Spin-orbit coupling and dissociation of CO2 molecules

Potential surfaces of the CO₂ molecule for the ground and excited ³ B ₂, ¹ B ₂ electronic states are calculated by quantum chemistry methods. The calculation of the spin-orbit coupling in the molecule shows a large the matrix element, which removes the prohibition for the dissociation-recombination process CO₂(X ¹Σ) + M ? CO(X ¹Σ) + O(³ P) + M. The barrier on the potential curve for ³ B ₂, the energy of which exceeds the limit of dissociation into components in the ground states, explains the data on the dissociation and recombination energies measured in experiments with shock tubes. The absorption cross section of CO₂ molecules in the UV spectral region measured at high temperatures allowed us to plot branches of potential curves near their minima for two upper singlet states assigned to the ¹ B ₂ and ¹ A ₂ symmetry.     

Adsorption of small molecules on transition metal doped rhodium clusters Rh3X (X = 3d, 4d atom): a first-principles investigation

The adsorption behaviours of seven molecules (CO, CO₂, N₂, NO, O₂, N₂O and NO₂) on Rh₃X (X?=Sc-Zn, Y-Cd) clusters are systematically investigated by density-functional calculations. Rh₃X clusters exhibit physical adsorption when interacting with CO₂, CO, N₂ and NO. The adsorption energies (E_ads) can be ranked as follows: NO?>?CO?>?CO_2?≥?N₂. Compared with pure Rh₄ cluster, the adsorption capacity changes with the doping element. Chemical adsorption can be obtained for Rh₃X when adsorbing O₂, N₂O and NO₂. E_ads shows an order of E_ads(O₂)?>?E_ads(NO₂)?>?E_ads(N₂O). When O₂ is adsorbed, energy barrier with doping Tc or Cr atom is substantially reduced, which indicates that chemical reactivity of O₂ on Rh₄ can be significantly enhanced. The doped rhodium clusters can be viewed as good candidates in the discrimination between different gas molecules.     

Application of Notched Long-Period Fiber Grating Based Sensor for CO2 Gas Sensing

An inductively coupled plasma etching process to fabricate notched long-period fiber gratings for CO₂ gas sensing is proposed in this article. In the gas sensing test, the 15% mixed CO₂ gas was used for characterization of CO₂ adsorption by the amine-modified nanoporous silica foams of the notched long-period fiber grating sensor. The results shows the spectra were changed with the CO₂ gas flow within 13 min. During the absorption process, the transmission of the resonant dip was decreased by 2.884?dB. Therefore, the proposed notched long-period fiber grating gas sensor shows good performance and is suitable as a gas sensor for monitoring the CO₂ adsorption process.     

Stoffliche und isotopische Untersuchungen zur Hochdruckadsorption verschiedener Gase

The general thermodynamics in high pressure sorption processes and the isotopic shifts of the gases H₂, N₂, CH₄ und CO₂ were investigated by adsorption and desorption experiments on charcoal at pressures up to 25 MPa. The calculations of thermodynamic relations in the mentioned systems were carried out on the basis of a new three parameter equation for high pressure adsorption isotherms as well as a modified RAYLEIGH equation, in particular for the isotopic experiments.     

Some crystallography,chemistry, physics,and thermodynamics of B12O2, B12P2, B12As2, and related alpha-boron type crystals

This paper shows that several alpha-boron type compounds may be useful as high-temperature semiconductors with decent carrier motilities, high electrical resistivity, good optical transparency, good stability under high radiation bombardment, and possess high neutron capture cross-sections. The most promising are B₁₂O₂, B₁₂P₂, and B₁₂As₂. Their relationship to alpha-boron, B₁₃C₂, and other derivative crystals is explained. A study of their chemical and thermodynamic properties indicates how single crystals useful for electronic devices can be grown.     

Investigation of chemical decomposition of CCl4 on TiO2 near room temperature

Dissociative adsorption of CCl₄ on TiO₂ at 35 °C has been studied by Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, and electron spin resonance. CCl₄ decompose to form CO, CO₂, and CO₃ on the surface, at such a low temperature, in which CO₂ formation is not from CO oxidation on TiO₂, but CO₃ can be produced by CO and CO₂ adsorption. The Cl generated from CCl₄ decomposition is left on the surface and bonded to titanium ions. Mineralization of CCl₄ on TiO₂ involves the lattice oxygens. Thermodynamical driving force and possible reaction routes for CO and CO₂ formation in the CCl₄ decomposition on TiO₂ are discussed.     

