photo-processed with a microwave discharge hydrogen lamp, generating VUV radiation with a spectral energy distribution representative for the interstellar medium. The characteristics, performance, and future potential of the system are discussed by describing three different applications. First, a new method is introduced, which uses broadband interference transmission fringes recorded during ice deposition, to determine the wavelength-dependent refractive index, nλ, of amorphous solid water. This approach is also applicable to other solids, pure and mixed. Second, the UV-vis and FTIR spectroscopy of an VUV-irradiated triphenylene:water ice mixture is discussed, monitoring the ionization efficiency of PAHs in interstellar ice environments. The third and final example investigates the stability of solid glycine upon VUV irradiation by monitoring the formation of dissociation products in real time.

The adsorption and thermal decomposition of PH 3 on Si(111)-(7 × 7)

NASA Astrophysics Data System (ADS)

Taylor, P. A.; Wallace, R. M.; Choyke, W. J.; Yates, J. T.

1990-11-01

The adsorption of PH 3, on Si(111)-(7 × 7) has been studied by Auger electron spectroscopy and temperature programmed desorption. PH 3 was found to exhibit two kinds of behavior on the surface. A small surface coverage of molecularly adsorbed PH 3 desorbs without any dissociative surface chemistry. For the majority of the adsorbed PH x species (3 ⩾ x ⩾ 1) dissociation occurs to form P(a) and H(a). At 120 K, PH 3 initially adsorbs as the reactive species with a sticking coefficient of S ≅ 1 up to ˜75% saturation. The reactive PH x species surface concentration saturates at (1.9 ± 0.3) × 10 14 PH x cm -2. Surface H(a), produc thermal decomposition, desorbs as H 2(g) at T > 700 K., and P(a) desorbs as P 2(g) at T > 900 K. Capping the Si-dangling bonds with atomic deuterium prevents PH 3 adsorption, indicating that the dangling bonds are the PH 3 adsorption sites. Isotopic studies involving Si-D surface species mixed with adsorbed PH x species indicate that PH 3 desorption does not occur through a recombination process. Finally, additional PH 3 may be adsorbed if the surface hydrogen produced by dissociation of PH 3 is removed. Evidence for P penetration into bulk Si(111) at 875 K is presented.

The study of 'microsurfaces' using thermal desorption spectroscopy

NASA Technical Reports Server (NTRS)

Thomas, M. E.; Poppa, H.; Pound, G. M.

1979-01-01

The use of a newly combined ultrahigh vacuum technique for studying continuous and particulate evaporated thin films using thermal desorption spectroscopy (TDS), transmission electron microscopy (TEM), and transmission electron diffraction (TED) is discussed. It is shown that (1) CO thermal desorption energies of epitaxially deposited (111) Ni and (111) Pd surfaces agree perfectly with previously published data on bulk (111) single crystal, (2) contamination and surface structural differences can be detected using TDS as a surface probe and TEM as a complementary technique, and (3) CO desorption signals from deposited metal coverages of one-thousandth of a monolayer should be detectable. These results indicate that the chemisorption properties of supported 'microsurfaces' of metals can now be investigated with very high sensitivity. The combined use of TDS and TEM-TED experimental methods is a very powerful technique for fundamental studies in basic thin film physics and in catalysis.

Thermal desorption of formamide and methylamine from graphite and amorphous water ice surfaces

NASA Astrophysics Data System (ADS)

Chaabouni, H.; Diana, S.; Nguyen, T.; Dulieu, F.

2018-04-01

Context. Formamide (NH2CHO) and methylamine (CH3NH2) are known to be the most abundant amine-containing molecules in many astrophysical environments. The presence of these molecules in the gas phase may result from thermal desorption of interstellar ices. Aims: The aim of this work is to determine the values of the desorption energies of formamide and methylamine from analogues of interstellar dust grain surfaces and to understand their interaction with water ice. Methods: Temperature programmed desorption (TPD) experiments of formamide and methylamine ices were performed in the sub-monolayer and monolayer regimes on graphite (HOPG) and non-porous amorphous solid water (np-ASW) ice surfaces at temperatures 40-240 K. The desorption energy distributions of these two molecules were calculated from TPD measurements using a set of independent Polanyi-Wigner equations. Results: The maximum of the desorption of formamide from both graphite and ASW ice surfaces occurs at 176 K after the desorption of H2O molecules, whereas the desorption profile of methylamine depends strongly on the substrate. Solid methylamine starts to desorb below 100 K from the graphite surface. Its desorption from the water ice surface occurs after 120 K and stops during the water ice sublimation around 150 K. It continues to desorb from the graphite surface at temperatures higher than160 K. Conclusions: More than 95% of solid NH2CHO diffuses through the np-ASW ice surface towards the graphitic substrate and is released into the gas phase with a desorption energy distribution Edes = 7460-9380 K, which is measured with the best-fit pre-exponential factor A = 1018 s-1. However, the desorption energy distribution of methylamine from the np-ASW ice surface (Edes = 3850-8420 K) is measured with the best-fit pre-exponential factor A = 1012 s-1. A fraction of solid methylamine monolayer of roughly 0.15 diffuses through the water ice surface towards the HOPG substrate. This small amount of methylamine desorbs later with higher binding energies (5050-8420 K) that exceed that of the crystalline water ice (Edes = 4930 K), which is calculated with the same pre-exponential factor A = 1012 s-1. The best wetting ability of methylamine compared to H2O molecules makes CH3NH2 molecules a refractory species for low coverage. Other binding energies of astrophysical relevant molecules are gathered and compared, but we could not link the chemical functional groups (amino, methyl, hydroxyl, and carbonyl) with the binding energy properties. Implications of these high binding energies are discussed.

Sorption-desorption of fipronil in some soils, as influenced by ionic strength, pH and temperature.

PubMed

Singh, Anand; Srivastava, Anjana; Srivastava, Prakash C

2016-08-01

The sorption-desorpion of fipronil insecticide is influenced by soil properties and variables such as pH, ionic strength, temperature, etc. A better understanding of soil properties and these variables in sorption-desorption processes by quantification of fipronil using liquid chromatography may help to optimise suitable soil management to reduce contamination of surface and groundwaters. In the present investigation, the sorption-desorption of fipronil was studied in some soils at varying concentrations, ionic strengths, temperatures and pH values, and IR specta of fipronil sorbed onto soils were studied. The sorption of fipronil onto soils conformed to the Freundlich isotherm model. The sorption-desorption of fipronil varied with ionic strength in each of the soils. Sorption decreased but desorption increased with temperature. Sorption did not change with increasing pH, but for desorption there was no correlation. The cumulative desorption of fipronil from soil was significantly and inversely related to soil organic carbon content. IR spectra of sorbed fipronil showed the involvement of amino, nitrile, sulfone, chloro and fluoro groups and the pyrazole nucleus of the fipronil molecule. The sorption of fipronil onto soils appeared to be a physical process with the involvement of hydrogen bonding. An increase in soil organic carbon may help to reduce desorption of fipronil. High-temperature regimes are more conducive to the desorption. © 2015 Society of Chemical Industry. © 2015 Society of Chemical Industry.

Effect of neutron energy and fluence on deuterium retention behaviour in neutron irradiated tungsten

NASA Astrophysics Data System (ADS)

Fujita, Hiroe; Yuyama, Kenta; Li, Xiaochun; Hatano, Yuji; Toyama, Takeshi; Ohta, Masayuki; Ochiai, Kentaro; Yoshida, Naoaki; Chikada, Takumi; Oya, Yasuhisa

2016-02-01

Deuterium (D) retention behaviours for 14 MeV neutron irradiated tungsten (W) and fission neutron irradiated W were evaluated by thermal desorption spectroscopy (TDS) to elucidate the correlation between D retention and defect formation by different energy distributions of neutrons in W at the initial stage of fusion reactor operation. These results were compared with that for Fe2+ irradiated W with various damage concentrations. Although dense vacancies and voids within the shallow region near the surface were introduced by Fe2+ irradiation, single vacancies with low concentration were distributed throughout the sample for 14 MeV neutron irradiated W. Only the dislocation loops were introduced by fission neutron irradiation at low neutron fluence. The desorption peak of D for fission neutron irradiated W was concentrated at low temperature region less than 550 K, but that for 14 MeV neutron irradiated W was extended toward the higher temperature side due to D trapping by vacancies. It can be said that the neutron energy distribution could have a large impact on irradiation defect formation and the D retention behaviour.

Excimer laser assisted very fast exfoliation and reduction of graphite oxide at room temperature under air ambient for Supercapacitors electrode

NASA Astrophysics Data System (ADS)

Malek Hosseini, S. M. B.; Baizaee, S. M.; Naderi, Hamid Reza; Dare Kordi, Ali

2018-01-01

Excimer laser was used for reduction and exfoliation of graphite oxide (GO) at room temperature under air ambient. The prepared excimer laser reduced graphite oxide (XLRGO) is characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), nitrogen adsorption/desorption (BET method), X-ray diffraction (XRD), X-ray photoemission spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and UV-vis absorption techniques for surface, structural functional groups and band gap analysis. Electrochemical properties are investigated using cyclic voltammetry, galvanostatic charge-discharge, electrochemical impedance spectroscopy (EIS) and continues cyclic voltammetry (CCV) in 0.5 M Na2SO4 as electrolyte. Electrochemical investigations revealed that XLRGO electrode has enhanced supercapacitive performance including specific capacitance of 299 F/g at a scan rate of 2 mV/s. Furthermore, CCV measurement showed that XLRGO electrode kept 97.8% of its initial capacitance/capacity after 4000 cycles. The obtained results from electrochemical investigations confirm that the reduction of GO by using an excimer laser produces high-quality graphene for supercapacitor applications without the need for additional operations.

Ammonia IRMS-TPD study on the distribution of acid sites in mordenite.

PubMed

Niwa, Miki; Suzuki, Katsuki; Katada, Naonobu; Kanougi, Tomonori; Atoguchi, Takashi

2005-10-13

Using an IRMS-TPD (temperature programmed desorption) of ammonia, we studied the nature, strength, crystallographic location, and distribution of acid sites of mordenite. In this method, infrared spectroscopy (IR) and mass spectroscopy (MS) work together to follow the thermal behavior of adsorbed and desorbed ammonia, respectively; therefore, adsorbed species were identified, and their thermal behavior was directly connected with the desorption of ammonia during an elevation of temperature. IR-measured TPD of the NH4(+) cation was similar to MS-measured TPD, thus showing the nature of Brønsted acidity. From the behavior of OH bands, it was found that the Brønsted acid sites consisted of two kinds of OH bands at high and low wavenumbers, ascribable to OH bands situated on 12- and 8-member rings (MR) of mordenite structure, respectively. The amount and strength of these Brønsted hydroxyls were measured quantitatively based on a theoretical equation using a curve fitting method. Up to ca. 30% of the exchange degree, NH4(+) was exchanged with Na+ on the 12-MR to arrive at saturation; therefore, in this region, the Brønsted acid site was situated on the large pore of 12-MR. The NH4(+) cation was then exchanged with Na+ on 8-MR, and finally exceeded the amount on 12-MR. In the 99% NH4-mordenite, Brønsted acid sites were located predominantly on the 8-MR more than on the 12-MR. Irrespective of the NH4(+) exchange degree, the strengths deltaH of Brønsted OH were 145 and 153 kJ mol(-1) on the 12- and 8-MR, respectively; that is, the strength of Brønsted acid site on the 8-MR was larger than that on the 12-MR. A density functional theory (DFT) calculation supported the difference in the strengths of the acid sites. Catalytic cracking activity of the Brønsted acid sites on the 8-MR declined rapidly, while that on the 12-MR was remarkably kept. The difference in strength and/or steric capacity may cause such a difference in the life of a catalyst.

Thermal desorption study of physical forces at the PTFE surface

NASA Technical Reports Server (NTRS)

Wheeler, D. R.; Pepper, S. V.

1987-01-01

Thermal desorption spectroscopy (TDS) of the polytetrafluoroethylene (PTFE) surface was successfully employed to study the possible role of physical forces in the enhancement of metal-PTFE adhesion by radiation. The thermal desorption spectra were analyzed without assumptions to yield the activation energy for desorption over a range of xenon coverage from less than 0.1 monolayer to more than 100 monolayers. For multilayer coverage, the desorption is zero-order with an activation energy equal to the sublimation energy of xenon. For submonolayer coverages, the order for desorption from the unirradiated PTFE surface is 0.73 and the activation energy for desorption is between 3.32 and 3.36 kcal/mol; less than the xenon sublimation energy. The effect of irradiation is to increase the activation energy for desorption to as high as 4 kcal/mol at low coverage.

Thermal desorption study of physical forces at the PTFE surface

NASA Technical Reports Server (NTRS)

Wheeler, D. R.; Pepper, S. V.

1985-01-01

Thermal desorption spectroscopy (TDS) of the polytetrafluoroethylene (PTFE) surface was successfully employed to study the possibile role of physical forces in the enhancement of metal-PTFE adhesion by radiation. The thermal desorption spectra were analyzed without assumptions to yield the activation energy for desorption over a range of xenon coverage from less than 0.1 monolayer to more than 100 monolayers. For multilayer coverage, the desorption is zero-order with an activation energy equal to the sublimation energy of xenon. For submonolayer coverages, the order for desorption from the unirradiated PTFE surface is 0.73 and the activation energy for desorption is between 3.32 and 3.36 kcal/mol; less than the xenon sublimation energy. The effect of irradiation is to increase the activation energy for desorption to as high as 4 kcal/mol at low coverage.

The reactions of thiophene on Mo(110) and Mo(110)-p(2×2)-S

NASA Astrophysics Data System (ADS)

Roberts, Jeffrey T.; Friend, C. M.

1987-07-01

The reactions of thiophene and 2,5-dideuterothiophene on Mo(110) and Mo(110)-p(2×2)-S have been investigated under ultrahigh vacuum conditions using temperature programmed reaction spectroscopy and Auger electron spectroscopy. Thiophene chemisorbed on Mo(110) decomposes during temperature programmed reaction to yield only gaseous dihydrogen, surface carbon, and surface sulfur. At low thiophene exposures, dihydrogen evolves from Mo(110) in a symmetric peak at 440 K. At saturation exposures, three dihydrogen peaks are detected at 360 K, at 420 K and at 565 K. Multilayers of thiophene desorb at 180 K. Temperature programmed reaction of 2,5-dideuterothiophene demonstrates that at high thiophene coverages, one of the α-C-H bonds (those nearest sulfur) breaks first. No bond breaking selectivity is observed at low thiophene exposures. The Mo(110)-p(2×2)-S surface is less active for thiophene decomposition. Thiophene adsorbed on Mo(110)-p(2×2)-S to low coverages decomposes to surface carbon surface sulfur, and hydrogen at 430 K. At reaction saturation, dihydrogen production is observed at 375 and 570 K. In addition, at moderate and high exposures, chemisorbed thiophene desorbs from Mo(110)-p(2×2)-S. At saturation the desorption temperature of the reversibly chemisorbed state is 215 K. Experiments with 2,5-dideuterothiophene demonstrate no surface selectivity for α-C-H bond breaking reactions on Mo(110)-p(2×2)-S. The decomposition mechanism and energetics of thiophene decomposition are proposed to be dependent on the coverage of thiophene. At low thiophene exposures, the ring is proposed to bond parallel to the surface. All C-H bonds in the parallel geometry are sterically available for activation by the surface, accounting for the lack of selectivity in C-H bond breaking. High thiophene coverages are suggested to result in perpendicularly bound thiophene which undergoes selective α-dehydrogenation to an α)-thiophenyl intermediate. The presence of sulfur leads to a high energy pathway for cleavage of C-H bonds in a thiophene derived intermediate. Carbon-hydrogen bonds survive on the surface up to temperatures of 650 K. Comparison of this study with work on Mo(100) demonstrates that the reaction of thiophene on molybdenum is relatively insensitive to the surface geometric structure.

Sorption of hydrogen by silica aerogel at low-temperatures

NASA Astrophysics Data System (ADS)

Dolbin, A. V.; Khlistyuck, M. V.; Esel'son, V. B.; Gavrilko, V. G.; Vinnikov, N. A.; Basnukaeva, R. M.; Martsenuk, V. E.; Veselova, N. V.; Kaliuzhnyi, I. A.; Storozhko, A. V.

2018-02-01

The programmed thermal desorption method is used at temperatures of 7-95 K to study the sorption and subsequent desorption of hydrogen by a sample of silica aerogel. Physical sorption of hydrogen owing to the weak van-der-Waals interaction of hydrogen molecules with the silicon dioxide walls of the pores of the sample was observed over the entire temperature range. The total capacity of the aerogel sample for hydrogen was ˜1.5 mass %. It was found that when the sample temperature was lowered from 95 to 60 K, the characteristic sorption times for hydrogen by the silica aerogel increase; this is typical of thermally activated diffusion (Ea ≈ 408 K). For temperatures of 15-45 K the characteristic H2 sorption times depended weakly on temperature, presumably because of the predominance of a tunnel mechanism for diffusion over thermally activated diffusion. Below 15 K the characteristic sorption times increase somewhat as the temperature is lowered; this may be explained by the formation of a monolayer of H2 molecules on the surface of the aerogel grains.

Catalytically Enhanced Hydrogen Sorption in Mg-MgH2 by Coupling Vanadium-Based Catalyst and Carbon Nanotubes

PubMed Central

Kadri, Atikah; Jia, Yi; Chen, Zhigang; Yao, Xiangdong

2015-01-01

Mg (MgH2)-based composites, using carbon nanotubes (CNTs) and pre-synthesized vanadium-based complex (VCat) as the catalysts, were prepared by high-energy ball milling technique. The synergistic effect of coupling CNTs and VCat in MgH2 was observed for an ultra-fast absorption rate of 6.50 wt. % of hydrogen per minute and 6.50 wt. % of hydrogen release in 10 min at 200 °C and 300 °C, respectively. The temperature programmed desorption (TPD) results reveal that coupling VCat and CNTs reduces both peak and onset temperatures by more than 60 °C and 114 °C, respectively. In addition, the presence of both VCat and CNTs reduces the enthalpy and entropy of desorption of about 7 kJ/mol H2 and 11 J/mol H2·K, respectively, as compared to those of the commercial MgH2, which ascribe to the decrease of desorption temperature. From the study of the effect of CNTs milling time, it is shown that partially destroyed CNTs (shorter milling time) are better to enhance the hydrogen sorption performance.

The formation of diethyl ether via the reaction of iodoethane with atomic oxygen on the Ag(110) surface

NASA Astrophysics Data System (ADS)

Jones, G. Scott; Barteau, Mark A.; Vohs, John M.

1999-01-01

The reactions of iodoethane (ICH 2CH 3) on clean and oxygen-covered Ag(110) surfaces were investigated using temperature-programmed desorption (TPD) and high-resolution electron energy-loss spectroscopy (HREELS). Iodoethane adsorbs dissociatively at 150 K to produce surface ethyl groups on both clean and oxygen-covered Ag(110) surfaces. The ethyl species couple to form butane on both surfaces, with the desorption peak maximum located between 218 and 238 K, depending on the ethyl coverage. In addition to butane, a number of oxidation products including diethyl ether, ethanol, acetaldehyde, surface acetate, ethylene, carbon dioxide and water were formed on the oxygen-dosed Ag(110) surface. Diethyl ether was the major oxygenate produced at all ethyl:oxygen ratios, and the peak temperature for ether evolution varied from 220 to 266 K depending on the relative coverages of these reactants. The total combustion products, CO 2 and H 2O, were primarily formed at low ethyl coverages in the presence of excess oxygen. The formation of ethylene near 240 K probably involves an oxygen-assisted dehydrogenation pathway since ethylene is not formed from ethyl groups on the clean surface. Acetaldehyde and ethanol evolve coincidentally with a peak centered at 270-280 K, and are attributed to the reactions of surface ethoxide species. The surface acetate which decomposes near 620 K is formed from subsequent reactions of acetaldehyde with oxygen atoms. The addition of ethyl to oxygen to form surface ethoxides was verified by HREELS results. The yields of all products exhibited a strong dependence on the relative coverages of ethyl and oxygen.

CO Adsorption on Reconstructed Ir(100) Surfaces from UHV to mbar Pressure: A LEED, TPD, and PM-IRAS Study

PubMed Central

2016-01-01

Clean and stable surface modifications of an iridium (100) single crystal, i.e., the (1 × 1) phase, the (5 × 1) reconstruction, and the oxygen-terminated (2 × 1)-O surface, were prepared and characterized by low energy electron diffraction (LEED), temperature-programmed desorption (TPD), infrared reflection absorption spectroscopy (IRAS) and polarization modulation IRAS (PM-IRAS). The adsorption of CO in UHV and at elevated (mbar) pressure/temperature was followed both ex situ and in situ on all three surface modifications, with a focus on mbar pressures of CO. The Ir(1 × 1) surface exhibited c(4 × 2)/c(2 × 2) and c(6 × 2) CO structures under low pressure conditions, and remained stable up to 100 mbar and 700 K. For the (2 × 1)-O reconstruction CO adsorption induced a structural change from (2 × 1)-O to (1 × 1), as confirmed by LEED, TPD, and IR. For Ir (2 × 1)-O TPD indicated that CO reacted with surface oxygen forming CO2. The (5 × 1) reconstruction featured a reversible and dynamic behavior upon CO adsorption, with a local lifting of the reconstruction to (1 × 1). After CO desorption, the (5 × 1) structure was restored. All three reconstructions exhibited CO adsorption with on-top geometry, as evidenced by IR. With increasing CO exposure the resonances shifted to higher wavenumber, due to adsorbate–adsorbate and adsorbate–substrate interactions. The largest wavenumber shift (from 2057 to 2100 cm–1) was observed for Ir(5 × 1) upon CO dosing from 1 L to 100 mbar. PMID:27257467

DOE Office of Scientific and Technical Information (OSTI.GOV)

Podlivaev, A. I., E-mail: AIPodlivayev@mephi.ru; Openov, L. A.

The initial stage of hydrogen desorption from fully hydrogenated carbon nanotubes (3.0) and (2.2) is numerically studied by the molecular dynamics method. The temperature dependence of the desorption rate is directly determined at T = 1800–2500 K. The characteristic desorption times are determined at temperatures outside this range by extrapolation. It is shown that hydrogen desorption leads to the appearance of electronic states in the band gap.

40 CFR 63.3167 - How do I establish the add-on control device operating limits during the performance test?

Code of Federal Regulations, 2013 CFR

2013-07-01

... record the desorption gas inlet temperature at least once every 15 minutes during each of the three runs... and record the average desorption gas inlet temperature. The minimum operating limit for the concentrator is 8 degrees Celsius (15 degrees Fahrenheit) below the average desorption gas inlet temperature...

40 CFR 63.3167 - How do I establish the add-on control device operating limits during the performance test?

Code of Federal Regulations, 2012 CFR

2012-07-01

... record the desorption gas inlet temperature at least once every 15 minutes during each of the three runs... and record the average desorption gas inlet temperature. The minimum operating limit for the concentrator is 8 degrees Celsius (15 degrees Fahrenheit) below the average desorption gas inlet temperature...

40 CFR 63.3167 - How do I establish the add-on control device operating limits during the performance test?

Code of Federal Regulations, 2014 CFR

2014-07-01

... record the desorption gas inlet temperature at least once every 15 minutes during each of the three runs... and record the average desorption gas inlet temperature. The minimum operating limit for the concentrator is 8 degrees Celsius (15 degrees Fahrenheit) below the average desorption gas inlet temperature...

40 CFR 63.3167 - How do I establish the add-on control device operating limits during the performance test?

Code of Federal Regulations, 2011 CFR

2011-07-01

... record the desorption gas inlet temperature at least once every 15 minutes during each of the three runs... and record the average desorption gas inlet temperature. The minimum operating limit for the concentrator is 8 degrees Celsius (15 degrees Fahrenheit) below the average desorption gas inlet temperature...

Defect annealing and thermal desorption of deuterium in low dose HFIR neutron-irradiated tungsten

NASA Astrophysics Data System (ADS)

Shimada, Masashi; Hara, Masanori; Otsuka, Teppei; Oya, Yasuhisa; Hatano, Yuji

2015-08-01

Three tungsten samples irradiated at High Flux Isotope Reactor at Oak Ridge National Laboratory were exposed to deuterium plasma (ion fluence of 1 × 1026 m-2) at three different temperatures (100, 200, and 500 °C) in Tritium Plasma Experiment at Idaho National Laboratory. Subsequently, thermal desorption spectroscopy was performed with a ramp rate of 10 °C min-1 up to 900 °C, and the samples were annealed at 900 °C for 0.5 h. These procedures were repeated three times to uncover defect-annealing effects on deuterium retention. The results show that deuterium retention decreases approximately 70% for at 500 °C after each annealing, and radiation damages were not annealed out completely even after the 3rd annealing. TMAP modeling revealed the trap concentration decreases approximately 80% after each annealing at 900 °C for 0.5 h.

Tunneling effects in the kinetics of helium and hydrogen isotopes desorption from single-walled carbon nanotube bundles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Danilchenko, B. A., E-mail: danil@iop.kiev.ua; Yaskovets, I. I.; Uvarova, I. Y.

2014-04-28

The kinetics of desorption both helium isotopes and molecules of hydrogen and deuterium from open-ended or γ-irradiated single-walled carbon nanotube bundles was investigated in temperature range of 10–300 K. The gases desorption rates obey the Arrhenius law at high temperatures, deviate from it with temperature reduction and become constant at low temperatures. These results indicate the quantum nature of gas outflow from carbon nanotube bundles. We had deduced the crossover temperature below which the quantum corrections to the effective activation energy of desorption become significant. This temperature follows linear dependence against the inverse mass of gas molecule and is consistent withmore » theoretical prediction.« less

Structural evolution of maize stalk/char particles during pyrolysis.

PubMed

Fu, Peng; Hu, Song; Sun, Lushi; Xiang, Jun; Yang, Tao; Zhang, Anchao; Zhang, Junying

2009-10-01

The structural evolution characteristics of maize stalk/char particles during pyrolysis were investigated. The char was prepared by pyrolyzing at temperatures ranging from 200 to 900 degrees C. Maize stalk and chars were characterized by thermogravimetric analysis, ultimate analysis (TGA), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), helium density measurement and N(2) adsorption/desorption method. The char yield decreased rapidly with increasing temperature until 400 degrees C. As temperature increased, the char became progressively more aromatic and carbonaceous. The hydroxyl, aliphatic C-H, carbonyl and olefinic C=C groups were lost at high temperatures. Below 500 degrees C, the removal of volatile matter made pore opening. High temperatures led to the occurrence of softening, melting, fusing and carbon structural ordering. The aromatization process started at approximately 350 degrees C and continued to higher temperatures. The shrinkage of carbon structure occurred above 500 degrees C, which was concurrent with the aromatization process.

Reactivity of a Thick BaO Film Supported on Pt(111): Adsorption and Reaction of NO2, H2O and CO2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mudiyanselage, Kumudu; Yi, Cheol-Woo W.; Szanyi, Janos

2009-09-15

Reactions of NO2, H2O, and CO2 with a thick (> 20 MLE) BaO film supported on Pt(111) were studied with temperature programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS). NO2 reacts with a thick BaO to form surface nitrite-nitrate ion pairs at 300 K, while only nitrates form at 600 K. In the thermal decomposition process of nitrite–nitrate ion pairs, first nitrites decompose and desorb as NO. Then nitrates decompose in two steps : at lower temperature with the release of NO2 and at higher temperature, nitrates dissociate to NO + O2. The thick BaO layer converts completely to Ba(OH)2more » following the adsorption of H2O at 300 K. Dehydration/dehydroxylation of this hydroxide layer can be fully achieved by annealing to 550 K. CO2 also reacts with BaO to form BaCO3 that completely decomposes to regenerate BaO upon annealing to 825 K. However, the thick BaO film cannot be converted completely to Ba(NOx)2 or BaCO3 under the experimental conditions employed in this study.« less

Rational design of template-free MnOx-CeO2 hollow nanotube as de-NOx catalyst at low temperature

NASA Astrophysics Data System (ADS)

Li, Chenlu; Tang, Xiaolong; Yi, Honghong; Wang, Lifeng; Cui, Xiaoxu; Chu, Chao; Li, Jingying; Zhang, Runcao; Yu, Qingjun

2018-01-01

MnOx-CeO2 hollow nanotube was synthesized for the low temperature selective catalytic reduction (SCR) of NOx with NH3. The nanotube was fabricated firstly through the interfacial oxidation-reduction reaction by dealing the Ce(OH)CO3 intermediate with KMnO4 aqueous solution, then followed by selective wash with HNO3. The catalysts were systematically examined by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, elemental mapping, X-ray photoelectron spectroscopy, NH3 temperature-programmed desorption measurements and catalytic activity test. It was found that the as-prepared MnOx-CeO2-B nanotube exhibited best NOx removal efficiency among the catalysts investigated, where 96% NOx conversion at 100 °C at a space velocity of 30000 h-1 was obtained. Meanwhile, superior resistance to H2O and SO2 was achieved as well as high thermal stability. On the basis of various analysis results, the remarkable de-NOx performance of the MnOx-CeO2-B nanobube could be attributed to the uniform distribution of active species, abundant content of Mn4+ and Oα species, and especially the hollow porous architectures provided huge specific surface area and sufficient acidic sites.

Dissociative adsorption of CCl 4 on the Fe 3O 4(1 1 1)-(2×2) selvedge of α-Fe 2O 3(0 0 0 1)

NASA Astrophysics Data System (ADS)

Adib, K.; Mullins, D. R.; Totir, G.; Camillone, N.; Fitts, J. P.; Rim, K. T.; Flynn, G. W.; Osgood, R. M.

2003-02-01

The surface reactions of CCl 4 with the Fe 3O 4(1 1 1)-(2×2) selvedge of naturally occurring α-Fe 2O 3(0 0 0 1) single-crystals have been investigated using synchrotron X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption (TPD). CCl 4 was found to dissociate on the Fe 3O 4 surface at 100 K producing chemisorbed Cl and adsorbed CCl 2. TPD shows that the large majority of the dissociatively adsorbed CCl 2 fragments extract lattice oxygen and desorb as phosgene at >275 K. However, the XPS spectra show no evidence for the formation of surface-bound phosgene, at 100 K, indicating that its formation involves two steps. The first step, dissociation, is spontaneous at 100 K, whereas the second, oxygen atom abstraction to form phosgene, requires thermal excitation. Cl chemisorption yielded two separate species, the mono- and dichloride terminations of surface iron sites. The identification of these two surface terminations is based on the coverage dependence and the surface temperature history of their Cl 2p 3/2 peak intensity. For example, heating to >450 K allows the monochloride to transform into iron dichloride, indicating Cl adatom mobility at these temperatures.

Evaluation of Surface Cleaning of Si(211) for Molecular-Beam Epitaxy Deposition of Infrared Detectors

NASA Astrophysics Data System (ADS)

Jaime-Vasquez, M.; Jacobs, R. N.; Benson, J. D.; Stoltz, A. J.; Almeida, L. A.; Bubulac, L. O.; Chen, Y.; Brill, G.

2010-07-01

We report an assessment of the reproducibility of the HF cleaning process and As passivation prior to the nucleation of ZnTe on the Si(211) surface using temperature desorption spectroscopy, ion scattering spectroscopy, and electron spectroscopy. Observations suggest full H coverage of the Si(211) surface with mostly monohydride and small amounts of dihydride states, and that F is uniformly distributed across the top layer as a physisorbed species. Variations in major contaminants are observed across the Si surface and at the CdTe-ZnTe/Si interface. Defects act as getters for impurities present on the Si surface, and some are buried under the CdTe/ZnTe heterostructure. Overall, the data show evidence of localized concentration of major impurities around defects, supporting the hypothesis of a physical model explaining the electrical activation of defects in long-wave infrared (LWIR) HgCdTe/CdTe/Si devices.

A Comparative Study of Hydrodeoxygenation of Furfural Over Fe/Pt(111) and Fe/Mo 2C Surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wan, Weiming; Jiang, Zhifeng; Chen, Jingguang G.

It is desirable to convert biomass-derived furfural to 2-methylfuran through the hydrodeoxygenation (HDO) reaction using an inexpensive catalyst with high stability. In this work, Mo 2C was used as an alternative substrate to replace precious Pt to support monolayer Fe for the HDO reaction of furfural. The HDO activity and stability of Fe/Pt(111) and Fe/Mo 2C/Mo(110) surfaces were compared. Density functional theory calculations and vibrational spectroscopy results indicated that both surfaces bonded to furfural with similar adsorption geometries and should be active toward the furfural HDO reaction. Temperature programmed desorption experiments confirmed a similar HDO activity between the two surfaces,more » with Fe/Mo 2C/Mo(110) being more thermally stable than Fe/Pt(111). As a result, the combined theoretical and experimental results demonstrated that Fe/Mo 2C should be a promising non-precious metal catalyst for the HDO reaction of furfural to produce 2-methylfuran.« less

A Comparative Study of Hydrodeoxygenation of Furfural Over Fe/Pt(111) and Fe/Mo 2C Surfaces

DOE PAGES

Wan, Weiming; Jiang, Zhifeng; Chen, Jingguang G.

2018-01-19

It is desirable to convert biomass-derived furfural to 2-methylfuran through the hydrodeoxygenation (HDO) reaction using an inexpensive catalyst with high stability. In this work, Mo 2C was used as an alternative substrate to replace precious Pt to support monolayer Fe for the HDO reaction of furfural. The HDO activity and stability of Fe/Pt(111) and Fe/Mo 2C/Mo(110) surfaces were compared. Density functional theory calculations and vibrational spectroscopy results indicated that both surfaces bonded to furfural with similar adsorption geometries and should be active toward the furfural HDO reaction. Temperature programmed desorption experiments confirmed a similar HDO activity between the two surfaces,more » with Fe/Mo 2C/Mo(110) being more thermally stable than Fe/Pt(111). As a result, the combined theoretical and experimental results demonstrated that Fe/Mo 2C should be a promising non-precious metal catalyst for the HDO reaction of furfural to produce 2-methylfuran.« less

The effect of impurities and incident angle on the secondary electron emission of Ni(110)

NASA Astrophysics Data System (ADS)

Lazar, Hadar; Patino, Marlene; Raitses, Yevgeny; Koel, Bruce E.; Gentile, Charles; Feibush, Eliot

2015-11-01

The investigation of secondary electron emission (SEE) of conducting materials used for magnetic fusion devices and plasma thrusters is important for determining device lifetime and performance. Methods to quantify the secondary electron emission from conducting materials and to characterize the effects that impurities and incident angles have on secondary electron emission were developed using 4-grid low energy electron diffraction (LEED) optics. The total secondary electron yield from a Ni(110) surface was continuously measured from the sample current as surface contamination increased from reactions with background gases in the ultrahigh vacuum chamber. Auger electron spectroscopy (AES) and temperature programmed desorption (TPD) were used to examine the composition and impurity levels on the Ni(110) surface. The total secondary electron yield was also measured at different incident angles. Thank you to the Princeton Plasma Physics Laboratory and the Department of Energy for the opportunity to work on this project through the Science Undergraduate Laboratory Internships.

Reaction pathways of furfural, furfuryl alcohol and 2-methylfuran on Cu(111) and NiCu bimetallic surfaces

DOE PAGES

Xiong, Ke; Wan, Weiming; Chen, Jingguang G.

2016-02-23

Hydrodeoxygenation (HDO) is an important reaction for converting biomass-derived furfural to value-added 2-methylfuran, which is a promising fuel additive. In this work, the HDO of furfural to produce 2-methylfuran occurred on the NiCu bimetallic surfaces prepared on either Ni(111) or Cu(111). The reaction pathways of furfural were investigated on Cu(111) and Ni/Cu(111) surfaces using density functional theory (DFT) calculations, temperature programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS) experiments. These studies provided mechanistic insights into the effects of bimetallic formation on enhancing the HDO activity. Specifically, furfural weakly adsorbed on Cu(111), while it strongly adsorbed on Ni/Cu(111)more » through an η 2(C,O) configuration which led to the HDO of furfural on Ni/Cu(111). Lastly, the ability to dissociate H 2 on Ni/Cu(111) is also an important factor for enhancing the HDO activity over Cu(111).« less

Selective deoxygenation of aldehydes and alcohols on molybdenum carbide (Mo2C) surfaces

NASA Astrophysics Data System (ADS)

Xiong, Ke; Yu, Weiting; Chen, Jingguang G.

2014-12-01

The selective deoxygenation of aldehydes and alcohols without cleaving the Csbnd C bond is crucial for upgrading bio-oil and other biomass-derived molecules to useful fuels and chemicals. In this work, propanal, 1-propanol, furfural and furfuryl alcohol were selected as probe molecules to study the deoxygenation of aldehydes and alcohols on molybdenum carbide (Mo2C) prepared over a Mo(1 1 0) surface. The reaction pathways were investigated using temperature programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS). The deoxygenation of propanal and 1-propanol went through a similar intermediate (propoxide or η2(C,O)-propanal) to produce propene. The deoxygenation of furfural and furfuryl alcohol produced a surface intermediate similar to adsorbed 2-methylfuran. The comparison of these results revealed the promising deoxygenation performance of Mo2C, as well as the effect of the furan ring on the selective deoxygenation of the Cdbnd O and Csbnd OH bonds.

Deoxygenation of glycolaldehyde and furfural on Mo2C/Mo(100)

NASA Astrophysics Data System (ADS)

McManus, Jesse R.; Vohs, John M.

2014-12-01

The desire to produce fuels and chemicals in an energy conscious, environmentally sympathetic approach has motivated considerable research on the use of cellulosic biomass feedstocks. One of the major challenges facing the utilization of biomass is finding effective catalysts for the efficient and selective removal of oxygen from the highly-oxygenated, biomass-derived platform molecules. Herein, a study of the reaction pathways for the biomass-derived platform molecule furfural and biomass-derived sugar model compound glycolaldehyde provides insight into the mechanisms of hydrodeoxygenation (HDO) on a model molybdenum carbide catalyst, Mo2C/Mo(100). Using temperature programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS), it was found that the Mo2C/Mo(100) catalyst was active for selective deoxygenation of the aldehyde carbonyl by facilitating adsorption of the aldehyde in an η2(C,O) bonding configuration. Furthermore, the catalyst showed no appreciable activity for furanic ring hydrogenation, highlighting the promise of relatively inexpensive Mo2C catalysts for selective HDO chemistry.

Reaction pathways of furfural, furfuryl alcohol and 2-methylfuran on Cu(111) and NiCu bimetallic surfaces

NASA Astrophysics Data System (ADS)

Xiong, Ke; Wan, Weiming; Chen, Jingguang G.

2016-10-01

Hydrodeoxygenation (HDO) is an important reaction for converting biomass-derived furfural to value-added 2-methylfuran, which is a promising fuel additive. In this work, the HDO of furfural to produce 2-methylfuran occurred on the NiCu bimetallic surfaces prepared on either Ni(111) or Cu(111). The reaction pathways of furfural were investigated on Cu(111) and Ni/Cu(111) surfaces using density functional theory (DFT) calculations, temperature-programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS) experiments. These studies provided mechanistic insights into the effects of bimetallic formation on enhancing the HDO activity. Specifically, furfural weakly adsorbed on Cu(111), while it strongly adsorbed on Ni/Cu(111) through an η2(C,O) configuration, which led to the HDO of furfural on Ni/Cu(111). The ability to dissociate H2 on Ni/Cu(111) is also an important factor for enhancing the HDO activity over Cu(111).

Biomass-derived oxygenate reforming on Pt(111): A demonstration of surface science using D-glucose and its model surrogate glycolaldehyde

NASA Astrophysics Data System (ADS)

McManus, Jesse R.; Yu, Weiting; Salciccioli, Michael; Vlachos, Dionisios G.; Chen, Jingguang G.; Vohs, John M.

2012-12-01

Molecules derived from cellulosic biomass, such as glucose, represent an important renewable feedstock for the production of hydrogen and hydrocarbon-based fuels and chemicals. Development of efficient catalysts for their reformation into useful products is needed; however, this requires a detailed understanding of their adsorption and reaction on catalytically active transition metal surfaces. In this paper we demonstrate that the standard surface science techniques routinely used to characterize the reaction of small molecules on metals are also amenable for use in studying the adsorption and reaction of complex biomass-derivatives on single crystal metal surfaces. In particular, Temperature Programmed Desorption (TPD) and High Resolution Electron Energy Loss Spectroscopy (HREELS) combined with Density Functional Theory (DFT) calculations were used to elucidate the adsorption configuration of D-glucose and glycolaldehye on Pt(111). Both molecules were found to adsorb in an η1 aldehyde configuration partially validating the use of simple, functionally-equivalent model compounds for surface studies of cellulosic oxygenates.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yuan, Chunqing; Smith, R. Scott; Kay, Bruce D.

The crystallization kinetics of nanoscale amorphous solid water (ASW) films are investigated using temperature-programmed desorption (TPD) and reflection absorption infrared spectroscopy (RAIRS). TPD measurements are used to probe surface crystallization and RAIRS measurements are used to probe bulk crystallization. Isothermal TPD results show that surface crystallization is independent of the film thickness (from 100 to 1000 ML). Conversely, the RAIRS measurements show that the bulk crystallization time increases linearly with increasing film thickness. These results suggest that nucleation and crystallization begin at the ASW/vacuum interface and then the crystallization growth front propagates linearly into the bulk. This mechanism was confirmedmore » by selective placement of an isotopic layer (5% D2O in H2O) at various positions in an ASW (H2O) film. In this case, the closer the isotopic layer was to the vacuum interface, the earlier the isotopic layer crystallized. These experiments provide direct evidence to confirm that ASW crystallization in vacuum proceeds by a “top-down” crystallization mechanism.« less

Decomposition pathways of C2 oxygenates on Rh-modified tungsten carbide surfaces

DOE PAGES

Kelly, Thomas G.; Ren, Hui; Chen, Jingguang G.

2015-03-27

Ethanol decomposition on tungsten monocarbide (WC) and Rh-modified WC was investigated using ultrahigh vacuum (UHV) surface science experiments and density functional theory (DFT) calculations. DFT calculations indicated that the binding energies of ethanol and its decomposition intermediates on WC(0001) were modified by Rh, with Rh/WC(0001) showing similar values to those on Rh(111). Through temperature-programmed desorption (TPD) experiments on polycrystalline WC and Rh-modified WC, it was shown that the selectivity for ethanol decomposition was different on these surfaces. On WC, the C-O bond of ethanol was preferentially broken to produce ethylene; on Rh-modified WC, the C-C bond was broken to producemore » carbon monoxide and methane. In addition, high-resolution electron energy loss spectroscopy (HREELS) was used to determine likely surface intermediates. On Rh-modified WC, ethanol first formed ethoxy through O-H scission, then reacted through an aldehyde intermediate to form the C1 products.« less

Adsorption and reaction of CO and H2O on WC(0001) surface: A first-principles investigation

NASA Astrophysics Data System (ADS)

Tong, Yu-Jhe; Wu, Shiuan-Yau; Chen, Hsin-Tsung

2018-01-01

We have performed a spin-polarized density functional theory (DFT) study for understanding the detailed reaction mechanism of CO and H2O on WC (0001) surface. The adsorption properties and vibrational frequencies of H2O, OH, O, H, CO and CO2 on the WC (0001) surface were illustrated. These results are well in consistent with the experimental observations studied by temperature-programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS). Based on the adsorption results, potential energy profiles of H2O and OH dehydrogenation and HCO, COH, COOH, and CO2 formation on the WC (0001) surface were predicted. The calculation results demonstrated that the WC (0001) surface as Fe (110) surface exhibits significantly reaction activity toward the dehydrogenation of H2O and OH but less activity toward the formation of HCO, COH, COOH and CO2 compared to the Cu (111) and Pt (111) surfaces.

