Ab Initio Study Of Zno-Based Gas-Sensing Mechanisms: Surface Reconstruction And Charge Transfer

Density functional theory (DFT) calculations were employed to explore the gas-sensing mechanisms of zinc oxide (ZnO) with surface reconstruction taken into consideration. Mix-terminated (10 (1) over bar0) ZnO surfaces were examined. By simulating the adsorption process of various gases, i.e., H-2, NH3, CO, and ethanol (C2H5OH) gases, on the ZnO (10 (1) over bar0) surface, the changes of configuration and electronic structure were compared. Based on these calculations, two gas-sensing mechanisms were proposed and revealed that both surface reconstruction and charge transfer result in a change of electronic conductance of ZnO. Also, the calculations were compared with existing experiments.

Adsorption of formaldehyde molecule on the intrinsic and Al-doped graphene: a first principle study

To search for a high sensitivity sensor for formaldehyde (H2CO), We investigated the adsorption of H2CO on the intrinsic and Al-doped graphene sheets using density functional theory (DFT) calculations. Compared with the intrinsic graphene, the Al-doped graphene system has high binding energy value and short connecting distance, which are caused by the chemisorption of H2CO molecule. Furthermore, the density of states (DOS) results show that orbital hybridization could be seen between H2CO and Al-doped graphene sheet, while there is no evidence for hybridization between the H2CO molecule and the intrinsic graphene sheet. Therefore, Al-doped graphene is expected to be a novel chemical sensor for H2CO gas. We hope our calculations are useful for the application of graphene in chemical sensor.

Gas-phase isothermal chromatography with short-lived technetium isotopes

In order to study the gas-phase chemical behavior of transactinides, an on-line isothermal chromatography apparatus has been developed and applied to separate short-lived technetium isotopes in the form of TcO3 from fission products. The fission products from a Cf-252 source were continuously and rapidly transported through the capillary to the isothermal chromatography apparatus using the N-2/KBr gas-jet techniques. Volatile oxide molecules were formed at the reaction zone kept at 900 degrees C since a trace amount of oxygen existed in the N-2 carrier gas. With the new developed isothermal chromatography apparatus, a selective separation of Tc from fission products was achieved. After isothermal chromatographic separation, Tc-101,Tc-103,Tc-104,Tc-105,Tc-106,Tc-107,Tc-108 were dominantly observed together with their Ru daughters in the gamma-spectrum, The chemical yields of Tc-101, and Tc-104 and Tc-105 isotopes with longer half-lives are about 55-57%, and those of Tc-103, Tc-106 and Tc-108 isotopes with shorter half-lives dropped down to 25-28%. The adsorption enthalpy of the investigated compounds on quartz surfaces was determined to be -150 +/- 5 kJ/mol by fitting the measured retention curves with a Monte Carlo model. The observed species of technetium oxide is attributed to TcO3, which is in good agreement with previous experimental results. That means our system worked properly and it can be used to investigate the gas-phase chemical behavior of transactinides.

Molecular dynamics simulation of adsorption of Ag particles on a graphite substrate

We have performed for the first time a molecular dynamics simulation of the adsorption of gas-phase Ag particles on a graphite substrate to provide an insight into the results of a comprehensive STM-based experiment on this system. Both pair-wise and many-body interatomic potentials have been employed, and a Morse-type Ag–C potential was specifically constructed to describe the interactions at the interface. Our simulation has successfully reproduced a significant portion of the experimental findings. We have also observed the intercalation of silver in graphite.

