energies

Review
Recent Advances in the Development of Automotive Catalytic
Converters: A Systematic Review
Laura Robles-Lorite 1 , Rubén Dorado-Vicente 1 , Eloísa Torres-Jiménez 1, * , Gorazd Bombek 2 and Luka Lešnik 2

1 Department of Mechanical and Mining Engineering, University of Jaén, Campus las Lagunillas, s/n,
23071 Jaén, Spain; lrl00024@red.ujaen.es (L.R.-L.); rdorado@ujaen.es (R.D.-V.)
2 Faculty of Mechanical Engineering, University of Maribor, Smetanova 17, SI-2000 Maribor, Slovenia;
gorazd.bombek@um.si (G.B.); luka.lesnik@um.si (L.L.)
* Correspondence: etorres@ujaen.es

Abstract: Despite the current boost in the use of electric vehicles to reduce the automotive sector’s
footprint, combustion vehicles are and will be present in our cities in both the immediate and long
term. In this sense, catalytic converters, which are exhaust gas post-treatment systems for vehicle
emission control, are critical for complying with increasingly stringent environmental regulations.
This work proposes a systematic review to identify the most relevant knowledge regarding the
parameters (materials, geometries, and engine conditions), conditions (cold start, oxygen storage,
and deactivation), and mathematical models to consider in the design of catalytic converters. The
Scopus database contains 283 records related to this review’s objective. After applying the inclusion
and exclusion criteria, 65 reports were retrieved for evaluation. A table was created to present the
results and prepare this manuscript. The evaluation revealed that the following topics were active:
the study of non-noble catalyst materials, as well as new substrate materials and geometries, for
designing more compact and cost-effective catalytic converters; the development of strategies to
improve conversion during cold starts; and the development of accurate and fast estimation models.

Keywords: systematic review; automotive converters; catalytic converter; emissions reduction;

exhaust gas post-treatment; catalyst deactivation; oxygen storage; numerical models
Citation: Robles-Lorite, L.;
Dorado-Vicente, R.; Torres-Jiménez,
E.; Bombek, G.; Lešnik, L. Recent
Advances in the Development of
Automotive Catalytic Converters: A 1. Introduction
Systematic Review. Energies 2023, 16, Despite the significant efforts currently being made in the development of electric
6425. https://doi.org/10.3390/ vehicles, most road transport is still powered by internal combustion engines, which
en16186425 primarily run on liquid fuels derived from petroleum and their blends with biofuels.
Academic Editor: João C. C. Many advantages of combustion engines are currently unattainable with electric
Henriques engines, especially in the transport sector. Some examples are the high power-to-weight
ratio and the high energy content of conventional fuels that enable a fast refill [1].
Received: 1 August 2023 Even with complete combustion and consequently no emissions of polluting gases,
Revised: 25 August 2023
CO2 emissions concern governments, as they contribute to global warming. However,
Accepted: 2 September 2023
recent studies based on life-cycle assessments demonstrate that until electricity genera-
Published: 5 September 2023
tion becomes green, the CO2 emission rate of electric vehicles is comparable to that of
internal combustion engine vehicles powered by gasoline and diesel [2]. Furthermore, a
significant reduction in CO2 emissions from internal combustion engines can be achieved
Copyright: © 2023 by the authors.
through the use of synthetic fuels [3], also called e-fuels, power-to-liquid (PtL) fuels, or
Licensee MDPI, Basel, Switzerland. power-to-gas (PtG) fuels.
This article is an open access article E-fuels are synthetic hydrocarbons resulting from the combination of renewable hydro-
distributed under the terms and gen and CO2 captured either from concentrated sources or from the air. They are classified
conditions of the Creative Commons as low-carbon sustainable fuels, and it is believed that they will play a crucial role in the
Attribution (CC BY) license (https:// decarbonization of transport.
creativecommons.org/licenses/by/ Synthetic fuels avoid some problems concerning the use of biomass-derived fuels,
4.0/). such as land use shortages and interference with food supplies [4]. Additional advantages

Energies 2023, 16, 6425. https://doi.org/10.3390/en16186425 https://www.mdpi.com/journal/energies

