Quaternary Oxide of Cerium, Terbium, Praseodymium and Zirconium for Three-Way Catalysts

Oxygen storage-capacity （OSC）, oxygen buffer capacity （OBC）, X-my diffraction and electron diffraction pattern, high resolution electron microscopy were used to study the quaternary oxides, i .e., of Ce, Tb, Pr and Zr. （Ce0.6 Tb0.2Zr0.2O2- δ and Ce0.6Pr0.2Zr0.2O2-δ ）. OSC and OBC data indicate that these oxides have very good oxygen transfer capacity （OTC） and their pseudo-solid solutions exhibit fluorite-type structure. These oxides may act as a good candidate for three-way catalysts （TWC）.

Influence of Ce_(0.35)Zr_(0.55)Y_(0.10) Solid Solution on Performance of Pt-Rh Three-Way Catalysts

Ce0.35Zr0.55Y0. 10 solid solution was prepared by co-precipitation technique and characterized by specific surface area measurements （BET） and X-ray diffraction （XRD）. Ce0.35Zr0.55Y0.10 was used to prepare low Pt-Rh threeway catalyst （TWC）, and its influence on the performance of TWC was investigated. The results revealed that Ce0.35 Zr0.55Y0.10 had a cubic structure similar to Ce0.50Zr0.50O2 and its specific surface area can maintain higher than Ce0.50 Zr0.50O2 after 1000 ℃ calcination for 5 h. Being hydrothermal aged at 1000 ℃ for 5 h, the catalyst containing Ce0.35 Zr0.55Y0.10 still exhibited higher conversion of C3H8, CO and NO and lower light-off temperature in comparison with Ce0.50Zr0.50O2 TWC.

Influences of (Ce-Zr-La-Pr)O Contents on Three-Way Catalyst Performances

A series of catalysts with (Ce-Zr-La-Pr)O contents range from 0 to 50% in coating and single-palladium loads on substrates were prepared to study effects of (Ce-Zr-La-Pr)O contents on catalytic activities and durability by contrasting the characteristics of light-off, A/F and catalytic conversions of the fresh catalysts with that of the aged catalysts. The results show that (Ce-Zr-La-Pr)O can enhance the catalysts light-off characteristics, widen A/F windows and increase catalytic conversions at a certain extent through optimizing physical structural and chemical property of the mixed coating. However, (Ce-Zr-La-Pr)O contents influence greatly on the catalysts activities and durability, and the catalysts with contents ranging from 10% to 30% exhibited better integrative properties in all samples, and 10% was the optical content to make the catalyst performance highest in this thesis. It is indicated that an suitable content of (Ce-Zr-La-Pr)O plays an important role in assisting catalysis, enhancing durability and increasing oxygen storage capability.

Regulated and Speciated Hydrocarbon Emissions from a Dual Fuel Light Duty Vehicle with and Without a Three-Way Catalyst

The regulated pollutants （CO,HC and NOx） and unregulated pollutants （volatile organic compounds and carbonyl compounds）,emitted from a dual fuel vehicle fueled with gasoline and E10 fuel,are measured under a transient cycle and steady modes.The impacts of a three-way catalyst （TWC） are investigated for the two types of fuels.The measured results show that NOx and acetaldehyde emitted from the E10-fueled car are much more than that from the gasoline-fueled car under the same modes.On the basis of maximum incremental reactivity （MIR） factors and emissions of organic gases,the ozone specific reactivity of the tailpipe gases are evaluated.

Effect of Sulfur on the Performance of Three-Way Catalysts

Sulfur content is one of the fuel properties to be monitored. Sulfur dioxide, the major product derived from organic sulfur compounds in the exhaust gas emissions, is a poison to the three-way catalysts (TWC). A gas mixture was applied to simulate the exhaust gases used in the TWC aging procedure tests. Two types of the TWC, REX-IIC and REX-IID, were tested in this study. The performance of both TWC's before and after the 100-hour sulfur aging program was compared. It was concluded that the Pt component in the TWC was apt to be poisoned by sulfur much easily than Rh. The performance of the REX-IID catalyst was generally better than that of the REX-IIC catalyst.

