Improvement of NOx uptake/release over Pd/Beta by propylene: shielding effect of intermediates on adsorbed NOx species.

Passive NOx adsorbers (PNAs) are capable of trapping NOx at low temperature and releasing the trapped NOx into the gas circuit at higher temperatures, where downstream NOx reduction catalysts are activated. Hydrocarbons have a significant effect on the performance of PNAs, nonetheless research in this area has been overlooked. Here the chemistry of NOx adsorption and desorption in the presence of C3H6 was studied. For different pore-size zeolites (BEA, MFI and CHA), the addition of C3H6 always increased the NOx adsorption capacity at a low temperature and raised the NOx desorption temperature. Spectroscopic and computational investigations were performed using the model Pd/Beta to unravel the relevant mechanism. Fourier transform infrared (FTIR) spectra indicated that more Pd+ was formed in the presence of C3H6, which contributed to higher NOx storage capacity. An intermediate Pd-NC3H6O was probed and its evolution procedure was modeled by density functional theory (DFT) calculations. The results showed that a shielding effect of Pd-NC3H6O on Pd+-NO improved the NOx desorption temperature. This investigation has important implications for how short-chain olefins and even more complex gas mixtures affect the NOx adsorption and desorption performance of Pd/zeolite.

The influence of adjacent Al atoms on the hydrothermal stability of H-SSZ-13: a first-principles study.

The Al concentration and distribution have a great influence on the hydrothermal stability of the H-SSZ-13 zeolites in experiments. In this work, first-principles calculations are performed to clarify the decomposition mechanism of an H-SSZ-13 framework with adjacent Al atom pair distribution under hydrothermal conditions. It is found that the adjacent Al atoms have a tendency to occupy the para-sites of the 4-membered rings (4MRs) in the framework. Water molecules are chemisorbed onto the Al atom one by one, and the hydroxylation of the neighboring O atoms induces the breaking of the Al-O bonds, which causes the first dealumination in 4MRs. The other Al atom in the para-site can be easily removed from the framework once the first one is lost. The feasible subsequent dealumination of adjacent Al atoms would break the linker of 6MRs in the framework, which is responsible for the degraded hydrothermal stability. Moreover, the partial substitution of metal ions (such as Na+ and Cu+) for the protons in the framework will greatly stabilize the Al-O bonds and enlarge the energy barrier of para-site Al dealumination, which leads to the improved hydrothermal stability of H-SSZ-13.

A sinter-resistant catalyst using an alumina support recycled from AlP fumigation residue: trash to treasure.

Sintering is a long-standing issue especially in high temperature catalytic applications. In this paper, we report an effective method to slow down metal particle migration and coalescence (PMC) by using a thermally stable alumina support. Noteworthily, the alumina sample was developed from AlP fumigation residue, which is a very dangerous substance for living creatures and environment protection. By optimizing the heated hydrolysis and ball-milling conditions, we recycled a phosphate-stabilized alumina material that retained a 117 m2 g-1 surface area after 1050 °C hydrothermal aging. The catalyst using this newly developed alumina support had Pd dispersion 1.7 times higher than that using a commercial alumina support after aging. The kinetics and XPS experiments showed that phosphate neither participated in the catalytic reaction process nor changed the active sites. This catalyst also exhibited extraordinary water tolerance and durability, making it a promising material in automotive exhaust purification and other catalytic applications.

Effects of Na+ on Cu/SAPO-34 for ammonia selective catalytic reduction.

Copper-exchanged chabazite (Cu/CHA) catalysts have been found to be affected by alkali metal and alkaline earth ions. However, the effects of Na+ ions on Cu/SAPO-34 for ammonia selective catalytic reduction (NH3-SCR) are still unclear. In order to investigate the mechanism, five samples with various Na contents were synthesized and characterized. It was observed that the introduced Na+ ion-exchanges with H+ and Cu2+ of Cu/SAPO-34. The exchange of H+ is easier than that of isolated Cu2+. The exchanged Cu2+ ions aggregate and form "CuAl2O4-like" species. The NH3-SCR activity of Cu/SAPO-34 decreases with increasing Na content, and the loss of isolated Cu2+ and acid sites is responsible for the activity loss.

