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The three-way catalytic converter

S342_1 Physical chemistry: principles of chemical change

The three-way catalytic converter

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The three-way catalytic converter

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open.3 Exhaust emission characteristics  4.1 Exhaust pollutants  4.5 Catalyst deterioration  Conclusion  Keep on learning  Acknowledgements Page 5 of 71 2nd March 2016 http://www. Overview  .The three-way catalytic converter Contents  Introduction  Learning outcomes  1.4 The chemical reactions  4.2 The three-way catalytic converter  4.

The three-way catalytic converter Introduction Ensuring good quality air is essential for the protection of public health. This OpenLearn course provides a sample of Level 3 study in Science. Governments worldwide have adopted a range of increasingly demanding measures to curb air pollution with a particular focus on the emissions from motor . This course takes an in-depth look at the construction of this converter for petrol-driven vehicles and investigates the catalytic chemistry taking place at the molecular level. It is assumed that you already have a scientific background. unburnt hydrocarbons and nitrogen Page 6 of 71 2nd March 2016 http://www. An important part of this strategy has been the development of the three-way catalytic converter to remove exhaust pollutants such as carbon monoxide.

hydrocarbons and oxides of nitrogen (NOx) from petrol vehicle exhausts interpret the results of experimental studies (involving activity tests. adsorption studies and/or various surface science techniques) of the three-way catalyst and appropriate model systems discuss possible mechanisms for the catalytic reactions removing CO. Page 7 of 71 2nd March 2016 http://www. kinetic measurements. depend on the air/fuel (A/F) ratio list the chemical reactions whereby the three-way catalyst removes carbon monoxide (CO).open. you should be able to:      discuss how the gas mixture expelled from the engine. hydrocarbons and NOx from vehicle exhausts outline the modes of deterioration of the three-way catalyst.The three-way catalytic converter Learning outcomes After studying this course. and the conversion performance of the three-way catalytic . and comment on the strategies that could be used to reduce H2S emissions.

aromatics and oxygenated species. but perhaps the most notorious consequence of exhaust emissions is their role in the formation of photochemical smog – a mixture of ozone. it may also arise from the oxidation of any nitrogeneous components in the .1 Exhaust pollutants The most important chemical reaction in a petrol engine – that is. Overview 4. there must be adequate mixing of the petrol and air. these two oxides of nitrogen are considered together and represented as NOx. the complete oxidation of the fuel depends on a number of factors: first.2.The three-way catalytic converter 1. On leaving the engine. combustion would be complete so that the only exhaust products would be carbon dioxide and steam. Although the ‘fixing’ of nitrogen from the air is the major source of NOx. Primary pollutants are defined as those gases emitted directly from the exhaust of a vehicle. including hydrocarbons (HC). The role of an emission control catalyst is to simultaneously remove the primary pollutants CO. 4. There is incomplete combustion of the fuel and this leads to emissions of the partial oxidation product. nitrogen dioxide. is the production of the oxides of nitrogen – nitric oxide (nitrogen monoxide. These emissions are particularly high during both idling and deceleration.2 The three-way catalytic converter 4. this monoxide cools down and is oxidized by oxidants in the atmosphere to form the dioxide. In internal combustion engines. when insufficient air is taken in for complete combustion to occur. NO) and nitrogen dioxide (NO2). steam (H2O) and nitrogen (N2). the time available for combustion is limited by the engine’s cycle to just a few milliseconds. VOCs and NOx by catalyzing their conversion to carbon dioxide (CO2). carbon monoxide (CO). there must be sufficient oxygen present. second. In an ‘ideal’ system. In practice. there must be sufficient time for the mixture to react at high temperature before the gases are cooled. Conventionally.1 Composition Page 8 of 71 2nd March 2016 other secondary products and small particulates. Another important result of the combustion process. At the high temperatures involved (in excess of 1 500 °C) nitrogen and oxygen in the air drawn in with the fuel may combine together to form NO. the one that provides the energy to drive the vehicle – is the combustion of fuel in air. and finally. None of these is a desirable addition to the atmosphere. and a wide range of volatile organic compounds (VOC). These secondary pollutants can cause severe damage to human health. particularly during acceleration.

particularly for small converters. Page 9 of 71 2nd March 2016 http://www. Figure Schematic diagram of the three-way catalytic converter. Metallic monoliths are also used. A typical monolith has 64 channel openings per cm2 (400 per in2). they flow through the channels in the ceramic monolith. γ-alumina (Al2O3). and other metal oxides. the exhaust gas temperature can reach several hundred degrees in less than a . It typically consists of a ceramic monolith of cordierite (2Mg. As the exhaust gases pass through it. 5SiO2) with strong porous walls enclosing an array of parallel channels.2Al2O3. containing the precious metals rhodium. but these are more expensive. ceria (CeO2). is placed in the exhaust system of the vehicle.The three-way catalytic converter The current three-way platinum and (to a lesser extent) palladium. where they encounter the particles of alumina impregnated with the metal catalysts. is generally a multicomponent material. The catalytic converter. shown schematically in Figure 1. This design allows a high rate of flow of exhaust gases Cordierite is used because it can withstand the high temperatures in the exhaust. and the high rate of thermal expansion encountered when the engine first starts – typically. in a metal canister.

as one might expect. Before we discuss the data in any detail. typically Pt. This system becomes the support for the precious metal components (Pt. with and without a three-way catalytic converter. VOC and NOx for a Catalyst performance Figure 3 shows the difference in the emission levels for CO. as chemical promoters. such as BaO.The three-way catalytic converter Figure 2 Electron micrograph of a cross section of a ceramic monolith coated with an alumina washcoat To achieve a large surface area for catalysis. 4. others use Rh together with only one of the other two. Exact catalyst formulations are. with oxides. It is evident that the catalytic converter reduces the emissions of all three classes of pollutants quite dramatically over a wide range of . Some compositions use all three metals. They are generally applied by deposition from solution. Page 10 of 71 2nd March 2016 http://www. a few words about how they were obtained are in order. known as the washcoat (Figure 2).2. the internal surfaces of the monolith are covered with a thin coating (30–50 μm) of a highly porous material. The washcoat generally consists of alumina (70–85%) with a large surface area. in which Pt constitutes 80–90% of the total precious metal mass. These metals constitute only a small fraction (1–2%) of the total mass of the washcoat. for example CeO2. although they may instead be introduced during formation of the washcoat itself. closely guarded secrets. as in the present generation of Pt-Rh converters used in the UK. Pd and Rh). but they are present in a highly dispersed form. The total surface area is now equivalent to that of about two or three football pitches. added as structural promoters (stabilisers to maintain surface area) and others.

The three-way catalytic converter Figure 3 Emission levels for CO. Some sort of smaller-scale testing is obviously required in the laboratory. Federal and European Test Procedures are used to test emissions from a complete ‘finished’ converter and engine together. The process of screening must provide a reliable means of identifying materials that will perform as active. activity testing fulfils the function of screening and comparing novel and modified catalysts. In the research and development of automotive . The test is then repeated using a different simulated exhaust-gas to represent a different engine mode. will meet the current emissions legislation. using a simulated exhaust-gas mixture flowing through a bed of powdered catalyst: the flow-rate has to be high enough to mimic the ‘through-put’ or space velocity of a catalytic converter (typically a contact time for the gases with the catalyst of 72 milliseconds is used). Ageing studies are Page 11 of 71 2nd March 2016 http://www. for instance. selective and durable catalysts under automotive conditions. to ensure that a new car The approach usually taken is to measure conversion of the pollutants as a function of temperature. VOC and NOx for petrol-engined vehicles as a function of speed. with (green) and without (black) a three-way catalytic converter. and examining their performance under different conditions.

the catalyst is not working at full efficiency. the activity of the catalyst is low. HC and . Figure 4 shows a typical graph of catalytic performance over the normal range of operating Figure 4 Activity of a three-way catalyst for the simultaneous conversion of CO (black). and often extreme conditions. NO x (solid green) and the hydrocarbon propene (C3H6) (dotted green) 4. from the engine depend on the ratio of air (A) to fuel (F) – the air/fuel ratio (or A/F ratio). This temperature. SAQ 1 Page 12 of 71 2nd March 2016 http://www. 100–600 °C. is known as the light-off temperature.The three-way catalytic converter performed by exposing the catalyst to different. Ideally the lightoff temperature should be as low as possible. for varying lengths of time. Until the incoming gases have heated the catalyst to around 250–300 °C. it is important to understand how the emissions of CO. and so CO. NOx and hydrocarbons will all be emitted from the exhaust pipe in significant amounts.3 Exhaust emission characteristics Before we consider how the three-way catalyst functions in any detail. This problem is known as cold start. The significance of this will become clear when we see that the ratio at which the threeway catalytic converter operates is crucial for its success. at which the efficiency of the catalyst rapidly increases. Until this temperature is reached.

