Journal of the Energy Institute 111 (2023) 101410

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Journal of the Energy Institute

journal homepage: www.elsevier.com/locate/joei

A technical review on low temperature combustion alternatives for

ultra-low emission vehicles
Dikra Bakhchin, Rajesh Ravi *, Mustapha Faqir, Elhachmi Essadiqi
School of Aerospace and Automotive Engineering, LERMA Laboratory, International University of Rabat, 11000, Morocco

A R T I C L E I N F O A B S T R A C T

Handling editor: Paul Williams Oxides of nitrogen (NOx) emissions have always been considered as the primary concern for the development of
diesel engines. Several post-treatment technologies have also been developed to fulfil the stringent standards for
Keywords: NOx emissions that cannot be controlled by fuel composition and combustion reaction. At present, the after-
Greenhouse gas treatment technologies employed include Selective Catalytic Reduction (SCR), Lean NOx Traps and SCR
Particulate matter
filtering. The current review article summarizes the investigations conducted earlier about the reduction of NOx
Nitrogen oxides
emissions from lean-burn engines and discusses the benefits and limitations of different types of SCRs. Among the
Heterogeneous catalysis materials
Supported catalysts available technologies, the urea SCR process is ultimately the most efficient process using Ad blue technology.
PGM alternative alloys Urea SCR process uses NH3 reduction agents to achieve 98% conversion efficiency. The article discussed some of
the operating parameters such as the nature of catalytic material, the range temperature of the catalyst and the
mixing of NH3 and NOx. Hybrid SCR such as the metals-impregnated SCR (M-SCR, HC- SCR, SCR + LNT)
moderately increases the catalytic activity and converts the exhaust gas into less harmful gases even at low
temperature. The novelty of the work, debates about the outrivaling importance of oxidation catalyst of the
modern diesel exhaust purification systems, techniques for enhancement and the optimization of oxidation
catalysts that are aimed at NOx and hydrocarbon conversion and the methods for reducing the Platinum Group
Metal (PGM) content in these catalytic systems via combination devices for thermal energy and further opti­
mization and material cost attenuation. There exists a requisite for continuous investigation of PM control
technology that comprises of regenerating systems to reduce the complexity of these systems and concomitant
fuel economic penalties. Future research works should be conducted extensively with different additives, sub­
strate materials, regenerating systems, and controls to develop optimal devices that are capable of reducing the
diesel particulate emissions levels.

1. Introduction engine design modifications in order to control the most severe harmful
emissions, greenhouse gases (GHGs) from Diesel engine [4,5].
Internal combustion engines (ICEs) are the utmost efficient and Currently, emissions regulations have been strictly addressed, especially
consistent power plant in fleet vehicles, heavy trucks and machineries for petrol engines, regarding the issue of exhaust rich particulate matter,
[1]. Though IC engines, in the form of diesel engine produce high energy fumes generation of these engine, in addition to the other harmful
density, still the greatest harmful emissions, and are expected to greenhouse gases present in both gasoline and diesel engines, bearing in
continue on road until: fossil fuel depletions, and stringent emissions mind that emission statute are intermittently updated with new pollut­
regulations and legislation are focusing more and more on engine ants threat, such NOx, sulfurs and GHGs like water vapors, and more­
manufacturer to develop less-polluting and more-efficient technologies over they might be restricting the emission criteria like particle size and
as an alternative to the conventional ICE, in regard to the environment particle number for the particulate matter [6].
and the climate change, mainly caused by the increasingly high atmo­ The largest anthropogenic source of tropospheric NO2 is the burning
sphere pollution [2,3]. of fossil fuels at point sources such as power stations and other traffic-
In the past two decades, emission catalytic control strategies, for the related area sources. Because of the source density, NO2 concentra­
automotive sector have been remarkably developed, along with fuel and tions in urban or heavily industrialized locations tend to far surpass

* Corresponding author.
E-mail address: [email protected] (R. Ravi).

https://doi.org/10.1016/j.joei.2023.101410
Received 14 July 2023; Received in revised form 11 September 2023; Accepted 21 September 2023
Available online 8 October 2023
1743-9671/© 2023 Energy Institute. Published by Elsevier Ltd. All rights reserved.
D. Bakhchin et al. Journal of the Energy Institute 111 (2023) 101410

background values in rural sites. Whereas, primary NO2 is emitted [11,12]. These include interest in the relationship between NO2 expo­
directly from a combustion source, secondary NO2 is formed in the at­ sure and acute and chronic mortality from non-accidental, respiratory,
mosphere by the reaction of NO with any of several photochemical ox­ and cardiovascular causes. The chief limitation in many of the studies,
idants, such as hydroxyl free radicals, alkylperoxy radicals, or ozone in has been the overreliance on the results from single pollutant rather than
the troposphere, NO2 is the main source of oxygen atoms for ozone multi-pollutant models that are capable of considering the strong cor­
formation, which is achieved when sun rays split nitrogen dioxide into relation of NO2 ambient air levels, with other pollutants such as PM and
NO and an oxygen atom [7,8]. This oxygen atoms then combines with an CO [13–15]. Consequently, to the previously mentioned ecosystem
oxygen molecule O2 to produce continuously ozone (O3), the process of pollution issues, the organization of environment and health have set
ozone cycle is illustrated in the reactions below (Fig. 1). stringent legislations beginning in the year of 1992 with Euro I followed
The atmospheric equilibrium that exists between (NO2, NO, and O3) by constantly developing legislation regulations (Table 1) until now.
is usually referred to as the ozone cycle. The reaction behind this cycle Subsequently of the assertions mentioned above, a tremendous
are as follows: growth in the production of optimized fuel-economy vehicles and of
ultra-low emissions, noise and cost vehicles have been reinvigorated in
HO2 • + NO → OH • + NO2(1)
the international market [16,17]. Nonetheless, the original engine
manufacturer had opted for advanced antipollution technologies in the
RO2 • + NO → RO • + NO2 (2)
modern ultra-low emissions vehicle. Mainly, catalytic converter has
NO2 + hν (240–310 nm) → NO + O (3) been the selected solution for this purpose. Significant developments
have been made on the materials used in the mentioned technologies
O3 + NO → NO2 + O2 (4) and many parameters are here to be taken into concern, in order to
understand the optimal working of the catalyst [18].
Conferring to the World Health Organization’s WHO (2005). Re­ In the next section, a careful description of the reactions occurring
visions regarding air quality guidelines is based on that NO2 is associ­ inside the catalytic converters is discussed, as well as the catalytic ma­
ated with an increase in morbidity, because of ambient air conditions. terial properties and the potential methods to improve the efficiency of
Studies have well focused on asthmatics, and how it can impair lung each after treatment system.
function, as well as the effects of CO2 exposure on bronchitis and lung
dysfunctions.
2. Review on diesel engine after treatment techniques
There is a focus, on the relationship between NO2 exposure, and
acute and chronic mortality from non-accidental, respiratory. and car­
2.1. Catalytic converter
diovascular causes, aggravating pneumonia, and allergies [9,10]. The
ambient air levels with other pollutants, such as PM and CO, have been
Diesel engines have numerous strength points comparing to petrol
found to be closely connected with the NO2 concentration, and there
engines, we state amongst the high-power density, greater torque, less
have been relevant facts relating PM, respiratory, cardiovascular, also
fuel penalty, resilience and lower carbon monoxide emanations, and
mucus cancer and skin cancer indirectly, by the alteration of ozone gap
moreover the possibility of biodiesel blends substitution of the con­
(Fig. 2). Which leads to non-equilibrium of the atmosphere threatening
ventional fuel [19]. However, the well-known drawbacks it has (noise,
the overall ecosystems. In fact, these issues in large measure formed the
heaviness, run-of-the-mill performance, dirtiness …), until now have
basis for the creation and continuation, of the annual limit value of 40
arrived not only in non-road plant but, in general fleet transport means,
μg/m3 and the 1-hr short-term limit of 200 μg/m3 set by the WHO.
which spreads out the pollution caused by inconvenience to these reli­
Although asthma and respiratory morbidity continues to be topic of
able engines. The call to deploying climate friendly vehicles, especially
great interest for researchers and regulators, several new areas of
in Europe, have imposed improvement over the engines design, as well
concern have emerged that have been the target of intensive research
as the process of internal combustion, in order to take benefit of its

Fig. 1. a) NOx, Sox and Particles 2.5 sourced from combustion. b) Tribowaste nitrogen reactions with free radicals, NO, O3 and cycles in the atmosphere [9].

