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At least 19 records

Water-gas shift: Characterization and testing of nanoscale YSZ supported Pt catalysts

Nano-scale Y-doped zirconium oxide materials were prepared with high surface areas (150-200 m(2)/g) and small nano-crystallites (<8 nm). A combination of XANES and EXAFS was used to show that ZrO2 exhibited the tetragonal phase, while the Zr0.5Y0.5O1.75 support displayed the cubic phase. A comparison with undoped zirconia suggests that the Zr0.9Y0.1O1.95 support was tetragonal in structure. A slight increase in d-spacing observed in HR-TEM for the Zr0.9Y0.1O1.95 support relative to undoped ZrO2, along with a shift to lower 2 theta in XRD, provide evidence that Y-doping caused macrostrain. STEM imaging confirmed that the Pt clusters ranged from 0.5 to 2 nm over all three supports. Catalyst reducibility was explored by H-2-TPR, XANES at the Zr K-edge, and TPR-XANES at the Pt L-III edge. A higher concentration of surface defects for the 0.5%Pt/Zr0.9Y0.1O1.95 catalyst relative to 0.5%Pt/ZrO2 was confirmed by DRIFTS of adsorbed CO, while a greater surface mobility of surface formate was suggested based on forward formate decomposition experiments in steam. The Y-doped Pt promoted catalysts displayed higher water-gas-shift activity relative to the 0.5%Pt/ZrO2 catalyst when the Y content was at or below 50%, with the best catalyst being 0.5%Pt/Zr0.9Y0.1O1.95. (C) 2015 Elsevier B.V. All rights reserved.

Pt/YSZ↗

Dynamic characteristics of gas-water interfacial plasma under water

Gas-water interfacial plasmas under water were generated in a compact space in a tube with a sandglass-like structure, where two metal wires were employed as electrodes with an applied 35 kHz ac power source. The dynamic behaviors of voltage/current were investigated for the powered electrode with/without water cover to understand the effect of the gas-water interface. It is found that the discharge exhibits periodic pulsed currents after breakdown as the powered electrode is covered with water, whereas the electrical current reveals a damped oscillation with time with a frequency about 10{sup 6} Hz as the powered electrode is in a vapor bubble. By increasing water conductivity, a discharge current waveform transition from pulse to oscillation presents in the water covering case. These suggest that the gas-water interface has a significant influence on the discharge property.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

A Structure Function Model Recovers the Many Formulations for Air-Water Gas Transfer Velocity: Air-Water Gas Transfer

Two ideas regarding the structure of turbulence near a clear air-water interface are used to derive a waterside gas transfer velocity kL for sparingly and slightly soluble gases. The first is that k L is proportional to the turnover velocity described by the vertical velocity structure function D ww (r), where r is separation distance between two points. The second is that the scalar exchange between the air-water interface and the waterside turbulence can be suitably described by a length scale proportional to the Batchelor scale lB=ηSc -1/2 , where Sc is the molecular Schmidt number and η is the Kolmogorov microscale defining the smallest scale of turbulent eddies impacted by fluid viscosity. Using an approximate solution to the von Kármán-Howarth equation predicting D ww (r) in the inertial and viscous regimes, prior formulations for k L are recovered including (i) k L =$\sqrt{2/15}$Sc -1/2 $v$, v K is the Kolmogorov velocity defined by the Reynolds number v K η/ν = 1 and ν is the kinematic viscosity of water; (ii) surface divergence formulations; (iii) k L ∝ SC -1/2 u * , where u * is the waterside friction velocity; (iv) k L ∝ Sc -1/2 $\sqrt{gv/u_*}$ for Keulegan numbers exceeding a threshold needed for long-wave generation, where the proportionality constant varies with wave age, g is the gravitational acceleration; and (v) k L = $\sqrt{2/15}$Sc -1/2 (vgβ o q o ) 1/4 in free convection, where qo is the surface heat flux and β o is the thermal expansion of water. The work demonstrates that the aforementioned k L formulations can be recovered from a single structure function model derived for locally homogeneous and isotropic turbulence.

