2009. "Characterization of Surface and Bulk Nitrates of γ-Al2O3-Supported Alkaline Earth Oxides using Density Functional Theory." Physical Chemistry Chemical Physics. PCCP 11(18):3380-3389. doi:10.1039/b819347a Abstract “Surface" and "bulk" nitrates formed on a series of alkaline earth oxides (AEOs), AE(NO3)2, were investigated using first-principles density functional theory calculations. The formation of these surface and bulk nitrates was modeled by the adsorption of NO2+NO3 pairs on gamma-Al2O3-supported monomeric AEOs (MgO, CaO, SrO, and BaO) and on the extended AEO(001) surfaces, respectively. The calculated vibrational frequencies of the surface and bulk nitrates based on our proposed models are in good agreement with experimental measurements of AEO/gamma-Al2O3 materials after prolonged NO2 exposure. This indicates that experimentally observed "surface" nitrates are most likely formed with isolated two dimensional (including monomeric) AEO clusters on the gamma-Al2O3 substrate, while the "bulk" nitrates are formed on exposed (including (001)) surfaces (and likely in the bulk as well) of large three dimensional AEO particles supported on the gamma-Al2O3 substrate. Also in line with the experiments, our calculations show that the low and high frequency components of the vibrations for both surface and bulk nitrates are systematically red shifted with the increasing basicity and cationic size of the AEOs. The adsorption strengths of NO2+NO3 pairs are nearly the same for the series of alumina-supported monomeric AEOs, while the adsorption strengths of NO2+NO3 pairs on the AEO surfaces increase in the order of MgO < CaO < SrO ~ BaO. Compared to the NO2+NO3 pair that only interacts with monomeric AEOs, the stability of NO2+NO3 pairs that interact with both the monomeric AEO and the gamma-Al2O3 substrate is enhanced by about 0.5 eV. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.
2009. "Metallic phases of cobalt-based catalysts in ethanol steam reforming: The effect of cerium oxide." Applied Catalysis. A, General 355(1-2):69-77. Abstract The catalytic activity of cobalt in the production of hydrogen via ethanol steam reforming has been investigated in its relation to the crystalline structure of metallic cobalt. At a reaction temperature of 350 8C, the specific hydrogen production rates show that hexagonal close-packed (hcp) cobalt possesses higher activity than face-centered cubic (fcc) cobalt. However, at typical reaction temperatures (400– 500 8C) for ethanol steam reforming, hcp cobalt is transformed to less active fcc cobalt, as confirmed by in situ X-ray diffractometry (XRD). The addition of CeO2 promoter (10 wt.%) stabilizes the hcp cobalt structure at reforming temperatures up to 600 8C. Moreover, during the pre-reduction process, CeO2 promoter prevents sintering during the transformation of Co3O4 to hcp cobalt. Both reforming experiments and in situ diffuse-reflectance infrared Fourier transform spectroscopy (DRIFTS) showed that the surface reactions were modified by CeO2 promoter on 10% Ce–Co (hcp) to give a lower CO selectivity and a higher H2 yield as compared with the unpromoted hcp Co.
2009. "Understanding the nature of surface nitrates in BaO/gamma-Al2O3 NOx storage materials: A combined experimental and theoretical study ." Journal of Catalysis 261(1):17-22. Abstract The special role of the interface between the active catalytic phase (metal or metal oxide) and the oxide support in determining the properties of practical catalysts has long been recognized; however, it is still very poorly understood in most systems
2009. "Coordinatively unsaturated Al3+ centers as binding sites for active catalyst phases on γ-Al2O3." Science 325(5948):1670-1673. doi:10.1126/science.1176745 Abstract A combination of ultrahigh resolution spectroscopy and microscopy techniques (ultrahigh magnetic field solid state magic angle spinning nuclear magnetic resonance (MAS-NMR) and high-resolution scanning transmission electron microscopy (HR-STEM)) coupled with first principles DFT calculations reveal the nature of anchoring sites of a catalytically active phase onto the surface of γ-Al2O3. The results obtained unambiguously prove that coordinatively unsaturated penta-coordinate Al3+ (Al3+penta) centers present on the (100) facets of the γ-Al2O3 surface are the sites where the anchoring of Pt occurs. At low loadings, the active catalytic phase is atomically dispersed on the support surface (Pt/ Al3+penta=1), while two dimensional Pt rafts form at higher coverages.
2009. "Effects of sulfation level on the desulfation behavior of pre-sulfated Pt BaO/Al2O3 lean NOx trap catalysts: a combined H2 Temperature-Programmed Reaction, in-situ sulfur K-edge X-ray Absorption Near-Edge Spectroscopy, X-ray Photoelectron Spectroscopy, and Time-Resolved X-ray Diffraction Study." Journal of Physical Chemistry C 113(17):7336-7341. doi:10.1021/jp900304h Abstract Desulfation by hydrogen of pre-sulfated Pt(2wt%) BaO(20wt%)/Al2O3 with various sulfur loading (S/Ba = 0.12, 0.31 and 0.62) were investigated by combining H2 temperature programmed reaction (TPRX), x-ray photoelectron spectroscopy (XPS), in-situ sulfur K-edge x-ray absorption near-edge spectroscopy (XANES), and synchrotron time-resolved x-ray diffraction (TR-XRD) techniques. We find that the amount of H2S desorbed during the desulfation in the H2 TPRX experiments is not proportional to the amount of initial sulfur loading. The results of both in-situ sulfur K-edge XANES and TR-XRD show that at low sulfur loadings, sulfates were transformed to a BaS phase and remained in the catalyst, rather than being removed as H2S. On the other hand, when the deposited sulfur level exceeded a certain threshold (at least S/Ba = 0.31) sulfates were reduced to form H2S, and the relative amount of the residual sulfide species in the catalyst was much less than at low sulfur loading. Unlike samples with high sulfur loading (e.g., S/Ba = 0.62), H2O did not promote the desulfation for the sample with S/Ba of 0.12, implying that the formed BaS species originating from the reduction of sulfates at low sulfur loading are more stable to hydrolysis. The results of this combined spectroscopy investigation provide clear evidence to show that sulfates at low sulfur loadings are less likely to be removed as H2S and have a greater tendency to be transformed to BaS on the material, leading to the conclusion that desulfation behavior of Pt BaO/Al2O3 lean NOx trap catalysts is markedly dependent on the sulfation levels.
