Performance of a tubular solid oxide fuel cell with model kerosene reformate gas

A performance of an anode-supported tubular Ni–8YSZ/Ni–ScSZ/ScSZ/GDC/LSC cell was investigated at 650–750 °C by feeding model kerosene reformate gas (H₂, H₂O, CO, CO₂, and CH₄) to a Ni–8YSZ/Ni–ScSZ anode. Variations of gas composition were observed not only between inlet and outlet of anode to estimate the degree of internal reforming, but also during current input by online quadrupole mass spectrometry and Fourier-transform infrared spectrometry.The electrochemical performance of the cell was independent of reforming temperature of kerosene, i.e. gas composition (in particular CH₄ concentration) at moderate anode gas flow rates. At open-circuit states, 10% or less methane in the kerosene-reformed gas was readily converted by steam or CO₂ over the Ni–8YSZ/Ni–ScSZ electrode so that gas compositions could almost follow the thermodynamic equilibrium at 650–750 °C. This suggests that the internal reforming should proceed almost completely over the Ni anode. Consumption of H₂ and CO and production of CO₂ were observed during current input. I–V characteristics remained constant at 650 °C as long as anodic W/F was more than 0.2 kg mmol^− 1 s. It was demonstrated that a catalytic activity of an anode electrode for hydrocarbons will be important for SOFCs with liquid fuels such as kerosene in order not to deteriorate cell performance.     

Multi-species laser absorption sensors for in situ monitoring of syngas composition

Tunable diode laser absorption spectroscopy sensors for detection of CO, CO₂, CH₄ and H₂O at elevated pressures in mixtures of synthesis gas (syngas: products of coal and/or biomass gasification) were developed and tested. Wavelength modulation spectroscopy (WMS) with 1f-normalized 2f detection was employed. Fiber-coupled DFB diode lasers operating at 2325, 2017, 2290 and 1352 nm were used for simultaneously measuring CO, CO₂, CH₄ and H₂O, respectively. Criteria for the selection of transitions were developed, and transitions were selected to optimize the signal and minimize interference from other species. For quantitative WMS measurements, the collision-broadening coefficients of the selected transitions were determined for collisions with possible syngas components, namely CO, CO₂, CH₄, H₂O, N₂ and H₂. Sample measurements were performed for each species in gas cells at a temperature of 25 °C up to pressures of 20 atm. To validate the sensor performance, the composition of synthetic syngas was determined by the absorption sensor and compared with the known values. A method of estimating the lower heating value and Wobbe index of the syngas mixture from these measurements was also demonstrated.     

Theoretical and experimental study of methane steam reforming reactions over nickel catalyst

In this work we perform DFT theoretical calculations of methane and steam interactions on Ni(1 1 1) surface. The calculations allow us to improve our understanding of the competition between these reactants by catalytic sites in methane steam reforming (MSR) process. For this purpose we compare theoretical results with kinetic measurements of MSR on a Ni(II)-Al(III) catalyst prepared from lamellar double hydroxides as precursor. This comparison shows that, for low H₂O/CH₄ ratios methane and water intermediate species adsorb on different catalytic sites. While CHO species adsorbs on top of Ni atom, OH one occupies preferentially a tri-coordinate surface site. On the other hand, for high H₂O/CH₄ ratios a competency between these species by Ni sites would establish, diminishing methane conversion. In addition competition between methane and steam for Ni sites would lead to a decrease in CO production. Nevertheless, intermediate species adsorbed on different active sites would produce CO₂, whatever the steam/methane ratio. Thus, it would be optimum steam concentration in hydrocarbon feed and active sites distribution on catalyst surface, which could maximize H₂ production and minimize CO selectivity. The theoretical findings agree with kinetic measurements, which show that maximum methane conversion depends on steam partial pressure in the feed; whereas always, selectivity to CO₂ increases and to CO diminishes.     

The adsorption of CO,H2, H2, CO2 and H2O on carburized and graphitized Ni(110)

A study of the adsorption/desorption behavior of CO, H₂O, CO₂ and H₂ on Ni(110)(4 × 5)-C and Ni(110)-graphite was made in order to assess the importance of desorption as a rate-limiting step for the decomposition of formic acid and to identify available reaction channels for the decomposition. The carbide surface adsorbed CO and H₂O in amounts comparable to the clean surface, whereas this surface, unlike clean Ni(110), did not appreciably adsorb H₂. The binding energy of CO on the carbide was coverage sensitive, decreasing from 21 to 12 $\text{kcal}\text{mol}$ as the CO coverage approached 1.1 × 10¹⁵ molecules cm^?2 at 200K. The initial sticking probability and maximum coverage of CO on the carbide surface were close to that observed for clean Ni(110). The amount of H₂, CO, CO₂ and H₂O adsorbed on the graphitized surface was insignificant relative to the clean surface. The kinetics of adsorption/desorption of the states observed are discussed.     