Synthesis of Dicyclopentadiene Oligomer Over Nanoporous Al-MCM-41 Catalysts.

PubMed

Park, Eunseo; Kim, Jinhan; Yim, Jin-Heong; Han, Jeongsik; Kwon, Tae Soo; Park, Y K; Jeon, Jong-Ki

2016-05-01

One step reaction composed of DCPD oligomerization and DCPD oligomer isomerization was investigated over nanoporous Al-MCM-41 catalysts. The effects of aluminum grafting over MCM-41 on the catalyst characteristics were studied with respect to the synthesis of TCPD isomer. Physical and chemical properties of the catalysts were analyzed by N2 adsorption, temperature-programmed desorption of ammonia, and infrared spectroscopy of adsorbed pyridine. The overall number of acid sites as well as the number of Lewis acid sites increased with increasing of aluminum content over MCM-41. When utilizing MCM-41 and Al-MCM-41 as the catalyst, DCPD oligomerization reaction activity greatly increased compared to the thermal reaction. The highest TCPD isomer selectivity over the Al-MCM-41 catalyst with the highest aluminum content could be ascribed to the largest amount of acid sites. This study showed an increased level of TCPD isomer selectivity by an increasing level of Lewis acid sites through aluminum addition over MCM-41.

The effects of impurities and incidence angle on the secondary electron emission of Ni(110)

NASA Astrophysics Data System (ADS)

Lazar, Hadar; Patino, Marlene; Raitses, Yevgeny; Koel, Bruce; Gentile, Charles; Feibush, Eliot

The investigation of secondary electron emission (SEE) of conducting materials used for magnetic fusion devices and plasma thrusters is important for determining device lifetime and performance. Methods to quantify the secondary electron emission from conducting materials and to characterize the effects that impurities and incidence angles have on secondary electron emission were developed using 4-grid low energy electron diffraction (LEED) optics. The total secondary electron yield from a Ni(110) surface was continuously measured from the sample current as surface contamination increased from reactions with background gases in the ultrahigh vacuum chamber. Auger electron spectroscopy (AES) and temperature programmed desorption (TPD) were used to examine the composition and impurity levels on the Ni(110) surface. The total secondary electron yield was also measured at different incidence angles. Thank you to the Princeton Plasma Physics Laboratory (PPPL) and the Department of Energy (DOE) for the opportunity to work on this project through the Science Undergraduate Laboratory Internships (SULI).

Methanol Steam Reforming Promoted by Molten Salt-Modified Platinum on Alumina Catalysts

PubMed Central

Kusche, Matthias; Agel, Friederike; Ní Bhriain, Nollaig; Kaftan, Andre; Laurin, Mathias; Libuda, Jörg; Wasserscheid, Peter

2014-01-01

We herein describe a straight forward procedure to increase the performance of platinum-on-alumina catalysts in methanol steam reforming by applying an alkali hydroxide coating according to the “solid catalyst with ionic liquid layer” (SCILL) approach. We demonstrate by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temperature-programmed desorption (TPD) studies that potassium doping plays an important role in the catalyst activation. Moreover, the hygroscopic nature and the basicity of the salt modification contribute to the considerable enhancement in catalytic performance. During reaction, a partly liquid film of alkali hydroxides/carbonates forms on the catalyst/alumina surface, thus significantly enhancing the availability of water at the catalytically active sites. Too high catalyst pore fillings with salt introduce a considerable mass transfer barrier into the system as indicated by kinetic studies. Thus, the optimum interplay between beneficial catalyst modification and detrimental mass transfer effects had to be identified and was found on the applied platinum-on-alumina catalyst at KOH loadings around 7.5 mass %. PMID:25124120

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao, Feng; Zheng, Yang; Kukkadapu, Ravi K.

Using a traditional aqueous solution ion-exchange method under a protecting atmosphere of N2, a series of Fe/SSZ-13 catalysts with various Fe loadings were synthesized. UV-Vis, EPR and Mössbauer spectroscopies, coupled with temperature programmed reduction and desorption techniques, were used to probe the nature of the Fe sites. The major monomeric and dimeric Fe species are extra-framework [Fe(OH)2]+ and [HO-Fe-O-Fe-OH]2+. Larger oligomers with unknown nuclearity, poorly crystallized Fe2O3 particles, together with isolated Fe2+ ions, are minor Fe-containing moieties. Reaction rate and Fe loading correlations suggest that isolated Fe3+ ions are the active sites for standard SCR while the dimeric sites aremore » the active centers for NO oxidation. NH3 oxidation, on the other hand, is catalyzed by sites with higher nuclearity. A low-temperature standard SCR reaction network is proposed that includes redox cycling of both monomeric and dimeric Fe species, for SCR and NO2 generation, respectively. The authors gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Program for the support of this work. The research described in this paper was performed at the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle.« less

Comprehensive investigation of HgCdTe metalorganic chemical vapor deposition

NASA Technical Reports Server (NTRS)

Raupp, Gregory B.

1993-01-01

The principal objective of this experimental and theoretical research program was to explore the possibility of depositing high quality epitaxial CdTe and HgCdTe at very low pressures through metalorganic chemical vapor deposition (MOCVD). We explored two important aspects of this potential process: (1) the interaction of molecular flow transport and deposition in an MOCVD reactor with a commercial configuration, and (2) the kinetics of metal alkyl source gas adsorption, decomposition and desorption from the growing film surface using ultra high vacuum surface science reaction techniques. To explore the transport-reaction issue, we have developed a reaction engineering analysis of a multiple wafer-in-tube ultrahigh vacuum chemical vapor deposition (UHV/CVD) reactor which allows an estimate of wafer or substrate throughput for a reactor of fixed geometry and a given deposition chemistry with specified film thickness uniformity constraints. The model employs a description of ballistic transport and reaction based on the pseudo-steady approximation to the Boltzmann equation in the limit of pure molecular flow. The model representation takes the form of an integral equation for the flux of each reactant or intermediate species to the wafer surfaces. Expressions for the reactive sticking coefficients (RSC) for each species must be incorporated in the term which represents reemission from a wafer surface. The interactions of MOCVD precursors with Si and CdTe were investigated using temperature programmed desorption (TPD) in ultra high vacuum combined with Auger electron spectroscopy (AES). These studies revealed that diethyltellurium (DETe) and dimethylcadmium (DMCd) adsorb weakly on clean Si(100) and desorb upon heating without decomposing. These precursors adsorb both weakly and strongly on CdTe(111)A, with DMCd exhibiting the stronger interaction with the surface than DETe.

Expanding the capability of reaction-diffusion codes using pseudo traps and temperature partitioning: Applied to hydrogen uptake and release from tungsten

DOE Office of Scientific and Technical Information (OSTI.GOV)

Simmonds, M. J.; Yu, J. H.; Wang, Y. Q.

Simulating the implantation and thermal desorption evolution in a reaction-diffusion model requires solving a set of coupled differential equations that describe the trapping and release of atomic species in Plasma Facing Materials (PFMs). These fundamental equations are well outlined by the Tritium Migration Analysis Program (TMAP) which can model systems with no more than three active traps per atomic species. To overcome this limitation, we have developed a Pseudo Trap and Temperature Partition (PTTP) scheme allowing us to lump multiple inactive traps into one pseudo trap, simplifying the system of equations to be solved. For all temperatures, we show themore » trapping of atoms from solute is exactly accounted for when using a pseudo trap. However, a single effective pseudo trap energy can not well replicate the release from multiple traps, each with its own detrapping energy. However, atoms held in a high energy trap will remain trapped at relatively low temperatures, and thus there is a temperature range in which release from high energy traps is effectively inactive. By partitioning the temperature range into segments, a pseudo trap can be defined for each segment to account for multiple high energy traps that are actively trapping but are effectively not releasing atoms. With increasing temperature, as in controlled thermal desorption, the lowest energy trap is nearly emptied and can be removed from the set of coupled equations, while the next higher energy trap becomes an actively releasing trap. Each segment is thus calculated sequentially, with the last time step of a given segment solution being used as an initial input for the next segment as only the pseudo and actively releasing traps are modeled. This PTTP scheme is then applied to experimental thermal desorption data for tungsten (W) samples damaged with heavy ions, which display six distinct release peaks during thermal desorption. Without modifying the TMAP7 source code the PTTP scheme is shown to successfully model the D retention in all six traps. In conclusion, we demonstrate the full reconstruction from the plasma implantation phase through the controlled thermal desorption phase with detrapping energies near 0.9, 1.1, 1.4, 1.7, 1.9 and 2.1 eV for a W sample damaged at room temperature.« less

Expanding the capability of reaction-diffusion codes using pseudo traps and temperature partitioning: Applied to hydrogen uptake and release from tungsten

DOE PAGES

Simmonds, M. J.; Yu, J. H.; Wang, Y. Q.; ...

2018-06-04

Simulating the implantation and thermal desorption evolution in a reaction-diffusion model requires solving a set of coupled differential equations that describe the trapping and release of atomic species in Plasma Facing Materials (PFMs). These fundamental equations are well outlined by the Tritium Migration Analysis Program (TMAP) which can model systems with no more than three active traps per atomic species. To overcome this limitation, we have developed a Pseudo Trap and Temperature Partition (PTTP) scheme allowing us to lump multiple inactive traps into one pseudo trap, simplifying the system of equations to be solved. For all temperatures, we show themore » trapping of atoms from solute is exactly accounted for when using a pseudo trap. However, a single effective pseudo trap energy can not well replicate the release from multiple traps, each with its own detrapping energy. However, atoms held in a high energy trap will remain trapped at relatively low temperatures, and thus there is a temperature range in which release from high energy traps is effectively inactive. By partitioning the temperature range into segments, a pseudo trap can be defined for each segment to account for multiple high energy traps that are actively trapping but are effectively not releasing atoms. With increasing temperature, as in controlled thermal desorption, the lowest energy trap is nearly emptied and can be removed from the set of coupled equations, while the next higher energy trap becomes an actively releasing trap. Each segment is thus calculated sequentially, with the last time step of a given segment solution being used as an initial input for the next segment as only the pseudo and actively releasing traps are modeled. This PTTP scheme is then applied to experimental thermal desorption data for tungsten (W) samples damaged with heavy ions, which display six distinct release peaks during thermal desorption. Without modifying the TMAP7 source code the PTTP scheme is shown to successfully model the D retention in all six traps. In conclusion, we demonstrate the full reconstruction from the plasma implantation phase through the controlled thermal desorption phase with detrapping energies near 0.9, 1.1, 1.4, 1.7, 1.9 and 2.1 eV for a W sample damaged at room temperature.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Zongyuan; Duchoň, Tomáš; Wang, Huanru

We have studied the reaction of ethanol and water over Ni–CeO 2-x(111) model surfaces to elucidate the mechanistic steps associated with the ethanol steam reforming (ESR) reaction. Our results provide insights about the importance of hydroxyl groups to the ESR reaction over Ni-based catalysts. Systematically, we have investigated the reaction of ethanol on Ni–CeO 2-x(111) at varying Ce³⁺ concentrations (CeO 1.8–2.0) with absence/presence of water using a combination of soft X-ray photoelectron spectroscopy (sXPS) and temperature-programmed desorption (TPD). Consistent with previous reports, upon annealing, metallic Ni formed on reduced ceria while NiO was the main component on fully oxidized ceria.more » Ni⁰ is the active phase leading to both the C–C and C–H cleavage of ethanol but is also responsible for carbon accumulation or coking. We have identified a Ni₃C phase that formed prior to the formation of coke. At temperatures above 600K, the lattice oxygen from ceria and the hydroxyl groups from water interact cooperatively in the removal of coke, likely through a strong metal–support interaction between nickel and ceria that facilitates oxygen transfer.« less

Nanostructured catalysts applied to degrade atrazine in aqueous phase by heterogeneous photo-Fenton process.

PubMed

Benzaquén, Tamara B; Barrera, Deicy A; Carraro, Paola M; Sapag, Karim; Alfano, Orlando M; Eimer, Griselda A

2018-06-02

SBA-15 and KIT-6 materials have been synthesized and modified with iron salts by the wet impregnation method with different metal loadings. The different mesostructures obtained were characterized by N 2 adsorption-desorption at 77 K, X-ray diffraction, temperature-programmed reduction, and ultraviolet-visible spectroscopy. These iron-containing mesostructured materials have been successfully tested for the heterogeneous photo-Fenton degradation of aqueous solutions of dangerous herbicides, such as atrazine, using UV-visible light irradiation, at room temperature and close to neutral pH. The results showed that the Fe/SBA-15 (10%) and Fe/KIT-6 (5%) catalysts exhibited the highest activities. However, the Fe/KIT-6 (5%) catalyst with minor Fe loading than Fe/SBA-15 (10%) presented a higher degradation of atrazine (above 98% in a reaction time of 240 min). Therefore, the interconnectivity of the cage-like mesopores had an important influence on the catalytic activity, favoring probably mass-transfer effects. Thus, the high performance of these materials indicates that the heterogeneous via of photo-Fenton process can also be efficiently employed to treat wastewaters containing pollutants such as herbicides, in order to reduce them to simplest and less toxic molecules.

Factors Influencing NO2 Adsorption/Reduction on Microporous Activated Carbon: Porosity vs. Surface Chemistry

PubMed Central

Ghouma, Imen; Limousy, Lionel; Bennici, Simona

2018-01-01

The textural properties and surface chemistry of different activated carbons, prepared by the chemical activation of olive stones, have been investigated in order to gain insight on the NO2 adsorption mechanism. The parent chemical activated carbon was prepared by the impregnation of olive stones in phosphoric acid followed by thermal carbonization. Then, the textural properties and surface chemistry were modified by chemical treatments including nitric acid, sodium hydroxide and/or a thermal treatment at 900 °C. The main properties of the parent and modified activated carbons were analyzed by N2-adsorption, scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR) techniques, in order to enlighten the modifications issued from the chemical and thermal treatments. The NO2 adsorption capacities of the different activated carbons were measured in fixed bed experiments under 500 ppmv NO2 concentrations at room temperature. Temperature programmed desorption (TPD) was applied after adsorption tests in order to quantify the amount of the physisorbed and chemisorbed NO2. The obtained results showed that the development of microporosity, the presence of oxygen-free sites, and the presence of basic surface groups are key factors for the efficient adsorption of NO2. PMID:29670008

Dipole-Oriented Molecular Solids Can Undergo a Phase Change and Still Maintain Electrical Polarization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cassidy, Andrew; Jørgensen, Mads R. V.; Rosu-Finsen, Alexander

2016-10-02

It has recently been demonstrated that nanoscale molecular films can spontaneously assemble to self-generate intrinsic electric fields that can exceed 10 8 V/m. These electric fields originate from polarization charges in the material that arise because the films self-assemble to orient molecular dipole moments. This has been called the spontelectric effect. Such growth of spontaneously polarized layers of molecular solids has implications for our understanding of how intermolecular interactions dictate the structure of molecular materials used in a range of applications, for example, molecular semiconductors, sensors, and catalysts. In this paper, we present the first in situ structural characterization ofmore » a representative spontelectric solid, nitrous oxide. Infrared spectroscopy, temperature-programmed desorption, and neutron reflectivity measurements demonstrate that polarized films of nitrous oxide undergo a structural phase transformation upon heating above 48 K. A mean-field model can be used to describe quantitatively the magnitude of the spontaneously generated field as a function of film-growth temperature, and this model also recreates the phase change. Finally, this reinforces the spontelectric model as a means of describing long-range dipole–dipole interactions and points to a new type of ordering in molecular thin films.« less

Exploring the nonequilibrium reactivity of molecules with platinum(111)

NASA Astrophysics Data System (ADS)

Dewitt, Kristin Marie

Various aspects of the nonequilibrium reactivity of several, catalytically important, small molecules with Pt(111)were explored. The effect of alkali metal promotion on the thermal chemistry and photochemistry of CH4,N 2, and CO2 was studied. Dissociative sticking coefficients for methane and ethane were measured as a function of gas temperature ( Tg) and surface temperature (Ts) using effusive molecular beam and angle-integrated gas dosing methods. Coupled with physisorbed complex microcanonical unimolecular rate theory these measurements provide a predictive understanding for the kinetics of these C-H bond activation reactions, i.e. allowing us to predict the sticking coefficient of CH 4 and C2H6 for any combination of T s and Tg. Work function thermal programmed desorption was used to examine the correlation between surface structure and surface work function for CH3Br and CO2. Preliminary two-photon photoemission and broad-band infrared-visible sum frequency generation experiments introduce these nonlinear spectroscopy techniques to the arsenal of surface characterization techniques available in our group. All of the disparate components of this work are tied together by one overall theme, developing an improved molecular-level understanding of the reaction dynamics of catalysis.

An infrared measurement of chemical desorption from interstellar ice analogues

NASA Astrophysics Data System (ADS)

Oba, Y.; Tomaru, T.; Lamberts, T.; Kouchi, A.; Watanabe, N.

2018-03-01

In molecular clouds at temperatures as low as 10 K, all species except hydrogen and helium should be locked in the heterogeneous ice on dust grain surfaces. Nevertheless, astronomical observations have detected over 150 different species in the gas phase in these clouds. The mechanism by which molecules are released from the dust surface below thermal desorption temperatures to be detectable in the gas phase is crucial for understanding the chemical evolution in such cold clouds. Chemical desorption, caused by the excess energy of an exothermic reaction, was first proposed as a key molecular release mechanism almost 50 years ago1. Chemical desorption can, in principle, take place at any temperature, even below the thermal desorption temperature. Therefore, astrochemical network models commonly include this process2,3. Although there have been a few previous experimental efforts4-6, no infrared measurement of the surface (which has a strong advantage to quantify chemical desorption) has been performed. Here, we report the first infrared in situ measurement of chemical desorption during the reactions H + H2S → HS + H2 (reaction 1) and HS + H → H2S (reaction 2), which are key to interstellar sulphur chemistry2,3. The present study clearly demonstrates that chemical desorption is a more efficient process for releasing H2S into the gas phase than was previously believed. The obtained effective cross-section for chemical desorption indicates that the chemical desorption rate exceeds the photodesorption rate in typical interstellar environments.

The Relationship between C_60 Mass Spectrum Intensity and C2 Vibrational Temperature in Microwave Helium Plasmas

NASA Astrophysics Data System (ADS)

Ueda, Kengo; Kuwahara, Kiyoshi; Fujiyama, Hiroshi

1998-10-01

The soot containing C_60 and C_70 was synthesized in helium plasmas generated in a quartz tube by microwave discharge. We used reticulated vitreous carbon (RVC) that was heated by electric field of TE_10 mode microwave and the plasma. During soot deposition, optical emission of plasmas was observed with a monochromator. The soot deposited on the quartz tube was analyzed by the laser desorption time-of-flight mass-spectroscopy (LD-TOF-MS). Up to the present, the most intense C_60 mass spectrum intensity was obtained for the condition of absorbed microwave power 200W and pressure 100Torr, where C2 vibrational temperature was about 5500K.

VizieR Online Data Catalog: IR absorbance spectra of CH4, C2H6, C3H8 & C4H10 (Turner+, 2018)

NASA Astrophysics Data System (ADS)

Turner, A. M.; Abplanalp, M. J.; Blair, T. J.; Dayuha, R.; Kaiser, R. I.

2018-03-01

In situ infrared data were collected by a Nicolet 6700 Fourier Transform Infrared Spectrometer at 4cm-1 resolution throughout the irradiation and temperature programmed desorption (TPD). (2 data files).

X-RAY MICROSCOPY AND SPECTROSCOPY STUDIES ON METAL BINDING IN BIOSOLIDS

EPA Science Inventory

Sorption/desorption data from intact and different fractions of biosolids and biosolids-amended soils indicated the importance of Fe and Mn fractions on both sorption and desorption of metals in biosolids and biosolids-amended soils. Extraction procedures used to separate organi...

X-RAY MICROSCOPY AND SPECTROSCOPY STUDIES ON METAL BINDING IN BIOSOLIDS (ABSTRACT)

EPA Science Inventory

Sorption/desorption data from intact and different fractions of biosolids and biosolids-amended soils indicated the importance of Fe and Mn fractions on both sorption and desorption of metals in biosolids and biosolids-amended soils. Extraction procedures used to separate organi...

Adsorption, Desorption, and Diffusion of Nitrogen in a Model Nanoporous Material: II. Diffusion Limited Kinetics in Amorphous Solid Water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zubkov, Tykhon; Smith, R. Scott; Engstrom, Todd R.

2007-11-14

Tykhon Zubkov, R. Scott Smith, Todd R. Engstrom, and Bruce D. Kay The adsorption, desorption, and diffusion kinetics of N2 on thick (up to ~9 mm) porous films of amorphous solid water (ASW) films were studied using molecular beam techniques and temperature programmed desorption (TPD). Porous ASW films were grown on Pt(111) at low temperature (<30 K) from a collimated H2O beam at glancing incident angles. In thin films (<1 mm), the desorption kinetics are well described by a model that assumes rapid and uniform N2 distribution throughout the film. In thicker films, (>1 mm), N2 adsorption at 27 Kmore » results in a non-uniform distribution where most of N2 is trapped in the outer region of the film. Redistribution of N2 can be induced by thermal annealing. The apparent activation energy for this process is ~7 kJ/mol, which is approximately half of the desorption activation energy at the corresponding coverage. Blocking adsorption sites near the film surface facilitates transport into the film. Despite the onset of limited diffusion, the adsorption kinetics are efficient, precursor-mediated and independent of film thickness. An adsorption mechanism is proposed, in which a high-coverage N2 front propagates into a pore by the rapid transport of physisorbed 2nd layer N2 species on top of the 1st layer chemisorbed layer.« less

Desorption of water from hydrophilic MCM-41 mesopores: positron annihilation, FTIR and MD simulation studies.

PubMed

Maheshwari, Priya; Dutta, D; Muthulakshmi, T; Chakraborty, B; Raje, N; Pujari, P K

2017-02-08

The desorption mechanism of water from the hydrophilic mesopores of MCM-41 was studied using positron annihilation lifetime spectroscopy (PALS) and attenuated total reflection Fourier transform infrared spectroscopy supplemented with molecular dynamics (MD) simulation. PALS results indicated that water molecules do not undergo sequential evaporation in a simple layer-by-layer manner during desorption from MCM-41 mesopores. The results suggested that the water column inside the uniform cylindrical mesopore become stretched during desorption and induces cavitation (as seen in the case of ink-bottle type pores) inside it, keeping a dense water layer at the hydrophilic pore wall, as well as a water plug at both the open ends of the cylindrical pore, until the water was reduced to a certain volume fraction where the pore catastrophically empties. Before being emptied, the water molecules formed clusters inside the mesopores. The formation of molecular clusters below a certain level of hydration was corroborated by the MD simulation study. The results are discussed.

Modelling of discrete TDS-spectrum of hydrogen desorption

NASA Astrophysics Data System (ADS)

Rodchenkova, Natalia I.; Zaika, Yury V.

2015-12-01

High concentration of hydrogen in metal leads to hydrogen embrittlement. One of the methods to evaluate the hydrogen content is the method of thermal desorption spectroscopy (TDS). As the sample is heated under vacuumization, atomic hydrogen diffuses inside the bulk and is desorbed from the surface in the molecular form. The extraction curve (measured by a mass-spectrometric analyzer) is recorded. In experiments with monotonous external heating it is observed that background hydrogen fluxes from the extractor walls and fluxes from the sample cannot be reliably distinguished. Thus, the extraction curve is doubtful. Therefore, in this case experimenters use discrete TDS-spectrum: the sample is removed from the analytical part of the device for the specified time interval, and external temperature is then increased stepwise. The paper is devoted to the mathematical modelling and simulation of experimental studies. In the corresponding boundary-value problem with nonlinear dynamic boundary conditions physical- chemical processes in the bulk and on the surface are taken into account: heating of the sample, diffusion in the bulk, hydrogen capture by defects, penetration from the bulk to the surface and desorption. The model aimed to analyze the dynamics of hydrogen concentrations without preliminary artificial sample saturation. Numerical modelling allows to choose the point on the extraction curve that corresponds to the initial quantity of the surface hydrogen, to estimate the values of the activation energies of diffusion, desorption, parameters of reversible capture and hydride phase decomposition.

Segregation of O2 and CO on the surface of dust grains determines the desorption energy of O2

NASA Astrophysics Data System (ADS)

Noble, J. A.; Diana, S.; Dulieu, F.

2015-12-01

Selective depletion towards pre-stellar cores is still not understood. The exchange between the solid and gas phases is central to this mystery. The aim of this paper is to show that the thermal desorption of O2 and CO from a submonolayer mixture is greatly affected by the composition of the initial surface population. We have performed thermally programmed desorption (TPD) experiments on various submonolayer mixtures of O2 and CO. Pure O2 and CO exhibit almost the same desorption behaviour, but their desorption differs strongly when mixed. Pure O2 is slightly less volatile than CO, while in mixtures, O2 desorbs earlier than CO. We analyse our data using a desorption law linking competition for binding sites with desorption, based on the assumption that the binding energy distribution of both molecules is the same. We apply Fermi-Dirac statistics in order to calculate the adsorption site population distribution, and derive the desorbing fluxes. Despite its simplicity, the model reproduces the observed desorption profiles, indicating that competition for adsorption sites is the reason for lower temperature O2 desorption. CO molecules push-out or `dislodge' O2 molecules from the most favourable binding sites, ultimately forcing their early desorption. It is crucial to consider the surface coverage of dust grains in any description of desorption. Competition for access to binding sites results in some important discrepancies between similar kinds of molecules, such as CO and O2. This is an important phenomenon to be investigated in order to develop a better understanding of the apparently selective depletion observed in dark molecular clouds.

Natural zeolite reactivity towards ozone: the role of compensating cations.

PubMed

Valdés, Héctor; Alejandro, Serguei; Zaror, Claudio A

2012-08-15

Among indoor pollutants, ozone is recognised to pose a threat to human health. Recently, low cost natural zeolites have been applied as alternative materials for ozone abatement. In this work, the effect of compensating cation content of natural zeolite on ozone removal is studied. A Chilean natural zeolite is used here as starting material. The amount of compensating cations in the zeolite framework was modified by ion exchange using an ammonium sulphate solution (0.1 mol L(-1)). Characterisation of natural and modified zeolites were performed by X-ray powder diffraction (XRD), nitrogen adsorption at 77K, elemental analysis, X-ray fluorescence (XRF), thermogravimetric analysis coupled with mass spectroscopy (TGA-MS), and temperature-programmed desorption of ammonia (NH(3)-TPD). Ozone adsorption and/or decomposition on natural and modified zeolites were studied by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Results show that the zeolite compensating cation content affects ozone interaction with zeolite active sites. Ammonium ion-exchange treatments followed by thermal out-gassing at 823 K, reduces ozone diffusion resistance inside the zeolite framework, increasing ozone abatement on zeolite surface active sites. Weak and strong Lewis acid sites of zeolite surface are identified here as the main active sites responsible of ozone removal. Copyright © 2012 Elsevier B.V. All rights reserved.

Cascade Reductive Etherification of Bioderived Aldehydes over Zr-Based Catalysts.

PubMed

Shinde, Suhas; Rode, Chandrashekhar

2017-10-23

An efficient one-pot catalytic cascade sequence has been developed for the production of value-added ethers from bioderived aldehydes. Etherification of 5-(hydroxymethyl)furfural with different aliphatic alcohols over acidic Zr-montmorillonite (Zr-Mont) catalyst produced a mixture of 5-(alkoxymethyl)furfural and 2-(dialkoxymethyl)-5-(alkoxymethyl)furan. The latter was selectively converted back into 5-(alkoxymethyl)furfural by treating it with water over the same catalyst. The synthesis of 2,5-bis(alkoxymethyl)furan was achieved through a cascade sequence involving etherification, transfer hydrogenation, and re-etherification over a combination of acidic Zr-Mont and the charge-transfer hydrogenation catalyst [ZrO(OH) 2 ]. This catalyst combination was further explored for the cascade conversion of 2-furfuraldehyde into 2-(alkoxymethyl)furan. The scope of this strategy was then extended for the reductive etherification of lignin-derived arylaldehydes to obtain the respective benzyl ethers in >80 % yield. Additionally, the mixture of Zr-Mont and ZrO(OH) 2 does not undergo mutual destruction, which was proved by recycling experiments and XRD analysis. Both the catalysts were thoroughly characterized using BET, temperature-programmed desorption of NH 3 and CO 2 , pyridine-FTIR, XRD, inductively coupled plasma optical emission spectroscopy, and X-ray photoelectron spectroscopy techniques. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Positron-induced Auger-electron study of the Ge(100) surface: Positron thermal desorption and surface condition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Soininen, E.; Schwab, A.; Lynn, K.G.

1991-05-01

Positron-annihilation-induced Auger-electron spectroscopy (PAES) was used to study the effects of oxygen, residual gases, and temperature on a Ge(100) surface. Three low-energy Auger peaks were detected at 50, 90, and 100--150 eV, attributed to {ital M}{sub 2,3}{ital M4}{ital M4}, {ital M}{sub 2,3}{ital M4}{ital V}, and {ital M}{sub 1}{ital M4}{ital M4} Auger transitions, respectively. An estimated (4{plus minus}1)% of the surface-trapped positrons annihilate with Ge 3{ital p}--level electrons. The sensitivity of PAES to the surface condition is demonstrated. The PAES yield from a Ge(100) surface is reduced at elevated temperatures, in accord with an activation process earlier found in several positroniummore » (Ps) -fraction experiments. A desorption model adopted from these studies does not describe accurately the PAES results at higher temperatures ({gt}500 {degree}C), where the PAES intensity levels off to 5% of the room-temperature value. Possible sources for the discrepancy are discussed and models for positron trapping to deep surface traps are introduced. On the Ge(100) surface, an upper limit for Ps emission near the melting point is 97%. The error in calibration parameters due to the earlier assumption of 100% Ps emission seems to introduce only small errors into the Ps-fraction measurements.« less

Graphene oxide-SiO2 nanocomposite as the adsorbent for extraction and preconcentration of plant hormones for HPLC analysis.

PubMed

Zhang, Xiaona; Niu, Jiahua; Zhang, Xiaoting; Xiao, Rui; Lu, Minghua; Cai, Zongwei

2017-03-01

In this research, a modified Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) method based on graphene oxide@SiO 2 (SiO 2 @GO) nanocomposite as adsorbent of dispersive solid-phase extraction (dSPE) combined with high performance liquid chromatography (HPLC) for the analysis of four plant hormones in different plants was established. The as-prepared SiO 2 @GO was characterized by scanning electron microscopy, transmission electron microscopy and infrared spectroscopy. The experimental conditions for dSPE, including the ratio of material to liquid, pH of sample, adsorption and desorption time, desorption temperature as well as desorption solution, were investigated. The detection limits for the analysis of indole-3-acetic acid, indole-3-butyric acid, 1-naphthylacetic acid and abscisic acid were achieved below 0.05μgmL -1 . The established method was applied to the analysis of the plant hormones in fruits, vegetables and other food samples. The obtained results indicated that the method was sensitive, accurate, convenient and quick, which provided an alternative analytical approach for plant hormones in complex matrices. Copyright © 2017 Elsevier B.V. All rights reserved.

Identifying the Thermal Decomposition Mechanism of Guaiacol on Pt(111): An Integrated X-ray Photoelectron Spectroscopy and Density Functional Theory Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hensley, Alyssa J.; Wockel, Claudia; Gleichweit, Christoph

Using a concerted effort from both experiment and theory, we determine the thermal decomposition mechanism for guaiacol on Pt(111), a reaction of interest in the area of bio-oil upgrading. This work serves as a demonstration of the power of combining in situ temperature-programmed X-ray photoelectron spectroscopy cos (TPXPS) and density functional theory (DFT) to elucidate complex reaction mechanisms occurring on heterogeneous surfaces. At low temperature (230 K), guaiacol was found to chemisorb with the aromatic ring parallel to the Pt(111) surface with five distinct carbon species and three oxygen species. As the temperature was increased, TPXPS showed several significant changesmore » to the surface species. The increase in the species associated with the decomposition of the functional groups of guaiacol is followed by their subsequent disappearance and an increase in the nonaromatic carbon signal. On the basis of an energetic analysis of the various mechanisms using DFT, along with the comparison of the experimentally and theoretically derived core-level binding energies, we determined that guaiacol's decomposition mechanism occurs via the dehydrogenation of both the methyl and hydroxyl functional groups, followed by demethylation of the CH2 or CH group to form 1,2-benzoquinone. Further heating to above 375 K likely breaks the aromatic ring and results in the rapid formation and desorption of CO, accounting for the disappearance of the 0 is signal above 450 K These results show that a knowledgeable application of TPXPS and DFT can result in the quantitative identification of surface species during complex reactions, providing insight useful for the design of future heterogeneous surfaces.« less

Investigation of Water Dissociation and Surface Hydroxyl Stability on Pure and Ni-Modified CoOOH by Ambient Pressure Photoelectron Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Zhu; Kronawitter, Coleman X.; Waluyo, Iradwikanari

Water adsorption and reaction on pure and Ni-modified CoOOH nanowires were investigated using ambient pressure photoemission spectroscopy (APPES). The unique capabilities of APPES enable us to observe water dissociation and monitor formation of surface species on pure and Ni-modified CoOOH under elevated pressures and temperatures for the first time. Over a large range of pressures (UHV to 1 Torr), water dissociates readily on the pure and Ni-modified CoOOH surfaces at 27 °C. With an increase in H 2O pressure, a greater degree of surface hydroxylation was observed for all samples. At 1 Torr H 2O, ratios of different oxygen speciesmore » indicate a transformation of CoOOH to CoO xH y in pure and Ni-modified CoOOH. In temperature dependent studies, desorption of weakly bound water and surface dehydroxylation were observed with increasing temperature. In conclusion, larger percentages of surface hydroxyl groups at higher temperatures were observed on Ni-modified CoOOH compared to pure CoOOH, which indicates an increased stability of surface hydroxyl groups on these Ni-modified surfaces.« less

Investigation of Water Dissociation and Surface Hydroxyl Stability on Pure and Ni-Modified CoOOH by Ambient Pressure Photoelectron Spectroscopy

DOE PAGES

Chen, Zhu; Kronawitter, Coleman X.; Waluyo, Iradwikanari; ...

2017-09-07

Water adsorption and reaction on pure and Ni-modified CoOOH nanowires were investigated using ambient pressure photoemission spectroscopy (APPES). The unique capabilities of APPES enable us to observe water dissociation and monitor formation of surface species on pure and Ni-modified CoOOH under elevated pressures and temperatures for the first time. Over a large range of pressures (UHV to 1 Torr), water dissociates readily on the pure and Ni-modified CoOOH surfaces at 27 °C. With an increase in H 2O pressure, a greater degree of surface hydroxylation was observed for all samples. At 1 Torr H 2O, ratios of different oxygen speciesmore » indicate a transformation of CoOOH to CoO xH y in pure and Ni-modified CoOOH. In temperature dependent studies, desorption of weakly bound water and surface dehydroxylation were observed with increasing temperature. In conclusion, larger percentages of surface hydroxyl groups at higher temperatures were observed on Ni-modified CoOOH compared to pure CoOOH, which indicates an increased stability of surface hydroxyl groups on these Ni-modified surfaces.« less

Retention and release of hydrogen isotopes in tungsten plasma-facing components: the role of grain boundaries and the native oxide layer from a joint experiment-simulation integrated approach

NASA Astrophysics Data System (ADS)

Hodille, E. A.; Ghiorghiu, F.; Addab, Y.; Založnik, A.; Minissale, M.; Piazza, Z.; Martin, C.; Angot, T.; Gallais, L.; Barthe, M.-F.; Becquart, C. S.; Markelj, S.; Mougenot, J.; Grisolia, C.; Bisson, R.

2017-07-01

Fusion fuel retention (trapping) and release (desorption) from plasma-facing components are critical issues for ITER and for any future industrial demonstration reactors such as DEMO. Therefore, understanding the fundamental mechanisms behind the retention of hydrogen isotopes in first wall and divertor materials is necessary. We developed an approach that couples dedicated experimental studies with modelling at all relevant scales, from microscopic elementary steps to macroscopic observables, in order to build a reliable and predictive fusion reactor wall model. This integrated approach is applied to the ITER divertor material (tungsten), and advances in the development of the wall model are presented. An experimental dataset, including focused ion beam scanning electron microscopy, isothermal desorption, temperature programmed desorption, nuclear reaction analysis and Auger electron spectroscopy, is exploited to initialize a macroscopic rate equation wall model. This model includes all elementary steps of modelled experiments: implantation of fusion fuel, fuel diffusion in the bulk or towards the surface, fuel trapping on defects and release of trapped fuel during a thermal excursion of materials. We were able to show that a single-trap-type single-detrapping-energy model is not able to reproduce an extended parameter space study of a polycrystalline sample exhibiting a single desorption peak. It is therefore justified to use density functional theory to guide the initialization of a more complex model. This new model still contains a single type of trap, but includes the density functional theory findings that the detrapping energy varies as a function of the number of hydrogen isotopes bound to the trap. A better agreement of the model with experimental results is obtained when grain boundary defects are included, as is consistent with the polycrystalline nature of the studied sample. Refinement of this grain boundary model is discussed as well as the inclusion in the model of a thin defective oxide layer following the experimental observation of the presence of an oxygen layer on the surface even after annealing to 1300 K.

Thermochemical Properties of the Lattice Oxygen in W,Mn-Containing Mixed Oxide Catalysts for the Oxidative Coupling of Methane

NASA Astrophysics Data System (ADS)

Lomonosov, V. I.; Gordienko, Yu. A.; Sinev, M. Yu.; Rogov, V. A.; Sadykov, V. A.

2018-03-01

Mixed NaWMn/SiO2 oxide, samples containing individual components (Na, W, Mn) and their double combinations (Na-W, Na-Mn, W-Mn) supported on silica were studied by temperature programmed reduction (TPR) and desorption (TPD), and heat flow calorimetry during their reoxidation with molecular oxygen in pulse mode. The NaWMn/SiO2 mixed oxide was shown to contain two different types of reactive lattice oxygen. The weakly-bonded oxygen can be reversibly released from the oxide in a flow of inert gas in the temperature range of 575‒900°C, while the strongly-bonded oxygen can be removed during the reduction of the sample with hydrogen at 700-900°C. The measured thermal effect of oxygen consumption for these two oxygen forms are 185 and 350 kJ/mol, respectively. The amount of oxygen removed at reduction ( 443 μmol/g) considerably exceeded the amount desorbed in an inert gas flow ( 56 μmol/g). The obtained results suggest that the reversible oxygen desorption is due to the redox process in which manganese ions are involved, while during the temperature programmed reduction, mainly oxygen bonded with tungsten is removed.

A new technique for Auger analysis of surface species subject to electron-induced desorption

NASA Technical Reports Server (NTRS)

Pepper, S. V.

1973-01-01

A method is presented to observe surface species subject to electron-induced desorption by Auger electron spectroscopy. The surface to be examined is moved under the electron beam at constant velocity, establishing a time independent condition and eliminating the time response of the electron spectrometer as a limiting factor. The dependence of the Auger signal on the surface velocity, incident electron current, beam diameter, and desorption cross section are analyzed. The method is illustrated by the Auger analysis of PTFE, in which the fluorine is removed by electron induced desorption.

High field 27Al MAS NMR and TPD studies of active sites in ethanol dehydration using thermally treated transitional aluminas as catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Jian Zhi; Xu, Suochang; Kwak, Ja Hun

High field quantitative 27Al MAS NMR and temperature programmed desorption (TPD) of ethanol are used to study the surface and phase transformation of gamma-Al2O3 during calcination in the temperature range of 500 to 1300 degrees C. Following ethanol adsorption, ethylene is generated during TPD with a desorption temperature > 200 degrees C. With increasing calcination temperature prior to TPD, the amount of ethylene produced decreases monotonically. Significantly, 27Al MAS NMR reveals that the amount of penta-coordinate Al3+ ions (Lewis acid sites) also decreases with increasing calcination temperature. In fact, a strong correlation between the amount of penta-coordinate Al3+ ions andmore » the amount of strongly adsorbed ethanol molecules (i.e., the ones that convert to ethylene during TPD) is obtained. This result indicates that the penta-coordinate aluminum sites are the catalytic active sites on alumina surfaces during ethanol dehydration reaction across the entire course of gamma- to alpha-Al2O3 phase transformations.« less

Carbon Dioxide Electroreduction into Syngas Boosted by a Partially Delocalized Charge in Molybdenum Sulfide Selenide Alloy Monolayers.

PubMed

Xu, Jiaqi; Li, Xiaodong; Liu, Wei; Sun, Yongfu; Ju, Zhengyu; Yao, Tao; Wang, Chengming; Ju, Huanxin; Zhu, Junfa; Wei, Shiqiang; Xie, Yi

2017-07-24

Structural parameters of ternary transition-metal dichalcogenide (TMD) alloy usually obey Vegard law well, while interestingly it often exhibits boosted electrocatalytic performances relative to its two pristine binary TMDs. To unveil the underlying reasons, we propose an ideal model of ternary TMDs alloy monolayer. As a prototype, MoSeS alloy monolayers are successfully synthesized, in which X-ray absorption fine structure spectroscopy manifests their shortened Mo-S and lengthened Mo-Se bonds, helping to tailor the d-band electronic structure of Mo atoms. Density functional theory calculations illustrate an increased density of states near their conduction band edge, which ensures faster electron transfer confirmed by their lower work function and smaller charge-transfer resistance. Energy calculations show the off-center charge around Mo atoms not only benefits for stabilizing COOH* intermediate confirmed by its most negative formation energy, but also facilitates the rate-limiting CO desorption step verified by CO temperature programmed desorption and electro-stripping tests. As a result, MoSeS alloy monolayers attain the highest 45.2 % Faradaic efficiency for CO production, much larger than that of MoS 2 monolayers (16.6 %) and MoSe 2 monolayers (30.5 %) at -1.15 V vs. RHE. This work discloses how the partially delocalized charge in ternary TMDs alloys accelerates electrocatalytic performances at atomic level, opening new horizons for manipulating CO 2 electroreduction properties. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic combustion of styrene over copper based catalyst: inhibitory effect of water vapor.

