Tuning the electronic and magnetic properties of germanene by surface adsorption of small nitrogen-based molecules

The structural, energetic and electronic properties of germanene adsorbed with small nitrogen-based molecules, including N₂, NH₃, NO₂ and NO, have been investigated by using first-principles calculations. The results show that all nitrogen-based molecules considered bind much stronger to germanene than to graphene due to the hybridized sp²-sp³ bonding of Ge atoms. The N₂, NO and NO₂ molecules all act as an acceptor, while the NH₃ molecule donates electrons to germanene. We also found sizable band gaps (2–158 meV) are opened at the Dirac point of germanene through N₂, NH₃, and NO₂ adsorptions, but with only slightly destroying its Dirac cone shape. The NO₂ molecule also shows a heavy p-type doping character and makes germanene to be metallic. Moreover, when adsorbed by NO molecule, the germanene can change to be a ferromagnetic half-metal with 100% spin-polarization at the Fermi level. Overall, the different adsorption behaviors of small nitrogen-based gas molecules on germanene provide a feasible way to exploit chemically modified germanene for a wide range of practical applications, such as field-effect transistors, gas sensors and spintronic devices.     

Promotion effect of Pt on a SnO2–WO3 material for NOx sensing

Metal-oxide nanocomposites were prepared over screen-printed gold electrodes to be used as room-temperature NO_x (nitric-oxide (NO) and nitrogen dioxide (NO₂)) sensors. Various weight ratios of SnO₂–WO₃ and Pt loadings were used for NO sensing. The sensing materials were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM) and BET surface analysis. The NO-sensing results indicated that SnO₂–WO₃ (1:2) was more effective than other materials were. The sensor response (S=resistance of N₂/resistance of NO=R_N2/R_NO) for detecting 1000 ppm of NO at room temperature was 2.6. The response time (T₉₀) and recovery time (TR₉₀) was 40 s and 86 s, respectively. By further loading with 0.5% Pt, the sensor response increased to 3.3. The response and recovery times of 0.5% Pt/SnO₂–WO₃ (1:2) were 40 s and 206 s, respectively. The linearity of the sensor response for a NO concentration range of 10–1000 ppm was 0.9729. A mechanism involving Pt promotion of the SnO₂–WO₃ heterojunction was proposed for NO adsorption, surface reaction, and adsorbed NO₂ desorption.     

Electrode materials for potentiometric hydrogen sensors

Due to their relatively high sensitivity, improved long-term stability, possibilities for miniaturization and low cost products, mixed potential solid electrolyte sensors can be competitive for the in situ measurement of hydrogen trace concentrations in oxygen containing gases. Their response behavior in non-equilibrated oxygen containing gas mixtures is mainly determined by the catalytic activity of the measuring electrode and depends strongly on preparation and measuring conditions. In this work the sensitivity of electrodes made of composites (Au/MeO) has been investigated in hydrogen containing gases in the concentration range φ(H₂) = 0…800 vol.-ppm using a two-chamber setup with Pt-air reference. Electrodes made of Au/Nb₂O₅ composites show the highest sensitivities of up to 20 mV/vol.-ppm at φ(H₂) = 10 vol.-ppm and the lowest catalytic activity for hydrogen oxidation. Selected composite materials were tested additionally in self-heated solid electrolyte sensors with both electrodes exposed to the same atmosphere (gas-symmetrical sensor).     

Facile synthesis of nanostructured CuO for low temperature NO2 sensing

Detection of environmental pollutant and health hazardous, nitrogen dioxide (NO₂) is reported using nanostructured CuO particulates (NPs). Powder X-ray diffraction and field emission scanning electron microscopy were used to probe crystalline phase and morphological details, respectively. Small crystallites of ∼10–12 nm and a strain of 4% were found in the leafy structure of CuO. Raman studies further supported the presence of nanosized CuO phase. This is the first instance of utilizing CuO NPs to detect 5 ppm of NO₂ even at a low operating temperature of 50 °C. The highest sensitivity for NO₂ was observed at 150 °C, for the first time, in CuO NPs. A low activation energy of 0.18 eV was found for sensing process. The CuO NPs sensor responded to NO₂ within a few seconds and recovered totally under a minute. The kinetics of the NO₂ gas adsorption on the CuO film surface was described following the Elovich model.     