Controlling N2O formation during regeneration of NOx storage and reduction catalysts: from impact of platinum-group metal type to rational utilization.

Herein, we report an effective strategy for minimization of N2O emissions based on elucidating the impact of the type of platinum-group metals (PGMs = Pt, Pd, or Rh) on by-product formation during regeneration of PGM-BaO/Al2O3 catalysts. The significant differences in N2O or NH3 formation were thoroughly investigated from the perspective of an in situ reaction. Kinetic analysis of NO reduction by CO shows different turnover frequency and apparent activation energy values over these catalysts. The results reveal that the apparent kinetics is dependent on the type of platinum-group metal chosen. In situ DRIFTS data indicate that the unique adsorption behaviors of reactants via which they access each PGM essentially determine their individual reaction kinetics. The preferential adsorption of NO or CO molecules on the PGM surface controls the dominant intermediate (NOad/Nad, COad, or NCOad) species, which is a major factor responsible for various yields of N2O and NH3 during the rich period. Finally, a feasible strategy has been proposed via optimizing catalyst formulation to effectively control the N2O emissions.

Hydrogenous spinel γ-alumina structure.

The structure of γ-Al2O3 is still under debate. Here we report a H spinel structure evolved from pseudo-boehmite. A unit cell with two octahedral cationic vacancies and one bulk H was preferential in terms of calculated Gibbs energy, which was well consistent with experimental data. Bulk H was found to migrate out with elevated temperatures. Through calculating the migration barriers of every step, we observed that the "hopping" step was rate-determining. The hopping rates were further estimated by assuming a Boltzmann distribution of energies, and as a result they increased by 2 to 3 orders of magnitude from 500 °C to 800 °C. This investigation will encourage us to study more uncertainties in material structures.

The mechanism of ammonium bisulfate formation and decomposition over V/WTi catalysts for NH3-selective catalytic reduction at various temperatures.

In this study, the mechanism of ammonium bisulfate (ABS) formation and decomposition over V/WTi for the NH3-selective catalytic reduction (SCR) at various temperatures was deeply investigated. Bridged bidentate, chelating bidentate, and tridentate sulfates bound to TiO2 were formed as dominant intermediates at 200, 250, and 300 °C, respectively. These sulfates reacted with affinitive ammonium species to form ammonium (bi)sulfate species and also covered the active sites and embedded the VOSO4 intermediates, which resulted in an inferior intrinsic NH3-SCR conversion rate at 200 °C and 250 °C. At 300 °C, trace amounts of ABS on TiO2 presented no influence on the NH3-SCR performance. The electrons deviating towards sulfates through the bond between ABS and metal oxides (WO3 and TiO2) weakened the stability of ABS and lowered its decomposition temperature, whereas the vanadia species played the opposite role due to the sulfur species existing in an electron saturation state with the formation of the VOSO4 intermediate. The presence of NO + O2 could break the bonds inside ABS and it could react with the ammonium species originating from ABS, which pulls NH3 out of the ABS formation equilibrium and accelerates its decomposition and competitively inhibits its formation. Correspondingly, the faster NH3-SCR conversion rate and higher N2 selectivity improve the ABS poisoning resistance of the V/WTi catalyst at low temperatures.

Elucidating N2O Formation during the Cyclic NOx Storage and Reduction Process Using CO as a Reductant.

The N2O formation pathway and effect of H2O on N2O formation during the NOx storage and reduction (NSR) process using CO as a reductant were investigated over a Pt-BaO/Al2O3 catalyst. The NSR activity measurements and transient in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments were performed to evaluate N2O evolution and elucidate the N2O formation mechanism. N2O is formed in the lean, rich, and delay2 phases. In the lean phase, N2O formation is related to the reactions between surface isocyanate and gaseous NO/O2 and NO is more responsible for N2O formation than O2. Moreover, N2O production decreases with H2O because of the hydrolysis of isocyanate species. In the rich phase, the amount of N2O formation also decreases in the presence of H2O at a higher temperature because of the high reduction ability of H2 generated from the water-gas shift (WGS) reaction. During the delay2 phase, N2O is mainly formed by nitrite species reacting with Pt(0)-CO. Furthermore, the presence of H2O decreases the stability of nitrites and results in more N2O production at a low temperature.

