Electron paramagnetic resonance in irradiated Ag sub 2 CO sub 3.
Gamma irradiated silver carbonate EPR at liquid nitrogen temperatures
Ashford, N. A.↗
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Rocket-Plume Spectroscopy Simulation for Hydrocarbon-Fueled Rocket Engines
The UV-Vis spectroscopic system for plume diagnostics monitors rocket engine health by using several analytical tools developed at Stennis Space Center (SSC), including the rocket plume spectroscopy simulation code (RPSSC), to identify and quantify the alloys from the metallic elements observed in engine plumes. Because the hydrocarbon-fueled rocket engine is likely to contain C2, CO, CH, CN, and NO in addition to OH and H2O, the relevant electronic bands of these molecules in the spectral range of 300 to 850 nm in the RPSSC have been included. SSC incorporated several enhancements and modifications to the original line-by-line spectral simulation computer program implemented for plume spectral data analysis and quantification in 1994. These changes made the program applicable to the Space Shuttle Main Engine (SSME) and the Diagnostic Testbed Facility Thruster (DTFT) exhaust plume spectral data. Modifications included updating the molecular and spectral parameters for OH, adding spectral parameter input files optimized for the 10 elements of interest in the spectral range from 320 to 430 nm and linking the output to graphing and analysis packages. Additionally, the ability to handle the non-uniform wavelength interval at which the spectral computations are made was added. This allowed a precise superposition of wavelengths at which the spectral measurements have been made with the wavelengths at which the spectral computations are done by using the line-by-line (LBL) code. To account for hydrocarbon combustion products in the plume, which might interfere with detection and quantification of metallic elements in the spectral region of 300 to 850 nm, the spectroscopic code has been enhanced to include the carbon-based combustion species of C2, CO, and CH. In addition, CN and NO have spectral bands in 300 to 850 nm and, while these molecules are not direct products of hydrocarbon-oxygen combustion systems, they can show up if nitrogen or a nitrogen compound is present as an impurity in the propellants and/or these can form in the boundary layer as a result of interaction of the hot plume with the atmosphere during the ground testing of engines. Ten additional electronic band systems of these five molecules have been included into the code. A comprehensive literature search was conducted to obtain the most accurate values for the molecular and the spectral parameters, including Franck-Cordon factors and electronic transition moments for all ten band systems. For each elemental transition in the RPSSC, six spectral parameters - Doppler broadened line width at half-height, pressure-broadened line width at half-height, electronic multiplicity of the upper state, electronic term energy of the upper state, Einstein transition probability coefficient, and the atomic line center - are required. Input files have been created for ten elements of Ni, Fe, Cr, Co, Cu, Ca, Mn, Al, Ag, and Pd, which retain only relatively moderate to strong transitions in 300 to 430 nm spectral range for each element. The number of transitions in the input files is 68 for Ni; 148 for Fe; 6 for Cr; 87 for Co; 1 for Ca; 3 for Mn; 2 each for Cu, Al, and Ag; and 11 for Pd.
Tejwani, Gopal D.↗
Gravitropism in higher plant shoots. I - A role for ethylene
Two inhibitors of ethylene synthesis, Co(2+) and aminoethoxyvinylglycine (AVG), and two inhibitors of ethylene action, Ag(+) and CO2, are shown to delay the gravitropic response of cocklebur (Xanthium strumarium L.), tomato (Lycopersicon esculentum Mill.), and castor bean (Ricinus communis L.) stems. Gentle shaking on a mechanical shaker does not inhibit the gravitropic response, but vigorous hand shaking for 120 seconds delays the response somewhat. AVG and Ag(+) further delay the response of mechanically stimulated plants. AVG retards the storage of bending energy but not of stimulus. In gravitropism, graviperception may first stimulate ethylene evolution, which may then influence bending directly, or responses involving ethylene could be more indirect.