Recent progress of Rh-based three-way catalysts

Three-way catalysts are widely used to control criterion pollutant emissions fromthe increasing gasoline engines.With the stringent requirements of automotivepollutant emission standards in various countries,Rh has become an irreplaceablecomponent of three-way catalysts due to its superior NOx elimination,high N2selectivity,and simultaneous elimination of CO and hydrocarbons.In this review,we systematically review the recent development of Rh-based three-way catalystsin terms of potential supports and effective active center construction strategies.We further summarize the key role of Rh metal in the three-way catalytic mechanismand reaction kinetics.Finally,we conclude the current challenges and futureopportunities facing Rh-based catalysts.It is believed that based on the deep understandingof Rh-based three-way catalysts,the design of Rh-based catalysts withgood low-temperature catalytic performance and low cost is expected to be realizedin the future.

Steam effects over Pd/Ce_(0.67)Zr_(0.33)O_2 three-way catalyst

In the purification process of automobile exhaust,existing water plays an important role as an oxidant,which converts CO and hydrocarbons（HCs） by the water-gas shift（WGS） and the steam reforming（SR） reactions,respectively,especially at high temperatures.Meanwhile it is major component of the exhaust which can affect significantly the thermal stability of the three-way catalyst.Activity experiments were carried out close to the real operation conditions（GHSV,concentration,etc.） with a Pd/Ce0.67Zr0.33O2 catalyst supplying information on the CO and C3H8 oxidation reactions in feedstream formed by different reactant combinations.The obtained results showed that the activity of the CO and C3H8 oxidation was promoted by the addition of steam due to the WGS and SR reactions.The WGS and SR reaction were competitive under oxygen-lean conditions.The kinetic analysis was considered for WGS and SR reactions.

Durability of three-way and close-coupled catalysts for Euro IV regulation

The durability of three-way catalyst （TWC） and corresponding close-coupled catalyst （CCC） for Euro Ⅳ stage regulation was investigated through Vehicle Road Running Mode tests, whereas emissions of regulated pollutants of three car fleet were investigated at every 100,000 km miles. The results showed that HC, NOx, and CO emission values could meet Euro Ⅳ regulation limits at every point. The redox properties of TWC and CCC were measured by CO reduction during each isothermal. It was obvious that both aged TWC and aged CCC behaved a good redox property at 673 and 773 K. Based on XRD and BET measurement results, TWC and CCC washcoat were characterized with good thermal stability.

Synthesis of neodymium modified CeO_2-ZrO_2-Al_2O_3 support materials and their application in Pd-only three-way catalysts

Ce-Zr-Al-Nd2O3 （CZAN） support materials were prepared by co-precipitation and impregnation methods, respectively. They were characterized by X-ray diffTaction （XRD）, low temperature nitrogen adsorption-desorption, oxygen pulsing technique, H2-temperamre programmed reduction （H2-TPR） and X-ray photoelectron spectroscopy （XPS）. The Pd-only three-way catalysts （Pd-TWC） supported on these materials were prepared by incipient wetness method and studied by activity tests. The results demonstrated that the CZAN supports obtained by the two methods showed better structural, textural and redox properties than the CZA without Nd2O3, and the addition of Nd203 improved the catalytic activity of TWC. Especially, the CZAN-i support prepared by impregnation method had better thermal stability and redox property. Meanwhile, the Pd/CZAN-i catalyst exhibited the best catalytic performance. XPS measurements indicated that the Nd-modified samples possessed more Ce3＋ and oxygen vacancies on the surface of samples, which led to a better redox property. The excellent redox property of support materials helped to improve the catalytic activity of TWC.