New Insights into the N2O formation mechanism over Pt-BaO/Al2O3 model catalysts using H2 as a reductant.

The N2O formation mechanism was investigated over a Pt-BaO/Al2O3 catalyst applied on light-duty diesel vehicles using H2 as a reductant in the absence and presence of H2O. In the absence of H2O, N2O forms mainly at the initial phase of lean NOx trapping; while in the presence of H2O, N2O appears mainly at the beginning of the rich reduction phase. In the lean period, N2O is formed via the gaseous NO/O2 reacting with the adsorbed H and NH3 that are formed during the previous rich period. The N2O formation in the rich period is insignificant in the absence of H2O but is greatly enhanced by the presence of H2O. The amount of N2O formed is proportional to the H2O level in the feed, and its formation is favored at low temperatures. Our FTIR data show that H2O enhances the rate of nitrite/nitrate reduction during the rich regeneration, which increases the amount of released NOx, an oxygen source for N2O formation. Our temperature-programmed experiments indicate that H2O competes with NH3 for adsorption sites on Pt surface. This competitive adsorption may increase the NH3 desorption rate at low temperatures in the rich phase and make Pt surface more accessible to NO.

[Diagnosis and Treatment for Four Cases of Sparganosis mansoni].

The data of 4 sparganosis mansoni cases were collected from January 2010 to September 2014, and analyzed by descriptive epidemiological methods. Among the cases, 3 cases had a history of eating raw frogs, and 1 case had a history of eating half-cooked frogs and drinking unboiled water. All cased and 3 out of 7 persons eating raw frogs together with case 3 were positive for anti-Sparganum mansoni antibody. 2 patients were cured by operation removal and praziquantel+alhendazole treatment, and the other 2 cases were cured by drugs only.

Preparation of Fe(x)Ce1-xOy solid solution and its application in Pd-only three-way catalysts.

FeOx-CeO2 mixed oxides with increasing Fe/(Ce+Fe) atomic ratio (1-20 mol%) were prepared by sol-gel method and characterized by X-ray powder diffraction (XRD), Brunauer-Emmett-Teller (BET) and Hydrogen temperature-programmed reduction (H2-TPR) techniques. The dynamic oxygen storage capacity (DOSC) was investigated by mass spectrometry with CO/O2 transient pulses. The powder XRD data following Rietveld refinement revealed that the solubility limit of iron oxides in the CeO2 was 5 mol% based on Fe/(Ce+Fe). The lattice parameters experienced a decrease followed by an increase due to the influence of the maximum solubility limit of iron oxides in the CeO2. TPR analysis revealed that Fe introduction into ceria strongly modified the textual and structural properties, which influenced the oxygen handling properties. DOSC results revealed that Ce-based materials containing Fe oxides with multiple valences contribute to the majority of DOSC. The kinetic analysis indicated that the calculated apparent kinetic parameters obey the compensation effect. The three-way catalytic performance for Pd-only catalysts based on the Fe doping support exhibited the redundant iron species separated out of the CeO2 and interacted with the ceria and Pd species on the surface, which seriously influenced the catalytic properties, especially after hydrothermal aging treatment.

Surface basicity on bulk modified phosphorus alumina through different synthesis methods.

Bulk modified phosphorus alumina samples were prepared by gel method (GPA) and hydrolysis of phosphide aluminum (HPA). The γ-Al(2)O(3) impregnated by phosphates precursor (IPA) was also compared. The basicity of the samples has been investigated through the CO(2) adsorption/desorption processes by in situ DRIFT and temperature programmed desorption experiments. It was found that the surface basicity can be adjusted by different location of phosphates species. For the GPA sample, the phosphates species tends to be located in the grain boundaries as they were not stable enough to overcome the structure rearrangement at high temperatures. In contrast, phosphorus was stably anchored in the crystal lattice of HPA sample. Considering the synthesis process of HPA samples, phosphorus changed its valence state from P(-3) to P(+5) and migrated from anion to cation sites. The anion vacancies left in the lattice facilitated the formation of unsaturated oxygen ions and results in the enhanced basicity.

Efficient Hydrothermal Synthesis of SSZ-13 with Variable Grain Size.

