CoII Cryptates Convert CO2 into CO and CH4 under Visible Light

Three Co^II octaazacryptates, with different substituents on the aromatic rings (Br, NO₂, CCH), were synthesised and characterised. These and the already published non-substituted cryptate catalysed CO₂ photoreduction to CO and CH₄ under blue visible light at room temperature. Although CO was observed after short irradiation times and a large range of catalyst concentrations, CH₄ was only observed after longer irradiation periods, such as 30 h, but with a small catalyst concentration (25 nm ). Experiments with ¹³C labelled CO₂ showed that CO is formed and reacts further when the reaction time is long. The CCH catalyst is deactivated faster than the others and the more efficient catalyst for CH₄ production is the one with Br. This reactivity trend was explained by an energy decomposition analysis based on DFT calculations.     

Thermal Activation of CH4 and H2 as Mediated by the Ruthenium Oxide Cluster Ions [RuOx]+ (x=1–3): On the Influence of Oxidation States

Thermal gas-phase reactions of the ruthenium-oxide clusters [RuO_x]⁺ (x=1–3) with methane and dihydrogen have been explored by using FT-ICR mass spectrometry complemented by high-level quantum chemical calculations. For methane activation, as compared to the previously studied [RuO]⁺/CH₄ couple, the higher oxidized Ru systems give rise to completely different product distributions. [RuO₂]⁺ brings about the generations of [Ru,O,C,H₂]⁺/H₂O, [Ru,O,C]⁺/H₂/H₂O, and [Ru,O,H₂]⁺/CH₂O, whereas [RuO₃]⁺ exhibits a higher selectivity and efficiency in producing formaldehyde and syngas (CO+H₂). Regarding the reactions with H₂, as compared to CH₄, both [RuO]⁺ and [RuO₂]⁺ react similarly inefficiently with oxygen-atom transfer being the main reaction channel; in contrast, [RuO₃]⁺ is inert toward dihydrogen. Theoretical analysis reveals that the reduction of the metal center drives the overall oxidation of methane, whereas the back-bonding orbital interactions between the cluster ions and dihydrogen control the H−H bond activation. Furthermore, the reactivity patterns of [RuO_x]⁺ (x=1–3) with CH₄ and H₂ have been compared with the previously reported results of Group 8 analogues [OsO_x]⁺/CH₄/H₂ (x=1–3) and the [FeO]⁺/H₂ system. The electronic origins for their distinctly different reaction behaviors have been addressed.     

Unravelling the Enigma of Nonoxidative Conversion of Methane on Iron Single-Atom Catalysts

The direct, nonoxidative conversion of methane on a silica-confined single-atom iron catalyst is a landmark discovery in catalysis, but the proposed gas-phase reaction mechanism is still open to discussion. Here, we report a surface reaction mechanism by computational modeling and simulations. The activation of methane occurs at the single iron site, whereas the dissociated methyl disfavors desorption into gas phase under the reactive conditions. In contrast, the dissociated methyl prefers transferring to adjacent carbon sites of the active center (Fe₁©SiC₂), followed by C−C coupling and hydrogen transfer to produce the main product (ethylene) via a key −CH−CH₂ intermediate. We find a quasi Mars–van Krevelen (quasi-MvK) surface reaction mechanism involving extracting and refilling the surface carbon atoms for the nonoxidative conversion of methane on Fe₁©SiO₂ and this surface process is identified to be more plausible than the alternative gas-phase reaction mechanism.     

Molecularly Engineered 6FDA-Based Polyimide Membranes for Sour Natural Gas Separation

Glassy polyimide membranes are attractive for industrial applications in sour natural gas purification. Unfortunately, the lack of fundamental understanding of relationships between polyimide chemical structures and their gas transport properties in the presence of H₂S constrains the design and engineering of advanced membranes for such challenging applications. Herein, 6FDA-based polyimide membranes with engineered structures were synthesized to tune their CO₂/CH₄ and H₂S/CH₄ separation performances and plasticization properties. Under ternary mixed sour gas feeds, controlling polymer chain packing and plasticization tendency of such polyimide membranes via tuning the chemical structures were found to offer better combined H₂S and CO₂ removal efficiency compared to conventional polymers. Fundamental insights into structure–property relationships of 6FDA-based polyimide membranes observed in this study offer guidance for next generation membranes for sour natural gas separation.     