Realization approach of Pd-only three-way catalysts with high catalytic performance and thermal stability

Pd-only three-way catalyst （TWC）, Pd supported on washcoating （the mixture of alumina and Ce-Zr solid solution）/cordierite, was prepared and its catalytic performance and the operation window （2-value） at 450 ℃ were evaluated with the simulated automotive exhaust feed gas. Surfactants such as Tween-80 and Span-20 were added in the process of preparing the catalyst in order to improve the thermal stability and catalytic performance of Pd-only TWC. The fresh and aged catalysts at 1000 ℃ for 4 h were characterized by low-temperature N2 adsorption, XRD, XPS, and H2-TPR techniques. The results show that the presence of surfactants in the synthesis slurry could influence the physicochemical properties of the final Pd-only TWC. The FTS catalyst prepared with the mixed surfactant of Tween-80 and Span-20 exhibited excellent three-way catalytic performance. After being aged at 1000℃ for 4 h, the catalytic performances of Pd-only TWCs slightly decreased, but the FTS catalyst still demonstrated higher catalytic performance and better thermal stability compared with the Pd-only catalysts prepared with single surfactant or without any surfactant. And the FTS catalyst has a wider 2 value （operation window） than other catalysts, even after being aged at 1000℃.

Low-content and highly effective zoned Rh and Pd three-way catalysts for gasoline particulate filter potentially meeting Euro 7

The next-generation Euro 7 standard proposed much lower pollutant limits from gasoline vehicles,specifically for CO and NO_(x),which would be challenging for the three-way catalysts(TWCs)utilized commercially to eliminate these pollutants.TWCs with reductive(Rh)and oxidative(Pd)active components on gasoline particulate filters(TWC on GPF)play importantly auxiliary roles in the remediation of CO and NO_(x)downstream the close coupled TWCs to meet their emission targets.Here,a low-content Rh-based TWC(0.17 wt%)zoned with a less expensive Pd-based TWC(0.29 wt%)for GPF applications(cGPF)is reported using improved colloidal deposition method.The supporting of Rh on Y-stabilized ZrO_(2)rather than on CeO_(2)-ZrO_(2)inhibits the formation of inactive Ce rhodate species,while Pd on CeO_(2)-ZrO_(2)not only guarantees the high oxygen storage capacity(OSC)but also enhances catalytic activity.The layout of the front one-fifth in volume being 0.29 wt%Pd on Ce_(0.43)Zr_(0.5)7O_(2)and the rear four-fifths being 0.17 wt%Rh on Zr_(0.85)Y_(0.15)O_(2)prevents the possible alloying of Rh with Pd.The highly effective zoned Rh and Pd TWCs show synergistic three-way activity before and after severe hydrothermal aging at 1000℃with 10%water for24 h,which could be potential choices for close coupled GPF application to satisfy the upcoming stringent emission standards,such as Euro 7 and China 6b.

Influence of surface Ce/Zr ratio on formation of κ-Ce_(2)Zr_(2)O_(8) superstructure and its application in three-way catalysis

Ceria-zirconia based(CZ) materials are still a crucial component of three-way catalysts(TWCs) now.Compared with traditional cubic or tetragonal phase,CZ material with pyrochlore-type κ-Ce_(2)Zr_(2)O_(8) phase shows an excellent oxygen storage capacity,and thus is examined as a promising material for developing TWCs.Considering the remarkable surface Ce/Zr ratio change during the κ-Ce_(2)Zr_(2)O_(8) formation,we investigated the effects of surface Ce/Zr ratio on the formation of κ-Ce_(2)Zr_(2)O_(8) and on the supported Pdonly three-way catalysts.Raman and transmission electron microscopy(TEM) results demonstrate that partial κ-Ce_(2)Zr_(2)O_(8) structure is formed in the three oxides,and the content of κ-Ce_(2)Zr_(2)O_(8) structure increases with increasing surface Ce/Zr ratio,but its stability declines.After thermal aging,the proportions of Ce^(3+) and oxidized palladium(Pd^(δ+)+Pd^(2+)) in the catalysts,which are shown to be positively correlated with catalytic activity,follow the same sequence as the stability of κ-Ce_(2)Zr_(2)O_(8),namely Pd/M0.33 ROa> Pd/M0.4 ROa> Pd/CeM0.33 ROa.In particular,Pd/M0.33 RO,which possesses 100%((Pd^(δ+)+Pd^(2+))/Pd) even after thermal aging at 900℃ for 4 h,owing to the strengthened metal-support interaction by the presence of stable κ-Ce_(2)Zr_(2)O_(8),shows the best catalytic performance.This work is instructive to the application of κ-Ce_(2)Zr_(2)O_(8) in three-way catalysis.

