乙二醇溶剂热合成的CeO2的可逆氧化还原性及CO2捕获性能

利用乙二醇的还原性,采用乙二醇溶剂热法制备了表面具有丰富氧空穴的CeO₂-GST纳米晶,对其进行了X射线衍射、透射电镜、X射线光电子能谱、原位H₂还原-O₂氧化循环和CO₂原位红外漫反射表征,并研究了其可逆氧化还原性及CO₂捕获性能. 结果表明,与CeO₂-nanorod和柠檬酸溶胶法合成的CeO₂-CA样品相比,CeO₂-GST纳米晶具有最好的可逆氧化还原性能和循环稳定性,同时在50 ℃下具有最好的CO₂吸附性能（149 μmol/g）. 利用原位红外漫反射光谱研究了CO₂在还原CeO₂表面的吸附情况,发现CO₂主要以双齿碳酸盐和桥连碳酸盐两种形式吸附在CeO₂表面,其中桥连碳酸盐物种不稳定,He吹扫可脱附. 此外,CO₂在CeO₂-nanorod上还会生成稳定的甲酸盐和单齿碳酸盐物种.     

Collision-induced absorption of infrared radiation by N2, O2 and CO2

The collision-induced absorption of the symmetric vibration of CO₂ has been observed in the pure gas at densities from 20.0 to 40.0 amagat and at temperatures of 273, 298, and 323 K using infrared techniques. From the integrated intensities of the bands and using the (exp ?4) model of van Kranendonk, it is possible to deduce a value for the first derivative of the quadrupole moment with respect to the vibrational coordinate. For CO₂ the contribution from quadrupole distortion to the binary absorption coefficient is reported for several temperatures. The (exp ?4) model of van Kranendonk is used to calculate the binary absorption coefficients for the fundamental vibrational bands of N₂ and O₂ at temperatures from 70 to 340 K. The parameters λ and p/σ describing the magnitude and range of the short-range collision-induced dipole moments were determined using the known experimental absorption coefficients. The contributions from atomic distortion and quadrupole distortion to the binary absorption coefficient are calculated for N₂ and O₂.     

Computational Study on Interactions between CO2 and (TiO2)n Clusters at Specific Sites

The energetic pathways of adsorption and activation of carbon dioxide (CO₂) on low-lying compact (TiO₂)_n clusters are systematically investigated by using electronic structure calculations based on density-functional theory (DFT). Our calculated results show that CO₂ is adsorbed preferably on the bridge O atom of the clusters, forming a "chemisorption" carbonate complex, while the CO is adsorbed preferably to the Ti atom of terminal Ti-O. The computed carbonate vibrational frequency values are in good agreement with the results obtained experimentally, which suggests that CO₂ in the complex is distorted slightly from its undeviating linear configuration. In addition, the analyses of electronic parameters, electronic density, ionization potential, HOMO-LUMO gap, and density of states (DOS) confirm the charge transfer and interaction between CO₂ and the cluster. From the predicted energy profiles, CO₂ can be easily adsorbed and activated, while the activation of CO₂ on (TiO₂)_n clusters are structure-dependent and energetically more favorable than that on the bulk TiO₂. Overall, this study critically highlights how the small (TiO₂)_n clusters can influence the CO₂ adsorption and activation which are the critical steps for CO₂ reduction the surface of a catalyst and subsequent conversion into industrially relevant chemicals and fuels.     

The ability of RP-type cobaltites to accommodate carbonate groups: A new layered oxide Sr4Co2(CO3)O5.86

The possibility to introduce carbonate groups inside a pure cobalt based Ruddlesden Popper type matrix is demonstrated. This paper reports the synthesis as a single phase of a new layered oxycarbonate Sr₄Co₂(CO₃)O_5.86 and its structural characterizations at room temperature combining TEM observations and powder neutron diffraction data. Close structural relationships are observed with the homologous Sr₄Fe_3−x(CO₃)_xO_10−4x series and deal with the presence of two specific carbonate configurations, namely coat hanger and flag. Magnetization measurements reveal a complex antiferromagnetic behavior below 50 K with three others transitions, at 160, 210 and 250 K. Such behavior can be ascribed to the latent reactivity in air of this largely oxygen deficient phase.     