Energies 2023, 16, 6425 2 of 24

of synthetic fuels are that they provide a variety of fuel sources, avoid dependence on
fuel-exporting countries, allow for the improvement of the fuel energy density [5], and can
replace fossil fuels without the need for modifications to the internal combustion engine
and without a complete overhaul of the energy supply chain and economics [6].
There are also health challenges related to electric vehicles, such as the disposal of their
batteries, which can create severe threats to the natural environment and public health [7].
In the case of internal combustion engines, despite the great advances in both engine
efficiency and the technologies used to control exhaust pollution, some small amounts
of undesirable emissions are released into the atmosphere, consisting mainly of carbon
monoxide (CO), hydrocarbons (HC), and nitrogen oxides (NOx ) [8]. In this regard, catalytic
converters (CCs) are the main technological solution for satisfying the stringent emissions
limits, as they can achieve very high conversion efficiencies, which range between 90 and
99.9% [9]. Catalytic converters are widely used in the automotive sector for reducing
harmful gas emissions, but they are also employed in other industrial applications such as
hydrogen production or methane autothermal reforming [10]. Automotive CCs perform
two main functions: reduction and oxidation. The first consists of reducing NOx to N2 + O2 ,
and the second to oxidizing CO to CO2 and HC to CO2 + H2 O.
Two-way catalytic converters only perform the oxidation reaction function. This
kind of converter is used in diesel engines because their high NOx emissions require
specific techniques to eliminate them. These techniques include exhaust gas recirculation
(EGR) [11] and selective catalytic reduction (SCR) systems [12]. SCR systems require an
injection of urea that is thermally decomposed to produce ammonia, which is the reagent
in the reduction reaction. Diesel oxidation catalysts (DOCs) are the most commonly used
converters for diesel engines since they can efficiently oxidize CO and HC, as well as
particulate matter (PM).
Three-way catalytic converters (TWCs) perform both oxidation and reduction func-
tions simultaneously. TWC systems are suitable for gasoline engines, as they emit very
low or negligible amounts of NOx [13]. There are two substrates inside a TWC. The first
is the reduction substrate, which acts on the exhaust gases, and the second performs the
oxidation process.
Scientific reviews aid in gathering, understanding, and applying the overwhelming
number of publications in specific fields, such as CCs. This work uses a systematic review
methodology to collect scientific works on the topic of CCs that comply with specific
eligibility criteria and answer a set of specific questions or review objectives.
The questions considered have been defined according to the population, intervention,
comparator, and outcome (PICO) framework. This approach for formulating research ques-
tions is usually limited to clinical studies. However, as the work of Nishikawa-Pacher [14]
claims, it can be extended to other disciplines like the present work.
Regarding the above PICO scheme, the following are considered:
• Population: Automotive catalytic converters (CCs);
• Intervention: Experimental tests and simulations;
• Comparison: Simulation vs. test-literature experimental data;
• Outcome: The responses to study and improve include the catalyst’s cost, cold-start
performance and light-off temperature, CC efficiency, catalyst poisoning, emissions,
the viability of alternative techniques, and simulation (agreement, computational time,
integration, or implementation complexity).
Taking into account the above definitions, the research questions or review objectives
include:
• What are the geometries, materials, and wash coats used in CCs, including both
conventional and recent alternatives?
• What are the strategies for improving the cold-start performance of CCs?
• What is the role of oxygen storage?
• What parameters influence deactivation and to what extent?
Energies 2023, 16, 6425 3 of 24

• What are the main mathematical or simulation methods used to understand the
performance of automotive CCs?
This review is organized as follows. Section 2 describes the eligibility criteria and the
search, screening, and synthesis procedures. Sections 3 and 4 present the synthesis results
collected to answer the above-mentioned research questions. Finally, the main conclusions
are drawn in Section 5.

2. Systematic Review Methodology

Review works aim to gain knowledge in specific scientific fields, as well as help
identify challenges being faced. Scholars, professionals, and policymakers trust scientific
literature to make decisions, but deepening a topic requires effort and time due to the
continuously growing records (conferences, papers, proceedings, etc.). These shortcomings
can be mitigated through adequate reviews.
To the best of the authors’ knowledge, literature or narrative reviews, as well as system-
atic ones, are the most common types used in engineering works. For interested readers, the
work of Grant et al. [15], which focuses on health research, identified 14 methodologies by
assessing the processes required in a review: search, appraisal, synthesis, and the analysis
SALSA framework.
Narrative reviews describe a particular topic with the help of existing publications.
This approach, which is conducted by experts, provides a chance to delete duplicates and
assess the value of existing works. Nevertheless, there is no specific review procedure;
therefore, this approach can inadvertently omit records, leading to bias.
On the other hand, systematic reviews gather existing investigations to answer specific
questions following a detailed search, appraisal, and synthesis protocol [16]. Despite
systematic reviews requiring more effort and time, these works are reproducible and
provide precise answers, thus reducing the risk of bias due to their comprehensive nature.

