Atmospheric Hydrogen Pressure Research Articles

Ps four-wave mixing measurements of electric field in a ns pulse discharge in a hydrogen diffusion flame

Time-resolved electric field in ns pulse discharge plasmas generated in room air and in an atmospheric pressure hydrogen diffusion flame has been measured by ps four-wave mixing, for plane-to-plane electrode geometry. Electric field is put on the absolute scale using the Laplacian field measured before breakdown. The results show that peak electric field during breakdown in the flame, approximately 40 kV/cm, is significantly lower compared to that in room air, 75 kV/cm, due to higher temperature of combustion products. In both cases, peak electric field is higher compared to DC breakdown field. Both in air and in the flame, the electric field follows the applied voltage before breakdown and decreases rapidly after breakdown, due to charge separation and plasma self-shielding. The electric field in air is compared with the predictions of an analytic model of ns pulse breakdown, showing good agreement between the predicted and the measured breakdown field. The model also predicts earlier breakdown as well as breakdown voltage reduction as the temperature is increased, in qualitative agreement with the experimental data. The use of the present ps four-wave mixing diagnostics for measurements of electric fields below ∼20 kV/cm in atmospheric pressure flames is challenging, due to low signal-to-noise. The sensitivity of the present diagnostics is controlled by the high temperature and low N2 fraction in the combustion product mixture, as well as by the limited bandwidth of the Stokes beam generated by the stimulated Raman cell, which provides access only to several rotational levels of nitrogen molecules. The present diagnostics will have much better sensitivity in high-pressure flames, since the four-wave mixing signal scales as the squared number density of nitrogen.

Pd Nanoparticles Supported on Cellulose as a Catalyst for Vanillin Conversion in Aqueous Media

Palladium nanoparticles were first anchored on modified biopolymer as an efficient catalyst for a biofuel upgrade. Fluorinated compounds was grafted onto cellulose to obtain amphiphilic supports for on water reactions. Pd catalyst was prepared by straightforward deposition of metal nanoparticles on modified cellulose. The catalyst exhibited excellent catalytic activity and selectivity in hydrodeoxygenation of vanillin (a typical model compound of lignin) to 2-methoxy-4-methylphenol under atmospheric hydrogen pressure in neat water without any other additives under mild conditions.

P-Stereogenic and Non-P-Stereogenic Ir-MaxPHOX in the Asymmetric Hydrogenation of N-Aryl Imines. Isolation and X-ray Analysis of Imine Iridacycles.

A small library of Ir-MaxPHOX catalysts has been applied to the asymmetric hydrogenation of N-aryl imines. A structure-activity analysis of the three-chiral-center MaxPHOX ligand has been performed. Using complex 1b, the hydrogenation of N-aryl imines took place with up to 96% enantiomeric excess at atmospheric pressure of hydrogen and low temperature. The impact of the stereochemical information at the phosphorus center is small with respect to the selectivity, but large with respect the catalyst activity. Non-P-stereogenic analogs of MaxPHOX were also synthesized and tested, but they provided lower selectivity. The selectivity observed could be explained by taking into account that the actual catalysts were cyclometalated imine complexes formed in situ. [IrHCl(MaxPHOX)(imine)] complexes 9 and 10 were synthesized and characterized by X-ray crystallography. These complexes, via chloride abstraction, provided the active catalytic species with the same levels of selectivity. Finally, the influence of the counterion on the catalyst performance was also studied.

Colloid and Nanosized Catalysts in Organic Synthesis: XIX.1 Influence of the Support Nature on Hydrogenation Catalysis of Cyclic Olefins by Nickel Nanoparticles

Gas-phase hydrogenation of cycloalkenes in the presence of nickel nanoparticles supported on Ceokar-2, BAU-A activated carbon, alumina, and NaX zeolite proceeds at 140–240°C and atmospheric pressure of hydrogen. The conversion and selectivity depend on the type of support and on the hydrogen excess.

Acetic acid hydrodeoxygenation on molybdenum carbide catalysts

Kinetics and site requirements of acetic acid hydrodeoxygenation on molybdenum carbide – a stable and selective catalyst under atmospheric hydrogen pressure.

