scholarly journals Reactivity of formic acid (HCOOH) with H atoms on cold surfaces of interstellar interest

2020 ◽  
Vol 636 ◽  
pp. A4
Author(s):  
Henda Chaabouni ◽  
Saoud Baouche ◽  
Stephan Diana ◽  
Marco Minissale
Keyword(s):  
Formic Acid ◽  
Pyrolytic Graphite ◽  
High Vacuum ◽  
Amorphous Solid ◽  
Product Formation ◽  
Ultra High Vacuum ◽  
Star Forming ◽  
Chemical Surface ◽  
Surface Temperatures ◽  
Temperature Programmed

Context. Formic acid (HCOOH) is the simplest organic carboxylic acid in chemical synthesis and the significant species in interstellar chemistry. HCOOH has been abundantly detected in interstellar ices, dense molecular clouds and star-forming regions. Aims. Laboratory hydrogenation experiments of HCOOH molecules with H atoms were performed with two cryogenic ultra-high vacuum devices on amorphous solid water ices, and highly oriented pyrolytic graphite surfaces. The aim of this work is to study the reactivity of HCOOH molecules with H atoms at low surface temperature 10 K, low surface coverage of one monolayer to three layers, and low H-atom flux of about 3.0 × 1012 molecule cm−2 s−1. Methods. HCOOH and H beams were deposited on cold surfaces held at 10 K, and the condensed films were analyzed by in-situ Reflection Absorption InfraRed Spectroscopy and temperature programmed desorption (TPD) mass spectrometry technique by heating the sample from 10 to 200 K. Results. Using the temperature programmed during exposure desorption technique, we highlight the possible dimerization of HCOOH molecules at low surface temperatures between 10 and 100 K. In our HCOOH+H experiments, we evaluated a consumption of 20–30% of formic acid by comparing the TPD curves at m/z 46 of pure and H-exposed HCOOH ice. Conclusions. The hydrogenation HCOOH+H reaction is efficient at low surface temperatures. The main products identified experimentally are carbon dioxide (CO2) and water (H2O) molecules. CO bearing species CH3OH, and H2CO are also detected mainly on graphite surfaces. A chemical surface reaction route for the HCOOH+H system is proposed to explain the product formation.

Thin Pyrolytic Graphite Films for Electron Microscope Substrates

1971 ◽  
Vol 29 ◽  
pp. 226-227 ◽  
Author(s):  
George H. N. Riddle ◽  
Benjamin M. Siegel
Keyword(s):  
Vacuum Chamber ◽  
Pyrolytic Graphite ◽  
High Vacuum ◽  
Dark Field ◽  
Ultra High Vacuum ◽  
Graphite Substrate ◽  
Nickel Substrate ◽  
Routine Procedure ◽  
Field Electron Microscopy ◽  
Dark Field Electron

A routine procedure for growing very thin graphite substrate films has been developed. The films are grown pyrolytically in an ultra-high vacuum chamber by exposing (111) epitaxial nickel films to carbon monoxide gas. The nickel serves as a catalyst for the disproportionation of CO through the reaction 2C0 → C + CO2. The nickel catalyst is prepared by evaporation onto artificial mica at 400°C and annealing for 1/2 hour at 600°C in vacuum. Exposure of the annealed nickel to 1 torr CO for 3 hours at 500°C results in the growth of very thin continuous graphite films. The graphite is stripped from its nickel substrate in acid and mounted on holey formvar support films for use as specimen substrates.The graphite films, self-supporting over formvar holes up to five microns in diameter, have been studied by bright and dark field electron microscopy, by electron diffraction, and have been shadowed to reveal their topography and thickness. The films consist of individual crystallites typically a micron across with their basal planes parallel to the surface but oriented in different, apparently random directions about the normal to the basal plane.

scholarly journals Nitrile versus isonitrile adsorption at interstellar grain surfaces

2017 ◽  
Vol 608 ◽  
pp. A50 ◽  
Author(s):  
M. Bertin ◽  
M. Doronin ◽  
X. Michaut ◽  
L. Philippe ◽  
A. Markovits ◽  
...  
Keyword(s):  
Density Functional ◽  
Surface Defects ◽  
High Vacuum ◽  
Solid Support ◽  
Ultra High Vacuum ◽  
Structural Defects ◽  
Adsorption Energies ◽  
The Difference ◽  
Temperature Programmed ◽  
Open Question