超声波作用下的制冷剂水合物结晶过程研究

首先分析了超声波对制冷剂水合物成核生长的影响机理,然后进行了实验研究。结果表明,超声波对水合物的结晶生长有明显的影响,阶梯形的超声探头作用下的成核引导时间比指数形锥体引导时间长,促进水合物生长的超声波功率P范闱是58W相似文献   

Methane-Derived Carbonates in a Native Sulfur Deposit: Stable Isotope and Trace Element Discriminations Related to the Transformation of Aragonite to Calcite

Abstract

Stable isotope (¹³C, ¹⁸O, ³⁴S) and trace element (Sr²⁺, Mg²⁺, Mn²⁺, Ba²⁺, Na⁺) investigations of elemental sulfur, primary calcites and mixtures of aragonite with secondary, post-aragonitic calcite from sulfur-bearing limestones have provided new insights into the geochemistry of the mineral forming environment of the native sulfur deposit at Machów (SE-Poland). The carbon isotopic composition of carbonates (δ¹³C = ?41 to ?47‰ vs. PDB) associated with native sulfur (δ³⁴S = + 10 to + 15‰ vs. V-CDT) relates their formation to the microbiological anaerobic oxidation of methane and the reduction of sulfate derived from Miocene gypsum. From a comparison with experimentally derived fractionation factors the element ratios of the aqueous fluids responsible for carbonate formation are estimated. In agreement with field and laboratory observations, ratios near seawater composition are obtained for primary aragonite, whereas the fluids were relatively enriched in dissolved calcium during the formation of primary and secondary calcites. Based on the oxygen isotope composition of the carbonates (δ¹⁸O = ?3.9 to ?5.9‰ vs. PDB) and a secondary SrSO₄ (δ¹⁸O = + 20‰ vs. SMOW; δ³⁴S = + 59‰ vs. V-CDT), maximum formation temperatures of 35°C (carbonates) and 47°C (celestite) are obtained, in agreement with estimates for West Ukraine sulfur ores. The sulfur isotopic composition of elemental sulfur associated with carbonates points to intense microbial reduction of sulfate derived from Miocene gypsum (δ³⁴S ≈ + 23‰) prior to the re-oxidation of dissolved reduced sulfur species.     

Numerical study of the effect of turbulence on rate of reactions in the MILD combustion regime

In this paper, the importance of fluctuations in flow field parameters is studied under MILD combustion conditions. In this way, a turbulent non-premixed CH₄+H₂ jet flame issuing into a hot and deficient co-flow air is modeled using the RANS Axisymmetric equations. The modeling is carried out using the EDC model to describe the turbulence-chemistry interaction. The DRM-22 reduced mechanism and the GRI2.11 full mechanism are used to represent the chemical reactions of H₂/methane jet flame. Results illustrate that although the fluctuations in temperature field are small and the reaction zone volume are large in the MILD regime, the fluctuations in temperature and species concentrations are still effective on the flow field. Also, inappropriate dealing with the turbulence effect on chemistry leads to errors in prediction of temperature up to 15% in the present flame. By decreasing of O₂ concentration of hot co-flow air, the effect of fluctuations in flow field parameters on flame characteristics are still significant and its effect on species reaction rates does not decrease. On the other hand, although decreasing of jet inlet Reynolds number at constant inlet turbulence intensity addresses to smaller fluctuations in flow filed, it does not lead to lower the effect of turbulence on species distribution and temperature field under MILD combustion conditions.     

Diode-laser measurements and calculations of H2-broadening coefficients in the ν3 band of CH3D

Using a tunable diode-laser spectrometer, we have measured at room temperature the H₂-broadening coefficients of for 36 lines belonging to QP and QR branches in the ν₃ parallel band. The recorded lines with J values ranging from 1 to 15 and K from 0 to 9 (K?J) are located between 1196 and 1412 cm⁻¹. The H₂-broadening coefficients were determined by fitting each spectral line with Voigt, Rautian, and Galatry profiles. They were also calculated on the basis of a semiclassical model of interacting linear molecules performed by considering in addition to the weak electrostatic contributions the atom-atom Lennard-Jones potential. The theoretical results are in reasonable agreement with the experimental data, except for high J transitions where they are overestimated and for K approaching or equal to J with J?3 where they are underestimated. The latter discrepancy may be caused by the assumption to consider only ΔK=0 collision-induced transitions, associated with |ΔJ| transitions up to 4.     

H2-broadening coefficients in the ν3 band of CH3D at low temperatures

Using a diode-laser spectrometer, we have measured H₂-broadening coefficients of CH₃D at low temperatures (153.5, 183.5, and 223.5 K) for four lines in the ν₃ band. The collisional widths are obtained by fitting each absorption line with three lineshape models: the Voigt, Rautian, and Galatry profiles. The broadening coefficients are also calculated on the basis of a semiclassical model of interacting linear molecules by considering an atom-atom Lennard-Jones potential in addition to electrostatic contributions. By comparing the broadening coefficients at room and low temperatures the temperature dependence of these broadenings has been determined both experimentally and theoretically.     

利用溶液理论计算饱和甲烷中二氧化碳溶解度

求取二氧化碳在饱和液态甲烷中的溶解度,对于在较高温度下实现液化天然气至关重要。文中在理想溶液基础上,采用正规溶液关系式和改进的Scatchard-H ildebrand关系式进行二氧化碳的溶解度计算,并且在临界点附近采用经验公式对其进行修正。将上述计算结果与Davis实验数据进行比较后表明,改进的正规溶液理论计算方法在低于140K温区时可推荐用于此项溶解度计算,经验公式可用于接近临界温度区域的溶解度计算。