2.1. PRISMA Framework

In the present review, we follow the Preferred Reporting Items for Systematic Reviews
and Meta-Analyses (PRISMA) framework. The proposed method (described in the follow-
ing paragraphs) adapts the PRISMA statement, which focuses on studies about the effects
of health interventions, to answer the engineering questions defined in Section 1, providing
a reproducible and updateable review.
A transparent review process based on a checklist of 27 items is critical according
to the PRISMA statement. The PRISMA checklist identifies the items to report in the
introduction, methods, results, and discussion sections of a systematic review. Among the
papers used to understand and apply the PRISMA approach, in this review, we consider
the 27-item checklist and its expanded version [17], as well as the PRISMA 2020 explanation
and elaboration document [18].

2.2. Method’s Main Elements

The PICO framework described in Section 1 helps define the records (title and abstract
of a published study indexed in a database or website) to be included. Specifically, only
records regarding the materials, manufacturing, and geometries of automotive CCs for
emission control (Population); existing experimental and simulation approaches used to
understand and improve their performance (Intervention); and conventional approaches
(experimental and/or numerical) are included for comparison against novel strategies
(Comparison), and only reports containing information about the selected PICO outcomes
(catalyst’s cost, cold-start performance, CC efficiency, etc. (Outcomes)) are included.
The records of research papers, conference proceedings, and book chapters in the
English language up to the present are eligible (eligibility criteria). Nevertheless, they
must include quantitative or trend results regarding the outcomes indicated by the PICO
framework (ineligible criteria).
Energies 2023, 16, 6425 4 of 24

Regarding the search procedure, the Scopus database was used to gather scientific
records from 1946 (database inception) to the search date of 19 June 2023. We did not
collect gray literature and did not examine references or cited works (no snowball or
forward searching).
To define an adequate keyword combination to obtain records that met the eligibility
criteria, we started with several tentative combinations, and the final one used in this work
in Scopus pseudo-code was:
( TITLE (“Catalytic converter*”) AND KEY (“Catalyst” OR “material*” OR “manu-
factur*” OR “monolith” OR “substrate” OR “geometry”) AND TITLE-ABS-KEY (“cost*”
OR “emission*” OR “agreement” OR “energy” OR “computation*” OR “time”) AND
TITLE-ABS-KEY ( automo* ) )
The search using the above combination resulted in 283 records, which were subjected
to a screening procedure (Figure 1 shows the screening flow diagram). We applied a
double-checking selection strategy. In the first step, we automatically selected 20% of the
records (50 works) that accounted for 80% of the citations. Pareto’s method automatically
identifies works that, according to most scholars, have made significant contributions to
the topic (Figure 2). The same number of the most relevant papers, considering the Scopus
relevance algorithm, were also selected. This statistical calculation relates to how well the
search criteria align with the database records [19], as per PRISMA guidelines. Finally, we
retrieved the last 50 records most recently published to incorporate updated information.
The resulting 150 records selected in the first step were then subjected to a second
check, where three reviewers read and assessed the titles and abstracts. In this step, each
reviewer screened 50 different records, checking the eligibility criteria. Disagreements were
resolved by consensus. Additionally, one reviewer identified duplicate records. After the
screening procedure, the final number of records to include was (after deleting duplicates)
26 (Pareto list) + 34 (most recently published) + 37 (Scopus relevance) = 97 records.

Identification of new studies via databases and registers

Identification

Records identified from: Records removed before screening:

Databases (n = 1): Records marked as ineligible by automation
Scopus (n = 283) tools (n = 155)

Records screened Records excluded

(n = 128) (n = 31)
Screening

Reports sought for retrieval Reports not retrieved

(n = 97) (n = 7)

Reports excluded:
Reports assessed for eligibility
No respond research questions (n = 5)
(n = 90)
No enough information (n = 20)
Included

Reports of new included studies

(n = 65)

Figure 1. Flow diagram of the screening and synthesis results (elaborated by the authors using the
online application described in [20]).
Energies 2023, 16, 6425 5 of 24

Figure 2. Pareto diagram for selecting the most cited records. The diagram only represents the
collected records.

For the synthesis, a table with different fields was completed after reading each of
the 90 reports retrieved (from 97 records, as the authors of this review did not have access
to 7 of the reports). Figure 3 shows the fields considered and an example of one row.
The authors decided on the list of fields by consensus after reading several reports, and
the information obtained was discussed, similar to a narrative review, and presented in
concise tables (comprising only critical fields) in Sections 3 and 4. The eligibility criteria
for including a report were similar to those used in the screening stage but were based on
the collected information summarized in the synthesis table. Inclusion was determined by
finding enough information in the synthesis table, including at least the paper’s objective,
approach study, and main results, and checking whether this information related to the
research questions.