Ab initio computation of vibrational relaxation rate coefficients for the collisions of CO2 with helium and neon atoms

Ab initio calculations of rate coefficients are reported for the vibrational relaxation of CO₂ molecules in collision with helium and neon atoms. Self consistent-field computations have been performed to parameterise simple three-dimensional potential energy functions which have been used in vibrational close-coupling, rotational infinite-order-sudden calculations of rate coefficients. Excellent agreement is obtained between the calculated and experimental rate coefficients for the deactivation of the (01₁0) vibrational level in the He + CO₂ system at temperatures of 300 K and above. The ab initio predictions of rate coefficients for relaxation of CO₂ vibrational levels such as (10⁰0) and (02⁰0) should be useful in computer simulations of CO₂ lasers.     

Low temperature fluorescence studies of the deactivation of the bend—stretch manifold of CO2

Laser fluorescence has been used to measure rate constants for the vibrational of the bend—stretch manifold of CO₂ between 300 and 170 K. The technique employed a pulsed chemical CO laser to produce vibrationally excited CO. This was used in a collisional pumping scheme designed to deposit an excess of vibrational energy in the bend—stretch manifold of CO₂. The deactivation of this vibrational manifold has been studied using the following collisional partners: CO₂, Ar, Xe, N₂ and H₂. Our results are compared with the limited amount of other low temperature data which have been published and with data obtained using a shock tube in the temperature range of about 1000 to 400 K. The present low temperature and the published high temperature results extrapolate together smoothly and clearly show the large deviations from Landau—Teller behaviour which occur at low temperatures.     

Vibrational excitations and structure of C2H4 adsorbed on Cu(100)

The adsorption of C₂H₄ on Cu(100) at 80 K has been investigated by angle-dependent high-resolution electron energy loss spectroscopy (EELS) and low-energy electron diffraction (LEED). Our observations are consistent with a model where the ethene molecule is adsorbed in a configuration parallel to the Cu(100) surface. The molecule-metal interaction is weak and presumably of π character.     

Adsorption of CO2 on nitrogen-enriched activated carbon and zeolite 13X

Adsorption may be a potentially attractive alternative to capturing CO₂ from stationary sources in the context of Carbon Capture and Sequestration (CCS) technologies. Activated carbon and zeolites are state-of-art adsorbents which may be used for CO₂ adsorption, however physisorption alone tends to be insignificant at high temperatures. In the present work, commercial adsorbents have been impregnated with monoethanolamine (MEA) and triethanolamine (TEA) in order to investigate the effect of the modified surface chemistry on CO₂ adsorption, especially above room temperature. Adsorption isotherms for CO₂, N₂ and CH₄ were measured in a gravimetrically system in the pressure range of UHV to 10 bar, at 298 and 348 K for activated carbon and zeolite 13X supports. The adsorbed concentration of CO₂ was significantly higher than those of CH₄ and N₂ for both adsorbents in the whole pressure range studied, zeolite 13X showing a remarkable affinity for CO₂ at very low pressures. However, at 348 K, the adsorbed concentration of CO₂ decreases significantly. The supports impregnated with concentrated amine solutions and dried in air suffered a detrimental effect on the textural properties, although CO₂ uptake became much less susceptible to temperature increase. Impregnations carried out with dilute solution followed by drying in inert atmosphere yielded materials with very similar textural characteristics as compared to the parent support. CO₂ isotherms in such materials showed a significant change with similar capacities at 348 K as compared to the original support at 298 K in the case of activated carbons. The impregnated zeolite showed a decrease in adsorbed phase concentration in low pressures for a given temperature, but the adsorbed amount also seemed to be less affected by temperature. These results are promising and indicate that CO₂ adsorption may be enhanced despite high process temperatures (e.g. 348 K), if convenient impregnation and drying methods are applied.     