2008. "NOx uptake on alkaline earth oxides (BaO, MgO, CaO and SrO) supported on γ-Al2O3." Catalysis Today 136(1-2):121-127. doi:doi:10.1016/j.cattod.2007.12.138 Abstract NOx uptake experiments were performed on a series of alkaline earth oxide (AEO) (MgO, CaO, SrO, BaO) on γ-alumina materials. Temperature Programmed Desorption (TPD) conducted on He flow revealed the presence of two kinds of nitrate species: i.e. bulk and surface nitrates. The ratio of these two types of nitrate species strongly depends on the nature of the alkaline earth oxide. The amount of bulk nitrate species increases with the basicity of the alkaline earth oxide. This conclusion was supported by the results of infrared and 15N solid state NMR studies of NO2 adsorption. Due to the low melting point of the precursor used for the preparation of MgO/Al2O3 material (Mg(NO3)2), a significant amount of Mg was lost during sample activation (high temperature annealing) resulting in a material with properties were very similar to that of the γ-Al2O3 support. The effect of water on the NOx species formed in the exposure of the AEO-s to NO2 was also investigated. In agreement with our previous findings for the BaO/γ-Al2O3 system, an increase of the bulk nitrate species and the simultaneous decrease of the surface nitrate phase were observed for all of these materials.
2008. "Adsorption and Formation of BaO Overlayers on Gamma-Al2O3 Surfaces ." Journal of Physical Chemistry C 112(46):18050–18060. doi:10.1021/jp806212z Abstract First-principles density functional theory slab calculations were used to investigate adsorption, clustering and overlayer formation of BaO on the gamma-Al2O3 surfaces. Multiple stable adsorption configurations were identified for the adsorbed BaO molecule and (BaO)2 on both (100) and (110) surfaces of gamma-Al2O3. Adsorption of BaO and (BaO)2 induces significant relaxation of the gamma-Al2O3 surfaces. At high BaO coverage, up to the ratio of BaO units to surface Al atoms being unity, the adsorbed BaO molecules were organized to form a buckled monolayer-like overlayer on the surface. Aggregation energy was used to characterize the organization of adsorbed BaO on the surface. Our results showed that the initial BaO adsorption configuration had a strong effect on clustering and overlayer formation. A weakly adsorbed BaO molecule will thermodynamically favor clustering over being isolated. On the fully dehydrated gamma-Al2O3(100) surface, the formation of BaO overlayer was thermodynamically unfavorable until 4.26 BaO/nm2 if the additional BaO was from the most stable site, corresponding to a low BaO loading, whereas aggregation became favorable if the additional BaO was from less stable sites, corresponding to a high BaO loading. On the fully dehydrated gamma-Al2O3(110) surface, the formation of a BaO dimer was found to have the highest energy cost. On the other hand, the presence of hydroxyls on the surface enhances the stability of the adsorbed BaO molecules. As such, isolated BaO islands, rather than a complete BaO overlayer, were expected on the hydroxylated gamma-Al2O3 surfaces, consistent with recent experimental observations. Pacific Northwest National Laboratory operated by Battelle for the U. S. Department of Energy.
2008. "Hydrogen Production from Ethanol Steam Reforming over Supported Cobalt Catalysts." Catalysis Letters 122(3-4):295-301. doi:10.1007/s10562-007-9375-3 Abstract Hydrogen production was carried out via ethanol steam reforming over supported cobalt catalysts. Wet incipient impregnation method was used to support cobalt on ZrO2, CeO2 and CeZrO4 followed by pre-reduction with H2 up to 677 °C to attain supported cobalt catalysts. It was found that the non-noble metal based 10 wt % Co/CeZrO4 is an efficient catalyst to achieve ethanol conversion of 100% and hydrogen yield of 82% (4.9 mol H2/ mol ethanol) at 450 oC , which is superior to 0.5 wt % Rh/Al2O3. The pre-reduction process is required to activate supported cobalt catalysts for high H2 yield of ethanol steam reforming. In addition, support effect is found significant for cobalt during ethanol steam reforming. 10% Co/CeO2 gave high H2 selectivity while suffered low conversion due to the poor thermal stability. In contrast to CeO2, 10 wt % Co/ZrO2 achieved high conversion while suffered lower H2 yield due to the production of methane. The synergistic effect of ZrO2 and CeO2 to promote high ethanol conversion while suppress methanation was observed when CeZrO4 was used as a support for cobalt. This synergistic effect of CeZrO4 support leads to a high hydrogen yield at low temperature for 10 wt % Co/CeZrO4 catalyst. Under the high weight hourly space velocity (WHSV) of ethanol (2.5 h-1), the hydrogen yield over 10 wt % Co/CeZrO4 was found to gradually decrease to 70% of its initial value in 6 hours possibly due to the coke formation on the catalyst.