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D. Bakhchin et al. Journal of the Energy Institute 111 (2023) 101410

Fig. 2. Effect of tribo-waste on the equilibrium of human health and the environment.

inside these catalysts needed an excess amount of atmospheric oxygen

Table 1 and for this purpose, air is dominant in lean burn engines, the following
Development of Euro 6 regulations legislations on pollutants [10].
reactions occurs for:
Emission Date CO (g/ NOx (g/ HC + NOx PM (g/
standard km) km) (g/km) km)
• CO oxidation:
Euro 1 July 1992 2.72 – 0.97 0.14
Euro 2 January 1996 1 – 0.7 0.08 CO (g) + ½ O2 (g) → CO2 (g) ΔH = − 566 kJ / mol . (5)
Euro 3 January 2000 0.64 0.5 0.56 0.05
Euro 4 January 2005 0.5 0.25 0.3 0.025
Which is indeed, somehow done by atmospheric N2 also giving
Euro 5 September 0.5 0.18 0.26 0.005
94 CO (g) + 47 O2 (g) + 25 (3.76 N2) (g) → 94 CO2 (g) + 94 N2 (g) (6)
2009
Euro 6 September 0.5 0.08 0.17 0.005
2014
Hydrocarbon oxidation:
1
advantages and overcome the latter problems [20]. CxHy (g) + (x + y / 4) O2 (g) ⟶ x CO2 (g) + y H2O (g) (7)
2
At the outset of emissions control era, flue gas oxidation catalyst
have been widely used. Oxidation catalysts were mainly using platinum Taking for instance Cetane combustion reaction contained in diesel
group metals (PGM) like rhodium Rd, palladium Pd, silver Ag. Sup­ Fuel:
ported and dispersed on support in the walls of the catalyst. Such 2 C16H34 (g) + 49 O2 (g) → 34 H2O (g) + 32 CO2 (g) (8)
alumina substrate regarding its high specific surface area (SSA), packed
into the metal sheath container welded into the expend duct [21]. The Considering this practical success of the catalytic converter, it is
oxidation catalyst in both petrol and gasoline engines, was introduced manufactured in many shapes, made with different materials (ceramics
with the beginning of emission legislation starting in the US, since 1979 and metals) support as (illustrated in Fig. 3), in order to guarantee a
and then by Europe in the early 80’s which entailed the control of the maximum exchange.
hydrocarbons and carbon, NOx and PM. Oxidation-reduction Catalyst is The other technological development was to address a major
created by coating the internal ceramic substrate with the following key pollutant in the lean engine which is NOx emissions. Complementarily
materials: Platinum Pt/Palladium Pd; Oxidizing catalysts for HC and CO. to the catalyst which oxidizes CO and hydrocarbons in the abundance of
Rhodium; reducing catalyst for NOx reduction, Cerium: Promotes oxy­ atmospheric NO2, the NOx reduction catalyst exploits the occurrence of
gen storage to improve oxidation efficiency [22]. When engine exhaust reductants such CO to convert NO2 to N2.
gases pass through the converter passageway, they are exposed to the Their mutually presence give the next reaction (9):
coated surface, which initiates the catalyst process. When the exhaust 2 NO (g) + 2 CO (g) → N2 (g) + 2 CO2 (g) ΔH = − 746.8 kJ / mol
and catalyst temperatures rise, a reaction occurs: N2 oxidation is (9)
reduced to carbon dioxide CO2, Hydrocarbons HC and carbon dioxide
CO2 are oxidized to produce H2O and CO2, and the efficiency of the In Diesel engines, a prerequisite amount of fuel is injected and mixed,
catalyst is greatly affected by two factors: the operating temperature and with an excessively diluted amount of atmospheric air in-cylinder. The
the composition of the feed gas [23]. The catalyst starts to operate at exhaust gas composition holds a considerable amount of O2, and hence,
~300 ◦ C. However, efficient purification can occur unless the catalyst oxidation-reduction catalyst that relies on the stoichiometric mixture of
reaches at least 415 ◦ C. In addition, engine exhaust gases requisite air-fuel ratio (Fig. 4), is less likely to be employed for efficient pollution
instantaneously alternate between high CO content for NOx reduction control [25].
and higher O2 content to oxidize CO and HC emissions [24]. Additional reactions with important influence on the Air-fuel ration
Carbonaceous matter oxidation is achieved via use of the diesel occurs on the behalf of the NO reduction are “the water-gas shift” re­
particulate trap and the oxidation catalyst, all the reaction taking place actions (10):

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D. Bakhchin et al. Journal of the Energy Institute 111 (2023) 101410

Fig. 3. Different type of ceramic/metal monolith substrate for the particulate oxidizer.

CO (g) + H2O (g)⇌ CO2 (g) + H2 (g) ΔH ◦ 298 = − 41, 1 kJ/mol (10) Generally, the combination of the up mentioned devices, might be
highly efficient against the four types of pollutants, giving for instance:
Reforming reaction (11):
putting a plant where the exhaust passes first by the particulate filter, to
CnHm (g) + n H2O (g) → n CO (g) + (n + m / 2) H2 (g) (11) remove the soot and carbonaceous particles from the flue gas, the par­
ticles may encapsulate oils, sulfur and nitrogen oxides. Followed by
Last, comes the NO reduction (12):
selective catalytic reduction, where NOx contained in the exhaust faces
2 NO (g) + 2H2 (g) → N2 (g) + 2H2O (g) (12) reduction with ammonia and goes through nitrates storage catalyst
(anti-slip) for effective NOx control [32].
Water injections can dramatically reduce NOx, but there are many
disadvantages. When combustion temperature is reduced, CO and UHC
3. Diesel oxidation catalyst
production increases. Water treatment costs to improve water purity
lead to higher operating costs. In addition, there is the possibility of
The catalyst is built as a monolith, (or monocrystal) honeycomb-
corrosion of the hot sections, resulting in increased maintenance costs.
shape, structured in tinny channels (Fig. 5) and decorated with pellets
Heat absorbed by water also increases fuel consumption. The power
of the oxidizing catalyst (Platinum).
output increased, but the net effect was to reduce the thermal efficiency
The catalyst is dispersed in a wash coat layer of (50–150 μm) within
[27].
the ceramic monolith. The latter is composed generally from cordierite
(2MgO, 2Al2O3, 5SiO2). It is used considering its refractory high prop­
2.2. Diesel after treatment systems erties, including high temperatures cooking [34].
Metallic catalyst, like Direct Bonded Aluminum substrate are
Diesel ATS are divided into multiple or combined device and are designed for the desired properties such (the bonding strength, wire-
composed of four main devices according to a review paper by Ref. [28]. bonding capacity, wetting ability, the break down voltage and the
Some of the most recent technologies, for reducing diesel engine NOx thermal resistance) [35]. The washcoat included in this catalytic con­
emissions are as follows: Lean NOX traps (LNTs), and LNT combined verter usually encompasses the following components [36]:
with selective catalytic reduction (SCRs), or ammonia SCRs (ASCs).
These technologies use catalysts to trap NOx under lean conditions and • The catalyst support substrate: alumina is broadly exploited as
reduce it under rich conditions by reduction agents such as diesel fuel or elementary material for catalytic support owing its high chemical
ammonia, which is selective catalytic reduction (urea/SCR) with urea inertness, strength and stiffness. ƴ-Alumina has high surface area due
injection [29]. This technology uses catalysts to reduce NOx and to the small size of particle, which outcomes in high activity of the
ammonia produced from urea under lean excursions. surface for a catalytic support.
DOC: oxidation catalyst for unburned hydrocarbon (UHC) and car­ • Catalyst additives: the additive/co-catalysts should be considered
bon monoxide (CO) removal and (LNT, SCR, ASC) combined DOC or when long-term continuous operation. It promotes additional prop­
pSCR. These technologies use catalysts for the oxidation of hydrocar­ erties to the main catalyst set up from noble metals.
bons and carbon dioxide and provide chemicals reduction such of NOx, • Active components of the catalyst: basically, platinum group metals
which have various advantages and disadvantages in terms of perfor­ (PGM), such (Ag, Rd, Pd, Pt).
mance, cost, durability, and complexity [30]. • Oxygen storing materials (OSM), like Ceria-lanthana (CL), ceria-
DPF: Diesel particulate filters designed as a ceramic monolith hon­ zirconia (CZ) solid solutions were developed since 1980s as excel­
eycomb to trap particulate matter PM. lent (OSM) for automotive catalysts. These materials comprise ceria
SCR: Selective catalytic reduction, for NOx reduction using doped with less than 20% mol of La4+ or Zr4+.
ammonia.