Comment on the difference between the value you obtain and the experimental value of at an A/F ratio of about 14.01. in theory. net oxidising conditions – low levels of HC and CO are produced in the engine. The diagram also shows qualitatively how the engine power output changes with the A/F ratio. 1. H. 16. NOx falls. HC and NOx released from the engine and the A/F ratio is shown in Figure 5. CO (black) and HC (dotted green) produced in the engine. At higher A/F values.7:1.SAQ 1 Figure 5 The effect of changing air/fuel ratio on the levels of NOx (solid green). estimate the stoichiometric A/F ratio (mass ratio) required for total combustion to . when the engine is operating under fuellean. Activity 1 Why do you think the CO and HC levels in Figure 5 increase under fuel-rich conditions. but the hydrocarbon concentration increases as the engine begins to misfire. and there is a peak in NOx concentration.7:1) – that is.The three-way catalytic converter Taking octane (C8H18) to be the only constituent of fuel. the concentrations of oxidising gases (NO and O2) and reducing gases (HC and CO) are matched. N.01.01. At A/F ratios somewhat above stoichiometric (14.) View answer . 12. O. at low A/F ratios? View discussion . At this stage neglect the effect of NO as an oxidant. that is.7:1 (Use the following relative atomic masses: C. and assuming that air is 20% O2 by volume.00. A general relationship between levels of CO. 14. it should then be possible to Page 13 of 71 2nd March 2016 http://www.Activity 1 When the exhaust gas is close to its stoichiometrically balanced composition.

CO (black) and HC (dotted green) as a function of the air/fuel ratio.) Activity 2 Ideally.g. would we want this window to be as wide or as narrow as possible? View discussion . Figure 6 Activity of a three-way catalyst for the simultaneous conversion of NOx (solid green). e. close to the stoichiometric ratio. within which it will promote simultaneously the nearly complete reduction of NOx to N2 and the nearly complete oxidation of CO and HC to CO2 and H2O. and so. This is. and the effect that this will have on the balance of reductants/oxidants present. The shaded area defines the window for conversions of 80% and above for all three pollutants. 14. You should consider how efficient the Page 14 of 71 2nd March 2016 for clarity. with the dotted lines defining the window for conversions of 80% and above. (Note that. which was also of growing importance at the time of development (1970s).edu/openlearn/science-maths-technology/science/chemistry/the-three-way-catalyticconverter/content-section-0 . it should be operated in a narrow band.7 instead of 14. H2O and N2. Study comment You should approach the following SAQ by thinking about how the mixture expelled from the engine will vary depending on the A/F ratio.7 : 1. Figure 6 shows the catalyst conversion efficiency for all three classes of pollutants as a function of A/F ratio. of course. the A/F ratios are expressed as the amount of air per unit of fuel.Activity 2 This window also happens to correspond closely to the optimum range for high performance of the vehicle (see engine power in Figure 5). the objective of the three-way catalytic converter. ideally.The three-way catalytic converter achieve complete conversion to produce only CO2. or window. We shall use this notation for the rest of this course.

7 ± . sensor as it is sometimes called). HC and 2 Engine control systems have been developed to include an oxygen sensor (or lambda. active for one or more of the many different reactions. oscillating about the stoichiometrically balanced composition (14. and our treatment will accordingly be divided into three subsections. The participation of a particular type of site at any given moment will depend on the conditions experienced by the catalyst. the ratio cycles very rapidly between slightly fuel-rich and slightly fuel-lean. because there are time delays in the A/F correction. stoichiometric.4. λ.4 The chemical reactions 4. 4.1 Introduction Since its development. or oxidising mixture. and hence. whether the gases are a net reducing. The data can often contribute to an understanding of the mechanisms by which the surface reactions occur. This reveals that although the catalyst functions as a composite material. They are also used to create reaction models that will predict the performance of the catalyst under various anticipated conditions. so that the exhaust composition is kept within the window for optimum conversion. SAQ 2 Using the information given in Figures 5 and 6.3) at a typical frequency of 1 cycle per second. with many contributing processes. and (b) less than the window for optimum conversion. The strategy of the three-way catalyst is to simultaneously remove CO. Minimising the amplitude of the oscillation increases the effectiveness of the converter. View answer . and an electronic module to regulate the A/F ratio. for example. leaving the catalyst). how this will affect the gases finally emitted from the exhaust (that is. However. The desired reactions can be expressed in simple terms as follows: Page 15 of 71 2nd March 2016 http://www. it can be divided into distinct groups of catalytic centres that provide several different types of site. The data provided can be correlated with the results of activity tests and kinetic measurements.The three-way catalytic converter catalyst will be in converting this mixture. which provide information on the performance of the catalyst. The overall reaction scheme is complicated. the three-way catalyst has been exposed to the full spectrum of techniques available for the characterisation of catalytic materials. explain the changes in conversion efficiency seen for all three pollutants when the A/F value is (a) greater than the window for optimum conversion. Measurements of intrinsic kinetics are usually carried out on simple gas mixtures to allow activation energies and reaction orders to be calculated for specific reactions.

The supported commercial catalyst is the one most difficult to study because of its complexity. are far removed from the real catalyst system and the conditions it experiences. It is therefore often simpler to study model systems. The following subsections will look more closely at the removal of each of the pollutants under various conditions. three-way catalytic converter Removal of CO CO oxidation: Water-gas shift (WGS) reaction: Removal of hydrocarbons Hydrocarbon oxidation: for example: Steam reforming: Removal of NO (plus CO or HC (not shown)) CO + NO redox reaction: or with hydrogen: Any number of these reactions may be occurring simultaneously as the A/F ratio goes through its cycle about the stoichiometric composition. such as Pt/Al2O3 or Rh/CeO2. These studies. often performed under ultrahigh vacuum (UHV). CeO2. and will also examine the role of the catalyst components. Al2O3. Hence. Rh. and if certain surface-science techniques are to be used. with a large number of different components – Pt. the ‘catalyst’ under study has to be even simpler – a particular face of a metal single . – present in one catalyst. it Page 16 of 71 2nd March 2016 http://www. BaO.

a hexagonal structure forms. The reaction on metals such as Pt is in many ways similar to that on Pd and. Although this metal is not a component of the current three-way catalyst used in the UK. LEED results for the adsorption of CO on Pd(111). The readiness with which the CO molecules can reposition themselves suggests that the activation energy for surface migration in the chemisorbed state is low. and the O atoms are found to be less mobile on the surface than CO molecules. at θ = 2/3 (Figure 7c). As θ is increased to 1/2 (Figure 7b). however. CO moves out of the hollow to a bridging site.3. have been interpreted in terms of the structural models shown in Figure 7. One of the significant observations from this work is the readiness with which one arrangement of CO on the surface evolves into . palladium is already being incorporated into future generations of catalytic converter.The three-way catalytic converter cannot be assumed automatically that the results will be directly relevant to what is actually happening in a converter fitted to an operational vehicle. one of the most intensively investigated examples being the Pd(111) surface. the CO occupies a hollow site where it can bind to three Pd atoms. in any case. and that CO is a highly mobile species under catalytic conditions. is the fact that this is one of the few cases in which surface-science techniques have successfully revealed the details of a ‘realworld’ catalytic mechanism. it is worth considering the results in some detail for a number of reasons. Specifically. Oxygen adsorbs dissociatively on Pd(111).2 Removal of CO Under fuel-lean conditions (excess O2). where it binds to two Pd atoms. obtained at room temperature and below. The structure of the chemisorbed layer at maximum coverage is shown in Figure 8. Finally. particularly for the US market. Page 17 of 71 2nd March 2016 http://www. we will see how surface studies of the adsorption of CO and oxygen on Pd(111) – both individually and together – have led to the current understanding of the mechanism of CO oxidation. Most while the remainder bind to single Pd atoms at terminal sites. in which half of the CO molecules reoccupy hollow sites. the oxidation of CO has been studied over a very large range of single crystals and model noble metal catalysts. Thus at a surface fractional coverage of θ = 1/3 (Figure 7a). 4.

of oxygen atoms. and so it will be relatively slow. (b) θ=1/2. and (c) θ=2/3. θ = 1/4). Because of mutual interactions. θ = 2/3) within a fixed lattice of O atoms (maximum coverage. SAQ 3 Identify the adsorbate structure shown in Figure 8 in terms of the (m×n) notation. the order in which adsorption is carried out is significant. the behaviour of two (or more) co-adsorbed species very often differs from their behaviour when adsorbed separately. In the case of CO and O2. and determine the fractional surface coverage. With lower coverages of CO. but the two species form separate domains on the surface (Figure 9a).edu/openlearn/science-maths-technology/science/chemistry/the-three-way-catalyticconverter/content-section-0 .open.SAQ 3 We might now assume that when CO and O2 are adsorbed together during the oxidation reaction. The surface layer would then consist of mobile CO (maximum coverage. as we shall see below.The three-way catalytic converter Figure 7 Structural models for the adsorption of CO on Pd(111) at a surface fractional coverage of (a) θ=1/3. the properties of the system will be a simple combination of those of the two molecules adsorbed separately. demonstrates an important point. to a coverage greater than one-third of a monolayer (θ = 1/3). dissociative oxygen adsorption does occur. The fact that this is not the case. If CO is adsorbed first. Page 18 of 71 2nd March 2016 http://www. subsequent oxygen adsorption is completely blocked. Oxidation will then take place only at the boundaries between domains. Figure 8 The surface structure of O atoms adsorbed on Pd(111) at maximum surface coverage View answer . θ.

