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At least 19 records

Accelerated reactions in field desorption mass spectrometry

Field desorption mass spectrometry under ambient conditions is used to study solution-phase organic reactions in micro-volumes. Reagent solution is transferred onto the microdendrites of the field emitter, and reaction products are examined online by mass spectrometry. Three reactions, hydrazone formation by phenyl hydrazine and indoline-2,3-dione, the Katritzky reaction between a pyrylium salt and anisidine, and the Hantzsch synthesis of 1,4-dihydropyridine, were investigated, and reaction acceleration was observed to different extents. The increase in rate relative to the corresponding bulk reactions is attributed to solvent evaporation (simple concentration effect) and to the increase of surface-to-volume ratio (enhanced interfacial reactions). A distinguishing feature of this method of reaction acceleration, relative to that based on nano electrospray ionization, is the observation of radical cations and the formation of radical cation products. The research also breaks new ground in using field emitters at atmospheric pressure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Field-Induced Desorption of Cesium from Rhenium

Desorption of cesium atoms from a rhenium point emitter in an electric field has been studied by method of field-desorption microscopy (FDM). Dependence of the desorbing field on degree of emitter surface coverage with Cs atoms is established. The heat of Cs-atom adsorption, which is dependent on the surface concentration of adsorbate and work function of the surface, is estimated in the framework of the model of mirror-image forces for field-induced desorption. Saturation of the rhenium emitter with carbon leads to changes in the character of desorption and in the distribution of desorption zones on the emitter surface.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Anomalous Field-Induced Desorption of Cesium from a Quasi-Spherical Surface of a Carbon-Saturated Rhenium Crystal

Investigation of the field-induced desorption of cesium atoms from the surface of rhenium crystal emitter carbon-saturated in benzene vapors showed that, after desorption from the surface, the process continues and there appears a contour of desorption around {10 1-bar 1} and {1 1-bar 00} faces that contracts toward the centers of faces with increasing field strength. This previously unreported anomalous behavior of the field-induced desorption is explained by the intercalation of cesium into graphite structures formed on the emitter surface.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Field Ion Source Development for Neutron Generators

An ion source based on the principles of electrostatic field desorption is being developed to improve the performance of existing compact neutron generators. The ion source is an array of gated metal tips derived from field electron emitter array microfabrication technology. A comprehensive summary of development and experimental activities is presented. Many structural modifications to the arrays have been incorporated to achieve higher tip operating fields, while lowering fields at the gate electrode to prevent gate field electron emission which initiates electrical breakdown in the array. The latest focus of fabrication activities has been on rounding the gate electrode edge and surrounding the gate electrode with dielectric material. Array testing results have indicated a steady progression of increased array tip operating fields with each new design tested. The latest arrays have consistently achieved fields beyond those required for the onset of deuterium desorption ({approx}20 V/nm), and have demonstrated the desorption of deuterium at fields up to 36 V/nm. The number of ions desorbed from an array has been quantified, and field desorption of metal tip substrate material from array tips has been observed for the first time. Gas-phase field ionization studies with {approx}10,000 tip arrays have achieved deuterium ion currents of {approx}50 nA. Neutron production by field ionization has yielded {approx}10{sup 2} n/s from {approx}1 mm{sup 2} of array area using the deuterium-deuterium fusion reaction at 90 kV.

36 MATERIALS SCIENCE↗

Electron beam assisted field evaporation of insulating nanowires/tubes

We demonstrate field evaporation of insulating materials, specifically BN nanotubes and undoped Si nanowires, assisted by a convergent electron beam. Electron irradiation leads to positive charging at the nano-object's apex and to an important increase of the local electric field thus inducing field evaporation. Experiments performed both in a transmission electron microscope and in a scanning electron microscope are presented. This technique permits the selective evaporation of individual nanowires in complex materials. Electron assisted field evaporation could be an interesting alternative or complementary to laser induced field desorption used in atom probe tomography of insulating materials.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Self-Supplied Liquid Injection Field Desorption/Ionization Ion Source for an Orthogonal Time-of-Flight Instrument