- Passive SCR (pSCR) and pSCR combined with LNT or ASC ammonia 3.1. Materials
storage catalyst. These technologies use catalysts to reduce NOx and
ammonia from NOx storage material under clean conditions [31]. The particular formula is determined contingent many factors
mentioning engine size, type, market, legislation and metal cost. PGMs
NSC/LNT: is a NOx storage catalyst, it is the key element for the are included because they are highly resistant to impurities, which
process optimization development. poisons the noble metal; For example, sulfurs contained in Diesel fuels
ASC: plays a major role in inhibiting NH3 slippage and recycling NO2 and exhaust emissions, these catalytic converters will stereotypically
and NH3 issued from SCR catalysts. function for periods exceeding the life of the vehicle. PGM are highly

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D. Bakhchin et al. Journal of the Energy Institute 111 (2023) 101410

Fig. 4. a) Exhaust hydrocarbons, CO, NO2 as function in fuel-air ratio [26]. b) NOx, UHC and CO conversions via three way catalyst following variying Fuel/air ratio
and temperature profile. c) NOx rate in lean premixed combustion zonning as a function of air-fuel ratio. (Source: Reprinted from Seinfield, J Atmospheric Chemistry
and Physics of Air pollution).

costly. However, it represents only a minor segment of the overall device

Ce2O3 + ½ O2 → 2 CeO2 (14)
wash coat, roughly ~1% (Fig. 6).
Adding Ceria (CeO3) to catalysts is compulsory to increase the Ceria also improves the water-gas shift activity (10) of Pt/catalyst
alteration of hydrocarbons (UHC), NOx and carbon monoxide. This is for and therefore promotes Carbon monoxide removal under fuel-rich
the reason that despite the excellent control, however, there is still some conditions; it can also act as a structural promoter to stabilize precious
fluctuations in the air-fuel ratio, but barely or marginally around the metals and particle grain fusion.
stoichiometry [37]. An advanced utility, improving the hydrocarbon performance, can
Ceria stores O2 present in the flue gas, in its lattice during the lean be added to the oxidation catalyst by the introduction crystalline micro
excursions, promotes reduction of NOx to N2, and then oxidizes hy­ porous aluminosilicates called zeolites, formed by TO4 (T = Si, Al, B, Ti,
drocarbons and CO using this oxygen under the lean environment. Thus, P) tetrahedrons. These adsorb hydrocarbons when the catalyst is at its
ceria reduces variation in the air-fuel ratio and improves catalyst per­ lowest temperature, during ‘‘cold start’’ directly after power up. The
formance in a broader operating environment [38]: hydrocarbons are de-sorbed and then oxidized as the temperature rises
to the requisite, for the of the occurrence catalytic oxidation [39].
2 CeO2 + CO → Ce2O3 + CO2 (13)
Further, down particular conditions, DOC contribute to some minor
Ceria regeneration reaction: reduction function of NOx, owing to their activity by using the hydro­
carbon present in the exhaust feed usually; this is truncated and merely

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D. Bakhchin et al. Journal of the Energy Institute 111 (2023) 101410

Fig. 5. Illustration of the honeycomb substrate channels of a DOC [33].

ensues above a slight temperature range.

CnHm(g)+(n+m/2)NO (g) → (n+m/4)N2(g)+n CO2(g)+m/2(H2O)
(15)

4. Diesel particulate filter technology

The most suggested solutions for particulate matter control are

particulate filters or catalyzed soot filters; that are made from materials
for carbonaceous matter trapping inside long channels wall-flow ducts,
also known as Diesel particulate filter [40]. Generally, made of ceramics
like: silicon carbide SiC, cordierite, even corporate Aluminum titanate.
The device captures the particulate matter inside the walls of the porous
structure (Fig. 7), as the exhaust gases pass through the inlet channel
[41].
To maintain the particulate filter performing for an optimal lifespan,
Fig. 6. Schematic illustration of diesel oxidation catalyst structural lay out the trapped PM built on the channel must be filtered, via means of pe­
[Johnson Matthey technology 2005]. riodic burning of the soot cake, which is called passive regeneration,
during the later PM and carbonaceous matter is oxidized using the NO2
abundant in the exhaust gas, particularly CO2. Moreover, optimal pas­
sive regeneration can be attained by the addition of Pt catalyst to the
DPF; this was the base of the effective continuous regenerating trap

Fig. 7. Schematic design of a metallic diesel oxidation catalyst channels [42].

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D. Bakhchin et al. Journal of the Energy Institute 111 (2023) 101410

(CRT) device [43]. In the case of the low temperatures, or at low con­ Which is sprayed upstream toward the flue gas inside the SCR system
centrations of NOx, active regeneration depending on excess oxygen [51]. This process of NOx reduction to N2 ensues in three steps reactions
contained in the exhaust gases, is occurring in temperature beyond [52].
500 ◦ C, unusually of the temperatures in most of Diesel exhaust gases
NO reduction 4NH3 + 4NO + O2 → 4N2 + 6H2O (16)
~250 ◦ C–300 ◦ C [44]. Hence, DOC active regeneration requires more
heat, provided generally by fuel injection into the exhaust to engender
NO2 reduction : 8 NH3 + 6 NO2 → 7 N2 + 12 H2O (17)
the exotherm. Active regeneration process can lead to fuel penalty, as it
also necessitates careful control of oxidation temperature and air-fuel Global SCR (fast reaction) : 2 NH3 + NO + NO2 → 2 N2 + 3 H2O (18)
ratio so as not to alter the filter material during regeneration [45].
The catalyst’s purpose is to reduce soot oxidation temperatures and Urea-SCR reaction occurs at mild temperatures of about
promote passive DPF regeneration. Passive regeneration is preferable to >200 ◦ C–450 ◦ C, beyond the temperatures of solid urea decomposition
active regeneration because it takes place at lower temperatures (with a (19) and Isocyanic acid hydrolysis (20):
beneficial effect on the lifespan of the filter) and involves a reduction in CO (NH2)2 → NH3 + HNCO. (19)
fuel-efficiency penalty [46].
There are three basic configurations depending on the location of the HNCO + H2O → NH3 + CO2. (20)
DPF catalyst:
Moreover, below the temperatures of Isocyanic reaction with urea at
• Oxidation Catalyst + uncatalyzed DPF ~230 ◦ C and Bi-uret formation:
• Oxidation Catalyst + CDPF CO (NH2)2 + HNCO (g) → NH2 − CO − NH − CO − NH2. (21)
• Catalyzed diesel particulate filter (CDPF)
Unfortunately, the use of urea solution poses problems, especially
Catalytic filters are used in filter systems using passive and active the potential for solid deposits made from condensed urea and decom­
regeneration. Most modernized DPF systems depend exclusively on position by-products. The main causes of the production of by-products
passive regeneration. In OEM, filter systems passive regeneration occurs are highly reactive HNCO intermediates involved in other processes
under high engine load conditions, while various thermal management than hydrolysis. Starting at 130 ◦ C, it is higher than the urea melting
methods are generally, used to increase exhaust gas temperature and point [53].
ensure reliable and actively supported recovery under low engine load The reaction of reduction via means of urea-SCR occurs at nearby
[47]. 250–450 ◦ C, yet at low temperatures, some modification in the design
In these latter “passive” filter systems, the catalyst’s role, addition­ and material state for appropriate temperature use. The reaction rate
ally to the reduction of the ash heating temperature, is to speed up the here is enhanced by dosing the NO/NO2 feed in a sort that 1:1 ratio is
ash oxidation rate in order to curtail fuel consumption penalties. The respected for lower temperatures of NOx with Urea-SCR. At higher
regeneration of a shorter duration also minimizes the probability of temperatures, other species from NH3 oxidation by products make
unanticipated and unwanted interruptions (for example, due to changes apparition and are reversible reactant, which can defeat the efficiency of
in engine operating conditions, engine management strategies to in­ the urea-SCR system. Otherwise, some secondary uncontrolled reactions
crease temperature can no longer be maintained). In catalyzed filters, can take place [54,55].
oxidation catalysts can also help to control excess CO/HC emissions that 4 NH3 + 3 O2 → 2 N2 + 6 H2O (Selective ammonia oxidation to nitrogen)
may arise during active regeneration, such as large amounts of soot (22)
burned over a narrow period of time [48].
NH3 + 5 O2 → 4 NO + 6 H2O (Unselective ammonia oxidation to NO)
5. NOx removal after treatment (23)

