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.     

Highly CO selective Ca and Zn hybrid metal-organic framework electrocatalyst for the electrochemical reduction of CO2

A transition metal (Zn) and alkaline earth metal (Ca)-hybridized metal-organic framework (MOF) based electrocatalyst was synthesized using a one-pot process. The as-prepared ZnCa-MOF74 (ZC) catalyst exhibited a low overpotential, an excellent CO selectivity, and high stability in the electrochemical reduction of CO₂ (ERC). The Faradaic efficiency of ZC towards CO was as high as 93%, which is two times higher than that of the Zn-MOF74 catalyst. The computational simulation also showed that Ca lowered the activation barrier of the rate-determining step during the ERC.     

Application of a CO2 dial system for infrared detection of forest fire and reduction of false alarm

Forest fires can be the cause of serious environmental and economic damages. For this reason considerable effort has been directed toward forest protection and fire fighting. The means traditionally used for early fire detection mainly consist in human observers dispersed over forest regions. A significant improvement in early warning capabilities could be obtained by using automatic detection apparatus. In order to early detect small forest fires and minimize false alarms, the use of a lidar system and dial technique will be considered. A first evaluation of the lowest detectable concentration will be estimated by numerical simulation. The theoretical model will also be used to get the capability of the dial system to control wooded areas. Fixing the burning rate for several fuels, the maximum range of detection will be evaluated. Finally results of simulations will be reported. PACS 42.68.Wt; 89.60.Ec; 92.60.Mt; 92.60.Iq     

Research on the phase-locking and beam characteristics of a new axisymmetric-fold-combination CO2 laser

A new type of axisymmetric-fold-combination CO₂ laser, which is constituted by several axisymmetric four-mirror cavities, is studied theoretically in this paper. The mutual energy coupling occurring within the communal discharge region of the unstable resonator to inject seed signals into each sub-resonator is demonstrated by theoretical deduction. The numerical results have proved that phase-locking could be achieved in this cavity, and the beams with phase-locking have both a higher intensity and a smaller light spot than the ones without phase-locking.     

降低空气中CO2浓度的低温液化法

为了防止封闭型工作环境空气中CO2的含量超标,应用低温液化的方法来分离空气中CO2。对采用级联式液化、氮膨胀液化降低空气中CO2浓度的流程进行了模拟计算和关键参数的比较,得出利用低温液化法从空气中分离出二氧化碳,达到净化空气、改善密闭空间空气品质的方案是可行的。     

Coherent focusing of high harmonics: a new way towards the extreme intensities

We demonstrate analytically and numerically that focusing of high harmonics produced by the reflection of a few-femtosecond laser pulse from a concave plasma surface opens a new way to unprecedentally high intensities. The key features allowing the boosting of the focal intensity are the harmonics coherency and the small exponent of the power-law decay of the harmonics spectrum. Using similarity theory and direct particle-in-cell simulations, we find that the intensity at the focus scales as I(CHF) alpha a(3)(0)I(0), where a(0) and I(0) alpha a(2)(0) are the dimensionless relativistic amplitude and the intensity of the incident laser pulse. The scaling suggests that due to the coherent harmonic focusing (CHF), the Schwinger intensity limit can be reached using lasers with I(0) approximately 10(22) W/cm(2). The pulse duration at the focus scales as tau(CHF) alpha 1/a(2)(0) and reaches the subattosecond range.     

DCOOD optically pumped by a 13CO2 laser: new terahertz laser lines

In this work we report on new optically pumped THz laser lines from deuterated formic acid (DCOOD). An isotopic ¹³CO₂ laser was used for the first time as a pump source for this molecule, and a Fabry–Perot cavity was used as a THz laser resonator. Optoacoustic absorption spectra were used as a guide to search for new THz laser lines. We could observe six new laser lines in the range from 303.8 μm (0.987 THz) to 725.1 μm (0.413 THz). The lines were characterized according to wavelength, relative polarization, relative intensity, and optimum working pressure. The transferred lamb-dip technique was used to measure the frequency absorption transition for both of these laser lines. Furthermore, we also present a catalogue of all THz laser lines generated from DCOOD.     

Multiline laser probing of CO:He, CO:N2, and CO:O2 active media in a wide-aperture pulsed amplifier

Multiline laser probing was applied for the diagnostics of the active medium of a wide-aperture carbon monoxide laser amplifier. The temporal behavior of the small-signal gain in the active medium of a pulsed electron-beam sustained discharge CO laser amplifier was studied with a specially designed probe CO laser in a wide range of ro-vibrational spectral lines (from V = 5 up to V = 31). The results were analyzed in order to reconstruct the temporal behavior of gas temperature and vibrational populations in CO-containing gas mixtures, CO:He and CO:N₂, and oxygen-rich CO: O₂ mixtures. __________ Translated from Preprint No. 13 of the P. N. Lebedev Physical Institute, Moscow (2005).     