Wheeler, Raymond M.↗
Characterization of Al-Cu-Mg-Ag Alloy RX226-T8 Plate
Aluminum-copper-magnesium-silver (Al-Cu-Mg-Ag) alloys that were developed for thermal stability also offer attractive ambient temperature strength-toughness combinations, and therefore, can be considered for a broad range of airframe structural applications. The current study evaluated Al-Cu-Mg-Ag alloy RX226-T8 in plate gages and compared performance with sheet gage alloys of similar composition. Uniaxial tensile properties, plane strain initiation fracture toughness, and plane stress tearing resistance of RX226-T8 were examined at ambient temperature as a function of orientation and thickness location in the plate. Properties were measured near the surface and at the mid-plane of the plate. Tensile strengths were essentially isotropic, with variations in yield and ultimate tensile strengths of less than 2% as a function of orientation and through-thickness location. However, ductility varied by more than 15% with orientation. Fracture toughness was generally higher at the mid-plane and greater for the L-T orientation, although the differences were small near the surface of the plate. Metallurgical analysis indicated that the microstructure was primarily recrystallized with weak texture and was uniform through the plate with the exception of a fine-grained layer near the surface of the plate. Scanning electron microscope analysis revealed Al-Cu-Mg second phase particles which varied in composition and were primarily located on grain boundaries parallel to the rolling direction. Fractography of toughness specimens for both plate locations and orientations revealed that fracture occurred predominantly by transgranular microvoid coalescence. Introduction High-strength, low-density Al-Cu-Mg-Ag alloys were initially developed to replace conventional 2000 (Al-Cu-Mg) and 7000 (Al-Zn-Cu-Mg) series aluminum alloys for aircraft structural applications [1]. During the High Speed Civil Transport (HSCT) program, improvements in thermal stability were demonstrated for candidate aircraft wing and fuselage skin materials through the addition of silver to Al-Cu-Mg alloys based on Al 2519 chemistry [2]. Thermal stability of the resulting Al-Cu-Mg-Ag alloys, C415-T8 and C416-T8, was due to co-precipitation of the thermally stable . (AlCu) and ' (Al2Cu) strengthening phases [1-4]. The strength and toughness behavior was investigated for these alloys produced as 0.090-inch thick rolled sheet in the T8 condition and after various thermal exposures. The mechanical properties were shown to be competitive with conventional aircraft alloys, 2519-T8 and 2618-T8 [2]. During the Integral Airframe Structure (IAS) program, advanced aluminum alloys were examined for use in an integrally stiffened airframe structure where the skin and stiffeners would be machined from plate and extruded frames would be mechanically attached (see Figure 1) [5]. Advantages of integrally stiffened structure include reduced part count, and reduced assembly times compared to conventional built-up airframe structure. The near-surface properties of a thick plate are of significance for a machined integrally stiffened airframe structure since this represents the skin location. Properties measured at the mid-plane of the plate are more representative of the stiffener web. RX226 was developed to exploit strength-toughness improvements and thermal stability benefits of Al-Cu-Mg-Ag alloys in plate gages. This study evaluated the microstructure and properties of three gages of plate produced in the T8 condition.
Lach, Cynthia L.↗
Thermal fatigue behavior of H-13 die steel for aluminum die casting with various ion sputtered coatings
Sputtered coatings of Mo, W, Pt, Ag, Au, Co, Cr, Ni, Ag + Cu, Mo + Pt, Si3N4, A1N, Cr3C2, Ta5Si3, and ZrO2 were applied to a 2-inch-square, 7-inch-long thermal fatigue test specimen which was then internally water cooled and alternately immersed in molten aluminum and cooled in air. After 15,000 cycles the thermal fatigue cracks at the specimen corners were measured. Results indicate that a significant improvement in thermal fatigue resistance was obtained with platinum, molybdenum, and tungsten coatings. Metallographic examination indicates that the improvement in thermal fatigue resistance resulted from protection of the surface of the die steel from oxidation. The high yield strength and ductility of molybdenum and tungsten contributed to the better thermal fatigue resistance.