CO2 reforming of methane over zirconia-supported nickel catalysts, II. Thermogravimetric analysis

Thermogravimetric analysis has been used to study carbon deposition during the CO₂ reforming of methane over Ni/ZrO₂ catalysts. The carbon deposits form on the reduced catalyst at a very fast rate during temperature-programmed surface reaction of reforming, and reach a steady state below 973 K. So, the amount of deposited carbon remains constant on the catalyst during the reaction at 973 K. A relationship between the amount of deposited carbon and the activity reveals that the initially formed carbon acts as a reaction intermediate and reacts with CO₂ to produce CO.     

From CH4 reforming with CO2 to pyrolysis over a platinum catalyst

At temperatures up to 1100°C, CH₄ and CO₂ react over a Pt wire to give mainly the reforming product CO, even at a CH₄/CO₂ ratio of 4.3. But if coke is present on the wire, the dominant reaction becomes the pyrolysis of CH₄ to form mainly C₂H₂ and C₆H₆. Thus, surface carbon poisons the reforming reaction and is autocatalytic for CH₄ pyrolysis. Higher temperatures and larger CH₄/O₂ ratios favor the formation of coke and the pyrolysis reaction. Molecular oxygen and, to a lesser extent, water have the opposite effect.     

Influence of CO2 activation on hydrogen storage behaviors of platinum-loaded activated carbon nanotubes

In this work, platinum (Pt) metal loaded activated multi-walled carbon nanotubes (MWNTs) were prepared with different structural characteristics for hydrogen storage applications. The process was conducted by a gas phase CO₂ activation method at 1200 °C as a function of the CO₂ flow time. Pt-loaded activated MWNTs were also formulated to investigate the hydrogen storage characteristics. The microstructures of the Pt-loaded activated MWNTs were characterized by XRD and TEM measurements. The textural properties of the samples were analyzed using N₂ adsorption isotherms at 77 K. The BET, D-R, and BJH equations were used to observe the specific surface areas and the micropore and mesopore structures. The hydrogen storage capacity of the Pt-loaded activated MWNTs was measured at 298 K at a pressure of 100 bar. The hydrogen storage capacity was increased with CO₂ flow time. It was found that the micropore volume of the activated MWNTs plays a key role in the hydrogen storage capacity.     

Valence state of Mo and surface coverage of alumina by molybdenum-oxygen species in MoOx/Al2O3

CO₂ chemisorption, BET surface area and the degree of reduction of Mo(VI) (e/Mo) have been determined in MoO_x/Al₂O₃ samples, reduced with hydrogen at temperatures between 673 and 1173 K. The free alumina surface figures calculated from the surface area and e/Mo values were identical with those obtained from direct CO₂ chemisorption measurements. This identity indicates that all of the oxygen ions of the surface molybdenum-oxygen species block the alumina surface.     

Syngas production in a novel perovskite membrane reactor with co-feed of CO2

Partial oxidation of methane（POM） co-fed with CO₂ to syngas in a novel catalytic BaCo_0.6Fe_0.2Ta_0.2O_3-δ oxygen permeable membrane reactor was successfully reported.Adding CO₂ to the partial oxidation of methane reaction not only alters the ratio of CO/H₂,but also increases the oxygen permeation flux and CH₄ conversion.Around 96%CH₄ conversion with more than 93%CO₂ conversion and 100%CO selectivity is achieved,which shows an excellent reaction performance.A steady oxygen permeation flux of 15 mL/（cm² min） is obtained during the 100-h operation,which shows good stability as well.     

High-pressure structure of Li2CO3

The high-pressure behavior of Li₂CO₃ is studied up to 25 GPa with synchrotron angle-dispersive powder X-ray diffraction in diamond anvil cells and synthesis using a multi-anvil apparatus. A new non-quenchable hexagonal polymorph (P6₃/mcm, Z=2) occurs above 10 GPa with carbonate groups in a staggered configuration along the c-axis—a=4.4568(2) Å and c=5.1254(6) Å at 10 GPa. Two columns of face-shared distorted octahedra around the Li atoms are linked through octahedral edges. The oxygen atoms are coordinated to one carbon atom and four lithium atoms to form a distorted square pyramid. Splittings of X-ray reflections for the new polymorph observed above about 22 GPa under non-hydrostatic conditions arise from orthorhombic or monoclinic distortions of the hexagonal lattice. The results of this study are discussed in relation to the structural features found in other Me₂CO₃ carbonates (Me: Na, K, Rb, Cs) at atmospheric conditions.     