Context. Almost 20% of the ~200 different species detected in the interstellar and circumstellar media present a carbon atom linked to nitrogen by a triple bond. Of these 37 molecules, 30 are nitrile R-CN compounds, the remaining 7 belonging to the isonitrile R-NC family. How these species behave in their interactions with the grain surfaces is still an open question. Aims. In a previous work, we have investigated whether the difference between nitrile and isonitrile functional groups may induce differences in the adsorption energies of the related isomers at the surfaces of interstellar grains of various nature and morphologies. This study is a follow up of this work, where we focus on the adsorption on carbonaceous aromatic surfaces. Methods. The question is addressed by means of a concerted experimental and theoretical approach of the adsorption energies of CH3CN and CH3NC on the surface of graphite (with and without surface defects). The experimental determination of the molecule and surface interaction energies is carried out using temperature-programmed desorption in an ultra-high vacuum between 70 and 160 K. Theoretically, the question is addressed using first-principle periodic density functional theory to represent the organised solid support. Results. The adsorption energy of each compound is found to be very sensitive to the structural defects of the aromatic carbonaceous surface: these defects, expected to be present in a large numbers and great diversity on a realistic surface, significantly increase the average adsorption energies to more than 50% as compared to adsorption on perfect graphene planes. The most stable isomer (CH3CN) interacts more efficiently with the carbonaceous solid support than the higher energy isomer (CH3NC), however.

Deposition of Iron on Si(111)-(7×7): Photo- and Electron-Assisted Decomposition of Fe(CO)5

1986 ◽  
Vol 75 ◽  
Author(s):  
J. R. Swanson ◽  
C. M. Friend ◽  
Y. J. Chabal
Keyword(s):  
Auger Electron ◽  
Silicon Crystal ◽  
High Vacuum ◽  
Low Frequency ◽  
Temperature Programmed Desorption ◽  
Thermal Reaction ◽  
Ultra High Vacuum ◽  
Temperature Programmed ◽  
Ultraviolet Photons ◽  
Induced Decomposition

AbstractLaser- and electron-assisted deposition of Fe on Si(111)-(7×7) surfaces using decomposition of Fe(CO)5 has been investigated with multiple internal reflection Fourier transform infrared, Auger electron and temperature programmed desorption spectroscopies and low energy electron diffraction under ultra-high vacuum conditions. No thermal reaction was apparent in temperature programmed desorption experiments: only molecular Fe(CO)5 desorption was observed at temperatures of 150 and 170 K, corresponding to desorption energies in the range of 7–10 kcal./mole. Fe(CO)5 decomposition could be induced using either incident 1.6 keV electrons or ultraviolet photons. Significant amounts of carbon were deposited from the electron induced decomposition, consistent with earlier reports on the Si(100) surface. In contrast, ultraviolet photolysis did not result in any detectable incorporation of carbon or oxygen into the iron deposits. No partially decarbonylated Fe(CO)x, x<5, fragments were detected subsequent to exposure to photons using infrared spectroscopy. However, a new, unresolved low frequency shoulder did appear in the infrared spectrum after exposing the Fe(CO)5 covered Si(111)-(7×7) crystal to the electron beam. Iron photodeposition was evident in the Auger electron spectra obtained subsequent to photolysis and annealing of the surface to either 300 K or 1000 K in order to desorb unreacted Fe(CO)5. These data suggest that there are no surface stable Fe(CO)x, x<5, species in the photodeposition process. Instead, photolysis yields Fe atoms directly, even at low temperatures. Annealing to temperatures on the order of 1000 K subsequent to iron deposition resulted in a significant decrease in the Fe:Si ratio as measured by Auger electron spectroscopy. In addition, CO could not be readsorbed on a surface where the Fe(CO)5 had been decomposed. This is attributed to dissolution of Fe into the bulk silicon crystal.

Hydridization and catalysis by lanthanide films

1984 ◽  
Vol 393 (1805) ◽  
pp. 257-276 ◽  
Keyword(s):  
Activation Energy ◽  
High Vacuum ◽  
Deuterium Atom ◽  
Ultra High Vacuum ◽  
Gas Uptake ◽  
Metal Sublattice ◽  
Hydrogen Deuterium ◽  
Higher Temperature ◽  
Temperature Programmed ◽  
Interstitial Hydrogen

