Mechanism of the selective reduction of nitrogen monoxide on platinum-based catalysts in the presence of excess oxygen
TL;DR: A range of alumina-supported platinum catalysts have been prepared and investigated for the selective reduction of nitrogen monoxide in the presence of a large excess of oxygen in steady state microreactor experiments.
Abstract: A range of alumina-supported platinum catalysts have been prepared and investigated for the selective reduction of nitrogen monoxide in the presence of a large excess of oxygen. Steady-state microreactor experiments have demonstrated that these catalysts are very active and selective for the reduction of nitrogen monoxide by propene at temperatures as low as 200°C. There does not appear to be a simple correlation between the activity for nitrogen monoxide reduction and the platinum surface area. Instead it is found that there is a very good inverse correlation between the maximum nitrogen monoxide reduction activity and the temperature. The most active catalysts for selective nitrogen monoxide reduction are those that generate activity at the lowest temperature. The technique of temporal analysis of products (TAP) has been used to obtain detailed mechanistic data about the selective nitrogen monoxide reduction reaction on an alumina-supported platinum catalyst. Using carbon monoxide, hydrogen or propene as reductant it has been demonstrated that the predominant mechanism for selective nitrogen monoxide reduction involves the decomposition of nitrogen monoxide on reduced platinum metal sites, followed by the regeneration of the active platinum sites by the reductant. In the decomposition step it has been shown that oxygen from nitrogen monoxide is retained on the surface of the platinum and blocks the surface for further adsorption/reaction of nitrogen monoxide; it has been observed that oxidised platinum catalysts are not active for the nitrogen monoxide reduction reaction. Under typical operating conditions, propene is a far more efficient reductant than either carbon monoxide or hydrogen. The greater efficiency of propene as a reductant is explained on the basis of the additional reducing power of the propene molecule, which can react with as many as nine adsorbed oxygen atoms, ensuring that 'patches' of reduced platinum are available for nitrogen monoxide adsorption/reaction. A small additional activity of reduced platinum in the presence of propene, which is not observed when carbon monoxide or hydrogen is used as reductant, has been explained on the basis of a second mechanism involving the carbon-assisted decomposition of nitrogen monoxide at sites on the reduced platinum adjacent to adsorbed carbon-containing moieties, believed to be fragments from adsorbed propene molecules. A model for the selective reduction of nitrogen monoxide on alumina-supported platinum catalysts is presented which is capable of explaining all the results obtained in this work and in the published literature on this subject.
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TL;DR: In this paper, the authors review the catalytic reactions for the removal of NO and discuss the reduction of NO in the presence of NH3, CO, H-2 or hydrocarbons as well as the decomposition of NO.
1,110 citations
TL;DR: In this article, the authors describe the work carried out in characterizing, developing, and understanding this catalyst technology for application in mobile exhaust gas aftertreatment, which includes five general steps involved in NOx reduction to N2 on NSR catalysts; NO oxidation, NO2 and NO sorption leading to nitrite and nitrate species.
Abstract: Over the last several years, nitrogen oxide(s) (NOx) storage/reduction (NSR) catalysts, also referred to as NOx adsorbers or lean NOx traps, have been developed as an aftertreatment technology to reduce NOx emissions from lean‐burn power sources. NSR operation is cyclic: during the lean part of the cycle, NOx are trapped on the catalyst; intermittent rich excursions are used to reduce the NOx to N2 and restore the original catalyst surface; and lean operation then resumes. This review will describe the work carried out in characterizing, developing, and understanding this catalyst technology for application in mobile exhaust‐gas aftertreatment. The discussion will first encompass the reaction process fundamentals, which include five general steps involved in NOx reduction to N2 on NSR catalysts; NO oxidation, NO2 and NO sorption leading to nitrite and nitrate species, reductant evolution, NOx release, and finally NOx reduction to N2. Major unresolved issues and questions are listed at the end of ...