Effect of buffer gases on the performance of SO2 trace measurement based on photoacoustic spectroscopy

In this experimental work a laser photoacoustic spectrometer designed and fabricated. System sensitivity for detection of SO₂ and NO₂ was measured. Resonance frequency variation versus pressure increase of Nitrogen, Argon, Helium and Air buffer gases was studied. Results show that, sensitivity of system for SO₂ and NO₂ are 353 ppb and 963 ppb respectively. It was shown that resonance frequency for Nitrogen, Argon, and Air buffer gases was not noticeably varied by buffer gas pressure increasing, but for Helium, resonance frequency not only is not in range of three other gases, but also grows by pressure increasing. The system noises were damped preparing two buffer chambers.     

Hydrogen adsorption and storage of Ca-decorated graphene with topological defects: A first-principles study

As a candidate for hydrogen storage medium, geometric stability and hydrogen capacity of Ca-decorated graphene with topological defects are investigated using the first-principle based on density functional theory (DFT), specifically for the experimentally realizable single carbon vacancy (SV), 585 double carbon vacancy (585 DCV) and 555–777 double carbon vacancy (555–777 DCV) defects. It is found that Ca atom can be stabilized on above defective graphenes since Ca׳s binding energy on vacancy defect is much larger than its cohesive energy. Up to six H₂ molecules can stably bind to a Ca atom on defective graphene with the average adsorption energies of 0.17–0.39 eV/H₂. The hybridization of the Ca-3d orbitals with H₂-σorbitals and the electrostatic interaction between the Ca cation and the induced H₂ dipole both contribute to the H₂ molecules binding. Double-side Ca-decorated graphene with 585 DCV and 555–777 DCV defects can theoretically reach a gravimetric capacity of 5.2 wt% hydrogen, indicating that Ca-decorated defective graphene can be used as a promising material for high density hydrogen storage.     

Optical gas sensing selectivity property of ruthenium (II)-metalloporphyrins Langmuir–Blodgett films

This paper reports the study of the selectivity property of a metalloporphyrins derivative Langmuir–Blodgett thin film, n-octaethyl porphine ruthenium (II) carbonyl (RuOEPCO), to several organic gas samples, namely the saturated vapor of acetone, 2-propanol, ethanol and cyclohexane. The sensing sensitivity was based on the change in the optical property of the film upon exposure to the gas samples that was measured at a particular wavelength, λ = 514 nm, of the light source. It was observed that the thin film exhibited excellent selectivity property to the gas samples by presenting clear differences amongst its responses. The selectivity property of the thin film was found to depend on the structure of the gaseous molecules of which the highest sensitivity was shown for the gaseous molecules with planar structure, such as cyclohexane. The mechanism for the thin films-gas interaction that promotes the selectivity characteristic is proposed.     

Experiment research on ellipsoidal structure methane using the absorption characteristics of 3.31 μm mid-infrared spectroscopy

The intensity distribution of absorption spectroscopy of methane mid-infrared fundamental absorption bands, near-infrared combination band of v₂ + 2v₃ and overtone band of 2v₃ were discussed in details in this paper. Quantitative data showed that the absorption intensities of fundamental bands are twice larger than overtone bands, and three times larger than combination bands. Based on the methane 3.31 μm (v₃) fundamental absorption bands and differential signal disposal method, a rotational ellipsoidal light structure was designed using ordinary light source and detector to improve gas detection sensitivity. The experimental results of concentration detection showed that the precision of concentration measurement can reach 3% and detection sensitivity is 50 ppm. Meanwhile, experiment was performed to investigate the influence of temperature on mid-infrared absorption performance of methane and the experience curve of 3.31 μm (v₃) fundamental absorption signal depending on temperature and its rate of change was drawn.     

Nitrogen fixed into HNO3 by pulsed high voltage discharge

By applying pulsed high voltage discharge to a needle-mesh reactor that using seven acupuncture needles as discharge electrode and stainless steel wire mesh as ground electrode, nitrogen from bubbling gas could be fixed into NO₂^? and NO₃^? with equivalent mol H⁺ produced in the liquid phase and a small amount of NO and NO₂ yielded in the gas phase. The HNO₂ was originally formed and then converted into HNO₃. The ·OH and H₂O₂ stimulated the conversion reaction from HNO₂ to HNO₃, which caused HNO₂ concentration increased in the first 12 min and then decreased until lower than its detection limit. The concentration of HNO₃ still increased with discharge time. After 36 min, HNO₃ was the only and ultimate product in the liquid. The total yield of HNO₂ and HNO₃ could be affected by processing parameters such as electric factors of peak voltage and frequency, mesh size of ground electrode and content of nitrogen in N₂/O₂ bubbling. Increasing peak voltage or frequency, the total yield of HNO₂ and HNO₃ increased. Gas composition had a heavy impact on the fixation efficiency that obtained its maximum value at an oxygen content of 66.7% with bubbling O₂/N₂ gas. At the end of the 36 min discharge, the HNO₃ concentration with bubbling air was 2.215 mmol L^?1 at an applied voltage of 25 kV, pulse repetition frequency of 140 Hz and ground electrode mesh of 20 × 20. The energy yield was about 1.22 g (HNO₃)/kWh.     