PubMed

Pan, Hongyan; Xu, Mingyao; Li, Zhong; Huang, Sisi; He, Chun

2009-07-01

The effects of water vapor on the activity of the copper based catalysts with different supports such as CuO/gamma-Al2O3, CuO/SiO2 and CuO/TiO2 for styrene combustion were investigated. The catalytic activity of the catalysts was tested in the absence of and presence of water vapor and the catalysts were characterized. Temperature programmed desorption (TPD) experiments and diffuse reflectance infrared fourier transform spectroscopy (DRIFTS) measurements were conducted in order to estimate and explain the water effects. Results showed that the existence of water vapor had a significant negative effect on the catalytic activity of these copper based catalysts due to the competition adsorption of water molecule. DRIFTS studies showed that the catalyst CuO/gamma-Al2O3 had the strongest adsorption of water, while the catalyst CuO/TiO2 had the weakest adsorption of water. H2O-TPD studies also indicated that the order of desorption activation energies of water vapor on the catalysts or the strength of interactions of water molecules with the surfaces of the catalysts was CuO/gamma-Al2O3>CuO/SiO2>CuO/TiO2. As a consequence of that, the CuO/TiO2 exhibited the better durability to water vapor, while CuO/gamma-Al2O3 had the poorest durability to water vapor among these three catalysts.

Irreversible metal-insulator transition in thin film VO2 induced by soft X-ray irradiation

NASA Astrophysics Data System (ADS)

Singh, V. R.; Jovic, V.; Valmianski, I.; Ramirez, J. G.; Lamoureux, B.; Schuller, Ivan K.; Smith, K. E.

2017-12-01

In this study, we show the ability of soft x-ray irradiation to induce room temperature metal-insulator transitions (MITs) in VO2 thin films grown on R-plane sapphire. The ability of soft x-rays to induce MIT in VO2 thin films is confirmed by photoemission spectroscopy and soft x-ray spectroscopy measurements. When irradiation was discontinued, the systems do not return to the insulating phase. Analysis of valence band photoemission spectra revealed that the density of states (DOSs) of the V 3d band increased with irradiation time, while the DOS of the O 2p band decreased. We use these results to propose a model in which the MIT is driven by oxygen desorption from thin films during irradiation.

Time and temperature dependent adsorption-desorption behaviour of pretilachlor in soil.

PubMed

Kaur, Paawan; Kaur, Pervinder

2018-06-04

Understanding and quantifying the adsorption-desorption behaviour of herbicide in soil is imperative for predicting their fate and transport in the environment. In the present study, the effect of time and temperature on the adsorption-desorption behaviour of pretilachlor in soils was investigated using batch equilibration technique. The adsorption-desorption kinetics of pretilachlor in soils was two step process and was well described by pseudo-second-order kinetic model. Freundlich model accurately predicted the sorption behaviour of pretilachlor. The adsorption-desorption of pretilachlor varied significantly with the concentration, temperature and properties of soil viz. organic matter and clay content. All the studied soils had non-linear slopes (n < 1) and degree of nonlinearity increased with increase in clay, organic matter content and temperature (p < 0.05). Desorption of pretilachlor was hysteretic in studied soils and hysteresis coefficient varied from 0.023 to 0.275. Thermodynamic analysis showed that pretilachlor adsorption onto soils was a feasible, spontaneous and endothermic process which becomes more favourable at high temperature. It could be inferred that the adsorption of pretilachlor on soils was physical in nature. Copyright © 2018 Elsevier Inc. All rights reserved.

High field electron paramagnetic resonance spectroscopy under ultrahigh vacuum conditions—A multipurpose machine to study paramagnetic species on well defined single crystal surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rocker, J.; Cornu, D.; Kieseritzky, E.

2014-08-01

A new ultrahigh vacuum (UHV) electron paramagnetic resonance (EPR) spectrometer operating at 94 GHz to investigate paramagnetic centers on single crystal surfaces is described. It is particularly designed to study paramagnetic centers on well-defined model catalysts using epitaxial thin oxide films grown on metal single crystals. The EPR setup is based on a commercial Bruker E600 spectrometer, which is adapted to ultrahigh vacuum conditions using a home made Fabry Perot resonator. The key idea of the resonator is to use the planar metal single crystal required to grow the single crystalline oxide films as one of the mirrors of themore » resonator. EPR spectroscopy is solely sensitive to paramagnetic species, which are typically minority species in such a system. Hence, additional experimental characterization tools are required to allow for a comprehensive investigation of the surface. The apparatus includes a preparation chamber hosting equipment, which is required to prepare supported model catalysts. In addition, surface characterization tools such as low energy electron diffraction (LEED)/Auger spectroscopy, temperature programmed desorption (TPD), and infrared reflection absorption spectroscopy (IRAS) are available to characterize the surfaces. A second chamber used to perform EPR spectroscopy at 94 GHz has a room temperature scanning tunneling microscope attached to it, which allows for real space structural characterization. The heart of the UHV adaptation of the EPR experiment is the sealing of the Fabry-Perot resonator against atmosphere. To this end it is possible to use a thin sapphire window glued to the backside of the coupling orifice of the Fabry Perot resonator. With the help of a variety of stabilization measures reducing vibrations as well as thermal drift it is possible to accumulate data for a time span, which is for low temperature measurements only limited by the amount of liquid helium. Test measurements show that the system can detect paramagnetic species with a density of approximately 5 × 10{sup 11} spins/cm{sup 2}, which is comparable to the limit obtained for the presently available UHV-EPR spectrometer operating at 10 GHz (X-band). Investigation of electron trapped centers in MgO(001) films shows that the increased resolution offered by the experiments at W-band allows to identify new paramagnetic species, that cannot be differentiated with the currently available methodology.« less

Monitoring N3 dye adsorption and desorption on TiO2 surfaces: a combined QCM-D and XPS study.

PubMed

Wayment-Steele, Hannah K; Johnson, Lewis E; Tian, Fangyuan; Dixon, Matthew C; Benz, Lauren; Johal, Malkiat S

2014-06-25

Understanding the kinetics of dye adsorption and desorption on semiconductors is crucial for optimizing the performance of dye-sensitized solar cells (DSSCs). Quartz crystal microbalance with dissipation monitoring (QCM-D) measures adsorbed mass in real time, allowing determination of binding kinetics. In this work, we characterize adsorption of the common RuBipy dye N3 to the native oxide layer of a planar, sputter-coated titanium surface, simulating the TiO2 substrate of a DSSC. We report adsorption equilibrium constants consistent with prior optical measurements of N3 adsorption. Dye binding and surface integrity were also verified by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy (XPS). We further study desorption of the dye from the native oxide layer on the QCM sensors using tetrabutylammonium hydroxide (TBAOH), a commonly used industrial desorbant. We find that using TBAOH as a desorbant does not fully regenerate the surface, though little ruthenium or nitrogen is observed by XPS after desorption, suggesting that carboxyl moieties of N3 remain bound. We demonstrate the native oxide layer of a titanium sensor as a valid and readily available planar TiO2 morphology to study dye adsorption and desorption and begin to investigate the mechanism of dye desorption in DSSCs, a system that requires further study.

Hydrogen retention in Li and Li-C-O films

NASA Astrophysics Data System (ADS)

Buzi, Luxherta; Nelson, Andrew O.; Yang, Yuxin; Kaita, Robert; Koel, Bruce E.

2017-10-01

The efficiency of Li in binding H isotopes has led to reduced recycling in magnetic fusion devices and improved plasma performance. Since elemental Li surfaces are challenging to maintain in fusion devices due to the presence of impurities, parameterizing and understanding the mechanisms for H retention in various Li compounds (Li-C-O), in addition to pure Li, is crucial for Li plasma-facing material applications. To determine H retention in Li and Li-C-O films, measurements were done under ultrahigh vacuum conditions using temperature programmed desorption (TPD). Thin Li films (20 monolayers) were deposited on a nickel single crystal substrate and irradiated with 500 eV H2+ions at surface temperatures from 90K to 520K. Initial measurements on Li and Li-O films showed that the retention was comparable and dropped exponentially with surface temperature, from 95% at 90 K to 35% at 520 K. Auger electron spectroscopy and TPD showed that H was retained as lithium hydride (LiH) in pure Li and as lithium hydroxide (LiOH) in Li2O, which decomposed to H2O and Li2O at temperatures higher than 470K. H retention in Li-C and Li-C-O films will be determined over a similar temperature range, and the sputtering rate of these layers with H ions will also be reported. This material is based upon work supported by the U.S. Department of Energy, Office of Science/Fusion Energy Sciences under Award Number DE-SC0012890.

Study on Desorption Process of n-Heptane and Methyl Cyclohexane Using UiO-66 with Hierarchical Pores.

PubMed

Chen, Sijia; Zhang, Lin; Zhang, Zhao; Qian, Gang; Liu, Zongjian; Cui, Qun; Wang, Haiyan

2018-06-06

UiO-66 (UiO for University of Oslo), is a zirconium-based MOF with reverse shape selectivity, gives an alternative way to produce high purity n-heptane used for the manufacture of high-purity pharmaceuticals. Couple of studies have shown that UiO-66 gives a high selectivity on the separation of n-/iso-alkanes. However, the microporous structure of UiO-66 causes poor mass transport during the desorption process. In this work, hierarchical-pore UiO-66 (H-UiO-66) was synthesized and utilized as an adsorbent of n-heptane (nHEP) and methyl cyclohexane (MCH) for systematically studying the desorption process of n/iso-alkanes. A suite of physical methods, including XRD patterns verified the UiO-66 structures and HRTEM showed the existence of hierarchical pores. N2 adsorption-desorption isotherms further confirmed the size distribution of hierarchical pores in H-UiO-66. Of particular note, the MCH/nHEP selectivity of H-UiO-66 is similar with UiO-66 in the same adsorption conditions, the desorption process of nHEP/MCH from H-UiO-66 is dramatically enhanced, viz, the desorption rates for nHEP/MCH from H-UiO-66 is enhanced by 30%/23% as comparing to UiO-66 at most. Moreover, desorption activation energy (Ed) derived from temperature-programmed desorption (TPD) experiments indicate that the Ed for nHEP/MCH is lower on H-UiO-66, i.e., the Ed of MCH on H-UiO-66 is ~37% lower than that on UiO-66 at most, leading to a milder condition for the desorption process. The introduction of hierarchical structures will be applicable for the optimization of desorption process during separation on porous materials.

Pyrrole Hydrogenation over Rh(111) and Pt(111) Single-Crystal Surfaces and Hydrogenation Promotion Mediated by 1-Methylpyrrole: A Kinetic and Sum-Frequency Generation Vibrational Spectroscopy Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kliewer, Christopher J.; Bieri, Marco; Somorjai, Gabor A.

Sum-frequency generation (SFG) surface vibrational spectroscopy and kinetic measurements using gas chromatography have been used to study the adsorption and hydrogenation of pyrrole over both Pt(111) and Rh(111) single-crystal surfaces at Torr pressures (3 Torr pyrrole, 30 Torr H{sub 2}) to form pyrrolidine and the minor product butylamine. Over Pt(111) at 298 K it was found that pyrrole adsorbs in an upright geometry cleaving the N-H bond to bind through the nitrogen evidenced by SFG data. Over Rh(111) at 298 K pyrrole adsorbs in a tilted geometry relative to the surface through the p-aromatic system. A pyrroline surface reaction intermediate,more » which was not detected in the gas phase, was seen by SFG during the hydrogenation over both surfaces. Significant enhancement of the reaction rate was achieved over both metal surfaces by adsorbing 1-methylpyrrole before reaction. SFG vibrational spectroscopic results indicate that reaction promotion is achieved by weakening the bonding between the N-containing products and the metal surface because of lateral interactions on the surface between 1-methylpyrrole and the reaction species, reducing the desorption energy of the products. It was found that the ring-opening product butylamine was a reaction poison over both surfaces, but this effect can be minimized by treating the catalyst surfaces with 1-methylpyrrole before reaction. The reaction rate was not enhanced with elevated temperatures, and SFG suggests desorption of pyrrole at elevated temperatures.« less

Facile preparation of multifunctional carbon nanotube/magnetite/polyaniline nanocomposite offering a strong option for efficient solid-phase microextraction coupled with GC-MS for the analysis of phenolic compounds.

PubMed

Tafazoli, Zahra; Azar, Parviz Aberoomand; Tehrani, Mohammad Saber; Husain, Syed Waqif

2018-04-20

The aim of this study the synthesis of a highly efficient organic-inorganic nanocomposite. In this research, the carbon nanotube/magnetite/polyaniline nanocomposite was successfully prepared through a facile route. Monodisperse magnetite nanospheres were prepared through the coprecipitation route, and polyaniline nanolayer as a modified shell with a high surface area was synthesized by an in situ growth route and characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray diffraction and energy dispersive X-ray spectroscopy. The prepared nanocomposite was immobilized on a stainless-steel wire for the fabrication of the solid-phase microextraction fiber. The combination of headspace solid-phase microextraction using carbon nanotube/magnetite/polyaniline nanocomposite fiber with gas chromatography and mass spectrometry can achieve a low limit of detection and can be applied to determine phenolic compounds in water samples. The effects of the extraction and desorption parameters including extraction temperature and time, ionic strength, stirring rate, pH, and desorption temperature and time have been studied. Under the optimum conditions, the dynamic linear range was 0.01-500 ng mL -1 and the limits of detection of phenol, 4-chlorophenol, 2,6-dichlorophenol, and 2,4,6-trichlorophenol were the lowest (0.008 ng mL -1 ) for three times. The coefficient of determination of all calibration curves was more than 0.990. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

In situ measurements of fuel retention by laser induced desorption spectroscopy in TEXTOR

NASA Astrophysics Data System (ADS)

Zlobinski, M.; Philipps, V.; Schweer, B.; Huber, A.; Stoschus, H.; Brezinsek, S.; Samm, U.; TEXTOR Team

2011-12-01

In future fusion devices such as ITER tritium retention due to tritium co-deposition in mixed material layers can be a serious safety problem. Laser induced desorption spectroscopy (LIDS) can measure the hydrogen content of hydrogenic carbon layers locally on plasma-facing components, while hydrogen is used as a tritium substitute. For several years, this method has been applied in the TEXTOR tokamak in situ during plasma operation to monitor the hydrogen content in space and time. This work shows the LIDS signal reproducibility and studies the effects of different plasma conditions, desorption distances from the plasma and different laser energies using a dedicated sample with constant hydrogen amount. Also the LIDS signal evaluation procedure is described in detail and the detection limits for different conditions in the TEXTOR tokamak are estimated.

Desorption Kinetics of H2O from Cab-O-Sil-M-7D and Hi-Sil-233 Silica Particles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dinh, L.; Balooch, M.; LeMay, J.D.

2000-01-26

Temperature programmed desorption (TPD) was performed at temperatures up to 850K on Cab-O-Sil-M-7D and Hi-Sil-233 silica particles. Physisorbed water molecules on both types of silica had activation energies in the range of 9-14.5 kcal/mol. However, the activation energies of desorption for chemisorbed water varied from {approx} 19 kcal/mol to > 59 kcal/mol for Cab-O-Sil-M-7D, and {approx} 23-37 kcal/mol for Hi-Sil-233. Our results suggest that physisorbed water can be effectively pumped away at room temperature (or preferably at 320 K) in a matter of hours. Chemisorbed water with high activation energies of desorption (>30 kcal/mol) will not escape the silica surfacesmore » in 100 years even at 320 K, while a significant amount of the chemisorbed water with medium activation energies (19-26 kcal/mol) will leave the silica surfaces in that time span. Most of the chemisorbed water with activation energies < 30 kcal/mol can be pumped away in a matter of days in a good vacuum environment at 500 K. We had previously measured about 0.1-0.4 wt. % of water in M9787 polysiloxane formulations containing {approx} 21% Cab-O-Sil-M-7D and {approx} 4% Hi-Sil-233. Comparing present results with these formulations, we conclude that absorbed H{sub 2}O and Si-OH bonds on the silica surfaces are the major contributors to water outgassing from M97 series silicones.« less

Extremely low-outgassing material: 0.2% beryllium copper alloy

NASA Astrophysics Data System (ADS)

Watanabe, Fumio

2004-01-01

Exploration for low-outgassing materials for use in ultrahigh vacuum and extreme high-vacuum systems is one of the most important topics of a vacuum researcher. We have found that a copper alloy containing 0.2% beryllium (0.2% BeCu) can attain an extremely low hydrogen outgassing rate of 10-14 Pa (H2) m/s order. Almost the entire surface of 0.2% BeCu is dominated by a BeO layer, after a 400 °C×72 h prebakeout treatment in an ultrahigh vacuum. This layer functions as a barrier to the processes of oxidization and permeation of hydrogen. In addition, this layer resists carbon contamination. Temperature-programmed desorption spectra show only a single peak for water at 150 °C and small quantities of any other desorption gases. Therefore, an in situ bakeout process in which the temperature simply ramps up to 150 °C and immediately ramps back down is enough for degassing; it does not require an ordinary sustained-temperature bakeout. Using an outgassing sample consisting of 0.2% BeCu disks housed in a 0.2% BeCu nipple chamber, a lowest outgassing rate of the 5.6×10-14 Pa (H2) m/s was measured by the pressure-rise method after pump cutoff. The pressure-rise versus time curve was completely nonlinear. It rises over time to a constant slope of 1/2 in a log-log plot, due to hydrogen diffusion from the bulk, but this requires over a week at room temperature. The hydrogen outgassing from the 0.2% BeCu bulk is completely dominated by a diffusion-limited mechanism. This article will describe why we obtain such low-outgassing rates with 0.2% BeCu. It is based on the observed surface changes with prebakeout treatment seen by x-ray photoelectron spectroscopy, and the improvement of hydrogen outgassing measurements by the pressure-rise method. A comparison is made to ordinary stainless steel. In addition, the concept of an outgassing reduction method will be discussed from a review of the published ultralow-outgassing data and reduction methods. .

Adsorption of small hydrocarbons on rutile TiO2(110)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Long; Smith, R. Scott; Kay, Bruce D.

2016-08-01

Temperature programmed desorption and molecular beam scattering were used to study the adsorption and desorption of small hydrocarbons (n-alkanes, 1-alkenes and 1-alkynes with 1 - 4 carbon atoms of C1-C4) on rutile TiO2(110). We show that the sticking coefficients for all the hydrocarbons are close to unity (> 0.95) at an adsorption temperature of 60 K. The desorption energies for hydrocarbons of the same chain length increase from n-alkanes to 1-alkenes and to 1-alkynes. This trend is likely a consequence of an additional dative bonding of the alkene and alkyne π system to the coordinatively unsaturated Ti5c sites. Similar tomore » previous studies on the adsorption of n-alkanes on metal and metal oxide surfaces, we find the desorption energies within each group (n-alkanes vs. 1-alkenes vs. 1-alkynes) from Ti5c sites increase linearly with the chain length. The absolute saturation coverages of each hydrocarbon on Ti5c sites were also determined. The saturation coverage of CH4, is found to be ~ 2/3 monolayer (ML). The saturation coverages of C2-C4 hydrocarbons are found nearly independent of the chain length with values of ~1/2 ML for n-alkanes and 1-alkenes and 2/3 ML for 1-alkynes. This result is surprising considering their similar sizes.« less

Adsorption of small hydrocarbons on rutile TiO 2(110)

DOE PAGES

Chen, Long; Smith, R. Scott; Kay, Bruce D.; ...

2015-11-21

Here, temperature programmed desorption and molecular beam scattering were used to study the adsorption and desorption of small hydrocarbons (n-alkanes, 1-alkenes and 1-alkynes of C 1–C 4) on rutile TiO 2(110). We show that the sticking coefficients for all the hydrocarbons are close to unity (> 0.95) at an adsorption temperature of 60 K. The desorption energies for hydrocarbons of the same chain length increase from n-alkanes to 1-alkenes and to 1-alkynes. This trend is likely a consequence of additional dative bonding of the alkene and alkyne π system to the coordinatively unsaturated Ti 5c sites. Similar to previous studiesmore » on the adsorption of n-alkanes on metal and metal oxide surfaces, we find that the desorption energies within each group (n-alkanes vs. 1-alkenes vs. 1-alkynes) from Ti 5c sites increase linearly with the chain length. The absolute saturation coverages of each hydrocarbon on Ti 5c sites were also determined. The saturation coverage of CH 4, is found to be ~ 2/3 monolayer (ML). The saturation coverages of C 2–C 4 hydrocarbons are found nearly independent of the chain length with values of ~ 1/2 ML for n-alkanes and 1-alkenes and 2/3 ML for 1-alkynes. This result is surprising considering their similar sizes.« less

Development and Characterization of a Laser-Induced Acoustic Desorption Source.

PubMed

Huang, Zhipeng; Ossenbrüggen, Tim; Rubinsky, Igor; Schust, Matthias; Horke, Daniel A; Küpper, Jochen

2018-03-20

A laser-induced acoustic desorption source, developed for use at central facilities, such as free-electron lasers, is presented. It features prolonged measurement times and a fixed interaction point. A novel sample deposition method using aerosol spraying provides a uniform sample coverage and hence stable signal intensity. Utilizing strong-field ionization as a universal detection scheme, the produced molecular plume is characterized in terms of number density, spatial extend, fragmentation, temporal distribution, translational velocity, and translational temperature. The effect of desorption laser intensity on these plume properties is evaluated. While translational velocity is invariant for different desorption laser intensities, pointing to a nonthermal desorption mechanism, the translational temperature increases significantly and higher fragmentation is observed with increased desorption laser fluence.

Analysis of ecstasy in oral fluid by ion mobility spectrometry and infrared spectroscopy after liquid-liquid extraction.

PubMed

Armenta, Sergio; Garrigues, Salvador; de la Guardia, Miguel; Brassier, Judit; Alcalà, Manel; Blanco, Marcelo

2015-03-06

We developed and evaluated two different strategies for determining abuse drugs based on (i) the analysis of saliva by ion mobility spectrometry (IMS) after thermal desorption and (ii) the joint use of IMS and infrared (IR) spectroscopy after liquid-liquid microextraction (LLME) to enable the sensitivity-enhanced detection and double confirmation of ecstasy (MDMA) abuse. Both strategies proved effective for the intended purpose. Analysing saliva by IMS after thermal desorption, which provides a limit of detection (LOD) of 160μgL(-1), requires adding 0.2M acetic acid to the sample and using the truncated negative second derivative of the ion mobility spectrum. The joint use of IMS and IR spectroscopy after LLME provides an LOD of 11μgL(-1) with the former technique and 800μgL(-1) with the latter, in addition to a limit of confirmation (LOC) of 1.5mgL(-1). Using IMS after thermal desorption simplifies the operational procedure, and using it jointly with IR spectroscopy after LLME allows double confirmation of MDMA abuse with two techniques based on different principles (viz., IMS drift times and IR spectra). Also, it affords on-site analyses, albeit at a lower throughput. Copyright © 2015 Elsevier B.V. All rights reserved.

Reprint of: Effects of cold deformation, electron irradiation and extrusion on deuterium desorption behavior in Zr-1%Nb alloy

NASA Astrophysics Data System (ADS)

Morozov, O.; Mats, O.; Mats, V.; Zhurba, V.; Khaimovich, P.

2018-01-01

The present article introduces the data of analysis of ranges of ion-implanted deuterium desorption from Zr-1% Nb alloy. The samples studied underwent plastic deformation, low temperature extrusion and electron irradiation. Plastic rolling of the samples at temperature ∼300 K resulted in plastic deformation with the degree of ε = 3.9 and the formation of nanostructural state with the average grain size of d = 61 nm. The high degree of defectiveness is shown in thermodesorption spectrum as an additional area of the deuterium desorption in the temperature ranges 650-850 K. The further processing of the sample (that had undergone plastic deformation by plastic rolling) with electron irradiation resulted in the reduction of the average grain size (58 nm) and an increase in borders concentration. As a result the amount of deuterium desorpted increased in the temperature ranges 650-900 K. In case of Zr-1% Nb samples deformed by extrusion the extension of desorption area is observed towards the temperature reduction down to 420 K. The formation of the phase state of deuterium solid solution in zirconium was not observed. The structural state behavior is a control factor in the process of deuterium thermodesorption spectrum structure formation with a fixed implanted deuterium dose (hydrogen diagnostics). It appears as additional temperature ranges of deuterium desorption depending on the type, character and defect content.

Modelling deuterium release during thermal desorption of D +-irradiated tungsten

NASA Astrophysics Data System (ADS)

Poon, M.; Haasz, A. A.; Davis, J. W.

2008-03-01

Thermal desorption profiles were modelled based on SIMS measurements of implantation profiles and using the multi-trap diffusion code TMAP7 [G.R. Longhurst, TMAP7: Tritium Migration Analysis Program, User Manual, Idaho National Laboratory, INEEL/EXT-04-02352 (2004)]. The thermal desorption profiles were the result of 500 eV/D + irradiations on single crystal tungsten at 300 and 500 K to fluences of 10 22-10 24 D +/m 2. SIMS depth profiling was performed after irradiation to obtain the distribution of trapped D within the top 60 nm of the surface. Thermal desorption spectroscopy (TDS) was performed subsequently to obtain desorption profiles and to extract the total trapped D inventory. The SIMS profiles were calibrated to give D concentrations. To account for the total trapped D inventory measured by TDS, SIMS depth distributions were used in the near-surface (surface to 30 nm), NRA measurements [V.Kh. Alimov, J. Roth, M. Mayer, J. Nucl. Mater. 337-339 (2005) 619] were used in the range 1-7 μm, and a linear drop in the D distribution was assumed in the intermediate sub-surface region (˜30 nm to 1 μm). Traps were assumed to be saturated so that the D distribution also represented the trap distribution. Three trap energies, 1.07 ± 0.03, 1.34 ± 0.03 and 2.1 ± 0.05 eV were required to model the 520, 640 and 900 K desorption peaks, respectively. The 1.34 and 1.07 eV traps correspond to trapping of a first and second D atom at a vacancy, respectively, while the 2.1 eV trap corresponds to atomic D trapping at a void. A fourth trap energy of 0.65 eV was used to fit the 400 K desorption peak observed by Quastel et al. [A.D. Quastel, J.W. Davis, A.A. Haasz, R.G. Macaulay-Newcombe, J. Nucl. Mater. 359 (2006) 8].

A new theoretical approach to adsorption desorption behavior of Ga on GaAs surfaces

NASA Astrophysics Data System (ADS)

Kangawa, Y.; Ito, T.; Taguchi, A.; Shiraishi, K.; Ohachi, T.

2001-11-01

We propose a new theoretical approach for studying adsorption-desorption behavior of atoms on semiconductor surfaces. The new theoretical approach based on the ab initio calculations incorporates the free energy of gas phase; therefore we can calculate how adsorption and desorption depends on growth temperature and beam equivalent pressure (BEP). The versatility of the new theoretical approach was confirmed by the calculation of Ga adsorption-desorption transition temperatures and transition BEPs on the GaAs(0 0 1)-(4×2)β2 Ga-rich surface. This new approach is feasible to predict how adsorption and desorption depend on the growth conditions.

C incorporation and segregation during Si 1- yC y/Si( 0 0 1 ) gas-source molecular beam epitaxy from Si 2H 6 and CH 3SiH 3

NASA Astrophysics Data System (ADS)

Foo, Y. L.; Bratland, K. A.; Cho, B.; Soares, J. A. N. T.; Desjardins, P.; Greene, J. E.

2002-08-01

We have used in situ D 2 temperature-programmed desorption (TPD) to probe C incorporation and surface segregation kinetics, as well as hydrogen desorption pathways, during Si 1- yC y(0 0 1) gas-source molecular beam epitaxy from Si 2H 6/CH 3SiH 3 mixtures at temperatures Ts between 500 and 650 °C. Parallel D 2 TPD results from C-adsorbed Si(0 0 1) wafers exposed to varying CH 3SiH 3 doses serve as reference data. Si 1- yC y(0 0 1) layer spectra consist of three peaks: first-order β 1 at 515 °C and second-order β 2 at 405 °C, due to D 2 desorption from Si monodeuteride and dideuteride phases, as well as a new second-order C-induced γ 1 peak at 480 °C. C-adsorbed Si(0 0 1) samples with very high CH 3SiH 3 exposures yielded a higher-temperature TPD feature, corresponding to D 2 desorption from surface C atoms, which was never observed in Si 1- yC y(0 0 1) layer spectra. The Si 1- yC y(0 0 1) γ 1 peak arises due to desorption from Si monodeuteride species with C backbonds. γ 1 occurs at a lower temperature than β 1 reflecting the lower D-Si * bond strength, where Si * represents surface Si atoms bonded to second-layer C atoms, as a result of charge transfer from dangling bonds. The total integrated monohydride (β 1+γ 1) intensity, and hence the dangling bond density, remains constant with y indicating that C does not deactivate surface dangling bonds as it segregates to the second-layer during Si 1- yC y(0 0 1) growth. Si * coverages increase with y at constant Ts and with Ts at constant y. The positive Ts-dependence shows that C segregation is kinetically limited at Ts⩽650 °C. D 2 desorption activation energies from β 1, γ 1 and β 2 sites are 2.52, 2.22 and 1.88 eV.

Synthesis of complex organic molecules in simulated methane rich astrophysical ices

NASA Astrophysics Data System (ADS)

Esmaili, Sasan; Bass, Andrew D.; Cloutier, Pierre; Sanche, Léon; Huels, Michael A.

2017-12-01

It has been proposed that organic molecules required for life on earth may be formed by the radiation processing of molecular ices in space environments, e.g., within our solar system. Such processes can be studied in the laboratory with surface science analytical techniques and by using low-energy electron (LEE) irradiation to simulate the effects of the secondary electrons that are generated in great abundance whenever ionizing radiation interacts with matter. Here we present new measurements of 70 eV LEE irradiation of multilayer films of CH4, 18O2, and CH4/18O2 mixtures (3:1 ratio) at 22 K. The electron stimulated desorption (ESD) yields of cations and anions have been recorded as a function of electron fluence. At low fluence, the prompt desorption of more massive multi-carbon or C—O containing cationic fragments agrees with our earlier measurements. However, new anion ESD signals of C2-, C2H-, and C2H2- from CH4/18O2 mixtures increase with fluence, indicating the gradual synthesis (and subsequent electron-induced fragmentation) of new, more complex species containing several C and possibly O atoms. Comparisons between the temperature programed desorption (TPD) mass spectra of irradiated and unirradiated films show the electron-induced formation of new chemical species, the identities of which are confirmed by reference to the NIST database of electron impact mass spectra and by TPD measurements of films composed of the proposed products. New species observed in the TPD of irradiated mixture films include C3H6, C2H5OH, and C2H6. Furthermore, X-ray photoelectron spectroscopy of irradiated films confirms the formation of C—O, C=O, and O=C—O— bonds of newly formed molecules. Our experiments support the view that secondary LEEs produced by ionizing radiation drive the chemistry in irradiated ices in space, irrespective of the radiation type.

Isothermal-desorption-rate measurements in the vicinity of the Curie temperature for H2 chemisorbed on nickel films

NASA Technical Reports Server (NTRS)

Shanabarger, M. R.

1979-01-01

Measurements of the isothermal desorption rate of H2 chemisorbed onto polycrystalline nickel films made for temperatures spanning the Curie temperature of the nickel film are presented. Desorption kinetics were followed by measuring the decay of the change in resistance of the nickel film brought about by hydrogen chemisorption after gas-phase H2 had been rapidly evacuated. The desorption rate is found to undergo an anomalous decrease in the vicinity of the Curie temperature, accompanied by an increase in the desorption activation energy and the equilibrium constant for the chemisorbed hydrogen. The results are interpreted in terms of anomalous variations in rate constants for the formation of the precursor molecular adsorbed state and the chemisorbed atomic state due to the phase transition in the nickel. The changes in rate constants are also considered to be in qualitative agreement with theoretical predictions based on a spin coupling between the adatom and the magnetic substrate.

Surface diffusion of CO on silica-supported Ru particles: 13C nuclear magnetic resonance studies

NASA Astrophysics Data System (ADS)

Duncan, T. M.; Thayer, A. M.; Root, T. W.

1990-02-01

Portions of CO adsorbed on Ru particles, selected by the orientation of the C-O bond relative to an external magnetic field, are labeled by inversion of the 13C nuclear magnetic dipole. Changes in the orientation of the CO bond of these labeled molecules are then observed with 13C NMR spectroscopy. The temperature dependence and rate of reorientation are consistent with surface diffusion on Ru particles with small numbers of flat faces. The insensitivity to CO pressure in the range 0.5-100 Torr discounts stimulated desorption by gas-phase CO.

The Interaction of Carbon Monoxide with Rhodium on Potassium-Modified CeO 2(111)

DOE PAGES

Mullins, David R.

2016-02-03

The adsorption and reactions of CO adsorbed on Rh particles deposited on K-covered CeO 2(111) were studied by temperature programmed desorption and photoelectron spectroscopy. K deposited on CeO 2(111) forms a KO X over-layer by extracting O from the ceria and partially reducing some of the Ce 4+ to Ce 3+. CO does not adsorb on the KO X / CeO 2-X(111) surface in the absence of Rh particles. CO adsorbed on Rh / K / CeO 2(111) adsorbs molecularly on the Rh at 200 K. As the surface is heated the CO spills-over and reacts with the KOX tomore » form carbonate. The carbonate decomposes at elevated temperature to produce CO and CO 2. The carbonate stabilizes the KO X so that K desorbs at a higher temperature than it would in the absence of CO. When the Rh and K deposition are reversed so that K is deposited on both the Rh and the CeO 2(111), CO adsorbs as CO 2- at 200 K. The CO 2- decomposes below 350 K to produce gas phase CO and adsorbed CO3 2- and CO. The CO is stabilized by the K on the Rh and desorbs above 540 K. The carbonate decomposes into gas phase CO and CO 2.« less

Study of ceria-carbonate nanocomposite electrolytes for low-temperature solid oxide fuel cells.

PubMed

Fan, L; Wang, C; Di, J; Chen, M; Zheng, J; Zhu, B

2012-06-01

Composite and nanocomposite samarium doped ceria-carbonates powders were prepared by solid-state reaction, citric acid-nitrate combustion and modified nanocomposite approaches and used as electrolytes for low temperature solid oxide fuel cells. X-ray Diffraction, Scanning Electron Microscope, low-temperature Nitrogen Adsorption/desorption Experiments, Electrochemical Impedance Spectroscopy and fuel cell performance test were employed in characterization of these materials. All powders are nano-size particles with slight aggregation and carbonates are amorphous in composites. Nanocomposite electrolyte exhibits much lower impedance resistance and higher ionic conductivity than those of the other electrolytes at lower temperature. Fuel cell using the electrolyte prepared by modified nanocomposite approach exhibits the best performance in the whole operation temperature range and achieves a maximum power density of 839 mW cm(-2) at 600 degrees C with H2 as fuel. The excellent physical and electrochemical performances of nanocomposite electrolyte make it a promising candidate for low-temperature solid oxide fuel cells.

Radioactive Cobalt(II) Removal from Aqueous Solutions Using a Reusable Nanocomposite: Kinetic, Isotherms, and Mechanistic Study

PubMed Central

Wang, Ximing; Chen, Zhangjing

2017-01-01

A lignocellulose/montmorillonite (LMT) nanocomposite was prepared as a reusable adsorbent for cobalt(II) ions, and characterized by nitrogen (N2) adsorption/desorption isotherm, X-ray Diffraction (XRD), Scanning Electron Microscope (SEM), Transmission Electron Microscopy (TEM), and Fourier Transform Infrared Spectroscopy (FTIR). LMT exhibited efficient adsorption of cobalt ions (Co(II)), and the adsorbed Co(II) was readily desorbed by nitric acid (HNO3). All parameters affecting the adsorption and/or desorption of Co(II), including initial Co(II) concentration, pH value, temperature, HNO3 concentration, and time, were optimized. The kinetic data analysis showed that the adsorption followed the pseudo-second-order kinetic model and fit well into the Langmuir isotherm equation. Notably, the nanocomposite can be used four times without significantly losing adsorbent capability. The Energy-Dispersive X-ray (EDX) and FTIR spectra analysis also revealed that the adsorption mechanism may be mainly a chemical adsorption dominated process. PMID:29186794

USGS Coal Desorption Equipment and a Spreadsheet for Analysis of Lost and Total Gas from Canister Desorption Measurements

USGS Publications Warehouse

Barker, Charles E.; Dallegge, Todd A.; Clark, Arthur C.

2002-01-01

We have updated a simple polyvinyl chloride plastic canister design by adding internal headspace temperature measurement, and redesigned it so it is made with mostly off-the-shelf components for ease of construction. Using self-closing quick connects, this basic canister is mated to a zero-head manometer to make a simple coalbed methane desorption system that is easily transported in small aircraft to remote localities. This equipment is used to gather timed measurements of pressure, volume and temperature data that are corrected to standard pressure and temperature (STP) and graphically analyzed using an Excel(tm)-based spreadsheet. Used together these elements form an effective, practical canister desorption method.

Photodesorption of Solid CO2 by Lyα

NASA Astrophysics Data System (ADS)

Bahr, D. A.; Baragiola, R. A.

2012-12-01

We measured desorption of atoms and molecules from films of solid carbon dioxide in an ultrahigh vacuum from 6 to 60 K under irradiation with Lyα (121.6 nm, 10.2 eV) photons, an important process in the balance between gas phase and condensed molecules in the interstellar medium. The measurements use microgravimetry and mass spectrometry during irradiation and temperature programmed desorption after irradiation. At low photon fluences, the desorption flux consists mainly of O atoms and, after ~1017 photons cm-2, it is dominated by CO with smaller amount of O2, C, and CO2, with the presence of O2 indicating solid-state chemical reactions. At high fluences (up to 1018 photons cm-2), the desorption yields saturate at values much higher than in previous studies. The yields (molecules/photon), derived assuming stoichiometric desorption, reach 0.014 at 6 K, growing to ~0.2 at 50 and 60 K. Warming the films during irradiation gives rise to pressure spikes that suggest desorption of trapped species in pores or at defects, possibly assisted by radical-induced reactions. Such an effect could be significant for radiation-processed CO2-coated interstellar grains that are heated by, i.e., cosmic ray impacts or grain-grain collisions. We discuss the experiments considering photochemical mechanisms and compare them to the results of ion irradiation.

Oxygen desorption from YBa2Cu3O(7-x) and Bi2CaSr2Cu2O(8 + delta) superconductors

NASA Technical Reports Server (NTRS)

Mesarwi, A.; Levenson, L. L.; Ignatiev, A.

1991-01-01

Oxygen desorption experiments from YBa2Cu3O(7-x) (YBCO) and Bi2CaSr2Cu2O(8 + delta) (BSCCO) superconductors were carried out using a quadrupole mass spectrometer for monitoring the desorbing species and X-ray photoemission spectroscopy for surface characterization. Molecular oxygen was found to desorb from both superconductors following photoirradiation with ultraviolet/optical radiation and subsequent heating at over 150 C. Both YBCO and BSCCO were found to have similar oxygen desorption rates and similar activation energies. The desorption data as well as the X-ray photoemission data indicate that the oxygen desorption is not intrinsic to the superconductors but rather due to molecular oxygen entrapped in the material.

Interaction of Formaldehyde with the Rutile TiO 2 (110) Surface: A Combined Experimental and Theoretical Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Xiaojuan; Zhang, Zhenrong; Yang, Chengwu

2016-06-16

The adsorption and reaction of formaldehyde (CH 2O) on the oxidized rutile TiO 2(110) surface were studied by temperature programmed desorption (TPD), scanning tunneling microscopy (STM), infrared reflection-absorption spectroscopy (IRRAS) and density functional theory (DFT) calculations. The experimental and theoretical data reveal the presence of various species depending on the temperature and coverage. After formaldehyde adsorption on TiO 2(110) at 65 K, the multilayer CH 2O was detected, which desorbs completely upon heating to 120 K. The isolated CH 2O monomer was identified after submonolayer adsorption at low temperatures (45-65 K), in which CH 2O is bound to the surfacemore » Ti5c sites via σ-donation and adopts a tilted geometry. With heating to higher temperatures the CH 2O monomers remain stable up to 70 K and then undergo coupling reactions to form paraformaldehyde (polyoxymethylene, POM) at the Ti 5c rows. The POM chain is oriented primarily along the [001] direction in a slightly disordered configuration. POM becomes the predominant species at 120 K and is decomposed releasing CH 2O at about 250 K. In addition, dioxymethylene (DOM) was detected as minority species formed via reaction of Ti 5c-bound CH 2O with both neighboring O 2c along the [1-10] direction and oxygen adatoms (Oad) at Ti 5c sites along [001] on the oxidized TiO 2(110) surface.« less

Dosimeter-Type NOx Sensing Properties of KMnO4 and Its Electrical Conductivity during Temperature Programmed Desorption

PubMed Central

Groβ, Andrea; Kremling, Michael; Marr, Isabella; Kubinski, David J.; Visser, Jacobus H.; Tuller, Harry L.; Moos, Ralf

2013-01-01

An impedimetric NOx dosimeter based on the NOx sorption material KMnO4 is proposed. In addition to its application as a low level NOx dosimeter, KMnO4 shows potential as a precious metal free lean NOx trap material (LNT) for NOx storage catalysts (NSC) enabling electrical in-situ diagnostics. With this dosimeter, low levels of NO and NO2 exposure can be detected electrically as instantaneous values at 380 °C by progressive NOx accumulation in the KMnO4 based sensitive layer. The linear NOx sensing characteristics are recovered periodically by heating to 650 °C or switching to rich atmospheres. Further insight into the NOx sorption-dependent conductivity of the KMnO4-based material is obtained by the novel eTPD method that combines electrical characterization with classical temperature programmed desorption (TPD). The NOx loading amount increases proportionally to the NOx exposure time at sorption temperature. The cumulated NOx exposure, as well as the corresponding NOx loading state, can be detected linearly by electrical means in two modes: (1) time-continuously during the sorption interval including NOx concentration information from the signal derivative or (2) during the short-term thermal NOx release. PMID:23549366

Desorption Product Yields Following Cl2 Adsorption on Si(111)7x7: Coverage and Temperature Dependence

DTIC Science & Technology

1991-04-12

only desorption product at approximately 950 K. At higher chloride coverages of 8/6s5 )0.t, a small’ SICl4 TrD signal -’as als:; monitored at 950 K...SiCI2 desorption along with SiCl4 descrption (20). SiCI4 desorbed from a low temperature desorption state at 400 K, whereas SiCI4 and SiCI2 both desorbed...The ratio of the S "l3 an,’ SiC]4 TPD areas suggests that the SiC]3 and SiC]4 TPD signals are both derived froin the desorption of SiCl4 . The growth

Characterization of pulsed metallic hydride vacuum arc discharge plasmas by optical emission spectroscopy

NASA Astrophysics Data System (ADS)

Tang, Jian; Deng, Chunfeng; Wu, Chunlei; Lu, Biao; Hu, Yonghong

2017-12-01

The characteristics of plasmas in a titanium hydride vacuum arc ion source were experimentally investigated by a temporally- and spatially-integrated optical emission spectroscopy method. A plasma emission spectral fitting model was developed to calculate the plasmas temperature and relative density of each particle component, assuming plasmas were in local thermodynamic equilibrium state and optical thin in this study. The good agreement was founded between the predicted and measured spectra in the interesting regions of 330-340 nm and 498-503 nm for Ti+ ion and Ti atom respectively, while varying the plasma temperature and density. Compared with conventional Boltzmann plot method, this method, therefore, made a significant improvement on the plasma diagnosis in dealing with the spectral profile with many lines overlapped. At the same time, to understand the mechanism of the occluded-gas vacuum arc discharge plasmas, the plasmas emission spectra, ion relative density, and temperature with different discharge conditions were studied. The results indicated that the rate of Ti metal evaporation and H desorption from the electrode would be enhanced with arc current, and the ionization temperature increased with the feed-in power of arc discharge, leading more H+ and Ti+ ions, but reducing the H+ proportion in arc discharged plasmas.