Mild and Selective Synthesis of Secondary Amines Direct from the Coupling of Two Aldehydes with Ammonia

Synthesis of secondary amines direct from the coupling of two aldehydes was first reported in the presence of NH3 and H2 molecules. A magnetic material supported palladium catalyst (γ-Fe2O3@HAP-Pd) was found to be active for this transformation at room temperature and atmospheric hydrogen pressure, providing structurally diverse secondary amines with good to excellent yields (70.0–92.3%).

Characterisation of SnSe thin films fabricated by chemical molecular beam deposition for use in thin film solar cells

SnSe thin films were fabricated the first time by chemical molecular beam deposition (CMBD) in atmospheric pressure hydrogen flow using polycrystalline tin selenium (SnSe) precursors. The morphological and electrical properties of the films were studied as a function of the precursor’s composition and the substrate temperature. Experimental data indicate that in the resulting thin films Se enrichment takes place at low substrate temperatures, despite the different compositions of the SnSe precursor during the synthesis. In this case, the grain sizes of the films vary in the range of (8–20) μm, depending on the substrate temperature. In addition, X-ray diffraction analysis of the samples shows that the films have an orthorhombic crystalline structure. The electrical conductivity of films measured by van der Pauw method varies between 6 and 90 (Ω × cm)−1. The optical measurements on selected SnSe thin films illustrate that the samples have an optical bandgap of (1.1–1.2) eV and the absorption coefficient of ∼105 cm−1, which is suitable for thin film solar cells.

Colloid and nanosized catalysts in organic synthesis: XVII. Reductive amination of carbonitriles in the presence of supported nickel nanoparticles

Reductive amination of carbonitriles catalyzed by nickel nanoparticles applied onto a solid support in a plug flow reactor in the gas phase or the gas–liquid–solid catalyst system occurs at atmospheric pressure of hydrogen affording the nonsymmetrical secondary or tertiary amines. The effect of the support type on the target product yield and conversion of the substrate has been studied.

Vibrational kinetics of electronically excited states in H2 discharges

The evolution of atmospheric pressure hydrogen plasma under the action of repetitively ns electrical pulse has been investigated using a 0D state-to-state kinetic model that self-consistently couples the master equation of heavy particles and the Boltzmann equation for free electrons. The kinetic model includes, together with atomic hydrogen states and the vibrational kinetics of H2 ground state, vibrational levels of singlet states, accounting for the collisional quenching, having a relevant role because of the high pressure. The mechanisms of excitations, radiative decay and collisional quenching involving the excited H2 states and the corresponding cross sections, integrated over the non-equilibrium electron energy distribution function (EEDF) to obtain kinetic rates, are discussed in the light of the kinetic simulation results, i.e. the time evolution during the pulse of the plasma composition, of the EEDF and of the vibrational distributions of ground and singlet excited states.

Design of tandem catalyst by co-immobilization of metal and enzyme on mesoporous foam for cascaded synthesis of (R)-phenyl ethyl acetate

Co-operative and complex catalytic transformations in biological systems comprise a set of diverse reactions in a single compartment. Herein, palladium and Cal B lipase were sequentially co-immobilized in the microenvironment of mesocellular foam to mimic biological systems and fully characterized. At optimal conditions, complete hydrogenation of acetophenone was achieved at atmospheric hydrogen pressure. The in-situ formed racemic 1-phenyl ethanol was then kinetically resolved selectively using lipase immobilized on the same support using vinyl acetate as (R)-phenylethyl acetate. For comparison, a single pot reaction was also conducted wherein supply of hydrogen was discontinued after complete conversion of acetophenone and further kinetic resolution was carried out in nitrogen atmosphere by adding vinyl acetate to system. The reaction showed complete conversion in 10h for hydrogenation step while lipase catalyzed gave 49.11% of selectivity towards R enantiomer with respect to racemic mixture with 100% enantiomeric excess (ee). The designed tandem catalyst avoids the use of multiple supports, purification of intermediate product as well as use of multiple reactors making process green and economical.