How does this simplify consideration of the above reactions? View discussion .The three-way catalytic converter Figure 9 Schematic representation of domains of CO(ad) and O(ad) on Pd(111). At first. These mixed domains bring CO(ad) and O(ad) into intimate contact. there are two such possibilities: Activity 3 Experiments show that exposure of a surface saturated with adsorbed CO to gas-phase O2 does not lead to CO2 formation. This is clear evidence for a Langmuir–Hinshelwood . an electronegative O atom will withdraw charge from the surface. and would have fallen continuously as the oxygen layer was consumed by the reaction. the surface will withdraw charge from neighbouring Pd–CO bonds.Activity 3 We can make a decision about reaction 9 on the basis of the information provided in Figure 10. in which the rate-limiting step involves reaction between an adsorbed species and a molecule in the gas phase. Page 19 of 71 2nd March 2016 http://www. First. the adsorbed CO is found in separate areas (as when CO is adsorbed first). subsequent CO adsorption occurs readily and compresses the O atoms into domains in which the local coverage reaches θ = 1/3. we are almost in a position to propose a detailed mechanism. When oxygen is adsorbed first to its maximum coverage. rapid CO oxidation can occur by way of a Langmuir–Hinshelwood type process (a surface reaction between two adsorbed species). In this case. we must consider the possibility of an alternative Eley–Rideal type mechanism. containing both CO and O. with the O atoms at twice the surface concentration possible in the absence of CO. If reaction 9 had been operative. Figure 10 shows that the rate became significant only after a population of CO had built up on the surface. θ = 1/4. (b) mixed domains (O2 adsorbed first). the stoichiometry is now that required for the oxidation reaction. Having thus established that. on Pd(111). but as more is added mixed domains form. each at a local coverage of θ = 1/2 (Figure 9b). A Pd(111) surface presaturated with a quarter of a monolayer of O atoms was exposed to a beam of gaseous CO. and the surface coverages and the oxidation rate were monitored with time. the rate would have been high initially. however. (a) Separate domains (CO adsorbed first). The net result is that the mixed domain is highly reactive and generates CO2 at temperatures far below room temperature. Thus. In turn. weakening them and so making the CO more readily available for reaction. and it reached a maximum when the coverages of O and CO were approximately equal.

But just how relevant are these surface studies to the practical catalysis taking place in the converter? Activity 4 How do the observations outlined below lead to the conclusion that studies of CO oxidation. such as those for Pd(111) can be of direct relevance to the catalysis taking place in the converter? Page 20 of 71 2nd March 2016 http://www.9×10 −11 atm. the mechanism finally proposed for CO oxidation on Pd(111) is deceptively simple: Although the exact nature of the surface intermediates is still not known.The three-way catalytic converter Figure 10 Changes in the rate of CO2 formation from CO and in the surface density of oxygen and CO on Pd(111). and then exposed to a constant stream of CO at a pressure of 7. using surface-science techniques such as LEED. The surface was precovered with a quarter of a monolayer of oxygen atoms at time zero. Given the research effort that was involved. the depth of understanding of the catalytic mechanism is quite an .

so that the surface is clean. depending only on the ratio of the partial pressures of CO and three-way catalytic converter  During the reaction. Figure 12 shows that in the case of rhodium there is excellent agreement between the rates of CO oxidation over a Rh(111) single crystal surface and over a Rh/Al2O3 catalyst. surface contaminants such as carbon or sulfur are burnt off the Pd catalyst.  The rate of CO oxidation is independent of pressure. with the exception of the adsorbed reactants. View discussion . Figure 11 Rates for the catalytic oxidation of CO over a variety of different Pd surfaces. is shown to be virtually identical on five different Pd surfaces. over a wide temperature range.Activity 4 . at least over a restricted range of conditions. Page 21 of 71 2nd March 2016 http://www. This is illustrated in Figure 11 where the rate of CO oxidation.  The catalytic activity does not depend on the crystallographic structure of the Pd metal surface.

it is the Pt that is mainly responsible for CO oxidation.The three-way catalytic converter Figure 12 Comparison of the rates for CO oxidation measured over Rh(111) (black) and over 0. In in which Pt constitutes 80–90% of the noble metal composition and Rh the remainder. Page 22 of 71 2nd March 2016 http://www. Under these circumstances.01 mass % Rh/Al2O3 (green) at p(CO)=p(O2)=0. Langmuir–Hinshelwood kinetics can be applied. and the segregation of the reactants in surface domains. as a function of temperature. complicates the detailed modelling of the kinetics. Figure 13 shows the comparative performance of single-metal catalysts for the oxidation of CO at a fixed .01 atm. The non-uniformity of the surface. the overall kinetics of the CO oxidation reaction is not. all three of the platinum group metals present in automotive catalysts are active for CO oxidation. results have shown that Rh may improve low-temperature activity. Evidently. In the current (1996) three-way catalyst used in the UK. when they are found to be randomly distributed over the surface and so satisfy one of the criteria for applicability of the Langmuir isotherm. The exception is the special case of low surface coverages of CO and O atoms. Although the sequence of elementary steps is quite simple.

The three-way catalytic converter Figure 13 Comparison of catalytic activity for CO oxidation at 400 °C for Pt.  via the water-gas shift reaction (equation 2). although the water-gas shift reaction removes CO.4. The hydrogen produced in this reaction will react. which will remove any O2 present: Page 23 of 71 2nd March 2016 . with any oxygen present. with ceria acting as an excellent promoter. conversion can also occur by one of the following routes: via the CO + NO redox reaction (reaction 6).open. Pt/CeO2–Al2O3 and Pt-Rh/CeO2–Al2O3 are particularly active combinations for the removal of CO under slightly fuel-rich conditions. This will be discussed in detail in section 4. because H2O is present in the exhaust gases as a product of combustion:  The water-gas shift reaction is catalysed by Pt and/or Rh. it also inhibits CO oxidation by producing hydrogen. Pd and Rh at different A/F ratios Under stoichiometric or slightly fuel-rich (reducing) conditions. where there is insufficient oxygen present to oxidise all of the CO. Hence. in preference to CO.

open.The three-way catalytic converter 4. in the current (1996) UK three-way catalytic converter. and we shall not consider it in any detail.3. Again (as in the case of CO).edu/openlearn/science-maths-technology/science/chemistry/the-three-way-catalyticconverter/content-section-0 . and they can also react with water vapour to produce CO and H2 – a reaction known as steam reforming: Page 24 of 71 2nd March 2016 http://www. Figure 14 Comparison of catalytic activity for HC oxidation at 400 °C for Pt. Pd and Pt all give high conversions for A/F ratios at and above stoichiometry.3 Removal of hydrocarbons Figure 14 shows a comparative study for hydrocarbon oxidation over single-metal catalysts: it can be seen that Rh. Pt is the main component responsible for oxidation of the hydrocarbons. The subsequent oxidation process is thought to be considerably more complicated than the oxidation of CO. whereas unsaturated and aromatic hydrocarbons adsorb either dissociatively or associatively as -complexes. alkane adsorption is dissociative. hydrocarbons compete effectively with CO for oxygen. Pd and Rh at different A/F ratios When the engine exhaust gas composition is reducing (fuel-rich). On noble metal surfaces.

a variety of products can be formed. For simplicity we shall consider only reduction with CO. N2O or NH3: Activity 5 Which reactions should a catalyst ideally promote? View discussion . thus reducing the amount of oxygen available to react with hydrocarbons and . as with the oxidation reaction. NO can be removed by reduction with CO and/or hydrocarbons. Pt and Pd are shown in Figure 5 The NOx activities of Rh. the H2 produced may react preferentially with any O2 present. In principle. particularly under net reducing conditions (low A/F).3. the situation with hydrocarbons is considerably more complicated. the combination Pt–Rh/CeO2–Al2O3 is particularly active. When the A/F ratio is stoichiometric (or below stoichiometry). under the conditions in the catalytic converter. As we noted earlier. It is evident that Rh has the highest activity. specifically: In addition.The three-way catalytic converter This is catalysed by Rh and/or Pt with ceria and. the decomposition of NO to O2 and N2 over noble metal catalysts is too slow to be significant. H2 produced from the water-gas shift or steam reforming reactions can reduce NO to N2. Page 25 of 71 2nd March 2016 http://www. 4. we need to consider the mechanism of the reaction. So why is Rh superior? To answer this question. the CO produced adds to the burden of carbon monoxide to be removed. In addition.4 Removal of NO Laboratory experiments have shown that. as in the case of the water-gas shift reaction.

that all products are desorbed as quickly as they are produced. but the exact mechanism is still Pt and Pd at different A/F ratios. will be formed initially. however. as NO is in fact first adsorbed associatively and then dissociates on the surface. You should recognise. The N atoms can combine to give N2. These and other processes that may be involved are listed below. (You should note that although we describe this as dissociative chemisorption strictly it does not meet the definition. no matter how transient. The catalytic reduction of NO by CO and/or H2 over a variety of surfaces has been the subject of a great deal of research.The three-way catalytic converter Figure 15 Comparison of catalytic activity for NOx reduction at 400 °C over Rh. Page 26 of 71 2nd March 2016 . for simplicity. One view is that the first step is the dissociative chemisorption of NO.) The O atoms produced are then removed by the reducing agents CO or H2. react with chemisorbed NO to give N2O (particularly important at low temperatures). Application of various surface-science techniques has provided some understanding of the elementary steps involved. or react with chemisorbed H atoms to form NH3. Adsorption Dissociation NO(ad) N(ad) + O(ad) In the following steps we have assumed. that adsorbed species.