54 ENVIRONMENTAL SCIENCES↗

Impact of Contaminants Present in Coal-Biomass Derived Synthesis Gas on Water-gas Shift and Fischer-Tropsch Synthesis Catalysts

Co-gasification of biomass and coal in large-scale, Integrated Gasification Combined Cycle (IGCC) plants increases the efficiency and reduces the environmental impact of making synthesis gas ("syngas") that can be used in Coal-Biomass-to-Liquids (CBTL) processes for producing transportation fuels. However, the water-gas shift (WGS) and Fischer-Tropsch synthesis (FTS) catalysts used in these processes may be poisoned by multiple contaminants found in coal-biomass derived syngas; sulfur species, trace toxic metals, halides, nitrogen species, the vapors of alkali metals and their salts (e.g., KCl and NaCl), ammonia, and phosphorous. Thus, it is essential to develop a fundamental understanding of poisoning/inhibition mechanisms before investing in the development of any costly mitigation technologies. We therefore investigated the impact of potential contaminants (H 2 S, NH 3 , HCN, AsH 3 , PH 3 , HCl, NaCl, KCl, AS 3 , NH 4 NO 3 , NH 4 OH, KNO 3 , HBr, HF, and HNO 3 ) on the performance and lifetime of commercially available and generic (prepared in-house) WGS and FT catalysts.

01 COAL, LIGNITE, AND PEAT↗

Catalysts synthesized by selective deposition of Fe onto Pt for the water-gas shift reaction

FePt bimetallic catalysts with intimate contact between the two metals were synthesized by controlled surface reactions (CSR) of (cyclohexadiene)iron tricarbonyl with hydrogen-treated supported Pt nanoparticles. Adsorption of the iron precursor on a Pt/SiO2 catalyst was studied, showing that the Fe loading could be increased by performing multiple CSR cycles, and the efficiency of this process was linked to the renewal of adsorption sites by a reducing pretreatment. The catalytic activity of these bimetallic catalysts for the water gas shift reaction was improved due to promotion by iron, likely linked to H2O activation on FeOx species at or near the Pt surface, mostly in the (II) oxidation state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A combined experimental and computational study of water-gas shift reaction over rod-shaped Ce 0.75 M 0.25 O 2 (M=Ti, Zr, and Mn) supported Cu catalysts

Water-gas shift (WGS) reaction over a series of ceria-based mixed oxides supported Cu catalysts was investigated using a combined experimental and theoretical method. The mixed rod-shaped Ce 0.75 M 0.25 O 2 (M = Ti 4+ , Zr 4+ , Mn 4+ ) solid solutions, which majorly expose the (110) and (100) facets, are synthesized by hydrothermal method and used to prepare supported Cu catalysts. We found that the Cu/Ce0.75Ti 0.25 O 2 (Cu-CT) exhibits the highest CO conversion in the temperature range of 150-250 °C among all supported Cu catalysts. This is mainly attributed to (i) good dispersion of Cu; (ii) largest amount of moderate copper oxide; and (iii) strongest Cu-support interaction of Cu-CT. And compared to other mixed metals, periodic density functional theory calculations performed, this work further suggest that the introduction of Ti into CeO 2 not only promotes oxygen vacancy formation and CO adsorption, but also facilitates the carboxyl (COOH) formation at the interface of the Cu cluster and the support, which leads to the enhanced catalytic activity of the Cu-CT toward WGS reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atomically Dispersed Au-(OH) x Species Bound on Titania Catalyze the Low-Temperature Water-Gas Shift Reaction

We report a new method for stabilizing appreciable loadings (~1 wt %) of isolated gold atoms on titania and show that these catalyze the low-temperature water-gas shift reaction. The method combines a typical gold deposition/precipitation method with UV irradiation of the titania support suspended in ethanol. Dissociation of H 2 O on the thus-created Au–O–TiO x sites is facile. At higher gold loadings, nanoparticles are formed, but they were shown to add no further activity to the atomically bound gold on titania. Removal of this “excess” gold by sodium cyanide leaching leaves the activity intact and the atomically dispersed gold still bound on titania. The new materials may catalyze a number of other reactions that require oxidized active metal sites.

Yang, Ming↗

In Situ Characterization of Mesoporous Co/CeO 2 Catalysts for the High-Temperature Water-Gas Shift

Here, mesoporous Co/CeO 2 catalysts were found to exhibit significant activity for the high-temperature water-gas shift (WGS) reaction with cobalt loadings as low as 1 wt %. The catalysts feature a uniform dispersion of cobalt within the CeO 2 fluorite type lattice with no evidence of discrete cobalt phase segregation. In situ XANES and ambient pressure XPS experiments were used to elucidate the active state of the catalysts as partially reduced cerium oxide doped with oxidized cobalt atoms. In situ XRD and DRIFTS experiments suggest facile cerium reduction and oxygen vacancy formation, particularly with lower cobalt loadings. In situ DRIFTS analysis also revealed the presence of surface carbonate and bidentate formate species under reaction conditions, which may be associated with additional mechanistic pathways for the WGS reaction. Deactivation behavior was observed with higher cobalt loadings. XANES data suggest the formation of small metallic cobalt clusters at temperatures above 400 °C may be responsible. Notably, this deactivation was not observed for the 1% cobalt loaded catalyst, which exhibited the highest activity per unit of cobalt.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