Techniques of NOx removal from the Diesel exhaust can be achieved 2 NH3 + 2 O2 → N2O + 2 H2O (Unselective ammonia oxidation to N2O)
via optimization of injection and burning modes of the fuel in-cylinder. (24)
The advanced combustion technologies, replacing the substitutionary
These reactions are generally relevant at high temperatures
combustion technology for conventional diesel combustion are
(>400 ◦ C) and in the absence of NO2. Conversely, to the previous sce­
Accordingly, three modes of advanced ignition homogeneous charge
nario, at the abundance of NO2 as oxidant, these reactions below are the
compression ignition, premixed charge compression ignition, and dual-
prevailing:
fuel premixed charge compression ignition, The characteristics of com­
bustion, emissions, and efficacy have been optimized, these techniques 4 NH3 + 4 NO + O2 → 4 N2 + 6 H2O (Standard SCR) (25)
were in compliance with NOx and PM emissions reductions simulta­
neously, further down regulations without an after treatment system 2 NH3 + NO + NO2 → 2 N2 + 3 H2O (Fast SCR) (26)
[49]. We pointed out that NOx formation is very sensitive to combustion
temperature. The introduction of heat sinks to reduce combustion 8 NH3 + 6 NO2 → 7 N2 + 12 H2O (NO2 SCR) (27)
temperatures can dramatically reduce the amount of NOx generated
during combustion reaching efficiencies of 80% removal. The use of 2 NH3 + 2 NO2 → NH4NO3 + N2 + H2O (Ammonium nitrate formation)
waste heat recovery processes is highly recommended, for advanced low (28)
emissions ICE. Low-temperature combustion mode reduces NOx (85%),
soot emissions (95%) and save-up fuel consumption up to (15%) [50]. 2 NH3 + 2 NO2 → N2O + N2 + 3 H2O (Nitrous oxide formation) (29)
Another issue limits this technology, is when the injection rate of
5.1. Urea-SCR urea is not well controlled, there is a risk of NH3 slippage into the
environment, which is considered as a harmful GHG. To avoid the latter
Catalytic removal of NOx from the feed gas downstream is commonly issue an Ammonia slip device (ASC), is tailored in the end-segment of the
realized by the adding of a reluctant additive (NH3) in the Urea/SCR urea-SCR catalyst system to contain the slippage issues: amongst we
case, such method is called selective catalytic reduction SCR. The Diesel mention Pt based slip ASC catalyst. Even though the introduction of ASC
exhaust fluid DEF, commercially known by the name ‘Ad Blue’, is an catalysts has led to the reduction of NH3 emissions, the use of these
aqueous solution of 32.5%W of high purity urea in deionized water.

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D. Bakhchin et al. Journal of the Energy Institute 111 (2023) 101410

systems has also caused an increase in N2O emissions [56].

NO oxidation 2NO + O2 → 2NO2 (34)
The Guanidine formate can form a very stable aqueous solution (30
<T < 60 ◦ C) and stores about 1.5 times the NH3 capacity of commercial
The storage of the Nitrates : Metal Oxides + 2 NO2 + ½ O2 → M (NO3)2.
catalytic DEF. Inopportunely, due to their stability, the full decompo­
(35)
sition requires special hydrogenation catalysts with dedicated heating.
In addition, reactions and decomposition mechanisms should be further
During rich operation or regeneration : M (NO3)2 + 3CO → MO + 2NO
studied to avoid problems similar to those of ammonium formate [57].
Studies on NH3 chemical storage stated that when metal amine + 3CO2 .
chlorides are used, gaseous NH3 is reversibly absorbed by the salt’s (36)
metal atoms, as a ligand and desorbed by endothermic heat. Due to their During this phase, NO is regenerated and nitrates are reduced by
high storage capacity, problems with salts include Mg(NH3)6Cl2, Ca other reductants present in flues gas:
(NH3)8Cl, and Sr(NH3)8Cl2. AMINEX’s technology, based on SrCl2, has
been deployed in the first pilot application and can release up to seven H2 reduction of the Nitrate : M (NO3)2 + 3H2 → MO + 2NO + 3H2O.
NH3 molecules at temperatures below 80 ◦ C. This is achieved by directly (37)

Hydrocarbon reduction of nitrate : M (NO3)2 + 1 / 3 C3H6 → MO + 2NO + H2O + CO2. (38)

using engine-cooling agent as a heat source [58]. However, this solution

can reach up to 6-bar pressure inside the NH3 storage cartridge and
requires a strong container. The main physical inconvenient of the use of Carbon monoxide reduction of NO : 2NO + 2CO → 2CO2 + N2. (39)
urea-SCR technology is ensuring the acquiescence of the NH3 storage
tank and refill, Nitrogen formation N2O and NH3 slip. Moreover, its cost H2 reduction of NO : 2NO + 2H2 → N2 + 2H2O. (40)
and size are evident challenges to overcome further [59]. LNT technology operating principle is storing NOx under lean burn
operational conditions, followed by the release and reduction of NOx,
• Effects of the SCR reaction on soot oxidation: during rich-burn pulse, for a short period. This operation entails
advanced engine operation and design, yet consequences in fuel penalty
The main disadvantage of SCR configuration is that NO2 is a key that should be optimized. A comparison between SCR and LNT is
catalyst that is essential to both low-temperature oxide and high-speed demonstrated herein in Table 2. A homologous advanced alternative to
SCR pathways and is limited in availability in general reactions. NOx control is hydrocarbon H-SCR. It converts NO2 to N2, via Nitrogen
NO + NO2 + 2NH3 → 2N2 + 3H2O (30) reduction reaction with hydrocarbons contained in fuel, in the incidence
of solid catalysts, under lean exhaust conditions. In this context, several
C + NO2 + O2 → NO + CO 2 + CO (31) catalysts have been investigated for thermal stability, physical proper­
ties, and catalytic selectivity, including Copper-supported on zeolites as
4NO + 4NH3 + O2 → 4N 2 + 6H2O (32) well as Alumina supported Ag, Pt, In, and Ga. Each of the catalysts ex­
hibits good activity under different temperature windows, dependent on
4NO2 + 4NH3 → 6H2O + 4 N2 + O2 (33) the nature of hydrocarbon injected and preparation process [63].
In order to enhance reduction assets during the rich phase, modern
where the chemical reaction in Eq. (30) is assigned as Fast-SCR, Reaction LNT also contain Rhodium as an active component. According to facil­
(32) is identified as Standard SCR, Reaction (33) is acknowledged as ity, Rhodium has diverse catalytic properties: Rh/ZrO2 effectively cat­
NO2 SCR, and Reaction (31) represents the soot oxidation mediated by alyzes the steam reform of hydrocarbons into H2, which reduces NOx,
NO2. Among the principal types of SCR reactions, the Fast SCR is while Pt Rh/CeO2 strongly promotes H2 production by the WGS reaction
kinetically profligate and takes place past the transition to standard SCR [64].
when NO2/NOx <0.5 (when NO2 is depleted) or NO2-SCR when NO2/ Nevertheless, production of H2 on supports other than Al2O3 does not
NOx >0.5 (when NO is depleted) [60]. improve only regeneration performance but increases the catalyst
sulfur-toxicity resistance. In some cases, LNT catalysts also contain ze­
5.2. Lean NOx trap catalysts olites, most of which are coated, but do not provide NOx storage capa­
bility. They are mainly responsible for preventing hydrocarbon leaks
Another catalyst technology conceived for NOx removal is lean NOx
trap technology (LNT), also called NOx storage/reduction catalyst
(NSR). It comprises (PGM) noble metals: Pt, Rd supported on high sur­ Table 2
face area reactive γ-Al2O3 in addition to a rare earth NOx adsorbing Limits and drawbacks of Urea SCR and LNT technologies.
component, commonly (Ba, Ce, and K oxides), or a mix of a bunch of LNT/ASC NH3-SCR
these elements, the advantage of this method is the tunability of the • Requires additional equipment. • It has an important cost since it
Catalyst performance in different engines and temperature range [61]. • -Requires refill and maintenance. contains PGM.
LNT catalyst reactions ensue in a lean-to rich cycle. NO is absorbed • Unselective reaction produce harmful • -Requires periodic high temperatures
into the storage material, oxidized to NO2 via the PM catalyst and stored Compounds N2O. desulfation because SOx deposition
• -Ammonia slip: wastes ammonia, so it occurs more strongly than that of
in the form of nitrates on the surface. During the rich cycle, stored NO2 is
shortens duration of Ad blue refilling. NOx.
released from the catalyst surface and reduced to N2 by oxidation hy­ • Regenerations lead to lower fuel • -A loss in the efficiency of the catalyst
drocarbons (HC), CO and H2 are intermediate components formed by economy. is reported.
combustion of fuels with PM catalysts. • -difficulty of lean-rich control of en­
During lean phase operation which occurs spontaneously in the gine operation and NOx storage and
maintain NO: NOx.
abundance of O2 [62].