Simultaneous detection of trace gases using multiplexed tunable diode lasers and a photoacoustic cell containing a cantilever microphone

We report what we believe to be a novel demonstration of simultaneous detection of multiple trace gases by near-IR tunable diode laser photoacoustic spectroscopy using a cell containing a cantilever microphone. Simultaneous detection of carbon monoxide (CO), ethyne (C₂H₂), methane (CH₄) and combined carbon monoxide/carbon dioxide (CO+CO₂) in nitrogen-based gas mixtures was achieved by modulation frequency division multiplexing the outputs of four near-IR tunable diode lasers. Normalized noise-equivalent absorption coefficients of 3.4×10^?9, 3.6×10^?9 and 1.4×10^?9 cm^?1?W?Hz^?1/2 were obtained for the simultaneous detection of CO, C₂H₂ and CH₄ at atmospheric pressure. These corresponded to noise-equivalent detection limits of 249.6 ppmv (CO), 1.5 ppmv (C₂H₂) and 293.7 ppmv (CH₄) respectively over a measurement period of 2.6 s at the relevant laser power. The performance of the system was not influenced by the number of lasers deployed, the main source of noise arising from ambient acoustic effects. The results confirm that small-volume photoacoustic cells can be used with low optical power tunable diode lasers for rapid simultaneous detection of trace gases with high sensitivity and specificity.     

Kinetic aspect of CO2 reforming of CH4 on Ni(1 1 1): A density functional theory calculation

Reaction pathways of CO₂ reforming of CH₄ on Ni(1 1 1) were investigated by using density functional theory calculation. The computed kinetic parameters agree with the available experimental data, and a new and simplified mechanism was proposed on the basis of computed energy barriers. The first step is CO₂ dissociation into surface CO and O (CO₂ → CO + O) and CH₄ sequentially dissociation into surface CH and H (CH₄ → CH₃ → CH₂ → CH). The second step is CH oxygenation into CHO (CH + O → CHO), which is more favored than its dissociation into C and hydrogen (CH → C + H). The third step is the dissociation of CHO into surface CO and H (CHO → CO + H). Finally, H₂ and CO desorb from Ni(1 1 1) and form free H₂ and CO. The rate-determining step is the CH₄ dissociative adsorption, and the key intermediate is surface adsorbed CHO. Parameters, which might modify the proposed mechanism, have been analyzed. In addition, the formation, deposition and elimination of surface carbon have been discussed accordingly.     

High-temperature emissivities of complex gas mixtures in the 4.8 μ region

Emissivities of dilute C-H-O and C-H-O-N gas mixtures have been measured in the 4.8 μ region behind reflected shock waves (2399≤T, °K≤3093) under near-equilibrium and equilibrium conditions. The emission may be satisfactorily accounted for in terms of emission from equilibrium mixtures of CO₂, CO and H₂O.     

On the reaction mechanism of CO2 reforming of methane over a bed of coal char

CO₂ reforming of methane was studied over a bed of coal char in a fixed bed reactor at temperatures between 1073 and 1223 K and atmospheric pressure with a feed composition of CH₄/CO₂/N₂ in the ratio of 1:1:8. Experimental results showed that the char was an effective catalyst for the production of syngas with a maximum H₂/CO ratio of one. It was also found that high H₂/CO ratios were favoured by low pressures and moderate to high temperatures. These results are supported by thermodynamic calculations. A mechanism of seven overall reactions was studied and three catalytic reactions of CH₄ decomposition, char gasification and the Boudouard reaction was identified as being of major importance. The first reaction produces carbon and H₂, the second consumes carbon, and the third (the Boudouard reaction) converts CO₂ to CO while consuming carbon. Equilibrium calculations and experimental results showed that any water present reacts to form H₂ and carbon oxides in the range of temperatures and pressures studied. Carbon deposition over the char bed is the major cause of deactivation. The rate of carbon formation depends on the kinetic balance between the surface reaction of the adsorbed hydrocarbons with oxygen containing species and the further dissociation of the hydrocarbon.     