Chemoselective hydrogenation of nitroarenes catalyzed by cellulose-supported Pd NPs

Cellulose-supported palladium nanoparticles (NPs) were prepared by straightforward deposition of metal NPs on modified cellulose. The catalyst exhibited excellent catalytic activity and selectivity in room-temperature hydrogenation of various nitroarenes to arylamines under atmospheric hydrogen pressure in neat water without any additives. High chemoselectivity was also achieved in the hydrogenation of substituted nitroarenes with multiple reducible groups. The catalyst can be recycled by simple centrifugation and reused for at least 4 times without significant decline of yields.

Catalytic Reduction of Nitroarenes by Dipalladium Complexes: Synergistic Effect

The direct reaction between 2,7-bis(2-pyridinyl)-1,8-naphthyridine (bpnp) and Pd(CH3COO)2 in CF3COOH yields the new dinuclear palladium(II) complex [Pd2(bpnp)(μ-OH)(CF3CO2)2](CF3CO2) (1). Similarly, substitution of Pd(CH3CN)4(BF4)2 with bpnp in DMF gives [Pd2(bpnp)(μ-OH)(DMF)2](BF4)3 (2). Treatment of 1 or 2 with Cl– readily provide the chloro-substituted species [Pd(bpnp)(μ-OH)(Cl)2]+. All complexes were characterized by spectroscopic methods, and the structure of 2 was further confirmed by X-ray crystallography. Complex 1 is an efficient catalyst for the reduction of aromatic nitro compounds leading to the corresponding aniline derivatives under atmospheric pressure of hydrogen at 50 °C. The mechanistic pathway of the catalysis is investigated. From the reaction pathway, it is suggested that a facile condensation of nitroso and hydroxylamine intermediates is enabled by the dipalladium system and the desired transformation proceeds smoothly under mild reaction conditions to yield the reduced product.

Hydrogenation of nitroarenes catalyzed by a dipalladium complex

A dipalladium complex [Pd2(L)Cl2](PF6)2 (2), via the substitution of (PhCN)2PdCl2 with 5‐phenyl‐2,8‐bis(6′‐bipyridinyl)‐1,9,10‐anthyridine (L) followed by the anion exchange, was found to be a good pre‐catalyst for the reduction of nitroarenes to yield the corresponding anilines under atmospheric pressure of hydrogen in methanol. This method provides a straightforward access to a diverse array of functionalized anilines, exhibiting a possible application in synthetic chemistry. The catalytic activity of this complex is enhanced by the di‐metallic system via the synergistic effect.

Chemoselective hydrogenation of cinnamaldehyde at atmospheric pressure over combustion synthesized Pd catalysts

A series of Pd-supported metal oxides (Al2O3, Fe2O3 and CeO2) have been prepared by a single step solution combustion synthesis (SCS) method. Their catalytic performance was evaluated for the selective hydrogenation of cinnamaldehyde (CAL) to hydrocinnamaldehyde (HCAL) under atmospheric pressure of hydrogen at 100 °C. Among these materials, combustion synthesized Pd (2 at.%)/Al2O3 catalyst exhibits the highest CAL conversion (69%) with complete HCAL selectivity. The analogous catalyst prepared by the incipient wetness impregnation (IWI) method shows an initially similar activity. X-ray diffraction and high resolution transmission electron microscopy analyses of the as prepared SCS sample show fine dispersion of PdO over the γ-Al2O3 support. On ageing, a major portion of PdO is reduced to metallic Pd (Pd2+:Pd0 = 36:64 for the SCS catalyst and Pd2+:Pd0 = 26:74 for the IWI catalyst from X-ray photoelectron spectroscopy studies) suggesting comparatively more ionic character of palladium in the SCS catalyst. In the hydrogen atmosphere, without distinguishing the reductive pretreatment of catalyst and the beginning of hydrogenation subsequent to CAL addition, the Pd-species undergoes rearrangement to form a core–shell like structure of Pd (core)–PdO (periphery) covered with alumina layer, bringing in additional stability to the Pd-species in the SCS catalyst and making it highly recyclable. The analogous IWI catalyst, on the contrary, contains a mixed Pd–PdO ensemble that does not increase the stability causing continuous loss of activity in the consecutive cycles of hydrogenation.