846 citations
TL;DR: In this paper, it is concluded that although there is indirect, mainly spectroscopic, evidence for various reaction intermediates on the catalyst surface, it is difficult to confirm that any of these are involved in a critical mechanistic step because of a lack of a direct quantitative correlation between infrared and kinetic measurements.
Abstract: Research on the selective reduction of NOx with hydrocarbons under lean-burn conditions using non-zeolitic oxides and platinum group metal (PGM) catalysts has been critically reviewed. Alumina and silver-promoted alumina catalysts have been described in detail with particular emphasis on an analysis of the various reaction mechanisms that have been put forward in the literature. The influence of the nature of the reducing agent, and the preparation and structure of the catalysts have also been discussed and rationalised for several other oxide systems. It is concluded for non-zeolitic oxides that species that are strongly adsorbed on the surface, such as nitrates/nitrites and acetates, could be key intermediates in the formation of various reduced and oxidised species of nitrogen, the further reaction of which leads eventually to the formation of molecular nitrogen. For the platinum group metal catalysts, the different mechanisms that have been proposed in the literature have been critically assessed. It is concluded that although there is indirect, mainly spectroscopic, evidence for various reaction intermediates on the catalyst surface, it is difficult to confirm that any of these are involved in a critical mechanistic step because of a lack of a direct quantitative correlation between infrared and kinetic measurements. A simple mechanism which involves the dissociation of NO on a reduced metal surface to give N(ads) and O(ads), with subsequent desorption of N2 and N2O and removal of O(ads) by the reductant can explain many of the results with the platinum group metal catalysts, although an additional contribution from organo-nitro-type species may contribute to the overall NOx reduction activity with these catalysts. It is concluded, after the investigation of hundreds of catalyst formulations, that many of the fundamental questions relating to lean deNOx reactions have been addressed and the main boundary conditions have been established. It seems clear that catalysts with sufficient activity, selectivity or stability to satisfy the demanding conditions that appertain in automotive applications are still far away. The rapidly growing interest in NOx storage systems reflects this situation, and it now seems to be the case that acceptable direct NOx reduction catalysts may be very difficult to find for lean-burn applications.
827 citations
TL;DR: In the early 1970s increased use of cars in some major cities had resulted in serious concerns about urban air quality caused by engine exhaust gas emissions themselves, and by the more harmful species derived from them via photochemical reactions.
Abstract: By the early 1970s increased use of cars in some major cities had resulted in serious concerns about urban air quality caused by engine exhaust gas emissions themselves, and by the more harmful species derived from them via photochemical reactions. The three main exhaust gas pollutants are hydrocarbons (including partially oxidised organic compounds), carbon monoxide and nitrogen oxides. Engine modifications alone were not sufficient to control them, and catalytic systems were introduced to do this. This catalytic chemistry involves activation of small pollutant molecules that is achieved particularly effectively over platinum group metal catalysts. Catalytic emissions control was introduced first in the form of platinum-based oxidation catalysts that lowered hydrocarbon and carbon monoxide emissions. Reduction of nitrogen oxides to nitrogen was initially done over a platinum/rhodium catalyst prior to oxidation, and subsequently simultaneous conversion of all three pollutants over a single three-way catalyst to harmless products became possible when the composition of the exhaust gas could be maintained close to the stoichiometric point. Today modern cars with three-way catalysts can achieve almost complete removal of all three exhaust pollutants over the life of the vehicle. There is now a high level of interest, especially in Europe, in improved fuel-efficient vehicles with reduced carbon dioxide emissions, and “lean-burn” engines, particularly diesels that can provide better fuel economy. Here oxidation of hydrocarbons and carbon monoxide is fairly straightforward, but direct reduction of NO x under lean conditions is practically impossible. Two very different approaches are being developed for lean-NO x control; these are NO x -trapping with periodic reductive regeneration, and selective catalytic reduction (SCR) with ammonia or hydrocarbon. Good progress has been made in developing these technologies and they are gradually being introduced into production. Because of the nature of the diesel engine combustion process they produce more particulate matter (PM) or soot than gasoline engines, and this gives rise to health concerns. The exhaust temperature of heavy-duty diesels is high enough (250–400 °C) for nitric oxide to be converted to nitrogen dioxide over an upstream platinum catalyst, and this smoothly oxidises retained soot in the filter. The exhaust temperature of passenger car diesels is too low for this to take place all the time, so trapped soot is periodically burnt in oxygen above 550 °C. Here a platinum catalyst is used to oxidise higher than normal amounts of hydrocarbon and carbon monoxide upstream of the filter to give sufficient temperature for soot combustion to take place with oxygen. Diesel PM control is discussed in terms of a range of vehicle applications, including very recent results from actual on-road measurements involving a mobile laboratory, and the technical challenges associated with developing ultra-clean diesel-powered cars are discussed.