Hybrid inorganic–organic proton conducting membranes for fuel cells and gas sensors

We developed new fast proton conducting membranes based on a hybrid inorganic–organic phosphosilicate polymer synthesized from othophosphoric acid, dichlorodimethylsilane, and tetraethoxysilane. The membranes were amorphous, translucent, and flexible. A high concentration of –OH groups and short distances between them promoted fast proton conductivity in dry atmosphere at increased temperatures. The proton conductivity was measured using the electrochemical impedance spectroscopy. Its value increased with rising temperature following the Arrhenius dependence with the activation energy 20 kJ/mol. In dry conditions at 120 °C, the conductivity was 1.6 S/m. The tests in a H₂/O₂ fuel cell confirmed that the membrane was able to operate at temperatures from 100 to 130 °C using dry input gas streams. The cell performance significantly improved with increasing temperature. The membrane was also tested in a potentiometric gas sensor with the TiH_x reference electrode and the Pt sensing electrode. The sensor exhibited fast, stable, and reproducible response to dry H₂ and O₂ gases at temperatures above 100 °C. We expect the application of our membrane in intermediate temperature fuel cells and gas sensors operating in dry conditions.     

Reactivity of the Cu2O(1 0 0) surface: Insights from first principles calculations

We present a summary of results of systematic first principles calculations of the electronic and geometric structures of the Cu₂O(1 0 0) surface and the process of CO oxidation on this surface (energetics and pathways of adsorption, diffusion and reactions of CO and O₂ on the surface). The (p, T) phase diagram of the Cu₂O(1 0 0) in equilibrium of with gas phase O₂ built using the ab initio thermodynamics approach suggests that the O-terminated surface is preferred over the Cu-terminated one within the entire ranges of pressures and temperatures in which the compound exists. Metastable Cu-terminated Cu₂O(1 0 0) is found to undergo a surface reconstruction in agreement with experiment. We find CO to oxidize spontaneously on the O-terminated Cu₂O(1 0 0) surface by consuming surface O atoms. Our calculations also show that the surface O-vacancies left in the course of the CO oxidation can be easily filled with dissociative adsorption of the gas phase O₂ molecules, which are usually present in reaction environment.     

Effects of NO2 addition on hydrogen ignition behind reflected shock waves

Ignition delay time measurements of H₂/O₂/NO₂ mixtures diluted in Ar have been measured in a shock tube behind reflected shock waves. Three different NO₂ concentrations have been studied (100, 400 and 1600 ppm) at three pressure conditions (around 1.5, 13, and 30 atm) and for various H₂–O₂ equivalence ratios for the 100 ppm NO₂ case. Results were compared to some recent ignition delay time measurements of H₂/O₂ mixtures. A strong dependence of the ignition delay time on the pressure and the NO₂ concentration was observed, whereas the variation in the equivalence ratio did not exhibit any appreciable effect on the delay time. A mechanism combining recent H₂/O₂ chemistry and a recent high-pressure NOx sub-mechanism with an updated reaction rate for H₂ + NO₂ ? HONO + H was found to represent correctly the experimental trends over the entire range of conditions. A chemical analysis was conducted using this mechanism to interpret the experimental results. Ignition delay time data with NO₂ and other NOx species as additives or impurities are rare, and the present study provides such data over a relatively wide pressure range.     

H2 splitting on Pt,Ru and Rh nanoparticles supported on sputtered HOPG

The equilibrium hydrogen exchange rate between adsorbed and gas phase hydrogen at 1 bar is measured for Pt, Ru and Rh nanoparticles supported on a sputtered HOPG substrate. The particles are prepared by Electron Beam Physical Vapor Deposition and the diameter of the particles varies between 2 and 5 nm. The rate of hydrogen exchange is measured in the temperature range 40–200 °C at 1 bar, by utilization of the H–D exchange reaction. We find that the rate of hydrogen exchange increases with the particle diameter for all the metals, and that the rate for Ru and Rh is higher than for Pt. In the case of Pt, the equilibrium dissociative sticking probability, S, is found to be nearly independent of particle diameter. For Ru and Rh, S is found to depend strongly on particle diameter, with the larger particles being more active. The apparent energy of desorption at equilibrium, E_app, shows a dramatic increase with decreasing particle diameter for diameters below 5 nm for Ru and Rh, whereas E_app is only weakly dependent on particle diameter for Pt. We suggest that the strong variation in the apparent desorption energy with particle diameter for Ru and Rh is due to the formation of compressed hydrogen adlayers on the terraces of the larger particles. Experiments are also carried out in the presence of 10 ppm CO. Pt is found to be very sensitive to CO poisoning and the H–D exchange rate drops below the detection limit when CO is added to the gas mixture. In the case of Ru and Rh nanoparticles, CO decreases the splitting rate significantly, also at 200 °C. The variation of the sensitivity to CO poisoning with particle diameter for Ru and Rh is found to be weak.     

