The effects of power ultrasound (24 kHz) on the electrochemical reduction of CO2 on polycrystalline copper electrodes

The electrochemical CO₂ reduction reaction (CO2RR) on polycrystalline copper (Cu) electrode was performed in a CO₂-saturated 0.10 M Na₂CO₃ aqueous solution at 278 K in the absence and presence of low-frequency high-power ultrasound (f = 24 kHz, P_T ~ 1.23 kW/dm³) in a specially and well-characterized sonoelectrochemical reactor. It was found that in the presence of ultrasound, the cathodic current (I_c) for CO₂ reduction increased significantly when compared to that in the absence of ultrasound (silent conditions). It was observed that ultrasound increased the faradaic efficiency of carbon monoxide (CO), methane (CH₄) and ethylene (C₂H₄) formation and decreased the faradaic efficiency of molecular hydrogen (H₂). Under ultrasonication, a ca. 40% increase in faradaic efficiency was obtained for methane formation through the CO2RR. In addition, and interestingly, water-soluble CO₂ reduction products such as formic acid and ethanol were found under ultrasonic conditions whereas under silent conditions, these expected electrochemical CO2RR products were absent. It was also found that power ultrasound increases the formation of smaller hydrocarbons through the CO2RR and may initiate new chemical reaction pathways through the sonolytic di-hydrogen splitting yielding other products, and simultaneously reducing the overall molecular hydrogen gas formation.     

The surface diffusion in CO oxidation on small supported Pd particles: Experimental evidence

Thermo-programmed heterogeneous catalytic oxidation of CO on Pd small particle/mica catalysts has been used to study the influence of the Pd particle number density on the catalytic turnover rate. Rapid increase is observed in the maximum CO₂ turnover rate with decreasing particle density. This effect can be explained by the surface migration of gas molecules on the mica substrate. In previous papers devoted to CO oxidation on Pd particles we pointed out that both the initial sticking coefficient s₀ of CO on Pd and the turnover rate r_CO2 (for CO₂ formation) increase when the particles size decreased. Measurements of the CO consumation rate N_c during an oxidation reaction have also demonstrated a similar particle size dependence for Nc. If the quantities s₀ and r_CO2 are calculated relative to the impinging flux of CO molecules J_i (J_i given by the kinetic theory of gases), the obtained values are always higher than unity for particle diameter smaller than 8 nm. In the light of these results it seems that the real CO flux should be higher than J_i. Ladas, Poppa and Boudart have suggested that the edge of the particles can receive more collisions than the face atoms, which could explain an increase of the mean CO flux with decreasing particle size.     

Defect-free growth of epitaxial silicon at low temperatures (500–800 °C) by atmospheric pressure plasma chemical vapor deposition

Epitaxial Si growth at low temperatures (500–800 °C) by atmospheric pressure plasma chemical vapor deposition has been investigated. Silicon films are deposited on (001) Si wafers using gas mixtures containing He, H₂, and SiH₄. The effects of deposition parameters (composition of reactive gases, very high frequency (VHF) power, and substrate temperature) on film properties are investigated by reflection high-energy electron diffraction, atomic force microscopy, cross-sectional transmission electron microscopy, and plasma emission spectroscopy. It is found that epitaxial temperature can be reduced by increasing VHF power, and that an optimum range of VHF power exists for Si epitaxy, depending on the substrate temperature and the composition of the reactive gases. The result of the H₂ concentration dependence of H_α emission intensity, shows that hydrogen atoms generated in the atmospheric pressure plasma play an important role in Si epitaxial growth. Under the optimized growth conditions, defect-free epitaxial Si films (as observed by transmission electron microscopy) with excellent surface flatness are grown at 500 °C with an average growth rate of approximately 0.25 μm/min. PACS 81.05.Cy; 81.15.Gh; 68.55.Jk     

Optimization of gas pressures ratio in a fast-axial-flow CO2 laser with genetic algorithm

In this paper, the laser output power of a fast-axial flow CO₂ laser was optimized with gas pressures ratio of CO₂:N₂:He using a genetic algorithm technique. The power of laser was increased from 500 W (un-optimized case) to 2200 W (simulated case), also experimentally the power has achieved the value of 700 W (optimized case).     