01 mass % Rh/Al2O3 (green) at p(CO)=p(NO)=0.The three-way catalytic converter Surface reactions and desorption Reactions with hydrogen Figure 16 compares the rate of the NO–CO reaction over a Rh(111) single crystal with that over a Rh/Al2O3-supported .open. Figure 16 Comparison of the rates for the NO–CO reaction measured over Rh(111) (black) and over 0.01 atm. as a function of temperature Activity 6 Page 27 of 71 2nd March 2016 http://www.

involving a different overall mechanism.The three-way catalytic converter After the reaction on Rh(111). Although this process may occur on surfaces that are extensive on the atomic we might expect the rate-limiting steps and the observed kinetics in the cases of Rh(111) and supported Rh to be different. the surface was found to have a high coverage of N atoms. the concentration of NO(ad) increases and reactions 22 and 23 would then be expected to contribute to N atom removal. it has been argued that such mobility will be insignificant on or between the small highly dispersed particles of Rh in the automotive catalyst. The elementary steps 21–23 all require surface mobility of N atoms (to encounter either NO(ad) or other adsorbed N atoms). which have been taken as evidence of a dinitrosyl species.Activity 6 This seems to be the case. O=N–N=O. What then is the rate-limiting step with the supported catalyst? One suggestion is NO dissociation (reaction 19) but there is a more radical alternative. particularly at higher temperatures. The Arrhenius-type plots in Figure 16 confirm that this is so: over Rh/ . such as those of single crystals or large supported crystallites. Therefore. At lower temperatures. What does this suggest about the mechanism? View discussion . formed by reaction 26: Page 28 of 71 2nd March 2016 http://www. the reaction has a higher activation energy (the plot in Figure 16 has a larger gradient) and a lower rate (at a given temperature) than over Rh(111). Infrared spectra for NO adsorbed on Rh/Al2O3 (Figure 17) show bands at 1 743 cm−1 and 1 825 cm−1.

the dinitrosyl species is thought to lose its two oxygen atoms by way of an N2O or NO dissociation followed by N-atom combination and N2 desorption – Page 29 of 71 2nd March 2016 . recorded at 300 K. other than diffusion of N(ad).The three-way catalytic converter Figure 17 Infrared spectra. of accomplishing the most important task in the reduction of NO. for NO adsorbed on Rh/Al 2O3 as a function of NO coverage. The bands at 1 743 cm −1 and 1 825 cm−1 have been assigned to the dinitrosyl species O=N–N=O. namely the pairing of two nitrogen atoms on the surface. This step provides a means. for example: To summarise Whichever mechanism is correct – NO pairing to form a dinitrosyl species. Once formed. increasing from spectrum A to spectrum D.

Os and Canada and the USA. with Pt. In South Africa. or 0. (b) Schematic energy-level diagram showing the highest occupied level of Rh and the lowest vacant level of Pt. For Pt (and also Pd). Figure 18 (a) The partial orbital energy-level diagram of molecular NO. weakening the N–O bond and hence facilitating dissociation. Pd and Rh form part of the platinum group metals. This picture provides an appealingly simple explanation for the observation that rhodium is the most active of the noble metals for NOx removal. they are also less selective. Vacant metal levels lie at energies below that of NO 2 *. promoting ammonia formation (reaction 17).1–0. highly dispersed over the surface – but even so. in relation to the 2π* molecular orbital of NO. and occur together in nature. for example. the former USSR. the situation is reversed. this charge would be used to coordinate the two NO molecules. catalytic converters account for around 90% of world rhodium demand (see Box 1).2 g.The three-way catalytic converter both require catalytic sites that can not only bind NO but also donate charge to the adsorbate. Box 1 Supply and demand of precious metals Pt. that of rhodium is found to be particularly suitable for facilitating charge transfer to adsorbed NO. and are found in only a few comparatively concentrated deposits – principally in South Africa. so charge will drain from this orbital to the surface. Because it is so active. Page 30 of 71 2nd March 2016 http://www. deposits are mined specifically for the platinum group metals. particularly undernet reducing conditions (Figure 15). however. whereas in Canada and the former USSR. the amount required is small – about 0. In the second . along with Ru. they are produced as byproducts from nickel and copper mining. The metals are all quite rare. Rhodium is therefore the essential ingredient in the automotive catalyst for NOx control. they are closely related in terms of chemical and physical properties. with the uppermost occupied electron levels of the metal at higher energy than the partially vacant 2 * antibonding orbital of NO (Figure 18). not only do Pt and Pd show lower activities. it would be transferred into the partially vacant 2 * antibonding orbital of NO (Figure 18).1 mass % of the catalyst. On examining the electronic structures of the noble metals. In the first case. In fact. strengthening the N–O bond.

the shortfall in Rh came. CO– NO–O2 and CO–NO mixtures The concentration of each of the reactants was 0. together with the costs incurred in refining the metals to the high purity kinetic experiments have demonstrated that NO has a strong inhibiting effect on the rate of the reaction of CO with O2: Figure 19 illustrates the point for a Rh/Al2O3 catalyst. for example. Figure 19 The temperature dependence of CO conversion rates over 0. Up to date prices of precious metals are always available on the world wide web. for . occur simultaneously in the presence of all the other exhaust constituents. jewellery.5 Postscript It is important to remember that the reactions discussed in sections 4. the percentage of total demand being 87% for Rh and 34% for Pt (1992). Automotive catalysts are a major application for platinum group metals.2–4. Because the ratio of Rh to Pt used in automotive catalysts is richer than the mine ratio. are so chemically similar in nature. makes their production an expensive business. and their compounds.01 mass % Rh/Al 2O3 in CO–O2. 4. with a price of approximately $18 250 per kg in July 1995 (compared with Pt ($15 300) and Pd ($5 500)).The three-way catalytic converter Separation of the metals is a long and difficult process because they. In addition. This difficulty in separation. This may have an effect on the efficiency of the individual reactions.3. For example.5 vol % in all cases. and often studied separately. until recently. Rhodium is essentially a by-product of platinum mining. huge amounts of the ore have to be mined and processed. Page 31 of 71 2nd March 2016 http://www. it takes approximately 350 kg of South African ore to yield just 1 g of platinum. and is by far the most expensive metal in the platinum group. from Pt mined for other uses.4.

Activity 8 Page 32 of 71 2nd March 2016 http://www. compare the temperatures at which each reaction reaches a rate of 1×10−6 mol CO (g cat)−1 s−1 (the dotted line) View discussion . Activity 8 What is the effect of CeO2 on the conversion efficiencies for CO. HC and NOx.3.Activity 7 4. The green lines show the conversions for the Pt catalyst with CeO 2 and the black lines those without. Figure 20 The effects of adding CeO2 to a Pt catalyst in terms of the simultaneous conversion of CO. hydrocarbons and NOx? View discussion .The three-way catalytic converter Activity 7 With reference to Figure 19.6 The role of CeO2 Figure 20 shows the effect on performance of adding CeO2 to a Pt catalyst for threeway catalytic conversion.

(Lanthanum oxide and/or barium oxide are also often added as stabilisers to help maintain the surface area of γ-Al2O3.The three-way catalytic converter Thus.9 mass % Pt/Al2O3 Activity 9 How does the addition of ceria to the catalyst (the coloured line in Figure 21) affect the Pt dispersion? View discussion . Figure 21 emphasises this point. with (green) and without (black) the addition of CeO2 to 0. for reaction with CO. it effectively dampens the variations in the A/F ratio as the exhaust gas mixture cycles about stoichiometry. Figure 21 The variation of dispersion stability as a function of ageing temperature. and hence promotes CO removal via the following reaction under fuel-rich conditions: Page 33 of 71 2nd March 2016 http://www.) 2: Ceria is known to be able to pick up and store oxygen from the gas phase under fuel-lean operating conditions (excess oxygen) – thus promoting the reduction of NO to N2 – and to release it under fuel-rich conditions (excess fuel). which is added with the alumina in the washcoat.Activity 9 Ceria also stabilises the γ-Al2O3 used in the support. the ceria also enhances the water-gas shift activity of Pt–Rh three-way . 3: As we have seen in section 4. thereby helping to keep operation within the desired window for optimum conversion over the catalyst. Thus. inhibiting a phase change to Al2O3. H2 or hydrocarbons. It plays a number of roles: 1: Ceria is a structural which has a lower surface area. stabilising the precious metals and alumina against sintering and particle growth. ceria. is an essential ingredient of the three-way catalyst.

under fuel-rich conditions.08 mass % Pt-Rha catalyst on γ-Al2O3 with 1.5. 7 4 0 0 9 m as s % Ce Page 34 of 71 2nd March 2016 http://www.0 and 8. 4.The three-way catalytic converter The point is illustrated by the results shown in Table 1 for CO conversion under fuel-rich conditions.18 mass %.) CO con vers ion/ % WW it it h h Ho 2 u Ot H 2 O 1. with and without water present.0 mass % Ce levels.) Table 1 CO conversion for a 1. Increasing the ceria content of the catalyst in the absence of water has no .9 mass % and Rh 0. 6 4 0 4 9 m as s % Ce 8. (aPt 0. (Addition of ceria also leads to an improvement in activity for steam but when water is present the water-gas shift reaction becomes increasingly important. 5 4 5 4 9 m as s % Ce 4.