Hydrogen absorption to give the dihydrides MH 2+1 containing interstitial hydrogen H i has been studied for the metals Gd, Dy, Er, Yb and Lu in the form of films deposited in ultra-high vacuum on glass. Film areas were determined by Kr adsorption, and hydrogen content, in particular inter­stitial hydrogen H i , characterized by gas uptake, temperature programmed desorption, electrical conductivity and work function measurements by the diode method. The catalytic activity of the dihydride films for the H 2 + D 2 → 2HD reaction was studied at a pressure of 1.1 Torr over 175-579 K, and at 273 K over 0.19-6.2 Torr. Arrhenius plots for the rate con­stant show a low temperature low activation energy region changing over at a temperature T c to a higher temperature higher activation energy régime, with T c on average for the five metals about 50 K below the tem­perature T max at which the interstitial hydrogen H i has disappeared. The suggested mechanisms are T < T c : D 2 + H i □ s → (D 2 H i )□ s → □ s D i + HD, (1) T > T c : D 2 + H 2 + 4□ s → 2(D i □ s ) (H i □ s ) → 4□ s + 2HD, (2) where H i □ s , D i □ s , denotes a hydrogen, deuterium, atom held on a surface octahedral site in the f. c. c. metal sublattice. These mechanisms agree with the observed approximate first-order pressure dependency down to 77 K. The rate constants at both 273 K (under T c ) and 573 K (over T c ) decrease over Gd, Dy, Er, to Yb, and rise again to Lu, and this is discussed in terms of the metal-hydrogen, H i □ s or D i □ s bond strength.

Novel Morphology of Voids in Single-Quasicrystalline Icosahedral Al70.5Pd21.0Mn8.5

1998 ◽  
Vol 53 (8) ◽  
pp. 679-683 ◽  
Author(s):  
Y. Waseda ◽  
S. Suzuki ◽  
K. Urbanb
Keyword(s):  
Electron Microscope ◽  
Scanning Electron Microscope ◽  
Electron Spectroscopy ◽  
Auger Electron ◽  
Surface Composition ◽  
High Vacuum ◽  
Ultra High Vacuum ◽  
Chemical Surface ◽  
Habit Planes ◽  
Scanning Electron

Abstract This paper deals with the morphology and surface chemistry of faceted voids existing in singlequasicrystalline icosahedral Al70.5Pd21.0Mn8.5. By observation with a scanning electron microscope of surfaces obtained by cleavage of the quasicrystal, the habit planes of the dodecahedral voids were identified. The chemical surface composition of the void surface was determined by Auger electron spectroscopy after cleavage in ultra-high vacuum.

Selective Oxidation of Ammonia on Ruthenium to Form p(2 x 2) Nitrogen Layer

2013 ◽  
Vol 6 (1) ◽  
Author(s):  
S. Balgooyen ◽  
I. Waluyo
Keyword(s):  
Low Temperature ◽  
High Vacuum ◽  
Hydrogenation Reaction ◽  
Ultra High Vacuum ◽  
Surface Chemical ◽  
Low Energy Electron Diffraction ◽  
Chemical Studies ◽  
Low Energy Electron ◽  
Temperature Programmed ◽  
Oxidation Of Ammonia

Oxidation of ammonia was used to prepare a p(2 x 2) nitrogen layer on the Ru(0001) surface as verified by temperature-programmed desorption (TPD) and low energy electron diffraction (LEED). The process takes place in an ultra-high vacuum (UHV) chamber. The surface is precovered with oxygen and then exposed to ammonia at low temperature. Upon heating, the ammonia is oxidized to form water, which desorbs at low temperature to leave a nitrogencovered surface. The resulting layer can be used in a variety of surface chemical studies, including a hydrogenation reaction, which is an important part in the study of the Haber-Bosch process, in which ruthenium is used as a catalyst.

IN SITU STM INVESTIGATION OF Ge NANOSTRUCTURES WITH AND WITHOUT Sb ON GRAPHITE

2006 ◽  
Vol 13 (02n03) ◽  
pp. 241-249
Author(s):  
SUNIL SINGH KUSHVAHA ◽  
ZHIJUN YAN ◽  
MAO-JIE XU ◽  
WENDE XIAO ◽  
XUE-SEN WANG
Keyword(s):  
Room Temperature ◽  
Pyrolytic Graphite ◽  
High Vacuum ◽  
Ultra High Vacuum ◽  
Scanning Tunneling ◽  
Tunneling Microscopy ◽  
Initial Stage ◽  
Defect Sites ◽  
Substrate Defects

Germanium was deposited onto highly oriented pyrolytic graphite (HOPG) with and without antimony in ultra-high vacuum. The surface morphology was analyzed using in situ scanning tunneling microscopy (STM) at room temperature (RT). The film grows exclusively in 3D island mode and was affected significantly by substrate defects. At initial stage, nucleation of cluster occurred at step edges and defect sites. Later, we found various types of Ge nanostructures on HOPG in different deposition conditions and stages, including cluster chains, cluster islands, nanowires, and double layer ramified islands at RT. Compact Ge islands were observed when depositing at a substrate temperature of 450 K or after an annealing at 600 K following RT deposition. In addition, the pre-deposited Sb on graphite enhances the sticking probability and suppresses the surface diffusion of Ge atoms, resulting in a significant increase in Ge cluster island density on HOPG terraces.