8
D. Bakhchin et al. Journal of the Energy Institute 111 (2023) 101410

Fig. 8. Mechanism of Lean NOx trap using PGM and a storage catalyst [Adapted from cataler technology].

during the engine-cooling phase, resulting from a catalyst’s excessively durability, compared to other catalysts such: Cu/ZSM5, which is a
low oxidation activity further down 200 ◦ C. Unreactive hydrocarbons zeolite metal-doped catalyst, and high N2 selectivity. Conversely, to Pt
are diffused in the zeolites pores until the catalyst reaches the oxidation catalyst that converts NOx to extensive amounts of N2O. Moreover, it is
temperature; therefore, achieving oxidation activity [65]. Fig. 8 shows relatively not high of a cost comparing to PGM. Its main drawback is that
the mechnism of Lean NOx trab using PGM and storage catalyst. it has a higher start-off point of 350 ◦ C operating in Diesel engines [68].
LNT catalyst technology correspondingly requires low-sulfur fuels Researchers have made remarkable progress in the modification of
for effective and durable operation, as sulfur, which is produced by SO3 the catalyst preparation process to control the fuel-NOx ratios, by
oxidation with metal oxides, as it is more stable than nitrates, leading to introducing hydrocarbon-activating components in its formulations.
a deposit on the micro facets of the catalyst and consequently, poisoning The latter is proficient of improving the AL2O3/SCR catalyst perfor­
of the catalyst owing to impurities contamination. This drop of the mance, in the way that under a specific HC:NOx ratio, as hydrocarbons
catalyst performance is overcomed by high temperature desulphation are used as reductants, the presence of a minimal amount of hydrogen
process [66]. (<103 ppm) is simultaneously eliminating NOx and particulate matter
[70]. Perceptibly, The Combined systems design, aim to complement the
5.3. Materials catalysis efficiency of each device next the other, in order to simulta­
neously and effectively mitigate NOx and PM, the close-coupled com­
Ag/Al2O3 has been shown to have numerous benefits over other bination layouts are shown in Fig. 10. Table 3 provides the conversion
potential H-SCR catalysts. This requires relatively low activity SO2 efficiency details of NOx, HC, PM.
oxidation (a main reason of catalytic sulfation and decrease of SCR ef­
ficiency) and comparatively, higher hydrothermal and thermal

Fig. 9. Illustration of the evolution of conventional LNT to SCR + LNT system for NOx storage and reduction (OC: oxidation catalyst; SC: storage catalyst). Adapted
from Ref. [67].

9
D. Bakhchin et al. Journal of the Energy Institute 111 (2023) 101410

Fig. 10. Current configuration of combined after treatment systems regarding Euro 6 legislation for Diesel engine [69].

6.1. Fuel formulations

Table 3
Conversion efficiency for NOx, HC, PM after treatment system [71].
Regarding the issue of heavily sulfated petrol and Diesel fuels,
Conversion efficiency % causing important emissions and pollution. As a result, many research
NOx Hydrocarbons & CO PM projects have been conducted on the use of energy concepts, to analyze
DOC 60–90% 10–20% and improve ICE operations using various renewable fuels and non-
DPF 60–80% 90% renewable fuel mixtures. Engine researchers tested novel types of bio­
Urea/SCR 70–95% fuels, which later have been extendedly used in some countries already
LNT with hydrocarbon injection. 70–90% and has seen light in the low temperature combustion to fit with the
modification done on premixing, injection modes for ultra-low emis­
5.4. The potential of emission reduction and energy consumption sions combustion engines [74].
attenuation in hybrid vehicles
6.2. Engine technology
In hybrid vehicles, the largest part of the energy supplied by the fuel
is lost in the exhaust gas, with an average exhaust gas heating flow of As stated previously in the last section, the new engine design will
8.1 kW and an average exergy of 5.7 kW, demonstrating the high po­ include integrating new injection strategies, homogeneously charged
tential for the recovery of waste heat in hybrid vehicles. The results compression ignition, even more optimized turbocharging and EGR. Into
show that the average waste heat flow of a typical vehicle is 5.0 kW. In the bargain dual-fuelled vehicles (methanol/Biodiesel …) may be a
hybrid vehicles running in charge maintenance mode, the average heat potential candidate empowering novel pollution-free engines and it is
flow of the exhaust is 8.1 kW. The comparison shows that the temper­ expected to continue in the forthcoming. Furthermore, green hydrogen
ature level of these emission gases is even higher than in conventional produced from renewable energies (biomass, wind and solar energy) can
cars. Furthermore, this work shows that, due to higher temperatures, be used for new types of fuel cells and IC engines, making it increasingly
exhaust gases allergies in hybrid vehicles are higher even when internal popular amongst the futuristic approved energy resources [75].
combustion engines operate at higher efficiency. The average emissions
energy for a conventional car in the comparison example is 3.2 kW, but 6.3. Catalytic converter technology
the average emissions energy for a hybrid vehicle is 5.7 kW [72]. The use
of WHR systems to recover spent engine energy may become interesting Substantial advancement has been made in the development of after-
in order to develop more efficient but also cleaner engines, even if many treatment technologies and used compulsory catalyst materials. This
of the researched emissions mitigation approaches have a negative leads to more efficient, durable, lightweight, compact, and cost-effective
impact on fuel economy to some extent. after-treatment device (for e. g, eliminating or reducing the PGM content
in multi-way catalysts) [76]. Elbow and V shaped box close-coupled
6. Future improvement and advance in catalytic converter after treatment systems are shown in Fig. 11.
technologies
7. Recent developments and potential improvements to include
Original equipment manufacturers have been renovating the after- in emission control
treatment technology, design, and simultaneously improving the en­
gine capacity, facing a big challenge of reducing the impact of internal • The close coupling (Fig. 9) of catalysts and filters into a single device,
combustion pollution. These challenges are existent for different mar­ leading to multifunctional catalysts. For example, catalyst DPF,
kets, in fleet, spaceships, and industry and marine. The technologies of including DOC functions, and diesel particulate NOx reduction
emissions after treatment will be mainly focusing on fuel technology, catalyst combine DPF and LNT called (DPNR).
engine design and catalyst formulation preparation [73]. • Catalyst dispersion, where the load of the catalyst may vary over the
extent of the catalyst system. This improves the performance of

10
D. Bakhchin et al. Journal of the Energy Institute 111 (2023) 101410

Fig. 11. a) Elbow configuration of close-coupled Combined after treatment systems. [Johnson Matthey technology]. b) V shaped box catalyst layout by Ref. [76].