Under slightly fuel-rich conditions. SAQ 4 What are the major roles proposed for the different components of the Pt-Rh/CeO2– Al2O3 three-way catalyst? View answer . C3H6 and NO at low temperatures have also been observed for Pt/CeO2 catalysts that have undergone a reducing pretreatment. to form CO2. It would be a good plan to try them. 5. 4. Dissociatively adsorbed O atoms undergo a surface reaction with adsorbed CO. Study comment The following SAQs invite you to collect together the different roles proposed for each component of the three-way catalyst. storing oxygen under fuel-lean conditions. 4. causing an increase in the number and activity of the active sites. where there is insufficient oxygen present for complete oxidation. and releasing it under fuel-rich conditions. stabilising both the noble metals and the support against particle growth and sintering. and as such is currently an essential ingredient of the three-way catalyst.7 Chemical reactions: summary 1. Whatever the detailed mechanism. 2. Rh is particularly active for this reaction. or by pairing of NO(ad) to give a dinitrosyl species. The NO-CO redox reaction is believed to proceed either by dissociation of NO(ad) followed by N atom combination.3. it is a promoter for the water-gas shift and steam reforming reactions and it can enhance the lowtemperature activity of the catalyst after certain types of pretreatment. before moving on. and check your answers. Both CO and hydrocarbons can be removed by reaction with NO under stoichiometric or fuel-rich conditions. followed by dissociation. CO can be removed by the water-gas shift reaction. 3.SAQ 4 SAQ 5 Page 35 of 71 2nd March 2016 http://www. Hydrocarbons can be removed by oxidation or by reaction with water (a process known as steam reforming).open. Ceria plays a number of important roles in the three-way catalyst: it is a structural promoter. using water produced in the combustion process in the . Surface studies of the adsorption of CO and O2 on single crystals and model catalysts have led to the development of a possible mechanism for the oxidation of CO. it is an oxygen-storage component. This is promoted by ceria. This is believed to be due to an interaction between Pt and CeO2 induced by the reduction.The three-way catalytic converter 4: Enhanced conversions of CO.

The three-way catalytic converter In Figures 13. three-way catalysts must currently (1996) meet emission standards for a life of 50. However. and trying to understand its nature. very high temperatures may be experienced if the catalyst is ‘close coupled’ to the engine. which also stabilises the alumina Page 36 of 71 2nd March 2016 http://www. has included post-mortem examinations of used catalysts.1 Introduction In the UK. and into the entire emission control system in the vehicle. Pd in its fresh state is seen to be superior to Pt for the conversion of all three pollutants.2 Thermal effects Exhaust catalysts usually operate in the temperature range 150–600 °C. and poisoning by contaminants in the exhaust (notably phosphorus. Such sintering particularly affects the low-temperature activity of the catalyst. The major causes of deterioration are thermal damage (due to exposure of the catalyst to high temperatures). It can be countered to some extent by the addition of ceria as a structural promoter. so that as the catalyst slowly deactivates. the catalyst may be exposed to conditions that result in more severe deactivation above and beyond that which is ‘allowed for’ in its lifetime. and simulated ageing studies. The conditions that can produce such high temperatures include repeated misfire (resulting in the oxidation of large amounts of unburned fuel over the catalyst) and high driving in which the catalyst is exposed to high temperatures or catalyst poisons.5. The noble metal particles may sinter (recall Figure 21 in section 4. which is one of the possible solutions to the cold-start problem. especially under oxidising conditions. lead and sulfur).000 miles.6).5 Catalyst deterioration 4.SAQ 5 4. Indeed the ability to withstand mild deactivation is built into the design of the catalyst. This is done by setting up vehicles at efficiencies well above the legal requirements at low mileage. 4. research efforts and legislation are set to double this requirement in the very near future to the current US standard of 100. what possible reason can you suggest for the current widespread use of Pt in threeway catalysts. however. rather than Pd? View answer .edu/openlearn/science-maths-technology/science/chemistry/the-three-way-catalyticconverter/content-section-0 . but they can experience temperatures of up to 1000 °C. Although commercial catalysts are designed to withstand occasional high-temperature operation prolonged and repeated exposure to temperatures in excess of 800 °C. High temperatures may affect all the components of the catalyst. 14 and 15. resulting in a decrease in the fraction of the metal available for catalytic reactions.000 miles. have a number of serious effects. The catalysts do deactivate with use. it will still meet the emission standards. In addition. Research aimed at detecting deterioration. Considering the properties we require of a catalyst.5.

edu/openlearn/science-maths-technology/science/chemistry/the-three-way-catalyticconverter/content-section-0 . This can be inhibited by the addition of barium and zirconium. the ceria may itself undergo crystallite growth at elevated temperatures. Figure 22 Comparison of catalytic activity for a Pt–Rh/CeO2 catalyst with (green) and without (black) the addition of Ba and Zr. after ageing at A/F=16. Mechanical loss of catalyst support material may also occur in cases where the washcoat shrinks and cracks. At very high temperatures the support may itself sinter or even undergo a phase change. Again. affecting the total surface area.5 at 950 °C for 40 hours. as shown by the comparison in Figure 22: it is apparent that barium and zirconium help to stabilise the catalytic activity. the problem can be overcome by incorporating so called ‘phase stabilisers’ – examples include barium and lanthanum – into the washcoat (Figure 23b). forming additional channels that may allow the exhaust gases to pass through the converter without contacting the catalyst. Page 37 of 71 2nd March 2016 http://www. At excessively high temperatures the ceramic monolith may even melt. causing it to separate from the monolith (Figure 23a).The three-way catalytic converter support against sintering.

ZrO2. This subsurface penetration and loss of active Rh can be slowed down if the reactivity of the support is minimised by first supporting the Rh on zirconia. Unfortunately. In (a) sintering has caused severe . whereas in (b) the addition of ‘phase stabilisers’ has prevented shrinkage cracking. whereas that of the standard Rh/γ-Al2O3 catalyst (a) is seriously diminished. and then incorporating the resulting powder into the γ-Al2O3 washcoat. or between a noble metal and base metals in the washcoat support. 4. In which are not yet suitable for high-speed production. High temperatures can also promote damaging interactions between the noble metals. An alternative approach has been suggested by work that indicates that the Rh/Al2O3 interaction may occur preferentially at the grain boundaries of the support. it has been established that Rh begins to penetrate the surface of γ-Al2O3 at temperatures greater than 600° C by a solid state reaction between Rh2O3 and γ-Al2O3. resulting in the formation of a less active alloy. The activity of the ZrO 2-supported catalyst (b) remains virtually intact after the calcination. Figure 24 shows the dramatic effect this can have on the catalytic activity of a Rh/γ-Al2O3 catalyst.3 The effect of poisons Page 38 of 71 2nd March 2016 http://www.5.The three-way catalytic converter Figure 23 Optical micrographs of a washcoat after exposure to high temperatures. Figure 24 Schematic comparison of the catalytic activity of (a) Rh/γ-Al 2O3 and (b) [Rh/ZrO2]/γ-Al2O3 after thermal treatment at 1 100 °C in air for 1 h. the incorporation of Rh/ZrO2 into three-way catalysts requires complex manufacturing methods. Ceria can be incorporated as a stabilizer into the alumina in an attempt to preferentially block this interaction.

the conversion efficiencies for the hydrocarbons (Figure 25b). particularly in the early days of the converter.000 miles of vehicle operation. Following the misfuelling. By contrast. and there have been many Page 39 of 71 2nd March 2016 http://www. and hence did not meet the emission regulations current at the time (1986). 95% for CO and 66% for NOx.26 g l−1) during 15. Figure 25 Effect of intermittent use of leaded petrol (black points) on catalyst efficiency (for a typical threeway catalyst) for the conversion of (a) CO (b) HC and (c) NO x. did not recover to passable values. The efficiency of a control vehicle (unleaded petrol only) was virtually unchanged at 94% for hydrocarbons.The three-way catalytic converter The use of catalytic converters was one of the major contributors to the phasing-in of unleaded petrol. intermittent operation with leaded fuel (0. and especially NOx (Figure 25c). the CO-conversion efficiency (Figure 25a) decreased. Figure 25 shows how the activity of a typical three-way catalyst is impaired . and following. of people disabling the catalyst by misfuelling. Lead in petrol is a severe poison for the catalyst. but subsequently recovered to an acceptable level.