2008. "The Role of PentaCoordinated Al3+ Ions in the High Temperature Phase Transformation of γ-Al2O3." Journal of Physical Chemistry C 112(25):9486–9492. doi:10.1021/jp802631u Abstract In this work, the structural stability of gamma-alumina (γ-Al2O3) was investigated by a combination of XRD and high resolution solid state 27Al MAS NMR at an ultra-high magnetic field of 21.1 tesla. XRD measurements show that γ-Al2O3 undergoes a phase transition to θ-Al2O3 during calcination at 1000oC for 10hr. The formation of the θ-Al2O3 phase is further confirmed by 27Al MAS NMR; additional 27Al peaks centered at 10.5 and ~78 ppm were observed in samples calcined at this high temperature. Both the XRD and NMR results indicate that, after calcination at 1000°C for 10 hrs, the ratio of the θ-Al2O3 phase to the total alumina in samples modified by either BaO or La2O3 is significantly reduced in comparison with γ-Al2O3. 27Al MAS NMR spectra revealed that the reduction in the extent of θ-Al2O3 formation was highly correlated with the reduction in the amount of penta-coordinated aluminum ions, measured after 500°C calcination, in both BaO- and La2O3-modified γ-Al2O3 samples. These results strongly suggest that the penta-coordinated aluminum ions, present exclusively on the surface of γ-Al2O3, play a critical role in the phase transformation of γ-Al2O3 to θ-Al2O3. The role of the modifiers, in our case BaO or La2O3, is to convert the penta-coordinated aluminum ions into octahedral ones, thereby improving the thermal stabilities of the samples. Oxide additives, on the other hand, had no beneficial effect on preventing the specific surface area reduction that occurred during high temperature (≤1000°C) calcination.
2008. "Excellent Sulfur Resistance of Pt/BaO/CeO2 Lean NOx Trap Catalysts." Applied Catalysis. B, Environmental 84(3-4):545-551. doi:10.1016/j.apcatb.2008.05.009 Abstract In this work, we investigated the NOx storage behavior of Pt-BaO/CeO2 catalysts, especially in the presence of SO2. High surface area CeO2 (~ 110 m2/g) with a rod like morphology was synthesized and used as a support. The Pt-BaO/CeO2 sample demonstrated slightly higher NOx conversion in the entire temperature range studied compared with Pt-BaO/γ-Al2O3. More importantly, this ceria-based catalyst showed higher sulfur tolerance than the alumina-based one. The time of complete NOx uptake was maintained even after exposing the sample to ~3 g/L of SO2. The same sulfur exposure, on the other hand, eliminated the complete NOx uptake time on the alumina-based NOx storage catalysts. TEM images show no evidence of either Pt sintering or BaS phase formation during reductive de-sulfation up to 600°C on the ceria based catalyst, while the same process over the alumina-based catalyst resulted in both a significant increase in the average Pt cluster size and the agglomeration of a newly-formed BaS phase into large crystallites. XPS results revealed the presence of about 5 times more residual sulfur after reductive de-sulfation at 600°C on the alumina based catalysts in comparison with the ceria-based ones. All of these results strongly support that, besides their superior intrinsic NOx uptake properties, ceria based catalysts have a) much higher sulfur tolerance and b) excellent resistance against Pt sintering when they are compared to the widely used alumina based catalysts.
2008. "Sequential high temperature reduction, low temperature hydrolysis for the regeneration of sulfated NOx trap catalysts." Catalysis Today 136(1-2):183-187. doi:doi:10.1016/j.cattod.2007.12.134 Abstract We describe a new method that minimizes irreversible Pt sintering during the desulfation of sulfated Pt/BaO/Al2O3 lean NOx trap (LNT) catalysts. While it is known that the addition of H2O to H2 promotes desulfation, we find that the significant and irreversible Pt sintering arising from the presence of water is unavoidable. Control of precious metal sintering is considered to be one of the critical issues in the development of durable LNT catalysts. The new method described here is a sequential desulfation process: the first step is to reduce the sulfates with hydrogen only at higher temperatures to form BaS, followed by a treatment of the thus reduced sample with water at low to moderate temperatures to convert BaS to BaO and H2S. The data showed that Pt sintering was significantly inhibited due to the absence of H2O during the desulfation at high temperatures, and also demonstrates the similar NOx uptake with the desulfated sample cooperatively with H2 and H2O. Therefore, the sequential desulfation process may find applications in realistic systems to inhibit the irreversible sintering of the Pt in the lean NOx trap catalyst, leading to a longer catalyst life.
2008. "Roles of Pt and BaO in the Sulfation of Pt/BaO/Al2O3 Lean NOx Trap Materials: Sulfur K-edge XANES and Pt LIII XAFS Studies." Journal of Physical Chemistry C 112(8):2981-2987. doi:10.1021/jp077563i Abstract The roles of barium oxide and platinum during the sulfation of Pt-BaO/Al2O3 lean NOx trap catalysts were investigated by S K edge XANES (X-ray absorption near-edge spectroscopy) and Pt LIII XAFS (X-ray absorption fine structure). All of the samples studied (Al2O3, BaO/Al2O3, Pt/Al2O3 and Pt-BaO/Al2O3) were pre-sulfated prior to the X-ray absorption measurements. It was found that barium oxide itself has the ability to directly form barium sulfate even in the absence of Pt and gas phase oxygen. In the platinum-containing samples, the presence of Pt-O species plays an important role in the formation of sulfate species. Even if barium and aluminum sites are available for SO2 to form sulfate, for the case of the BaO(8)/Al2O3 sample, where the barium coverage is about 0.26 ML, S XANES spectroscopy results show that barium sulfates are preferentially produced over aluminum sulfates . When oxygen is absent from the gas phase, the sulfation route that involves Pt-O is eliminated after the initially present Pt-O species are completely consumed. In this case, formation of sulfates is suppressed unless barium oxide is also present. Pt LIII XAFS results show that the first coordination sphere around the Pt atoms in the Pt particles is dependent upon the redox nature of the gas mixture used during the sulfation process. Sulfation under reducing environments (e.g. SO2+H2) leads to formation of Pt-S bonds, while oxidizing conditions (e.g. SO2+O2) continue to show the presence of Pt-O bonds. In addition, the former condition was found to give rise to a higher degree of Pt sintering than the latter one. This result explains why samples sulfated under reducing conditions had lower NOx uptakes than those sulfated under oxidizing conditions. Therefore, our results provide needed information for the development of optimum practical operation conditions (e.g. sulfation or desulfation) for lean NOx trap catalysts that minimize deactivation by sulfur.