人造金刚石低压气相生长的相图计算

用非平衡热力学耦合模型计算了由CH₄/H₂，CO/H₂和乙炔火焰等气相体系生长金刚石的相图．与经典平衡热力学理论计算结果不同的是这些相图都有一个金刚石生长区存在．相图中的金刚石生长区是实现金刚石气相生长的热力学基础，它的存在体现了超平衡氢原子等激活粒子对石墨的激活和对金刚石的稳定作用．计算的相图与报道的实验结果基本相符，因而对金刚石气相生长的理论和实验研究具有重要的指导意义 关键词：     

Adsorption and decomposition of formic acid on the NiO(111)-p(2 × 2) surface: TPD and steady state kinetics studies

The adsorption and decomposition of formic acid on NiO(111)-p(2 × 2) films grown on Ni(111) single crystal surface were studied by temperature-programmed desorption (TPD) spectroscopy. Exposure of formic acid at 163 K resulted in both molecular adsorption and dissociation to formate. The adsorbed formate underwent further dissociation to H₂, CO₂ and CO. H₂ and CO₂ desorbed at the same temperatures of 340, 390 and 520 K, while CO desorbed at 415 and 520 K. The desorption features varied with the formic acid exposure. Two reaction channels were identified for the decomposition of formate under equilibrium with gas-phase formic acid with a pressure of 2.5 × 10⁻⁴Pa, one preferentially producing H₂ and CO₂ with an activation energy of 22 ± 2 kJ mol⁻¹ and the other preferentially producing CO and H₂O with an activation energy of 16 ± 2 kJ mol⁻¹. The order of both reaction paths was 0.5 with respect to the pressure of formic acid.     

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.     

Density-dependent magnetic shielding in gas phase 13C N.M.R.

Density-dependent ¹³C nuclear magnetic shielding has been found for each of the pure gases CH₄, C₂H₆, C₂H₄, CO and CO₂, and for several binary mixtures of gases. For methane gas the density dependence is greater at higher temperatures in contrast to expectation and the observed temperature dependence of the shielding at zero density is attributable to nuclear motion. ¹³C magnetic shielding is considerably higher in the gas phase than in the liquid phase and the difference varies for chemically non-equivalent ¹³C nuclei by amounts which are well above the level of experimental error.     

Acetic acid decomposition on a polycrystalline platinum surface

The decomposition of CH¹³₃COOH on a polycrystalline platinum surface has been examined at temperatures between 300 and 900 K during continuous exposure to CH¹³₃COOH at 7×10^-4 Torr. On an initially clean platinum surface ¹³CO, CO, ¹³CO₂, H₂ and adsorbed carbon-12 are the major reaction products. The adsorbed carbon eventually poisons completely the reactions that produce these products. For temperatures above approximately 800 K, the carbon overlayer that is formed is graphitic and saturates at a carbon adatom concentration of (2.6-3.5)×10¹⁵ cm^-2. The reaction quantities of ¹³CO and ¹³CO₂ that are produced depend both on the surface temperature and the carbon coverage. Lower temperatures and higher carbon coverages favor the production of ¹³CO. On the graphitized platinum surface, the catalytic dehydration of acetic acid to ketene and water proceeds at steady-state.     

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.     

Oxidation of H2/CO2 mixtures and effect of hydrogen initial concentration on the combustion of CH4 and CH4/CO2 mixtures: Experiments and modeling

An experimental investigation of the oxidation of hydrogen diluted by nitrogen in presence of CO₂ was performed in a fused silica jet-stirred reactor (JSR) over the temperature range 800-1050 K, from fuel-lean to fuel-rich conditions and at atmospheric pressure. The mean residence time was kept constant in the experiments: 120 ms at 1 atm and 250 ms at 10 atm. The effect of variable initial concentrations of hydrogen on the combustion of methane and methane/carbon dioxide mixtures diluted by nitrogen was also experimentally studied. Concentration profiles for O₂, H₂, H₂O, CO, CO₂, CH₂O, CH₄, C₂H₆, C₂H₄, and C₂H₂ were measured by sonic probe sampling followed by chemical analyses (FT-IR, gas chromatography). A detailed chemical kinetic modeling of the present experiments and of the literature data (flame speed and ignition delays) was performed using a recently proposed kinetic scheme showing good agreement between the data and this modeling, and providing further validation of the kinetic model (128 species and 924 reversible reactions). Sensitivity and reaction paths analyses were used to delineate the important reactions influencing the kinetic of oxidation of the fuels in absence and in presence of additives (CO₂ and H₂). The kinetic reaction scheme proposed helps understanding the inhibiting effect of CO₂ on the oxidation of hydrogen and methane and should be useful for gas turbine modeling.     