Mechanistic Insights of Ethanol Steam Reforming over Ni–CeO x (111): The Importance of Hydroxyl Groups for Suppressing Coke Formation

DOE PAGES

Liu, Zongyuan; Duchoň, Tomáš; Wang, Huanru; ...

2015-07-30

We have studied the reaction of ethanol and water over Ni–CeO 2-x(111) model surfaces to elucidate the mechanistic steps associated with the ethanol steam reforming (ESR) reaction. Our results provide insights about the importance of hydroxyl groups to the ESR reaction over Ni-based catalysts. Systematically, we have investigated the reaction of ethanol on Ni–CeO 2-x(111) at varying Ce³⁺ concentrations (CeO 1.8–2.0) with absence/presence of water using a combination of soft X-ray photoelectron spectroscopy (sXPS) and temperature-programmed desorption (TPD). Consistent with previous reports, upon annealing, metallic Ni formed on reduced ceria while NiO was the main component on fully oxidized ceria.more » Ni⁰ is the active phase leading to both the C–C and C–H cleavage of ethanol but is also responsible for carbon accumulation or coking. We have identified a Ni₃C phase that formed prior to the formation of coke. At temperatures above 600K, the lattice oxygen from ceria and the hydroxyl groups from water interact cooperatively in the removal of coke, likely through a strong metal–support interaction between nickel and ceria that facilitates oxygen transfer.« less

A comparative study on the quality of bio-oil derived from green macroalga Enteromorpha clathrata over metal modified ZSM-5 catalysts.

PubMed

Wang, Shuang; Cao, Bin; Liu, Xinlin; Xu, Lujiang; Hu, Yamin; Afonaa-Mensah, Stephen; Abomohra, Abd El-Fatah; He, Zhixia; Wang, Qian; Xu, Shannan

2018-05-01

The green macroalga Enteromorpha clathrata was pyrolyzed with or without catalysts at the temperature of 550 °C for producing high-quality bio-oil. The ZSM-5 and 1,2,3 mmol Mg-Ce/ZSM-5 catalysts were introduced to investigate the yields and components distribution of bio-oil. Increase of bio-oil production was obtained with the use of ZSM-5 and 1,2,3 mmol Mg-Ce/ZSM-5 catalysts. The 1 mmol Mg-Ce/ZSM-5 catalyst exhibited more promising property for promoting the relative content of C 5 -C 7 compounds, and decreasing the relative content of acids in bio-oil. The results suggested that E. clathrata had potential as pyrolysis feedstocks for producing the high-quality bio-oil with large amounts of C 5 -C 7 compounds and low relative content of acids when the 1 mmol Mg-Ce/ZSM-5 catalyst was used. Furthermore, the physicochemical properties of ZSM-5 and 1 mmol Mg-Ce/ZSM-5 catalysts were investigated by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and temperature-programmed desorption of ammonia. Copyright © 2018 Elsevier Ltd. All rights reserved.

One-Pot synthesis of phosphorylated mesoporous carbon heterogeneous catalysts with tailored surface acidity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fulvio, Pasquale F; Mahurin, Shannon Mark; Mayes, Richard T

2012-01-01

Soft-templated phosphorylated mesoporous carbons with homogeneous distributions of phosphate groups were prepared by a 'one-pot' synthesis method using mixtures of phosphoric acid with hydrochloric, or nitric acids in the presence of Pluronic F127 triblock copolymer. Adjusting the various ratios of phosphoric acid used in these mixtures resulted in carbons with distinct adsorption, structural and surface acidity properties. The pore size distributions (PSDs) from nitrogen adsorption at -196 C showed that mesoporous carbons exhibit specific surface areas as high as 551 m{sup 2}/g and mesopores as large as 13 nm. Both structural ordering of the mesopores and the final phosphate contentsmore » were strongly dependent on the ratios of H{sub 3}PO{sub 4} in the synthesis gels, as shown by transmission electron microscopy (TEM), X-ray photoelectron (XPS) and energy dispersive X-ray spectroscopy (EDS). The number of surface acid sites determined from temperature programmed desorption of ammonia (NH{sub 3}-TPD) were in the range of 0.3-1.5 mmol/g while the active surface areas are estimated to comprise 5-54% of the total surface areas. Finally, the conversion temperatures for the isopropanol dehydration were lowered by as much as 100 C by transitioning from the least acidic to the most acidic catalysts surface.« less

Counterion adsorption and desorption rate of a charged macromolecule

NASA Astrophysics Data System (ADS)

Shi, Yu; Yang, Jingfa; Zhao, Jiang

The rate constant of counterion adsorption to and desorption from a synthetic polyelectrolyte, polystyrene sulfonate (PSS-), is measured in aqueous solution by single molecule fluorescence spectroscopy. The results show that both adsorption and desorption rate of counterions have strong dependence on polymer concentration, salt concentration as well as the molecular weight of polyelectrolytes. The results clearly demonstrate that the contribution of electrostatic interaction and the translational entropy to the distribution of counterions of a polyelectrolyte molecule. The information is helpful to the understanding of polyelectrolyte physics. National Natural Science Foundation of China.

The Adsorption and Desorption of Pb(2+) and Cd(2+) in Freeze-Thaw Treated Soils.

PubMed

Li, Linhui; Ma, Jincai; Xu, Meng; Li, Xu; Tao, Jiahui; Wang, Guanzhu; Yu, Jitong; Guo, Ping

2016-01-01

Adsorption and desorption are important processes that influence the potential toxicity and bioavailability of heavy metals in soils. However, information regarding adsorption and desorption behavior of heavy metals in soils subjected to freeze-thaw cycles is poorly understood. In the current study, the effect of freeze-thaw cycles with different freezing temperature (-15, -25, -35°C) on soil properties was investigated. Then the adsorption and desorption behavior of Pb(2+) and Cd(2+) in freeze-thaw treated soils was studied. The adsorption amounts of Pb(2+) and Cd(2+) in freeze-thaw treated soils were smaller than those in unfrozen soils (p < 0.05), due to the fact that pH, cation exchange capacity, organic matter content, free iron oxide content, and CaCO3 content in freeze-thaw treated soils were smaller than those in unfrozen soils. The adsorption amounts of Pb(2+) and Cd(2+) in soils treated with lower freezing temperatures were higher than those in soils treated with higher freezing temperatures. Desorption percentages of Pb(2+) and Cd(2+) in unfrozen soils were smaller than those in freeze-thaw treated soils (p < 0.05). The desorption percentages of Pb(2+) and Cd(2+) were smaller in soils treated with lower freezing temperatures than those in soils treated with higher freezing temperatures. The results obtained highlight the change of the adsorption and desorption behavior of typical heavy metals in freeze-thaw treated soils located in seasonal frozen soils zone in northeast China.

The interaction of NO2 with BaO: from cooperative adsorption to Ba(NO3)2 formation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yi, Cheol-Woo W.; Kwak, Ja Hun; Szanyi, Janos

2007-10-25

The effect of water on the morphology of BaO/Al2O3-based NOx storage materials was investigated using Fourier transform infrared spectroscopy, temperature programmed desorption, and time-resolved synchrotron X-ray diffraction techniques. The results of this multi-spectroscopy study reveal that, in the presence of water, surface Ba-nitrates convert to bulk nitrates, and water facilitates the formation of large Ba(NO3)2 particles. The conversion of surface to bulk Ba-nitrates is completely reversible, i.e. after the removal of water from the storage material a significant fraction of the bulk nitrates re-convert to surface nitrates. NO2 exposure of a H2O-containing (wet) BaO/Al2O3 sample results in the formation ofmore » nitrites and bulk nitrates exclusively, i.e. no surface nitrates form. After further exposure to NO2, the nitrites completely convert to bulk nitrates. The amount of NOx taken up by the storage material is, however, essentially unaffected by the presence of water, regardless of whether the water was dosed prior to or after NO2 exposure. Based on the results of this study we are now able to explain most of the observations reported in the literature on the effect of water on NOx uptake on similar storage materials.« less

Water-induced morphology changes in BaO/γ-Al2O3 NOx storage materials: an FTIR, TPD, and time-resolved synchrotron XRD study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Szanyi, Janos; Kwak, Ja Hun; Kim, Do Heui

2007-03-29

The effect of water on the morphology of BaO/Al2O3-based NOx storage materials was investigated using Fourier transform infrared spectroscopy, temperature programmed desorption, and time-resolved synchrotron X-ray diffraction techniques. The results of this multi-spectroscopy study reveal that, in the presence of water, surface Ba-nitrates convert to bulk nitrates, and water facilitates the formation of large Ba(NO3)2 particles. This process is completely reversible, i.e. after the removal of water from the storage material a significant fraction of the bulk nitrates re-convert to surface nitrates. NO2 exposure of a H2O-containing (wet) BaO/Al2O3 sample results in the formation of nitrites and bulk nitrates exclusively,more » i.e. no surface nitrates form. After further exposure to NO2, the nitrites completely convert to bulk nitrates. The amount of NOx taken up by the storage material is, however, essentially unaffected by the presence of water, regardless of whether the water was dosed prior to or after NO2 exposure. Based on the results of this study we are now able to explain most of the observations reported in the literature on the effect of water on NOx uptake on similar storage materials.« less

Assembly of a check-patterned CuSx-TiO2 film with an electron-rich pool and its application for the photoreduction of carbon dioxide to methane

NASA Astrophysics Data System (ADS)

Lee, Homin; Kwak, Byeong Sub; Park, No-Kuk; Baek, Jeom-In; Ryu, Ho-Jung; Kang, Misook

2017-01-01

A new check-patterned CuSx-TiO2 film was designed to improve the photoreduction of CO2 to CH4. The check-patterned CuSx-TiO2 film with a 3D-network microstructure was fabricated by a facile squeeze method. The as-synthesized TiO2 and CuSx powders, as well as the patterned film, were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), UV-visible spectroscopy, cyclic voltammetry (CV), and photoluminescence (PL) spectroscopy, as well as photocurrent density and CO2 temperature-programmed desorption (TPD) measurements. Compared to pure CuSx and TiO2, the check-patterned CuSx-TiO2 film exhibited significantly increased adsorption of CO2 on its networked microstructure, attributed to the enlarged interfaces between the microparticles. The check-patterned CuSx-TiO2 film exhibited superior photocatalytic behavior, with 53.2 μmolgcat-1 L-1 of CH4 produced after 8 h of reaction, whereas 18.1 and 7.3 μmolgcat-1 L-1 of CH4 were produced from pure TiO2 and CuSx films under the same reaction conditions, respectively. A model for enhanced photoactivity over the check-patterned CuSx - TiO2 film was proposed. Results indicated that the check-patterned CuS-TiO2 material is quite promising as a photocatalyst for the reduction of CO2 to CH4.

Interactions on External MOF Surfaces: Desorption of Water and Ethanol from CuBDC Nanosheets.

PubMed

Elder, Alexander C; Aleksandrov, Alexandr B; Nair, Sankar; Orlando, Thomas M

2017-10-03

The external surfaces of metal-organic framework (MOF) materials are difficult to experimentally isolate due to the high porosities of these materials. MOF surface surrogates in the form of copper benzenedicarboxylate (CuBDC) nanosheets were synthesized using a bottom-up approach, and the surface interactions of water and ethanol were investigated by temperature-programmed desorption (TPD). A method of analysis of diffusion-influenced TPD was developed to measure the desorption properties of these porous materials. This approach also allows the extraction of diffusion coefficients from TPD data. The transmission Fourier transform infrared spectra, powder X-ray diffraction patterns, and TPD data indicate that water desorbs from CuBDC nanosheets with activation energies of 44 ± 2 kJ/mol at edge sites and 58 ± 1 kJ/mol at external surface and internal and pore sites. Ethanol desorbs with activation energies of 58 ± 1 kJ/mol at internal pore sites and 66 ± 0.4 kJ/mol at external surface sites. Co-adsorption of water and ethanol was also investigated. The presence of ethanol was found to inhibit the desorption of water, resulting in a water desorption process with an activation energy of 68 ± 0.7 kJ/mol.

A soil-column gas chromatography (SCGC) approach to explore the thermal desorption behavior of hydrocarbons from soils.

PubMed

Yu, Ying; Liu, Liang; Shao, Ziying; Ju, Tianyu; Sun, Bing; Benadda, Belkacem

2016-01-01

A soil-column gas chromatography approach was developed to simulate the mass transfer process of hydrocarbons between gas and soil during thermally enhanced soil vapor extraction (T-SVE). Four kinds of hydrocarbons-methylbenzene, n-hexane, n-decane, and n-tetradecane-were flowed by nitrogen gas. The retention factor k' and the tailing factor T f were calculated to reflect the desorption velocities of fast and slow desorption fractions, respectively. The results clearly indicated two different mechanisms on the thermal desorption behaviors of fast and slow desorption fractions. The desorption velocity of fast desorption fraction was an exponential function of the reciprocal of soil absolute temperature and inversely correlated with hydrocarbon's boiling point, whereas the desorption velocity of slow desorption fraction was an inverse proportional function of soil absolute temperature, and inversely proportional to the log K OW value of the hydrocarbons. The higher activation energy of adsorption was found on loamy soil with higher organic content. The increase of carrier gas flow rate led to a reduction in the apparent activation energy of adsorption of slow desorption fraction, and thus desorption efficiency was significantly enhanced. The obtained results are of practical interest for the design of high-efficiency T-SVE system and may be used to predict the remediation time.

Low-Temperature Desorption of N2O from NO on Rutile TiO2(110)-1x1

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Boseong; Li, Zhenjun; Kay, Bruce D.

2014-05-08

We find that NO dosed on rutile TiO2(110)-1×1 at substrate temperatures as low as 50 K readily reacts to produce N2O which desorbs promptly from the surface leaving an oxygen adatom behind. The desorption rate of N2O reaches a maximum value after 1 – 2 sec at an NO flux of 1.2 ×1014 NO/cm2∙sec and then decreases rapidly as the initially clean, reduced TiO2(110) surface with ~5% oxygen vacancies (VO’s) becomes covered with oxygen adatoms and unreacted NO. The maximum desorption rate is also found to increase as the substrate temperature is raised up to about 100 K. Interestingly, themore » N2O desorption during the low-temperature (LT) NO dose is strongly suppressed when molecular oxygen is predosed, whereas it persists on the surface with VO’s passivated by surface hydroxyls. Our results show that the surface charge, not the VO sites, plays a dominant role in the LT N2O desorption induced by a facile NO reduction at such low temperatures.« less

The feasibility of desorption on Zeolite-water pair using dry gas

NASA Astrophysics Data System (ADS)

Oktariani, E.; Nakashima, K.; Noda, A.; Xue, B.; Tahara, K.; Nakaso, K.; Fukai, J.

2018-04-01

The increase in temperature, reduction in partial pressure, reduction in concentration, purging with an inert fluid, and displacement with a more strongly adsorbing species are the basic things that occur in the practical method of desorption. In this study, dry gas at constant temperature and pressure was employed as the aid to reduce the partial pressure in the water desorption on the zeolite 13X. The objective of this study is to confirm the feasibility of desorption using dry gas experimentally and numerically. The implication of heat and mass transfers were numerically investigated to find the most influential. The results of numerical simulation agree with the experimental ones for the distribution of local temperature and average water adsorbed in the packed bed.

Surface and bulk crystallization of amorphous solid water films: Confirmation of “top-down” crystallization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yuan, Chunqing; Smith, R. Scott; Kay, Bruce D.

2016-01-11

Here, the crystallization kinetics of nanoscale amorphous solid water (ASW) films are investigated using temperature-programmed desorption (TPD) and reflection absorption infrared spectroscopy (RAIRS). TPD measurements are used to probe surface crystallization and RAIRS measurements are used to probe bulk crystallization. Isothermal TPD results show that surface crystallization is independent of the film thickness (from 100 to 1000 ML). Conversely, the RAIRS measurements show that the bulk crystallization time increases linearly with increasing film thickness. These results suggest that nucleation and crystallization begin at the ASW/vacuum interface and then the crystallization growth front propagates linearly into the bulk. This mechanism wasmore » confirmed by selective placement of an isotopic layer (5% D 2O in H 2O) at various positions in an ASW (H 2O) film. In this case, the closer the isotopic layer was to the vacuum interface, the earlier the isotopic layer crystallized. These experiments provide direct evidence to confirm that ASW crystallization in vacuum proceeds by a “top-down” crystallization mechanism.« less

Methanol steam reforming promoted by molten salt-modified platinum on alumina catalysts.

PubMed

Kusche, Matthias; Agel, Friederike; Ní Bhriain, Nollaig; Kaftan, Andre; Laurin, Mathias; Libuda, Jörg; Wasserscheid, Peter

2014-09-01

We herein describe a straight forward procedure to increase the performance of platinum-on-alumina catalysts in methanol steam reforming by applying an alkali hydroxide coating according to the "solid catalyst with ionic liquid layer" (SCILL) approach. We demonstrate by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temperature-programmed desorption (TPD) studies that potassium doping plays an important role in the catalyst activation. Moreover, the hygroscopic nature and the basicity of the salt modification contribute to the considerable enhancement in catalytic performance. During reaction, a partly liquid film of alkali hydroxides/carbonates forms on the catalyst/alumina surface, thus significantly enhancing the availability of water at the catalytically active sites. Too high catalyst pore fillings with salt introduce a considerable mass transfer barrier into the system as indicated by kinetic studies. Thus, the optimum interplay between beneficial catalyst modification and detrimental mass transfer effects had to be identified and was found on the applied platinum-on-alumina catalyst at KOH loadings around 7.5 mass%. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Template growth of Au, Ni and Ni–Au nanoclusters on hexagonal boron nitride/Rh(111): a combined STM, TPD and AES study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Fanglue; Huang, Dali; Yue, Yuan

In this study, the template growth of Au, Ni, and Ni–Au bimetallic nanoclusters on hexagonal boron nitride/Rh(111), i.e. h-BN/Rh(111), was investigated via scanning tunneling microscopy (STM), temperature programmed-desorption (TPD), and Auger electron spectroscopy (AES). STM study shows that template growth of Au clusters on h-BN/Rh(111) forms mainly well-dispersed monolayer clusters. In contrast, Ni forms large multilayer clusters showing a relatively high diffusivity on h-BN/Rh(111) substrate. Ni–Au bimetallic clusters are effectively formed first by Au deposition followed by Ni deposition, with the Au clusters functioning as nucleation sites for the subsequently deposited Ni. Further structural analysis was carried out via TPDmore » and AES. The resulting TPD and AES data show the surface composition and charge transfer between Au and Ni of the bimetallic clusters. These results suggest that the h-BN/Rh(111) substrate represents a unique candidate for supporting Ni–Au bimetallic clusters in further catalytic reactions.« less

Template growth of Au, Ni and Ni–Au nanoclusters on hexagonal boron nitride/Rh(111): a combined STM, TPD and AES study

DOE PAGES

Wu, Fanglue; Huang, Dali; Yue, Yuan; ...

2017-09-12

In this study, the template growth of Au, Ni, and Ni–Au bimetallic nanoclusters on hexagonal boron nitride/Rh(111), i.e. h-BN/Rh(111), was investigated via scanning tunneling microscopy (STM), temperature programmed-desorption (TPD), and Auger electron spectroscopy (AES). STM study shows that template growth of Au clusters on h-BN/Rh(111) forms mainly well-dispersed monolayer clusters. In contrast, Ni forms large multilayer clusters showing a relatively high diffusivity on h-BN/Rh(111) substrate. Ni–Au bimetallic clusters are effectively formed first by Au deposition followed by Ni deposition, with the Au clusters functioning as nucleation sites for the subsequently deposited Ni. Further structural analysis was carried out via TPDmore » and AES. The resulting TPD and AES data show the surface composition and charge transfer between Au and Ni of the bimetallic clusters. These results suggest that the h-BN/Rh(111) substrate represents a unique candidate for supporting Ni–Au bimetallic clusters in further catalytic reactions.« less

NH3 adsorption on anatase-TiO2(101)

NASA Astrophysics Data System (ADS)

Koust, Stig; Adamsen, Kræn C.; Kolsbjerg, Esben Leonhard; Li, Zheshen; Hammer, Bjørk; Wendt, Stefan; Lauritsen, Jeppe V.

2018-03-01

The adsorption of ammonia on anatase TiO2 is of fundamental importance for several catalytic applications of TiO2 and for probing acid-base interactions. Utilizing high-resolution scanning tunneling microscopy (STM), synchrotron X-ray photoelectron spectroscopy, temperature-programmed desorption (TPD), and density functional theory (DFT), we identify the adsorption mode and quantify the adsorption strength on the anatase TiO2(101) surface. It was found that ammonia adsorbs non-dissociatively as NH3 on regular five-fold coordinated titanium surface sites (5f-Ti) with an estimated exothermic adsorption energy of 1.2 eV for an isolated ammonia molecule. For higher adsorbate coverages, the adsorption energy progressively shifts to smaller values, due to repulsive intermolecular interactions. The repulsive adsorbate-adsorbate interactions are quantified using DFT and autocorrelation analysis of STM images, which both showed a repulsive energy of ˜50 meV for nearest neighbor sites and a lowering in binding energy for an ammonia molecule in a full monolayer of 0.28 eV, which is in agreement with TPD spectra.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jia, Y.F.; Thomas, K.M.

Various types of oxygen functional groups were introduced onto the surface of coconut shell derived activated carbon by oxidation using nitric acid. Fourier-transform infrared spectroscopy (FTIR), temperature-programmed desorption (TPD), and selective neutralization were used to characterize the surface oxygen functional groups. The oxidized carbons were also heat treated to provide a suite of carbons where the oxygen functional groups of various thermal stabilities were varied progressively. The adsorption of cadmium ions was enhanced dramatically by oxidation of the carbon. The ratio of released protons to adsorbed cadmium ions on oxidized carbon was approximately 2, indicating cation exchange was involved inmore » the process of adsorption. Na{sup +} exchange studies with the oxidized carbon gave a similar ratio. After heat treatment of the oxidized carbons to remove oxygen functional groups, the ratio of H{sup +} released to Cd{sup 2+} adsorbed and the adsorption capacity decreased significantly. Both reversible and irreversible processes were involved in cadmium ion adsorption with reversible adsorption having higher enthalpy. The irreversible adsorption resulted from cation exchange with carboxylic acid groups, whereas the reversible adsorption probably involved physisorption of the partially hydrated cadmium ion.« less

Air separation with temperature and pressure swing

DOEpatents

Cassano, Anthony A.

1986-01-01

A chemical absorbent air separation process is set forth which uses a temperature swing absorption-desorption cycle in combination with a pressure swing wherein the pressure is elevated in the desorption stage of the process.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petrik, Nikolay G.; Henderson, Michael A.; Kimmel, Gregory A.

Angle-resolved photon stimulated desorption (PSD) combined with infrared reflection-adsorption spectroscopy and temperature programmed desorption reveal two distinct channels in the photochemistry of acetone on rutile TiO₂(110) surface. During UV irradiation of co-adsorbed oxygen and acetone molecules, methyl radicals (CH₃) are ejected in two different directions: i) normal to the surface and ii) off-normal at ~±66° to the surface normal in the azimuth (i.e. perpendicular to the rows of bridging oxygen and Ti atoms). Both components are relatively narrow and non-cosine, indicating non-thermal evolution of CH₃ radicals. The direction of the “off-normal” PSD component is consistent with orientation of the C–CH₃more » bonds in the n²-acetone diolate—a photoactive form of acetone chemisorption on the oxidized TiO₂(110) surface proposed earlier from experimental and theoretical studies. The direction of the “normal” PSD component requires an orientation of a C–CH₃ bond which is not consistent with the n²-acetone diolate structure. The angular distribution of the CH₃ PSD depends on the acetone coverage. The “off-normal” PSD component dominates at lower acetone coverage (< 0.2 ML), but does not increase at higher coverages in accord with the acetone diolate peak intensity in the infrared reflection-absorption spectra. The “normal” PSD component grows with the acetone coverage up to 0.6 ML. The newly discovered “normal” PSD channel is tentatively assigned to a photo-produced n²- acetone enolate as a potential precursor based on the H/D exchange experiments« less

Gold atoms and clusters on MgO(100) films; an EPR and IRAS study

NASA Astrophysics Data System (ADS)

Yulikov, M.; Sterrer, M.; Risse, T.; Freund, H.-J.

2009-06-01

Single gold atoms deposited on single crystalline MgO(1 0 0) films grown on Mo(1 0 0) are characterized by electron paramagnetic resonance spectroscopy as well as IR spectroscopy using CO as probe molecules. In this article we describe the first angular dependent measurements to determine the principal hyperfine components of a secondary hyperfine interaction, namely, with 17O of the MgO. The values determined here are in perfect agreement with theoretical expectations and corroborate the previously reported binding mechanism of Au atoms on the oxygen anions of the MgO terrace. The temperature dependent EPR data reveal an onset of Au atom mobility at about 80 K while the formation of Au particles occurs only above 125 K. By an analysis of the EPR line width in combination with STM measurements it is possible to deduce an increase of the interatomic distance above 80 K. The Au/CO complexes show a somewhat smaller temperature stability as compared to the Au atoms. The observed thermal stability is in perfect agreement with theoretical predictions for CO desorption.

High performance NO2 sensor using MoS2 nanowires network

NASA Astrophysics Data System (ADS)

Kumar, Rahul; Goel, Neeraj; Kumar, Mahesh

2018-01-01

We report on a high-performance NO2 sensor based on a one dimensional MoS2 nanowire (NW) network. The MoS2 NW network was synthesized using chemical transport reaction through controlled turbulent vapor flow. The crystal structure and surface morphology of MoS2 NWs were confirmed by X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy. Further, the sensing behavior of the nanowires was investigated at different temperatures for various concentrations of NO2 and the sensor exhibited about 2-fold enhanced sensitivity with a low detection limit of 4.6 ppb for NO2 at 60 °C compared to sensitivity at room temperature. Moreover, it showed a fast response (16 s) with complete recovery (172 s) at 60 °C, while sensitivity of the device was decreased at 120 °C. The efficient sensing with reliable selectivity toward NO2 of the nanowires is attributed to a combination of abundant active edge sites along with a large surface area and tuning of the potential barrier at the intersections of nanowires during adsorption/desorption of gas molecules.

Single molecule atomic force microscopy and force spectroscopy of chitosan.

PubMed

Kocun, Marta; Grandbois, Michel; Cuccia, Louis A

2011-02-01

Atomic force microscopy (AFM) and AFM-based force spectroscopy was used to study the desorption of individual chitosan polymer chains from substrates with varying chemical composition. AFM images of chitosan adsorbed onto a flat mica substrate show elongated single strands or aggregated bundles. The aggregated state of the polymer is consistent with the high level of flexibility and mobility expected for a highly positively charged polymer strand. Conversely, the visualization of elongated strands indicated the presence of stabilizing interactions with the substrate. Surfaces with varying chemical composition (glass, self-assembled monolayer of mercaptoundecanoic acid/decanethiol and polytetrafluoroethylene (PTFE)) were probed with chitosan modified AFM tips and the corresponding desorption energies, calculated from plateau-like features, were attributed to the desorption of individual polymer strands. Desorption energies of 2.0±0.3×10(-20)J, 1.8±0.3×10(-20)J and 3.5±0.3×10(-20)J were obtained for glass, SAM of mercaptoundecanoic/dodecanethiol and PTFE, respectively. These single molecule level results can be used as a basis for investigating chitosan and chitosan-based materials for biomaterial applications. Copyright © 2010 Elsevier B.V. All rights reserved.

Graphene oxide decorated with silver nanoparticles as a coating on a stainless-steel fiber for solid-phase microextraction.

PubMed

Wang, Licheng; Hou, Xiudan; Li, Jubai; Liu, Shujuan; Guo, Yong

2015-07-01

A novel graphene oxide decorated with silver nanoparticles coating on a stainless-steel fiber for solid-phase microextraction was prepared. Scanning electron microscopy and X-ray photoelectron spectroscopy were used to characterize the coating surface and showed that silver nanoparticles were dispersed on the wrinkled graphene oxide surface. Coupled to gas chromatography with flame ionization detection, the extraction abilities of the fiber for polycyclic aromatic hydrocarbons were examined in the headspace solid-phase microextraction mode. The extraction parameters including adsorption time, adsorption temperature, salt concentration, desorption time and desorption temperature were investigated. Under the optimized condition, wide linearity with low limits of detection from 2 to 10 ng/L was obtained. The relative standard deviations for single-fiber repeatability and fiber-to-fiber reproducibility were less than 10.6 and 17.5%, respectively. The enrichment factors were from 1712.5 to 4503.7, showing the fiber has good extraction abilities. Moreover, the fiber exhibited a good stability and could be reused for more than 120 times. The established method was also applied for determination of polycyclic aromatic hydrocarbons in two real water samples and the recoveries of analytes ranged from 84.4-116.3% with relative standard deviations less than 16.2%. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Desorption of Mercury(II) on Kaolinite in the Presence of Oxalate or Cysteine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Senevirathna, W. U.; Zhang, Hong; Gu, Baohua

2011-01-01

Sorption and desorption of Hg(II) on clay minerals can impact the biogeochemical cycle and bio- uptake of Hg in aquatic systems. We studied the desorption of Hg(II) on kaolinite in the presence of oxalate or cysteine, representing the ligands with carboxylic and thiol groups of different affinities for Hg(II). The effects of pH (3, 5, 7), ligand concentration (0.25, 1.0 mM), and temperature (15, 25, 35 C) on the Hg(II) desorption were investigated through desorption kinetics. Our study showed that the Hg(II) desorption was pH-dependant. In the absence of any organic ligand, >90% of the previously adsorbed Hg(II) desorbed atmore » pH 3 within 2 h, compared to <10% at pH 7. Similar results were observed in the presence of oxalate, showing that it hardly affected the Hg(II) desorption. Cysteine inhibited the Hg(II) desorption significantly at all the pH tested, especially in the first 80 min with the desorption less than 20%, but it appeared to enhance the Hg(II) desorption afterwards. The effect of ligand concentration on the Hg(II) desorption was small, especially in the presence of oxalate. The effect of temperature on the desorption was nearly insignificant. The effect of the organic acids on the Hg(II) sorption and desorption is explained by the formation of the ternary surface complexes involving the mineral, ligand, and Hg(II). The competition for Hg(II) between the cysteine molecules adsorbed on the particles and in the solution probably can also affect the Hg(II) desorption.« less

Partially-irreversible sorption of formaldehyde in five polymers

NASA Astrophysics Data System (ADS)

Ye, Wei; Cox, Steven S.; Zhao, Xiaomin; Frazier, Charles E.; Little, John C.

2014-12-01

Due to its environmental ubiquity and concern over its potential toxicity, the mass-transfer characteristics of formaldehyde are of critical importance to indoor air quality research. Previous studies have suggested that formaldehyde mass transfer in polymer is partially irreversible. In this study, mechanisms that could cause the observed irreversibility were investigated. Polycarbonate and four other polymeric matrices were selected and subjected to formaldehyde sorption/desorption cycles. Mass transfer of formaldehyde was partially irreversible in all cases, and three potential mechanisms were evaluated. First, attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) analysis was used to investigate possible formaldehyde polymerization on polymer surfaces. ATR-FTIR showed no detectable paraformaldehyde or formaldehyde on the film surfaces that had been exposed to formaldehyde and air. ATR-FTIR did detect aliphatic acids suggesting oxidation had occurred on film surfaces as a result of exposure to formaldehyde. However, additional study suggested that air is not the primary cause for irreversibility. Second, statistical physics theory was tested as a possible explanation. According to this theory, reversible and irreversible sorption could be taking place simultaneously. The irreversible fraction should be constant during sorption and the fraction could be determined by performing a complete sorption/desorption test. The sorption/desorption data was consistent with this theory. Third, chemisorption was considered as another possible cause for irreversibility. Extraction/fluorimetry testing of post-sorption and post-desorption polymer films showed measurable quantities of formaldehyde suggesting that some of the chemisorbed formaldehyde was reversible at the higher extraction temperature. Further quantitative study on chemical reaction products is needed.

Zeolite catalysis in the synthesis of isobutylene from hydrous ethanol

NASA Astrophysics Data System (ADS)

Phillips, Cory Bernard

1999-11-01

This work deals with the synthesis of isobutylene from a hydrous ethanol feedstock over zeolites. The synthesis is accomplished in three steps: (1) low-temperature direct ethanol conversion to ethylene on H-ZSM-5 zeolite, (2) ethylene conversion to butene products over metal-exchanged zeolites, and (3) butene skeletal rearrangement to isobutylene over FER zeolites. The key to understanding and optimizing each synthesis step lies in the ability to control and regulate the zeolite acidity (Bronsted and Lewis)---both strength and number. Therefore, the continuous temperature programmed amine desorption (CTPAD) technique was further developed to simultaneously count the Bronsted acid sites and quantitatively characterize their strength. The adsorption of ethanol, reaction products, amines, coke and ethanol-derived residue (EDR) were monitored gravimetrically using the highly sensitive, novel Tapered Element Oscillating Microreactor (TEOM) apparatus. The TEOM was also used also in conjunction with CTPAD to characterize Bronsted acidity which is a new application for the instrument. For the first synthesis step, a parallel reaction exists which simultaneously produces diethyl ether and ethylene directly over H-ZSM-5. The reaction rates for each pathway were measured directly using a differential reactor operating at low temperatures (<473 K). Water in the ethanol feed enhances the rate of ethylene formation. A mechanism and kinetic expression are proposed for this reaction over H-ZSM-5, with diethyl-ether desorption and ethylene formation as the rate limiting steps. Heat of adsorption values measured from the independent microcalorimetry work reported in the literature are incorporated into the kinetic analysis which reduces the number of regressed parameters. For the remaining synthesis steps, several zeolite structures (ZSM-5, Y, FER) partially exchanged with Pd, Ti, Ni and Au were prepared and tested. It was determined from this screening study that the zeolites containing Pd are the most efficient catalysts for the dimerization reaction. Characterization results from x-ray diffraction (XRD), electron paramagnetic resonance (EPR) spectroscopy, and CTPAD suggest a stable, Pd species with a low oxidation state as part of the active site in Pd-exchanged zeolites. Isobutylene was present in the C4 fraction at reasonable quantities for most of the catalyst candidates, especially those containing an alkali metal co-cation.

Cobalt coated substrate for matrix-free analysis of small molecules by laser desorption/ionization mass spectrometry

NASA Astrophysics Data System (ADS)

Yalcin, Talat; Li, Liang

2009-12-01

Small molecule analysis is one of the most challenging issues in matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. We have developed a cobalt coated substrate as a target for matrix-free analysis of small molecules in laser desorption/ionization mass spectrometry. Cobalt coating of 60-70 nm thickness has been characterized by scanning electron microscopy, energy dispersive X-ray analysis, X-ray diffraction, and laser induced breakdown spectroscopy. This target facilitates hundreds of samples to be spotted and analyzed without mixing any matrices, in a very short time. This can save a lot of time and money and can be a very practical approach for the analysis of small molecules by laser desorption/ionization mass spectrometry.

A study on the reaction between chlorine trifluoride gas and glass-like carbon

NASA Astrophysics Data System (ADS)

Saito, Yoji; Nishizawa, Takashi; Hamaguchi, Maki

2005-02-01

The reaction between glass-like carbon (GC) and chlorine trifluoride (ClF 3) gas was investigated with weight measurements, surface analysis, and gas desorption measurements, where the ClF 3 gas is used for the in situ cleaning of tubes in silicon-related fabrication equipment. From Auger electron spectroscopy and X-ray photoelectron spectroscopy measurements, a carbon mono-fluoride, -(CF) n-, film near the surface of GC is considered to be grown onto the GC surface above 400 °C by the chemical reaction with ClF 3, and this thickness of the fluoride film depends on the temperature. The grown fluoride film desorbs by annealing in a vacuum up to 600 °C. Although GC is apparently etched by ClF 3 over 600 °C, the etch rate of GC is much lower than that of SiC and quartz.

Strong influence of coadsorbate interaction on CO desorption dynamics on Ru(0001) probed by ultrafast x-ray spectroscopy and ab initio simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xin, H.; LaRue, J.; Oberg, H.

2015-04-16

We show that coadsorbed oxygen atoms have a dramatic influence on the CO desorption dynamics from Ru(0001). In contrast to the precursor-mediated desorption mechanism on Ru(0001), the presence of surface oxygen modifies the electronic structure of Ru atoms such that CO desorption occurs predominantly via the direct pathway. This phenomenon is directly observed in an ultrafast pump-probe experiment using a soft x-ray free-electron laser to monitor the dynamic evolution of the valence electronic structure of the surface species. This is supported with the potential of mean force along the CO desorption path obtained from density-functional theory calculations. Charge density distributionmore » and frozen-orbital analysis suggest that the oxygen-induced reduction of the Pauli repulsion, and consequent increase of the dative interaction between the CO 5σ and the charged Ru atom, is the electronic origin of the distinct desorption dynamics. Ab initio molecular dynamics simulations of CO desorption from Ru(0001) and oxygen-coadsorbed Ru(0001) provide further insights into the surface bond-breaking process.« less

Kinetics of electron-induced decomposition of CF2Cl2 coadsorbed with water (ice): A comparison with CCl4

NASA Astrophysics Data System (ADS)

Faradzhev, N. S.; Perry, C. C.; Kusmierek, D. O.; Fairbrother, D. H.; Madey, T. E.

2004-11-01

The kinetics of decomposition and subsequent chemistry of adsorbed CF2Cl2, activated by low-energy electron irradiation, have been examined and compared with CCl4. These molecules have been adsorbed alone and coadsorbed with water ice films of different thicknesses on metal surfaces (Ru; Au) at low temperatures (25 K; 100 K). The studies have been performed with temperature programmed desorption (TPD), reflection absorption infrared spectroscopy (RAIRS), and x-ray photoelectron spectroscopy (XPS). TPD data reveal the efficient decomposition of both halocarbon molecules under electron bombardment, which proceeds via dissociative electron attachment (DEA) of low-energy secondary electrons. The rates of CF2Cl2 and CCl4 dissociation increase in an H2O (D2O) environment (2-3×), but the increase is smaller than that reported in recent literature. The highest initial cross sections for halocarbon decomposition coadsorbed with H2O, using 180 eV incident electrons, are measured (using TPD) to be 1.0±0.2×10-15 cm2 for CF2Cl2 and 2.5±0.2×10-15 cm2 for CCl4. RAIRS and XPS studies confirm the decomposition of halocarbon molecules codeposited with water molecules, and provide insights into the irradiation products. Electron-induced generation of Cl- and F- anions in the halocarbon/water films and production of H3O+, CO2, and intermediate compounds COF2 (for CF2Cl2) and COCl2, C2Cl4 (for CCl4) under electron irradiation have been detected using XPS, TPD, and RAIRS. The products and the decomposition kinetics are similar to those observed in our recent experiments involving x-ray photons as the source of ionizing irradiation.

Chemisorption on the (111) and (100) faces of platinum-tin bimetallic surfaces

NASA Astrophysics Data System (ADS)

Panja, Chameli

2000-10-01

Chemisorption and reaction of CH3OH (methanol), C2H 5OH (ethanol), and H2O (water) on Pt(111) and Sn/Pt(111) alloys, and CO (carbon monoxide), NO (nitric oxide), and C2D 2 (acetylene) on Pt(100) and Sn/Pt(100) have been studied under ultrahigh vacuum conditions using temperature programmed desorption (TPD), Auger electron spectroscopy (AES), low energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS) and high resolution electron energy loss spectroscopy (HREELS). Small organic molecules like CH3OH and C2H5OH are potential fuels for low-temperature hydrocarbon fuel cells and it is important to understand the role of tin as a promoter in electrooxidation of these molecules. Also, the catalytic reactions of CO, NO and C2H2 are of considerable interest for improving of automotive exhaust-gas catalytic converters and other heterogeneous catalysts. Ordered Pt-Sn alloys can be prepared by vapor deposition of Sn on Pt surfaces. A (2 x 2) structure (theta Sn = 0.25) and a (√3x√/3)R30° structure are formed on Pt(111), and a c(2 x 2) and (3√2x√2)R45° structures with theta Sn = 0.5 and 0.67, respectively, are formed on Pt(100). CH3OH, C2H5OH and H2O are all weakly bound and reversibly adsorbed on Pt(111) and both of the Sn/Pt(111) alloys under UHV conditions. Alloying Sn into the Pt(111) surface weakens the adsorption of these molecules from that on Pt(111) and leads to a lower reactivity as the surface concentration of Sn increases. TPD measurements reveal a reduction in the saturation coverage and chemisorption bond energy for CO, NO and C2HL chemisorption, on the two Sn/Pt(100)alloys compared to that on Pt(100). CO chemisorption is completely reversible on these two Sn/Pt(100) alloys. However, NO is partially reduced to form N2O on these alloys, so that N2O along with NO and O2 desorption was observed. We propose that dinitrosyl species, i.e., two NO molecules bound to one Pt atom, are intermediates in N2O formation from adsorbed NO on these Sn/Pt(100) surface alloys. Irreversible dissociative adsorption of acetylene was strongly suppressed (˜80--90%) on both of the two Sn/Pt(100) alloys. About 15% of the adsorbed acetylene monolayer was converted to benzene and desorbed during TPD on the (3√2x√2)R45°Sn/Pt(100) alloy, but no benzene was desorbed from the c(2x2) alloy.

Improved method for producing catalytic carbon and the potential for increasing its use in commercial applications

USGS Publications Warehouse

Kruse, C.W.; Lizzio, A.A.; DeBarr, J.A.; Feizoulof, C.A.