To meet the industrial needs for SSZ-13, variable sizes of SSZ-13 with different Si/Al ratios were firstly obtained by conventional hydrothermal synthesis using the seed method. Using a set of characterizations, like X-ray fluorescence (XRF), X-ray diffraction (XRD), and scanning electron microscopy (SEM), the physicochemical structure and size distribution could be traced. After the specific Si/Al ratio of SSZ-13 zeolites was optimized, synthesized by changing the amounts of structure-directing agents (SDAs) and NaOH, the obtained SSZ-13 showed a high degree of crystallinity. With the limitation of the pH values, the variation of the alkalinity and water content was not helpful to generate different grain sizes of SSZ-13 materials. With the help of ground seed, the various grain sizes of SSZ-13s from 0.4 to 4 µm had a similar degree of crystallinity and size distribution. Moreover, due to the identical intensity of the Al peak in the NMR results, the different grain sizes of SSZ-13s had the same acidity. Our study revealed that using the seed method was an easy and efficient way to synthesize SSZ-13s with different sizes.

The Influence of Si/Al Ratios on Adsorption and Desorption Characterizations of Pd/Beta Served as Cold-Start Catalysts.

: The majority of NOx is exhausted during the cold-start period for the low temperature of vehicle emissions, which can be solved by using Pd/zeolite catalysts to trap NOx at low temperature and release NOx at a high temperature that must be higher than the operating temperature of selective catalytic reduction catalysts (SCR). In this work, several Pd/Beta catalysts were prepared to identify the influence of Si/Al ratios on NO and C3H6 adsorption and desorption characterizations. The physicochemical properties were identified using N2 physical adsorption, Fourier Transform Infrared Spectroscopy (FT-IR), transmission electron microscopy (TEM), X-ray photo electron spectroscopy (XPS), and Na⁺ titration, while the adsorption and desorption characterizations were investigated by catalyst evaluation. The results indicated that the amount of dispersed Pd ions, the main active sites for NO and C3H6 adsorption, decreased with the increase of Si/Al ratios. Besides this, the intensity of Brønsted and Lewis acid decreased with the increase of Si/Al ratios, which also led to the decrease of NO and C3H6 adsorption amounts. Therefore, Pd dispersion and the acidic properties of Pd/Beta together determined the adsorption ability of NO and C3H6. Moreover, lower Si/Al ratios resulted in the formation of an additional dispersed Pd cationic species, Pd(OH)⁺, from which adsorbed NO released at a much lower temperature. Finally, an optimum Si/Al ratio of Pd/Beta was found at around 55 due to the balanced performance between the adsorption amounts and desorption temperature.

Tuning the structure of bifunctional Pt/SmMn2O5 interfaces for promoted low-temperature CO oxidation activity.

The interfacial structure of metal-oxide composite catalysts plays a vital role in heterogeneous catalysis, which is crucial to the adsorption and activation of reactants. Herein, the interfacial effects of bare and Fe/Co/Ni doped SmMn2O5 mullite oxide supported Pt clusters on CO oxidation have been investigated by first-principles based microkinetics analysis. A robust formation of Pt/Mn2 trimer structures is demonstrated at the bifunctional interfaces irrespective of the Ptn cluster's size, which can provide spatially separated sites for CO adsorption and O2 dissociation. The binding strength of CO at the interfacial Pt sites is in the optimal range due to the charge transfer from Pt clusters to oxide, while the strong polarization of Mn2 dimers induced by Pt clusters with stable three-dimensional morphologies can lower the energy barrier of O2 dissociation. Based on the microkinetics analysis, the O2 dissociation is the rate-determining step in the full CO oxidation cycle, and the introduction of Mn-Fe hetero-dimers at the interface is predicted to further enhance the low temperature CO oxidation activity of Pt/SmMn2O5 catalysts.

Surpassing the single-atom catalytic activity limit through paired Pt-O-Pt ensemble built from isolated Pt1 atoms.