selective catalytic activity, maintains long-term stability, and us a better understanding of the specifics of the catalytic chemistry of all
significantly reduces the manufacturing cost. Scattering can also be kinetics of the oxidation and reduction reactions. It is expected that
cast-off for the manufacture of catalysts and filter systems, such as further properties of the mentioned materials will be investigated in the
DOC, or to implement different catalysts in diverse parts of catalyst future, importantly the kinetic activity during regeneration processes
substrates. and transient storage occurring through NOx catalyst, isotopic experi­
• Development of multifunctional catalysts through layering singular ments are the main key to address the mechanism of NOx sorption
catalysts, for example, the NOx trap/SCR system layering, which process and nitrogen formation and its spectro-kinetics, to associate
potentially improves performance in a wider operating range. In fact, analytics of exhaust gas with surface concentrations. It has been prom­
a combination of technological progress is needed to comply with inent that LNT-SCR coupled structures, using LNT to produce ammonia
increasingly stringent regulations, with the catalytic after-treatment during rich excursions and then store it and recycling afterwards in SCR
systems. The challenge will be the design of a post-treatment system catalyst, are of a particular interest. They are being improved to endorse
that can operate successfully in an extensive range of engines oper­ advanced NOx removal effectiveness granting reducing the platinum
ations, temperatures, and low temperature combustion conditions group metals usage and toxicity. Ammonia production from the NSR and
[77]. creating optimal device configurations for recycling it instead of slip
• The aim of future works is the design of integrated combined system, propagation is ultimately a genius solution for this purpose. The key
comprising a metal particulate filter with a lean NOx trap impreg­ challenge of maintaining a Diesel engine as essentially a prime choice for
nated with Ag/MgCO3, Ceria CeO2 and silicon carbide SiC, for high LD and HD passengers is combining energy density and fuel economy as
activity UHC mitigation and lean NOx trap close coupled with well as lessening pollution emissions and diminishing rates of carbon
ammonia slip catalyst ASC for regeneration of ammonia as re­ emissions especially during warming up and regeneration conditions.
ductants agent. The trend in this system has to be managed via the
use of electro-catalysis tuning of both materials the metal filter • Manufacturers may choose the proper thermally active materials to
substrate and through LNT alloys depending on the range of tem­ lower the light up temperature of catalyst, and join the procedure of
peratures required. energy recovery, to recycle energy through the catalytic process.
• Electrically heating methods need to be developed through energy
8. Conclusions & recommendations for future research work recuperation, and the waste heat recovery process (WHR) is a po­
tential solution to improve these innovative methods’ performance
The design and development of innovative catalytic technologies for and to overcome issues such cold start combustion and regeneration.
PM/NOx emission mitigation for lean burn vehicles has been lately a • Additionally, further testing and experimentation with combined
prevalent technical achievement. NOx Catalytic converters are in a catalyst systems of (DOC - LNT-SCR) and (cDPF -LNT) with SCR.
marketable position and are currently widespread in automotive appli­ • The eradication of NOx is considerably possible via means of post-
cation; research has been completed on diverse features of the synthesis, treatment procedure, more vulnerable than with thermodynamic
performance, and formulation of these devices. Currently, NSR and SCR methods like LTC modes, owing to the complexity of the control of
are representing the most powerful candidates for NOx emissions miti­ the aforementioned kinetics in-cylinder.
gation in lean engines. SCR is the most established technology that en­ • The combination of diverse processes is potentially the way that
tails onboarding urea containers, so it is used generally for heavy-duty, Diesel engines will be given a second chance through optimization to
and it is considered for light-duty vehicles. NSR has no requirement for keep its way running on roads, and will offer an ultra-low emissions,
large design modification for the reason that it utilizes exhaust gas as a increased system efficiency and decreasing its cost.
reductant, which is the most practical method for passenger vehicles. It
is very important for understanding the reagent trade-off synergy to
address the catalytic reaction process. Declaration of competing interest
Experimental and theoretical utensils are now accessible which give
The authors declare the following financial interests/personal

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D. Bakhchin et al. Journal of the Energy Institute 111 (2023) 101410

relationships which may be considered as potential competing interests: [13] K. Arole, M. Velhal, M. Tajedini, P.G. Xavier, E. Bardasz, M.J. Green, H. Liang,
Impacts of particles released from vehicles on environment and health, Tribol. Int.
Dikra Bakhchin reports financial support was provided by National
184 (2023), 108417, https://doi.org/10.1016/j.triboint.2023.108417.
Center For Scientific and Technical Research. [14] Rajesh Ravi, Pachamuthu Senthilkumar, K. Mohanraj, Design of heat exchanger for
exhaust heat recovery of a single cylinder compression ignition engine, J. Eng. Sci.
Acknowledgements Technol. 13 (2018) 2153–2165.
[15] R. Ravi, P. Senthilkumar, S.K. Vijayalakshmi, P. Kasinathan, A. Sundaram,
Jagannathan Sundarababu, CFD analysis of innovative protracted finned counter
This research work was fully funded by The National Center of Sci­ flow heat exchanger for diesel engine exhaust waste heat recovery, AIP Conf. Proc.
entific and Technical Research in Morocco and Foundation UM6P under 2316 (2021), https://doi.org/10.1063/5.0036457.
[16] W.J. Shaughnessy, M.M. Venigalla, D. Trump, Health effects of ambient levels of
the APRD project “Design and development of exhaust heat recovery respirable particulate matter (PM) on healthy, young-adult population, Atmos.
system and emission reduction technology for multi cylinder CRDI en­ Environ. 123 (2015) 102–111.
gine”. The authors would like to thank LERMA Labs, Rabat International [17] T. Vadivelu, L. Ramanujam, R. Ravi, S.K. Vijayalakshmi, M. Ezhilchandran, An
exploratory study of Direct injection (DI) diesel engine performance using
University, for ensuring the availability of facilities. CNSL—ethanol biodiesel blends with hydrogen, Energies 16 (2023) 415, https://
doi.org/10.3390/en16010415.
Abbreviations [18] I. Manisalidis, E. Stavropoulou, A. Stavropoulos, E. Bezirtzoglou, Environmental
and health impacts of air pollution: a review, Front. Public Health 8 (2020) 14,
https://doi.org/10.3389/fpubh.2020.00014. PMID: 32154200; PMCID:
ICE Internal combustion engines PMC7044178.
ATS After treatment systems [19] M.A. Mokhri, N.R. Abdullah, S.A. Abdullah, S. Kasalong, R. Mamat, Soot filtration
recent simulation analysis in diesel particulate filter (DPF), Procedia Eng. 41
NOx Nitrogen Oxides (NO, NO2)
(2012), https://doi.org/10.1016/j.proeng.2012.07.378.
SCR Selective Catalytic Reduction [20] N. Hooftman, M. Messagie, J. Van Mierlo, T. Coosemans, A review of the European