edu/openlearn/science-maths-technology/science/chemistry/the-three-way-catalyticconverter/content-section-0 . which. With which element. it can combine with lead oxide to form a stable lead sulfate. and present in the exhaust mixture) to SO3: indeed. is Pb associated? View discussion .5. although a poison itself. The whiter the area on the map.4 Phosphorus Page 40 of 71 2nd March 2016 http://www. in the form of SO3. The fact that Pt is more resistant to lead poisoning than Rh or Pd is largely due to an indirect effect. Activity 10 Figure 26 shows electron probe elemental maps of Pt/γ-Al2O3 after exposure to a simulated exhaust gas mixture containing 0. Clues to the mechanism of lead poisoning have come from model systems. and Pt is by far the most resistant. Only Pt.Activity 10 Figure 26 Electron probe elemental maps of Pt/γ-Al2O3 after exposure to Pb for 24 hours at 700 °C. The small amount of sulfur also present in fuel can act as a scavenger for lead. it is used for this purpose in the industrial production of sulfuric acid. is a good catalyst for the oxidation of SO2 (produced from sulfur in the combustion reaction. Pt or Al. Rh is slightly less susceptible. however. This deposition of lead specifically onto the noble metal is believed to occur because the molecules that ‘carry’ the lead out of the engine. 4. EPMA allows quantitative determination of the composition of solids with a resolution of the order of 1 μm. the higher the concentration of the element under study. is not site-specific.The three-way catalytic converter Of the various noble metal components. decompose on the noble metal. Pd is the most sensitive to lead poisoning. which are amenable to detailed surface analysis. leaving the lead on the surface.33 g l−1 of Pb. Provided that the sulfur is in its hexavalent oxidation state (SVI). probably halides or oxyhalides. The X-ray spectrophotometer is a common attachment on scanning and transmission electron microscopes. Electron probe microanalysis (EPMA) is based on the emission of ‘characteristic’ X-ray photons following the ionisation of atoms by high-energy electrons. Its activity decreases when there are just trace amounts in the

and it is this susceptibility to poisoning that limits its use in the UK at the moment. and M is the metal content of the catalyst (proportional to the total number of metal atoms).5 Sulfur Deactivation The presence of sulfur in the exhaust gas mixture causes a reduction in the activity of the three-way catalyst. and oils with reduced levels are appearing on the market. and their ability to recover from it. with which phosphorus may form an alloy. however. let alone that which will apply in the future. where CO is the amount of CO chemisorbed by a fixed mass of catalyst (proportional to the number of surface metal atoms). Some understanding of the mechanism of catalyst deactivation by sulfur has been obtained by examining the effects of SO2 on the surface area of metals The physical adsorption of N2 can be used to determine the ‘total’ surface area of a catalyst. base-metal oxidation catalysts. under development for the US market – where there are stricter controls over the contaminant levels in fuel. 4. could achieve a reduction in emissions from vehicles currently in use. It is typically expressed as the ratio CO/M. even if all the sulfur in fuel were to be removed. it is unlikely that base-metal activity (or durability) would be sufficient to meet emission control requirements. phosphorus levels in engine oil are becoming an issue. The general resistance of Pt and Rh to sulfur poisoning. Notice. Phosphorus derived from the engine oil is believed to react with the alumina support.) Pd is more susceptible to long-term damage. were two of the factors in the original decision in the 1970s to use noble metals rather than the less active.5. however. Sulfur also decreases the efficiency of NOx removal. This deactivation is particularly important for Pd. the higher the surface area of the metal.The three-way catalytic converter Phosphorus is recognised as a potential poison for automotive catalysts. but cheaper. This is significant because it suggests that a change in the sulfur content of fuel (average 208 mg l−1 in the UK). The deleterious effect of exposure to SO2 on the catalytic activity of a commercial monolithic catalyst (Pt–Rh/CeO2–Al2O3) is evident in Figure 27. The phosphorus level in fuel is generally very low (2×10−5 g l−1). and also to reduce the activity of the noble metal component. (In terms of the more stringent legislation now in force. particularly for the water-gas shift and steam reforming reactions – processes that are important mechanisms for the removal of CO and hydrocarbons under fuel-rich conditions. that the conversion efficiency recovers quite rapidly once the sulfur has been removed from the gas stream. Pd-only catalysts . Table 2 gives values of the CO Page 41 of 71 2nd March 2016 http://www.2 g l−1). but it is present in higher concentrations in engine oils (1. At the time of writing. Figure 27 Interactive content is not available in this format. The capacity of a supported metal catalyst to chemisorb CO can be used as a measure of the free metal surface The higher the value of CO/M.

open. 0.79. in the presence and absence of SO2. 0 2 7 0 8 55 . 0 1 3 0 9 Activity 11 What is the effect of SO2 on the chemisorption capacity of the catalyst? What do you suggest is happening to the metal surface in the presence of SO2? Page 42 of 71 2nd March 2016 http://www. 0. A ge in g te m pe ra tu re/ °C CO /M afte r agei ng I I n n t t h h e e p a re b se se n n c c e e of of S S OO 2 2 40 0.The three-way catalytic converter chemisorption capacity of a Pt–Rh/CeO2–Al2O3 model catalyst after ageing in a fuelrich mixture. 0. Table 2 Effect of fuel-rich ageing on the metal-surface area (expressed as CO/M) for a Pt–Rh/CeO2–Al2O3 catalyst. The value of CO/M for a fresh sample is 0. in the presence and absence of SO2. 0 1 6 2 9 70 0.

are larger than expected. Table 3 XPS data recorded for various cerium and sulfur compounds.Activity 11 Because the effects are not permanent. when the gas-surface equilibrium is shifted in favour of the gas-phase by removal of SO2 from the gaseous mixture (Figure 27). and the sulfur storage by the catalyst has been found to increase with increasing Ce content. there has been a great deal of interest in the interactions of sulfur with the three-way catalyst. sulfur in the fuel is released to the exhaust gases as SO2. this is converted into H2S over Pt. the suggested mechanism involving the formation of the metal sulfide as a reaction intermediate. However. and the activity of the catalyst is regenerated. however. that the amounts of H2S generated when engine conditions become fuel-rich. Under fuel-rich (reducing) conditions. As a result it is desorbed. The catalyst can apparently ‘store’ sulfur under lean conditions and release it under rich conditions. the odour of hydrogen sulfide (H2S). XPS studies (some results of which are collected in Table 3) have been used to study the nature of the species involved. has been an issue. adsorption studies with both model catalysts and the commercial (fully formulated) catalyst have shown that sulfur storage under lean conditions can occur by interaction of SO2 with both CeO2 and Al2O3 in the support. CeO2 provides the preferred adsorption but rather because of a smelly side-effect. say) or decelerates sharply after cruising. 8 air . Ever since catalytic converters were introduced. Page 43 of 71 2nd March 2016 http://www. This is particularly noticeable when a car in front accelerates after idling (at traffic lights or a roundabout. described as ‘smelling like rotten eggs’. following prolonged running under fuel-lean (or oxidising) conditions. not so much because of its impact on activity. The production of hydrogen sulfide Recently.The three-way catalytic converter View discussion . The noble metals do not retain any sulfur under these conditions. After combustion in the engine. Sa Hist Bin m ory din pl g e ene rgy/ eV CS e 2 3 p d Ce 550 8 – O2 °C. It has been found. Under typical conditions. this sulfur species is presumably relatively weakly adsorbed.

6 H2 O 8 – 8 8 6 SO2 1. how would you assign the sulfur species present when CeO2 is exposed to SO2 at 20 °C and 550 °C? View discussion .Activity 12 Activity 13 Page 44 of 71 2nd March 2016 http://www. 9 Activity 12 Comparing the S 2p binding energies with the typical values for SVI and SIV compounds included in Table 3. 3 – 1 6 7. 9 SIV co m po un ds – 1 6 . 5 – 1 6 8. 3 SVI co m po un ds – 1 6 8. 8. 8. 8 8 Ce (N O3 )3 . 6 0 Ce 550 8 1 O2 °C. 8 6 SO2 2.The three-way catalytic converter 7 Ce 20 8 1 O2 °C.