scholarly journals Conducting High-Spin (S = 1) Organic Diradical with Robust Stability

2020 ◽  
Author(s):  
Shuyang Zhang ◽  
Maren Pink ◽  
Tobias Junghoefer ◽  
Wenchao Zhao ◽  
Sheng-Ning Hsu ◽  
...  
Keyword(s):  
Thin Films ◽  
Robust Stability ◽  
Ground State ◽  
Pyrolytic Graphite ◽  
High Vacuum ◽  
Ultra High Vacuum ◽  
Paramagnetic Resonance ◽  
Triplet Ground State ◽  
Out Of Plane ◽  
Electron Paramagnetic

Triplet ground-state organic molecules are of interest with respect to several emerging technologies but usually show limited stability, especially, as thin films. We report an organic diradical, based entirely on two Blatter radicals, that possesses triplet ground state (2J/k ≈ 220 K, EST ≈ 0.4 kcal mol-1 ) and robust stability, with onset of decomposition above 264 C (TGA). Polycrystalline diradical is a good electrical conductor with conductivity comparable to the out-of-plane conductivity in highly oriented pyrolytic graphite (HOPG). The diradical is evaporated under ultra-high vacuum to form thin films, which are stable on air for at least 18 and 48 h, as demonstrated by X-ray photoelectron and electron paramagnetic resonance (EPR) spectroscopies, respectively. <br>

scholarly journals Segregation effect and N2 binding energy reduction in CO-N2 systems adsorbed on water ice substrates

2018 ◽  
Vol 619 ◽  
pp. A111 ◽  
Author(s):  
T. Nguyen ◽  
S. Baouche ◽  
E. Congiu ◽  
S. Diana ◽  
L. Pagani ◽  
...  
Keyword(s):  
Binding Energy ◽  
Gas Phase ◽  
Adsorption Energy ◽  
High Vacuum ◽  
Amorphous Solid ◽  
Abundant Species ◽  
Binding Energies ◽  
Ultra High Vacuum ◽  
Pure Species ◽  
Water Ice

Context. CO and N2 are two abundant species in molecular clouds. CO molecules are heavily depleted from the gas phase towards the centre of pre-stellar cores, whereas N2 maintains a high gas phase abundance. For example, in the molecular cloud L183, CO is depleted by a factor of ≈400 in its centre with respect to the outer regions of the cloud, whereas N2 is only depleted by a factor of ≈20. The reason for this difference is not yet clear, since CO and N2 have identical masses, similar sticking properties, and a relatively close energy of adsorption. Aims. We present a study of the CO-N2 system in sub-monolayer regimes, with the aim to measure, analyse and elucidate how the adsorption energy of the two species varies with coverage, with much attention to the case where CO is more abundant than N2. Methods. Experiments were carried out using the ultra-high vacuum (UHV) set-up called VENUS. Sub-monolayers of either pure 13CO or pure 15N2 and 13CO:15N2 mixtures were deposited on compact amorphous solid water ice, and crystalline water ice. Temperature-programmed desorption experiments, monitored by mass spectrometry, are used to analyse the distributions of binding energies of 13CO and 15N2 when adsorbed together in different proportions. Results. The distribution of binding energies of pure species varies from 990 K to 1630 K for 13CO, and from 890 K to 1430 K for 15N2. When a CO:N2 mixture is deposited, the 15N2 binding energy distribution is strongly affected by the presence of 13CO, whereas the adsorption energy of CO is unaltered. Conclusions. Whatever types of water ice substrate we used, the N2 effective binding energy was significantly lowered by the presence of CO molecules. We discuss the possible impact of this finding in the context of pre-stellar cores.

scholarly journals Surface effects on a photochromic spin-crossover iron(ii) molecular switch adsorbed on highly oriented pyrolytic graphite

Nanoscale ◽  
2019 ◽  
Vol 11 (42) ◽  
pp. 20006-20014 ◽  
Author(s):  
Lorenzo Poggini ◽  
Giacomo Londi ◽  
Magdalena Milek ◽  
Ahmad Naim ◽  
Valeria Lanzilotto ◽  
...  
Keyword(s):  
Thin Films ◽  
Spin Crossover ◽  
Pyrolytic Graphite ◽  
High Vacuum ◽  
Surface Effects ◽  
Molecular Switch ◽  
Ultra High Vacuum ◽  
Highly Oriented Pyrolytic Graphite

Thin films of Fe(ii) complex with a diarylethene-based ligand featuring spin-crossover have been grown by sublimation in ultra-high vacuum on highly oriented pyrolytic graphite and spectroscopically characterized through a multi technique approach.

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