1997-01-01

This paper describes an improved method for producing a catalytic carbon, which was first produced in the late 1960s. The new activated carbon (AC) removes and destroys organic pollutants in aqueous solutions. To determine the effects of altering the pore structure and surface chemistry of activated carbons, carbons differing in the amount of functional groups on their surfaces were prepared in three steps: (1) oxidizing AC with boiling nitric acid, (2) washing oxidized AC with water to remove the acid, and (3) heating oxidized AC to temperatures beteween 100 and 925 ??C. The surfaces of the products were characterized by determining the amount of CO2 and CO evolved during temperature-programmed desorption. Depending on the desorption temperature, these modified carbons showed enhanced adsorptive and/or catalytic properties that included (1) carbon molecular sieves for separating oxygen from nitrogen, (2) increased capacity for adsorbing sulfur dioxide, (3) stronger adsorption of p-nitrophenol from water, and (4) catalysis of dehydrochlorination reactions. A dehydrohalogenation catalyst produced by the oxidation/ desorption steps was found to be similar to one prepared in the 1960s by oxidizing AC with air at 500-700 ??C. The dehydrohalogenation catalyst produced by either the old method or the new method involves an oxidized surface that has been exposed to a 500-700 ??C temperature range. This carbon catalyst retains modified adsorptive properties of the AC from which it is produced. It can be used both to adsorb pollutants from liquid or gaseous streams and to convert them to recyclable products.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Huogen; Chen, Liang

Ti-Zr-Ni quasicrystals have been demonstrated to store a large number of hydrogen atoms, which implies strong potential application in hydrogen energy field for them. However, the desorption of hydrogen atoms in the quasicrystals is quite difficult, with the indication of high desorption temperature and slow desorption rate. The shortage limits their use in the field to a large extent. But this kind of quasicrystals might be used in nuclear fusion energy field, because tritium as a coral fuel for nuclear fusion needs tight storage. However, equilibrium pressure at room temperature of Ti-Zr-Ni quasicrystals, important for their application in fusion energymore » field, has not been clear yet. In this work, we designed a gas-solid reaction system with the pressure resolution of 10{sup −8}Pa and carried out hydrogen desorption investigation at different temperatures on Ti{sub 36}Zr{sub 40}Ni{sub 20}Pd{sub 4} icosahedral quasicrystal. Based on three Pressure-Composition-Temperature desorption curves, we speculate according to Van’t Hoff theory about hydrogen storage that its equilibrium pressure at room temperature could be at the magnitude of 10{sup −6}Pa, displaying good stability of hydrogen in the quasicrystal and also implying application prospects in fusion energy field for quasicrystals of this type.« less

Temperature dependence of liquid lithium film formation and deuterium retention on hot W samples studied by LID-QMS. Implications for future fusion reactors

NASA Astrophysics Data System (ADS)

de Castro, A.; Sepetys, A.; González, M.; Tabarés, F. L.

2018-04-01

Liquid metal (LM) divertor concepts explore an alternative solution to the challenging power/particle exhaust issues in future magnetic fusion reactors. Among them, lithium (Li) is the most promising material. Its use has shown important advantages in terms of improved H-mode plasma confinement and heat handling capabilities. In such scenario, a possible combination of tungsten (W) on the first wall and liquid Li on the divertor could be an acceptable solution, but several issues related to material compatibility remain open. In particular, the co-deposition of Li and hydrogen isotopes on W components could increase the associated tritium retention and represent a safety risk, especially if these co-deposits can uncontrollably grow in remote/plasma shadowed zones of the first wall. In this work, the retention of Li and deuterium (D) on tungsten at different surface temperature (200 °C-400 °C) has been studied by exposing W samples to Li evaporation under several D2 gaseous environments. Deuterium retention in the W-Li films has been quantified by using laser induced desorption-mass spectrometry (LID-QMS). Additional techniques as thermal desorption spectroscopy, secondary ion mass spectrometry, profilemetry and flame atomic emission spectroscopy were implemented to corroborate the retention results and for the qualitative and quantitative characterization of the films. The results showed a negligible (below LID sensibility) D uptake at T surface  =  225 °C, when the W-Li layer is exposed to simultaneous Li evaporation and D2 gas exposition (0.67 Pa). Pre-lithiated samples were also exposed to higher D2 pressures (133.3 Pa) at different temperatures (200 °C-400 °C). A non-linear drastic reduction in the D retention with increasing temperatures was found on the W-Li films, presenting a D/Li atomic ratio at 400 °C lower than 0.1 at.% on a thin film of  ≈100 nm thick. These results bode well (in terms of tritium inventory) for the potential utilization of this material combination in a real reactor scenario.

The effect of H2O on the adsorption of NO2 on γ-Al2O3: an in situ FTIR/MS study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Szanyi, Janos; Kwak, Ja Hun; Chimentao, Ricardo J.

2007-02-15

The effect of water on the adsorption of NO2 onto a γ-Al2O3 catalyst support surface was investigated using Fourier transform infrared spectroscopy (FTIR) and mass spectrometry (MS). Upon room temperature exposure of the alumina surface to small amounts of NO2, nitrites and nitrates are formed, and at higher NO2 doses only nitrates are observed. The surface nitrates formed were of bridging monodentate, bridging bidentate, and monodentate configuration. At elevated NO2 pressures, the surface hydroxyls were consumed in their reaction with NO2 giving primarily bridge-bound nitrates. A significant amount of weakly adsorbed N2O3 was seen as well. Exposure of the NO2-saturatedmore » γ-Al2O3 surface to H2O resulted in the desorption of some NO2 + NO as H2O interacted with the weakly-held N2O3, while the bridging monodentate surface nitrates converted into monodentate nitrates. The conversion of these oxide-bound nitrates to water-solvated nitrates was observed at high water doses when the presence of liquid-like water is expected on the surface. The addition of H2O to the NO2-saturated γ-Al2O3 did not affect the amount of NOx strongly adsorbed on the support surface. In particular, no NOx desorption was observed when the NO2-saturated sample was heated to 573K prior to room temperature H2O exposure. The effect of water is completely reversible; i.e., during TPD experiments following NO2 and H2O coadsorption, the same IR spectra were observed at temperatures above that required for H2O desorption as seen for NO2 adsorption only experiments.« less

A new technique for Auger analysis of surface species subject to electron-induced desorption.

NASA Technical Reports Server (NTRS)

Pepper, S. V.

1973-01-01

A method is presented to observe surface species subject to electron-induced desorption by Auger electron spectroscopy. The surface to be examined is moved under the electron beam at constant velocity, establishing a time-independent condition and eliminating the time response of the electron spectrometer as a limiting factor. The dependence of the Auger signal on the sample velocity, incident electron current, beam diameter, and desorption cross section is analyzed. It is shown that it is advantageous to analyze the moving sample with a high beam current, in contrast to the usual practice of using a low beam current to minimize desorption from a stationary sample. The method is illustrated by the analysis of a friction transfer film of PTFE, in which the fluorine is removed by electron-induced desorption. The method is relevant to surface studies in the field of lubrication and catalysis.

The Effects of Temperature and Oxidation on Deuterium Retention in Solid and Liquid Lithium Films on Molybdenum Plasma-Facing Components

NASA Astrophysics Data System (ADS)

Capece, Angela

2014-10-01

Liquid metal plasma-facing components (PFCs) enable in-situ renewal of the surface, thereby offering a solution to neutron damage, erosion, and thermal fatigue experienced by solid PFCs. Lithium in particular has a high chemical affinity for hydrogen, which has resulted in reduced recycling and enhanced plasma performance on many fusion devices including TFTR, T11-M, FTU, CDX-U, LTX, TJ-II, and NSTX. A key component to the improvement in plasma performance is deuterium retention in Li; however, this process is not well understood in the complex tokamak environment. Recent surface science experiments conducted at the Princeton Plasma Physics Laboratory have used electron spectroscopy and temperature programmed desorption to understand the mechanisms for D retention in Li coatings on Mo substrates. The experiments were designed to give monolayer-control of Li films and were conducted in ultrahigh vacuum under controlled environments. An electron cyclotron resonance plasma source was used to deliver a beam of deuterium ions to the surface over a range of ion energies. Our work shows that D is retained as LiD in metallic Li films. However, when oxygen is present in the film, either by diffusion from the subsurface at high temperature or as a contaminant during the deposition process, Li oxides are formed that retain D as LiOD. Experiments indicate that LiD is more thermally stable than LiOD, which decomposes to liberate D2 gas and D2O at temperatures 100 K lower than the LiD decomposition temperature. Other experiments show how D retention varies with substrate temperature to provide insight into the differences between solid and liquid lithium films. This work was supported by DOE Contract No. DE AC02-09CH11466.

Coverage-Dependent Anchoring of 4,4'-Biphenyl Dicarboxylic Acid to CoO(111) Thin Films.

PubMed

Mohr, Susanne; Schmitt, Tobias; Döpper, Tibor; Xiang, Feifei; Schwarz, Matthias; Görling, Andreas; Schneider, M Alexander; Libuda, Jörg

2017-05-02

We investigated the adsorption behavior of 4,4'-biphenhyl dicarboxylic acid (BDA) on well-ordered CoO(111) films grown on Ir(100) as a function of coverage and temperature using time-resolved and temperature-programmed infrared reflection absorption spectroscopy (TR-IRAS, TP-IRAS) in combination with density functional theory (DFT) and scanning tunneling microscopy (STM) under ultrahigh vacuum (UHV) conditions. To compare the binding behavior of BDA as a function of the oxide film thickness, three different CoO(111) film thicknesses were explored: films of about 20 bilayers (BLs) (approximately 5 nm), 2 BLs, and 1 BL. The two carboxylic acid groups of BDA offer two potential anchoring points to the oxide surface. At 150 K, intact BDA adsorbs on 20 BL thick oxide films in planar geometry with the phenyl rings aligned parallel to the surface. With decreasing oxide film thickness, we observe an increasing tendency for deprotonation and the formation of flat-lying BDA molecules anchored as dicarboxylates. After saturation of the first monolayer, intact BDA multilayers grow with molecules aligned parallel to the surface. The BDA multilayer desorbs at around 360 K. Completely different growth behavior is observed if BDA is deposited above the multilayer desorption temperature. Initially, doubly deprotonated dicarboxylates are formed by adopting a flat-lying orientation. With increasing exposure, however, the adsorbate layer transforms into upright standing monocarboxylates. A sharp OH stretching band (3584 cm -1 ) and a blue-shifted CO stretching band (1759 cm -1 ) indicate weakly interacting apical carboxylic acid groups at the vacuum interface. The anchored monocarboxylate phase slowly desorbs in a temperature range of up to 470 K. At higher temperature, a flat-lying doubly deprotonated BDA is formed, which desorbs and decomposes in a temperature range of up to 600 K.

Understanding the flowing atmospheric-pressure afterglow (FAPA) ambient ionization source through optical means.

PubMed

Shelley, Jacob T; Chan, George C-Y; Hieftje, Gary M

2012-02-01

The advent of ambient desorption/ionization mass spectrometry (ADI-MS) has led to the development of a large number of atmospheric-pressure ionization sources. The largest group of such sources is based on electrical discharges; yet, the desorption and ionization processes that they employ remain largely uncharacterized. Here, the atmospheric-pressure glow discharge (APGD) and afterglow of a helium flowing atmospheric-pressure afterglow (FAPA) ionization source were examined by optical emission spectroscopy. Spatial emission profiles of species created in the APGD and afterglow were recorded under a variety of operating conditions, including discharge current, electrode polarity, and plasma-gas flow rate. From these studies, it was found that an appreciable amount of atmospheric H(2)O vapor, N(2), and O(2) diffuses through the hole in the plate electrode into the discharge to become a major source of reagent ions in ADI-MS analyses. Spatially resolved plasma parameters, such as OH rotational temperature (T(rot)) and electron number density (n(e)), were also measured in the APGD. Maximum values for T(rot) and n(e) were found to be ~1100 K and ~4×10(19) m(-3), respectively, and were both located at the pin cathode. In the afterglow, rotational temperatures from OH and N(2)(+) yielded drastically different values, with OH temperatures matching those obtained from infrared thermography measurements. The higher N(2)(+) temperature is believed to be caused by charge-transfer ionization of N(2) by He(2)(+). These findings are discussed in the context of previously reported ADI-MS analyses with the FAPA source. © American Society for Mass Spectrometry, 2011

Understanding the Flowing Atmospheric-Pressure Afterglow (FAPA) Ambient Ionization Source through Optical Means

NASA Astrophysics Data System (ADS)

Shelley, Jacob T.; Chan, George C.-Y.; Hieftje, Gary M.

2012-02-01

The advent of ambient desorption/ionization mass spectrometry (ADI-MS) has led to the development of a large number of atmospheric-pressure ionization sources. The largest group of such sources is based on electrical discharges; yet, the desorption and ionization processes that they employ remain largely uncharacterized. Here, the atmospheric-pressure glow discharge (APGD) and afterglow of a helium flowing atmospheric-pressure afterglow (FAPA) ionization source were examined by optical emission spectroscopy. Spatial emission profiles of species created in the APGD and afterglow were recorded under a variety of operating conditions, including discharge current, electrode polarity, and plasma-gas flow rate. From these studies, it was found that an appreciable amount of atmospheric H2O vapor, N2, and O2 diffuses through the hole in the plate electrode into the discharge to become a major source of reagent ions in ADI-MS analyses. Spatially resolved plasma parameters, such as OH rotational temperature (Trot) and electron number density (ne), were also measured in the APGD. Maximum values for Trot and ne were found to be ~1100 K and ~4 × 1019 m-3, respectively, and were both located at the pin cathode. In the afterglow, rotational temperatures from OH and N{2/+} yielded drastically different values, with OH temperatures matching those obtained from infrared thermography measurements. The higher N{2/+} temperature is believed to be caused by charge-transfer ionization of N2 by He{2/+}. These findings are discussed in the context of previously reported ADI-MS analyses with the FAPA source.

In-situ Probing of Radiation-induced Processing of Organics in Astrophysical Ice Analogs—Novel Laser Desorption Laser Ionization Time-of-flight Mass Spectroscopic Studies

NASA Astrophysics Data System (ADS)

Gudipati, Murthy S.; Yang, Rui

2012-09-01

Understanding the evolution of organic molecules in ice grains in the interstellar medium (ISM) under cosmic rays, stellar radiation, and local electrons and ions is critical to our understanding of the connection between ISM and solar systems. Our study is aimed at reaching this goal of looking directly into radiation-induced processing in these ice grains. We developed a two-color laser-desorption laser-ionization time-of-flight mass spectroscopic method (2C-MALDI-TOF), similar to matrix-assisted laser desorption and ionization time-of-flight (MALDI-TOF) mass spectroscopy. Results presented here with polycyclic aromatic hydrocarbon (PAH) probe molecules embedded in water-ice at 5 K show for the first time that hydrogenation and oxygenation are the primary chemical reactions that occur in astrophysical ice analogs when subjected to Lyα radiation. We found that hydrogenation can occur over several unsaturated bonds and the product distribution corresponds to their stabilities. Multiple hydrogenation efficiency is found to be higher at higher temperatures (100 K) compared to 5 K—close to the interstellar ice temperatures. Hydroxylation is shown to have similar efficiencies at 5 K or 100 K, indicating that addition of O atoms or OH radicals to pre-ionized PAHs is a barrierless process. These studies—the first glimpses into interstellar ice chemistry through analog studies—show that once accreted onto ice grains PAHs lose their PAH spectroscopic signatures through radiation chemistry, which could be one of the reason for the lack of PAH detection in interstellar ice grains, particularly the outer regions of cold, dense clouds or the upper molecular layers of protoplanetary disks.

Sorption and desorption studies of a reactive azo dye on effective disposal of redundant material.

PubMed

Çelekli, Abuzer; Bozkurt, Hüseyin

2013-07-01

The effective disposal of redundant elephant dung (ED) is important for environmental protection and utilization of resource. The aim of this study was to remove a toxic-azo dye, Reactive Red (RR) 120, using this relatively cheap material as a new adsorbent. The FTIR-ATR spectra of ED powders before and after the sorption of RR 120 and zero point charge (pHzpc) of ED were determined. The sorption capacity of ED for removing of RR 120 were carried out as functions of particle size, adsorbent dose, pH, temperature, ionic strength, initial dye concentration, and contact time. Sorption isotherm, kinetic, activation energy, thermodynamic, and desorption parameters of RR 120 on ED were studied. The sorption process was found to be dependent on particle size, adsorbent dose, pH, temperature, ionic strength, initial dye concentration, and contact time. FTIR-ATR spectroscopy indicated that amine and amide groups have significant role on the sorption of RR 120 on ED. The pHzpc of ED was found to be 7.3. Sorption kinetic of RR 120 on ED was well described by sigmoidal Logistic model. The Langmuir isotherm was well fitted to the equilibrium data. The maximum sorption capacity was 95.71 mg g(-1). The sorption of RR 120 on ED was mainly physical and exothermic according to results of D-R isotherm, Arrhenius equation, thermodynamic, and desorption studies. The thermodynamic parameters showed that this process was feasible and spontaneous. This study showed that ED as a low-cost adsorbent had a great potential for the removal of RR 120 as an alternative eco-friendly process.

Adsorption of Benzoic Acid in Aqueous Solution by Bagasse Fly Ash

NASA Astrophysics Data System (ADS)

Suresh, S.

2012-09-01

This paper reports the studies on the benzoic acid (BA) onto bagasse fly ash (BFA) was studied in aqueous solution in a batch system. Physico-chemical properties including surface area, surface texture of the GAC before and after BA adsorption onto BFA were analysed using X-ray diffractometer (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX). The optimum initial pH for the adsorption of BA was found to be 5.56. The adsorbent dose was 10 g/l for BFA and the equilibrium time 8 h of reaction. Pseudo first and second order models were used to find the adsorption kinetics. It was found that intraparticle diffusion played important role in the adsorption mechanisms of BA and the adsorption kinetics followed pseudo-second order kinetic model rather than the pseudo first order kinetic model. Isotherm data were generated for BA solution having initial concentrations of BA in the range of 10-200 mg/l for the BFA dosage of 10 g/l at temperatures of 288, 303, and 318 K. The adsorption of BA onto BFA was favorably influenced by an increase in temperature. Equilibrium data were well represented by the Redlich-Peterson isotherm model. Values of the change in entropy ( ΔS 0), heat of adsorption ( ΔH 0) for adsorption of BA on BFA was found to be 120.10 and 19.61 kJ/mol respectively. The adsorption of BA onto BFA was an endothermic reaction. Desorption of BA from BFA was studied by various solvents method. Acetic acid was found to be a better eluant for desorption of BA with a maximum desorption efficiency of 55.2 %. Owing to its heating value, spent BFA can be used as a co-fuel for the production of heat in boiler furnaces.

Angle-Dependent Atomic Force Microscopy Single-Chain Pulling of Adsorbed Macromolecules from Planar Surfaces Unveils the Signature of an Adsorption-Desorption Transition.

PubMed

Grebíková, Lucie; Whittington, Stuart G; Vancso, Julius G

2018-05-23

The adsorption-desorption behavior of polymer chains is at the heart of macromolecular surface science and technology. With the current developments in atomic force microscopy (AFM), it has now become possible to address the desorption problem from the perspective of a single macromolecule. Here, we report on desorption of single polymer chains on planar surfaces by AFM-based single molecule force spectroscopy (SMFS) as a function of the pulling angle with respect to the surface-normal direction. SMFS experiments were performed in water with various substrates using different polymers covalently attached to the AFM probe tip. End-grafting at the AFM tip was achieved by surface-initiated polymerization using initiator functionalized tips. We found that the desorption force increases with a decreasing pulling angle, i.e., an enhanced adhesion of the polymer chain was observed. The magnitude of the desorption force shows a weak angular dependence at pulling angles close to the surface normal. A significant increase of the force is observed at shallower pulling from a certain pulling angle. This behavior carries the signature of an adsorption-desorption transition. The angular dependence of the normalized desorption force exhibits a universal behavior. We compared and interpreted our results using theoretical predictions for single-chain adsorption-desorption transitions.

Angle-Dependent Atomic Force Microscopy Single-Chain Pulling of Adsorbed Macromolecules from Planar Surfaces Unveils the Signature of an Adsorption–Desorption Transition

PubMed Central

2018-01-01

The adsorption–desorption behavior of polymer chains is at the heart of macromolecular surface science and technology. With the current developments in atomic force microscopy (AFM), it has now become possible to address the desorption problem from the perspective of a single macromolecule. Here, we report on desorption of single polymer chains on planar surfaces by AFM-based single molecule force spectroscopy (SMFS) as a function of the pulling angle with respect to the surface-normal direction. SMFS experiments were performed in water with various substrates using different polymers covalently attached to the AFM probe tip. End-grafting at the AFM tip was achieved by surface-initiated polymerization using initiator functionalized tips. We found that the desorption force increases with a decreasing pulling angle, i.e., an enhanced adhesion of the polymer chain was observed. The magnitude of the desorption force shows a weak angular dependence at pulling angles close to the surface normal. A significant increase of the force is observed at shallower pulling from a certain pulling angle. This behavior carries the signature of an adsorption–desorption transition. The angular dependence of the normalized desorption force exhibits a universal behavior. We compared and interpreted our results using theoretical predictions for single-chain adsorption–desorption transitions. PMID:29712430

Interaction of hydrogen chloride with alumina. [atmospheric effluent concentrations and interaction of solid rocket propellants used in space shuttle

NASA Technical Reports Server (NTRS)

Bailey, R. R.; Wightman, J. P.

1978-01-01

The influence of temperature, pressure, and outgas conditions on the absorption of hydrogen chloride and water vapor on both alpha and gamma alumina was studied. Characterization of the adsorbents was performed using X-ray powder diffraction, scanning electron microscopy (SEM), low temperature nitrogen adsorption desorption measurements, BET nitrogen surface area measurements and electron spectroscopy for chemical analysis (ESCA). Water vapor adsorption isotherms at 30, 40, and 50 C were measured on alpha and gamma alumina after outgassing at 80, 200, and 400 C. Both outgas temperature and adsorption temperature influenced the adsorption of water vapor on the aluminas. The water vapor adsorption was completely reversible. Alpha alumina absorbed more water per unit area than gamma alumina. Differences in the adsorption capacity for water vapor of the two aluminas were explained on the basis of ideal surface models of alpha and gamma alumina. Isosteric heats of adsorption for water vapor on the aluminas were determined over a limited range of surface coverage.

Electron-stimulated reactions in nanoscale water films adsorbed on (alpha)-Al2O3(0001)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petrik, Nikolay G.; Kimmel, Gregory A.

2018-05-11

The radiation-induced decomposition and desorption of nanoscale amorphous solid water (D2O) films adsorbed on -Al2O3(0001) surface was studied at low temperature in ultrahigh vacuum using temperature programmed desorption (TPD) and electron stimulated desorption (ESD) with a mono-energetic, low energy electron source. ESD yields of molecular products ( D2, O2 and D¬2O) and the total sputtering yield increased with increasing D2O coverage up to ~15 water monolayers (i.e. ~15 1015 cm-2) to a coverage-independent level for thicker water films. Experiments with isotopically-layered water films (D2O and H2O) demonstrated that the highest water decomposition yields occurred at the interfaces of the nanoscalemore » water films with the alumina substrate and vacuum. However, the increased reactivity of the water/alumina interface is relatively small compared to the enhancements in the non-thermal reactions previously observed at the water/Pt(111) and water/TiO2(110) interfaces. We propose that the relatively low activity of Al2O3(0001) for the radiation-induced production of molecular hydrogen is associated with lower reactivity of this surface with hydrogen atoms, which are likely precursors for the molecular hydrogen.« less

Electron-stimulated reactions in nanoscale water films adsorbed on α-Al 2 O 3 (0001)

DOE PAGES

Petrik, Nikolay G.; Kimmel, Greg A.

2018-04-11

The radiation-induced decomposition and desorption of nanoscale amorphous solid water (D 2O) films adsorbed on an α-Al 2O 3(0001) surface was studied at low temperature in ultrahigh vacuum using temperature programmed desorption (TPD) and electron stimulated desorption (ESD) with a mono-energetic, low energy electron source. ESD yields of molecular products (D 2, O 2 and D 2O) and the total sputtering yield increased with increasing D 2O coverage up to ~15 water monolayers (i.e. ~15 x 10 15 cm -2) to a coverage-independent level for thicker water films. Experiments with isotopically-layered water films (D 2O and H 2O) demonstrated thatmore » the highest water decomposition yields occurred at the interfaces of the nanoscale water films with the alumina substrate and vacuum. However, the increased reactivity of the water/alumina interface is relatively small compared to the enhancements in the non-thermal reactions previously observed at the water/Pt(111) and water/TiO 2(110) interfaces. Here, we propose that the relatively low activity of Al 2O 3(0001) for the radiation-induced production of molecular hydrogen is associated with lower reactivity of this surface with hydrogen atoms, which are likely precursors for the formation of molecular hydrogen.« less

Electron-stimulated reactions in nanoscale water films adsorbed on α-Al 2 O 3 (0001)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petrik, Nikolay G.; Kimmel, Greg A.

The radiation-induced decomposition and desorption of nanoscale amorphous solid water (D 2O) films adsorbed on an α-Al 2O 3(0001) surface was studied at low temperature in ultrahigh vacuum using temperature programmed desorption (TPD) and electron stimulated desorption (ESD) with a mono-energetic, low energy electron source. ESD yields of molecular products (D 2, O 2 and D 2O) and the total sputtering yield increased with increasing D 2O coverage up to ~15 water monolayers (i.e. ~15 x 10 15 cm -2) to a coverage-independent level for thicker water films. Experiments with isotopically-layered water films (D 2O and H 2O) demonstrated thatmore » the highest water decomposition yields occurred at the interfaces of the nanoscale water films with the alumina substrate and vacuum. However, the increased reactivity of the water/alumina interface is relatively small compared to the enhancements in the non-thermal reactions previously observed at the water/Pt(111) and water/TiO 2(110) interfaces. Here, we propose that the relatively low activity of Al 2O 3(0001) for the radiation-induced production of molecular hydrogen is associated with lower reactivity of this surface with hydrogen atoms, which are likely precursors for the formation of molecular hydrogen.« less

Modeling of HT and HTO release from irradiated lithium metazirconate

NASA Astrophysics Data System (ADS)

Beloglazov, S.; Nishikawa, M.; Glugla, M.; Kinjyo, T.

2004-08-01

Modeling studies of tritium release from irradiated Li 2ZrO 3 (MAPI) pebbles have been carried out in order to evaluate the effect of purge gas composition on tritium release behavior. The release characteristics were obtained by temperature programmed desorption (TPD) technique in the series of post-irradiation experiments in JRR-4 research reactor of JAERI. Nitrogen with hydrogen at various partial pressures (100 and 1000 Pa) was used as a purge gas. Two sets of ionization chambers and its dedicated electrometers allowed the tritium concentration to be monitored in the chemical form of HT and overall tritium concentration in the mixture HT and HTO simultaneously during desorption runs. The tritium release curves were numerically fitted in order to evaluate the mass transfer coefficients.

Mechanism of Hg(0) oxidation in the presence of HCl over a commercial V2O5-WO3/TiO2 SCR catalyst.

PubMed

Liu, Ruihui; Xu, Wenqing; Tong, Li; Zhu, Tingyu

2015-10-01

Experiments were conducted in a fixed-bed reactor containing a commercial V2O5/WO3/TiO2 catalyst to investigate mercury oxidation in the presence of HCl and O2. Mercury oxidation was improved significantly in the presence of HCl and O2, and the Hg(0) oxidation efficiencies decreased slowly as the temperature increased from 200 to 400°C. Upon pretreatment with HCl and O2 at 350°C, the catalyst demonstrated higher catalytic activity for Hg(0) oxidation. Notably, the effect of pretreatment with HCl alone was not obvious. For the catalyst treated with HCl and O2, better performance was observed with lower reaction temperatures. The results showed that both HCl and Hg(0) were first adsorbed onto the catalyst and then reacted with O2 following its adsorption, which indicates that the oxidation of Hg(0) over the commercial catalyst followed the Langmuir-Hinshelwood mechanism. Several characterization techniques, including Hg(0) temperature-programmed desorption (Hg-TPD) and X-ray photoelectron spectroscopy (XPS), were employed in this work. Hg-TPD profiles showed that weakly adsorbed mercury species were converted to strongly bound species in the presence of HCl and O2. XPS patterns indicated that new chemisorbed oxygen species were formed by the adsorption of HCl, which consequently facilitated the oxidation of mercury. Copyright © 2015. Published by Elsevier B.V.

Reactions of NO2 with BaO/Pt(111) Model Catalysts: The Effects of BaO Film Thickness and NO2 Pressure on the Formation of Ba(NOx)2 Species

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mudiyanselage, Kumudu; Yi, Cheol-Woo; Szanyi, Janos

2011-05-31

The adsorption and reaction of NO2 on BaO (<1, ~3, and >20 monolayer equivalent (MLE))/Pt(111) model systems were studied with temperature programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS), and infrared reflection absorption spectroscopy (IRAS) under ultra-high vacuum (UHV) as well as elevated pressure conditions. NO2 reacts with sub-monolayer BaO (<1 MLE) to form nitrites only, whereas the reaction of NO2 with BaO (~3 MLE)/Pt(111) produces mainly nitrites and a small amount of nitrates under UHV conditions (PNO2 ~ 1.0 × 10-9 Torr) at 300 K. In contrast, a thick BaO(>20 MLE) layer on Pt(111) reacts with NO2 to form nitrite-nitratemore » ion pairs under the same conditions. At elevated NO2 pressures (≥ 1.0 × 10-5 Torr), however, BaO layers at all these three coverages convert to amorphous barium nitrates at 300 K. Upon annealing to 500 K, these amorphous barium nitrate layers transform into crystalline phases. The thermal decomposition of the thus-formed Ba(NOx)2 species is also influenced by the coverage of BaO on the Pt(111) substrate: at low BaO coverages, these species decompose at significantly lower temperatures in comparison with those formed on thick BaO films due to the presence of Ba(NOx)2/Pt interface where the decomposition can proceed at lower temperatures. However, the thermal decomposition of the thick Ba(NO3)2 films follows that of bulk nitrates. Results obtained from these BaO/Pt(111) model systems under UHV and elevated pressure conditions clearly demonstrate that both the BaO film thickness and the applied NO2 pressure are critical in the Ba(NOx)2 formation and subsequent thermal decomposition processes.« less

Energy transfer and photochemistry on a metal surface: Mo(CO)/sub 6/ on Rh(100)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Germer, T.A.; Ho, W.

1989-05-01

The occurrence of photoinduced reactions on solid surfaces depends on the relative rates between the excited-state decomposition and the energy transfer to the surface. In this study, the photodecomposition of Mo(CO)/sub 6/ on Rh(100) at 90 K by 325-nm UV irradiation has been studied as a function of coverage and surface preparation using thermal desorption spectroscopy, electron energy-loss spectroscopy, and photoinduced desorption spectroscopy. It is found that Mo(CO)/sub 6/ adsorbs dissociatively on Rh(100) into carbonyl fragments and CO in the first monolayer and molecularly in multilayers. Photoinduced desorption of CO is observed for the multilayers adsorbed onto the dissociated firstmore » layer via a nonthermal electronic excitation of adsorbed metal carbonyls. The presence of the metal surface prevents complete decarbonylation as in the gas phase; deexcitation of electronically excited carbonyls is not sufficiently fast to quench all the observed photochemistry. It is also found that Mo(CO)/sub 6/ adsorbs molecularly on a presaturated CO ordered overlayer on Rh(100) and undergoes photodissociation to a greater degree than on the dissociated and disordered surface of carbonyl fragments. The ordered CO layer effectively screens the interaction between the molecular carbonyls and the Rh(100) layer surface.« less

Effect of Iron(II) on Arsenic Sequestration by δ-MnO 2 : Desorption Studies Using Stirred-Flow Experiments and X-Ray Absorption Fine-Structure Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Yun; Li, Wei; Sparks, Donald L.

2015-10-18

Arsenic (As) mobility in the environment is greatly affected by its oxidation state and the degree to which it is sorbed on metal oxide surfaces. Manganese (Mn) and iron (Fe) oxides are ubiquitous solids in terrestrial systems and have high sorptive capacities for many trace metals, including As. Although numerous studies have studied the effects of As adsorption and desorption onto Fe and Mn oxides individually, the fate of As within mixed systems representative of natural environments has not been resolved. In this research, As(III) was initially reacted with a poorly crystalline phyllomanganate (δ-MnO 2) in the presence of Fe(II)more » prior to desorption. This initial reaction resulted in the sorption of both As(III) and As(V) on mixed Fe/Mn-oxides surfaces. A desorption study was carried out using two environmentally significant ions, phosphate (PO 4 3–) and calcium (Ca 2+). Both a stirred-flow technique and X-ray absorption fine-structure spectroscopy (XAFS) analysis were used to investigate As desorption behavior. Results showed that when As(III)/Fe(II) = 1:1 in the initial reaction, only As(V) was desorbed, agreeing with a previous study showing that As(III) is not associated with the Fe/Mn-oxides. When As(III)/Fe(II) = 1:10 in the initial reaction, both As(III) and As(V) can be desorbed from the Fe/Mn-oxide surface, and more As(III) is desorbed than As(V). Neither of the desorbents used in this study completely removed As(III) or As(V) from the Fe/Mn-oxides surface. However, the As desorption fraction decreases with increasing Fe(II) concentration in the initial reactions.« less

Effect of Iron(II) on Arsenic Sequestration by δ-MnO2: Desorption Studies Using Stirred-Flow Experiments and X-Ray Absorption Fine-Structure Spectroscopy.

PubMed

Wu, Yun; Li, Wei; Sparks, Donald L

2015-11-17

Arsenic (As) mobility in the environment is greatly affected by its oxidation state and the degree to which it is sorbed on metal oxide surfaces. Manganese (Mn) and iron (Fe) oxides are ubiquitous solids in terrestrial systems and have high sorptive capacities for many trace metals, including As. Although numerous studies have studied the effects of As adsorption and desorption onto Fe and Mn oxides individually, the fate of As within mixed systems representative of natural environments has not been resolved. In this research, As(III) was initially reacted with a poorly crystalline phyllomanganate (δ-MnO2) in the presence of Fe(II) prior to desorption. This initial reaction resulted in the sorption of both As(III) and As(V) on mixed Fe/Mn-oxides surfaces. A desorption study was carried out using two environmentally significant ions, phosphate (PO4(3-)) and calcium (Ca(2+)). Both a stirred-flow technique and X-ray absorption fine-structure spectroscopy (XAFS) analysis were used to investigate As desorption behavior. Results showed that when As(III)/Fe(II) = 1:1 in the initial reaction, only As(V) was desorbed, agreeing with a previous study showing that As(III) is not associated with the Fe/Mn-oxides. When As(III)/Fe(II) = 1:10 in the initial reaction, both As(III) and As(V) can be desorbed from the Fe/Mn-oxide surface, and more As(III) is desorbed than As(V). Neither of the desorbents used in this study completely removed As(III) or As(V) from the Fe/Mn-oxides surface. However, the As desorption fraction decreases with increasing Fe(II) concentration in the initial reactions.

MEASUREMENT OF VOCS DESORBED FROM BUILDING MATERIALS--A HIGH TEMPERATURE DYNAMIC CHAMBER METHOD

EPA Science Inventory

Mass balance is a commonly used approach for characterizing the source and sink behavior of building materials. Because the traditional sink test methods evaluate the adsorption and desorption of volatile organic compounds (VOC) at ambient temperatures, the desorption process is...

Distribution and removal of organochlorine pesticides in waste clay bricks from an abandoned manufacturing plant using low-temperature thermal desorption technology.

PubMed

Cong, Xin; Li, Fasheng; Kelly, Ryan M; Xue, Nandong

2018-04-01

The distribution of pollutants in waste clay bricks from an organochlorine pesticide-contaminated site was investigated, and removal of the pollutants using a thermal desorption technology was studied. The results showed that the contents of HCHs in both the surface and the inner layer of the bricks were slightly higher than those of DDTs. The total pore volume of the bricks was 37.7 to 41.6% with an increase from external to internal surfaces. The removal efficiency by thermal treatment was within 62 to 83% for HCHs and DDTs in bricks when the temperature was raised from 200 to 250 °C after 1 h. HCHs were more easily removed than DDTs with a higher temperature. Either intraparticle or surface diffusion controls the desorption processes of pollutants in bricks. It was feasible to use the polluted bricks after removal of the pollutants by low-temperature thermal desorption technology.

Manganese Oxide Nanoarray-Based Monolithic Catalysts: Tunable Morphology and High Efficiency for CO Oxidation

DOE PAGES

Chen, Sheng-Yu; Song, Wenqiao; Lin, Hui-Jan; ...

2016-03-08

In this work, a generic one-pot hydrothermal synthesis route has been successfully designed and utilized to in situ grow uniform manganese oxide nanorods and nanowires onto the cordierite honeycomb monolithic substrates, forming a series of nanoarray-based monolithic catalysts. During the synthesis process, three types of potassium salt oxidants have been used with different reduction potentials, i.e., K 2Cr 2O 7, KClO 3, and K 2S 2O 8, denoted as HM-DCM, HM-PCR, and HM-PSF, respectively. The different reduction potentials of the manganese source (Mn 2+) and oxidants induced the formation of manganese oxide nanoarrays with different morphology, surface area, and reactivitymore » of carbon monoxide (CO) oxidation. K 2Cr 2O 7 and KClO 3 can induce sharp and long nanowires with slow growth rates due to their low reduction potentials. In comparison, the nanoarrays of HM-PSF presented shorter nanorods but displayed an efficient 90% CO oxidation conversion at 200 °C (T90) without noble-metal loading. Reducibility tests for the three monolithic catalysts by hydrogen temperature-programmed reduction revealed an activation energy order of HM-PSF > HM-DCM > HM-PCR for CO oxidation. The characterizations of oxygen temperature-programmed desorption and X-ray photoelectron spectroscopy indicated the abundant surface-adsorbed oxygen and lattice oxygen contributing to the superior reactivity of HM-PSF. Finally, the straightforward synthetic process showed a scalable, low-cost, and template-free method to fabricate manganese oxide nanoarray monolithic catalysts for exhaust treatment.« less

Interfacial chemistry of a perfluoropolyether lubricant studied by X-ray photoelectron spectroscopy and temperature desorption spectroscopy

NASA Technical Reports Server (NTRS)

Herrera-Fierro, Pilar; Jones, William R., Jr.; Pepper, Stephen V.

1993-01-01

The interfacial chemistry of Fomblin Z25, a commercial perfluoropolyether used as lubricant for space applications was studied with different metallic surfaces: 440C steel, gold, and aluminum. Thin layers of Fomblin Z25 were evaporated onto the oxide-free substrates, and the interfacial chemistry was studied using XPS and TDS. The reactions were induced by heating the substrate and by rubbing the substrate with a steel ball. Gold was found to be completely unreactive towards Fomblin at any temperature. Reaction at room temperature was observed only in the case of the aluminum substrate, the most reactive towards Fomblin Z25 of the substrates studied. It was necessary to heat the 440C steel substrate to 190 C to induce decomposition of the fluid. The degradation of the fluid was indicated by the formation of a debris layer at the interface. This debris layer, composed of inorganic and organic reaction products, when completely formed, passivated the surface from further attack to the Fromblin on top. The tribologically induced reactions on 440C steel formed a debris layer of similar chemical characteristics to the thermally induced layer. In all cases, the degradation reaction resulted in preferential consumption of the difluoroformyl carbon (-OCF2O-).

Reflectance-difference spectroscopy of GaAs crystal growth by OMCVD

NASA Astrophysics Data System (ADS)

Colas, Etienne G.; Aspnes, David E.; Bhat, Rajaram J.; Studna, A. A.; Koza, M. A.; Keramidas, Vassilis G.

1990-02-01

This paper summarizes results of our investigations of growth on (001) and (110) GaAs by atmospheric-pressure organometallic chemical vapor deposition (OMCVD). We follow evolutions of surface species to a sensitivity of 0.01 monolayer (ML) on a time scale of 0.1 s under alternating flows of trimethylgallium (TMG) and arsine (AsH3) as functions of partial pressure, sample temperature, and surface orienta-tion. The reaction of TMG with an AsH3-saturated (001) surface is rate-limited by com-petition between desorption and decomposition of TMG molecules chemisorbed to surface lattice sites via an excluded-volume mechanism, while the reaction of AsH3 with the TMG-saturated (001) surface is essentially instantaneous. In contrast, TMG reacts essentially instantaneously with the AsH3 -saturated (110) surface while the AsH3 reaction with the TMG-saturated (110) surface is the rate-limiting step. However, the latter rate is not intrinsic to the AsH3-surface reaction but appears to be determined by desorption of adsorbed species that block active sites.

Enhancement of deuterium retention in damaged tungsten by plasma-induced defect clustering

NASA Astrophysics Data System (ADS)

Jin, Younggil; Roh, Ki-Baek; Sheen, Mi-Hyang; Kim, Nam-Kyun; Song, Jaemin; Kim, Young-Woon; Kim, Gon-Ho

2017-12-01

The enhancement of deuterium retention was investigated for tungsten in the presence of both 2.8 MeV self-ion induced cascade damage and fuel hydrogen isotope plasma. Vacancy clustering in cascade damaged polycrystalline tungsten occurred due to deuterium irradiation and was observed near the grain boundary by using all-step transmission electron microscopy analysis. Analysis of the highest desorption temperature peak using thermal desorption spectroscopy supports reasonable evidence of defect clustering in the damaged polycrystalline tungsten. The defect clustering was neither observed on the damaged polycrystalline tungsten without deuterium irradiation nor on the damaged single-crystalline tungsten with deuterium irradiation. This result implies the synergetic role of deuterium and grain boundary on defect clustering. This study proposes a path for the defect transform from point defect to defect cluster, by the agglomeration between irradiated deuterium and cascade damage-induced defect. This agglomeration may induce more severe damage on the tungsten divertor at which the high fuel hydrogen ions, fast neutrons, and self-ions are irradiated simultaneously and it would increase the in-vessel tritium inventory.

A star-shaped polythiophene dendrimer coating for solid-phase microextraction of triazole agrochemicals.

PubMed

Abolghasemi, Mir Mahdi; Habibiyan, Rahim; Jaymand, Mehdi; Piryaei, Marzieh

2018-02-14

A nanostructured star-shaped polythiophene dendrimer was prepared and used as a fiber coating for headspace solid phase microextraction of selected triazolic pesticides (tebuconazole, hexaconazole, penconazole, diniconazole, difenoconazole, triticonazole) from water samples. The dendrimer with its large surface area was characterized by thermogravimetric analysis, UV-Vis spectroscopy and field emission scanning electron microscopy. It was placed on a stainless steel wire for use in SPME. The experimental conditions for fiber coating, extraction, stirring rate, ionic strength, pH value, desorption temperature and time were optimized. Following thermal desorption, the pesticides were quantified by GC-MS. Under optimum conditions, the repeatability (RSD) for one fiber (for n = 3) ranges from 4.3 to 5.6%. The detection limits are between 8 and 12 pg mL -1 . The method is fast, inexpensive (in terms of equipment), and the fiber has high thermal stability. Graphical abstract Schematic presentation of a nanostructured star-shaped polythiophene dendrimer for use in headspace solid phase microextraction of the triazolic pesticides (tebuconazole, hexaconazole, penconazole, diniconazole, difenoconazole, triticonazole). They were then quantified by gas chromatography-mass spectrometry.