Nieh, C. Y.↗
Chemical fractionations in meteorites. V - Volatile and siderophile elements in achondrites and ocean ridge basalts.
Eighteen achondrites and 4 terrestrial basalts (3 ocean ridge, 1 continental) were analyzed by radiochemical neutron activation analysis for Ag, Au, Bi, Br, Cd, Co, Cs, Cu, Ga, In, Ir, Rb, Se, Tl and Zn. Samples included 7 eucrites, 5 howardites, 2 nakhlites, 2 shergottites, an angrite, and an aubrite. Light and dark portions of the gas-rich meteorites Kapoeta and Pesyanoe were analyzed separately. Nakhlites and shergottites have volatile element abundances similar to those in ocean ridge basalts; eucrites, howardites, and angrites show greater depletions by an order of magnitude and less similar abundance patterns. In terms of a two-component model of planetary accretion, the parent planets contained the following percentages of low-temperature material: eucrites 0.8, nakhlites 38, shergottites 28. Shergottites may be genetically related to L-chondrites. The siderophile element pattern of achondrites resembles that of the moon, but with less extreme depletions.
Laul, J. C.↗
Real Time Nitrogen Monitoring and Quality Control System for NASA Astromaterials Collection
The Nitrogen system is a vital utility supporting the curation office within NASA's Astromaterials Re-search and Exploration Science (ARES) Division at the Johnson Space center (JSC). Since the Apollo samples were returned in 1969. It has played an essential role in preserving NASA’s astromaterial collections (now nine collections) by maintaining contamination-free, controlled environments required for long term curation and advanced scientific research. To meet the stringent purity requirements for contamination control, high purity modified Grade C Liquid Nitrogen (LN2) is delivered weekly by an industrial gas vendor to a 15,000-gallon tank located outside at NASA JSC near the ARES facility. This nitrogen is vital for creating an inert atmosphere to store the collection in, ensuring they are continuously shielded from contaminants and alterations through a constant N2purge. For most of the past 65 years deliveries of LN2 have required a CoA (Certificate of Analysis) prior to delivery. If those were not available, then LN2 deliver were sent to third-party laboratories for verification, creating an operational bottleneck and quality gap. To address this challenge and maintain rigorous quality control, NASA JSC Infrastructure and Astromaterials Acquisition & Curation Office initiated the development of an on-site Analytical Gas Sampling (AGS) Laboratory. Designed to streamline quality verification if a CoA unavailable, the AGS lab was constructed by a subcontractor in Newton, NJ. After a successful factory acceptance test conducted by the NASA ARES Infrastructure team, the lab was trans-ported to NASA JSC, where it was anchored and integrated into the site’s nitrogen pressure system using stainless steel, oxygen-cleaned tubing. The ARES nitrogen system was modified to provide parallel flows to the AGS lab for quality control and to the astromaterials collection labs for maintaining an inert environment. The AGS lab features two operational modes: (1)Primary: Gaseous Nitrogen (GN2) Quality Monitoring –The AGS system continuously samples the site’s GN2 supply every 15 minutes to ensure compliance with required purity levels. (2) Secondary: LN2 Quality Verification when a comprehensive CoA is not available, a cryogenic vaporizer converts LN2 to GN2, which is then analyzed for impurities: H₂, Ar, O₂, CO, CO₂, H₂O, and total hydrocarbons (THC). By significantly enhancing on-site analytical capabilities, the AGS lab eliminates reliance on external testing, ensures uninterrupted quality monitoring of the nitrogen pressure system, and reinforces NASA’s commitment to preserving pristine astromaterials under the highest standards of curation and research integrity.