The effect of CO on CO2-char gasification

The effect of CO on the gasification of a Polish coal-derived char was investigated in a fluidised bed from 1123 to 1248 K. Rate expressions developed from Ergun's mechanism or a modified three-step reaction mechanism, coupled with Cylindrical Pore Interpolation Model (CPIM) to account for the intra-particle mass transfer, were developed to predict gasification and the effect of CO. Compared to the Ergun's rate expression, the three-step expression has an extra term for p_co, making the inhibition effect of CO more pronounced. The agreement between experimental and numerical results was satisfactory for both models simulating gasification by CO₂/N₂. Then, when CO (1% or 3%) was intentionally introduced in the feed gas (CO₂/N₂), the gasification rates significantly decreased. It was found that the model based on Ergun's mechanism over-estimated the gasification rate, while the results from the model with the three-step mechanism agreed with the experimental data.     

The NO + CO reaction on Pt(100)

The interaction of NO with CO and with H₂ on Pt(100) was studied by temperature programmed desorption (TPD), isothermal desorption mass spectrometry, and low energy electron diffraction (LEED), TPD of NO and CO coadsorbed at 120 K yields almost complete reaction with both N₂ and CO₂ products desorbing as sharp, simultaneous peaks at ≈ 410 K. with full widths at half maximum as narrow as 3 K. Isothermal desorption mass spectrometry yields N₂ and CO₂ rates that exhibit a maximum with time. Both experiments indicate that the reaction mechanism is autocatalytic. Annealing NO-CO adlayers formed at 120 K to temperatures above 300 K causes the subsequent N₂ and CO₂ TPD peaks to broaden.'TPD of NO coadsorbed with H₂ yields sharp N₂ and H₂O product peaks that closely resemble the N₂ and CO₂ peaks observed in the NO + CO reaction. LEED experiments during TPD and isothermal desorption showed that the (1 × 1) → hex substrate phase transformation sometimes accompanies desorption of N₂ and CO₂. The TPD and isothermal desorption results can be fit by two simple models: chemical autocatalysis, in which an intermediate chemical species participates in a “chain propagation” reaction, and structural autocatalysis, which involves the formation of a reactive intermediate structure involving Pt atom displacements.     

Redox reactions and inward cationic diffusion in glasses caused by CO and H2 gases

We find that inward diffusion of network-modifying cations can occur in an iron-containing silicate glass when it is heat-treated in CO/CO₂ (98/2 v/v) or H₂/N₂ (1/99 v/v) gases at temperatures around the glass transition temperature. The inward diffusion is caused by the reduction of ferric to ferrous ions and this diffusion leads to formation of a silica-rich surface layer with a thickness of 200–600 nm. The diffusion coefficients of the network-modifying divalent cations are calculated and they are different for the glasses treated in the CO and H₂ gases. At the applied partial pressures of CO and H₂, the H₂-bearing gas creates the silica-rich layer more effectively than the CO-bearing gas. The layer increases the hardness and chemical durability of the glass due to the silica network structure in the surface layer.     

Analysis of sodium aerosol using transversely excited atmospheric CO2 laser-induced gas plasma spectroscopy

Taking advantages of the special characteristics of a transversely excited atmospheric (TEA) CO₂ laser, the analysis of sodium aerosol has been successfully conducted by using laser-induced gas plasma spectroscopy (LIGPS) method. In this study, the sodium aerosol was deposited on a nickel metal plate; the metal plate functions as a subtarget to initiate a gas plasma. When a pulsed TEA CO₂ laser was focused on the metal surface, a large-volume and high-temperature gas plasma was induced. The fine particles of sodium then entered into the gas plasma region to be dissociated and excited. By using this technique, a semi quantitative analysis of sodium aerosol was made. The detection limit of sodium was approximately 200 ppb.     