2008. "Promotional Effects of H2O Treatment on NOx Storage over Fresh and Thermally Aged Pt-BaO/Al2O3 Lean NOx Trap Catalysts ." Catalysis Letters 124(1-2):39-45. doi:10.1007/s10562-008-9505-6 Abstract A simple liquid water treatment applied to fresh and thermally aged Pt(2wt%)-BaO(20wt%)/Al2O3 lean NOx trap catalysts at room temperature induces morphological and structural changes in the barium species as followed by XRD and TEM analysis. During the water treatment, liquid water sufficient to fill the catalyst pore volume is brought into contact with the samples. It was found that irrespective of the original barium chemical state (highly dispersed BaO or crystalline BaAl2O4), exposing the sample to this liquid water treatment promotes the formation of BaCO3 crystallites (about 15 – 25 nm of its size) without changing the Pt particle size. Such transformations of the barium species are found to significantly promote NOx uptake from 250 °C to 450 °C. The increase in the NOx uptake for the water-treated samples can be attributed to an enhanced Pt-Ba interaction through the redistribution of barium species. These results provide useful information for the regeneration of aged lean NOx trap catalysts since water is plentiful in the exhaust of diesel or lean-burn engines.
2007. "HRTEM Study of Diesel Soot Collected from Diesel Particulate Filters ." Carbon 45(1):70-77. doi:10.1016/j.carbon.2006.08.005 Abstract HRTEM study of several soot samples collected on Diesel Particulate Filters (DPF) under conditions relevant to practical applications of DPF technology, revealed nano-structure, to our knowledge, not reported previously for diesel soot. In particular, some of the primary particles were found to have hollow interior, and the outer shell exhibiting evidence of graphitization, with a higher crystallinity compared to the non-hollowed particles. The percentage of such particles varied between different soot samples and tentatively appeared to be related to the oxidation history of the sample. Remarkably, similar effect was not reproduced for a carbon black sample, Printex-U, suggesting that propensity to such oxidation-induced graphitization is related to the original nano-structure of the particle. These initial observations were independently confirmed for the same set of soot samples by two different HRTEM facilities, at NASA-Glenn and PNNL.
2007. "Synthesis of nanoporous zirconium oxophosphate and application for removal of U(VI)." Water Research 41(15):3217-3226. Abstract Uniformly arrayed zirconium-phosphate nanoporous material was synthesized, characterized, and used as an adsorbent for removal of U(VI) in a NaNO3 solution with varying background conditions including pH, ionic strength, U(VI) concentrations, and carbonate concentrations. Batch U(VI) adsorption results showed that U(VI) adsorption reached steady state condition within 48 hours and all the dissolved U(VI) (10-6 M) was removed by this material at neutral pH and closed conditions to atmospheric CO2(g). The U(VI) adsorption followed a traditional Langmuir adsorption isotherm, and the distribution coefficient (Kd) calculated from the linear region of the Langmuir isotherm was 105,000 mL/g. Because this phosphate bearing nanoporous material exhibits high stability at temperature and has a very high Kd value, it can be applied as an efficient adsorbent for removing U(VI) from various contaminated waste streams, such as those present at U.S. Department of Energy defense sites and the proposed geologic radioactive waste disposal facility at Yucca Mountain in Nevada.
2007. "Water-induced morphology changes in BaO/γ-Al2O3 NOx storage materials: an FTIR, TPD, and time-resolved synchrotron XRD study." Journal of Physical Chemistry C 111(12):4678-4687. doi:10.1021/jp067932v Abstract The effect of water on the morphology of BaO/Al2O3-based NOx storage materials was investigated using Fourier transform infrared spectroscopy, temperature programmed desorption, and time-resolved synchrotron X-ray diffraction techniques. The results of this multi-spectroscopy study reveal that, in the presence of water, surface Ba-nitrates convert to bulk nitrates, and water facilitates the formation of large Ba(NO3)2 particles. This process is completely reversible, i.e. after the removal of water from the storage material a significant fraction of the bulk nitrates re-convert to surface nitrates. NO2 exposure of a H2O-containing (wet) BaO/Al2O3 sample results in the formation of nitrites and bulk nitrates exclusively, i.e. no surface nitrates form. After further exposure to NO2, the nitrites completely convert to bulk nitrates. The amount of NOx taken up by the storage material is, however, essentially unaffected by the presence of water, regardless of whether the water was dosed prior to or after NO2 exposure. Based on the results of this study we are now able to explain most of the observations reported in the literature on the effect of water on NOx uptake on similar storage materials.
2007. "Water-induced morphology changes in BaO/γ-Al2O3 NOx storage materials." Chemical Communications 2007(9):984-986. doi:10.1039/b613674e Abstract Exposure of NO2-saturated BaO/γ-Al2O3 NOx storage materials to H2O vapour results in the conversion of surface nitrates to Ba(NO3)2 crystallites, causing dramatic morphological changes in the Ba-containing phase, demonstrating a role for water in affecting the NOx storage/reduction properties of these materials.