Activity 13 . and hence inhibits the formation of. Phosphorus appears to be a likely candidate. it has been proposed that a Ce–P–O species (possibly CePO4) is formed. This is believed to be a consequence of the considerable improvements made in catalyst activity over the years.6H2O. Page 45 of 71 2nd March 2016 http://www. At 550 °C the CeIV oxide. including S and Pb from the fuel. those that had been ‘on the road’ for 50. because it has been found that phosphorus-doped Pt–Rh/CeO2–Al2O3 catalysts exhibit a lower capacity for adsorption of SO2 than an undoped reference catalyst. it would seem that several different strategies could be used to reduce H2S emissions: (i) decreasing the Ce surface area (however. CeO2. interpretation of the XPS data suggests that. (iv) including an H2S scavenger in the catalyst (in the USA nickel is used. Examination of an aged catalyst revealed traces of the usual poisons. were much lower than those from the fresh catalyst. SO2 is adsorbed on CeO2. However. it was noted that H2S emissions from ‘engine-aged’ catalysts. what do you conclude about the Ce species present when CeO2 is exposed to SO2 at 20 °C and 550 °C? View discussion . This suggested that at least one of these components can reduce the storage of sulfur by the Pt–Rh/CeO2– Al2O3 system. Ce2(SO4)3). a Ce–S–O species (for example. and phosphorus (and zinc) from the engine oil. Indeed. which is more stable than. the sulfur is oxidised to SVI and the cerium is reduced to CeIII.000 miles. This suggests that the phosphorus is somehow ‘interfering’ with the component of the catalyst that adsorbs the SO2 – the ceria. and hence of reducing the size of the H2S spike on going from lean to rich conditions.The three-way catalytic converter Comparing the Ce 3d binding energies with those for CeO2 in air and for Ce(NO3)3. there has been an increase in the levels emitted in recent years. To summarise In view of the discussion above. (iii) reducing the sulfur content of the fuel. which are then converted into H2S over the noble metal component of the catalyst. at room temperature. The sulfate/sulfite species formed under fuel-lean conditions with the cerium and aluminium in the support decompose in fuel-rich conditions to release the SO2/SO3 species. appears to participate in a redox reaction with SO2. Ce2(SO4) that is. This would have the effect of reducing the storage capabilities of the ceria. possibly resulting in the formation of cerium(III) sulfate. during one study into this effect. (ii) improving the A/F control. Although it has been known for some time that automobile exhaust catalysts can produce H2S in fuel-rich exhaust streams. but in Europe this is prohibited because of concern that it could lead to the formation and release of carcinogenic nickel carbonyl). this will have detrimental effects on the catalyst activity). the H2S ‘spikes’ when going from lean to rich conditions were found to be much smaller on the engine-aged catalyst. Catalysts that do not contain noble metals do not produce H2S. possibly to form a sulfite species (that is. In addition. a species containing SIV).

It has been found that adsorption of SO2. The sulfur is believed to be stored as Ce2(SO4)3. forming a weakly adsorbed species that is desorbed when the sulfur is removed from the gas stream. and is believed to associate with the noble metal. It can cause deactivation of the catalyst. particularly for Pd. can also occur at high temperatures. SAQ 6 Refer back to the CO/M values listed in the final column of Table 2.5. The interaction between Rh2O3 and γ-Al2O3 can be slowed down by first supporting the Rh2O3 on ZrO2.6 Catalyst deterioration: summary 1. 7. are reduced in the presence of phosphorus. Sulfur can also be stored under fuel-lean conditions by Al2O3. 5. The preferential formation of a Ce–P–O species (possibly CePO4) inhibiting formation of the Ce–S–O species (Ce2(SO4)3) has been . 3. releasing SO2. Damaging interactions between the noble metals. 8. An ability to withstand mild deactivation is built into the design of the catalytic converter. which is believed to block sites on the metal this can be prevented to some extent by the addition of ceria as a structural promoter. 4. The major causes of deactivation are thermal damage and poisoning. in the support. On going to fuel-rich conditions.SAQ 6 Page 46 of 71 2nd March 2016 http://www. which is converted into H2S over the noble metal. Phosphorus from engine oil can contaminate the catalyst and cause deactivation. How would you explain the variation in these CO/M values with increasing ageing temperature? View answer . and especially CeO2. However. and it also leads to generation of H2S. or with the support. and hence the storage capabilities of a Pt– Rh/CeO2–Al2O3 catalyst. severe deactivation could prevent the system from meeting emissions legislation. Lead is a severe poison. this species decomposes. and released as H2S under fuel-rich conditions. Sulfur present in fuel has two major undesirable effects. High temperatures may cause sintering of the metals and/or the support. 2. 6. Sulfur is oxidised to SO2.The three-way catalytic converter 4.

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under licence.
Grateful acknowledgement is made to the following sources for permission to
reproduce material in this course:
Course image: Ray T in Flickr made available under Creative Commons
Attribution 2.0 Licence.
Figure 2 Nortier, P. and Soustelle, M. (1987) 'Alumina carriers for automotive
pollution control', in Cruecq, A. and Frennet, A. (eds) Catalysis and Automotive
Pollution Control, Elsevier Science Publishers;
Figure 3 Eggleston, H. S. et al. (1991) Corinair Working Group on
Emmision Factors for Calculating 1990 Emissions from Road Traffic,
Volume 1: Methodology and Emission Factors, Commission of the
European Communities;
Figure 4 Courtesy of Dr S. Golunski, Johnson Matthey;
Figure 5 Acres, C. J. K., Thomas, J. M. and Zamaraev, K. I. (1991) Perspectives
in Catalysis, Blackwell Science Ltd;
Figure 6 Reprinted from Catalysis and Automotive Pollution Control,
Gandhi, H. S. and Shelef, M. (1987) 'The role of research in the development of new
generation automotive catalysts', p. 200, with kind permission of Elsevier Science NL, Sara Burgerhartstraat 25, 1055 KV, Amsterdam, The Netherlands;
Figure 7 and 9 Reprinted from Surface Science, 76, (2), 1978, Conrad, H. et al.
'Interactions between oxygen and carbon monoxide on a palladium(III) surface';
Figure 8, 11 and 8A Reprinted from The Chemical Physics of Solid Surfaces
and Heterogeneous Catalysis, Volume 4, Engel,T. and Ertl, G. 'The role of
research in the development of new generation automotive catalysts', 1982, with kind
permission of Elsevier Science - NL, Sara Burgerhartstraat 25, 1055 KV, Amsterdam,
The Netherlands;
Figure 10 Engel, T. and Ertl, G. 'A molecular beam investigation of the catalytic
oxidation of CO on Pd(111)', Journal of Chemical Physics, 69, (3), August
1978, The American Institute of Physics;
Figure 12 and 16 Reprinted from Journal of Catalysis, 1986, 100, Oh, S. H. et
al. 'Comparative kinetic studies of CO-O2 and CO-NO reactions over single crystal
Page 50 of 71
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The three-way catalytic converter

and supported rhodium catalysts', p. 360, with kind permission of Elsevier Science NL, Sara Burgerhartstraat 25, 1055 KV, Amsterdam, The Netherlands;
Figure 13, 14, 15, 20 and 22 Reprinted from Catalysis Today, 1991, 10, Funabiki,
M. et al. 'Auto exhaust catalysts', pp. 34 and 35, with kind permission of Elsevier
Science - NL, Sara Burgerhartstraat 25, 1055 KV, Amsterdam, The Netherlands;
Figure 17 Liang, J. et al. 'FT-IR study of nitric oxide chemisorbed on Rh/Al2O3',
Journal of Physical Chemistry, 89, 1985, American Chemical Society;
Figure 19 Reprinted from Journal of Catalysis, 1986, 101, Oh, S. H. and
Carpenter, J. E. 'Role of nitric oxide in inhibiting carbon dioxide over aluminasupported rhodium', p. 114, with kind permission of Elsevier Science - NL, Sara
Burgerhartstraat 25, 1055 KV, Amsterdam, The Netherlands;
Figure 21 Reprinted from Catalysis and Automotive Pollution Control II,
1991, Diwell, A. F. et al. 'The role of ceria in three-way catalysts', p. 142, with kind
permission of Elsevier Science - NL, Sara Burgerhartstraat 25, 1055 KV, Amsterdam,
The Netherlands;
Figure 23 Courtesy of Johnson Matthey;
Figure 24 Society of Automotive Engineers (1980) SAE Paper 800843, Copyright
© 1980 Society of Automotive Engineers, Inc.;
Figure 25 McIntyre, B. R. and Faix, L. J. (1986) 'Lead detection in Catalytic emission
systems and effects on emissions', SAE Paper 860488, Copyright © 1986 Society
of Automotive Engineers, Inc.;
Figure 26 Shelef, M. (1987) 'The role of research in the development of new
generation automotive catalysts', in Cruecq, A. and Frennet, A. (eds) Catalysis and
Automotive Pollution Control, Elsevier Science Publishers;
Figure 27 Reprinted from Catalysis and Automotive Pollution Control II,
1991, Monroe, D. R. et al. 'The effect of sulfur on three-way catalysts', p. 612, with
kind permission of Elsevier Science - NL, Sara Burgerhartstraat 25, 1055 KV,
Amsterdam, The Netherlands;
Table 1 Reprinted from Catalysis and Automotive Pollution Control II,
1991, Diwell, A. F. et al. 'The role of ceria in the three-way catalysts', p. 145, with
kind permission of Elsevier Science - NL, Sara Burgerhartstraat 25, 1055 KV,
Amsterdam, The Netherlands;
Table 2 Ansell, G. P. et al. (1991) 'Effects of SO2 on the alkane activity of three-way
catalysts', Catalysis Letters, 11, p. 187, © J. C. Baltzer A.G. Scientific Publishing
Page 51 of 71
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SAE Paper 872163. F. you may be interested in joining the millions of people who discover our free learning resources and qualifications by visiting The Open University .edu/openlearn/science-maths-technology/science/chemistry/the-three-way-catalyticconverter/content-section-0 . three-way catalytic converter Table 3 Diwell. et al. Copyright © 1987 Society of Automotive Engineers. Don't miss out: If reading this text has inspired you to learn more.www. We gratefully acknowledge the help of Dr Stan Golunski and Dr Andrew Walker in the preparation of the original material. (1987) 'The impact of sulphar storage on emissions from three-way catalysts' Page 52 of 71 2nd March 2016 http://www.