Converted
Reference Study Type Engine Fuel Objective Approach Assumptions
species

1-D transient 1D transient

Identify SAi • !Dimensional model
emission analysis model (cold start
Simplified HC, NOx, optimal • Chemical reactions:
of LPG engine SI LPG period) of the city
catalytic
Model co operating Langmuir-Hinshelwood
driving CVS-75
conditions type equations
converter ... mode

Computational Testing Catalyst Monolith Manufacturing

Software Monolith dimensions and structure
time method Material material technique

Two CC:
600 cpsi, Wall thickness 0,114 mm
Platinum and
AMESim Ceramic 400 cpsi, Wall thickness 0,140 mm
rhodium
Average CC dimensions / mm: D118,
L136

Advantages/Disadvantages Input Output Validation Informed Results Inclusion

Advantages: SAi facilitates Optimal SAi & operational conditions

warm-up during cold start decreased HC and CO emissions
by encouraging exothermic SAi optimal operation conditions: 1.6 g/s
SAi air flow
oxidation of residual Emissions of air flow rate for 30 s
rate Experimental
hydrocarbons during At optimal condition: Light-off time was YES
Supply data
Disadvantages: Radial mass cold start 6.9 s faster and HC and CO emissions
time
transport and diffusion decreased 29% and 50%, respectively
inside monoliths were not while NO emissions increased
considered approximately 12%

Figure 3. Synthesis table fields: example of one row.

The outcomes collected during the synthesis stage were expressed in mm and cells
per square inch (cpsi) for the monolith geometry, as well as in percentage conversions
for species emissions. International units were used for temperature, pressure, or other
measurements when reported. Different abbreviations (summarized in the Abbreviations
Energies 2023, 16, 6425 6 of 24

section) were used to simplify the summary tables generated during synthesis. This review
does not present a statistical or meta-analysis of the report results due to the qualitative
and quantitative nature of the data, and the variables related to the outcomes considered
vary widely among the records.
Finally, the most probable bias risks are the omission of some records during the
search procedure, as it did not consider forward or snowball searching, and the first step of
the proposed double-checking procedure, where an automatic procedure was used as a
reliability assessment tool for selecting records.

3. Experimental Studies—Critical Aspects in CC Design

Many factors affect a CC’s efficiency, such as the cold start, the CC’s capacity to store
O2 , catalyst deactivation, the catalyst’s material, and the internal geometry of the catalytic
converter (CC). The study of these factors allows researchers to improve the efficiency of
CCs. This section reviews the experimental methods analyzed to improve the efficiency
of CCs.

3.1. Cold Start

The light-off temperature is the temperature at which the conversion efficiency reaches
50%. When the CC reaches that temperature, it is said to be activated, and the time that
elapses until that moment is called the light-off time. During the light-off time, the efficiency
of the CC is close to zero. The tailpipe-polluting gases emitted during this period are called
cold-start emissions, which account for 60 to 80% of the total emissions [21]. Consequently,
much of the research related to CCs is focused on reducing cold-start emissions.
Emissions during a cold start can be reduced by decreasing the light-off time, which
lasts about 180 s. Active and passive methods can be applied to reach this target. Active
methods comprise heating systems, such as electrical and fuel-burner systems, as well
as air or hydrogen injection systems. Passive methods include the use of a pre-catalyst,
thermal management, and placing the CC closer to the exhaust manifold. All of these
systems must be appropriately designed to avoid excessively high temperatures that can
lead to durability problems.
Electrical systems require 1 to 2 kW in 20 to 40 s to reduce the light-off time, and the
alternator or battery must supply the electrical energy, which requires twice this energy
from the fuel. Fuel-burner systems are faster in reaching light-off than electrical ones
since they can deliver significantly more power (10 to 20 kW) but are more complex [22].
Bhaskar et al. [23] tested the influence of air supply, together with an electrically heated pre-
catalyst, both placed before the main catalytic converter, on the final conversion efficiency.
The pre-catalyst was heated using a band-type resistance heater (RHCC). It was composed
of a stainless-steel substrate for a quick warm-up and was coated with copper oxide metal
as the catalyst due to its low cost. The experimental results showed that this combination
of strategies significantly reduced CO and HC emissions during cold starts. The best
improvement was achieved by combining the RHCC and 90 L/min of air supply for a
duration of 40 s from the engine’s cold start.
Injecting air into the exhaust manifold helps the oxidation reaction of CO and HC,
which is an exothermic reaction that allows the temperature of the gases to rise before they
reach the CC inlet. Injecting air and using pre-catalysts are methods supported by the
high HC levels attributed to the rich operation required during the engine’s cold start [24].
However, the high temperatures reached require optimization of the CC so that it can
endure the harsh environment.
Yun performed experimental tests to validate a 1D simulation of the entire exhaust
system of a liquefied petroleum gas (LPG) vehicle equipped with a secondary air injection
(SAI) system. The author found that, during the cold-start period, at the optimal operating
condition of this supplementary system (1.6 g/s of air flow rate for 30 s), the light-off time
was 6.9 s faster, leading to a decrease in HC and CO emissions of 29% and 50%, respectively,
Energies 2023, 16, 6425 7 of 24