glove box↗
Effect of Silicon on Activity Coefficients of P, Bl, CD, SN, and AG in Liquid Fe-Si, and Implications for Differentiation and Core Formation
Cores of differentiated bodies (Earth, Mars, Mercury, Moon, Vesta) contain light elements such as S, C, Si, and O. We have previously measured small effects of Si on metal-silicate partitioning of Ni and Co [1,2], and larger effects for Mo, Ge, Sb, As [2]. The effect of Si on many siderophile elements could be an important, and as yet unquantified, influence on the core-mantle partitioning of SE. Here we report new experiments designed to quantify the effect of Si on the partitioning of Bi, Cd, Sn, Ag, and P between metal and silicate melt. The results will be applied to Earth, Mars, Mercury, Moon, and Vesta, for which we have excellent constraints on the mantle Bi, Cd, Sn, Ag, and P concentrations from mantle and/or basalt samples.
Righter, K.↗
Meteoritic and non-meteoritic trace elements in Luna 16 samples.
Two Luna 16 soils have been analyzed for Ag, Au, Bi, Br, Cd, Co, Cs, Cu, Ga, Ge, In, Ur, Ni, Rb, Re, Sb, Se, Te, Tl, and Zn. A meteoritic component similar to that in Apollo 11 and 12 soils seems to be present, corresponding to about 1.5 to 2% Cl chondrites or equivalent. It probably consists largely of micrometeorites. Three elements show strong enrichments compared to Apollo 11 and 12 soils: Cd (5 x to 200 x), Ag (5 x to 10 x), and Bi (3 x). Presumably these elements were brought in by Cd-Ag-Bi rich material, similar to that in Unit VI of Apollo core 12028.
Laul, J. C.↗
On the chemical composition of L-chondrites
Radiochemical neutron activation analysis of Ag, As, Au, Bi, Co, Cs, Ga, In, Rb, Sb, Te, Tl, and Zn and major element data in 14 L4-6 and 3 LL5 chondrites indicates that the L group is unusually variable and may represent at least 2 subgroups differing in formation history. Chemical trends in the S/Fe rich subgroup support textural evidence indicating late loss of a shock formed Fe-Ni-S melt; the S/Fe poor subgroup seemingly reflects nebular fractionation only. Highly mobile In and Zn apparently reflect shock induced loss from L chondrites. However, contrasting chemical trends in several L chondrite sample sets indicate that these meteorites constitute a more irregular sampling of, or more heterogeneous parent material than do carbonaceous or enstatite chondrites. Data for 15 chondrites suggest higher formation temperatures and/or degrees of shock than for LL5 chondrites.
Neal, C. W.↗
Chemical studies of L-chondrites. I - A study of possible chemical sub-groups
Radiochemical neutron activation analysis of Ag, As, Au, Bi, Co, Cs, Ga, In, Rb, Sb, Te, Tl and Zn and major element data in 14 L4-6 and 3 LL5 chondrites indicates that the L-group is unusually variable and may represent at least 2 sub-groups differing in formation history. Chemical trends in the S/Fe-rich sub-group support textural evidence indicating late loss of a shock-formed Fe-Ni-S melt; the S/Fe-poor sub-group seemingly reflects nebular fractionation only. Highly mobile In and Zn apparently reflect shock-induced loss from L-chondrites. Data for L5 chondrites suggest higher formation temperatures and/or degrees of shock than for LL5 chondrites.
Neal, C. W.↗
Solar Powered CO.Sub.2 Conversion
Methods and devices for reducing CO.sub.2 to produce hydrocarbons are disclosed. A device comprises a photoanode capable of splitting H.sub.2O into electrons, protons, and oxygen; an electrochemical cell cathode comprising an electro-catalyst capable of reducing CO.sub.2; H.sub.2O in contact with the surface of the photoanode; CO.sub.2 in contact with the surface of the cathode; and a proton-conducting medium positioned between the photoanode and the cathode. Electrical charges associated with the protons and the electrons move from the photoanode to the cathode, driven in part by a chemical potential difference sufficient to drive the electrochemical reduction of CO.sub.2 at the cathode. A light beam is the sole source of energy used to drive chemical reactions. The photoanode can comprise TiO.sub.2 nanowires or nanotubes, and can also include WO.sub.3 nanowires or nanotubes, quantum dots of CdS or PbS, and Ag or Au nanostructures. The cathode can comprise a conductive gas diffusion layer with nanostructures of an electro-catalyst such as Cu or Co.