Ultrasonic-assisted synthesis of porous S-doped carbon nitride ribbons for photocatalytic reduction of CO2

A series of porous S-doped carbon nitride ribbons (PSCN) were prepared by one-pot hydrothermal and sonochemical synthesis techniques. The morphologies and nanostructures of the catalysts were characterized by SEM, XRD and IR, which confirmed the pristine graphitic structures of carbon nitrides retained in the products. Due to sonication treatment, PSCN has porous structures in the thin ribbon and larger specific surface areas (PSCN 43.5 m²/g, SCN 26.6 m²/g and GCN 6.5 m²/g). XPS and elemental mappings verified that sulfur atoms were successfully introduced into the carbon nitride framework. Diffuse reflectance spectroscopy (DRS) results showed S-doping in the carbon nitride reduced the bandgap energy and enhanced their capability of the utilization of visible light, which contributed to higher photo-generated current. Photoluminescence (PL) analysis indicates the recombination of photogenerated carriers was suppressed in PSCN. Moreover, the photocatalytic performance showed that S-doping and porous and thin ribbon nanostructures may effectively boost the CO₂ reduction rate (to as much as 5.8 times of GCN) when illuminated by visible light (>420 nm) without the need of sacrificial materials. The preliminary mechanisms of the formation of PSCN and its applications in photocatalytic CO₂ reduction are proposed. It highlights the potential of the current technique to produce effective, nonmetal-doped carbon nitride photocatalysts.     

Underwater restoration and retention of gases on superhydrophobic surfaces for drag reduction

Superhydrophobic (SHPo) surfaces have shown promise for passive drag reduction because their surface structures can hold a lubricating gas film between the solid surface and the liquid in contact with it. However, the types of SHPo surfaces that would produce any meaningful amount of reduction get wet under liquid pressure or at surface defects, both of which are unavoidable in the real world. In this Letter, we solve the above problem by (1)?discovering surface structures that allow the restoration of a gas blanket from a wetted state while fully immersed underwater and (2)?devising a self-controlled gas-generation mechanism that maintains the SHPo condition under high liquid pressures (tested up to 7?atm) as well as in the presence of surface defects, thus removing a fundamental barrier against the implementation of SHPo surfaces for drag reduction.     

A DFT-based microkinetic theory for Fe2O3 reduction by CO in chemical looping

Redox kinetics of oxygen carrier in chemical looping is an important component for material preparation, reactor design and process demonstration. How to bridge the gap between the microscale density functional theory (DFT) and the macroscale redox kinetics and develop a first-principle-based theoretical model is still a challenge in the field of chemical looping. This study addresses this challenge and proposes a DFT-based microkinetic rate equation theory to calculate the heterogeneous kinetics of Fe₂O₃ reduction by CO in chemical looping. Firstly, the DFT calculation is adopted to search the reaction pathways and to obtain the energy barriers of elementary reactions. Secondly, the DFT results are introduced into the transition state theory (TST) to calculate the reaction rate constants and build the rate equations of elementary surface reactions. Finally, by considering the bulk diffusion, a rate equation is developed to bridge the gap between the elementary surface reactions and the grain conversion. In the theory, the reaction mechanism obtained from DFT and kinetic rate constants obtained from TST are directly implemented into the rate equation to predict the reduction kinetics of oxygen carriers without fitting experimental data. The accuracy of the developed theory is validated by experimental data of two Fe₂O₃ oxygen carriers obtained from the thermogravimetric analyzer (TGA). The microkinetic rate equation theory is based on the first principles calculation and can predict directly the redox kinetics of oxygen carriers without depending on the experimental kinetic data, therefore, it provides a powerful theoretical tool to screen the oxygen carrier materials and optimize the microstructure of oxygen carriers.     

Cu纳米粒催化CO2还原反应机理的理论研究

此文采用密度泛函理论,研究了Cu₃₈纳米粒催化剂模型,分别研究了CO₂和H₂O分子在催化剂上不同吸附位,确了稳定的吸附构型,并进一步研究了CO₂催化还原反应机理,确定催化剂的活性.本文主要研究催化CO₂还原生成CO过程,研究了两条可行的反应路径,路径I为水分子的H原子直接转移到CO₂上,路径II为H原子先迁移到Cu₃₈纳米粒上再转移到CO₂上,研究结果发现此步反应机理路径I优先.从微观角度解释了实验研究结果.     