DPF Diesel Particulate Filter passenger car regulations – real driving emissions vs local air quality, Renew.
DOC Diesel Oxidation Catalyst Sustain. Energy Rev. 86 (2018) 1–21, https://doi.org/10.1016/j.rser.2018.01.012.
[21] D. Bauner, S. Laestadius, N. Iida, Evolving technological systems for diesel engine
LNT Lean NOx trap emission control: balancing GHG and local emissions, Clean Technol. Environ.
cDPF Catalyzed DPF Policy 11 (2009) 339–365.
LD - HD light duty & heavy-duty [22] A.K. Sharma, P.K. Sharma, V. Chintala, N. Khatri, A. Patel, Environment-friendly
biodiesel/diesel blends for improving the exhaust emission and engine
PM Particulate matter performance to reduce the pollutants emitted from transportation fleets, Int. J.
OSM Oxygen storing material Environ. Res. Publ. Health 17 (11) (2020) 3896, https://doi.org/10.3390/
NSC NOx storage catalyst ijerph17113896. PMID: 32486369; PMCID: PMC7312013.
[23] J. Usabiaga, M. Castells, F. Martínez, A. Olcer, A simulation model for road and
PGM Platinum group material maritime environmental performance assessment, J. Environ. Protect. 4 (7) (2013)
683–693, https://doi.org/10.4236/jep.2013.47079, 2013.
References [24] A. Gremminger, J. Pihl, M. Casapu, J. Grunwaldt, T.J. Toops, O. Deutschmann,
PGM based catalysts for exhaust-gas after-treatment under typical diesel, gasoline
and gas engine conditions with focus on methane and formaldehyde oxidation,
[1] A. Albatayneh, M. Assaf, D. Alterman, M. Jaradat, Comparison of the overall
Appl. Catal. B Environ. 265 (2020), 118571, https://doi.org/10.1016/j.
energy efficiency for internal combustion engine vehicles and electric vehicles,
apcatb.2019.118571.
Environ. Clim. Technol. 24 (1) (2020) 669–680, https://doi.org/10.2478/rtuect-
[25] G. Gerasimov, M. Pogosbekian, Nanostructured catalysts in vehicle exhaust control
2020-0041.
systems, in: L. Martínez, O. Kharissova, B. Kharisov (Eds.), Handbook of
[2] J.R. Serrano, R. Novella, P. Piqueras, Why the development of internal combustion
Ecomaterials, Springer, Cham, 2019, https://doi.org/10.1007/978-3-319-68255-
engines is still necessary to fight against global climate change from the perspective
6_120.
of transportation, Appl. Sci. 9 (21) (2019) 4597, https://doi.org/10.3390/
[26] S.K. Hoekman, Review of nitrous oxide (N2O) emissions from motor vehicles, SAE
app9214597.
International Journal of Fuels and Lubricants 13 (1) (2020) 79–98.
[3] O. Douadi, R. Ravi, M. Faqir, E. Essadiqi, A conceptual framework for waste heat
[27] P. Choudhury, S. Deo, An innovative approach for emission control using copper
recovery from compression ignition engines: technologies, working fluids & heat
plate catalytic converter, Int. J. Adv. Sci. Eng. Technol. (2014).
exchangers, Energy Convers. Manag. X 16 (2022), 100309, https://doi.org/
[28] M.K.A. Wardana, O. Lim, Review of improving the NOx conversion efficiency in
10.1016/j.ecmx.2022.100309. ISSN 2590-1745.
various diesel engines fitted with SCR system technology, Catalysts 13 (1) (2023)
[4] P. Bielaczyc, J. Woodburn, Trends in automotive emission legislation: impact on
67, https://doi.org/10.3390/catal13010067, 2023.
LD engine development, fuels, lubricants and test methods: a global view, with a
[29] S. Verhelst, J. Demuynck, R. Sierens, R. Scarcelli, N.S. Matthias, T. Wallner, Update
focus on WLTP and RDE regulations, Emiss. Control Sci. Technol. 5 (2019) 86–98,
on the progress of hydrogen-fueled internal combustion engines, Renew. Hydrogen
https://doi.org/10.1007/s40825-019-0112-3, 2019.
Technol. (2013) 381–400, https://doi.org/10.1016/B978-0-444-56352-1.00016-7.
[5] Rajesh Ravi, Pachamuthu Senthilkumar, Experimental investigation on innovatory
[30] H. Chu, W. Han, W. Cao, C. Tao, M. Raza, L. Chen, Experimental investigation of
waste heat recovery system impacts on DIESEL engine exhaust emissions, Energy
soot morphology and primary particle size along axial and radial direction of an
Sources, Part A Recovery, Util. Environ. Eff. (2020) 1–24, https://doi.org/
ethylene diffusion flame via eletron microscopy, J. Energy Inst. (2018), https://
10.1080/15567036.2020.1758247.
doi.org/10.1016/j.joei.2018.10.005.
[6] C. Pénard-Morand, I. Annesi-Maesano, Air pollution: from sources of emissions to
[31] C. Xu, H. Cho, Effect of methanol/water mixed fuel compound injection on engine
health effects, J. Breathe 1 (2) (2004) 108–119, 2004.
combustion and emissions, Energies 14 (2021) 4491, https://doi.org/10.3390/
[7] Paul J. Crutzen, Ozone production rates in an oxygen-hydrogen-nitrogen oxide
en14154491, 2021.
atmosphere, J. Geophys. Res. 76 (30) (1971) 7311–7327, 1971.
[32] Ferenc Martinovic, Lidia Castoldi, Fabio Alessandro Deorsola, Aftertreatment
[8] Rajesh Ravi, Oumaima Douadi, Manoranjitham Ezhilchandran, Mustapha Faqir,
technologies for diesel engines: an overview of the combined systems, Catalysts
Elhachmi Essadiqi, Merouan Belkasmi, Shivaprasad K. Vijayalakshmi, A practical
(2021). https://doi:10.3390/catal11060653.
approach-based technical review on effective utilization of exhaust waste heat from
[33] Z. Zhang, J. Tian, J. Li, C. Cao, S. Wang, J. Lv, W. Zheng, D. Tan, The development
combustion engines, Energy Sources, Part A Recovery, Util. Environ. Eff. 45 (4)
of diesel oxidation catalysts and the effect of sulfur dioxide on catalysts of metal-
(2023) 10010–10033, https://doi.org/10.1080/15567036.2023.2242321.
based diesel oxidation catalysts: a review, Fuel Process. Technol. 233 (2022),
[9] J. Kim, J. Kim, H. Kim, H. Kim, S. Kang, J. Ryu, S. Shim, Reduction of NOx emission
107317, https://doi.org/10.1016/j.fuproc.2022.107317.
from the cement industry in South Korea: a review, Atmosphere 13 (1) (2022) 121,
[34] T. Selleri, A.D. Melas, A. Joshi, D. Manara, A. Perujo, An overview of lean exhaust
https://doi.org/10.3390/atmos13010121.
deNOx aftertreatment technologies and NOx emission regulations in the European
[10] Rajesh Ravi, Pachamuthu Senthilkumar, Design and development of innovative
union, Catalysts 11 (3) (2021) 404, https://doi.org/10.3390/catal11030404.
protracted-finned counter flow heat exchanger (PFCHE) for an engine WHR and its
[35] R. Dong, Z. Zhang, Y. Oui, H. Huang, C. Cao, Examen des filtres à particules pour
impact on exhaust emissions, Energies 11 (2018) 2717, https://doi.org/10.3390/
les moteurs à combustion interne, Processus 10 (2022) 993, https://doi.org/
en11102717.
10.3390/pr10050993.
[11] A. Sousa, M. Pastorinho, M. Masjedi, M. Urrutia-Pereira, M. Arrais, E. Nunes, T. To,
[36] V. Palma, P. Ciambelli, E. Meloni, Optimising the catalyst load for microwave
A. Ferreira, C. Robalo-Cordeiro, C. Borrego, J. Teixeira, L. Taborda-Barata, Issue 1 -
susceptible catalyzed DPF, Chem. Eng. Trans. 29 (2012) 637–642.
“Update on adverse respiratory effects of outdoor air pollution, Pulmonology 28
[37] M. Adamowska, P.D. Costa, Structured Pd/γ-al2o3 prepared by washcoated
(5) (2022) 376–395, https://doi.org/10.1016/j.pulmoe.2021.12.007.
deposition on a ceramic honeycomb for compressed natural gas applications,
[12] Rajesh Ravi, Senthilkumar Pachamuthu, Padmanathan Kasinathan, Computational
J. Nanopart. 2015 (2015) 1–9, https://doi.org/10.1155/2015/601941.
and experimental investigation on effective utilization of waste heat from diesel
[38] A.C. Marques, A. Mocanu, N.Z. Tomić, S. Balos, E. Stammen, A. Lundevall, S.
engine exhaust using a fin protracted heat exchanger, Energy 200 (2020), 117489,
T. Abrahami, R. Günther, J.M. de Kok, Review on adhesives and surface treatments
https://doi.org/10.1016/j.energy.2020.117489. ISSN 0360-5442.
for structural applications: recent developments on sustainability and