Densely mapping the phase diagram of cuprate superconductors using a spatial composition spread approach

A novel spatial composition spread approach was used successfully to deposit a 52-member library of La_2?xSr_xCuO₄ (0 ? x ? 0.18) using magnetron sputtering combined with physical masking techniques. Two homemade targets of La₂CuO₄ and La_1.82Sr_0.18CuO₄ were sputtered at a power of 41 W RF and 42 W DC, respectively, in a process gas of 15 mTorr argon. The libraries were sputtered onto LaSrAlO₄ (0 0 1), SrTiO₃ (1 0 0) and MgO (1 0 0) substrates through a 52-slot shadow mask for which a ?20 V substrate bias was applied to prevent resputtering. The resulting amorphous films were post-annealed (800 °C for 1 h then at 950 °C for 2 h) in a tube sealed with oxygen gas. Wavelength Dispersive Spectroscopy (WDS) analysis revealed the expected linear variation of Sr content from 0 to 0.18 with an approximate change of 0.003 per library member. Transport measurements revealed superconducting transitions as well as changes in the quasiparticle scattering rate. These transitions and scattering rate changes were mapped to produce the T-hole concentration phase diagram.     

Shock tube/laser absorption studies of the decomposition of methyl formate

Reaction rate coefficients for the major high-temperature methyl formate (MF, CH₃OCHO) decomposition pathways, MF → CH₃OH + CO (1), MF → CH₂O + CH₂O (2), and MF → CH₄ + CO₂ (3), were directly measured in a shock tube using laser absorption of CO (4.6 μm), CH₂O (306 nm) and CH₄ (3.4 μm). Experimental conditions ranged from 1202 to 1607 K and 1.36 to 1.72 atm, with mixtures varying in initial fuel concentration from 0.1% to 3% MF diluted in argon. The decomposition rate coefficients were determined by monitoring the formation rate of each target species immediately behind the reflected shock waves and modeling the species time-histories with a detailed kinetic mechanism [12]. The three measured rate coefficients can be well-described using two-parameter Arrhenius expressions over the temperature range in the present study: k₁ = 1.1 × 10¹³ exp(?29556/T, K) s^?1, k₂ = 2.6 × 10¹² exp(?32052/T, K) s^?1, and k₃ = 4.4 × 10¹¹ exp(?29 078/T, K) s^?1, all thought to be near their high-pressure limits. Uncertainties in the k₁, k₂ and k₃ measurements were estimated to be ±25%, ±35%, and ±40%, respectively. We believe that these are the first direct high-temperature rate measurements for MF decomposition and all are in excellent agreement with the Dooley et al. [12] mechanism. In addition, by also monitoring methanol (CH₃OH) and MF concentration histories using a tunable CO₂ gas laser operating at 9.67 and 9.23 μm, respectively, all the major oxygen-carrying molecules were quantitatively detected in the reaction system. An oxygen balance analysis during MF decomposition shows that the multi-wavelength laser absorption strategy used in this study was able to track more than 97% of the initial oxygen atoms in the fuel.     

Interaction of NO with the O-rich RuO2(1 1 0) surface at 300 K

The interaction of NO with the O-rich RuO₂(1 1 0) surface, exposing coordinatively unsaturated O-bridge, O-cus, and Ru-cus atoms, was studied at 300 K by thermal desorption spectroscopy (TDS) and high-resolution electron energy-loss spectroscopy (HREELS). The conclusions are validated by isotope substitution experiments with ¹⁸O. During exposure to NO an O···N–O surface group (NO₂-cus) is formed with O-cus. Additionally, a smaller number of empty Ru-cus sites are filled by NO-cus. If one warms the sample to 400 K, NO₂-cus does not desorb but decomposes into O and NO again, the latter being either released into gas phase or adsorbed as NO-cus. With O-bridge such a surface group is not stable at 300 K. Our experiments further prove that O-cus is more reactive than O-bridge.     