A new implementation of a dedicated ion source for field ionization (FI), field desorption (FD), and liquid injection field desorption/ionization (LIFDI) for the JEOL AccuTOF GC series of orthogonal-acceleration time-of-flight instruments is presented. In contrast to existing implementations, this third-party LIFDI probe and source combination does not require the exchange of the entire ion source comprising ion source block and lens stack to switch from electron ionization (EI) to LIFDI. Rather, the methods may be swapped conveniently by only exchanging the ion source block for a mechanical probe guide and inserting the LIFDI probe in place of the standard direct insertion probe (DIP) via the vacuum lock. Further, this LIFDI setup does not require any changes of the electronics or software of the AccuTOF mass spectrometer because it is self-supplied in terms of power supply, observation optics, and computer control. The setup offers advanced FI/FD/LIFDI control features such as emission-controlled emitter heating current and emitter flash baking during elongated runs as required for gas chromatography-FI-mass spectrometry (MS). The LIFDI source and probe and its operation are reported in detail. FI spectra of the volatile analytes toluene, heptane, and pentafluoroiodobenzene are presented. LIFDI operation is demonstrated for the analysis of the saturated hydrocarbon dotriacontane and the low-mass hydrocarbon polymers polystyrene 484 and polystyrene 1050. Further, the air-sensitive 2nd-generation Hoveyda–Grubbs catalyst is analyzed by LIFDI-MS. For comparison with long-established LIFDI instrumentation, some of the spectra obtained with the new setup are also compared with those from a double-focusing magnetic sector instrument. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

A compact ion source and accelerator based on a piezoelectric driver

Compact ion sources and accelerators using piezoelectric devices for the production of energetic ion beams are being evaluated. A coupled source-accelerator is being tested as a neutron source to be incorporated into oil-well logging diagnostics. Two different ion sources are being investigated, including a piezoelectric transformer-based plasma source and a silicon-based field ion source. The piezoelectric transformer plasma ion source uses a cylindrical, resonantly driven piezoelectric crystal to produce high voltage inside a confined volume filled with low pressure deuterium gas. The plasma generated in the confined chamber is ejected through a small aperture into an evacuated drift region. The silicon field ion source uses localized electric field enhancement produced by an array of sharp emitters etched into a silicon blank to produce ions through field desorption ionization. A second piezoelectric device of a different design is used to generate an accelerating potential on the order of 130 kV; this potential is applied to a deuterated target plate positioned perpendicular to the ion stream produced by either plasma source. This paper discusses the results obtained by the individual components as they relate to the final neutron source.

07 ISOTOPE AND RADIATION SOURCES↗

Integrated field emission array for ion desorption

An integrated field emission array for ion desorption includes an electrically conductive substrate; a dielectric layer lying over the electrically conductive substrate comprising a plurality of laterally separated cavities extending through the dielectric layer; a like plurality of conically-shaped emitter tips on posts, each emitter tip/post disposed concentrically within a laterally separated cavity and electrically contacting the substrate; and a gate electrode structure lying over the dielectric layer, including a like plurality of circular gate apertures, each gate aperture disposed concentrically above an emitter tip/post to provide a like plurality of annular gate electrodes and wherein the lower edge of each annular gate electrode proximate the like emitter tip/post is rounded. Also disclosed herein are methods for fabricating an integrated field emission array.

47 OTHER INSTRUMENTATION↗

Integrated field emission array for ion desorption

An integrated field emission array for ion desorption includes an electrically conductive substrate; a dielectric layer lying over the electrically conductive substrate comprising a plurality of laterally separated cavities extending through the dielectric layer; a like plurality of conically-shaped emitter tips on posts, each emitter tip/post disposed concentrically within a laterally separated cavity and electrically contacting the substrate; and a gate electrode structure lying over the dielectric layer, including a like plurality of circular gate apertures, each gate aperture disposed concentrically above an emitter tip/post to provide a like plurality of annular gate electrodes and wherein the lower edge of each annular gate electrode proximate the like emitter tip/post is rounded. Also disclosed herein are methods for fabricating an integrated field emission array.

36 MATERIALS SCIENCE↗

Mass spectrometry

Advances in mass spectrometry (MS) and its applications over the past decade are reviewed in depth, with annotated literature references. New instrumentation and techniques surveyed include: modulated-beam MS, chromatographic MS on-line computer techniques, digital computer-compatible quadrupole MS, selected ion monitoring (mass fragmentography), and computer-aided management of MS data and interpretation. Areas of application surveyed include: organic MS and electron impact MS, field ionization kinetics, appearance potentials, translational energy release, studies of metastable species, photoionization, calculations of molecular orbitals, chemical kinetics, field desorption MS, high pressure MS, ion cyclotron resonance, biochemistry, medical/clinical chemistry, pharmacology, and environmental chemistry and pollution studies.