whereas NO emissions increased by approximately 12%. These results demonstrate that SAI
systems facilitate warm-up during cold starts by encouraging exothermic oxidation [25].
Kovacev et al. [26] studied the effect of adding hydrogen on the light-off behavior
of new substrate geometries obtained via additive manufacturing and experimentally
demonstrated that the addition of hydrogen shifts the light-off curves of CO, total hy-
drocarbons (THC), and NO to lower temperatures, which leads to an improvement in
cold-start emissions.
Passive methods can achieve the same improvements in the inlet gas temperature.
This is the case when using pre-catalysts (close-coupled catalyst converters) placed before
the main catalytic converter (also called underfloor catalytic converters) and close to the
engine’s exhaust manifold to increase conversion efficiency through a fast light-off time.
According to a study by Lee et al. [27], a significant reduction in the light-off time can
be achieved using pre-catalysts if the ignition retard and misfire are controlled to avoid
catalyst temperatures above 1050 ◦ C, as these temperatures cause drastic thermal aging in
the CC, leading to its deactivation and, consequently, to lower conversion efficiency. The
spark retard increases with the engine load. If the misfire or spark retard increases, the
afterburn in the exhaust increases, resulting in a rapid rise in the exhaust gas temperature.
Mahadevan and Subramanian [21] tested several approaches to simultaneously reduce
the light-off time, thermal degradation, and aging through the use of a Dynamic Catalytic
Converter System (DCCS), consisting of a telescopic pipe, which enables regulating the
length of the pipe so that it can be placed very close to the exhaust manifold during cold
start of the vehicle. Once it attains the light-off temperature, it can be moved to the position
of any other conventional catalyst to reduce damage from overheating. They tested the
DCCS at different positions from the exhaust manifold and also its combination with a
pre-catalyst (PC) and hot air injected at the exhaust manifold. They concluded that all
methods tested resulted in a reduction in the light-off time; however, the lowest time to
light-off (10 s for CO and 13 s for HC) was observed with a combination of the DCCS
and preheated air delivered at 80 ◦ C and 20 L/min. The authors also observed that HC
becomes oxidized at higher temperatures compared to CO, which is supported by the
lower activation energy needed to oxidize CO to CO2 as it is a single-step reaction.
Improved passive methods are based on thermal management, which allows the
storage or regulation of the amount of heat released by the exhaust gases so that the
converter is above the light-off temperature for as long as possible. These methods include
the use of refractory substrates or air around the converter itself. Some problems related to
conventional insulation are that they do not provide more than 3 h of heat retention, and
they can lead to exceeding temperature safety limits, resulting in thermal degradation and
lower conversion efficiency. These problems can be overcome using variable-conductance
insulation to regulate the heat released and the phase change material to increase heat
storage [22].
Similar to the cold start is the cool-down process, which produces high tail-pipe
emissions because the temperature of the CC falls below the light-off temperature. This
problem is also critical for hybrid vehicles since the engine goes offline due to the hybrid
nature of the vehicle. In this regard, Young et al. [28] proposed to include additional
engine starts in the supervisory control strategy to prevent the CC from falling below the
light-off temperature.

3.2. Substrate Design and Interaction with the Exhaust System

In this section, substrate design refers to the geometrical characteristics and the choice
of material for the substrate.
The core of a CC is the catalyst support, also called the monolith or substrate, which
is made of ceramic or metal. Ceramic monoliths usually have an internal honeycomb
structure with square section channels. The geometrical characteristics of the honeycomb
monolith significantly influence the efficiency of the converter. Extruded ceramic monoliths
made of cordierite (2MgO·2Al2 O3 ·5SiO2 ) are the most widely used, mainly because of their
Energies 2023, 16, 6425 8 of 24