Numerical modelling of adsorption of metallic particles on graphite substrate via molecular dynamics simulation

A computer-based numerical modelling of the adsorption process of gas phase metallic particles on the surface of a graphite substrate has been performed via the application of molecular dynamics simulation method. The simulation relates to an extensive STM-based experiment performed in this field, and reproduces part of the experimental results. Both two-body and many-body inter-atomic potentials have been employed. A Morse-type potential describing the metal-carbon interactions at the interface was specifically formulated for this modelling. Intercalation of silver in graphite has been observed as well as the correct alignments of monomers, dimers and two-dimensional islands on the surface. PACS numbers: 02.60.Cb, 07.05.Tp, 68.55.-a, 81.05.Tp

Investigations on the adsorption of acidic gases using activated dolomite

In this work activated dolomite adsorption was investigated for removal of acidic gaseous pollutants. Charring was found to be an effective method for the activation of dolomite. This thermal processing resulted in partial decomposition, yielding a calcite and magnesium oxide structure. Adsorbents were produced over a range of char temperatures (750, 800 and 850 °C) and char times (1–8 h). The surface properties and the adsorption capability of raw and thermally treated dolomite sorbents were investigated using porosimetry, SEM and XRD. The sorbates individually investigated were CO2 and NO2. Volumetric equilibrium isotherm determinations were produced in order to quantify sorbate capacity on the various sorbents. The equilibrium data were successfully described using the Freundlich isotherm model. Despite relatively low surface area characteristics of the activated dolomite, there was a high capacity for the acidic gas sorbates investigated, showing a maximum of 12.6 mmol/g (554 mg/g) for CO2 adsorption and 9.93 mmol/g (457 mg/g) for NO2 adsorption. Potentially the most cost effective result from the work concerns the adsorptive capacity for the naturally occurring material, which gave a capacity of 9.71 mmol/g (427 mg/g) for CO2 adsorption and 4.18 mmol/g (193 mg/g) for NO2 adsorption. These results indicate that dolomitic sorbents are potentially cost effective materials for acidic gases adsorption.

Negative apparent kinetic order in steady-state kinetics of the water-gas shift reaction over a Pt-CeO2 catalyst

The kinetics of the water-gas shift reaction Were Studied on a 0.2% Pt/CeO2 catalyst between 177 and 300 degrees C over a range of CO and steam pressures. A rate decrease with increasing partial pressure of CO was experimentally observed over this sample, confirming that a negative order in CO can occur under certain conditions at low temperatures. The apparent reaction order of CO measured at 197 degrees C was about -0.27. This value is significantly larger than that (i.e, -0.03) reported by Ribeiro and co-workers [A.A. Phatak, N. Koryabkina, S. Rai, J.L. Ratts, W. Ruettinger, R.J. Farrauto, G.E. Blau, W.N. Delgass, F.H. Ribeiro, Catal. Today 123 (2007) 224] at a similar temperature. A kinetic peculiarity was also evidenced, i.e. a maximum of the reaction rate as a function of the CO concentration or possibly a kinetic break, which is sometimes observed in the oxidation of simple molecules. These observations support the idea that competitive adsorption of CO and H2O play an essential role in the reaction mechanism. (C) 2008 Elsevier B.V. All rights reserved.

Turbulent diffusion and mixing in interstellar dark clouds with adsorption onto grains

This paper reports the results of models of dark cloud chemistry incorporating a depth dependent density distribution with diffusive mixing and adsorption onto grains. The model is based on the approach taken by Xie et al. (1995), with the addition of grain accretion effects. Without diffusion, the central regions of the cloud freeze out in less than 10(7) years. Freeze-out time is dependent on density, so the diffuse outer region of the cloud remains abundant in gas for about an order of magnitude longer. We find that fairly small amounts of diffusive mixing can delay freeze-out at the centre of the model cloud for a time up to an order of magnitude greater than without diffusion, due to material diffusing inward from the edges of the cloud. The gas-phase lifetime of the cloud core can thus be increased by up to an order of magnitude or more by this process. We have run three different grain models with various diffusion coefficients to investigate the effects of changing the sticking parameters.