Conversion of nitrogen oxides in N2:O2:CO2 and N2:O2:CO2:NO2 mixtures subjected to a dc corona discharge

This paper concerns the influence of a direct current (dc) corona discharge on production and reduction of NO, NO₂ and N₂O in N₂:O₂:CO₂ and N₂:O₂:CO₂:NO₂ mixtures. The corona discharge was generated in a needle-to-plate reactor. The positively polarized electrode consisted of 7 needles. The grounded electrode was a stainless steel plate. The gas flow rate through the reactor was varied from 28 to 110 cm³/s. The time-averaged discharge current ranged from 0 to 6 mA. It was found that in the N₂:O₂:CO₂ mixture the corona discharge produced NO, NO₂ and N₂O. In the N₂:O₂:CO₂:NO₂ mixture the reduction of NO₂ was between 6–56%, depending on the concentration of O₂, gas flow rate and corona discharge current. The NO₂ reduction was accompanied by production of NO and N₂O. The results show that efficient reduction of nitrogen oxides by a corona discharge cannot be expected in the mixtures containing N₂ and O₂ if reducing additives are not employed.     

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介绍了一种软X射线多道能谱测量的新方法,该方法用软件实现实时采集、数据处理并通过软X射线能谱计算及时显示电子温度。和传统的脉高分析器(PHA)相比,道数和时间分辨率可用软件设定。新方法采用一台配有高速A/D采集卡的个人计算机获取原始的模拟信号,开发了专用的处理软件用来处理电子温度。新方法已经应用于HL-2A装置实验,与其它方法测到的电子温度具有较好的一致性。     

Studies in laser safety of new high-output systems: 2. TEA CO2 laser impacts

The new TEA (transversely excited atmospheric pressure) CO₂ laser can produce ionization of air. No information is as yet available of the effect of this new high-power output laser on man. Repeated impacts of 30 mJ pulses with 100 kW, which produced ionization of air, caused non-specific superficial coagulation necrosis which healed promptly.     

Optimization of the CO2:N2:He Ratio in the Active Media of Continuous-Wave Electric-Discharge CO2 Lasers

It is shown that the optimum ratio between the main components CO₂:N₂:He of the active medium of continuous-wave electric-discharge CO₂ lasers depends on the temperature of the active medium. Continuous-wave CO₂ lasers can operate effectively at high temperatures of their active medium (T 1000 K) if in their composition the fraction of N₂ molecules is increased as compared to the fraction of CO₂ molecules (CO₂:N₂ < 1:15) and the fraction of He atoms is decreased (He n< CO₂ + N₂).     

Concentration of CO2 dissociation products in a capillary discharge in a CO2-N2-He mixture

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 51, No. 1, pp. 12–16, July, 1989.     

Catalytic reduction of N_2O by CO over Pt_lAu-m~- clusters:A first-principles study

Based on the density functional theory, we investigate negatively charged clusters PtlAu-m(l + m = 4), which show significant catalytic properties in the simultaneous removal of N2O and CO. We find that in these clusters, the platinum atom acts as the adsorption center for N2O, the gold and Pt atoms act as electron donors during the reaction, and the charge transfers from the bimetallic cluster to the N2O molecule. As the proportion of Au in the cluster increases, the d band center shifts down further away from the Fermi level, meanwhile more charge is transferred to the N2O molecule, resulting in weaker N–O bond strength. Therefore bimetallic cluster PtAu-3 shows better catalytic properties than the other clusters,especially pure Pt4- and Au4-clusters. This means that there is a synergetic effect between the Pt and Au atoms in the negatively charged bimetallic clusters. Our results help to reveal the mechanism of Pt l Au-m bimetallic clusters as excellent catalysts.     

Structure effects on the energetics of the electrochemical reduction of CO2 by copper surfaces

Polycrystalline copper electrocatalysts have been experimentally shown to be capable of reducing CO₂ into CH₄ and C₂H₄ with relatively high selectivity, and a mechanism has recently been proposed for this reduction on the fcc(211) surface of copper, which was assumed to be the most active facet. In the current work, we use computational methods to explore the effects of the nanostructure of the copper surface and compare the effects of the fcc(111), fcc(100) and fcc(211) facets of copper on the energetics of the electroreduction of CO₂. The calculations performed in this study generally show that the intermediates in CO₂ reduction are most stabilized by the (211) facet, followed by the (100) facet, with the (111) surface binding the adsorbates most weakly. This leads to the prediction that the (211) facet is the most active surface among the three in producing CH₄ from CO₂, as well as the by-products H₂ and CO. HCOOH production may be mildly enhanced on the more close-packed surfaces ((111) and (100)) as compared to the (211) facet, due to a change in mechanism from a carboxyl intermediate to a formate intermediate. The results are compared to published experimental data on these same surfaces; the predicted trends in voltage requirements are consistent between the experimental and computational data.