low manufacturing costs despite having a higher wall thickness (0.178 mm) that leads to
lower open frontal areas (69%) compared to metallic substrates [29]. Metallic monoliths
are used in high-performance vehicles [30] and have the great advantage of very high
open frontal areas (91% open area) as a consequence of the ability to manufacture a very
low wall thickness (0.050 mm), which provides a higher flow contact surface area while
offering a lower resistance to flow (back pressure) [31]. Additional advantages of metallic
substrates include their high thermal conductivity and low heat capacity, which allow very
fast heating and a shorter light-off time.
Regarding new materials for substrates, Mahyon et al. [32] tested a new micro-
structured ceramic hollow fiber substrate impregnated with less than 0.7 wt% of palladium
(Pd) as the catalyst and observed many advantages such as high geometric surface areas,
low pressure drop, and light-off temperatures of CO oxidation comparable to those of
commercial counterparts. Gambarotta et al. [33] numerically compared a honeycomb
substrate as a baseline to two open-cell foam-like structures with the aim of analyzing
the effects of foam substrates on engine performance and overcoming some drawbacks
related to honeycomb monoliths such as low mass transfer and poor flow homogenization.
They concluded that foams, compared to honeycombs, warm up and cool down faster,
which facilitates rapidly reaching light-off temperatures and increases conversion efficiency,
higher mass transfer properties that allow for more compact converters, and higher pressure
drops that result in a total fuel consumption increase lower than 0.20%.
Srinivasa and Venkateswara [34] tested clay marbles as a substrate for CCs, since their
high porosity provides a good absorption capacity of the chemical coating and the spherical
surface provides maximum gas contact area. At the same time, the voids between successive
balls facilitate the passage of gases, causing minimum back pressure. The authors also
demonstrated that hexagonal is the best geometry for the substrate channels since it results
in a minimum pressure drop compared to triangular, square, and circular geometries.
The geometry of the whole monolith cross-section also influences the efficiency of
the CC. For example, as the length of the substrate increases, the length of its channels
and the residence time increase, leading to improved efficiency. An increase in the surface
area contacting the exhaust flow also increases the efficiency of the CC. This contact area
depends on the number of cells per square inch (cpsi). New geometries and materials for
CC substrates are being investigated. Circular or nearly circular monolith contours have
several advantages, such as promoting symmetric and uniform temperature distribution,
uniform pressure distribution, and minimizing localized pressure peaks and deformation,
which increase durability [35].
Regarding the influence of the internal geometry of the CC on its efficiency, factors
influencing performance include the geometric configuration of the substrate channel, such
as the hydraulic diameter, channel length, cell density, and wall thickness. It has been
observed that higher cell densities, longer channels, thinner walls, and smaller hydraulic
diameters can increase conversion efficiency, but longer channels produce a higher pressure
drop [36]. The magnitude of the pressure drop and local friction coefficients also depends
on the specific channel shape [10].
A study by Lapisa et al. [37] also showed that the geometric parameters significantly
affect the conversion of HC and CO. They found that using folded perforated plates as a
substrate resulted in good performance in terms of decreasing the HC (−93.6%) and CO
(−0.56%) levels, as the zig-zag plate shape in their model increased the surface contact and
intensity of the gas-catalyst collision.
Advances in internal geometries for the substrate are being investigated with the aid
of additive manufacturing techniques. This is the case of diamond-based lattice substrates
obtained through additive manufacturing, which have been compared to a conventional
400 cpsi honeycomb catalyst design, resulting in a significant improvement in the light-off
temperatures for the CO, THC, and NO of the 3D-printed substrates [26].
The use of higher cell densities to achieve a faster light-off is one of the generally
accepted geometrical approaches, despite the increase in the back pressure that ensues [38].
Energies 2023, 16, 6425 9 of 24

Brück et al. [39] performed experimental tests in metallic substrates and proposed low
cell densities for underfloor catalytic converters and high cell densities for close-coupled
catalysts to improve cold-start behavior. On the other hand, several studies have analyzed
substrates with variable cell densities. A dual-zone monolith consisting of a high-cell-
density core and a low-cell-density outer annulus did not improve the performance of
the CC in terms of the light-off [38]. However, Yang et al. [40] proposed a new monolith
structure with uniformly changing cell density and a new heater, which improved the flow
field uniformity and NO conversion.