Probing the interaction of noble gases with pristine and nitrogen-doped graphene through Raman spectroscopy

NASA Astrophysics Data System (ADS)

Cunha, Renato; Perea-López, Néstor; Elías, Ana Laura; Fujisawa, Kazunori; Carozo, Victor; Feng, Simin; Lv, Ruitao; dos Santos, Maria Cristina; Terrones, Mauricio; Araujo, Paulo T.

2018-05-01

The interactions of adsorbates with graphene have received increasing attention due to its importance in the development of applications involving graphene-based coatings. Here, we present a study of the adsorption of noble gases on pristine and nitrogen-doped graphene. Single-layer graphene samples were synthesized by chemical vapor deposition (CVD) and transferred to transmission electron microscopy (TEM) grids. Several noble gases were allowed to adsorb on the suspended graphene substrate at very low temperatures. Raman spectra show distinct frequency blue shifts in both the 2D and G bands, which are induced by gas adsorption onto high quality single layer graphene (1LG). These shifts, which we associate with compressive biaxial strain in the graphene layers induced by the noble gases, are negligible for nitrogen-doped graphene. Additionally, a thermal depinning transition, which is related to the desorption of a noble gas layer from the graphene surface at low temperatures (ranging from 20 to 35 K), was also observed at different transition temperatures for different noble gases. These transition temperatures were found to be 25 K for argon and 35 K for xenon. Moreover, we were able to obtain values for the compressive biaxial strain in graphene induced by the adsorbed layer of noble gases, using Raman spectroscopy. Ab initio calculations confirmed the correlation between the noble gas-induced strain and the changes in the Raman features observed.

Experimentally Determined Binding Energies of Astrophysically Relevant Hydrocarbons in Pure and H2O-Layered Ices

NASA Astrophysics Data System (ADS)

Behmard, Aida; Graninger, Dawn; Fayolle, Edith; Oberg, Karin I.

2017-01-01

Small hydrocarbons represent an important organic reservoir in a variety of interstellar environments. Constraints on desorption temperatures and binding energies of hydrocarbons are thus necessary for accurate predictions of where and in which phase these molecules exist. Through a series of temperature programmed desorption experiments, we determined binding energies of 1, 2, and 3-carbon interstellar hydrocarbons (CH4, C2H2, C2H4, C2H6, C3H4, C3H6, and C3H8) in pure ices and in relation to water ice, the dominant ice constituent during star and planet formation. These empirically determined values can be used to inform observations and models of the molecular spatial distribution in protoplanetary disks, thus providing insight into planetesimal composition. In addition, knowledge of hydrocarbon binding energies will refine simulations of grain surface chemistry, allowing for better predictions of the chemical conditions that lead to the production of complex organic molecules vital for life.

Acetone Chemistry on Oxidized and Reduced TiO 2(110)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Henderson, Michael A

2004-12-09

The chemistry of acetone on the oxidized and reduced surfaces of TiO 2(110) was examined using temperature programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS). The reduced surface was prepared with about 7% oxygen vacancy sites by annealing in ultrahigh vacuum (UHV) at 850 K, and the oxidized surface was prepared by exposure of the reduced surface to molecular oxygen at 95 K followed by heating the surface to a variety of temperatures between 200 and 500 K. Acetone adsorbs molecularly on the reduced surface with no evidence for either decomposition or preferential binding at vacancy sites.more » Based on HREELS, the majority of acetone molecules adsorbed in an η¹ configuration at Ti⁴⁺ sites through interaction of lone pair electrons on the carbonyl oxygen atom. Repulsive acetone-acetone interactions shift the desorption peak from 345 K at low coverage to 175 K as the first layer saturates with a coverage of ~ 1 ML. In contrast, about 7% of the acetone adlayer decomposes when the surface is pretreated with molecular oxygen. Acetate is among the detected decomposition products, but only comprises about 1/3rd of the amount of acetone decomposed and its yield depends on the temperature at which the O₂ exposed surface was preheated to prior to acetone adsorption. Aside from the small level of irreversible decomposition, about 0.25 ML of acetone is stabilized to 375 K by coadsorbed oxygen. These acetone species exhibit an HREELS spectrum unlike that of η¹-acetone or of any other species proposed to exist from the interaction of acetone with TiO₂ powders. Based on the presence of extensive ¹⁶O/¹⁸O exchange between acetone and coadsorbed oxygen in the 375 K acetone TPD state, it is proposed that a polymeric form of acetone forms on the TiO₂(110) surface through nucleophilic attack of oxygen on the carbonyl carbon atom of acetone, and is propagated to neighboring η¹-acetone molecules. This process is initiated at temperatures as low as 135 K based on HREELS. Although the dominant thermal pathway of this surface species is to liberate acetone in UHV, it may be a key intermediate in acetone thermal and photolytic chemistry on TiO₂ surfaces.« less

Studies of solid carbon dioxide in interstellar ice analogs subject to thermal processing

NASA Astrophysics Data System (ADS)

White, Douglas W.

2010-09-01

Solid CO2 has been detected in many lines of sight in the interstellar medium from infrared observatories. Spectral profiles from space-based observatories have suggested that CO2 on icy grain mantles is mixed with other common molecules such as H2O and CH 3OH in interstellar regions and that thermal annealing has occurred. The vibrational mode at 658 cm-1 (15.2 mum) is suspected to be a powerful diagnostic tool as to the composition of species on icy grain mantles as well as thermal histories. However, previous studies have not systematically investigated ice composition and temperature. Laboratory spectra of interstellar ice analogs have been created in this study order to better understand the physical properties of solid CO2 in these interstellar environments. Existing databases of ice composition studies and effects of ice thermal history were updated in this study to include a more systematic approach. The 658 cm-1 (15.2 mum) bending mode feature of CO2 is examined here and the subsequent astrophysical implications stated. In the first set of experiments, 47 mixtures of H2O,CH3OH, andCO2 were slowly warmed and mid-infrared absorption spectra were recorded at 5K intervals. The second set of experiments involved examining the CO2 bending mode feature of 10 different CO2-containing ice mixtures at different temperatures where ice segregation was suspected. In these experiments, the ice mixtures were slowly heated to the desired temperature for increasing time intervals before cooling down and recording mid-IR absorption spectra. These studies may be used to analyze IR data from space-based observatories such as the Spitzer Space Telescope Infrared Spectrograph as well other future IR observations of the interstellar medium. Finally, mass spectroscopy measurements were taken from temperature programmed desorption (TPD) experiments performed on several binary mixtures of H2O + CO2 and CH 3OH + CO2. Physical properties such as desorption energy of CO2 can be determined from the TPD traces of these experiments. The work provided here addresses the physical properties of solid CO 2 thermally processed in ice mixtures in interstellar environments by laboratory simulations spectroscopically analyzed by mid-infrared absorption profiles and TPD.

Physics of lithium bromide (LiBr) solution dewatering through vapor venting membranes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Isfahani, RN; Fazeli, A; Bigham, S

2014-01-01

The physics of water desorption from a lithium bromide (LiBr) solution flow through an array of microchannels capped by a porous membrane is studied. The membrane allows the vapor to exit the flow and retains the liquid. Effects of different parameters such as wall temperature, solution and vapor pressures, and solution mass flux on the desorption rate were studied. Two different mechanisms of desorption are analyzed. These mechanisms consisted of: (1) direct diffusion of water molecules out of the solution and their subsequent flow through the membrane and (2) formation of water vapor bubbles within the solution and their ventingmore » through the membrane. Direct diffusion was the dominant desorption mode at low surface temperatures and its magnitude was directly related to the vapor pressure, the solution concentration, and the heated wall temperature. Desorption at the boiling regime was predominantly controlled by the solution flow pressure and mass flux. Microscale visualization studies suggested that at a critical mass flux, some bubbles are carried out of the desorber through the solution microchannels rather than being vented through the membrane. Overall, an order of magnitude higher desorption rate compare to a previous study on a membrane-based desorber was achieved. Published by Elsevier Ltd.« less

Effect of K loadings on nitrate formation/decomposition and on NOx storage performance of K-based NOx storage-reduction catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Do Heui; Mudiyanselage, Kumudu K.; Szanyi, Janos

2013-10-25

We have investigated nitrate formation and decomposition processes, and measured NOx storage performance on Pt-K2O/Al2O3 catalysts as a function of potassium loading. After NO2 adsorption at room temperature, ionic and bidentate nitrates were observed by fourier transform infra-red (FTIR) spectroscopy. The ratio of the former to the latter species increased with increasing potassium loading up to 10 wt%, and then stayed almost constant with additional K, demonstrating a clear dependence of loading on the morphology of the K species. Although both K2O(10)/Al2O3 and K2O(20)/Al2O3 samples have similar nitrate species after NO2 adsorption, the latter has more thermally stable nitrate speciesmore » as evidenced by FTIR and NO2 temperature programmed desorption (TPD) results. With regard to NOx storage performance, the temperature of maximum NOx uptake (Tmax) is 573 K up to a potassium loading of 10 wt%. As the potassium loading increases from 10 wt% to 20 wt%, Tmax shifted from 573 K to 723 K. Moreover, the amount of NO uptake (38 cm3 NOx/g catal) at Tmax increased more than three times, indicating that efficiency of K in storing NOx is enhanced significantly at higher temperature, in good agreement with the NO2 TPD and FTIR results. Thus, a combination of characterization and NOx storage performance results demonstrates an unexpected effect of potassium loading on nitrate formation and decomposition processes; results important for developing Pt-K2O/Al2O3 for potential applications as high temperature NOx storage-reduction catalysts.« less

CHARACTERISTICS OF MERCURY DESORPTION FROM SORBENTS AT ELEVATED TEMPERATURES. (R822721C697)

EPA Science Inventory

This study investigated the dynamic desorption characteristics of mercury during the thermal treatment of mercury-loaded sorbents at elevated temperatures under fixed-bed operations. Experiments were carried out in a 25.4 mm ID quartz bed enclosed in an electric furnace. ...

CHARACTERISTICS OF MERCURY DESORPTION FROM SORBENTS AT ELEVATED TEMPERATURES. (R826694C697)

EPA Science Inventory

This study investigated the dynamic desorption characteristics of mercury during the thermal treatment of mercury-loaded sorbents at elevated temperatures under fixed-bed operations. Experiments were carried out in a 25.4 mm ID quartz bed enclosed in an electric furnace. ...

Chitosan coatings onto polyethylene terephthalate for the development of potential active packaging material

NASA Astrophysics Data System (ADS)

Zemljič, Lidija Fras; Tkavc, Tina; Vesel, Alenka; Šauperl, Olivera

2013-01-01

In this paper advanced surface treatment of PET plastic film is presented for introduction of antimicrobial properties as a potential application for food (as for example meat) packaging material. Adsorption/desorption of chitosan onto PET plastic film surface was studied using several analytical techniques such as: X-Ray Photoelectron Spectroscopy (XPS), ATR-FTIR spectroscopy and titrations. Kinetic desorption of chitosan from PET surface was analysed by polyelectrolyte titration and spectrophotometric Ninhydrine reaction. Standard antimicrobial test ASTM E2149-01 was performed for functionalised PET materials in order to determine their antimicrobial properties; i. e. to measure the reductions of some of the meat pathogens; such as bacteria Salmonella enterica, Campylobacter spp., Escherichia coli, Listeria monocytogenes and fungi Candida albicans.

Comparison of Ti-Based Coatings on Silicon Nanowires for Phosphopeptide Enrichment and Their Laser Assisted Desorption/Ionization Mass Spectrometry Detection

PubMed Central

Kurylo, Ievgen; Hamdi, Abderrahmane; Addad, Ahmed; Coffinier, Yannick

2017-01-01

We created different TiO2-based coatings on silicon nanowires (SiNWs) by using either thermal metallization or atomic layer deposition (ALD). The fabricated surfaces were characterized by X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDX), and reflectivity measurements. Surfaces with different TiO2 based coating thicknesses were then used for phosphopeptide enrichment and subsequent detection by laser desorption/ionization mass spectrometry (LDI-MS). Results showed that the best enrichment and LDI-MS detection were obtained using the silicon nanowires covered with 10 nm of oxidized Ti deposited by means of thermal evaporation. This sample was also able to perform phosphopeptide enrichment and MS detection from serum. PMID:28914806

Selective liquid phase oxidation of benzyl alcohol to benzaldehyde by tert-butyl hydroperoxide over γ-Al2O3 supported copper and gold nanoparticles

NASA Astrophysics Data System (ADS)

Ndolomingo, Matumuene Joe; Meijboom, Reinout

2017-03-01

Benzyl alcohol oxidation to benzaldehyde was performed by tert-butyl hydroperoxide (TBHP) in the absence of any solvent using γ-Al2O3 supported copper and gold nanoparticles. Li2O and ionic liquids were used as additive and stabilizers for the synthesis of the catalysts. The physico-chemical properties of the catalysts were characterized by atomic absorption spectroscopy (AAS), X-ray diffraction spectroscopy (XRD), N2 absorption/desorption (BET), transmission electron microscopy (TEM), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and temperature programmed reduction (TPR), whereas, the oxidation reaction was followed by gas chromatography with a flame ionization detector (GC-FID). The as prepared catalysts exhibited good catalytic performance in terms of conversion and selectivity towards benzaldehyde. The performance of the Au-based catalysts is significantly higher than that of the Cu-based catalysts. For both Cu and Au catalysts, the conversion of benzyl alcohol increased as the reaction proceeds, while the selectivity for benzaldehyde decreased. Moreover, the catalysts can be easily recycled and reused with neither significant loss of activity nor selectivity. A kinetic study for the Cu and Au-catalyzed oxidation of benzyl alcohol to benzyldehyde is reported. The rate at which the oxidation of benzyl alcohol is occurring as a function of catalyst and oxidant amounts was investigated, with the apparent rate constant, kapp being proportional to the amount of nano catalyst and oxygen present in the system.

The Role of Low-Energy (less than 20 eV) Electrons in Astrochemistry: A Tale of Two Molecules

NASA Astrophysics Data System (ADS)

Arumainayagam, Chris

2016-07-01

In the interstellar medium, UV photolysis of ice mantles encasing dust grains is thought to be the mechanism that drives the synthesis of "complex" molecules. The source of this reaction-initiating UV light is assumed to be local because externally-sourced UV radiation cannot pass through the ice-containing dark, dense molecular clouds. Externally sourced cosmic rays (E_{max} ˜10^{20} eV), in addition to producing UV light within these clouds, also produce large numbers of low-energy (≤ 20 eV) secondary electrons. The goal of our studies is to understand the low-energy electron-induced processes that occur when high-energy cosmic rays interact with interstellar ices. Using electron stimulated desorption (ESD), post-irradiation temperature-programmed desorption (TPD), and infrared reflection absorption spectroscopy (IRAS), we have investigated the radiolysis initiated by electrons in condensed methanol and ammonia at ˜90K under ultrahigh vacuum (1 × 10^{-9} Torr) conditions. We have identified fifteen low-energy electron-induced methanol radiolysis products, many of which have been previously identified as being formed by methanol UV photolysis in the interstellar medium. We have also found evidence for the electron-induced formation from ammonia of hydrazine (N_2 H_4), diazene (N_2 H_2), cyclotriazane/triazene (N_3 H_3) and triazane (N_3 H_5). We have investigated the reaction yields' dependence on film thickness, irradiation time, incident current, electron energy, and metal substrate. These results provide a basis from which we can begin to understand the mechanisms by which methanol and ammonia can form more complex species in cosmic ices. Studies such as ours may ultimately help us better understand the initial stages of the genesis of life.

The Role of Low-Energy Electrons in Astrochemistry: A Tale of Two Molecules

NASA Astrophysics Data System (ADS)

Arumainayagam, Chris; Cambell, Jyoti; Leon Sanche, Michael Boyer, and Petra Swiderek.

2016-06-01

In the interstellar medium, UV photolysis of ice mantles encasing dust grains is thought to be the mechanism that drives the synthesis of “complex” molecules. The source of this reaction-initiating UV light is assumed to be local because externally-sourced UV radiation cannot pass through the ice-containing dark, dense molecular clouds. Externally sourced cosmic rays (Emax ~ 1020 eV), in addition to producing UV light within these clouds, also produce large numbers of low-energy (≤ 20 eV) secondary electrons. The goal of our studies is to understand the low-energy electron-induced processes that occur when high-energy cosmic rays interact with interstellar ices. Using electron stimulated desorption (ESD), post-irradiation temperature-programmed desorption (TPD), and infrared reflection absorption spectroscopy (IRAS), we have investigated the radiolysis initiated by electrons in condensed methanol and ammonia at ~ 90 K under ultrahigh vacuum (1×10-9 Torr) conditions. We have identified fifteen low-energy (≤ 20 eV) electron-induced methanol radiolysis products, many of which have been previously identified as being formed by methanol UV photolysis in the interstellar medium. We have also found evidence for the electron-induced formation from ammonia of hydrazine (N2H4), diazene (N2H2), cyclotriazane/triazene (N3H3) and triazane (N3H5). We have investigated the reaction yields’ dependence on film thickness, irradiation time, incident current, electron energy, and metal substrate. These results provide a basis from which we can begin to understand the mechanisms by which methanol and ammonia can form more complex species in cosmic ices. Studies such as ours may ultimately help us better understand the initial stages of the genesis of life.

Robust Mesoporous CoMo/γ-Al2O3 Catalysts from Cyclodextrin-Based Supramolecular Assemblies for Hydrothermal Processing of Microalgae: Effect of the Preparation Method.

PubMed

Bleta, Rudina; Schiavo, Benedetto; Corsaro, Natale; Costa, Paula; Giaconia, Alberto; Interrante, Leonardo; Monflier, Eric; Pipitone, Giuseppe; Ponchel, Anne; Sau, Salvatore; Scialdone, Onofrio; Tilloy, Sébastien; Galia, Alessandro

2018-04-18

Hydrothermal liquefaction (HTL) is a promising technology for the production of biocrude oil from microalgae. Although this catalyst-free technology is efficient under high-temperature and high-pressure conditions, the biocrude yield and quality can be further improved by using heterogeneous catalysts. The design of robust catalysts that preserve their performance under hydrothermal conditions will be therefore very important in the development of biorefinery technologies. In this work, we describe two different synthetic routes (i.e., impregnation and cyclodextrin-assisted one-pot colloidal approach), for the preparation in aqueous phase of six high surface area CoMo/γ-Al 2 O 3 catalysts. Catalytic tests performed on the HTL of Nannochloropsis gaditana microalga indicate that solids prepared by the one-pot colloidal approach show higher hydrothermal stability and enhanced biocrude yield with respect to the catalyst-free test. The positive effect of the substitution of the block copolymer Tetronic T90R4 for Pluronic F127 in the preparation procedure was evidenced by diffuse reflectance UV-visible spectroscopy, X-ray diffraction, N 2 -adsorption-desorption, and H 2 -temperature-programmed reduction measurements and confirmed by the higher quality of the obtained biocrude, which exhibited lower oxygen content and higher-energy recovery equal to 62.5% of the initial biomass.

Carbon monoxide reaction with UO2(111) single crystal surfaces: A theoretical and experimental study

NASA Astrophysics Data System (ADS)

Senanayake, S. D.; Soon, A.; Kohlmeyer, A.; Söhnel, T.; Idriss, H.

2005-07-01

The reaction of CO has been investigated on the surfaces of UO2(111) single crystal. Over the stoichiometric surface CO does not adsorb at 300 K and no further reaction is noticed. Over UO2-x (prepared by Ar+ bombardment), CO molecules adsorb and in presence of traces of H2 they couple to form acetylene molecules that desorb in two temperature domains during temperature programmed desorption (TPD). In the presence of excess H2 the coupling product is found to be ethylene. X-ray photoelectron spectroscopy (XPS) of the core level shows the presence of an U 4f line at 377 eV on the UO2-x surface, attributed to U metal. This line disappears upon CO adsorption (5 L and above) at 300 K indicating oxidation of U metal atoms by O from dissociatively adsorbed CO. XPS C 1s shows that the only C containing species formed is carbide. Computation of a α-U metal 2d-periodic slab was also conducted using plane-wave pseudopotential in the density functional theoretical framework. Two modes of CO adsorption were considered: molecular and dissociative. The dissociative adsorption was found more energetically favoured by 0.46 eV. From TPD, XPS and computation results it is strongly suggested that CO is dissociatively adsorbed on UO2-x and that a stable U-C species is formed at 300 K.

Modification of the acid/base properties of γ-Al2O3 by oxide additives: An ethanol TPD investigation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kwak, Ja Hun; Lee, Jaekyoung; Szanyi, Janos

2016-02-26

The electronic properties of oxide-modified γ Al2O3 surfaces were investigated by using ethanol TPD. Ethanol TPD showed remarkable sensitivity toward the surface structures and electronic properties of the aluminas modified by various transition metal oxides. Maximum desorption rates for the primary product of ethanol adsorption, ethylene, were observed at 225 °C on non-modified γ-Al2O3. Desorption temperature of ethanol over a γ Al2O3 samples with different amounts of BaO linearly increased with increasing loading. On the contrary, ethanol desorption temperature on Pt modified γ-Al2O3 after calcined at 500 oC linearly decreased with increasing Pt loading. These results clearly suggested that themore » acid/base properties of the γ-Al2O3 surface can be strongly affected by ad-atoms. For confirming these arguments, we performed ethanol TPD experiments on various oxide modified γ-Al2O3 and normalized the maximum desorption temperatures based on the same number of oxide dopants. These normalized ethanol desorption temperatures linearly correlate with the electronegativity of the metal atom in the oxide. This linear relationship clearly demonstrates that the acidic properties of alumina surfaces can be systematically changed by ad-atoms.« less

Development of TRPN dendrimer-modified disordered mesoporous silica for CO{sub 2} capture

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Xiaoyun; Zhang, Sisi; Qin, Hongyan

2014-08-15

Highlights: • A novel series of TRPN dendrimers are synthesized. • Structurally disordered mesoporous silica was used to develop the CO{sub 2} adsorbent. • The CO{sub 2} adsorption capacity is relatively high. • The sorbent exhibits a high stability after 12 cycling runs. • The sorbent achieves complete desorption at low temperature (60 °C). - Abstract: A novel series of tri(3-aminopropyl) amine (TRPN) dendrimers were synthesized and impregnated on structurally disordered mesoporous silica (DMS) to generate CO{sub 2} adsorbents (TS). The physicochemical and adsorption properties of the adsorbents before and after dendrimer modification were characterized by X-ray diffraction (XRD), thermogravimetricmore » analysis (TGA), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and N{sub 2} adsorption–desorption (N{sub 2}-BET) techniques. CO{sub 2} adsorption–desorption tests indicated that the sorbent demonstrates high CO{sub 2} adsorption capacity (138.1 mg g{sup −1} for G1 sample TS-G1-3CN-50 and 91.7 mg g{sup −1} for G2 sample TS-G2-6CN-50), and can completely desorb CO{sub 2} under vacuum at 60 °C. Its CO{sub 2} adsorption capacity at 25 °C increases with the amine loading, achieving the highest adsorption capacity (140.6 mg g{sup −1} for TS-G1-3CN) at 60%. The developed TS materials exhibited excellent cycling stability. After 12 consecutive adsorption–desorption runs, TS-G1-3CN-50 shows an adsorption capacity of 136.0 mg g{sup −1}, retaining 98.5% of its original value.« less

Second Harmonic Correlation Spectroscopy: Theory and Principles for Determining Surface Binding Kinetics.

PubMed

Sly, Krystal L; Conboy, John C

2017-06-01

A novel application of second harmonic correlation spectroscopy (SHCS) for the direct determination of molecular adsorption and desorption kinetics to a surface is discussed in detail. The surface-specific nature of second harmonic generation (SHG) provides an efficient means to determine the kinetic rates of adsorption and desorption of molecular species to an interface without interference from bulk diffusion, which is a significant limitation of fluorescence correlation spectroscopy (FCS). The underlying principles of SHCS for the determination of surface binding kinetics are presented, including the role of optical coherence and optical heterodyne mixing. These properties of SHCS are extremely advantageous and lead to an increase in the signal-to-noise (S/N) of the correlation data, increasing the sensitivity of the technique. The influence of experimental parameters, including the uniformity of the TEM00 laser beam, the overall photon flux, and collection time are also discussed, and are shown to significantly affect the S/N of the correlation data. Second harmonic correlation spectroscopy is a powerful, surface-specific, and label-free alternative to other correlation spectroscopic methods for examining surface binding kinetics.

Adsorptive removal of malachite green from aqueous solutions by almond gum: Kinetic study and equilibrium isotherms.

PubMed

Bouaziz, Fatma; Koubaa, Mohamed; Kallel, Fatma; Ghorbel, Rhoudha Ellouz; Chaabouni, Semia Ellouz

2017-12-01

This work aimed at investigating the potential of almond gum as low cost adsorbent for the removal of the cationic dye; malachite green from aqueous solutions. Almond gum was first analyzed by scanning electron microscopy (SEM) and Fourier transforms infrared spectroscopy (FTIR), and then the adsorption behavior was studied in batch system. The effects of the adsorption parameters (adsorbent dose, pH, contact time, particle size, initial dye concentration, temperature and agitation) on the dye removal have been studied. Adsorption equilibrium and isotherms were evaluated depending on temperature using the isotherms of Freundlich, Langmuir, and Tempkin. The obtained result showed that both Langmuir and Freundlich models were adapted to study the dye sorption. The maximum adsorption capacities were equal to 172.41mg/g, 181.81mg/g, and 196.07mg/g at 303.16K, 313.16K, and 323.16K, respectively. The kinetics of sorption were following the pseudo-second order model. The thermodynamic changes in enthalpy (ΔH), entropy (ΔS), and free energy (ΔG) indicated that the adsorption of malachite green at the surface of almond gum is endothermic and occurs spontaneously. Desorption experiments were conducted to regenerate almond gum, showing great desorption capacity when using HCl at pH 2. Copyright © 2017 Elsevier B.V. All rights reserved.

Magnetic biochar combining adsorption and separation recycle for removal of chromium in aqueous solution.

PubMed

Xin, Ouyang; Yitong, Han; Xi, Cao; Jiawei, Chen

2017-03-01

Biochar has been developed in recent years for the removal of contaminants such as Cr (VI) in water. The enhancement of the adsorption capacity of biochar and its recyclable use are still challenges. In this study, magnetic biochar derived from corncobs and peanut hulls was synthesized under different pyrolysis temperatures after pretreating the biomass with a low concentration of 0.5 M FeCl 3 solution. The morphology, specific surface area, saturation magnetization and Fourier transform infrared spectroscopy (FT-IR) spectra were characterized for biochar. The magnetic biochar performed well in combining adsorption and separation recycle for the removal of Cr (VI) in water. The Cr (VI) adsorbance of the biochar was increased with the increase in pyrolysis temperature, and the magnetic biochar derived from corncobs showed better performance for both magnetization and removal of Cr (VI) than that from peanut hulls. The Langmuir model was used for the isothermal adsorption and the maximum Cr (VI) adsorption capacity of corncob magnetic biochar pyrolyzed at 650 °C reached 61.97 mg/g. An alkaline solution (0.1 M NaOH) favored the desorption of Cr (VI) from the magnetic biochar, and the removal of Cr (VI) still remained around 77.6% after four cycles of adsorption-desorption. The results showed that corncob derived magnetic biochar is a potentially efficient and recoverable adsorbent for remediation of heavy metals in water.

Growth, stability and decomposition of Mg2Si ultra-thin films on Si (100)

NASA Astrophysics Data System (ADS)

Sarpi, B.; Zirmi, R.; Putero, M.; Bouslama, M.; Hemeryck, A.; Vizzini, S.

2018-01-01

Using Auger Electron Spectroscopy (AES), Scanning Tunneling Microscopy/Spectroscopy (STM/STS) and Low Energy Electron Diffraction (LEED), we report an in-situ study of amorphous magnesium silicide (Mg2Si) ultra-thin films grown by thermally enhanced solid-phase reaction of few Mg monolayers deposited at room temperature (RT) on a Si(100) surface. Silicidation of magnesium films can be achieved in the nanometric thickness range with high chemical purity and a high thermal stability after annealing at 150 °C, before reaching a regime of magnesium desorption for temperatures higher than 350 °C. The thermally enhanced reaction of one Mg monolayer (ML) results in the appearance of Mg2Si nanometric crystallites leaving the silicon surface partially uncovered. For thicker Mg deposition nevertheless, continuous 2D silicide films are formed with a volcano shape surface topography characteristic up to 4 Mg MLs. Due to high reactivity between magnesium and oxygen species, the thermal oxidation process in which a thin Mg2Si film is fully decomposed (0.75 eV band gap) into a magnesium oxide layer (6-8 eV band gap) is also reported.

Identifying the Constituents of and Transformations in Diatomaceous Earth and Polysiloxane Foams Through the Use of Electron Paramagnetic Resonance Spectroscopy

NASA Astrophysics Data System (ADS)

Blair, Michael; Muenchausen, Ross; Bennett, Bryan; Smith, James; Stephens, Thomas; Cooke, Wayne

2007-03-01

The chemical aging of polymeric materials is largely governed by the characteristics of the storage environment. For polysiloxane foams, the diatomaceous earth (DE) filler is a small component of the foam, but it plays a large role in the handling of water in the system. The DE filler can act as either a ``source'' or a ``sink'' for water via both chemical hydroxylation/ dehydroxylation and physical adsorption/ desorption processes, depending on the processing history and storage conditions. We have used electron paramagnetic resonance (EPR) spectroscopy to examine composite foam material as well as the DE filler alone. Intense, broad (400 Gauss) resonances were recorded at room temperature as a function of the microwave power at X-band frequency. The observed spectra have been assigned to the iron oxide compounds goethite, lepidocrocite, hematite, and magnetite based upon the measured EPR spectra of these minerals. As the presence or absence of free H2O and the temperature of processing and storage also affects the interconversion of these various iron oxides, we indicate how this process can be followed by monitoring changes in the EPR spectra.

Synthesis of triple-stranded complexes using bis(dipyrromethene) ligands.

PubMed

Zhang, Zhan; Dolphin, David

2010-12-20

The reaction of an α-free, β,β'-linked bis(dipyrromethene) ligand with Fe(3+) or Co(3+) led to noninterconvertible triple-stranded helicates and mesocates. In the present context, a stable α-free ligand 2 has been developed and complexation of ligands 1 and 2 with diamagnetic Co(3+), Ga(3+), and In(3+) has been studied. The triple-stranded M(2)1(3) (M = Ga, In) and M(2)2(3) (M = Co, Ga, In) complexes were characterized using matrix-assisted laser desorption ionization time-of-flight spectrometry, (1)H NMR and UV-vis spectroscopy, and X-ray crystallography. Again, the (1)H NMR analysis showed that both the triple-stranded helicates and mesocates were generated in this metal-directed assembly. Consistent with our previous finding on coordinatively inert Co(3+) complexes, variable-temperature NMR spectroscopy indicated that the triple-stranded helicate and mesocate of labile In(3+) did not interconvert in solution, either. However, the diastereoselectivity of the M(2)2(3) complexes was found to improve with an increase in the reaction temperature. Taken together, this study complements the coordination chemistry of poly(dipyrromethene) ligands and provides further insight into the formation of helicates versus mesocates.

Hydrogen storage properties of nano-structural carbon and metal hydrides composites

NASA Astrophysics Data System (ADS)

Miyaoka, Hiroki; Ichikawa, Takayuki; Isobe, Shigehito; Fujii, Hironobu

2006-08-01

Thermodynamic and structural properties of some ball-milled mixtures composed of the hydrogenated nanostructural carbon (C nanoH x) and metal hydride (MH; M=Li, Na, Mg and Ca) were examined from thermal desoroption mass spectroscopy and powder X-ray diffraction, respectively. The results showed that the hydrogen desorption temperatures are significantly lowered from those of each hydride (C nanoH x, MH) in the composites. This indicates that a new type of interaction exists between C nanoH x and MH, which destabilizes C-H and/or M-H bonding as well. Therefore, the above Metal-C-H system would be recognized as a new family of hydrogen storage materials.

Conversion of kraft lignin over hierarchical MFI zeolite.

PubMed

Kim, Seong-Soo; Lee, Hyung Won; Ryoo, Ryong; Kim, Wookdong; Park, Sung Hoon; Jeon, Jong-Ki; Park, Young-Kwon

2014-03-01

Catalytic pyrolysis of kraft lignin was carried out using pyrolysis gas chromatography/mass spectrometry. Hierarchical mesoporous MFI was used as the catalyst and another mesoporous material Al-SBA-15 was also used for comparison. The characteristics of mesoporous MFI were analyzed by X-ray diffraction patterns, N2 adsorption-desorption isotherms, and temperature programmed desorption of NH3. Two catalyst/lignin mass ratios were tested: 5/1 and 10/1. Aromatics and alkyl phenolics were the main products of the catalytic pyrolysis of lignin over mesoporous MFI. In particular, the yields of mono-aromatics such as benzene, toluene, ethylbenzene, and xylene were increased substantially by catalytic upgrading. Increase in the catalyst dose enhanced the production of aromatics further, which is attributed to decarboxylation, decarbonlyation, and aromatization reactions occurring over the acid sites of mesoporous MFI.

Fast synthesis of multilayer carbon nanotubes from camphor oil as an energy storage material.

PubMed

TermehYousefi, Amin; Bagheri, Samira; Shinji, Kawasaki; Rouhi, Jalal; Rusop Mahmood, Mohamad; Ikeda, Shoichiro

2014-01-01

Among the wide range of renewable energy sources, the ever-increasing demand for electricity storage represents an emerging challenge. Utilizing carbon nanotubes (CNTs) for energy storage is closely being scrutinized due to the promising performance on top of their extraordinary features. In this work, well-aligned multilayer carbon nanotubes were successfully synthesized on a porous silicon (PSi) substrate in a fast process using renewable natural essential oil via chemical vapor deposition (CVD). Considering the influx of vaporized multilayer vertical carbon nanotubes (MVCNTs) to the PSi, the diameter distribution increased as the flow rate decreased in the reactor. Raman spectroscopy results indicated that the crystalline quality of the carbon nanotubes structure exhibits no major variation despite changes in the flow rate. Fourier transform infrared (FT-IR) spectra confirmed the hexagonal structure of the carbon nanotubes because of the presence of a peak corresponding to the carbon double bond. Field emission scanning electron microscopy (FESEM) images showed multilayer nanotubes, each with different diameters with long and straight multiwall tubes. Moreover, the temperature programmed desorption (TPD) method has been used to analyze the hydrogen storage properties of MVCNTs, which indicates that hydrogen adsorption sites exist on the synthesized multilayer CNTs.

Fast Synthesis of Multilayer Carbon Nanotubes from Camphor Oil as an Energy Storage Material

PubMed Central

TermehYousefi, Amin; Bagheri, Samira; Shinji, Kawasaki; Rouhi, Jalal; Rusop Mahmood, Mohamad; Ikeda, Shoichiro

2014-01-01

Among the wide range of renewable energy sources, the ever-increasing demand for electricity storage represents an emerging challenge. Utilizing carbon nanotubes (CNTs) for energy storage is closely being scrutinized due to the promising performance on top of their extraordinary features. In this work, well-aligned multilayer carbon nanotubes were successfully synthesized on a porous silicon (PSi) substrate in a fast process using renewable natural essential oil via chemical vapor deposition (CVD). Considering the influx of vaporized multilayer vertical carbon nanotubes (MVCNTs) to the PSi, the diameter distribution increased as the flow rate decreased in the reactor. Raman spectroscopy results indicated that the crystalline quality of the carbon nanotubes structure exhibits no major variation despite changes in the flow rate. Fourier transform infrared (FT-IR) spectra confirmed the hexagonal structure of the carbon nanotubes because of the presence of a peak corresponding to the carbon double bond. Field emission scanning electron microscopy (FESEM) images showed multilayer nanotubes, each with different diameters with long and straight multiwall tubes. Moreover, the temperature programmed desorption (TPD) method has been used to analyze the hydrogen storage properties of MVCNTs, which indicates that hydrogen adsorption sites exist on the synthesized multilayer CNTs. PMID:25258714

Adsorption and oligomerization of 1,3-phenylene diisocyanide on Au(111)

DOE PAGES

Kestell, John; Walker, Joshua; Bai, Yun; ...

2016-04-18

The adsorption and self-assembly of 1,3-phenylene diisocyanide (1,3-PDI) are studied on Au(111) using reflection–adsorption infrared spectroscopy (RAIRS), scanning tunneling microscopy (STM), and temperature-programmed desorption (TPD) supplemented by density functional theory (DFT) calculations and the results compared with the structures formed from 1,4-PDI where it assembled to form –(Au–PDI)– oligomer chains that incorporate gold adatoms. The infrared spectra display a single isocyanide feature consistent with the isocyanide binding to gold adatoms, while DFT calculations confirm that isocyanide binding to gold adatoms is more energetically favorable than binding to the surface. STM images show that 1,3-PDI forms zigzag chains containing hairpin bendsmore » that cause the chains to double back on each other, consistent with the 120° angle between the isocyanide groups. Hexagonal structural motifs are also observed that are proposed to be due to the self-assembly of three isocyanides as well as small structures that are assigned to 1,3-PDI dimers. Furthermore, the results suggest that the formation of gold-containing oligomers from isocyanide-containing molecules is a general phenomenon.« less

Precursor effect on the property and catalytic behavior of Fe-TS-1 in butadiene epoxidation

NASA Astrophysics Data System (ADS)

Wu, Mei; Zhao, Huahua; Yang, Jian; Zhao, Jun; Song, Huanling; Chou, Lingjun

2017-11-01

The effect of iron precursor on the property and catalytic behavior of iron modified titanium silicalite molecular sieve (Fe-TS-1) catalysts in butadiene selective epoxidation has been studied. Three Fe-TS-1 catalysts were prepared, using iron nitrate, iron chloride and iron sulfate as precursors, which played an important role in adjusting the textural properties and chemical states of TS-1. Of the prepared Fe-TS-1 catalysts, those modified by iron nitrate (FN-TS-1) exhibited a significant enhanced performance in butadiene selective epoxidation compared to those derived from iron sulfate (FS-TS-1) or iron chloride (FC-TS-1) precursors. To obtain a deep understanding of their structure-performance relationship, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Temperature programmed desorption of NH3 (NH3-TPD), Diffuse reflectance UV-Vis spectra (DR UV-Vis), Fourier transformed infrared spectra (FT-IR) and thermal gravimetric analysis (TGA) were conducted to characterize Fe-TS-1 catalysts. Experimental results indicated that textural structures and acid sites of modified catalysts as well as the type of Fe species influenced by the precursors were all responsible for the activity and product distribution.

Anode-supported single-chamber solid oxide fuel cell based on cobalt-free composite cathode of Nd0.5Sr0.5Fe0.8Cu0.2O3-δ-Sm0.2Ce0.8O1.9 at intermediate temperatures

NASA Astrophysics Data System (ADS)

Yin, Jie-Wei; Zhang, Chunming; Yin, Yi-Mei; Shi, Huangang; Lin, Ye; Lu, Jun; Ma, Zi-Feng

2015-07-01

As a candidate of cathode material of single-chamber solid oxide fuel cell (SC-SOFC), cobalt-free mixed ionic electronic conductor (MIEC) Nd0.5Sr0.5Fe0.8Cu0.2O3-δ (NSFCu) is synthesized by sol-gel method with ethylene diamine tetraacetic acid and citric acid as co-complexing agents. The XRD shows NSFCu is stable after CO2 treatment and chemical compatible with SDC at high temperatures. CO2-TPD (CO2-temperature programmed desorption) demonstrates both CO2 adsorption and desorption phenomenon on NSFCu surface. However, the polarization resistances (Rp) of NSFCu and SDC (10:4 in weight) composite electrodes showed no decay in 5% CO2. Single cell using N2-O2-CH4 mixed gas (CH4 to O2 ratio = 1.5) as fuel shows maximum power density of 635 mW cm-2 at 700 °C. These results suggest that NSFCu-SDC is a promising composite cathode material for application in single-chamber solid oxide fuel cell.

Impact of temperature during He+ implantation on deuterium retention in tungsten, tungsten with carbon deposit and tungsten carbide

NASA Astrophysics Data System (ADS)

Oya, Yasuhisa; Sato, Misaki; Li, Xiaochun; Yuyama, Kenta; Fujita, Hiroe; Sakurada, Shodai; Uemura, Yuki; Hatano, Yuji; Yoshida, Naoaki; Ashikawa, Naoko; Sagara, Akio; Chikada, Takumi

2016-02-01

Temperature dependence on deuterium (D) retention for He+ implanted tungsten (W) was studied by thermal desorption spectroscopy (TDS) to evaluate the tritium retention behavior in W. The activation energies were evaluated using Hydrogen Isotope Diffusion and Trapping (HIDT) simulation code and found to be 0.55 eV, 0.65 eV, 0.80 eV and 1.00 eV. The heating scenarios clearly control the D retention behavior and, dense and large He bubbles could work as a D diffusion barrier toward the bulk, leading to D retention enhancement at lower temperature of less than 430 K, even if the damage was introduced by He+ implantation. By comparing the D retention for W, W with carbon deposit and tungsten carbide (WC), the dense carbon layer on the surface enhances the dynamic re-emission of D as hydrocarbons, and induces the reduction of D retention. However, by He+ implantation, the D retention was increased for all the samples.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ryota Ochiai; M. Azhar Uddin; Eiji Sasaoka

The effect of the presence of HCl and SO{sub 2} in the simulated coal combustion flue gas on the Hg{sup 0} removal by a commercial activated carbon (coconut shell AC) was investigated in a laboratory-scale fixed-bed reactor in a temperature range of 80-200{sup o}C. The characteristics (thermal stability) of the mercury species formed on the sorbents under various adsorption conditions were investigated by the temperature-programmed decomposition desorption (TPDD) technique. It was found that the presence of HCl and SO{sub 2} in the flue gas affected the mercury removal efficiency of the sorbents as well as the characteristics of the mercurymore » adsorption species. The mercury removal rate of AC increased with the HCl concentration in the flue gas. In the presence of HCl and the absence of SO{sub 2} during Hg{sup 0} adsorption by AC, a single Hg{sup 0} desorption peak at around 300{sup o}C was observed in the TPDD spectra and intensity of this peak increased with the HCl concentration during mercury adsorption. The peak at around 300{sup o}C may be derived from the decomposition and desorption of mercury chloride species. The presence of SO{sub 2} during mercury adsorption had an adverse effect on the mercury removal by AC in the presence of HCl. In the presence of both HCl and SO{sub 2} during Hg{sup 0} adsorption by AC, the major TPDD peak temperatures changed drastically depending upon the concentration of HCl and SO{sub 2} in flue gas during Hg{sup 0} adsorption. 16 refs., 7 figs.« less

Time-resolved SFG study of formate on a Ni( 1 1 1 ) surface under irradiation of picosecond laser pulses

NASA Astrophysics Data System (ADS)

Noguchi, H.; Okada, T.; Onda, K.; Kano, S. S.; Wada, A.; Domen, K.