On the mechanism of inhibition of a hydrogen flame by propane

Numerical simulations demonstrated that small additives of propane to rich hydrogen-air mixtures suppress the formation of HO₂ and OH in the low-temperature region of the flame zone, thereby causing a substantial decrease in the laminar flame speed. In the low-and high-temperature regions, propane interacts predominantly with OH and H, respectively. In the flame zone, propane is completely converted to CO, CO₂, CH₄, C₂H₂, H₂, and H₂O, being oxidized concurrently with hydrogen at that.     

Electron energy loss spectroscopy of the decomposition of formic acid on Ru(001)

Electron energy loss spectroscopy has demonstrated the existence of both a monodentate and a symmetric bidentate bridging formate as stable intermediates in the decomposition of formic acid on the Ru(001) surface. The monodentate formate converts upon heating to the bidentate formate which decomposes via two pathways: CH bond cleavage to yield CO₂ and adsorbed hydrogen; and CO bond cleavage to yield adsorbed hydrogen, oxygen and CO. Thermal desorption spectra demonstrate the evolution of H₂,H₂O, CO and CO₂ as gaseous products of the decomposition reaction. The observation of this product distribution from Ru(100), Ni(100) and Ni(110) had prompted the proposal of a formic anhydride intermediate, the existence of which is rendered questionable by the spectroscopic results reported here.     

Monte Carlo simulation of carbon monoxide,carbon dioxide and methane adsorption on activated carbon

In this study, the adsorption capacity of pure and activated carbon with regard to carbon monoxide (CO), carbon dioxide (CO₂) and methane (CH₄) gases at 298?K and pressure from 0.01 up to 2.0?MPa has been investigated computationally. Computational work refers to Monte Carlo (MC) simulation of each adsorbed gas on a graphite model with varying density of activation sites. The Grand Canonical Monte Carlo (GCMC) simulation technique was employed to obtain the uptake of each adsorbed gas by considering a graphite model of parallel sheets activated by carboxyl and hydroxyl groups, as observed experimentally. The simulation adsorption data for these gases within the examined carbon pore material are presented and discussed in terms of the adsorbate fluid molecular characteristics and corresponding interactions between adsorbate species and adsorbent material. We found that the simulated adsorption uptake of the examined graphite model under these conditions with regard to the aforementioned fluids increases in the order CO?<?CH₄?<?CO₂.     

Analysis of the product gas from biomass gasification by means of laser spectroscopy

The use of biomass and waste for decentralised combined heat and power production (CHP) requires highly efficient gasification processes. In the Technische Universität München (TUM), an innovative gasification technology has been developed. This allothermal gasifier is producing a hydrogen- rich, high-calorific gas, that can be further used in a microturbine or a fuel cell producing energy. For the operation of such a system, the online analysis of the composition of the product gas is of high importance, since the efficient working of the machines is linked with the gas quality. For this purpose an optical measurement system based on laser spectroscopy has been applied. This system can measure not only the basic components of the product gas (H₂, CH₄, CO, CO₂, H₂O), but it also gives information concerning the content of high hydrocarbons, the so-called tars, in the product gas.     

Insight into the reaction mechanism of ethanol steam reforming catalysed by Co–Mo6S8

The production of hydrogen via steam reforming of ethanol (SRE) is favourable for the use of hydrogen as an alternative fuel. Co–Mo₆S₈ possesses high activity and stability for SRE to sustainably produce hydrogen. The competition among reaction pathways related to C–H, O–H, C–C, C–O cleavage and H₂ formation was studied. The adsorption and reaction of related intermediates in the ESR reaction pathway are described. The results indicated that the most feasible route for the decomposition of ethanol catalysed by Co–Mo₆S₈ is CH₃CH₂OH*→CH₃CH₂O*→CH₃CHO*→CH₂CHO*→CHCHO*→CHCO*→CH*+CO*. The CH* can be decomposed into C*+H*, and CO* can be oxidised via the redox mechanism of the water gas shift (WGS) reaction. Thus the final products are CO₂ and H₂. The present result may help people to design an SRE catalyst, which has the ability to break C–C to form CO and H₂, then CO react with H₂O in the WGS reaction generating CO₂ and H₂.