3.3. Catalyst Material

The low porosity of the substrates used in CCs (both ceramic and metallic) makes
them inappropriate as catalyst supports. To overcome this problem, a thin layer of porous
material, such as γ-Al2 O3 (a type of alumina), is applied to the channel walls. This layer,
called a wash coat, is used to disperse the catalyst materials, mainly precious metals
that promote oxidation and reduction reactions with a very high conversion efficiency.
Increasing the precious metal loading is a straightforward way to increase the efficiency of
CCs, especially at low temperatures. However, the use of a high precious metal loading
increases the price of a CC and favors sintering at high temperatures, leading to the
deactivation of the CC [29]. The process used for the deposition of the catalyst on the
substrate also affects the efficiency of a CC [41]. Additionally, wash-coat materials, such as
ceria-based oxides, are added as oxygen storage agents [42].
The noble metals that usually function as catalyst materials are palladium and plat-
inum, which enable the oxidation of HC and CO, and rhodium for NOx reduction. The high
cost of these metals, due to their scarcity, has prompted researchers to study alternative
catalyst materials.
Using copper (CU) as an alternative low-cost catalyst material is one of the most
investigated methods for emissions reduction. Dey and Chandra [43] reviewed the use of
copper oxide catalysts for decreasing CO emissions and concluded that copper oxides are
effective in CO oxidation. However, the crystal size significantly influences CO oxidation.
The increase in temperature also promotes CO conversion rates unless it leads to the
sintering of the catalyst. Venkatesan et al. [44] studied the influence of copper oxide catalyst
on HC, NOx , CO, and smoke and observed maximum reductions at full load: 32% in HC
and smoke, 61% in NOx , and 21% in CO when considering emissions without a CC as the
baseline.
The combination of copper with other metals has also been studied. Chafidz et al. [45]
tested a copper-zinc (Zn) metal as the catalyst, observing reductions in CO and HC emis-
sions of up to 47.71% and 55.34%, respectively. Additionally, the activation energy of
oxidation CO and HC was found to be 132.54 kJ/mol and 37.55 kJ/mol, respectively. The
efficiency of the chrome-coated copper plate (Cu + Cr) as a catalyst was analyzed by [46],
who found that the combination of these metals reduces CO and HC by 95.35% and 79.28%,
respectively. A mixture of CU and manganese (Mn) oxides, (CuMnOx ), is the best-known
catalyst for CO oxidation at low temperatures [47].
Calcium titanium oxide (CaTiO3 ), referred to as perovskite, performs well as a low-
cost catalyst due to its high activity and stability at different temperatures, which pro-
vide CO and HC conversion efficiencies of up to 77.89% and 68.50%, respectively [47].
Keav et al. [48] reviewed the main advantages of perovskite, highlighting its robust crystal
structure and flexible oxygen content, which are helpful in redox reactions. In addition,
its good oxidation activity can be facilitated by using noble metals. Calcium carbonate
(CaCO3 ), referred to as limestone, was tested as a catalyst due to its low cost, good dura-
bility characteristics, and poison-resistant nature, showing potential for reducing HC, CO,
and NOx emissions [49].
Barium oxide (BaO) and magnesium oxide (MgO) were tested as catalysts, resulting
in reductions in CO and HC emissions but not in NOx emissions. Both catalysts achieved
significant and similar reductions in HC emissions. CO emissions were also reduced, but
Energies 2023, 16, 6425 10 of 24

the BaO catalyst had better conversion efficiency [50]. Barium chloride (BaCl2 ) has also
shown potential to decrease HC and NOx emissions, with reductions of 60.2% and 50%,
respectively, as observed by [51].
It is also possible to find studies in which the monolith was manufactured using
low-cost materials acting as catalysts. This was the case in a study by Ghofur et al. [52],
who tested fly ash produced in the coal industry as a catalyst with two objectives: reducing
environmental problems related to fly ash and decreasing exhaust emissions from engines.
Based on a developed prototype of a CC combined with an air injection system, the authors
observed reductions in HC and CO emissions of up to 48% and 45%, respectively. Zeolites
have also been tested as substrates to act as catalysts. A study by Subramanian and
Gnanasikamani [53] analyzed the conversion efficiency of two zeolites, ZSM 4A and ZSM
5A, over the exhaust gases of an engine fueled with a blend of diesel and pyrolysis oil from
waste plastic. ZSM 5A performed better than ZSM 4A due to the amplification of the pore
structure. For ZSM 5A, NO, HC, and CO emissions were reduced by 18%, 22%, and 10%,
respectively, and for ZSM 4A, they were reduced by 12%, 16%, and 8%, respectively.
Although researchers have achieved significant improvements in emissions reduction
through the use of alternative catalyst materials, more efforts are needed to reach the
conversion efficiency levels achieved through the use of noble metals.