Protecting group and switchable pore-discriminating adsorption properties of a hydrophilic-hydrophobic metal-organic framework

Formed by linking metals or metal clusters through organic linkers, metal-organic frameworks are a class of solids with structural and chemical properties that mark them out as candidates for many emerging gas storage, separation, catalysis and biomedical applications. Important features of these materials include their high porosity and their flexibility in response to chemical or physical stimuli. Here, a copper-based metal-organic framework has been prepared in which the starting linker (benzene-1,3,5-tricarboxylic acid) undergoes selective monoesterification during synthesis to produce a solid with two different channel systems, lined by hydrophilic and hydrophobic surfaces, respectively. The material reacts differently to gases or vapours of dissimilar chemistry, some stimulating subtle framework flexibility or showing kinetic adsorption effects. Adsorption can be switched between the two channels by judicious choice of the conditions. The monoesterified linker is recoverable in quantitative yield, demonstrating possible uses of metal-organic frameworks in molecular synthetic chemistry as 'protecting groups' to accomplish selective transformations that are difficult using standard chemistry techniques.

Exceptional Behavior over the Whole Adsorption-Storage-Delivery Cycle for NO in Porous Metal Organic Frameworks

Two porous metal organic frameworks (MOFs), [M-2(C8H2O6)(H2O)(2)] center dot 8H(2)O (M = Co, Ni), perform exceptionally well for the adsorption, storage, and water-triggered delivery of the biologically important gas nitric oxide. Adsorption and powder X-ray diffraction studies indicate that each coordinatively unsaturated metal atom in the structure coordinates to one NO molecule. All of the stored gas is available for delivery even after the material has been stored for several months. The combination of extremely high adsorption capacity (similar to 7 mmol of NO/g of MOF) and good storage stability is ideal for the preparation of NO storage solids. However, most important is that the entire reservoir of stored gas is recoverable on contact with a simple trigger (moisture). The activity of the NO storage materials is proved in myography experiments showing that the NO-releasing MOFs cause relaxation of porcine arterial tissue.

The adsorption, storage and release of nitric oxide using ion exchanged zeolites

Zeolites exchanged with transition metal cations Co2+, Mn2+, Zn2+ and Cu2+ are capable of storing and delivering a large quantity of nitric oxide in a range of 1.2-2.7 mmolg(-1). The metal ion exchange impacts the pore volumes of zeolite FAU more significantly than LTA. The storage of NO mainly involves coordination of NO to metal cation sites. By exposing zeolites to a moisture atmosphere, the stored nitric oxide can be released. The NO release takes more than 2 hours for the NO concentration decreasing below similar to 5ppb in outlet gas. Its release rate can be controlled by tailoring zeolite frameworks and optimising release conditions.

Pulse-response TAP studies of the reverse water-gas shift reaction over a Pt/CeO2 catalyst

The temporal analysis of products (TAP) technique was successfully applied for the first time to investigate the reverse water-gas shift (RWGS) reaction over a 2% Pt/CeO2 catalyst. The adsorption/desorption rate constants for CO2 and H-2 were determined in separate TAP pulse-response experiments, and the number of H-containing exchangeable species was determined using D-2 multipulse TAP experiments. This number is similar to the amount of active sites observed in previous SSITKA experiments. The CO production in the RWGS reaction was studied in a TAP experiment using separate (sequential) and simultaneous pulsing Of CO2 and H-2. A small yield of CO was observed when CO2 was pulsed alone over the reduced catalyst, whereas a much higher CO yield was observed when CO2 and H-2 were pulsed consecutively. The maximum CO yield was observed when the CO2 pulse was followed by a H-2 pulse with only a short (1 s) delay. Based on these findings, we conclude that an associative reaction mechanism dominates the RWGS reaction under these experimental conditions. The rate constants for several elementary steps can be determined from the TAP data. In addition, using a difference in the time scale of the separate reaction steps identified in the TAP experiments, it is possible to distinguish a number of possible reaction pathways. (c) 2005 Elsevier Inc. All rights reserved.