常温常圧下での Pd・C 触媒による芳香族ニトロ化合物の接触水素還元 : 反応水素ガスの体積を測定する

常温常圧下での Pd・C 触媒による芳香族ニトロ化合物の接触水素還元 : 反応水素ガスの体積を測定する

Growth of MWCNTs on Flexible Stainless Steels without Additional Catalysts

Multiwalled carbon nanotubes (MWCNTs) were synthesized on austenitic stainless steel foils (Type 304) using a home-built thermal chemical vapor deposition (CVD) under atmospheric pressure of hydrogen (H2) and acetylene (C2H2). During the growth, the stainless steel substrates were heated at different temperatures of 600, 700, 800, and 900°C. It was found that MWCNTs were grown on the stainless steel substrates heated at 600, 700, and 800°C while amorphous carbon film was grown at 900°C. The diameters of MWCNTs, as identified by scanning electron microscope (SEM) images together with ImageJ software program, were found to be 67.7, 43.0, and 33.1 nm, respectively. The crystallinity of MWCNTs was investigated by an X-ray diffractometer. The number of graphitic walled layers and the inner diameter of MWCNTs were investigated using a transmission electron microscope (TEM). The occurrence of Fe3O4 nanoparticles associated with carbon element can be used to reveal the behavior of Fe in stainless steel as catalyst. Raman spectroscopy was used to confirm the growth and quality of MWCNTs. The results obtained in this work showed that the optimum heated stainless steel substrate temperature for the growth of effective MWCNTs is 700°C. Chemical states of MWCNTs were investigated by X-ray photoelectron spectroscopy (XPS) using synchrotron light.

Reactive catalytic fast pyrolysis of biomass to produce high-quality bio-crude

Reactive catalytic fast pyrolysis with atmospheric pressure hydrogen improved yield and quality of the resulting bio-crude.

Dihydride formation in the palladium–rhodium alloys under high hydrogen pressure

Palladium, rhodium and their alloys were studied in a diamond anvil cell in a high pressure hydrogen atmosphere up to 20 GPa by X-ray diffraction at room temperature. Formation of a monohydride with H/(Rh + Pd) = 1 ratio was observed for each alloy at hydrogen pressures less than 3 GPa. The corresponding volume expansion of the metal lattice was 2.2–2.8 Å3 per metal atom. A formation of the dihydride with H/(Rh + Pd) = 2 was observed at a hydrogen pressure around 10 GPa for the alloys with rhodium content Rh/(Rh + Pd) ≥ 50 at.%. The dihydride formation is accompanied by a volume expansion of metal lattice by 3.2–3.9 Å3 per metal atom. For Pd-rich alloys with Rh/(Rh + Pd) ≤ 25 at.% and pure Pd the dihydride formation was not observed up to maximum reached hydrogen pressure. All observed phases had a fcc structure of metal lattice.

Colloidal and nanosized catalysts in organic synthesis: XV. Gas-phase hydrogenation of alkenes catalyzed by supported nickel nanoparticles

Gas-phase hydrogenation of alkenes and their derivatives, catalyzed by nickel nanoparticles supported on zeolite or silica gel support occurs at 150–250°С and an atmospheric hydrogen pressure and results in a high conversion. The selectivity of the hydrogenation depends on the amount of hydrogen: at a low diene (triene)–hydrogen ratio, selective hydrogenation of one multiple bond in the substrate is possible.

Laser induced plasma expansion and existence of local thermodynamic equilibrium

In this paper we present a simple model of the laser induced plasma (LIP) expansion in a low pressure surrounding atmosphere. The model is based on assumption that expansion process is dominantly governed by kinematics of the heavy particles. The model is accompanied with a simple, yet effective, Monte-Carlo simulation. Results of the simulation are compared with spectroscopic measurements of the laser induced copper plasma expanding in low pressure (200Pa) hydrogen atmosphere. We found that characteristic expansion time of the LIP is proportional to the linear dimension of the initial volume heated up by the laser. For sufficiently large initial volume copper plasma remains in local thermodynamic equilibrium on the submicrosecond-microsecond scale. It is shown that diagnostics based on the spectral lines of the hydrogen atmosphere is not suitable for characterization of the core of the copper plasma. We have demonstrated importance of radially resolved spectroscopic measurements as a key step for correct diagnostics and understanding of laser induced plasma.