Preparation of Fe_x Ce_(1-x) O_y 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-Emrnett-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.

A new approach of CeO_2 and La_2O_3 effects on the three-way catalysts containing low precious metals

A series of three-way catalysts (TWCs),containing a small amount of precious metals (PMs,including Pt,Pd and Rh) and a large amount of promoters CeO2 and La2O3,were prepared with different precursor compounds and various doped manners.Crystal phases,dispersion of cerium and lanthanum,textural structure and thermal stability of the catalysts were investigated by XRD,XPS and pore parameters determination.The catalytic performance was studied by the measurements of CO,C3H6 and NO conversions on dependence of temperature at stoichimetric number point (S=1.00),and from S=0.75 to 1.30 at 280℃ or 340℃ for fresh or aged samples,respectively.The correlation between the catalytic performance and the characteristics of fresh and aged samples were discussed.The results show that the sample,in which CeO2 and La2O3 are doped with mixed oxide powders,possesses poor dispersion and less thermal stability,and the conversions of NO and C3H6 are apparently lower than those of the samples aged at 850℃ The main reason is due to the lanthanum enrichment on the surface.The precious metals and cerium may be covered and enveloped,and the PMs located on the internal microporous surface where no cerium and lanthanum exist,are easier to sinter and oxidize.For the sample doped with La(NO3)3 and Ce(NO3)3 aqueous solutions,high dispersion and thermal stable CeO2 La2O3 solid solution on all the surface of microporous γ-Al2O3 is identified.The solid solution CeO2-La2O3 also possessed high dispersion in the sample doped with La2O3 powder and Ce(NO3)3 aqueous solution.The last two aged samples keep higher NO conversion at S≥1 region.

SO_(4)^(2-)-modified La,Y-doped ceria-zirconia with high oxygen storage capacity and its application in Pd-only three-way catalysts

As the oxygen redox ability shows great effects on the catalytic performances of ceria-zirconia based materials,many strategies have been utilized to improve the oxygen storage capacity.Here in this study,we report a simple and facile approach to prepare a SO_(4)^(2-)-modified La,Y-doped ceria-zirconia material(SO/CZLY-f)with high oxygen storage capacity.Due to the additional redox process between SO_(4)^(2-)and S^(2-),oxygen storage capacity of SO/CZLY-f(745.3μmol O_(2)/g)is about 1.6 times higher than that of La,Ydoped ceria-zirconia material without SO_(4)^(2-)modification.Moreover,the catalytic activities and stability of the corresponding Pd-only three-way catalyst were measured.Compared to that of Pd@CZLY-f,the operation window of CO,full conversion temperature of HC and NO over Pd@SO/CZLY-f are obviously widened and lowered,respectively.After aging treatment at 1100℃for 4 h,the superiority of aged Pdloading composite is still maintained.