DFT investigation of gas sensing characteristics of Au-doped vanadium dioxide

Vanadium dioxide compounds are affordable and effective materials with large potential in gas sensing applications. However, it is still very challenging for available experiments to provide an in-depth understanding of sensing mechanism of VO₂-based materials. In this work, density functional theory and molecular dynamics are applied to explore adsorption and diffusion of H₂, CO₂, CO and CH₄ gases molecules in Au-VO₂. Based on calculated adsorption energy, change transfer, charge density difference and density of state, a strong sensing characteristics of Au-VO₂ toward CH₄ gas is concluded, which is consistent with experimental conclusions. It is also inferred that H₂, CO and CO₂ relate physical adsorption, and CH₄ corresponds to a chemical adsorption. The diffusion of CH₄ in Au-VO₂ is more difficult than the other gases due to the chemical adsorption of CH₄.     

Crystal face specificity of nitrogen adsorption on a platium field emission tip

The adsorption of nitrogen on platinum is studied with a field emission microscope equipped with a probe-hole assembly to enable quantitative emission measurements on individual crystal faces. The results are implemented by photoelectric measurements on platinum films. Adsorption at 80 K is found to result in a large and face-specific decrease in the work function. On crystal planes containing B₅ and B₆ sites this decrease is larger than on those exposing B₃ and B₄ sites only. No significant crystal face specificity is found, however, for the rate of temperature programmed desorption of nitrogen. It follows that the heat of nitrogen adsorption is essentially equal for faces with B₃, B₄, B₅ and B₆ sites. This result is at variance with certain postulates in the literature.     

Can bowl-like B30 nanostructure sense toxic cyanogen gas in air?: a theoretical study

In this work, an attempt has been made to study sensing performance of bowl-like B₃₀ nanostructure towards toxic cyanogen gas using density functional theory (DFT) at B97D/6-31+G(d) computational level. The results reveal that B₃₀ nanostructure is a proper sensor for sensing of toxic cyanogen gas. The most favourite adsorption site of B₃₀ is the exterior boron atoms that lead to the adsorption energy of ?78.48 (kJ/mol) with the remarkable change in electronic properties of B₃₀. The competitive sensing of cyanogen gas in the presence of water, oxygen and nitrogen molecules is also considered. Significant changes in the electronic properties of B₃₀ due to adsorption of cyanogen in presence of O₂, H₂O and N₂ gases enable it to be used in the detection of toxic cyanogen gas in air.     

Molecular simulation of adsorption of NO and CO2 mixtures by a Cu-BTC metal organic framework

Environmental problems due to the discharge of gases, including NO and CO₂, in addition, diseases caused by improper concentration of NO and CO₂ in vivo must be resolved. In this study, Grand canonical Monte Carlo (GCMC) simulations are combined with density functional theory (DFT) to calculate the adsorption of NO and CO₂ from a dual-component mixture to the Cu-BTC metal organic framework. The results show that the adsorption isotherms for various molar ratios of the gaseous mixture followed a Langmuir distribution. At higher pressures more CO₂ than NO was adsorbed by Cu-BTC, with NO showing a tendency to desorb. However, better results for adsorption of NO were observed at lower pressures. For the different pressure and molar ratios of the gaseous mixture examined, more CO₂ than NO was always adsorbed. Compared with three-way catalysts, Cu-BTC offers benefits to adsorption of CO₂ and NO from gaseous mixtures without increased durability problems.     

Magnetic hysteresis loops for several amorphous alloys after various heat treatments below the curie point

The hysteresis loops of amorphous Fe₈₀B₂₀, Fe₄₀Ni₄₀B₂₀, and Co₅₈Ni₁₀Fe₅Si₁₁B₁₆ alloys are investigated before and after various heat treatments in zero, dc, and ac magnetic fields and under different stress conditions. After definite treatments wasp-waisted or shifted hysteresis loops appear. A qualitative analysis of the results shows that the domain structure originally determined by stresses is stabilized by the formation of induced anisotropies during the heat treatment.     