Despite the maximized metal dispersion offered by single-atom catalysts, further improvement of intrinsic activity can be hindered by the lack of neighboring metal atoms in these systems. Here we report the use of isolated Pt1 atoms on ceria as "seeds" to develop a Pt-O-Pt ensemble, which is well-represented by a Pt8O14 model cluster that retains 100% metal dispersion. The Pt atom in the ensemble is 100-1000 times more active than their single-atom Pt1/CeO2 parent in catalyzing the low-temperature CO oxidation under oxygen-rich conditions. Rather than the Pt-O-Ce interfacial catalysis, the stable catalytic unit is the Pt-O-Pt site itself without participation of oxygen from the 10-30 nm-size ceria support. Similar Pt-O-Pt sites can be built on various ceria and even alumina, distinguishable by facile activation of oxygen through the paired Pt-O-Pt atoms. Extending this design to other reaction systems is a likely outcome of the findings reported here.

Bifunctional CO oxidation over Mn-mullite anchored Pt sub-nanoclusters via atomic layer deposition.

CO oxidation is a widely used model system for understanding fundamental aspects of heterogeneous catalysis. While platinum (Pt) continues to be a reference material for CO oxidation catalysis, poisoning of Pt catalysts presents a critical issue that blocks reaction sites and impedes subsequent reaction steps. Fabrication of CO poison-free Pt catalysts remains a great challenge due to its CO-philic nature. Herein, we report a Pt based catalyst to effectively tackle CO poisoning by tightly anchoring Pt sub-nanoclusters onto Mn-mullite oxide (SmMn2O5) via atomic layer deposition. Superior CO oxidation activity has been observed with a significantly lowered light-off temperature and apparent activation energy. In situ diffuse reflectance infrared Fourier transform spectroscopy analysis, oxygen isotope experiments and density functional theory calculations confirm that the low-temperature activity originates from active oxygen atom sources at the bifunctional interface structure.

Highly dispersed Pd on macroporous SmMn2O5 mullite for low temperature oxidation of CO and C3H8.

The catalytic behavior of a palladium catalyst supported on macroporous SmMn2O5 mullite (Pd/SMO-EG&M) for CO and C3H8 oxidation was measured under lean-burn conditions. Different analytical techniques including XRD, Raman, BET, CO chemisorption, SEM, FTEM, XPS, TPD, TPR and CO + O2 pulse were undertaken to evaluate its physical and chemical properties. It was concluded that the crystal structure, morphology and specific surface area (SSA) of SmMn2O5 remained unchanged after Pd addition. The Pd/SMO-EG&M exhibited a low complete transformation temperature for CO (105 °C) and C3H8 (350 °C) oxidation. Such remarkable oxidation activity was attributed to high Pd dispersion (38.4%), which improved the reducibility and mobility of oxygen species, as revealed by TPR and TPD measurements. The high activity of oxygen species for Pd/SMO-EG&M above 250 °C accelerated the oxidation capacity as well. In a word, our study indicates that the macroporous Pd-mullite catalyst has potential applications in exhaust purification for gasoline vehicle.

Influence of ethanol-gasoline blended fuel on emission characteristics from a four-stroke motorcycle engine.

Emission characteristics from a four-stroke motorcycle engine using 10% (v/v) ethanol-gasoline blended fuel (E10) were investigated at different driving modes on the chassis dynamometers. The results indicate that CO and HC emissions in the engine exhaust are lower with the operation of E10 as compared to the use of unleaded gasoline, whereas the effect of ethanol on NO(X) emission is not significant. Furthermore, species of both unburned hydrocarbons and their ramifications were analyzed by the combination of gas chromatography/mass spectrometry (GC/MS) and gas chromatography/flame ionization detection (GC/FID). This analysis shows that aromatic compounds (benzene, toluene, xylene isomers (o-xylene, m-xylene and p-xylene), ethyltoluene isomers (o-ethyltoluene, m-ethyltoluene and p-ethyltoluene) and trimethylbenzene isomers (1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene and 1,3,5-trimethylbenzene)) and fatty group ones (ethylene, methane, acetaldehyde, ethanol, butene, pentane and hexane) are major compounds in motorcycle engine exhaust. It is found that the E10-fueled motorcycle engine produces more ethylene, acetaldehyde and ethanol emissions than unleaded gasoline engine does. The no significant reduction of aromatics is observed in the case of ethanol-gasoline blended fuel. The ethanol-gasoline blended fuel can somewhat improve emissions of the rest species.