Shock-tube study on high-temperature CO formation during dry methane reforming

The use of natural-gas-fueled combustion engines at unusual operating conditions to provide electrical and/or chemical energy on demand emphasizes the need for fundamental research on decomposition and formation of base chemicals at these conditions. In this work, the CO formation behind reflected shock waves from the pyrolysis of CO₂/CH₄ mixtures was investigated for the first time in the context of engine-based dry methane reforming, to understand the interaction of CO₂ and CH₄ at high temperatures and to test the validity of literature reaction mechanisms. Different CO₂/CH₄ mixtures at atmospheric pressure and temperatures between 1900 K and 2700 K were investigated. Time-resolved CO measurements were performed by laser absorption using a quantum cascade laser.With increasing CO₂ addition later reaction onset was observed, showing a reduction in the overall reactivity. Rate of production and sensitivity analyses highlight competing reactions in the pyrolysis and oxidation pathways and that the number of available H radicals is limited, which is attributed to the reduced reactivity. However, the analysis shows that CO₂ is also a source for OH radicals (via CO₂ + H ⇌ CO + OH), which enhance methane decomposition. The comparison with literature reaction mechanisms showed that none of the tested mechanisms can perfectly predict the time-resolved CO formation, highlighting the need for the validation of detailed kinetics models under nontypical conditions.     

OH number densities and plasma jet behavior in atmospheric microwave plasma jets operating with different plasma gases (Ar,Ar/N<Subscript>2</Subscript>, and Ar/O<Subscript>2</Subscript>)

OH radical number density in multiple atmospheric pressure microwave plasma jets is measured using UV cavity ringdown spectroscopy of the OH (A–X) (0–0) band at 308 nm. The plasma cavity was excited by a 2.45 GHz microwave plasma source and plasma jets of 2–12 mm long were generated by using three different plasma gases, argon (Ar), Ar/N₂, and Ar/O₂. Comparative characterization of the plasma jets in terms of plasma shape, stability, gas temperature, emission intensities of OH, NO, and N₂, and absolute number density of the OH radical was carried out under different plasma gas flow rates and powers at various locations along the plasma jet axis. With three different operating gases, the presence of OH radicals in all of the plasma jets extended to the far downstream. As compared to the argon plasma jets, the plasma jets formed with Ar/N₂ and Ar/O₂ are more diffuse and less stable. Plasma gas temperatures along the jet axis were measured to be in the range of 470–800 K for all of the jets formed in the different gas mixtures. In each plasma jet, OH number density decreases along the jet axis from the highest OH density in the vicinity of the jet tip to the lowest in the far downstream. OH density ranges from 1.3 × 10¹² to 1.1 × 10¹⁶, 4.1 × 10¹³ to 3.9 × 10¹⁵, and 7.0 × 10¹² to 4.6 × 10¹⁶ molecule/cm³ in the Ar, Ar/N₂, and Ar/O₂ plasma jets, respectively. The OH density dependence on plasma power and gas flow rate in the three plasma jets is also investigated.     

New cw far-infrared D2O, 12CH3F and 14NH3 laser lines

The operation of a continuous CO₂ waveguide laser at nearly atmospheric pressure is reported. A plasma injection technique is used to produce a uniform discharge at atmospheric pressure. Continuous output power of 0.6 W was obtained at the inlet pressure of 800 torr. Corresponding outlet pressure was 340 torr. While the maximum output power was 1.4 W at the inlet pressure of 600 torr. The gas mix ratio was CO₂ : N₂ : He = 1 : 1 : 6.     