Vibrational deactivation of CO2(0001) by ethane

The deactivation of CO₂(00⁰1) by ethane in the temperature range 300–600 K has been studied using a laser induced fluorescence technique. The energy transfer cross section decreased from 0.23 Ų at 300 K to 0.16 Ų at 600 K. The magnitude of the cross section is consistent with the expectation that near resonant V-V energy transfer processes are responsible for the energy transfer between CO₂(00⁰1) and ethane during collisions even though the observed temperature dependence of the energy transfer cross section does not follow that predicted by the existing theories.     

Semiclassical calculation of rate costants for energy transfer between the asymmetric stretch mode of CO2 and N2

By using a semiclassical method for energy transfer in polyatomic molecules we have calculated 21 rate constants for vibration-vibration transitions between the asymmetric stretch mode of CO₂ and the vibrational mode of N₂ in the temperature range 50–700 K.     

Vibrational relaxation of CO2(v3) by O atoms

The vibrational relaxation time for CO₂(v₃) + O(³P) has been measured by laser fluorescence. The observed value, βCO₂.O = 0.21 ± 0.04 μsec, is an order of magnitude lower than the relaxation time for self-collisions.     

A study on methanol steam reforming to CO2 and H2 over the La2CuO4 nanofiber catalyst

The La₂CuO₄ crystal nanofibers were prepared by using single-walled carbon nanotubes as templates under mild hydrothermal conditions. The steam reforming of methanol (SRM) to CO₂ and H₂ over such nanofiber catalysts was studied. At the low temperature of 150 °C and steam/methanol=1.3, methanol was completely (100%, 13.8 g/h g catalyst) converted to hydrogen and CO₂ without the generation of CO. Within the 60 h catalyst lifespan test, methanol conversion was maintained at 98.6% (13.6 g/h g catalyst) and with 100% CO₂ selectivity. In the meantime, for distinguishing the advantage of nanoscale catalyst, the La₂CuO₄ bulk powder was prepared and tested for the SRM reaction for comparison. Compared with the La₂CuO₄ nanofiber, the bulk powder La₂CuO₄ showed worse catalytic activity for the SRM reaction. The 100% conversion of methanol was achieved at the temperature of 400 °C, with the products being H₂ and CO₂ together with CO. The catalytic activity in terms of methanol conversion dropped to 88.7% (12.2 g/h g catalyst) in 60 h. The reduction temperature for nanofiber La₂CuO₄ was much lower than that for the La₂CuO₄ bulk powder. The nanofibers were of higher specific surface area (105.0 m²/g), metal copper area and copper dispersion. The in situ FTIR and EPR experiments were employed to study the catalysts and catalytic process. In the nanofiber catalyst, there were oxygen vacancies. H₂-reduction resulted in the generation of trapped electrons [e] on the vacancy sites. Over the nanofiber catalyst, the intermediate H₂CO/HCO was stable and was reformed to CO₂ and H₂ by steam rather than being decomposed directly to CO and H₂. Over the bulk counterpart, apart from the direct decomposition of H₂CO/HCO to CO and H₂, the intermediate H₂COO might go through two decomposition ways: H₂COO=CO+H₂O and H₂COO=CO₂+H₂.     

Temperature dependence of the vibration-vibration transfer rates from CO2 and N2O excited in the (0001) vibrational level to 14N2 and 15N2 molecules

V-V transfer rates from CO₂ and N₂O excited in the (00⁰1) vibrational level to ¹⁴N₂ and ¹⁵N₂ are determined from 150 to 1200 K using the laser fluorescence method, and compared with values calculated on the basis of dipole-quadrupole interactions.