Chen, Bin↗
Labile trace elements in carbonaceous chondrites - A survey
Data are presented on 14 trace elements, including Co, Au, Ga, Rb, Sb, Ag, Se, Cs, Te, Zn, Cd, Bi, Tl, and In (nearly all of which are moderately or highly labile in meteorites), obtained by radiochemical neutron activation analyses of 42 C2-C6 chondrites, all but three from Antarctica. The data indicate that carbonaceous chondrites of petrographic types 2-6 define compositional continua. It is suggested that carbonaceous C2-C6 chondrites may reflect a mixture of material that formed at low temperatures and that contained cosmic levels of highly labile elements, with material that was devoid of them.
Xiao, Xiaoyue↗
Thermally Mobile Trace Elements in Carbonaceous Chondrites from Cold and Hot Deserts
Some decades ago, Anders and co-workers used RNAA to classify a number of trace elements as being volatile during nebular condensation and accretion into primitive objects based upon their strong depletion in (equilibrated) ordinary chondrites relative to C1 chondrites. Such elements, e.g. Ag, Bi, Cd, Cs, In, Se, Te, Tl, Zn and others, exhibit nearly constant, C1-normalized atomic abundances in C2 (CM2) and in C3 chondrites. They interpreted the near-constancy of these abundances according to a 2-component model in which volatiles were introduced into carbonaceous (and other) chondrites as Cl material which was diluted with differing proportions of high-temperature (i.e. volatile-free) components. In this view, mean volatile element abundances of 0.48 in C2 and 0.24-0.29 x C1 in C3 chondrites indicated that C2 and C3 chondrites are, respectively, about 1:1 and 1:2-3 mixtures of Cl-like and high temperature materials. More recently, C1 normalized abundances of such volatile elements are nearly constant in most C2-6 chondrites (i.e. 25 non-Antarctic meteorites, nearly all falls, and 36 Antarctic finds) consistent with a 2- component mixing model. However, rather than being quantized, mean volatile element contents in each chondrite define a continuum from 0.92-0.14 x Cl for these 61 chondrites. A few carbonaceous chondrites - the first having been the NIPR consortium samples B-7904, Y-82162 and Y-86720 - show an altered pattern: many of the volatile elements in each exhibit the usual constancy of C1-normalized atomic abundances, but modified by further depletion of Cd and other elements like Tl and Bi. These are the most mobile trace elements, i.e. those most readily vaporized and lost from primitive meteorites during week-long heating at greater than or equal to 400 C under low ambient pressures (initially 10 (exp -5) atm H2), simulating metamorphic conditions in a primitive parent body. Similarities between mobile element data for B-7904, Y-82162 and Y-86720 with those for Murchison heated at 500-700 C suggest that these Antarctic C1 and C2-like chondrites were metamorphosed at temperatures like these in the interiors of their parent bodies. Metamorphic temperatures inferred from RNAA data and textural/mineralogic alterations are internally consistent, agreeing with those evident in heated Murchison samples. These 3 chondrites were also heated late in their histories since all have lost cosmogenic 3-He, presumably during close solar approach, and B-7904 and Y-86720 seem also to have lost substantial proportions of radiogenic He-4 and Ar-40, cf. data. Similarities in spectral reflectance data for C-, G-, B- and F- asteroids, for these meteorites and for heated Murchison samples suggest that thermally metamorphosed interior materials in these asteroids were excavated by impacts and re-deposited on them, forming their present surfaces. Establishment of the thermal metamorphic histories of carbonaceouis chondrites, then, is essential to establishing the evolution and present-day nature of C-type and related asteroids.