2007. "Penta-coordinated Al3+ ions as preferential nucleation sites for BaO on γ-Al2O3: an ultra-high magnetic field 27Al MAS NMR study." Journal of Catalysis 251(2):189-194. doi:10.1016/j.jcat.2007.06.029 Abstract In this paper, we report the first observation of preferential anchoring of an impregnated catalytic phase onto penta-coordinated Al3+ sites on the surface of γ Al2O3. The interaction of barium oxide with a γ alumina support was investigated by high resolution solid state 27Al magic angle spinning NMR at an ultra-high magnetic field of 21.1T and at sample spinning rates of up to 23 kHz. Under these experimental conditions, a peak in the NMR spectrum at ~ 23 ppm with relatively low intensity, assigned to 5-coordinated Al3+ ions, is clearly distinguished from the two other peaks representing Al3+ ions in tetra-, and octahedral coordination sites. Spin-lattice 27Al relaxation time measurements clearly show that these penta-coordinated Al3+ sites are located on the surface of the γ alumina support. BaO deposition onto this γ alumina sample resulted in the loss of intensity of the 23 ppm peak. The intensity loss observed was linearly proportional to the amount of BaO deposited. The results of this study strongly suggest that, at least for BaO, these penta-coordinated Al3+ ions are the nucleation sites.
2007. "Water-induced Bulk Ba(NO3)2 Formation From NO2 Exposed Thermally Aged BaO/Al2O3." Applied Catalysis. B, Environmental 72(3-4):233-239. Abstract Phase changes in high temperature treated (> 900 °C) 8 or 20 wt% BaO supported on Al2O3 model lean NOx trap (LNT) catalysts, induced by NO2 and/or H2O adsorption, were investigated with powder X-ray Diffraction (XRD), solid state 27Al Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR) spectroscopy, and NO2 Temperature Programmed Desorption (TPD) experiments. After calcination in dry air at 1000 °C, the XRD and solid state 27Al MAS NMR results confirm that stable surface BaO and bulk BaAl2O4 phases are formed for 8 and 20 wt% BaO/Al2O3, respectively. Following NO2 adsorption over these thermally treated samples, no additional phase changes are observed based on XRD results. However, when water was added to the thermally aged samples after NO2 exposure, the formation of crystalline Ba(NO3)2 particles was observed in both samples. Solid state 27Al MAS NMR is shown to be a good technique for identifying the various Al species present in the materials during the processes studied here. NO2 TPD results demonstrate a significant loss of uptake for the 20 wt% model catalysts upon thermal treatment. However, the described phase transformations upon subsequent water treatment gave rise to the partial recovery of NOx uptake, demonstrating that such a water treatment of thermally aged catalysts can provide a potential method to regenerate LNT materials.
2007. "Design of a reaction protocol for decoupling sulfur removal and thermal aging effects during desulfation of Pt-BaO/Al2O3 lean NOx trap catalysts." Industrial and Engineering Chemistry Research 46(9):2735-2740. doi:10.1021/ie061542d Abstract A novel reaction protocol was designed to decouple the effects of thermal deactivation from those due to, for example, incomplete de-sulfation during regeneration steps of Ba-based lean NOx trap catalysts. The protocol was applied to two samples: a Pt-BaO/Al2O3 model catalyst, and an enhanced model sample doped with promoter species. The results obtained from the reaction protocol demonstrate that regeneration (desulfation) temperatures need to be maintained below those that lead to significant Pt sintering in order to prevent permanent deactivation. In addition, the modified reaction protocol allows us to compare the regeneration behavior of samples with varying degrees of sulfation, while other approaches have difficulty differentiating the effects of thermal aging from those of sulfation. We believe that this approach provides a convenient way both to assess the relative sensitivities of various catalysts to regeneration conditions, and to develop regeneration strategies that minimize the separate but often linked deactivation effects of sulfation and high temperatures.
2006. "Morphological Evolution of Ba(NO3)2 Supported on -Al2O3(0001): An In-Situ TEM Study." Journal of Physical Chemistry B 110(24):11878-11883. doi:10.1021/jp060235i Abstract One of the key questions for the BaO-based NOx catalyst system is the morphological evolution of Ba(NO3)2 to BaO upon heating for releasing of NOx or vice versa from BaO to Ba(NO3)2 upon uptaking of NOx. However, associated with the small crystallite size of high-surface area Al2O3, it can be difficult to extract structural and morphological features of Ba(NO3)2 supported on -Al2O3 by any direct imaging method including transmission electron microscopy. In this work, by choosing a model system of Ba(NO3)2 particles supported on single crystal -Al2O3, we have investigated the structural and morphological features of Ba(NO3)2 as well as the formation of BaO from Ba(NO3)2 during the release of NOx using ex-situ and in-situ TEM imaging, electron diffraction, energy dispersive spectroscopy (EDS), and Wulff shape construction. We find that Ba(NO3)2 supported on -Al2O3 possesses a platelet morphology, with the interface and facets being invariably the 8 {111} planes. Formation of the platelet structure leads to an enlarged interface area between Ba(NO3)2 and -Al2O3, indicating that the interfacial energy is lower than the Ba(NO3)2 surface free energy. In fact, Wulff shape constructions indicate that the interfacial energy is ~1/4 of the {111} surface free energy of Ba(NO3)2. The orientation relationship between Ba(NO3)2 and the -Al2O3 is: -Al2O3[0001]//Ba(NO3)2[111] and -Al2O3(1-2 10)//Ba(NO3)2(110).
