Rule of 100:An inherent limitation or performance measure in oxidative coupling of methane?

The oxidative coupling of methane over La 2 O 3 /CaO type-catalyst in a fixed-bed reactor is studied under a wide range of operating conditions(973相似文献   

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.     

Crystal structures and luminescence of two cadmium(II) polymers constructed from aromatic polycarboxylate and bis(1,2,4-triazol-1-yl)methane ligands

Two new coordination compounds, {[Cd₂(btrm)(ip)₂(H₂O)₂]?·?2H₂O} _n (1) and {[Cd₂(btrm)(hip)₂(H₂O)₄]?·?3H₂O} _n (2) (btrm?=?bis(1,2,4-triazol-1-yl)methane, H₂ip?=?isophthalic acid, H₂hip?=?5-hydroxy isophthalic acid), have been synthesized and structurally characterized. Compound 1 is a 3-D network with CdSO₄ topology. Compound 2 contains 1-D ladder structures, which are interconnected by classical hydrogen-bonding interactions (O–H?···?O) to lead to 3-D supramolecular architectures. Luminescence was performed on 1 and 2, both of which showed strong fluorescent emissions in the solid state at room temperature.     

Reinvestigation of the ν2 + 2ν3 subband in the overtone icosad of 12CH4 using cavity ring-down (CRD) spectroscopy of a supersonic jet expansion

We report a detailed reinvestigation of the ν₂?+?2ν₃ combination band of methane ¹²CH₄ centred at (7510.3378?±?0.003)?cm^?1 ((225.154263?±?0.0001)?THz) within the icosad of the overtone absorption. A new experimental setup is described, allowing us to carry out cw-laser cavity ring-down spectroscopy (cw-CRDS) at instrumental resolution in the MHz range in seeded supersonic jet expansions down to rotational temperature of 7?K compared to previous cw-CRDS measurements in our group achieving about 50?K in expansions of neat CH₄. We provide a careful re-analysis on the basis of our new experimental results for the Q and R branch transitions including data obtained between about 7 and 300?K under various conditions. We resolve previously observed discrepancies of assignments and are able to present a definitive assignment for lines involving angular momentum quantum numbers up to J?=?4. The analysis of relative intensities in spectra taken at rotational and effective translational temperatures between about 50?K and less than 10?K indicate conservation of nuclear spin symmetry upon supersonic jet expansion, in agreement with previous results using other techniques and covering other spectral ranges.     

Real‐Time Measurement of the Size Distribution of Diesel Exhaust Particles using a Portable 4‐stage Electrical Low Pressure Impactor

For this study, a 4 stage electrical low pressure impactor was designed to measure the real‐time size distribution of diesel particulate matter (DPM). For the performance evaluation, sodium chloride (NaCl) particles and dioctyl sebacate (DOS) particles were used. After evaluating the collection efficiency of each stage of the impactor, the size distributions of test particles were estimated using electrical current data and their inversion algorithm, and this was found to agree with the results obtained by a scanning mobility particle sizer (SMPS). For measurement of DPM, a common‐rail direct injection (CRDI) diesel engine, for engine speeds of 1,200 rpm and 1,500 rpm at 2.7 kgf·m, was used. Therefore, it was found that the size distribution of the DPM could be easily obtained, with the currents measured by the impactor and the data inversion algorithm, in less than 5 seconds. Furthermore, the effective density of the DPM could be obtained using the calculated results and the SMPS data.     

Surface Modification of Bituminous Coal and Its Effects on Methane Adsorption

This paper studied the role of O‐containing groups over the coal surface in methane adsorption. The coal was modified with H₂SO₄, (NH₄)₂S₂O₈ or H₂SO₄/(NH₄)₂S₂O₈), respectively, to introduce O‐containing functional groups, and characterized by proximate analysis, ultimate analysis, Boehm titration, X‐ray photoelectron spectroscopy (XPS) and nitrogen adsorption. The results of ultimate analysis, Boehm titration and XPS indicate that there were increases in terms of both the content of oxygen and the quantities of O‐containing groups over the modified coals surface, especially for the carboxyl. Nitrogen adsorption shows that the modified coals possessed higher surface area and pore volume than that of 0‐XQ. The methane adsorption data were measured at 298 K at pressures up to 4.0 MPa by the volumetric method and fitted well by Langmuir model. Experimental results implied that O‐containing groups and pore structure affected methane adsorption. The adsorption capacities decreased as increasing quantities of O‐containing groups.     

Fe/MgO催化裂解甲烷制备碳纳米带

采用溶胶-凝胶法制备了Fe/MgO催化剂(E)。以甲烷为碳源,通过催化化学气相沉积法在E上生长出了碳纳米带(F),其结构和形貌经SEM和TEM表征。在最佳制备条件[E中Fe负载量为50%,甲烷流速70mL·min-1,于870℃反应1 h]下制备的F宽度约135 nm,厚约89 nm,长度在几十微米量级。     

Stabilization of the Triphosphallyl Ligand η3‐P3{P(O)H} at Iridium via Alkaline Activation of P4

The selective functionalization of the polyphosphorus moiety Ph₂PCH₂PPh₂PPPP present as a tetrahapto‐ligand in complex [Ir(dppm)(Ph₂PCH₂PPh₂PPPP)]⁺ ( 1 , dppm=Ph₂PCH₂PPh₂) was obtained by reaction of 1 with water under basic conditions at room temperature. The formation of the new triphosphaallyl moiety η³‐P₃{P(O)H} was determined in solution by NMR spectroscopy, and confirmed in the solid state by a single‐crystal X‐ray structure of the stable product [Ir(κ²‐dppm)(κ¹‐dppm)(η³‐P₃{P(O)H})] ( 2 ). In solution, 2 has a fluxional behavior attributable to the four P atoms belonging to the tetraphosphorus moiety in 1 and exhibits a chemical exchange process involving the two PPh₂ moieties of the same bidentate ligand, as determined by 1D and 2D NMR spectroscopy experiments carried out at variable temperature. The mechanism of the reaction was investigated at the DFT level, which suggested a selective attack of an in‐situ generated OH^? anion on one of the non‐coordinated phosphorus atoms of the P₄ moiety. The reaction then evolves through an acid‐assisted tautomerization, which leads to the final compound 2 . Bonding analysis pointed out that the new unsubstituted P₃‐unit in the η³‐P₃{P(O)H} moiety behaves as a triphosphallyl ligand.