Lipschutz, M. E.↗
Thermally Mobile Trace Elements in Carbonaceous Chondrites From Cold and Hot Deserts
Some decades ago, Anders and co-workers used RNAA to classify a number of trace elements as being volatile during nebular condensation and accretion into primitive objects based upon their strong depletion in (equilibrated) ordinary chondrites relative to C1 chondrites. Such elements, e.g. Ag, Bi, Cd, Cs, In, Se, Te, Tl, Zn and others, exhibit nearly constant, C1-normalized atomic abundances in C2 (CM2) and in C3 chondrites. They interpreted the near-constancy of these abundances according to a 2-component model in which volatiles were introduced into carbonaceous (and other) chondrites as C1 material which was diluted with differing proportions of high-temperature (i.e. volatile-free) components. In this view, mean volatile element abundances of 0.48 in C2 and 0.24-0.29 x C1 in C3 chondrites indicated that C2 and C3 chondrites are, respectively, about 1:1 and 1:2-3 mixtures of C1-like and high temperature materials. More recently, Xiao and Lipschutz found that C-normalized abundances of such volatile elements are nearly constant in most C2-6 chondrites (i.e. 25 non-Antarctic meteorites, nearly all falls, and 36 Antarctic finds) consistent with a 2-component mixing model. However, rather than being quantized, mean volatile element contents in each chondrite define a continuum from 0.92-0.14 x C1 for these 61 chondrites. A few carbonaceous chondrites, the first having been the NIPR consortium samples B-7904, Y-82162 and Y-86720, show an altered pattern: many of the volatile elements in each exhibit the usual constancy of C1-normalized atomic abundances, but modified by further depletion of Cd and other elements like Tl and Bi. These are the most mobile trace elements, i.e. those most readily vaporized and lost from primitive meteorites during week-long heating at greater than or equal to 400 C under low ambient pressures (initially 10(exp -5) atm H2), simulating metamorphic conditions in a primitive parent body. Similarities between mobile element data for B-7904, Y-82162 and Y-86720 with those for Murchison heated at 500-700 C, suggest that these Antarctic C1 - and C2-like chondrites were metamorphosed at temperatures like these in the interiors of their parent bodies. Metamorphic temperatures inferred from RNAA data and textural/mineralogic alterations are internally consistent, agreeing., with those evident in heated Murchison samples. These 3 chondrites were also heated late in their histories since all have lost cosmogenic He-3, presumably during close solar approach, and B-7904 and Y-86720 seem also to have lost substantial proportions of radiogenic He-4 and Ar-40 cf. data in. Similarities in spectral reflectance data for C-, G-, B- and F- asteroids, for these meteorites and for heated Murchison samples suggest that thermally metamorphosed interior materials in these asteroids were excavated by impacts and re-deposited on them, forming their present surfaces. Establishment of the thermal metamorphic histories of carbonaceous chondrites, then, is essential to establishing the evolution and present-day nature of C-type and related asteroids.