2006. "Reduction of Stored NOx on Pt/Al₂O₃ and Pt/BaO/Al₂O₃ Catalysts with H₂ and CO." Journal of Catalysis 239(1):51-64. doi:10.1016/j.jcat.2006.01.014 Abstract In situ FTIR spectroscopy coupled with mass spectrometry, and time resolved X-ray diffraction were used to study the efficiency of nitrate reduction with CO and H₂ on Pt/Al₂O₃ and Pt/BaO/Al₂O₃ NOx storage-reduction (NSR) catalysts. Surface nitrates were generated by NO₂ adsorption and their reduction efficiencies were examined on the catalysts together with the analysis of the gas phase composition in the presence of the two different reductants. H₂ was found to be a more effective reducing agent than CO. In particular, the reduction of surface nitrates proceeds very efficiently with H₂ even at low temperatures (~420 K). During reduction with CO, isocyanates were observed to form on every catalyst component. These surface isocyanates, however, readily react with water to form CO₂ and ammonia. The thus formed NH₃, in turn, reacts with stored NOx at higher temperatures (>473K) to produce N₂. In the absence of H₂O, the NCO species are stable to high temperatures, and removed only from the catalyst when they react with NOx thermal decomposition products to form N₂ and CO₂. The results of this study point to a complex reaction mechanism that involves the removal of surface oxygen atoms from the Pt particles by either H₂ or CO, the direct reduction of stored NOx with H₂ (low temperature NOx reduction), the formation and the subsequent hydrolysis of NCO species, as well as the direct reaction of NCO with decomposing NOx (high temperature NOx reduction).
2006. "Effects of Ba loading and calcination temperature on BaAl2O4 formation for BaO/Al2O3 NOx Storage and Reduction Catalysts." Catalysis Today 114(1):86-93. doi:10.1016/j.cattod.2006.02.016 Abstract The effect of thermal treatment on the structure and chemical properties of Ba-oxide-based NOx storage/reduction catalysts with different Ba loadings was investigated using BET, TEM, EDS, TPD and FTIR techniques. On the basis of the present and previously reported results, we propose that moderate (< ~873 K) temperature calcinations result in a single monolayer (ML) ‘coating’ of BaO on the alumina surface. At high Ba loading in excess of that required for a full monolayer ‘coating’ (> 8 wt.% BaO), small (~5 nm) particles of ‘bulk’ BaO are present on top of the 1 ML BaO/Al2O3 surface. We did not observe any detectable morphological changes upon higher temperature thermal treatment of 2 and 8 wt% BaO/Al2O3 samples, while dramatic changes occurred for the 20 wt% sample. In this latter case, the transformations included BaAl2O4 formation at the expense of the bulk BaO phase. In particular, we conclude that the surface (ML) BaO phase is quite stable against thermal treatment, while the bulk phase provides the source of Ba for BaAl2O4 formation.
2006. "NOx Uptake Mechanism on Pt/BaO/Al2O3 Catalysts." Catalysis Letters 111(3-4):119-126. Abstract The NOx adsorption mechanism on Pt/BaO/Al2O3 catalysts was investigated by performing NOx storage/reduction cycles, NO2 adsorption and NO + O2 adsorption on 2%Pt/(x)BaO/Al2O3 (x = 2, 8 and 20 wt%) catalysts. NOx uptake profiles on 2%Pt/20%BaO/Al2O3 at 523 K show complete uptake behavior for almost 5 min, and then the NOx level starts gradually increasing with time and it reaches 75% of the inlet NOx concentration after 30 min time-on-stream. Although this catalyst shows fairly high NOx conversion at 523 K, only ~ 2.4 wt% out of 20 wt% BaO is converted to Ba(NO3)2. Adsorption studies by using NO2 and NO + O2 suggest two different NOx adsorption mechanisms. The NO2 uptake profile on 2%Pt/20%BaO/Al2O3 shows the absence of a complete NOx uptake period at the beginning of adsorption and the overall NOx uptake is controlled by the gas-solid equilibrium between NO2 and BaO/Ba(NO3)2 phase. When we use NO + O2, complete initial NOx uptake occurs and the time it takes to convert ~ 4 % of BaO to Ba(NO3)2 is independent of the NO concentration. These NOx uptake characteristics suggest that the NO + O2 reaction on the surface of Pt particles produces NO2 that is subsequently transferred to the neighboring BaO phase by spill over. At the beginning of the NOx uptake, this spill-over process is very fast and so it is able to provide complete NOx storage. However, the NOx uptake by this mechanism slows down as BaO in the vicinity of Pt particles are converted to Ba(NO3)2. The formation of Ba(NO3)2 around the Pt particles results in the development of a diffusion barrier for NO2, and increases the probability of NO2 desorption and consequently, the beginning of NOx slip. As NOx uptake by NO2 spill-over mechanism slows down due to the diffusion barrier formation, the rate and extent of NO2 uptake are determined by the diffusion rate of nitrate ions into the BaO bulk, which, in turn, is determined by the gas phase NO2 concentration.
2006. "Relationship of Pt Particle Size with the NOx Storage Performance of Thermally Aged Pt/BaO/Al2O3 Lean NOx Trap Catalysts." Industrial and Engineering Chemistry Research 45(26):8815-8821. doi:10.1021/ie060736q Abstract Relationship between Pt particle size and NOx storage performance was investigated over a model Pt/BaO/Al2O3 and an enhanced lean NOx trap catalyst (LNT). These catalysts were treated at elevated temperature to mimic the effect of thermal aging encountered during the desulfation step in NOx trap catalyst regeneration. Combination of in situ time-resolved X-ray Diffraction (TR-XRD), DRIFT measurement after CO adsorption and TEM observation over the thermally aged samples clearly shows the sintering behavior of Pt crystalline as a function of time and temperature. Under elevated temperatures, the crystalline growth of Pt occurs within a short time (e.g. 1.5 hr) followed by the gradual increase with time. NOx storage reaction performed after successive thermal treatments of catalyst under oxygen and in situ XRD experiment have allowed us to correlate the NOx storage performance with phase change. Comparing the simple Pt-BaO/Al2O3 sample with the enhanced one which shows much less Pt sintering, it was confirmed that the Pt crystalline size plays a critical role in determining the NOx storage activity, in other words, the retention of the small Pt particles after thermal aging is crucial to maintain a higher activity. In conclusion, the prevention of Pt sintering when operated at elevated temperature must be a key factor to design the more durable LNT catalyst, thus potentially implying the practical importance for the improvement of the LNT technology.