Adsorption behavior and reaction properties of NO and CO on Rh(1 1 1)

Reactions between NO and CO on Rh(1 1 1) surfaces were investigated using infrared reflection absorption spectroscopy, X-ray photoelectron spectroscopy, and temperature-programmed desorption. NO adsorbed on the fcc, atop, and hcp sites in that order, whereas CO adsorbed initially on the atop sites and then on the hollow (fcc + hcp) sites. The results of experiments with NO exposure on CO-preadsorbed Rh(1 1 1) surfaces indicated that the adsorption of NO on the hcp sites was inhibited by preadsorption of CO on the atop sites, and NO adsorption on the atop and fcc sites was inhibited by CO preadsorbed on each type of site, which indicates that NO and CO competitively adsorbed on Rh(1 1 1). From a Rh(1 1 1) surface with coadsorbed NO and CO, N₂ was produced from the dissociation of fcc-NO, and CO₂ was formed by the reaction of adsorbed CO with atomic oxygen from dissociated fcc-NO. The CO₂ production increased remarkably in the presence of hollow-CO. Coverage of fcc-NO and hollow-CO on Rh(1 1 1) depended on the composition ratio of the NO/CO gas mixture, and a gas mixture with NO/CO ? 1/2 was required for the co-existence of fcc-NO and hollow-CO at 273 K.     

Adsorption and reaction of CO2 and CO2/O CO-adsorption on Ni(110): Angle resolved photoemission (ARUPS) and electron energy loss (HREELS) studies

Molecular adsorption is observed on a Ni(110) surface at 80 K. The relative binding energies of the valence ion states as determined by ARUPS are consistent with those in the gas as well as in the condensed phase, and indicate that the electronic structure of the adsorbed molecule is only slightly distorted upon adsorption at this temperature. The adsorbate spectra show E versus k_∥ dispersions indicating some long-range order in the adsorbate. The variations in relative ionisation probabilities of the ion states as a function of electron emission angle suggest that the molecular axis is oriented parallel to the surface within ± 20°. Upon heating the adsorbate to above 100 K. (i.e. 140 K) the spectrum changes. A new species causing an increase in work function by 1 eV can be identified. Comparison with calculations suggests that it is an anionic bent CO; molecule. Electron energy loss studies on this intermediate species support the proposed bent CO₂ geometry and favour a coordination site with C_2v symmetry. The bent CO₂ moiety is stable up to 230 K. Further heating to room temperature leads to dissociation of the bent CO₂ molecule into adsorbed CO and O. The CO molecule is oriented with its axis perpendicular to the surface. The bent CO₂ species appears to be a precursor to dissociation. Results on CO₂ adsorption on an oxygen precovered surface show that CO₂ interacts with oxygen at 85 K. Upon heating the co-adsorbate to near room temperature a reaction product is formed the nature of which cannot yet be clearly identified.     

CO and H2O adsorption and reaction on Au(310)

We have studied desorption of ¹³CO and H₂O and desorption and reaction of coadsorbed, ¹³CO and H₂O on Au(310). From the clean surface, CO desorbs mainly in, two peaks centered near 140 and 200 K. A complete analysis of desorption spectra, yields average binding energies of 21 ± 2 and 37 ± 4 kJ/mol, respectively. Additional desorption states are observed near 95 K and 110 K. Post-adsorption of H₂O displaces part of CO pre-adsorbed at step sites, but does not lead to CO oxidation or significant shifts in binding energies. However, in combination with electron irradiation, ¹³CO₂ is formed during H₂O desorption. Results suggest that electron-induced decomposition products of H₂O are sheltered by hydration from direct reaction with CO.     

K-shell excitation spectra of CO,N2 and O2

Electron energy loss spectra of CO, N₂ and O₂ have been recorded in the regions of carbon, nitrogen and oxygen K-shell excitation and ionisation. These results are compared to previous energy loss, photoabsorption and theoretical studies of the same spectral regions. Several inconsistencies in the published spectra are clarified in the present work. Comparisons with recent calculations of the K-shell continua of these molecules are presented. Vibrational structure in the K → π * transitions of CO (C 1s) and N₂ (N 1s) has been resolved in high-resolution studies (< 0.1 eV FWHM) of these species.     