783 citations
TL;DR: In this article, the authors present the present status and the perspective of de-NO x SCR catalysis for stationary sources, that is based on the reduction of NO x by NH 3 to form water and nitrogen.
Abstract: This paper surveys the present status and the perspective of de-NO x SCR catalysis for stationary sources, that is based on the reduction of NO x by NH 3 to form water and nitrogen. After a brief description of the SCR chemistry the characteristics of commercial SCR catalysts, their physico-chemical properties and reactivity, and their performances in both NO x reduction and SO 2 oxidation are presented. The mechanism of the SCR reactions, the mathematical modeling of the reactor and the arrangements of the reactor and process are then described. Finally the emerging technologies for NO x removal and the future perspectives of the SCR catalysis are outlined.
760 citations
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TL;DR: In this article, the catalytic decomposition of nitrous oxide to nitrogen and oxygen was studied over a number of catalysts and the effects of oxygen and nitric oxide addition, metal loading, and pretreatment upon the catalyst activity were evaluated.
Abstract: The catalytic decomposition of nitrous oxide to nitrogen and oxygen was studied over a number of catalysts. Copper and cobalt exchanged ZSM-5, mordenite, zeolite beta, ZSM-11 and ferrierite are much more active than other cation-exchanged zeolites (Cu-Y, Co-Y, Co-erionite, Cu-L, Co-L, Ni-ZSM-5, Mn-ZSM-5) and metal oxides (CuO/Al2O3, and CoO/Al2O3). For noble metal catalysts, a cation exchanged ZSM-5 has higher activity than the Al2O3 supported form. Rhodium is the most active catalyst, but surprisingly Pt-ZSM-5 is one of the least active catalysts of all. Also, the effects of oxygen and nitric oxide addition, metal loading, and pretreatment upon the catalyst activity were evaluated.
280 citations
TL;DR: In this paper, the performances of platinum-group metals, platinum, iridium, palladium, rhodium and ruthenium supported on γ-alumina, as catalysts for the selective reduction of nitrogen oxides by hydrocarbons were investigated.
Abstract: The performances of platinum-group metals, platinum, iridium, palladium, rhodium and ruthenium supported on γ-alumina, as catalysts for the selective reduction of nitrogen oxides by hydrocarbons were investigated. Platinum and rhodium had high nitric oxide conversion activities both in model mixtures and in real diesel exhaust gases, especially at relatively low temperatures between 200 and 350°C. It was confirmed that the platinum-rhodium and platinum catalysts have higher activity and durability than a catalyst composed of copper supported on ZSM-5 under real diesel exhaust conditions. The platinum-containing catalysts, however, produced more nitrous oxide than nitrogen. It is expected that platinum-group metal catalysts will be able to be used for practical purposes if once their selectivity toward nitrogen is improved.
253 citations
TL;DR: In this article, the acidity of a series of silica-alumina catalysts is suggested to be one of the main factors that determine catalytic activity. But this is not the case for all catalysts.
Abstract: Highly selective reduction of nitrogen oxides to dinitrogen occurs to a high level in oxygen-rich atmospheres by using a small amount of propane as a reducing agent over alumina, silica-alumina, titania and zirconia catalyst. Judging from the data of activity and ammonia TPD measurement on a series of silica-alumina catalysts, acidity is suggested to be one of the main factors that determine catalytic activity.
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