Lithium-functionalized germanene: A promising media for CO2 capture

Density functional theory (DFT) is employed to investigate the interactions of CO₂ gas molecules with pristine and lithium-functionalized germanene. It is discovered that although a single CO₂ molecule is weakly physisorbed on pristine germanene, a significant improvement on its adsorption energy is found by utilizing Li-functionalized germanene as the adsorbent. Excitingly, the moderate adsorption energy at high CO₂ coverage secures an easy release step. Moreover, the structure of Li-functionalized germanene can be fully recovered after removal of CO₂ gas molecules. Our results suggest that Li-functionalized germanene show promise for CO₂ sensing and capture with a storage capacity of 12.57 mol/kg.     

SO2 adsorption capacity of K2CO3-impregnated activated carbon as a function of K2CO3 content loaded by soaking and incipient wetness

The SO₂ adsorption capacity of K₂CO₃-impregnated activated carbons, prepared by soaking carbon in large volumes of K₂CO₃ in solution of various concentrations, varies linearly with respect to the loading of K₂CO₃ on the carbon up to about 12% K₂CO₃ by weight. Above 12%, the capacity for SO₂ levels out and then decreases. This suggests that at high loadings the K₂CO₃ either aggregates and/or blocks pores of the activated carbon. In contrast, the adsorption capacity of carbons prepared by repeatedly (maximum of three times total) loading K₂CO₃ via incipient wetness is much larger than that of the soaked samples, up to 70% more, when the loading of K₂CO₃ is greater than 12%. Static and dynamic adsorption, DSC, SEM, EDX and incipient wetness studies of the samples show that the impregnant aggregates but does not block carbon pores.     

Pd修饰Cu电极的电化学CO2还原

利用微分电化学质谱和电化学原位衰减全反射红外光谱技术探究了Cu和CuPd催化剂上CO₂和CO的电化学还原行为. 红外光谱观察到了生成甲醇、甲烷与乙烯的CH_x中间物种. 在CuPd电极CO₂还原过程中，红外光谱的CO吸附峰起始电位比Cu正移大约300 mV，说明CuPd能够有效促进CO₂还原；CO饱和溶液中，Cu和CuPd电极CO起始吸附电位基本相同；两电极上CO谱带出现的电位与CO₃^2-的谱带降低的电位基本相同，说明CO的吸附需要CO₃^2-的脱附. 利用电化学在线质谱发现在CuPd电极上CO还原产生CH₄和CH₃OH的起始电位比Cu电极正移约200 mV. 推测催化活性的提升可能是由于Pd的引入改变了Cu的d能带，且Pd吸附更多的H，从而促进CO₂还原，使CO能够与H结合并被深度还原.     

A reduced mechanism for primary reactions of coal volatiles in a plug flow reactor

In the present paper, the authors study the primary reactions of coal volatiles and a detailed mechanism has been made for three different environments: thermal decomposition (pyrolysis), partial oxidation (O₂) and O₂/CO₂ gasification in a plug flow reactor to analyze the combustion component. The computed results have similar trend for three different environments with the experimental data. A systematically reduced mechanism for O₂/CO₂ gasification has also been derived by examination of Rate of Production (ROP) analysis from the detailed mechanism (255 species and 1095 reactions). The reduced mechanism shows similar result and has been validated by comparing the calculated concentrations of H₂, CH₄, H₂O, CO, CO₂ and polycyclic aromatic hydrocarbon (PAH) with those of the detailed mechanism in a wide range of operating conditions. The authors also predicted the concentration profiles of H₂, CO, CO₂ and PAH at high temperature and high pressure.     

Electronic decoupling of surface layers from bulk and its influence in oxidation catalysis: A molecular beam study

Interactions between oxygen and Pd-surfaces have important implications, especially towards oxidation reactions, and influence of subsurface oxygen to oxidation reactions is the focus of the present study. In our efforts to understand the above aspects, CO oxidation reactions have been carried out with mixed molecular beam (MB), consisting CO and O₂, on Pd(1 1 1) surfaces under a wide variety of conditions (T = 400-900 K, CO:O₂ = 7:1 to 1:10). A new aspect of the above reaction observed in the transient kinetics regime is the evidence for oxygen diffusion into Pd subsurface layers, and its significant influence towards CO oxidation at high temperatures (≥600 K). Interesting information derived from the above studies is the necessity to fill up the subsurface layers with oxygen atoms to a threshold coverage (θ_O-sub), above which the reactive CO adsorption occurs on the surface and simultaneous CO₂ production begins. There is also a significant time delay (Γ) observed between the onset of oxygen adsorption and CO adsorption (and CO₂ production). Above studies suggest an electronic decoupling of oxygen covered surface and subsurface layers, which is slightly oxidized, from the metallic bulk, which induces CO adsorption at high temperatures and simultaneous oxidation to CO₂.     