2003-03-01

Time-resolved sum-frequency generation spectroscopy was carried out on a deuterated formate (DCOO) adsorbed on Ni(1 1 1) surface to investigate the surface reaction dynamics under instantaneous surface temperature jump induced by the irradiation by picosecond laser pulses. The irradiation of pump pulse (800 nm) caused the rapid intensity decrease of both CD and OCO stretching modes of bridged formate on Ni(1 1 1). Different temporal behaviors of intensity recovery between these two vibrational modes were observed, i.e., CD stretching mode recovered faster than OCO. This is the first result to show that the dynamics of adsorbates on metals strongly depends on the observed vibrational mode. From the results of temperature and pump fluence dependence, we concluded that the observed intensity change was not due to the decomposition or desorption, but was induced by a non-thermal process.

The effect of oxygen vacancies on the binding interactions of NH3 with rutile TiO2(110) -1×1

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Boseong; Li, Zhenjun; Kay, Bruce D.

2012-11-21

A series of NH3 temperature-programmed desorption (TPD) spectra was taken after the NH3 dose at 70 K on rutile TiO2(110)-1×1 surfaces with the oxygen vacancy (VO) concentrations of ~0% (p-TiO2) and 5% (r-TiO2), respectively, to study the effect of VO’s on the desorption energy of NH3 as a function of the coverage, θ. Our results show that at zero coverage limit, the desorption energy of NH3 on r-TiO2 is 115 kJ/mol, which is 10 kJ/mol less than that on p-TiO2. The desorption energy from the Ti4+ sites decreases with increasing θ due to the repulsive NH3 - NH3 interactions andmore » approaches ~ 55 kJ/mol upon the saturation of Ti4+ sites (θ = 1 monolayer, ML) on both p- and r-TiO2. The absolute saturation coverage is determined to be about 10% smaller on r-TiO2 than that on p-TiO2. Further, the trailing edges of the NH3 TPD spectra on the hydroxylated TiO2(110) (h-TiO2) appear to be the same as that on r-TiO2 while those on oxidized TiO2(110) (o-TiO2) shift to higher temperatures. We present the detailed analysis of the results and reconcile the observed differences based on the repulsive adsorbate-adsorbate interactions between neighboring NH3 molecules and the surface charge associated with the presence of VO’s. Besides NH3, no other reaction products are observed in the TPD spectra.« less

Optimization of the secondary drying step in freeze drying using TDLAS technology.

PubMed

Schneid, Stefan C; Gieseler, Henning; Kessler, William J; Luthra, Suman A; Pikal, Michael J

2011-03-01

The secondary drying phase in freeze drying is mostly developed on a trial-and-error basis due to the lack of appropriate noninvasive process analyzers. This study describes for the first time the application of Tunable Diode Laser Absorption Spectroscopy, a spectroscopic and noninvasive sensor for monitoring secondary drying in laboratory-scale freeze drying with the overall purpose of targeting intermediate moisture contents in the product. Bovine serum albumin/sucrose mixtures were used as a model system to imitate high concentrated antibody formulations. First, the rate of water desorption during secondary drying at constant product temperatures (-22 °C, -10 °C, and 0 °C) was investigated for three different shelf temperatures. Residual moisture contents of sampled vials were determined by Karl Fischer titration. An equilibration step was implemented to ensure homogeneous distribution of moisture (within 1%) in all vials. The residual moisture revealed a linear relationship to the water desorption rate for different temperatures, allowing the evaluation of an anchor point from noninvasive flow rate measurements without removal of samples from the freeze dryer. The accuracy of mass flow integration from this anchor point was found to be about 0.5%. In a second step, the concept was successfully tested in a confirmation experiment. Here, good agreement was found for the initial moisture content (anchor point) and the subsequent monitoring and targeting of intermediate moisture contents. The present approach for monitoring secondary drying indicated great potential to find wider application in sterile operations on production scale in pharmaceutical freeze drying. © 2011 American Association of Pharmaceutical Scientists

Electrocatalytic oxidation of cellulose at a gold electrode.

PubMed

Sugano, Yasuhito; Latonen, Rose-Marie; Akieh-Pirkanniemi, Marceline; Bobacka, Johan; Ivaska, Ari

2014-08-01

The electrochemical properties of cellulose dissolved in NaOH solution at a Au surface were investigated by cyclic voltammetry, FTIR spectroscopy, the electrochemical quartz crystal microbalance technique, and electrochemical impedance spectroscopy. The reaction products were characterized by SEM, TEM, and FTIR and NMR spectroscopy. The results imply that cellulose is irreversibly oxidized. Adsorption and desorption of hydroxide ions at the Au surface during potential cycling have an important catalytic role in the reaction (e.g., approach of cellulose to the electrode surface, electron transfer, adsorption/desorption of the reaction species at the electrode surface). Moreover, two types of cellulose derivatives were obtained as products. One is a water-soluble cellulose derivative in which some hydroxyl groups are oxidized to carboxylic groups. The other derivative is a water-insoluble hybrid material composed of cellulose and Au nanoparticles (≈4 nm). Furthermore, a reaction scheme of the electrocatalytic oxidation of cellulose at a gold electrode in a basic medium is proposed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

CO2 hydrogenation on a metal hydride surface.

PubMed

Kato, Shunsuke; Borgschulte, Andreas; Ferri, Davide; Bielmann, Michael; Crivello, Jean-Claude; Wiedenmann, Daniel; Parlinska-Wojtan, Magdalena; Rossbach, Peggy; Lu, Ye; Remhof, Arndt; Züttel, Andreas

2012-04-28

The catalytic hydrogenation of CO(2) at the surface of a metal hydride and the corresponding surface segregation were investigated. The surface processes on Mg(2)NiH(4) were analyzed by in situ X-ray photoelectron spectroscopy (XPS) combined with thermal desorption spectroscopy (TDS) and mass spectrometry (MS), and time-of-flight secondary ion mass spectrometry (ToF-SIMS). CO(2) hydrogenation on the hydride surface during hydrogen desorption was analyzed by catalytic activity measurement with a flow reactor, a gas chromatograph (GC) and MS. We conclude that for the CO(2) methanation reaction, the dissociation of H(2) molecules at the surface is not the rate controlling step but the dissociative adsorption of CO(2) molecules on the hydride surface. This journal is © the Owner Societies 2012

Real-time observation of the dehydrogenation processes of methanol on clean Ru(001) and Ru(001)-p(2×2) O surfaces by a temperature-programmed electron-stimulated desorption ion angular distribution/time-of-flight system

NASA Astrophysics Data System (ADS)

Sasaki, Takehiko; Itai, Yuichiro; Iwasawa, Yasuhiro

1999-12-01

Decomposition processes of methanol on clean and oxygen-precovered Ru(001) surfaces have been visualized in real time with a temperature-programmed (TP) electron-stimulated desorption ion angular distribution (ESDIAD)/time-of-flight (TOF) system. The mass of desorbed ions during temperature-programmed surface processes was identified by TOF measurements. In the case of methanol (CH 3OD) adsorption on Ru(001)-p(2×2)-O, a halo pattern of H + from the methyl group of methoxy species was observed at 100-200 K, followed by a broad pattern from the methyl group at 230-250 K and by a near-center pattern from O + ions originating from adsorbed CO above 300 K. The halo pattern is attributed to a perpendicular conformation of the CO bond axis of the methoxy species, leading to off-normal CH bond scission. On the other hand, methanol adsorbed on clean Ru(001) did not give any halo pattern but a broad pattern was observed along the surface normal, indicating that the conformation of the methoxy species is not ordered on the clean surface. Comparison between the ESDIAD images of the oxygen-precovered surface and the clean surface suggests that the precovered oxygen adatoms induce ordering of the methoxy species. Real-time ESDIAD measurements revealed that the oxygen atoms at the Ru(001)-p(2×2)-O surface have a positive effect on selective dehydrogenation of the methoxy species to CO+H 2 and a blocking effect on CO bond breaking of the methoxy species.

Temperature and pH influence adsorption of cellobiohydrolase onto lignin by changing the protein properties.

PubMed

Lu, Xianqin; Wang, Can; Li, Xuezhi; Zhao, Jian

2017-12-01

Non-productive adsorption of cellulase onto lignin restricted the movement of cellulase and also hindered the cellulase recycling in bioconversion of lignocellulose. In this study, effect of temperature and pH on adsorption and desorption of cellobiohydrolase (CBH) on lignin and its possible mechanism were discussed. It found that pH value and temperature influenced the adsorption and desorption behaviors of CBH on lignin. Different thermodynamic models suggested that the action between lignin and CBH was physical action. More CBH was adsorbed onto lignin, but lower initial adsorption velocity was detected at 50°C comparing with 4°C. Elevating pH value could improve desorption of cellulase from lignin. The changes of hydrophobicity and electric potential on protein surface may partially explain the impact of environmental conditions on the adsorption and desorption behaviors of CBH on lignin, and comparing to electrical interaction, the hydrophobicity may be the dominating factor influencing the behaviors. Copyright © 2017 Elsevier Ltd. All rights reserved.

EFFECTS OF TEMPERATURE ON TRICHLOROETHYLENE DESORPTION FROM SILICA GEL AND NATURAL SEDIMENTS. 2. KINETICS. (R822626)

EPA Science Inventory

Isothermal desorption rates were measured at 15, 30, and 60 src="/ncer/pubs/images/deg.gif">C for trichloroethylene (TCE) on a silica gel,
an aquifer sediment, a soil, a sand fraction, and a clay and silt fraction, all
at 100% relative humidity. Temperature-st...

A novel experimental system of high stability and lifetime for the laser-desorption of biomolecules.

PubMed

Taherkhani, Mehran; Riese, Mikko; BenYezzar, Mohammed; Müller-Dethlefs, Klaus

2010-06-01

A novel laser desorption system, with improved signal stability and extraordinary long lifetime, is presented for the study of jet-cooled biomolecules in the gas phase using vibrationally resolved photoionization spectroscopy. As a test substance tryptophane is used to characterize this desorption source. A usable lifetime of above 1 month (for a laser desorption repetition rate of 20 Hz) has been observed by optimizing the pellets (graphite/tryptophane, 3 mm diameter and 6 mm length) from which the substance is laser-desorbed. Additionally, the stability and signal-to-noise ratio has been improved by averaging the signal over the entire sample pellet by synchronizing the data acquisition with the rotation of the sample rod. The results demonstrate how a combination of the above helps to produce stable and conclusive spectra of tryptophane using one-color and two-color resonant two-photon ionization studies.

Effect of calcination temperatures on microstructures and photocatalytic activity of tungsten trioxide hollow microspheres.

PubMed

Yu, Jiaguo; Qi, Lifang; Cheng, Bei; Zhao, Xiufeng

2008-12-30

Tungsten trioxide hollow microspheres were prepared by immersing SrWO4 microspheres in a concentrated HNO3 solution, and then calcined at different temperatures. The prepared tungsten oxide samples were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectra, differential thermal analysis-thermogravimetry, UV-visible spectrophotometry, scanning electron microscopy, N2 adsorption/desorption measurements. The photocatalytic activity of the samples was evaluated by photocatalytic decolorization of rhodamine B aqueous solution under visible-light irradiation. It was found that with increasing calcination temperatures, the average crystallite size and average pore size increased, on the contrary, Brunauer-Emmett-Teller-specific surface areas decreased. However, pore volume and porosity increased firstly, and then decreased. Increasing calcination temperatures resulted in the changes of surface morphology of hollow microspheres. The un-calcined and 300 degrees C-calcined samples showed higher photocatalytic activity than other samples. At 400 degrees C, the photocatalytic activity decreased greatly due to the decrease of specific surface areas. At 500 degrees C, the photocatalytic activity of the samples increased again due to the junction effect of two phases.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lucia, M., E-mail: mlucia@pppl.gov; Kaita, R.; Majeski, R.

The Materials Analysis and Particle Probe (MAPP) is a compact in vacuo surface science diagnostic, designed to provide in situ surface characterization of plasma facing components in a tokamak environment. MAPP has been implemented for operation on the Lithium Tokamak Experiment at Princeton Plasma Physics Laboratory (PPPL), where all control and analysis systems are currently under development for full remote operation. Control systems include vacuum management, instrument power, and translational/rotational probe drive. Analysis systems include onboard Langmuir probes and all components required for x-ray photoelectron spectroscopy, low-energy ion scattering spectroscopy, direct recoil spectroscopy, and thermal desorption spectroscopy surface analysis techniques.

Mesoporous Carbons With Self-Assembled High-Activity Surfaces (PREPRINT)

DTIC Science & Technology

2006-07-07

temperature-programmed desorption, and potentiometric titrations . Journal of Colloid and Interface Science 2001; 240: 252–258. [40] Rotkin SV, Gogotsi Y...selected carbon samples were treated with nitric acid and the total acid site density determined by base titration [32-34 Boehm 1994; Boehm 2002; 32...washed thoroughly using distilled/deionized water, and dried in the oven. For the titration , 50 mg of HNO3-treated carbon powder was added to 20 ml

Thermal and structural characterization of synthetic and natural nanocrystalline hydroxyapatite.

PubMed

Sofronia, Ancuta M; Baies, Radu; Anghel, Elena M; Marinescu, Cornelia A; Tanasescu, Speranta

2014-10-01

The aim of this work was to study the thermal stability on heating and to obtain the processing parameters of synthetic and bone-derived hydroxyapatite over temperatures between room temperature and 1400°C by thermal analysis (thermogravimetry (TG)/differential scanning calorimetry (DSC) and thermo-mechanical analysis-TMA). Structural and surface modifications related to samples origin and calcination temperature were investigated by Fourier transformed infrared (FTIR) and Raman spectroscopy, X-ray diffraction (XRD) and BET method. FTIR spectra indicated that the organic constituents and carbonate are no longer present in the natural sample calcined at 800°C. Raman spectra highlighted the decomposition products of the hydroxyapatite. The calcination treatment modifies the processes kinetics of the synthetic samples, being able to isolate lattice water desorption processes of decarbonization and the dehydroxylation processes. Shrinkage of calcined synthetic sample increases by 10% compared to uncalcined synthetic powder. From the TMA correlated with TG analysis and heat capacity data it can be concluded that sintering temperature of the synthetic samples should be chosen in the temperature range of the onset of dehydroxylation and the temperature at which oxyapatite decomposition begins. Copyright © 2014 Elsevier B.V. All rights reserved.

Fundamental studies of catalytic processing of synthetic liquids. Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Watson, P.R.

1994-06-15

Liquids derived from coal contain relatively high amounts of oxygenated organic compounds, mainly in the form of phenols and furans that are deleterious to the stability and quality of these liquids as fuels. Hydrodeoxygenation (HDO) using Mo/W sulfide catalysts is a promising method to accomplish this removal, but our understanding of the reactions occurring on the catalyst surface during HDO is very limited. Rather than attempting to examine the complexities of real liquids and catalysts we have adopted an approach here using model systems amenable to surface-sensitive techniques that enable us to probe in detail the fundamental processes occurring duringmore » HDO at the surfaces of well-defined model catalysts. The results of this work may lead to the development of more efficient, selective and stable catalysts. Above a S/Mo ratio of about 0.5 ML, furan does not adsorb on sulfided Mo surfaces; as the sulfur coverage is lowered increasing amounts of furan can be adsorbed. Temperature-programmed reaction spectroscopy (TPRS) reveals that C-H, C-C and C-O bond scission occurs on these surfaces. Auger spectra show characteristic changes in the nature and amount of surface carbon. Comparisons with experiments carried out with CO, H{sub 2} and alkenes show that reaction pathways include -- direct abstraction of CO at low temperatures; cracking and release of hydrogen below its normal desorption temperature; dehydrogenatin of adsorbed hydrocarbon fragments; recombination of C and O atoms and dissolution of carbon into the bulk at high temperatures. Performing the adsorption or thermal reaction in 10{sup {minus}5} torr of hydrogen does not change the mode of reaction significantly.« less

Infrared and TPD studies of nitrates adsorbed on Tb{sub 4}O{sub 7}, La{sub 2}O{sub 3}, BaO, and MgO/{gamma}-Al{sub 2}O{sub 3}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chi, Y.; Chuang, S.S.C.

2000-05-18

NO and O{sub 2} coadsorption on {gamma}-Al{sub 2}O{sub 3}-supported Tb{sub 4}O{sub 7}, La{sub 2}O{sub 3}, BaO, and MgO has been investigated by in situ infrared spectroscopy coupled with temperature-programmed decomposition and desorption. BaO/{gamma}-Al{sub 2}O{sub 3} and MgO/{gamma}-Al{sub 2}O{sub 3} possess a higher NO{sub x} storage capability than Tb{sub 4}O{sub 7}/{gamma}-Al{sub 2}O{sub 3} and La{sub 2}O{sub 3}/{gamma}-Al{sub 2}O{sub 3}. NO/O{sub 2} coadsorbed on Tb{sub 4}O{sub 7}, La{sub 2}O{sub 3}, and BaO in the form of bridging bidentate, chelating bidentate, and monodentate nitrates, and on MgO in the form of bridging bidentate and monodentate nitrates via the reaction of adsorbed NO withmore » adsorbed oxygen at 298 K. NO/O{sub 2} coadsorbed as a chelating bidentate nitrate on Tb{sub 4}O{sub 7} and La{sub 2}O{sub 3}, and as a distinctive bridging bidentate nitrate on BaO and MgO via the reaction of adsorbed NO with surface lattice oxygen at 523 K. These various forms of adsorbed nitrate differ in structure and reactivity from Tb(NO{sub 3}){sub 3}, La(NO{sub 3}){sub 3}, Ba(NO{sub 3}){sub 2}, and Mg(NO{sub 3}){sub 2}, the precursor used to prepare metal oxides for NO/O{sub 2} coadsorption. Temperature-programmed desorption (TPD) of chelating bidentate nitrate on Tb{sub 4}O{sub 7}, La{sub 2}O{sub 3}, and BaO produced primarily NO and O{sub 2}, with maxima at 640 and 670 K, respectively. TPD of bridging bidentate nitrate and monodentate nitrate on Tb{sub 4}O{sub 7}, La{sub 2}O{sub 3}, and BaO produced NO and O{sub 2} as major products and N{sub 2} and N{sub 2}O as minor products, at 320--500 K. Decomposition of bridging bidentate on MgO produced NO as a major product and N{sub 2}O as a minor product at a peak temperature of 690 K. Peak temperatures for Tb(NO{sub 3}){sub 3}, La(NO{sub 3}){sub 3}, Ba(NO{sub 3}){sub 2}, and Mg(NO{sub 3}){sub 2} decomposition occurred between those for bridging and chelating nitrates. The difference in stability between chelating and bridging bidentate nitrates on various metal oxides/{gamma}-Al{sub 2}O{sub 3} may provide a wide range of operating temperatures for NO{sub x} storage.« less

Synthesis of octahedral like Cu-BTC derivatives derived from MOF calcined under different atmosphere for application in CO oxidation

NASA Astrophysics Data System (ADS)

Yang, Yiqiong; Dong, Han; Wang, Yin; He, Chi; Wang, Yuxin; Zhang, Xiaodong

2018-02-01

A series of octahedral structure Cu-BTC derivatives were successfully achieved through direct calcination of copper based metal organic framework Cu-BTC under different atmosphere (CO reaction gas, oxidizing gas O2, reducing gas H2, inert gas Ar). The Cu-BTC derivatives were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), laser Raman spectroscopy (LRS), N2 adsorption-desorption isotherm, element analysis, H2-temperature program reduction (H2-TPR) and X-ray photoelectron spectroscopic (XPS). It is found that Cu-BTC derivative derived from MOF calcined under reaction gas/O2 (Cu-BTC-CO/Cu-BTC-O) only retain Cu2O and CuO species. In addition, a weak Cu-BTC structure and Cu particles were observed on Cu-BTC derivative derived from MOF calcined under H2 (Cu-BTC-H). Obviously differently, Cu-BTC derivative derived from MOF calcined under Ar (Cu-BTC-Ar) still retains good MOF structure. The catalytic performance for CO oxidation over Cu-BTC derivatives was studied. It was found that Cu-BTC-CO showed a smaller specific surface area (8.0 m2/g), but presented an excellent catalytic performance, long-term stability and cycling stability with a complete CO conversion temperature (T100) of 140 °C, which was ascribed to the higher Cu2O/CuO ratio, good low temperature reduction behavior and a high quantity of surface active oxygen species.

GC-MS determination of parabens, triclosan and methyl triclosan in water by in situ derivatisation and stir-bar sorptive extraction.

PubMed

Casas Ferreira, Ana María; Möder, Monika; Fernández Laespada, María Esther

2011-01-01

Stir-bar sorptive extraction in combination with an in situ derivatisation reaction and thermal desorption-gas chromatography-mass spectrometry was successfully applied to determine parabens (methylparaben, isopropylparaben, n-propylparaben, butylparaben and benzylparaben), triclosan and methyltriclosan in water samples. This approach improves both the extraction efficiency and the sensitivity in the GC in a simple way since the derivatisation reaction occurs at the same time as the extraction procedure. The in situ derivatisation reaction was carried out with acetic anhydride under alkaline conditions. Thermal desorption parameters (cryofocusing temperature, desorption flow, desorption time, desorption temperature) were optimised using a Box-Behnken experimental design. All the analytes gave recoveries higher than 79%, except methylparaben (22%). The method afforded detection limits between 0.64 and 4.12 ng/L, with good reproducibility and accuracy values. The feasibility of the method for the determination of analytes in water samples was checked in tap water and untreated and treated wastewater.

Bacterial desorption from food container and food processing surfaces.

PubMed

McEldowney, S; Fletcher, M

1988-03-01

The desorption ofStaphylococcus aureus, Acinetobacter calcoaceticus, and a coryneform from the surfaces of materials used for manufacturing food containers (glass, tin plate, and polypropylene) or postprocess canning factory conveyor belts (stainless steel and nylon) was investigated. The effect of time, pH, temperature, and adsorbed organic layers on desorption was studied.S. aureus did not detach from the substrata at any pH investigated (between pH 5 and 9).A. calcoaceticus and the coryneform in some cases detached, depending upon pH and substratum composition. The degree of bacterial detachment from the substrata was not related to bacterial respiration at experimental pH values. Bacterial desorption was not affected by temperature (4-30°C) nor by an adsorbed layer of peptone and yeast extract on the substrata. The results indicate that bacterial desorption, hence bacterial removal during cleaning or their transfer via liquids flowing over colonized surfaces, is likely to vary with the surface composition and the bacterial species colonizing the surfaces.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harris, J.M.

Chemical phenomena occurring at boundaries between insulating solids and liquids (adsorption, partition, monolayer self-assembly, catalysis, and chemical reactions) are important to energy-related analytical chemistry. These phenomena are central to chromatography, solid-phase extraction, immobilized analytical reagents, and optical sensors. Chemical interactions in these processes cannot generally be identified solely by equilibrium surface concentrations, since the steady-state behavior does not reveal the mechanism or rates of surface reactions. Goal therefore is to develop surface-sensitive spectroscopies by which chemical kinetics at liquid/solid interfaces can be observed on time-scales from nanoseconds to seconds. In the first year, we have used Joule-discharge heating kinetics tomore » study pore structure of silica gels; effects of pore diameter, particle size, and chemical modification on pore connectivity were investigated. Temperature-jump relaxation measurements of sorption/desorption kinetics at liquid/solid interfaces were also carried out using Joule heating; kinetic barriers to sorption of ions from solution were found for both C18 and Cl surfaces. Through a collaboration with Fritz-Haber Institute in Berlin, we were able to acquire laser temperature-jump data on kinetics at liquid/solid interfaces using a colloidal sample. We also quantified the rate of migration of covalently attached ligands on silica surfaces; from the temperature dependence, the large energy barrier to migration was estimated. A review of applications of electronic spectroscopy (absorption and fluorescence) to reversed-phase chromatographic interfaces was published.« less

Sulfur resistance of Ce-Mn/TiO2 catalysts for low-temperature NH3–SCR

PubMed Central

Yang, Wenjing; Cui, Shitong; Street, Jason; Luo, Yan

2018-01-01

Ce-Mn/TiO2 catalyst prepared using a simple impregnation method demonstrated a better low-temperature selective catalytic reduction of NO with NH3 (NH3–SCR) activity in comparison with the sol-gel method. The Ce-Mn/TiO2 catalyst loading with 20% Ce had the best low-temperature activity and achieved a NO conversion rate higher than 90% at 140–260°C with a 99.7% NO conversion rate at 180°C. The Ce-Mn/TiO2 catalyst only had a 6% NO conversion rate decrease after 100 ppm of SO2 was added to the stream. When SO2 was removed from the stream, the catalyst was able to recover completely. The crystal structure, morphology, textural properties and valence state of the metals involving the novel catalysts were investigated using X-ray diffraction, N2 adsorption and desorption analysis, X-ray photoelectron spectroscopy, scanning electron microscopy and energy dispersive spectroscopy, respectively. The decrease of NH3–SCR performance in the presence of 100 ppm SO2 was due to the decrease of the surface area, change of the pore structure, the decrease of Ce4+ and Mn4+ concentration and the formation of the sulfur phase chemicals which blocked the active sites and changed the valence status of the elements. PMID:29657791

Sulfur resistance of Ce-Mn/TiO2 catalysts for low-temperature NH3-SCR

NASA Astrophysics Data System (ADS)

Xu, Quan; Yang, Wenjing; Cui, Shitong; Street, Jason; Luo, Yan

2018-03-01

Ce-Mn/TiO2 catalyst prepared using a simple impregnation method demonstrated a better low-temperature selective catalytic reduction of NO with NH3 (NH3-SCR) activity in comparison with the sol-gel method. The Ce-Mn/TiO2 catalyst loading with 20% Ce had the best low-temperature activity and achieved a NO conversion rate higher than 90% at 140-260°C with a 99.7% NO conversion rate at 180°C. The Ce-Mn/TiO2 catalyst only had a 6% NO conversion rate decrease after 100 ppm of SO2 was added to the stream. When SO2 was removed from the stream, the catalyst was able to recover completely. The crystal structure, morphology, textural properties and valence state of the metals involving the novel catalysts were investigated using X-ray diffraction, N2 adsorption and desorption analysis, X-ray photoelectron spectroscopy, scanning electron microscopy and energy dispersive spectroscopy, respectively. The decrease of NH3-SCR performance in the presence of 100 ppm SO2 was due to the decrease of the surface area, change of the pore structure, the decrease of Ce4+ and Mn4+ concentration and the formation of the sulfur phase chemicals which blocked the active sites and changed the valence status of the elements.

The analysis of clingfilms by infrared spectroscopy and thermal desorption capillary gas chromatography.

PubMed

Gilburt, J; Ingram, J M; Scott, M P; Underhill, M

1991-01-01

An automated thermal desorption gas chromatography technique has been adapted to analyse traces of volatile compounds in proprietary food-wrapping films. Fourteen brands of polyvinylchloride film, seven brands of polyethylene film and one polyvinylidene chloride film were discriminated. Prior infrared analysis was used to identify the polymer type. The chromatograms showed minor changes in volatiles along the length of a roll of film and major changes in films exposed to daylight or in contact with cannabis resin.

Current-Driven Hydrogen Desorption from Graphene: Experiment and Theory.

PubMed

Gao, Li; Pal, Partha Pratim; Seideman, Tamar; Guisinger, Nathan P; Guest, Jeffrey R

2016-02-04

Electron-stimulated desorption of hydrogen from the graphene/SiC(0001) surface at room temperature was investigated with ultrahigh vacuum scanning tunneling microscopy and ab initio calculations in order to elucidate the desorption mechanisms and pathways. Two different desorption processes were observed. In the high electron energy regime (4-8 eV), the desorption yield is independent of both voltage and current, which is attributed to the direct electronic excitation of the C-H bond. In the low electron energy regime (2-4 eV), however, the desorption yield exhibits a threshold dependence on voltage, which is explained by the vibrational excitation of the C-H bond via transient ionization induced by inelastic tunneling electrons. The observed current independence of the desorption yield suggests that the vibrational excitation is a single-electron process. We also observed that the curvature of graphene dramatically affects hydrogen desorption. Desorption from concave regions was measured to be much more probable than desorption from convex regions in the low electron energy regime (∼2 eV), as would be expected from the identified desorption mechanism.

Current-Driven Hydrogen Desorption from Graphene: Experiment and Theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao, L.; Pal, Partha P.; Seideman, Tamar

2016-02-04

Electron-stimulated desorption of hydrogen from the graphene/SiC(0001) surface at room temperature was investigated with ultrahigh vacuum scanning tunneling microscopy and ab initio calculations in order to elucidate the desorption mechanisms and pathways. Two different desorption processes were observed. In the high electron energy regime (4-8 eV), the desorption yield is independent of both voltage and current, which is attributed to the direct electronic excitation of the C-H bond. In the low electron energy regime (2-4 eV), however, the desorption yield exhibits a threshold dependence on voltage, which is explained by the vibrational excitation of the C-H bond via transient ionizationmore » induced by inelastic tunneling electrons. The observed current-independence of the desorption yield suggests that the vibrational excitation is a singleelectron process. We also observed that the curvature of graphene dramatically affects hydrogen desorption. Desorption from concave regions was measured to be much more probable than desorption from convex regions in the low electron energy regime (~ 2 eV), as would be expected from the identified desorption mechanism« less

Influence of cell temperature on sulfur dioxide contamination in proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Zhai, Y.; Bender, G.; Bethune, K.; Rocheleau, R.

2014-02-01

The effects of temperature on sulfur dioxide (SO2) contamination in PEMFCs are investigated by operating single cells with 2 ppm SO2 in the cathode at different temperatures. Cell performance response shows that voltage degradation was delayed and appears a transition of multiple processes at low temperatures; a similar performance loss is observed when performances reached steady state. The restored performance from the reversible and the irreversible degradations highly depends on temperature. At low temperature, the performance recovery is only negligible with neat air operation (self-recovery), while full recovery is observed after cyclic voltammetry (CV) scanning. As temperature increased, so did the self-recovery performance. However, the total recovery performance decreased. Electrochemical impedance spectroscopy analysis indicates that the potential-dependent poisoning process was delayed at low temperature, and the removal of the sulfur species from Pt/C was inhibited during the self-recovery. Water balance analysis implies that the delay could be attributed to the effect of liquid water scavenging and the mass transport of SO2 in the membrane electrode assemblies. The CV analysis confirms that the decomposition/desorption of the sulfur adsorbates was inhibited and indicates that the SO2 crossover from the cathode to the anode side was also mitigated at low temperature.

A study of ethanol reactions on O2-treated Au/TiO2. Effect of support and metal loading on reaction selectivity

NASA Astrophysics Data System (ADS)

Nadeem, M. A.; Waterhouse, G. I. N.; Idriss, H.

2016-08-01

The reactions of ethanol have been studied on bare and Au supported TiO2 polymorphs (anatase and rutile) in order to understand the effect of Au loading and prior O2 treatment on the reaction selectivity and conversion using temperature programmed desorption (TPD). Although O2 treatment has negligible effect on the reaction selectivity of ethanol on TiO2 alone it considerably affects the reaction on Au/TiO2. Au/TiO2 had three main effects on the reaction when compared to TiO2 alone. First, it switches the reaction selectivity of the dehydration (to ethylene) in favor of dehydrogenation (to acetaldehyde) on both polymorphs. Second, it decreases the desorption temperature of the main reaction products. Third, it increases secondary reaction products (mainly C4 (crotonaldehyde, butene, furan) reaching ca. 78% of the overall carbon selectivity for the 8 wt.% Au/TiO2 anatase. These effects are more pronounced on the anatase phase when compared to that on the rutile phase. Reasons for these are discussed.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Allendorf, M.D.; Arsenlis, A.; Bastasz, R.

Titanium nitride (TiN) films deposited by chemical vapor deposition (CVD) techniques are of interest for a wide range of commercial applications. In this report, the authors describe a mechanism that predicts Tin film growth rates from TiCl{sub 4}/NH{sub 3} mixtures as a function of process parameters, including inlet reactant concentrations, substrate temperatures, reactor pressures, and total gas flow rates. Model predictions were verified by comparison with the results of TiN deposition experiments in the literature and with measurements made in a new stagnation-flow reactor developed for the purpose of testing deposition mechanisms such as this. In addition, they describe abmore » initio calculations that predict thermodynamic properties for titanium-containing compounds. The results of calculations using Moeller-Plesset perturbation theory, density functional theory, and coupled cluster theory are encouraging and suggest that these methods can be used to estimate thermodynamic data that are essential for the development of CVD models involving transition-metal compounds. Finally, measurements of the adsorption and desorption kinetics of NH{sub 3} on TiN films using temperature-programmed desorption are described and their relevance to TiN CVD and mechanism development are discussed.« less

Interface chemistry and surface morphology evolution study for InAs/Al2O3 stacks upon in situ ultrahigh vacuum annealing

NASA Astrophysics Data System (ADS)

Wang, Xinglu; Qin, Xiaoye; Wang, Wen; Liu, Yue; Shi, Xiaoran; Sun, Yong; Liu, Chen; Zhao, Jiali; Zhang, Guanhua; Liu, Hui; Cho, Kyeongjae; Wu, Rui; Wang, Jiaou; Zhang, Sen; Wallace, Robert M.; Dong, Hong

2018-06-01

A systematic study of the interfacial chemistry for the HCl pretreated and native oxide InAs(100) samples upon atomic layer deposition (ALD) of Al2O3, and the post deposition annealing (PDA) process has been carried out, using in situ synchrotron radiation photoelectron spectroscopy. The "clean up" effect for the native oxide sample is detected, but it is not observed for the HCl pretreated sample. The out-diffusion and desorption of both In and As oxides have been characterized during the ALD process and the following PDA process. The surface morphology evolution during the PDA process is studied by in situ photo-emission electron microscopy. The bubbles emerged after PDA at 360 °C and grew up at 370 °C. After PDA at 400 °C and at higher temperatures, pits are seen in some areas, and the tear up of the Al2O3 film is seen in other areas with the formation of indium droplets. This study gives insight in the mechanism of elemental diffusion/desorption, which may associate the reliability of III-V semiconductor based devices.

Adsorption of n-butane on graphene/Ru(0001)—A molecular beam scattering study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sivapragasam, Nilushni; Nayakasinghe, Mindika T.; Burghaus, Uwe, E-mail: uwe.burghaus@ndsu.edu

2016-07-15

Adsorption kinetics/dynamics of n-butane on graphene, physical vapor deposited on Ru(0001) (hereafter G/Ru), and bare Ru(0001) (hereafter Ru) are discussed. The chemical activity of the supported-graphene as well as the support was probed by thermal desorption spectroscopy (adsorption kinetics). In addition and to the best of our knowledge, for the first time, molecular beam scattering data of larger molecules were collected for graphene (probing the adsorption dynamics). Furthermore, samples were inspected by x-ray photoelectron spectroscopy and Auger electron spectroscopy. At the measuring conditions used here, n-butane adsorption kinetics/dynamics are molecular and nonactivated. Binding energies of butane on Ru and G/Rumore » are indistinguishable within experimental uncertainty. Thus, G/Ru is “kinetically transparent.” Initial adsorption probabilities, S{sub 0}, of n-butane decrease with increasing impact energy (0.76–1.72 eV) and are adsorption temperature independent for both Ru and G/Ru, again consistent with molecular adsorption. Also, S{sub 0} of Ru and G/Ru are indistinguishable within experimental uncertainty. Thus, G/Ru is “dynamically transparent.” Coverage dependent adsorption probabilities indicate precursor effects for graphene/Ru.« less

Gas adsorption and desorption effects on high pressure small volume cylinders and their relevance to atmospheric trace gas analysis

NASA Astrophysics Data System (ADS)

Satar, Ece; Nyfeler, Peter; Pascale, Céline; Niederhauser, Bernhard; Leuenberger, Markus

2017-04-01

Long term atmospheric monitoring of trace gases requires great attention to precision and accuracy of the measurement setups. For globally integrated and well established greenhouse gas observation networks, the World Meteorological Organization (WMO) has set recommended compatibility goals within the framework of its Global Atmosphere Watch (GAW) Programme [1]. To achieve these challenging limits, the measurement systems are regularly calibrated with standard gases of known composition. Therefore, the stability of the primary and secondary gas standards over time is an essential issue. Past studies have explained the small instabilities in high pressure standard gas cylinders through leakage, diffusion, regulator effects, gravimetric fractionation and surface processes [2, 3]. The latter include adsorption/desorption, which are functions of temperature, pressure and surface properties. For high pressure standard gas mixtures used in atmospheric trace gas analysis, there exists only a limited amount of data and few attempts to quantify the surface processes [4, 5]. Specifically, we have designed a high pressure measurement chamber to investigate trace gases and their affinity for adsorption on different surfaces over various temperature and pressure ranges. Here, we focus on measurements of CO2, CH4 and CO using a cavity ring down spectroscopy analyzer and quantify the concentration changes due to adsorption/desorption. In this study, the first results from these prototype cylinders of steel and aluminum will be presented. References [1] World Meteorological Organization (WMO), Global Atmosphere Watch.(GAW): Report No. 229, 18th WMO/IAEA Meeting on Carbon Dioxide, Other Greenhouse Gases and Related Tracers Measurement Techniques (GGMT-2015), 2016. [2] Keeling, R. F., Manning, A. C., Paplawsky, W. J., and Cox, A. C.: On the long-term stability of reference gases for atmospheric O2 /N2 and CO2 measurements, Tellus B, 59, 10.3402/tellusb.v59i1.16964, 2007. [3] Langenfelds, R. L., van der Schoot, M. V., Francey, R. J., Steele, L. P., Schmidt, M., and Mukai, H.: Modification of air standard composition by diffusive and surface processes, Journal of Geophysical Research: Atmospheres, 110, n/a-n/a, 10.1029/2004JD005482, 2005. [4] Leuenberger, M. C., Schibig, M. F., and Nyfeler, P.: Gas adsorption and desorption effects on cylinders and their importance for long-term gas records, Atmos. Meas. Tech., 8, 5289-5299, 10.5194/amt-8-5289-2015, 2015 [5] Miller, W. R., Rhoderick, G. C., and Guenther, F. R.: Investigating Adsorption/Desorption of Carbon Dioxide in Aluminum Compressed Gas Cylinders, Analytical Chemistry, 87, 1957-1962, 10.1021/ac504351b, 2015.

Surface characterizations of oxides synthesized by successive ionic layer deposition

NASA Astrophysics Data System (ADS)

Gilbert, Thomas I.

Successive ionic layer deposition (SILD) is an aqueous technique for depositing thin oxide films on a surface in a layer-by-layer fashion through a series of chemical reactions. This dissertation examines empirical aspects of the SILD technique by characterizing thin oxide films synthesized on model planar supports and then extends the SILD technique to synthesize supported oxide nanostructures on three dimensional supports of interest to catalysis. Atomic force microscopy, x-ray photoelectron spectroscopy, and scanning electron microscopy provided insight into the SILD of zirconia, alumina, and barium oxide thin films on silicon wafers. The SILD conditions that most affected the surface morphology of the thin oxide films were the selection of aqueous metal salt precursors comprising the SILD solutions and the total number of SILD cycles. Recent studies suggest that a highly dispersed phase of barium oxide supported on alumina interacts differently with NO2 than a bulk-like phase of barium oxide SILD was used to synthesize disperse nanoislands or rafts of barium oxide on larger rafts of alumina supported on a silicon wafer. The SILD method was then extended to deposit barium oxide on an alumina powder support comprised of dense 150 nm spherical crystallites fused together into 1-2 pm particles. Equally weight loaded samples of barium oxide on the fused alumina powder were prepared by SILD and wet impregnation. The NO2 storage behavior of the barium oxide, evaluated by thermogravimetric analysis during NO2 temperature programmed desorption (TPD) experiments, provided insight into the dispersion of barium oxide that resulted from each of the loading techniques. The highly dispersed barium oxide rafts synthesized by SILD on fused alumina released NO2 at temperatures below 500°C during TPD. By comparison, the barium oxide loaded by wet impregnation showed a higher temperature desorption feature above 500°C indicative of bulk-like barium oxide nanoparticles. The NO2 weight loss curves were also used to calculate the relative percentages of BaO in the dispersed phase and bulk-like phase for each loading technique. The ability of SILD to synthesize highly disperse and uniform, conformal oxide coatings on three dimensional supports provides fundamental insight into the interactions between catalysts and supports.

Near-equilibrium desorption of helium films

NASA Astrophysics Data System (ADS)

Weimer, M.; Housley, R. M.; Goodstein, D. L.

1987-10-01

The thermal desorption of helium films in the presence of their equilibrium vapor is studied experimentally for small but rapid departures from ambient temperature. The results are analyzed within the framework of a quasithermodynamic phenomenological model based on detailed balance. Under the usual experimental conditions, isothermal desorption at the temperature of the substrate is a general prediction of the model which seems to be substantiated. For realistic adsorption isotherms the time evolution of the net desorption flux nevertheless appears to be governed by a highly nonlinear equation. In such circumstances, a number of characteristic relaxation times may be identified. These time scales are distinct from, and in general unrelated to, the coverage-dependent mean lifetime of an atom on the surface. To characterize the overall nonlinear evolution towards steady state, a global time scale, defined in terms of both initial- and steady-state properties, is introduced to summarize the experimental data. Internal evidence suggests a criterion for judging when collisions among desorbed atoms are unimportant. When this condition is satisfied, data for near-equilibrium desorption agree well with the predictions of the model. Combining our results with earlier data at higher substrate temperatures and different ambient conditions, the overall picture is consistent with scaling properties implied by the theory. We show that the values of the parameters deduced from a Frenkel-Arrhenius parametrization of the global relaxation times, as well as a variety of other aspects of desorption kinetics, are actually consequences of the shape of the equilibrium adsorption isotherm.

Swift heavy ion irradiation of Pt nanocrystals: II. Structural changes and H desorption

DOE Office of Scientific and Technical Information (OSTI.GOV)

Giulian, R.; Araujo, L.L.; Kluth, P.

2014-09-24

The structural properties and H desorption from embedded Pt nanocrystals (NCs) following irradiation with swift heavy ions were investigated as a function of energy and fluence. From x-ray absorption near-edge spectroscopy analysis, Pt-H bonding was identified in NCs annealed in a forming gas (95% N{sub 2} + 5% H{sub 2}) ambient. The H content decreased upon irradiation and the desorption process was NC-size dependent such that larger NCs required a higher fluence to achieve a H-free state. Pt-H bonding and NC dissolution both perturbed the NC structural parameters (coordination number, bond-length and mean-square relative displacement) as determined with extended x-raymore » absorption fine structure measurements.« less

Thermal coupling potential of Solid Oxide Fuel Cells with metal hydride tanks: Thermodynamic and design considerations towards integrated systems

NASA Astrophysics Data System (ADS)

Yiotis, Andreas G.; Kainourgiakis, Michael E.; Kosmidis, Lefteris I.; Charalambopoulou, Georgia C.; Stubos, Athanassios K.