Lipschutz, M. E.↗
Graded Compression Stockings Prevent Post-spaceflight Orthostatic Hypotension
Post-spaceflight orthostatic intolerance is characterized by hypotension and presyncope in 20-30% of returning astronauts. Previous data from our laboratory suggests that this is largely a result of decreased venous return. Currently, NASA astronauts wear an anti-gravity suit (AGS) which consists of inflatable air bladders over the calves, thighs and abdomen, which are typically pressurized from 0.5 to 1.5 PSI (~27 to 78 mmHg). ISS crew members sometimes wear Russian Kentavr suits which consist of laced compression shorts and gaiters, providing ~30 mmHg nominally. While these garments are effective during reentry, there are a number of drawbacks that make them impractical for postflight use. We studied the ability of commercially available, custom fit, graded compression stockings (Jobst, 55 mmHg at ankle to 6 mmHg at top of thigh, 25 mmHg mean compression) to prevent postflight orthostatic intolerance, hypothesizing that these garments would prevent orthostatic intolerance following short duration space flight. Crew members from a single Space Shuttle flight were tilted to 80 degrees for 10 min while wearing the stockings (n=5 males) upon arrival at the clinic (~2 hrs after landing). Hemodynamic data were compared to data from all crewmembers tilted (without countermeasures) since return to flight (n=9). Two-way, repeated measures ANOVA, using the entire tilt time curve (0-10 min) show that systolic blood pressure (SBP, group effect p=0.008), stroke volume (SV, group effect p=0.003), and cardiac output (CO, group effect p=0.004) were higher in crewmembers who wore the Jobst stockings. A one-way ANOVA comparing the last minute standing also showed that SV (p=0.001) and CO (p less than 0.001) were higher and SBP tended to be higher (p=0.06) in Jobst subjects compared to controls. Control subjects had a higher rate of presyncope than Jobst subjects (3/9 vs 0/5) during the tilt on landing day. Orthostatic hypotension continues to present following spaceflight, despite fluid loading and other countermeasures. This preliminary study shows that commercially available compression stockings may ameliorate this problem. These stockings are readily available, inexpensive, and can be worn for days following landing. We have observed similar protection against orthostatic intolerance in ground-based studies of hypovolemic test subjects. Further refinements to the design and compression of the stockings are in progress.
Platts, S. H.↗
Relating FTS Catalyst Properties to Performance
During the reporting period June 23, 2011 to August 31, 2013, CAER researchers carried out research in two areas of fundamental importance to the topic of cobalt-based Fischer-Tropsch Synthesis (FTS): promoters and stability. The first area was research into possible substitute promoters that might be used to replace the expensive promoters (e.g., Pt, Re, and Ru) that are commonly used. To that end, three separate investigations were carried out. Due to the strong support interaction of γ-Al2O3 with cobalt, metal promoters are commonly added to commercial FTS catalysts to facilitate the reduction of cobalt oxides and thereby boost active surface cobalt metal sites. To date, the metal promoters examined have been those up to and including Group 11. Because two Group 11 promoters (i.e., Ag and Au) were identified to exhibit positive impacts on conversion, selectivity, or both, research was undertaken to explore metals in Groups 12 - 14. The three metals selected for this purpose were Cd, In, and Sn. At a higher loading of 25%Co on alumina, 1% addition of Cd, In, or Sn was found to-on average-facilitate reduction by promoting a heterogeneous distribution of cobalt consisting of larger lesser interacting cobalt clusters and smaller strongly interacting cobalt species. The lesser interacting species were identified in TPR profiles, where a sharp low temperature peak occurred for the reduction of larger, weakly interacting, CoO species. In XANES, the Cd, In, and Sn promoters were found to exist as oxides, whereas typical promoters (e.g., Re, Ru, Pt) were previously determined to exist in an metallic state in atomic coordination with cobalt. The larger cobalt clusters significantly decreased the active site density relative to the unpromoted 25%Co/Al2O3 catalyst. Decreasing the cobalt loading to 15%Co eliminated the large non-interacting species. The TPR peak for reduction of strongly interacting CoO in the Cd promoted catalyst occurred at a measurably lower temperature than in the unpromoted catalyst. Nevertheless, the Co clusters remained slightly larger, on average, in comparison with the unpromoted 15%Co/Al2O3 reference catalyst. None of the promoted catalysts (i.e., with Cd, In, or Sn) exhibited surface Co0 site densities higher than that of the unpromoted catalyst. In activity testing, the activities were even much lower than what was expected from the H2-TPD results. Two possible explanations were proposed: (1) the promoters may be located on the surfaces of cobalt particles, blocking surface Co0 but being able to desorb hydrogen or (2) the promoters may facilitate Co oxidation during FTS, as previously observed by Huffman and coworkers when K was added to cobalt catalysts.
Zirconia↗