官能团及修饰位点对金属有机骨架化合物（MOFs）CO2/CH4分离性能的影响：蒙特卡洛模拟研究

In order to explore the in uence of modification sites of functional groups on landfill gas (CO₂/CH₄) separation performance of metal-organic frameworks (MOFs), six types of organic linkers and three types of functional groups (i.e. -F, -NH₂, -CH₃) were used to construct 36 MOFs of pcu topology based on copper paddlewheel. Grand canonical Monte Carlo simulations were performed in this work to evaluate the separation performance of MOFs at low (vacuum swing adsorption) and high (pressure swing adsorption) pressures, respectively. Simulation results demonstrated that CO₂ working capacity of the unfunctionalized MOFs generally exhibits pore-size dependence at 1 bar, which increases with the decrease in pore sizes. It was also found that -NH₂ functionalized MOFs exhibit the highest CO₂ uptake due to the enhanced Coulombic interactions between the polar -NH₂ groups and the quadrupole moment of CO₂ molecules, which is followed by -CH₃ and -F functionalized ones. Moreover, positioning the functional groups -NH₂ and -CH₃ at sites far from the metal node (site b) exhibits more significant enhancement on CO₂/CH₄ separation performance compared to that adjacent to the metal node (site a).     

CO2 adsorption on branched polyethyleneimine-impregnated mesoporous silica SBA-15

Adsorption of pure CO₂ on SBA-15 impregnated with branched polyethyleneimine (PEI) has been studied. Materials were prepared by impregnating the pore surface of SBA-15 mesoporous silica with different amounts of branched PEI (10, 30, 50 and 70 wt%). Textural properties, elemental analysis and low angle XRD measurements of the prepared samples showed a progressive pore filling of SBA-15 as PEI loading was increased. Pure CO₂ adsorption isotherms on these modified SBA-15 materials were obtained at 45 °C, showing high adsorption efficiency for CO₂ removal at 1 bar. Chemisorption of CO₂ on amino sites of the modified SBA-15 seems to be the main adsorption mechanism. PEI content of impregnated SBA-15 influences the adsorption capacity of the material, being a relevant variable for CO₂ removal by adsorption. Temperature effect on adsorption was also studied in the range 25-75 °C, showing that temperature strongly influences CO₂ adsorption capacity. Adsorption capacity was also tested after regeneration of the PEI-impregnated SBA-15 materials. Our results show that these branched PEI-impregnated materials are very efficient even at low pressure and after several adsorption-regeneration cycles.     

Sims studies of the adsorption of O2, CO and CO2 on titanium using low primary energies

The influence of the adsorption of O₂, CO and CO₂ on secondary ion yields from titanium has been examined using 500 eV primary argon ions. Secondary ion energy distributions were also measured. Electron-induced desorption was used as an auxiliary technique. For oxygen adsorption there is agreement with measurements using other techniques and the adsorption process is shown to occur in two stages, an initial rapid chemisorption regime followed by an oxide regime. For carbon monoxide adsorption, the measurements suggest that dissociation does not occur significantly at room temperature. For CO₂, the results are more complex. Complete dissociation seems unlikely but there may be partial dissociation. Some tentative generalizations are made concenrning the influence of adsorption on secondary ion yields.     

Adsorption of CO2 on PbO at ambient temperature

The adsorption of CO₂ on metal oxides at ambient temperature received less study largely due to the small adsorption amount. However, the adsorption is of interest in refreshing the atmosphere of isolated spaces. It was shown in the present work that P_bO was sensitive to low concentration CO₂ in the presence of water. An XPS examination indicated that P_bO changed to P_bCO₃ after the adsorption of CO₂; therefore, the adsorption is chemical in nature. In order to enlarge the CO₂ capacity, P_bO was dispersed on the surface of a silica gel with large surface area (710 m²/g). Both CO₂ capacity and adsorption rate indicated that the optimal dispersion manner of P_bO is the mono-molecular layer surface coverage. Breakthrough experiments showed that the prepared adsorbent could effectively capture low-concentration CO₂ at ambient temperature and pressure yielding a CO₂ capacity of 59.1 mg g⁻¹. The saturated adsorbent was regenerated on heating at 380 °C and the CO₂ capability was recovered.