2014-12-01

We study the thermal coupling potential between a high temperature metal hydride (MH) tank and a Solid Oxide Fuel Cell (SOFC) aiming towards the design of an efficient integrated system, where the thermal power produced during normal SOFC operation is redirected towards the MH tank in order to maintain H2 desorption without the use of external heating sources. Based on principles of thermodynamics, we calculate the energy balance in the SOFC/MH system and derive analytical expressions for both the thermal power produced during SOFC operation and the corresponding thermal power required for H2 desorption, as a function of the operating temperature, efficiency and fuel utilization ratio in the SOFC, and the MH enthalpy of desorption in the tank. Based on these calculations, we propose an integrated SOFC/MH design where heat is transferred primarily by radiation to the tank in order to maintain steady-state desorption conditions. We develop a mathematical model for this particular design that accounts for heat/mass transfer and desorption kinetics in the tank, and solve for the dynamics of the system assuming MgH2 as a storage material. Our results focus primarily on tank operating conditions, such as pressure, temperature and H2 saturation profiles vs operation time.

Enhanced saturation of sputtered amorphous SiN film frameworks using He- and Ne-Penning effects

NASA Astrophysics Data System (ADS)

Sugimoto, Iwao; Nakano, Satoko; Kuwano, Hiroki

1994-06-01

Optical emission spectroscopy reveals that helium and neon gases enhance the nitridation reactivity of the nitrogen plasma by Penning effects during magnetron sputtering of the silicon target. These excited nitrogen plasmas promote the saturation of frameworks of the resultant silicon nitride films. X-ray photoelectron spectroscopy, electron spin resonance, and x-ray diffraction analyses provide insight into the structure of these films, and thermal desorption mass spectroscopy reveals the behavior of volatile species in these films.

Zinc Vacancy Formation and its Effect on the Conductivity of ZnO

NASA Astrophysics Data System (ADS)

Khan, Enamul; Weber, Marc; Langford, Steve; Dickinson, Tom

2010-03-01

Exposing single crystal ZnO to 193-nm ArF excimer laser radiation can produce metallic zinc nanoparticles along the surface. The particle production mechanism appears to involve interstitial-vacancy pair formation in the near-surface bulk. Conductivity measurements made with one probe inside the laser spot and the other outside show evidence for rectifying behavior. Positron annihilation spectroscopy confirms the presence of Zn vacancies. We suggest that Zn vacancies are a possible source of p-type behavior in irradiated ZnO. Quadrupole mass spectroscopy shows that both oxygen and zinc are emitted during irradiation. Electron-hole pair production has previously been invoked to account for particle desorption from ZnO during UV illumination. Our results suggest that preexisting and laser-generated defects play a critical role in particle desorption and Zn vacancy formation.

Development of Carbotrap B-packed needle trap device for determination of volatile organic compounds in air.

PubMed

Poormohammadi, Ali; Bahrami, Abdulrahman; Farhadian, Maryam; Ghorbani Shahna, Farshid; Ghiasvand, Alireza

2017-12-08

Carbotrap B as a highly pure surface sorbent with excellent adsorption/desorption properties was packed into a stainless steel needle to develop a new needle trap device (NTD). The performance of the prepared NTD was investigated for sampling, pre-concentration and injection of benzene, toluene, ethyl benzene, o-xylene, and p-xylene (BTEX) into the column of gas chromatography-mass spectrometry (GC-MS) device. Response surface methodology (RSM) with central composite design (CCD) was also employed in two separate consecutive steps to optimize the sampling and device parameters. First, the sampling parameters such as sampling temperature and relative humidity were optimized. Afterwards, the RSM was used for optimizing the desorption parameters including desorption temperature and time. The results indicated that the peak area responses of the analytes of interest decreased with increasing sampling temperature and relative humidity. The optimum values of desorption temperature were in the range 265-273°C, and desorption time were in the range 3.4-3.8min. The limits of detection (LODs) and limits of quantitation (LOQs) of the studied analytes were found over the range of 0.03-0.04ng/mL, and 0.1-0.13ng/mL, respectively. These results demonstrated that the NTD packed with Carbotrap B offers a high sensitive procedure for sampling and analysis of BTEX in concentration range of 0.03-25ng/mL in air. Copyright © 2017 Elsevier B.V. All rights reserved.

Cesium Sorption/Desorption Experiments with IONSIV(R) IE-911 in Radioactive Waste

DOE Office of Scientific and Technical Information (OSTI.GOV)

Walker, D.D.

2001-02-13

This report describes cesium desorption from IONSIV IE-911 during ambient temperature storage and following temperature increases to 35 and 55 degrees C. This report also describes cesium sorption following return to ambient temperature. The IONSIV IE-911 used in these tests was loaded with cesium from Tank 44F radioactive waste in an ion exchange column test in 1999. Cesium desorbed and resorbed in the presence of Tank 44F waste and simulated waste solutions.

Adsorption and Photodesorption of CO from Charged Point Defects on TiO 2 (110)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mu, Rentao; Dahal, Arjun; Wang, Zhi-Tao

Adsorption and photodesorption of weakly-bound carbon monoxide, CO, from reduced and hydroxylated rutile TiO2(110) (r- and h- TiO2(110)) at sub-monolayer coverages is studied with atomically-resolved scanning tunneling microscopy (STM) along with ensemble-averaged temperature-programmed desorption (TPD) and angle-resolved photon-stimulated desorption (PSD) at low temperatures ( 50 K). STM data weighted by the concentration of each kind of adsorption sites on r-TiO2(110) give an adsorption probability which is the highest for the bridging oxygen vacancies (VO) and very low for the Ti5c sites closest to VO. Occupancy of the remaining Ti5c sites with CO is significant, but smaller than for VO. Themore » probability distribution for the different adsorption sites corresponds to a very small difference in CO adsorption energies: < 0.02 eV. We also find that UV irradiation stimulates both diffusion and desorption of CO at low temperature. CO photodesorbs primarily from the vacancies with a bi-modal angular distribution. In addition to a major, normal to the surface component, there is a broader cosine component indicating scattering from the surface which likely also leads to photo-stimulated diffusion. Hydroxylation of VO’s does not significantly change the CO PSD yield and angular distribution, indicating that not atomic but rather electronic surface defects are involved in the site-specific PSD process. We suggest that photodesorption can be initiated by recombination of photo-generated holes with excess unpaired electrons localized near the surface point-defect (either VO or bridging hydroxyl), leading to the surface atoms rearrangement and ejection of the weakly-bound CO molecules.« less

Activated carbon-supported CuO nanoparticles: a hybrid material for carbon dioxide adsorption

NASA Astrophysics Data System (ADS)

Boruban, Cansu; Esenturk, Emren Nalbant

2018-03-01

Activated carbon-supported copper(II) oxide (CuO) nanoparticles were synthesized by simple impregnation method to improve carbon dioxide (CO2) adsorption capacity of the support. The structural and chemical properties of the hybrid material were characterized by scanning electron microscopy (SEM), energy dispersive X-ray (EDX), X-ray diffraction (https://www.google.com.tr/url?sa=t&rct=j&q=&esrc=s&source=web&cd=3&cad=rja&uact=8&ved=0CCsQFjAC&url=http%3A%2F%2Fwww.intertek.com%2Fanalytical-laboratories%2Fxrd%2F&ei=-5WZVYSCHISz7Aatqq-IAw&usg=AFQjCNFBlk-9wqy49foh8tskmbD-GGbG9g&sig2=eKrhYjO75rl_Id2sLGpq4w&bvm=bv.96952980,d.bGg) (XRD), X-ray photoelectron spectroscopy (XPS), atomic absorption spectroscopy (AAS), and Brunauer-Emmett-Teller (BET) analyses. The analyses showed that CuO nanoparticles are well-distributed on the activated carbon surface. The CO2 adsorption behavior of the activated carbon-supported CuO nanoparticles was observed by thermogravimetric analysis (TGA), temperature programmed desorption (TPD), Fourier transform infrared (FTIR), and BET analyses. The results showed that CuO nanoparticle loading on activated carbon led to about 70% increase in CO2 adsorption capacity of activated carbon under standard conditions (1 atm and 298 K). The main contributor to the observed increase is an improvement in chemical adsorption of CO2 due to the presence of CuO nanoparticles on activated carbon.

Synthesis of mesoporous zeolite single crystals with cheap porogens

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tao Haixiang; Li Changlin; Ren Jiawen

2011-07-15

Mesoporous zeolite (silicalite-1, ZSM-5, TS-1) single crystals have been successfully synthesized by adding soluble starch or sodium carboxymethyl cellulose (CMC) to a conventional zeolite synthesis system. The obtained samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen sorption analysis, {sup 27}Al magic angle spinning nuclear magnetic resonance ({sup 27}Al MAS NMR), temperature-programmed desorption of ammonia (NH{sub 3}-TPD) and ultraviolet-visible spectroscopy (UV-vis). The SEM images clearly show that all zeolite crystals possess the similar morphology with particle size of about 300 nm, the TEM images reveal that irregular intracrystalmore » pores are randomly distributed in the whole crystal. {sup 27}Al MAS NMR spectra indicate that nearly all of the Al atoms are in tetrahedral co-ordination in ZSM-5, UV-vis spectra confirm that nearly all of titanium atoms are incorporated into the framework of TS-1. The catalytic activity of meso-ZSM-5 in acetalization of cyclohexanone and meso-TS-1 in hydroxylation of phenol was also studied. The synthesis method reported in this paper is cost-effective and environmental friendly, can be easily expended to prepare other hierarchical structured zeolites. - Graphical abstract: Mesoporous zeolite single crystals were synthesized by using cheap porogens as template. Highlights: > Mesoporous zeolite (silicalite-1, ZSM-5, TS-1) single crystals were synthesized. > Soluble starch or sodium carboxymethyl cellulose (CMC) was used as porogens. > The mesoporous zeolites had connected mesopores although closed pores existed. > Higher catalytic activities were obtained.« less

Determination of Phenols Isomers in Water by Novel Nanosilica/Polydimethylsiloxane-Coated Stirring Bar Combined with High Performance Liquid Chromatography-Fourier Transform Infrared Spectroscopy.

PubMed

Zheng, Bei; Li, Wentao; Liu, Lin; Wang, Xin; Chen, Chen; Yu, Zhiyong; Li, Hongyan

2017-08-18

A novel nanosilica/polydimethylsiloxane (SiO 2 /PDMS) coated stirring bar was adopted in the sorption extraction (SBSE) of phenols in water, and the high performance liquid chromatography-fourier transform infrared spectroscopy (HPLC-FTIR) was subsequently used to determination of phenol concentration. The SiO 2 /PDMS coating was prepared by sol-gel method and characterized with respect to morphology and specific surface area. The results of field-emission scanning electron microscope (FE-SEM) and N 2 adsorption-desorption as well as phenol adsorption experiments denoted that SiO 2 /PDMS has larger surface area and better adsorption capacity than commercial PDMS. The extraction efficiency of phenol with SiO 2 /PDMS coated stirring bar was optimized in terms of ion strength, flow rate of phenol-involved influent, type of desorption solvent and desorption time. More than 75% of phenol desorption efficiency could be kept even after 50 cycles of extraction, indicating the high stability of the SiO 2 /PDMS coated stirring bar. Approximately 0.16 mg/L 2, 5-dimethylphenol (2, 5-DMP), which was 34-fold more toxic than phenol, was detected in water through HPLC-FTIR. However, 2, 5-DMP could be oxidized to 5-methy-2-hydroxy benzaldehyde after disinfection in drinking water treatment process. Therefore, the proposed method of SiO 2 /PDMS-SBSE-HPLC-FTIR is successfully applied in the analysis of phenols isomers in aqueous environment.

Utilization of a by-product produced from oxidative desulfurization process over Cs-mesoporous silica catalysts.

PubMed

Kim, Hyeonjoo; Jeong, Kwang-Eun; Jeong, Soon-Yong; Park, Young-Kwon; Kim, Do Heui; Jeon, Jong-Ki

2011-02-01

We investigated the use of Cs-mesoporous silica catalysts to upgrade a by-product of oxidative desulfurization (ODS). Cs-mesoporous silica catalysts were characterized through N2 adsorption, XRD, CO2-temperature-programmed desorption, and XRF. Cs-mesoporous silica prepared by the direct incorporation method showed higher catalytic performance than a Cs/MCM-41 catalyst by impregnation method for the catalytic decomposition of sulfone compounds produced from ODS process.

Reduced deuterium retention in simultaneously damaged and annealed tungsten

NASA Astrophysics Data System (ADS)

Simmonds, M. J.; Wang, Y. Q.; Barton, J. L.; Baldwin, M. J.; Yu, J. H.; Doerner, R. P.; Tynan, G. R.

2017-10-01

Deuterium (D) retention in polycrystalline tungsten (W) with copper (Cu) ion damage concurrently produced at elevated surface temperature is investigated. An in situ heated stage held W samples at a controlled temperature up to 1243 K, which were subjected to displacement damage produced by 3.4 MeV Cu ions. D retention is subsequently explored by exposure of the W samples held at 383 K to a D2 plasma ion fluence of 1024 D+/m2. Nuclear reaction analysis (NRA), utilizing the D(3He,p)4He nuclear reaction, is used to probe the D concentration in the near surface up to 6 μm. Thermal desorption spectroscopy (TDS) is used to measure outgassed HD and D2 molecules to determine the bulk D concentration. Both NRA and TDS measure a significant reduction in D retention for samples damaged at elevated temperature. TDS quantitatively shows that the lowest energy trap remains largely unaffected while higher energy traps, induced by Cu ions, are annealed and approach intrinsic concentrations as the temperature during ion damage approaches 1243 K. Analysis of TDS data yields an activation energy of (0.10 ± 0.02) eV for recovery of ion-damage induced traps at elevated temperature.

Hydrogen storage material and process using graphite additive with metal-doped complex hydrides

DOEpatents

Zidan, Ragaiy [Aiken, SC; Ritter, James A [Lexington, SC; Ebner, Armin D [Lexington, SC; Wang, Jun [Columbia, SC; Holland, Charles E [Cayce, SC

2008-06-10

A hydrogen storage material having improved hydrogen absorbtion and desorption kinetics is provided by adding graphite to a complex hydride such as a metal-doped alanate, i.e., NaAlH.sub.4. The incorporation of graphite into the complex hydride significantly enhances the rate of hydrogen absorbtion and desorption and lowers the desorption temperature needed to release stored hydrogen.

Chemical and Physical Characterization of Comp A-3 Type II Prills

DTIC Science & Technology

2013-06-01

the composition and properties of the explosive for implementation into modeling and simulation tools as part of the Multi-scale Response of...emulsion were identified using desorption-gas chromatography/mass spectroscopy (D-GC- MS) and Fourier transform infrared ( FTIR ) spectroscopy. Quantitative...understanding the microstructure of the pressed explosive and provides critical information for the development of a high fidelity particle-based course-grain

Ultrahigh vacuum and high-pressure coadsorption of CO and H2 on Pd(111): A combined SFG, TDS, and LEED study

NASA Astrophysics Data System (ADS)

Morkel, Matthias; Rupprechter, Günther; Freund, Hans-Joachim

2003-11-01

Sum frequency generation (SFG) vibrational spectroscopy was carried out in conjunction with thermal desorption spectroscopy, low-energy electron diffraction, and Auger electron spectroscopy to examine the coadsorption of CO and H2 on Pd(111). Sequential dosing as well as various CO/H2 mixtures was utilized to study intermolecular interactions between CO and H2. Preadsorbed CO effectively prevented the dissociative adsorption of hydrogen for CO coverages ⩾0.33 ML. While preadsorbed hydrogen was able to hinder CO adsorption at low temperature (100 K), hydrogen was replaced from the surface by CO at 150 K. When 1:1 mixtures of CO/H2 were used at 100 K, hydrogen selectively hindered CO adsorption on on-top sites, while above ˜125 K no blocking of CO adsorption was observed. The observations are explained in terms of mutual site blocking, of a CO-H phase separation, and of a CO-assisted hydrogen dissolution in the Pd bulk. The temperature-dependent site blocking effect of hydrogen is attributed to the ability (inability) of surface hydrogen to diffuse into the Pd bulk above (below) ˜125 K. Nonlinear optical SFG spectroscopy allowed us to study these effects not only in ultrahigh vacuum but also in a high-pressure environment. Using an SFG-compatible ultrahigh vacuum-high-pressure cell, spectra of 1:10 CO/H2 mixtures were acquired up to 55 mbar and 550 K, with simultaneous gas chromatographic and mass spectrometric gas phase analysis. Under reaction conditions, CO coverages ⩾0.5 ML were observed which strongly limit H2 adsorption and thus may be partly responsible for the low CO hydrogenation rate. The high-pressure and high-temperature SFG spectra also showed indications of a reversible surface roughening or a highly dynamic (not perfectly ordered) CO adsorbate phase. Implications of the observed adsorbate structures on catalytic CO hydrogenation on supported Pd nanoparticles are discussed.

Photon-induced Processing of Interstellar Ices in the Laboratory. Focus on Their Non-thermal Desorption.

NASA Astrophysics Data System (ADS)

Martin-Domenech, Rafael; Munoz Caro, Guillermo; Cruz-Diaz, Gustavo A.; Oberg, Karin I.

2018-06-01

Some of the processes that take place in the interstellar medium (ISM)can be simulated in laboratories on Earth under astrophysically relevant conditions. For example, the energetic processing of the ice mantles that accrete on top of dust grains in the coldest regions of the ISM, leading to the production of new species and their desorption to the gas phase. In particular, observation of complex organic molecules (COMs) in cold interstellar environments stress the need for not only a solid state formation but also for non-thermal desorption mechanisms that can account for the observed abundances in regions where thermal desorption is inhibited. Laboratory Astrophysics can be used to test different non-thermal desorption processes and extract yields than can be extrapolated to the astrophysical scenario with theoretical models. 0th generation COMs like CH3OH and H2CO can be formed at very low temperatures. In this talk, we present laboratory simulations of the UV photoprocessing of a binary ice mixture composed by water (the main component of astrophysical ices) and methane. Formation of CO, CO2, CH3OH and H2CO was confirmed by IR spectroscopy and subsequent TPD. At the same time, photodesorption of CO and H2CO was detected by means of a Quadrupole Mass Spectrometer, with yields on the order of 10-4 and 10-5 molecules per incident photon, respectively. In general, photodesorption can take place through a direct mechanism, where the absorbing molecule (or its photofragments) are desorbed; or through an indirect mechanism where the absorbed energy is transferred to a surface molecule which is the one finally desorbing. In the case of photoproducts, the evolution of the photodesorption yield gives information on the photodesorption mechanism: a constant photodesorption yield is observed when the photoproducts are desorbed right after their formation; while an increasing yield is measured when the photoproducts are desorbed later after energy transfer from another absorbing molecule, allowing to roughly distinguish between different mechanisms.

Thermal desorption of metals from tungsten single crystal surfaces

NASA Technical Reports Server (NTRS)

Bauer, E.; Bonczek, F.; Poppa, H.; Todd, G.

1975-01-01

After a short review of experimental methods used to determine desorption energies and frequencies the assumptions underlying the theoretical analysis of experimental data are discussed. Recent experimental results on the flash desorption of Cu, Ag, and Au from clean, well characterized W (110) and (100) surfaces are presented and analyzed in detail with respect to the coverage dependence. The results obtained clearly reveal the limitations of previous analytical methods and of the experimental technique per se (such as structure and phase changes below and in the temperature region in which desorption occurs).

Surface and interfacial chemistry of high-k dielectric and interconnect materials on silicon

NASA Astrophysics Data System (ADS)

Kirsch, Paul Daniel

Surfaces and interfaces play a critical role in the manufacture and function of silicon based integrated circuits. It is therefore reasonable to study the chemistries at these surfaces and interfaces to improve existing processes and to develop new ones. Model barium strontium titanate high-k dielectric systems have been deposited on ultrathin silicon oxynitride in ultrahigh vacuum. The resulting nanostructures are characterized with secondary ion mass spectroscopy (SIMS) and X-ray photoelectron spectroscopy (XPS). An interfacial reaction between Ba and Sr atoms and SiOxNy was found to create silicates, BaSixOy or SrSi xOy. Inclusion of N in the interfacial oxide decreased silicate formation in both Ba and Sr systems. Furthermore, inclusion of N in the interfacial oxide decreased the penetration of Ba and Sr containing species, such as silicides and silicates. Sputter deposited HfO2 was studied on nitrided and unnitrided Si(100) surfaces. XPS and SIMS were used to verify the presence of interfacial HfSixOy and estimate its relative amount on both nitrided and unnitrided samples. More HfSixOy formed without the SiNx interfacial layer. These interfacial chemistry results are then used to explain the electrical measurements obtained from metal oxide semiconductor (MOS) capacitors. MOS capacitors with interfacial SiNx exhibit reduced leakage current and increased capacitance. Lastly, surface science techniques were used to develop a processing technique for reducing thin films of copper (II) and copper (I) oxide to copper. Deuterium atoms (D*) and methyl radicals (CH3*) were shown to reduce Cu 2+ and/or Cu1+ to Cu0 within 30 min at a surface temperature of 400 K under a flux of 1 x 1015 atoms/cm2s. Temperature programmed desorption experiments suggest that oxygen leaves the surface as D2O and CO2 for the D* and CH3* treated surfaces, respectively.

Heat treatment effect on the electronic and magnetic structures of nanographene sheets investigated through electron spectroscopy and conductance measurements.

PubMed

Takashiro, Jun-ichi; Kudo, Yasuhiko; Kaneko, Satoshi; Takai, Kazuyuki; Ishii, Takafumi; Kyotani, Takashi; Enoki, Toshiaki; Kiguchi, Manabu

2014-04-28

The heat treatment effect on the electronic and magnetic structures of a disordered network of nanographene sheets has been investigated by in situ measurements of X-ray photoemission spectroscopy, near-edge X-ray absorption fine structure (NEXAFS), and electrical conductance, together with temperature-programmed desorption measurements. Oxygen-containing functional groups bonded to nanographene edges in the pristine sample are almost completely decomposed under heat treatment up to 1300-1500 K, resulting in the formation of edges primarily terminated by hydrogen. The removal of the oxygen-containing groups enhances the conductance owing to the decrease in the electron transport barriers between nanographene sheets. Heat treatment above 1500 K removes also the hydrogen atoms from the edges, promoting the successive fusion of nanographene sheets at the expense of edges. The decrease in the π* peak width in NEXAFS indicates the progress of the fusion reaction, that is, the extension of the π-conjugation, which agrees with the increase in the orbital susceptibility previously reported. The fusion leads to the formation of local π/sp(2) bridges between nanographene sheets and brings about an insulator-to-metal transition at 1500-1600 K, at which the bridge network becomes infinite. As for the magnetism, the intensity of the edge state peak in NEXAFS, which corresponds to the number of the spin-polarized edge states, decreases above 1500 K, though the effective edge-state spin density per edge state starts decreasing at approximately 200 K lower than the temperature of the edge state peak change. This disagreement indicates the development of antiferromagnetic short range ordering as a precursor of a spin glass state near the insulator-metal transition, at which the random network of inter-nanographene-sheet exchange interactions strengthened with the formation of the π/sp(2) bridges becomes infinite.

First-principles study of water desorption from montmorillonite surface.

PubMed

Zhang, Yao; Meng, Yingfeng; Liu, Houbin; Yang, Mingli

2016-05-01

Knowledge about water desorption is important to give a full picture of water diffusion in montmorillonites (MMT), which is a driving factor in MMT swelling. The desorption paths and energetics of water molecules from the surface of MMT with trapped Li(+), Na(+) or K(+) counterions were studied using periodic density functional theory calculations. Two paths--surface and vacuum desorption--were designed for water desorption starting from a stationary structure in which water bonds with both the counterion and the MMT surface. Surface desorption is energetically more favorable than vacuum desorption due to water-surface hydrogen bonds that help stabilize the intermediate structure of water released from the counterion. The energy barriers of water desorption are in the order of Li(+) > Na(+) > K(+), which can be attributed to the short ionic radius of Li(+), which favors strong binding with the water molecule. The temperature dependence of water adsorption and desorption rates were compared based on the computed activation energies. Our calculations reveal that the water desorption on the MMT surface has a different mechanism from water adsorption, which results from surface effects favoring stabilization of water conformers during the desorption process.

EVALUATION OF SOLID PHASE MICROEXTRACTION FOR THE ANALYSIS OF HYDROPHILIC COMPOUNDS

EPA Science Inventory

Two commercially available solid phase microextractions (SPME) fibers, polyacrylate and carboxem/polydimethylsiloxane (PDMS), were evaluated for their ability to extract hydrophilic compounds from drinking water. Conditions, such as desorption time, desorption temperature, sample...

Graphene nanoplate-MnO2 composites for supercapacitors: a controllable oxidation approach

NASA Astrophysics Data System (ADS)

Huang, Huajie; Wang, Xin

2011-08-01

Graphene nanoplate-MnO2 composites have been synthesized by oxidising part of the carbon atoms in the framework of graphene nanoplates at ambient temperature. The composites were characterized by means of X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV). It was found that the oxidation extent of the carbon atoms in the graphene framework in these composites was dependent on the reaction time, which also influenced their microstructure, morphology and electrochemical properties. Compared with MnO2 nanolamellas, the nanocomposite prepared with a reaction time of 3 h reveals better electrochemical properties as a supercapacitor electrode material.Graphene nanoplate-MnO2 composites have been synthesized by oxidising part of the carbon atoms in the framework of graphene nanoplates at ambient temperature. The composites were characterized by means of X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV). It was found that the oxidation extent of the carbon atoms in the graphene framework in these composites was dependent on the reaction time, which also influenced their microstructure, morphology and electrochemical properties. Compared with MnO2 nanolamellas, the nanocomposite prepared with a reaction time of 3 h reveals better electrochemical properties as a supercapacitor electrode material. Electronic supplementary information (ESI) available: Fig. S1, AFM image (5 μm × 5 μm) of graphene nanoplate-MnO2 composite obtained at 3 h; Fig. S2, nitrogen adsorption/desorption isotherm of graphene nanoplate-MnO2 composite obtained at 3 h. See DOI: 10.1039/c1nr10229j

Electron-beam-induced topographical, chemical, and structural patterning of amorphous titanium oxide films.

PubMed

Kern, P; Müller, Y; Patscheider, J; Michler, J

2006-11-30

Electrolytically deposited amorphous TiO2 films on steel are remarkably sensitive to electron beam (e-beam) irradiation at moderate energies at 20 keV, resulting in controlled local oxide reduction and crystallization, opening the possibility for local topographical, chemical, and structural modifications within a biocompatible, amorphous, and semiconducting matrix. The sensitivity is shown to vary significantly with the annealing temperature of as-deposited films. Well-defined irradiation conditions in terms of probe current IP (5 microA) and beam size were achieved with an electron probe microanalyzer. As shown by atomic force and optical microscopy, micro-Raman spectroscopy, wavelength-dispersive X-ray (WDX), and Auger analyses, e-beam exposure below 1 Acm-2 immediately leads to electron-stimulated oxygen desorption, resulting in a well-defined volume loss primarily limited to the irradiated zone under the electron probe and in a blue color shift in this zone because of the presence of Ti2O3. Irradiation at 5 Acm(-2) (IP = 5 microA) results in local crystallization into anatase phase within 1 s of exposure and in reduction to TiO after an extended exposure of 60 s. Further reduction to the metallic state could be observed after 60 s of exposure at approximately 160 Acm(-2). The local reduction could be qualitatively sensed with WDX analysis and Auger line scans. An estimation of the film temperature in the beam center indicates that crystallization occurs at less than 150 degrees C, well below the atmospheric crystallization temperature of the present films. The high e-beam sensitivity in combination with the well-defined volume loss from oxygen desorption allows for precise electron lithographic topographical patterning of the present oxides. Irradiation effects leading to the observed reduction and crystallization phenomena under moderate electron energies are discussed.

Analysis of acid-base interactions at Al2O3 (11-20) interfaces by means of single molecule force spectroscopy

NASA Astrophysics Data System (ADS)

Mosebach, Bastian; Ozkaya, Berkem; Giner, Ignacio; Keller, Adrian; Grundmeier, Guido

2017-10-01

Single molecule force spectroscopy (SMFS) was employed to investigate the interaction forces between aliphatic amino, hydroxyl and ether groups and aluminum oxide single crystal surfaces in an aqueous electrolyte at pH = 6. The force studies were based on the variation of the terminal group of polyethylene glycol which was bound via a Ssbnd Au bond to the gold coated AFM tip. X-ray Photoelectron Spectroscopy (XPS) was performed to characterize the surface chemistry of the substrate. Force distance curves were measured between the PEG-NH2, sbnd OH and sbnd OCH3 functionalized atomic force microscope (AFM) tip and the non-polar single crystalline Al2O3(11-20) surface. The experimental results exhibit non-equilibrium desorption events which hint at acid-base interactions of the electron donating hydroxyl and amino groups with Al-ions in the surface of the oxide. The observed desorption forces for the sbnd NH2, sbnd OH/Al2O3(11-20) were in the range of 100-200 pN.

A mass spectrometric system for analyzing thermal desorption spectra of ion-implanted argon and cesium in tungsten. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Wood, G. M., Jr.

1974-01-01

A mass spectrometric system for determining the characteristics of materials used in instrumental development and aerospace applications was developed. The desorption spectra of cesium that was ion-implanted into polycrystalline tungsten and the effects on the spectra of bombardment of the tungsten by low energy (70 eV) electrons were investigated. Work function changes were measured by the retarding potential diode method. Flash desorption characteristics were observed and gas-reaction mechanisms of the surface of heated metal filaments were studied. Desorption spectra were measured by linearly increasing the sample temperature at a selected rate, the temperature cycling being generated from a ramp-driven dc power supply, with the mass spectrometer tuned to a mass number of interest. Results of the study indicate an anomolous desorption mechanism following an electron bombardment of the sample surface. The enhanced spectra are a function of the post-bombardment time and energy and are suggestive of an increased concentration of cesium atoms, up to 10 or more angstroms below the surface.

Kinetics of Cation and Oxyanion Adsorption and Desorption on Ferrihydrite: Roles of Ferrihydrite Binding Sites and a Unified Model.

PubMed

Tian, Lei; Shi, Zhenqing; Lu, Yang; Dohnalkova, Alice C; Lin, Zhang; Dang, Zhi

2017-09-19

Quantitative understanding the kinetics of toxic ion reactions with various heterogeneous ferrihydrite binding sites is crucial for accurately predicting the dynamic behavior of contaminants in environment. In this study, kinetics of As(V), Cr(VI), Cu(II), and Pb(II) adsorption and desorption on ferrihydrite was studied using a stirred-flow method, which showed that metal adsorption/desorption kinetics was highly dependent on the reaction conditions and varied significantly among four metals. High resolution scanning transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy showed that all four metals were distributed within the ferrihydrite aggregates homogeneously after adsorption reactions. Based on the equilibrium model CD-MUSIC, we developed a novel unified kinetics model applicable for both cation and oxyanion adsorption and desorption on ferrihydrite, which is able to account for the heterogeneity of ferrihydrite binding sites, different binding properties of cations and oxyanions, and variations of solution chemistry. The model described the kinetic results well. We quantitatively elucidated how the equilibrium properties of the cation and oxyanion binding to various ferrihydrite sites and the formation of various surface complexes controlled the adsorption and desorption kinetics at different reaction conditions and time scales. Our study provided a unified modeling method for the kinetics of ion adsorption/desorption on ferrihydrite.

CCl 4 chemistry on the reduced selvedge of a α-Fe 2O 3(0 0 0 1) surface: a scanning tunneling microscopy study

NASA Astrophysics Data System (ADS)

Rim, Kwang Taeg; Fitts, Jeffrey P.; Müller, Thomas; Adib, Kaveh; Camillone, Nicholas; Osgood, Richard M.; Joyce, S. A.; Flynn, George W.

2003-09-01

Scanning tunneling microscopy (STM) and low energy electron diffraction (LEED) were used to study the degradation of CCl 4 on the reduced selvedge of a natural single crystal α-Fe 2O 3(0 0 0 1) surface in ultrahigh vacuum. Before exposure to CCl 4, STM images indicate that approximately 85% of the reduced surface exhibits a Fe 3O 4(1 1 1) 2 × 2 termination, while the remaining 15% is terminated by 1 × 1 and superstructure phases. Images obtained after room temperature dosing with CCl 4 and subsequent flashing to 600 K reveal that chlorine atoms are adsorbed only on surface regions with the Fe 3O 4(1 1 1) 2 × 2 termination, not on 1 × 1 and superstructure regions. Chlorine atoms from dissociative adsorption of CCl 4 are observed to occupy two distinct positions located atop lattice protrusions and in threefold oxygen vacancy sites. However, in companion chemical labeling experiments, chlorine atoms provided by room temperature, dissociative Cl 2 adsorption on this surface are found to occupy sites atop lattice protrusions exclusively. The clear dissimilarity in STM feature shape and brightness at the two distinct chlorine adsorption sites arising from CCl 4 dissociation as well as the results of the Cl 2 chemical labeling experiments are best explained via reactions on a Fe 3O 4(1 1 1) 2 × 2 selvedge terminated by a 1/4 monolayer of tetrahedrally coordinated iron atoms. On this surface, adsorption atop an iron atom occurs for both the CCl 4 and Cl 2 dissociative reactions. A second adsorption site, assigned as binding to second layer iron atoms left exposed following surface oxygen atom abstraction resulting in the formation of phosgene (COCl 2), only appears in the case of reaction with CCl 4. The reaction mechanism and active site requirements for CCl 4 degradation on iron oxide surfaces are discussed in light of this evidence and in the context of our previously reported results from Auger electron spectroscopy (AES), LEED, temperature-programmed desorption (TPD), and X-ray photoelectron spectroscopy studies.

Kinetic and isothermal adsorption-desorption of PAEs on biochars: effect of biomass feedstock, pyrolysis temperature, and mechanism implication of desorption hysteresis.

PubMed

Jing, Fanqi; Pan, Minjun; Chen, Jiawei

2018-04-01

Biochar has the potential to sequester biomass carbon efficiently into land, simultaneously while improving soil fertility and crop production. Biochar has also attracted attention as a potential sorbent for good performance on adsorption and immobilization of many organic pollutants such as phthalic acid esters (PAEs), a typical plasticizer in plastic and presenting a current environmental issue. Due to lack of investigation on the kinetic and thermodynamic adsorption-desorption of PAEs on biochar, we systematically assessed adsorption-desorption for two typical PAEs, dimethyl phthalate (DMP) and diethyl phthalate (DEP), using biochar derived from peanut hull and wheat straw at different pyrolysis temperatures (450, 550, and 650 °C). The aromaticity and specific surface area of biochars increased with the pyrolysis temperature, whereas the total amount of surface functional groups decreased. The quasi-second-order kinetic model could better describe the adsorption of DMP/DEP, and the adsorption capacity of wheat straw biochars was higher than that of peanut hull biochars, owing to the O-bearing functional groups of organic matter on exposed minerals within the biochars. The thermodynamic analysis showed that DMP/DEP adsorption on biochar is physically spontaneous and endothermic. The isothermal desorption and thermodynamic index of irreversibility indicated that DMP/DEP is stably adsorbed. Sorption of PAEs on biochar and the mechanism of desorption hysteresis provide insights relevant not only to the mitigation of plasticizer mobility but also to inform on the effect of biochar amendment on geochemical behavior of organic pollutants in the water and soil.

Time-resolved spectroscopy at surfaces and adsorbate dynamics:insights from a model-system approach

NASA Astrophysics Data System (ADS)

Boström, Emil; Mikkelsen, Anders; Verdozzi, Claudio

We introduce a finite-system, model description of the initial stages of femtosecond laser induced desorption at surfaces. Using the exact many-body time evolution and also results from a novel time-dependent DFT description for electron-nuclear systems, we analyse the competition between several surface-response mechanisms and electronic correlations in the transient and longer time dynamics under the influence of dipole-coupled fields. Our model allows us to explore how coherent multiple-pulse protocols impact desorption in a variety of prototypical experiments.

Acidity, oxophilicity and hydrogen sticking probability of supported metal catalysts for hydrodeoxygenation process

NASA Astrophysics Data System (ADS)

Lup, A. Ng K.; Abnisa, F.; Daud, W. M. A. W.; Aroua, M. K.

2018-03-01

Hydrodeoxygenation is an oxygen removal process that occurs in the presence of hydrogen and catalysts. This study has shown the importance of acidity, oxophilicity and hydrogen sticking probability of supported metal catalysts in having high hydrodeoxygenation activity and selectivity. These properties are required to ensure the catalyst has high affinity for C-O or C=O bonds and the capability for the adsorption and activation of H2 and O-containing compounds. A theoretical framework of temperature programmed desorption technique was also discussed for the quantitative understanding of these properties. By using NH3-TPD, the nature and abundance of acid sites of catalyst can be determined. By using H2-TPD, the nature and abundance of metallic sites can also be determined. The desorption activation energy could also be determined based on the Redhead analysis of TPD spectra with different heating rates.

Hydrodeoxygenation of Guaiacol Over Pt/Al-SBA-15 Catalysts.

PubMed

Yu, Mi Jin; Park, Sung Hoon; Jeon, Jong-Ki; Ryu, Changkook; Sohn, Jung Min; Kim, Sang Chai; Park, Young-Kwon

2015-01-01

Upgrading of bio-oil through catalytic hydrodeoxygenation (HDO) reaction was investigated for guaiacol as a model compound. A batch reactor was used for the reaction condition of 40 bar and 250 degrees C. The target product was cyclohexane. Pt/Al-SBA-15 with the Si/Al ratios of 20, 40, and 80 and Pt/HZSM-5 were used as the catalyst. The SBA-15 catalysts were characterized by N2 adsorption-desorption, X-ray diffraction analysis, and temperature programmed desorption of ammonia. The order of cyclohexane yield was Pt/Al-SBA-15 (Si/Al = 20) > Pt/Al-SBA-15(40) > Pt/Al-SBA-15 (80), indicating that the quantity of acid sites plays an important role in the HDO reaction. On the other hand, Pt/HZSM-5 led to a very low cyclohexane yield, in spite of its abundant strong acid sites, due to its small pore size.

Experimental study and modelling of deuterium thermal release from Be-D co-deposited layers

NASA Astrophysics Data System (ADS)

Baldwin, M. J.; Schwarz-Selinger, T.; Doerner, R. P.

2014-07-01

A study of the thermal desorption of deuterium from 1 µm thick co-deposited Be-(0.1)D layers formed at 330 K by a magnetron sputtering technique is reported. A range of thermal desorption rates 0 ⩽ β ⩽ 1.0 K s-1 are explored with a view to studying the effectiveness of the proposed ITER wall and divertor bake procedure (β = 0 K s-1) to be carried out at 513 and 623 K. Fixed temperature bake durations up to 24 h are examined. The experimental thermal release data are used to validate a model input into the Tritium Migration and Analysis Program (TMAP-7). Good agreement with experiment is observed for a TMAP-7 model incorporating trap populations of activation energies for D release of 0.80 and 0.98 eV, and a dynamically computed surface D atomic to molecular recombination rate.

MnFe2O4-graphene oxide magnetic nanoparticles as a high-performance adsorbent for rare earth elements: Synthesis, isotherms, kinetics, thermodynamics and desorption.

PubMed

Ghobadi, Misagh; Gharabaghi, Mahdi; Abdollahi, Hadi; Boroumand, Zohreh; Moradian, Marzieh

2018-06-05

In recent decades, considerable amounts of rare earth elements have been used and then released into industrial wastewater, which caused serious environmental problems. In this work, in order to recycle rare earth cations (La 3+ and Ce 3+ ) from aqueous solutions, MnFe 2 O 4 -Graphene oxide magnetic nanoparticles were synthesized and after characterization studies, their adsorption isotherms, kinetics, thermodynamics and desorption were comprehensively investigated. Characterized was performed using XRD, FE-SEM, FT-IR, Raman spectroscopy, VSM, BET and DLS. REE adsorption on MnFe 2 O 4 -GO was studied for the first time in the present work and the maximum adsorption capacity at the optimum condition (room temperature and pH = 7) for La 3+ and Ce 3+ were 1001 and 982 mg/g respectively, and the reactions were completed within 20 min. In addition, the adsorption data were well matched with the Langmuir model and the adsorption kinetics were fitted with the pseudo-second order model. The thermodynamic parameters were calculated and the reactions were found to be endothermic and spontaneous. Moreover, the Dubinin-Radushkevich model predicted chemical ion-exchange adsorption. Desorption studies also demonstrated that MnFe 2 O 4 -GO can be regenerated for multiple reuses. Overall, high adsorption capacity, chemical stability, reusability, fast kinetics, easy magnetic separation, and simple synthesis method indicated that MnFe 2 O 4 -GO is a high-performance adsorbent for REE. Copyright © 2018. Published by Elsevier B.V.

40 CFR 65.145 - Nonflare control devices used to control emissions from storage vessels or low-throughput...

Code of Federal Regulations, 2012 CFR

2012-07-01

... inlet stream and, if applicable, the desorption schedule, the regeneration stream pressure or temperature, and the flow rate of the regeneration stream. For vacuum desorption, pressure drop shall be...

40 CFR 65.145 - Nonflare control devices used to control emissions from storage vessels or low-throughput...

Code of Federal Regulations, 2013 CFR

2013-07-01

... inlet stream and, if applicable, the desorption schedule, the regeneration stream pressure or temperature, and the flow rate of the regeneration stream. For vacuum desorption, pressure drop shall be...

40 CFR 63.985 - Nonflare control devices used to control emissions from storage vessels and low throughput...

Code of Federal Regulations, 2011 CFR

2011-07-01

... inlet stream and, if applicable, the desorption schedule, the regeneration stream pressure or temperature, and the flow rate of the regeneration stream. For vacuum desorption, pressure drop shall be...

40 CFR 63.985 - Nonflare control devices used to control emissions from storage vessels and low throughput...

Code of Federal Regulations, 2012 CFR

2012-07-01

... inlet stream and, if applicable, the desorption schedule, the regeneration stream pressure or temperature, and the flow rate of the regeneration stream. For vacuum desorption, pressure drop shall be...

40 CFR 63.985 - Nonflare control devices used to control emissions from storage vessels and low throughput...

Code of Federal Regulations, 2014 CFR

2014-07-01

... inlet stream and, if applicable, the desorption schedule, the regeneration stream pressure or temperature, and the flow rate of the regeneration stream. For vacuum desorption, pressure drop shall be...

40 CFR 65.145 - Nonflare control devices used to control emissions from storage vessels or low-throughput...

Code of Federal Regulations, 2014 CFR

2014-07-01

... inlet stream and, if applicable, the desorption schedule, the regeneration stream pressure or temperature, and the flow rate of the regeneration stream. For vacuum desorption, pressure drop shall be...