Explosive production of CO2 from (NO + CO)/Pd(100)

Explosive CO₂ production followed by the gradual N₂ production has been observed by TDS as a result of the NO-CO reaction on the Pd(100) surface which does not reconstruct. The location and width of the CO₂ desorption peak have been found to be almost independent of the total coverage. For this autocatalytic reaction, the vacancy requirement model is considered to be valid. Change in the CO₂ production by varying the NO coverage (with the CO coverage fixed) has been also studied, from which information on the island formation is derived.     

Detection of CO using bulk ZnO Schottky rectifiers

Bulk Pt/ZnO Schottky rectifiers show gas sensitivities for CO of 4% and 8%, respectively, at 150 °C for 1 and 10% CO in N₂. The current or voltage changes are time dependent, with an activation energy of 40.7 kJmol^-1. Over a limited range of partial pressures of CO (P_CO) in the ambient gas, the on-state resistance R of the sensor at fixed bias voltage decreased according to R=(R_O+A(P_CO)^0.5)^-1, where A is a constant and R_O is the resistance in N₂. Since these devices are also sensitive to H₂ and C₂H₄, the ZnO rectifiers appear promising for a range of gas-sensing applications. PACS 81.05.Dz; 73.61.Ga; 72.80.Ey     

A computer model of a transverse discharge cw CO laser

A kinetic model has been developed for the investigation of the novel performance of a CO laser, on which efficient extraction of laser power was obtained by exciting a subsonic gas mixture of CO/N₂/He/O₂ through transverse dc discharge. Kinetic equations for direct excitation by electron impact, V-V and V-R/T energy transfer, and stimulated emission are coupled with a semi-one-dimensional flow model. Careful consideration is devoted especially to the V-V transfer process of CO–N₂ and N₂–N₂. The laser power was calculated by a constant gain method. The laser output performance, examined as a function of gas mixture ratio, temperature, flow velocity, and discharge current, was in good agreement with the experiment.     

Ultrasound-boosted selectivity of CO in CO2 electrochemical reduction

Among the possible products of CO₂ electrochemical reduction, CO plays a unique and vital role, which can be an ideal feedstock for further reduction to C₂₊ products, and also the important component of syngas that can be used as feedstock for value-added chemicals and fuels. However, it is still a challenge to tune the CO selectivity on Cu electrode. Here we newly construct an ultrasound-assisted electrochemical method for CO₂ reduction, which can tune the selectivity of CO₂ to CO from less than 10% to >80% at −1.18 V versus (vs.) reversible hydrogen electrode (RHE). The partial current density of CO production is significantly improved by 15 times. By in-situ Raman study, the dominating factor for the improved CO production is attributed to the accelerated desorption of *CO intermediate. This work provides a facile method to tune the product selectivity in CO₂ electrochemical reduction.     

Temperature Dependence of the Vibrational Relaxation Rate Constants of CO2 (0001) in Binary Mixtures

The rate constants of intramolecular intermode relaxation of the CO₂ molecule (00⁰1) in pure CO₂ and in binary mixtures with He, Ar, H₂, O₂, N₂, CO, NO, N₂O, and H₂O were measured in the temperature range 300–1000 K by means of a laser-induced luminescence method. It is shown that these relaxation rate constants K for all the gas mixtures investigated increase with increase in the gas temperature in this range; the most efficient in deactivation of the 00⁰1 level are the collisions of CO₂ molecules with H₂O molecules; the mechanisms of relaxation of the 00⁰1 level of CO₂ and their channels depend not only on the temperature but also on the parameters of colliding particles; for each of the colliding partners of the CO₂ molecules there is a certain temperature T _c above which the temperature dependence of K is coordinated with the Landau–Teller dependence, and, moreover, the simpler the structure of the colliding partner of the CO₂ molecule, the higher the temperature T _c. Deviations from these dependences at temperatures T < T _c are attributed to the influence of intermolecular forces of attraction, change of relaxation channels, and formation of molecular clusters. For all the colliding partners of the CO₂ molecules, the interaction radii are determined from the intermolecular potentials of interaction used in the theoretical model.