edu/openlearn/science-maths-technology/science/chemistry/the-three-way-catalyticconverter/content-section-0 .26 = 15. the A/F mass ratio for complete combustion is: A/F = 1 801/114.5 (32. because we have used a very simplified system.7:1.8:1 This is as close as you would expect to the experimental value of 14.02) g = 1 801 g. Assuming air to be approximately 20% O2 and 80% N2 (by volume). We had not included NO as an oxidant or the other hydrocarbons. Back Page 53 of 71 2nd March 2016 http://www. Thus. not the real mix of hydrocarbons in petrol. The mass of 1 mol of octane is (8 × + 4 × 28. CO or H2 as reductants.26 g.01) g = 114.01 + 18 × 1.The three-way catalytic converter SAQ 1 Answer The stoichiometric equation for the complete combustion of octane can be written as follows: C8H18 + 121/2O2 = 8CO2 + 9H2O So combustion of 1 mol of octane will require 12. the mass of air required will be 12.5 mol of oxygen. and we have used octane.

in the absence of the three-way converter the levels of CO. As there is a simultaneous increase in the total amount of oxidants (air + NOx). However. The three-way catalytic converter is therefore unsuitable for engines that run lean. and then remains constant in the net oxidising conditions beyond that point. so the NOx conversion will still be high (as seen in Figure 6).edu/openlearn/science-maths-technology/science/chemistry/the-three-way-catalyticconverter/content-section-0 . (b) At A/F ratios below the window value there is less NOx and more HC and CO present in the mixture expelled from the engine (Figure 5). We would therefore expect to see an increase in the HC and CO levels emitted from the exhaust. The sharp fall in NOx conversion for A/F values approaching and above stoichiometric is understandable in terms of the virtual elimination of reductants in this region. we see a decrease in catalyst efficiency for destroying HC and CO. we would expect to see an increase in NOx emissions from the exhaust. the overall conversion of CO and HC increases to approach effective completion at the stoichiometric ratio. as there are insufficient oxidants present for complete conversion. All the NOx present will react over the catalyst. Obviously in both three-way catalytic converter SAQ 2 Answer (a) Figure 5 shows that over the narrow range of A/F ratios covered in Figure 6 the amounts of CO and HC emitted form the engine decrease as A/F increases. HC and NOx emitted for the exhaust would be much higher. Back Page 54 of 71 2nd March 2016 http://www. Because the system is unable to remove all of the NOx.

so the full description of this structure should be Pd(111)(2 × 2)–O. showing the substrate unit mesh and the adsorbate unit mesh.The three-way catalytic converter SAQ 3 Answer The unit meshes of the substrate (1 × 1) structure and of the adsorbate structure are shown in Figure 8A. For adsorption on a single crystal surface. Back Page 55 of 71 2nd March 2016 http://www. the fractional surface coverage is given by θ = x/(m × n) where x is the number of adsorbate species within the (m × n) adsorbate unit . In this case (Figure 8A). O atoms occur only at the corners of the mesh. so the latter contains a total of (4 × 1/4) = 1 the latter is (2 × 2) in the (m × n) notation. Evidently. Hence θ = 1/(2 × 2) = 1/4 Figure 8A The surface structure of O atoms adsorbed on Pd(111) at maximum surface coverage.

open.The three-way catalytic converter SAQ 4 Answer The major roles proposed for the different components of the Pt-Rh/CeO2–Al2O3 three-way catalyst can be summarised as follows: Platinum    CO oxidation HC oxidation steam reforming and water-gas shift reactions (with CeO2) Rhodium   CO–NO redox reaction steam reforming and water-gas shift reactions (with CeO2) Ceria oxgen storage structural promoter maintaining both metal and support surface areas chemical promoter for the water-gas shift and steam reforming reactions  enhancement in low-temperature activity of Pt after reducing pretreatment    Back Page 56 of 71 2nd March 2016 .

especially lead and sulfur. selectivity and stability. Pd has a high susceptibility to poisons. The principal properties we require of a catalyst are activity. stability. reducing the activity of the latter. this should lead us to consider the third.The three-way catalytic converter SAQ 5 Answer Pd is in fact cheaper than Pt (Box 1). and can also form an alloy with . Because we have seen that the first two of these are at least as good for Pd as for Pt. In fact. as we shall discover in section 5. Back Page 57 of 71 2nd March 2016 http://www. it sinters in reducing atmospheres. In addition. so the reason for using Pt is not an economic one.

Back Page 58 of 71 2nd March 2016 http://www. This is likely to be due to sintering of the noble-metal particles.The three-way catalytic converter SAQ 6 Answer The decrease in the value of CO/M observed as the ageing temperature increases indicates that the free metal surface area of the catalyst is decreasing with increasing . and/or the

open. below the stoichiometric ratio.The three-way catalytic converter Activity 1 Discussion The levels released in the engine increase because. there is insufficient oxygen present for total combustion Back Page 59 of 71 2nd March 2016 .

The three-way catalytic converter Activity 2 Discussion A wide window is desirable for catalytic emission control as it lessens the need to tighten the A/F control of the . Back Page 60 of 71 2nd March 2016

Back Page 61 of 71 2nd March 2016 . reaction three-way catalytic converter Activity 3 Discussion This observation rules out the Eley–Rideal reaction between CO(ad) and O2(g).

and independent of the total pressure of the reactants. . the conclusions drawn about mechanism from surface studies may not be too far removed from those that apply in the case of the ‘real’ catalyst. In addition. Back Page 62 of 71 2nd March 2016 http://www. hence the effects of the adsorbed CO and O are likely to be the only relevant factors.The three-way catalytic converter Activity 4 Discussion Techniques such as LEED examine adsorption at very low pressures onto clean single crystal surfaces. We are not dealing with a single crystal or a defined crystal plane. according to the factors listed above. the catalyst surface is clean. but the real catalytic system is more complicated than this. CO oxidation has been shown to be independent of the Pd surface the first observation suggests that under real conditions. and the pressures involved are much higher. However.

The three-way catalytic converter Activity 5 Discussion Comment The aim of the catalyst is to selectively promote reactions 6 and 7 to produce N2. rather than N2O (a greenhouse gas) or NH3 (a potentially serious general pollutant). Back Page 63 of 71 2nd March 2016 .

edu/openlearn/science-maths-technology/science/chemistry/the-three-way-catalyticconverter/content-section-0 .open.The three-way catalytic converter Activity 6 Discussion It suggests that N atom combination (reaction 21) may be the rate-limiting step in the overall NO–CO reaction on Rh(111). Back Page 64 of 71 2nd March 2016 http://www.

When NO is present (the CO–NO–O2 mixture) the overall CO conversion rate decreases. In fact. becomes significant. Therefore. and approaches a value of 1×10−6 mol CO (g cat)−1 s−1 only at about 290 °C. this is close to the temperature at which the CO–NO This approaches a value of 1×10−6 mol CO (g cat)−1 s−1 at about 230 °C.The three-way catalytic converter Activity 7 Discussion Comment The green line labelled CO–O2 in Figure 19 shows the CO conversion rate for the CO–O2 reaction in the absence of NO. Back Page 65 of 71 2nd March 2016 http://www. the inhibition of the CO–O2 reaction is believed to be due to blocking of the active sites by adsorbed . shown as the dashed line in Figure 19.

open. Back Page 66 of 71 2nd March 2016 http://www. particularly at A/F ratios just below .The three-way catalytic converter Activity 8 Discussion Comment Substantial improvements in all three conversion efficiencies are seen.

Addition of CeO2 results in a significant stabilization of the Pt metal dispersion up to 700–800 °C. in the absence of ceria.The three-way catalytic converter Activity 9 Discussion Clearly. Back Page 67 of 71 2nd March 2016 http://www. substantial sintering of Pt occurs between 500 °C and 600 ° .open. causing a sharp reduction in dispersion.

Similar results are obtained whether the metal is . because the Pt and Pb maps are exactly superimposable. Pd or Rh.The three-way catalytic converter Activity 10 Discussion Comment Pb is associated with Back Page 68 of 71 2nd March 2016 http://www.

edu/openlearn/science-maths-technology/science/chemistry/the-three-way-catalyticconverter/content-section-0 .open. blocking sites previously available to chemisorb CO.The three-way catalytic converter Activity 11 Discussion Comment At a given ageing temperature. the CO chemisorption capacity of the catalyst is dramatically decreased in the presence of SO2. This suggests that some sort of sulfur species has been formed on the metal surface. Back Page 69 of 71 2nd March 2016 http://www. and possibly also inhibiting CO adsorption at neighbouring sites.

but it may be attributed to SIV associated with a highly charged cation such as CeIV or CeIII. Back Page 70 of 71 2nd March 2016 http://www. The value at 20 °C is slightly harder to .The three-way catalytic converter Activity 12 Discussion Comment The typical values suggest that at 550 °C. the sulfur exists as SVI. .The three-way catalytic converter Activity 13 Discussion Comment The Ce 3d binding energy of CeO2 in SO2 at 20 °C is similar to that of CeIV oxide (CeO2 in air). Back Page 71 of 71 2nd March 2016 http://www. suggesting that reduction of some of the surface sites to CeIII may have occurred.6H2O. The value at 550 °C agrees reasonably well with that for CeIII in Ce(NO3)3.