12
D. Bakhchin et al. Journal of the Energy Institute 111 (2023) 101410

implementation for metal and composite substrates, Materials 13 (24) (2020) [58] S. Tischer, M. Börnhorst, J. Amsler, G. Schoch, O. Deutschmann, Thermodynamics
5590, https://doi.org/10.3390/ma13245590. and reaction mechanism of urea decomposition, Phys. Chem. Chem. Phys. (2019),
[39] I. Kocemba, I. Śmiechowicz, M. Jędrzejczyk, J. Rogowski, J.M. Rynkowski, High https://doi.org/10.1039/c9cp01529a.
catalytic activity of Pt/Al2O3 catalyst in CO oxidation at room temperature—a [59] Y. Chen, H. Huang, Z. Li, H. Wang, B. Hao, Y. Chen, G. Huang, X. Guo, Study of
new insight into strong metal–support interactions, Catalysts 11 (12) (2021) 1475, reducing deposits formation in the urea-SCR system: mechanism of urea
https://doi.org/10.3390/catal11121475. decomposition and assessment of influential parameters, Chem. Eng. Res. Des. 164
[40] Marc Ziemba, Christian Schilling, M. Verónica Ganduglia-Pirovano, Christian Hess, (2020) 311–323, https://doi.org/10.1016/j.cherd.2020.10.010.
Toward an Atomic-Level Understanding of Ceria-Based Catalysts: when Experiment [60] S. Halonen, T. Kangas, M. Haataja, et al., Urea-water-solution properties: density,
and Theory Go Hand in Hand, 2021, https://doi.org/10.1021/acs. viscosity, and surface tension in an under-saturated solution, Emiss. Control Sci.
accounts.1c00226. Technol. 3 (2017) 161–170, https://doi.org/10.1007/s40825-016-0051-1.
[41] Y. Li, M. Kottwitz, J.L. Vincent, et al., Dynamic structure of active sites in ceria- [61] T.D. Elmøe, R.Z. Sørensen, U. Quaade, C.H. Christensen, J.K. Nørskov,
supported Pt catalysts for the water gas shift reaction, Nat. Commun. 12 (2021) T. Johannessen, A high-density ammonia storage/delivery system based on Mg
914, https://doi.org/10.1038/s41467-021-21132-4. (NH3)6Cl2 for SCR–DeNOx in vehicles, Chem. Eng. Sci. 61 (8) (2006) 2618–2625,
[42] M. Twigg, Advanced integrated exhaust aftertreatment systems and the https://doi.org/10.1016/j.ces.2005.11.038.
mechanisms of NOx emissions control. Internal Combustion Engines: performance, [62] R. You, M. Meng, J. Zhang, L. Zheng, T. Hu, X. Li, A noble-metal-free SCR-LNT
Fuel Econ. Emissions (2013) 219–229, https://doi.org/10.1533/ coupled catalytic system used for high-concentration NOx reduction under lean-
9781782421849.6.219. burn condition, Catal. Today 327 (2019) 347–356, https://doi.org/10.1016/j.
[43] S. Roy, J. Ling-Chin, T. Bohl, A. Giampieri, A. Smallbone, A.P. Roskilly, Biodiesel: cattod.2018.03.022.
Emissions and Control, Challenges, Potential and Prospects, second ed., [63] M. Iwasaki, H. Shinjoh, A comparative study of “standard”, “fast” and “NO2” SCR
Comprehensive Renewable Energy, 2022, pp. 372–386, https://doi.org/10.1016/ reactions over Fe/zeolite catalyst, Appl. Catal. A: Gene. 390 (1–2) (2010) 71–77,
B978-0-12-819727-1.00063-7. https://doi.org/10.1016/j.apcata.2010.09.034.
[44] B. Haynes, H. Wagner, Soot formation, Prog. Energy Combust. Sci. 7 (4) (1981) [64] B. Kim, H. Jeong, J. Bae, P.S. Kim, C.H. Kim, H. Lee, Lean NOx trap catalysts with
229–273, https://doi.org/10.1016/0360-1285(81)90001-0. high low-temperature activity and hydrothermal stability, Appl. Catal. B Environ.
[45] A.D. Jatkar, A New Catalyst Support Structure for Automotive Catalytic 270 (2020), 118871, https://doi.org/10.1016/j.apcatb.2020.118871.
Converters, 1997, https://doi.org/10.4271/971032. SAE Technical Paper 971032. [65] C.D. DiGiulio, J.A. Pihl, J. Choi, J.E. Parks, M.J. Lance, T.J. Toops, M.D. Amiridis,
[46] R. Gao, C. Tong, H. You, X. Zhou, X. Huang, M. Pan, Research on regeneration NH3 formation over a lean NOX trap (LNT) system: effects of lean/rich cycle timing
characteristics of diesel particulate filter based on fluid-thermal-solid coupling, and temperature, Appl. Catal. B Environ. 147 (2014) 698–710, https://doi.org/
Process Saf. Environ. Protect. 163 (2022) 298–307, https://doi.org/10.1016/j. 10.1016/j.apcatb.2013.09.012.
psep.2022.05.031. [66] Schönebaum Simon, Jürgen Dornseiffer, Peter Mauermann, Composition/
[47] A. Porta, T. Pellegrinelli, L. Castoldi, et al., Low temperature NOx adsorption study performance evaluation of lean NOx trap catalysts for coupling with SCR
on Pd-promoted zeolites, Top. Catal. 61 (2018) 2021–2034, https://doi.org/ technology, ChemCatChem (2021), https://doi.org/10.1002/cctc.202001761.
10.1007/s11244-018-1045-8. [67] W. Karim, C. Spreafico, A. Kleibert, et al., Catalyst support effects on hydrogen
[48] T. Huang, G. Hu, Z. Meng, D. Zeng, Exhaust temperature control for safe and spillover, Nature 541 (2017) 68–71, https://doi.org/10.1038/nature20782.
efficient thermal regeneration of diesel particulate filter, Appl. Therm. Eng. 189 [68] P. Forzatti, L. Lietti, L. Castoldi, Storage and reduction of NO x over LNT catalysts,
(2021), 116747, https://doi.org/10.1016/j.applthermaleng.2021.116747. Catal. Lett. 145 (2015) 483–504, https://doi.org/10.1007/s10562-014-1343-0.
[49] X. Mei, X. Zhu, Y. Zhang, et al., Decreasing the catalytic ignition temperature of [69] R. Mrad, A. Aissat, R. Cousin, D. Courcot, S. Siffert, Catalysts for NOx selective
diesel soot using electrified conductive oxide catalysts, Nat. Catal. 4 (2021) catalytic reduction by hydrocarbons (HC-SCR), Appl. Catal. Gen. 504 (2015)
1002–1011, https://doi.org/10.1038/s41929-021-00702-1. 542–548, https://doi.org/10.1016/j.apcata.2014.10.021.
[50] V. Palma, P. Ciambelli, E. Meloni, A. Sin, Catalytic DPF microwave assisted active [70] K. Lee, B. Choi, HC-SCR system combining Ag/Al2O3 and Pd/Al2O3 catalysts with
regeneration, Fuel 140 (2015) 50–61, https://doi.org/10.1016/j.fuel.2014.09.051. resistance to hydrothermal aging for simultaneous removal of NO, HC, and CO,
[51] Yh Zhang, Dm Lou, Pq Tan, et al., Study of spatial and temporal aging J. Ind. Eng. Chem. 102 (2021) 51–68, https://doi.org/10.1016/j.jiec.2021.06.030.
characteristic of catalyzed diesel particulate filter catalytic performance used for [71] Z. Ye, L. Zhao, A. Nikiforov, J. Giraudon, Y. Chen, J. Wang, X. Tu, A review of the
diesel vehicle, Sci. Rep. 10 (2020), 19761, https://doi.org/10.1038/s41598-020- advances in catalyst modification using nonthermal plasma: process, Mechanism
76634-w. and Applications, Adv. Colloid Interface Sci. 308 (2022), 102755, https://doi.org/
[52] B. Choi, K. Lee, G. Son, Review of recent after-treatment technologies for de-NOx 10.1016/j.cis.2022.102755.
process in diesel engines, Int. J. Automot. Technol. 21 (2020) 1597–1618, https:// [72] T. Selleri, A.D. Melas, A. Joshi, D. Manara, A. Perujo, An overview of lean exhaust
doi.org/10.1007/s12239-020-0150-4. deNOx aftertreatment technologies and NOx emission regulations in the European
[53] S. Wang, Y. Niu, G. Zhu, Y. Ding, X. Guo, S. Hui, NO formation and destruction union, Catalysts 11 (3) (2021) 404, https://doi.org/10.3390/catal11030404.
during combustion of high temperature preheated pulverized coal, J. Energy Inst. [73] A. Giampieri, J. Ling-Chin, Z. Ma, A. Smallbone, A. Roskilly, A review of the
99 (2021) 82–87, https://doi.org/10.1016/j.joei.2021.08.009. current automotive manufacturing practice from an energy perspective, Appl.
[54] L. Han, S. Cai, M. Gao, J.Y. Hasegawa, P. Wang, J. Zhang, L. Shi, D. Zhang, Energy 261 (2020), 114074, https://doi.org/10.1016/j.apenergy.2019.114074.
Selective catalytic reduction of NOx with NH3 by using novel catalysts: state of the [74] Seyed Ehsan Hosseini, Brayden Butler, An overview of development and challenges
art and future prospects, Chem. Rev. 119 (19) (2019 Oct 9) 10916–10976, https:// in hydrogen powered vehicles, Int. J. Green Energy 17 (1) (2020) 13–37, https://
doi.org/10.1021/acs.chemrev.9b00202. Epub 2019 Aug 15. PMID: 31415159. doi.org/10.1080/15435075.2019.1685999.
[55] M. Seneque, F. Can, D. Duprez, X. Courtois, ACS Catal. 6 (7) (2016) 4064–4067, [75] C. Soares, Basic Design Theory. Gas Turbines, second ed., 2015, pp. 913–958,
https://doi.org/10.1021/acscatal.6b00785. https://doi.org/10.1016/B978-0-12-410461-7.00019-5.
[56] W. Li, K. Li, Y. Ye, et al., Efficient electrocatalytic nitrogen reduction to ammonia [76] V. Praveena, M.L.J. Martin, A review on various after treatment techniques to
with aqueous silver nanodots, Commun. Chem. 4 (2021) 10, https://doi.org/ reduce NOx emissions in a CI engine, J. Energy Inst. 91 (5) (2018) 704–720,
10.1038/s42004-021-00449-7. https://doi.org/10.1016/j.joei.2017.05.010.
[57] A.M. Bernhard, D. Peitz, M. Elsener, A. Wokaun, O. Kröcher, Hydrolysis and [77] R. Parashuram Chitragar, K.V. Shivaprasad, G.N. Kumar, Use of hydrogen in
thermolysis of urea and its decomposition byproducts biuret, cyanuric acid and internal combustion engines: a comprehensive study, J. Mech. Eng. Biomech. 1 (3)
melamine over anatase TiO2, Appl. Catal. B Environ. 115-116 (2012) 129–137, (2016) 84–96, 2016.
https://doi.org/10.1016/j.apcatb.2011.12.013.

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