2006. "Effect of Barium Loading on the Desulfation of Pt-BaO/Al2O3 Studied by H2 TPRX, TEM, Sulfur K-edge XANES, and in Situ TR-XRD." Journal of Physical Chemistry B 110(21):10441-10448. doi:10.1021/jp060119f Abstract Desulfation processes were investigated over sulfated Pt BaO/Al2O3 with different barium loading (8 wt% and 20 wt%) by using H2 temperature programmed reaction (TPRX), transmission electron microscope (TEM) with energy dispersive spectroscopy (EDS), sulfur K-edge X-ray absorption near-edge spectroscopy (XANES), and in situ time-resolved X-ray diffraction (TR-XRD) techniques. Both sulfated samples (8 wt% and 20 wt%) form sulfate species (primarily BaSO4) as evidenced by S K-edge XANES and in situ TR-XRD. However, the desulfation behavior is strongly dependant on the barium loading. Sulfated Pt BaO(8)/Al2O3, consisting predominantly of surface BaO/BaCO3 species, displays more facile desulfation by H2 at lower temperatures than sulfated Pt BaO(20)/Al2O3, a material containing primarily bulk BaO/BaCO3 species. Therefore, after desulfation with H2 up to 1073 K, the amount of the remaining sulfur species on the former, mostly as BaS, is much less than on the latter. This suggests that the initial morphology differences between the two samples play a crucial role in determining the extent of desulfation and the temperature at which it occurs. It is concluded that the removal of sulfur is significantly easier at lower barium loading. This finding can potentially be important in developing more sulfur resistant LNT catalyst systems.
2005. "Differential Kinetic Analysis of Diesel Particulate Matter (Soot) Oxidation by Oxygen Using a Step-Response Technique." Applied Catalysis. B, Environmental 61(1-2):120-129. Abstract A novel step-response technique was developed for the kinetic study of diesel soot oxidation. Using this technique, various aspects of the oxidation process can be probed while consuming only differential amounts of carbon, and the impact of the reaction heat on the measured rates can be minimized. Due to its high throughput, the technique allows broad parametric studies to be performed rapidly and in a kinetically rigorous manner. The technique was applied to soot oxidation by O2, one of the major regeneration mechanisms for the catalytic soot filter systems. It was found that, after decoupling effects due to the sample history, carbon oxidation by O2 in the absence of H2O can be well described by an unmodified Arhenius equation, with similar activation energy values for diesel and model soot samples (137±8.7 and 132±5.1 kJ/mol, respectively). The reaction order in O2 for these samples was found to be 0.61±0.03 and 0.71±0.03, respectively, and was remarkably independent of the temperature, suggesting that the fractional order is not due to mixed kinetic control. The reaction mechanism was also found to be independent of carbon conversion. The density of the reaction sites, however, appeared to increase with oxidation. This increase could not be accounted for by the changes in the specific surface area, either directly measured, or derived from such simplified models as the shrinking core formalism. The entire set of obtained experimental results can be described using a kinetically uncomplicated model in a broad range of temperatures, partial pressures of oxygen and degrees of soot oxidation.
2005. "Differential kinetic analysis of diesel particulate matter (soot) oxidation by oxygen using a step–response technique." Applied Catalysis. B, Environmental 61(1-2):120-129. Abstract The effects of a catalytic coating on the oxidation of captured soot over diesel particulate filters (DPF) is debated in the literature, since a catalyzed filter wall appears to lack sufficiently tight contact with soot deposits to exercise direct catalytic action. The topology of soot– catalyst contact may change with progressive oxidation of the soot layer; hence, a technique capable of probing catalytic action via detailed kinetic analysis at different stages of oxidation is required to conclusively resolve this problem. A novel step–response technique was developed in this work as a methodological foundation for such study. Using this technique, various aspects of the oxidation process can be probed while consuming only differential amounts of carbon, and the impact of the reaction heat on the measured rates can be minimized. This technique was applied to soot oxidation by O2 and showed that, after decoupling effects due to the sample history, carbon oxidation by O2 in the absence of H2O can be well-described by an unmodified Arrhenius equation, with similar activation energy values for diesel and model soot samples (137 _ 8.7 and 132 _ 5.1 kJ/mol, respectively). The reaction order in O2 for these samples was found to be 0.61 _ 0.03 and 0.71 _ 0.03, respectively, and was remarkably independent of the temperature, suggesting that the fractional order is not due to mixed kinetic control. The reaction mechanism was also found to be independent of carbon conversion. The density of the reaction sites, however, appeared to increase with oxidation. This increase could not be accounted for by the changes in the specific surface area, either directly measured orderived from such simplified models as the shrinking-core formalism. The entire set of obtained experimental results can be described using a kinetically uncomplicated model in a broad range of temperatures, partial pressures of oxygen and degrees of soot oxidation.