Steam effects over Pd/Ce_(0.67)Zr_(0.33)O_2-Al_2O_3 three-way catalyst

Ceria-zirconia-alumina （CZA） solid solution was prepared by sol-gel method in the present study. 0.5 wt.% Pd supported on CZA was prepared by incipient wetness impregnation. The steam effects for CO and C3H8 oxidation, three-way catalytic activity and stoichiometric window property were studied. The light-off temperature of the CO oxidation reaction shifted to a lower temperature due to the water-gas shift （WGS） reactions. The oxidation of C3H8 was enhanced due to the steam reforming （SR） reactions. The steam promoted the C3H8 oxidation and NO reduction in three-way catalytic reaction. The amplitude of stoichiometric window was amplified by the addition of water to the feed stream.

Rule acquisition of three-way semi-concept lattices in formal decision context

Three-way concept analysis is an important tool for information processing,and rule acquisition is one of the research hotspots of three-way concept analysis.However,compared with three-way concept lattices,three-way semi-concept lattices have three-way operators with weaker constraints,which can generate more concepts.In this article,the problem of rule acquisition for three-way semi-concept lattices is discussed in general.The authors construct the finer relation of three-way semi-concept lattices,and propose a method of rule acquisition for three-way semi-concept lattices.The authors also discuss the set of decision rules and the relationships of decision rules among object-induced three-way semi-concept lattices,object-induced three-way concept lattices,classical concept lattices and semi-concept lattices.Finally,examples are provided to illustrate the validity of our conclusions.

Influences of Platinum Precursors and Solution Acidities on REO-Based Catalysts Performances

Important effects exist between precious metals and rare earths oxides in three-way catalyst, especially the coordinated effects. These effects were studied by using H2PtCl6, Pt(NH3)2(NO2)2 and Pt(OH)2(C2H5ONH2)2 as Pt precursors, and the mixed oxide of (Ce-Zr-La-Pr)O as base material to prepare a series of catalysts, and their performances of the catalysts were studied by TPR and CO pulse titration technologies. The results shown that Pt precursors and their solutions pH values influenced the oxygen storage capabilities, the active metal distribution degrees of the catalysts obviously, and every catalyst prepared by different precursors had an optimal pH values. It indicates that the active metals precursors and their solutions acidities have outstanding influences on the catalysts performances for the mutual effects existing between the active metals and the Rare Earth metal oxides, which results from the mate groups of the precursors and the solution acidity.

Three-way group decision making with linguistic evaluations

Based on linguistic evaluations, a linguistic threeway decision method is proposed. First, the alternatives are rated in linguistic forms and divided into acceptance, rejection and uncertainty regions. Secondly, the linguistic three-way group decision steps are provided. Specifically, the experts determine the lower bound and upper bound of the uncertainty region, respectively. When the evaluation is superior to the upper bound, the corresponding alternative is put into the acceptance region directly. Similarly, when the evaluation is inferior to the lower bound, the corresponding alternative is put into the rejection region directly, and the remaining alternatives are put into the uncertain region. Moreover, the objects in the uncertainty region are especially discussed. The linguistic terms are transformed into fuzzy numbers and then aggregated. Finally, a recommendation example is provided to illustrate the practicality and validity of the proposed method.

An adaptive dwell time scheduling model for phased array radar based on three-way decision

Real-time resource allocation is crucial for phased array radar to undertake multi-task with limited resources,such as the situation of multi-target tracking,in which targets need to be prioritized so that resources can be allocated accordingly and effectively.A three-way decision-based model is proposed for adaptive scheduling of phased radar dwell time.Using the model,the threat posed by a target is measured by an evaluation function,and therefore,a target is assigned to one of the three possible decision regions,i.e.,positive region,negative region,and boundary region.A different region has a various priority in terms of resource demand,and as such,a different radar resource allocation decision is applied to each region to satisfy different tracking accuracies of multi-target.In addition,the dwell time scheduling model can be further optimized by implementing a strategy for determining a proper threshold of three-way decision making to optimize the thresholds adaptively in real-time.The advantages and the performance of the proposed model have been verified by experimental simulations with comparison to the traditional twoway decision model and the three-way decision model without threshold optimization.The experiential results demonstrate that the performance of the proposed model has a certain advantage in detecting high threat targets.