Mott insulator-superfluid phase transition in p-band triangle optical lattices with on-site rotation

In order to exploit the potential applications of graphene as gas sensors, the adsorptions of a series of small gas molecules (such as CO, O₂, NO₂ and H₂O) on pristine graphene (PG) and Si-doped graphene (SiG) have been investigated by ab initio calculations. Our results indicate that the electronic properties of PG are sensitive to O₂ and NO₂ molecules, but not changed much by the adsorption of CO and H₂O molecules. Compared with PG, SiG is much more reactive in the adsorption of CO, O₂, NO₂ and H₂O. The strong interactions between SiG and the adsorbed molecules induce dramatic changes to the electronic properties of SiG. Therefore, we suggest that SiG could be a good gas sensor for CO, O₂, NO₂ and H₂O.     

Synthesis of epitaxial graphene on rhodium from 3-pentanone

The synthesis of high quality single layer graphene on rhodium, g/Rh(111), is reported. The graphene layers are grown at 1060 K by low pressure chemical vapor deposition (CVD) using 3-pentanone as a precursor molecule. The presented growth technique shows an easy high quality production method for epitaxial graphene monolayers. The chemical composition and structural properties of such self-assembled monolayers were characterized by X-ray photoelectron spectroscopy (XPS) and low energy electron diffraction (LEED). Scanning Tunneling Microscopy (STM) confirms the formation of a 3 nm super cell and a unique surface morphology which establishes the potential of g/Rh(111) as a template for molecules.     

Spin and orbital magnetic moments and spin anisotropy energies of light rare earth atoms embedded in graphene: A first-principles study

The geometries, electronic structures, spin magnetic moments (SMMs), orbital magnetic moments (OMMs) and spin anisotropy energies (SAEs) of light rare earth atoms (La, Ce, Pr, Nd, Pm, Sm, Eu, and Gd) embedded in graphene were studied by using first-principles calculations based on Density Functional Theory (DFT). The spin-orbital coupling effect was taken into account and GGA+U method was adopted to describe the strongly localized and correlated 4f electrons. There is a significant deformation of the graphene plane after doping and optimization. The deformation of Gd doped graphene is the largest, while Eu the smallest. The results show that the valence is +3 for La, Ce, Pr, Nd, Pm, Sm and Gd, and +2 for Eu. Except Eu and Gd, there are obvious OMMs. When the spin is in the Z direction, the OMMs are −0.941 μ_B, −1.663 μ_B, −3.239 μ_B, −3.276 μ_B and −3.337 μ_B for Ce, Pr, Nd, Pm and Sm, respectively, and point the opposite direction of SMMs. All the doped systems except Gd show considerable SAEs. For Ce, Pr, Nd, Pm, Sm, and Eu, the SAEs are −0.928 meV, 20.941 meV, −8.848 meV, 7.855 meV, 75.070 meV and 0.810 meV, respectively. When the spin orientation is different, different orbital angular moments lead to apparent charge density difference of the 4f atoms, which can also explain the origin of SAEs.     

Soot low-temperature combustion on Cu–Zr/ZSM-5 catalysts in O2/He and NO/O2/He atmospheres

Zirconium doped Cu/ZSM-5 catalysts were prepared and characterized in this investigation. Catalytic activity during soot combustion was determined in both O₂/He and NO/O₂/He atmospheres by temperature-programmed oxidation. The use of zirconium reduces the temperature of maximum soot oxidation rate by 229 °C in O₂/He atmosphere and 270 °C in NO/O₂/He atmosphere. The promoting effect of zirconium is discussed in terms of surface dispersion, enrichment of active components, and creation of oxygen vacancies where molecular oxygen or NO_x is adsorbed forming basic surface oxygen species active for soot oxidation. The NO₂ formed at the copper–zirconium interface sites leads to the ignition temperature being significantly decreased to 93 °C, which is inside the exhaust temperature range of diesel engines. To understand the combustion reaction kinetics, the activation energy and reaction order of soot combustion were evaluated. According to the Redhead method, the activation energy for non-catalyzed reaction is 164 kJ/mol under the O₂/He atmosphere. For the Cu/ZSM-5 and Cu–Zr/ZSM-5, the activation energies under the O₂/He atmosphere (134–151 kJ/mol) are slightly higher than those under the NO/O₂/He atmosphere (128–135 kJ/mol). The Freeman–Carroll method is suitable to describe the soot combustion in the NO/O₂/He atmosphere, with the activation energies for the catalysts in the range of 97–112 kJ/mol and the average value of reaction order equal to 1.36.