2005. "NO2 Adsorption on BaO/Al2O3: The Nature of Nitrate Species." Journal of Physical Chemistry B 109(1):27-29. doi:10.1021/jp045082i Abstract The nature of nitrate species formed in the Al₂O₃, 8wt%, and 20wt% BaO/Al₂O₃ catalysts was investigated in a combined TPD, FTIR and 15N solid state NMR study. The results strongly suggest the formation of a monolayer bidentate nitrate on the alumina support that forms upon NO₂ exposure. This monolayer nitrate decomposes at lower temperature than bulk Ba(NO₃)₂ and its only decomposition product is NO₂. A bulk-like Ba(NO₃)₂ phase also forms with its characteristic set of TPD, IR and NMR features. The amount of NOx stored in the monolayer nitrate is proportional to the surface area of the catalyst, while that in the bulk nitrate increases with BaO coverage.
2005. "Changes in Ba phases in BaO/Al₂O₃ upon thermal aging and H₂O treatment." Catalysis Letters 105(3-4):259-268. doi:10.1007/s10562-005-8700-y Abstract The effects of thermal aging and H₂O treatment on the physicochemical properties of a BaO/Al₂O₃ model catalyst were investigated by means of XRD, BET, TEM/EDX and NO₂ TPD. Thermal aging at 1000 °C for 10 hrs resulted in conversion of dispersed BaCO₃ into low surface area crystalline BaAl₂O₄. It was found that H₂O treatment on a BaO/Al₂O₃ sample at room temperature transformed not only the BaAl₂O₄, but also the dispersed BaCO₃ into highly crystalline BaCO₃ segregated from the Al₂O₃ support, as evidenced in TEM/EDX and XRD analysis. The sample containing dispersed BaCO3 in the initial phase segregated more severely than the BaAl₂O₄ containing one, with the Ba in the BaAl₂O₄ matrix exhibiting higher resistance towards segregation. Contacting the BaO/Al₂O₃ sample with liquid water over a prolong period of time leads to an increase in crystallinity of the segregated BaCO₃. These phenomena imply that special care must be taken during catalyst synthesis and during realistic operation of Pt/BaO/Al₂O₃ NOx trap catalysts since both processes involve potential exposure of the material with liquid H₂O. Based on the results, a model to explain the behavior of Ba containing species upon thermal aging and H₂O treatment is proposed.
2004. "Mechanisms of Sulfur Poisoning of NOx Adsorber Materials." Chapter III.I in Advanced Combustion Engine R&D: 2003 Annual Progress Report, ed. G Singh, pp. 141-145. US Department of Energy, Washington, DC. Abstract This annual report will review progress of the initial 4 months of a three-year effort between Cummins Engine Company and Pacific Northwest National Laboratory to understand and improve the performance and sulfur tolerance of the materials used in the NOx adsorber after-treatment technology in order to meet both performance and reliability standards required for diesel engines. The goal of this project is to enable NOx after-treatment technologies that will meet both EPA 2007 emission standards and customer cost, reliability and durability requirements. The project will consist of three phases. First, the efforts will focus on understanding the current limitation of capture, regeneration and durability of existing NOx adsorber materials, especially with respect to their sulfur tolerance. With this developing understanding, efforts will also be focused on the optimization of the NOx absorber chemical and material properties to increase performance and durability over many regeneration cycles. We anticipate that improved materials will be tested and evaluated, in partnership with Cummins, on diesel vehicle engines over expected operating conditions.
2004. "Synergism Between Pt/Al₂O₃ and Au/TiO₂ in the Low Temperature Oxidation of Propene." Catalysis Letters 98(1):11-15. Abstract The low temperature (<170°C) oxidation activity of supported Pt catalysts is impeded in the presence of CO. Supported Au catalysts are very effective in the removal of CO, but not propene (C₃H₆) at low temperatures (<200°C). Addition of Au/TiO₂ to Pt /Al₂O₃ either in the form of a physical mixture or as a pre-catalyst reduced the light-off temperature (T₅₀) for C₃H₆ oxidation over supported a Pt catalyst by ~54 °C in a feed of 1% CO, 400 ppm C₃H₆, 14% O₂, 2% H₂O.
2004. "Comparison of Two Preparation Methods in the Redox Properties of Pd/CeO₂/Ta/Si Model Catalysts: Spin Coating versus Sputter Deposition ." Catalysis Letters 98(1):23-28. Abstract Pd/CeO2/Ta/Si model catalysts were prepared by spin coating and sputter deposition method, and characterized by means of AFM, SEM and in situ XPS, especially focusing on the redox properties of Ce and Pd elements. Compared with thin CeO₂ films (about 2.2 nm), the thicker ones (about 22 nm) maintained Ce⁴⁺ oxidation state even after treatment with H₂ up to 500 °C while the presence of Pd facilitated the reduction of ceria. The reduction of ceria brought about following that of PdO, which was explained by the spillover of hydride in Pd to CeO₂ originating from hydrogen adsorption on the Pd surface. Compared with the sputter deposition method, spin coating produced the smaller size of Pd particles, thus leading to formation of the stable PdO species against hydrogen. Based on these results, a schematic model of Pd/CeO₂/Ta/Si was suggested and it might be assumed that spin coating method provided with an environment similar to the conventional impregnation.
2003. "Effect of V2O5 on the catalytic activity of Pt-based diesel oxidation catalyst." Applied Catalysis. B, Environmental 45(4):269-279. Abstract We investigated the suppression of SO₂ oxidation activity by vanadium oxide in Pt-based diesel oxidation catalyst using reaction experiments, temperature programmed desorption (TPD), infrared (IR) and X-ray photoelectron spectroscopy (XPS). There was no interaction between Pt and S indicated by the XPS results. SO₂ was not adsorbed on Pt at room temperature indicated by the absence of peak arising from SO₂ in SO2 TPD spectra. SO₂ molecules were adsorbed on the hydroxyl groups of TiO₂ and migrated to Pt particles to react with oxygen adsorbed on it. V₂O₅ decreased the adsorption of SO₂ on TiO₂ by the blockage of V₂O₅ on TiO₂.