Burlingame, A. L.↗

GoAmazon 2014/15 Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS) Field Campaign Report

The Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS) deployment to the U.S. Department of Energy (DOE)’s Atmospheric Radiation Measurement (ARM) Climate Research Facility T3 site in Manacapuru, Brazil, was motivated by two main scientific objectives of the Green Ocean Amazon (GoAmazon) 2014/15 field campaign. 1) Study the interactions between anthropogenic and biogenic emissions by determining important molecular species in ambient nanoparticles. To address this, TDCIMS data will be combined with coincident measurements such as gas-phase sulfuric acid to determine the contribution of sulfuric acid condensation to nucleation and growth. We can then compare that result to TDCIMS-derived nanoparticle composition to determine the fraction of growth that can be attributed to the uptake of organic compounds. The molecular composition of sampled particles will also be used to attribute specific chemical species and mechanisms to growth, such as the condensation of low-volatility species or the oligomerization of α-dicarbonyl compounds. 2) Determine the source of new ambient nanoparticles in the Amazon. The hypothesis prior to measurements was that potassium salts formed from the evaporation of primary particles emitted by fungal spores can provide a unique and important pathway for new particle production in the Amazon basin. To explore this hypothesis, the TDCIMS recorded the mass spectra of sampled ambient particles using a protonated water cluster Chemical Ionization Mass Spectrometer (CIMS). Laboratory tests performed using potassium salts show that the TDCIMS can detect potassium with high sensitivity with this technique.

54 ENVIRONMENTAL SCIENCES↗

Elucidating the Roles of Electric Fields in Catalysis: A Perspective

This Perspective illustrates how the presence of internal and external electric fields can affect catalytic activity and selectivity, with a focus on heterogeneous catalysts. Specifically, experimental investigations of the electric field influence on catalyst selectivity in pulsed field mass desorption microscopes, scanning tunneling microscopes, probe–bed–probe reactors, continuous-circuit reactors, and capacitor reactors are described. Through these examples, we show how the electric field, whether externally applied or intrinsically present, can affect the behavior of a wide number of materials relevant to catalysis. Here, we review some of the theoretical methods that have been used to elucidate the influence of external electric fields on catalytic reactions, as well as the application of such methods to selective methane activation. In doing so, we illustrate the breadth of possibilities in field-assisted catalysis.

03 NATURAL GAS↗

The effect of Cu/Zn molar ratio on CO{sub 2} hydrogenation over Cu/ZnO/ZrO{sub 2}/Al{sub 2}O{sub 3} catalyst

Catalytic hydrogenation of carbon dioxide (CO{sub 2}) to methanol is an attractive way to recycle and utilize CO{sub 2}. A series of Cu/ZnO/Al{sub 2}O{sub 3}/ZrO{sub 2} catalysts (CZAZ) containing different molar ratios of Cu/Zn were prepared by the co-precipitation method and investigated in a stirred slurry autoclave system. The catalysts were characterized by temperature-programmed reduction (TPR), field emission scanning electron microscopy-energy dispersive analysis (FESEM-EDX), X-ray diffraction (XRD) and N{sub 2} adsorption-desorption. Higher surface area, SA{sub BET} values (42.6–59.9 m{sup 2}/g) are recorded at low (1) and high (5) Cu/Zn ratios with the minimum value of 35.71 m{sup 2}/g found for a Cu/Zn of 3. The reducibility of the metal oxides formed after calcination of catalyst samples was also affected due to change in metal-support interaction. At a low reaction temperature of 443 K, total gas pressure of 3.0 MPa and 0.1 g/mL of the CZAZ catalyst, the selectivity to methanol decreased as the Cu/Zn molar ratio increased, and the maximum selectivity of 67.73 was achieved at Cu/Zn molar ratio of 1. With a reaction time of 3h, the best performing catalyst was CZAZ75 with Cu/Zn molar ratio of 5 giving methanol yield of 79.30%.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