3.4. Oxygen Storage Capacity

The signal delay from the lambda sensor present in most current vehicles leads to
oscillations in feed gas concentrations around a desired reference. Despite this being seen
as a drawback, oscillation feeding has a practical advantage. Since the 1980s, several studies
have revealed that control of the oscillating feed gas amplitude and frequency affects the
efficiency of CCs. In this sense, Lie, Hoebink, and Marin [54] studied the influence of cycle
CO exhaust concentration on the average CC conversion time. They observed an increment
in the average conversion time below the light-off temperature and the opposite effect
above it. This last fact highlights the use of a close stoichiometric ratio above the light-off
temperature. An increment in the oscillation amplitude, as well as in the initial oxygen
excess, prompted the observed results.
The oxygen storage capacity (OSC) explains the aforementioned behavior. The capacity
of the CC to store and release O2 influences the TWC’s efficiency since the reduction process
is more effective for rich mixtures (low amount of O2 ), in contrast to what occurs in the
oxidation process, which is more efficient when the engine runs lean [55].
Cerium (Ce), which is usually present in the wash coat, is a key promoter of the
OSC. It boosts the dynamic redox processes and is important for wash-coat stabilization
and thermal resistance. While Ce provides oxygen storage capacity, the temperature and
redox environment define the amount of oxygen stored. Koltsakis, Konstantinidis, and
Stamatelos studied the OSC as a function of temperature and redox environment [56] and
obtained the following results: in lean environments, the CC stores oxygen in the form of
Ce oxides, and the oxygen capacity is reduced under stoichiometric conditions, whereas in
rich environments, the temperature-storage capacity profile exhibits a convex shape (Ce
oxidation increases the storage up to a maximum value, and after that, slower hydrocarbon
oxidation consumes all oxygen, and there is no storage at all).
The development of an oxygen storage model concerning the oxygen storage from
NO and the release from CO in a wash coat with Ce allowed Ohsawa et al. [57] to identify
a larger amount of oxygen storage at the CC inlet, whereas a lower stoichiometry deviation
at the outlet demonstrated the reduction effect of oxygen storage on air–fuel oscillations.
Zhang and Cheng experimentally investigated OSC deterioration due to aging and
fuel sulfur [58]. Their study revealed that OSC decreased faster at the initial aging stage
and by 10% for every 150 ppm of fuel sulfur. Additionally, the authors claimed that the
loss of efficiency in the NO reduction in aged CCs is a consequence of the deactivation of
precious metals and not of OSC inadequacy.
Energies 2023, 16, 6425 11 of 24

Investigations into improving the OSC using different wash coats have been conducted
in parallel with investigations into the relationship between conversion efficiency and
the interaction between the OSC and the air-fuel ratio. The interesting work by Kašpar,
Fornasiero, and Hickey [29] reviewed studies on the advantages of CeO2 –ZrO2 oxides
(higher thermal stability and CC surface area) over conventional CeO2 , explaining the
reasons for their substitution since 1995. More recently, Khosh et al. [59] proposed a
method for manufacturing nanorods of CeO2 doped with Zr that can be used in automotive
CCs, and the experimental tests performed showed a significant increase in the specific
surface area.
There is clear, solid knowledge about the OSC effect according to the experiments and
simulations considered in this review. It is worth mentioning that the physical design of
CCs, as well as the development of exhaust emissions control systems, have to consider
this critical phenomenon.

3.5. Catalyst Deactivation

The causes of catalyst deactivation have also been investigated. Poisoning and high
temperatures promote the loss of conversion or the deterioration of CCs. Automotive
manufacturers are interested in the use of diagnostic tools to determine the deactivation
of CCs. A simple approach consists of using thermocouples placed in the CC bricks to
measure the exotherm (temperature rise due to chemical reactions) and correlate it with
CCs’ steady-state HC conversion [60].
Typical studies on the deterioration of CCs conduct Rapid Aging Tests (RAT) to
evaluate the failure modes of CCs. These tests can be performed in a vehicle, an engine test
bench, or a laboratory. After vehicle aging, Beck, Sommers, and DiMaggio [61] studied the
effect of thermal aging and poisoning (phosphorous and zinc) through the axial direction of
coupled and underfloor CCs. They noticed an axial gradient in the light-off and warm-up
for CO and HC conversion in the entrance of CCs. While poisoning influenced CO and
NOx activity, thermal deterioration affected the conversion of HC.
On the other hand, Poulopoulos and Philippopoulos [62] subjected a CC to laboratory
thermal aging to evaluate its conversion performance after partial deactivation. Their
experimental results indicated a larger influence on HC oxidation than on CO and an
increase in the time required to start the conversion. More recently, Grane et al. [63] aged
CCs in a CATAGEN Omega test reactor and used the changes in the light-off curves to
determine the deactivation of the CCs (usually, aging moves light-off curves to higher
temperatures [64]).
There are also environmental concerns about the emissions of noble metals due to the
deterioration of CCs. A comparison between gasoline and diesel platinum-group element
emissions (in soluble and particulate fractions) [65] revealed that unlike diesel engines,
whose platinum emissions are at the same levels for both fresh and aged systems, aged
gasoline engines produced lower noble metal emissions than fresh ones. On the other
hand, aging increases the amount of soluble emissions, which are more dangerous than
particulate ones.
The main characteristics of the studies cited in Section 3 are summarized in Table 1.
This summary includes the characteristics of the engine/vehicle or alternative testing
system, the fuel used for powering the engine if it differs from regular diesel or gasoline
fuel, the converted species analyzed in the study, the characteristics of the CC such as the
dimensions and structure of monolith and catalyst materials, and finally, the characteristics
of the engine/vehicle operating regime tested or the synthetic flow generated in the reactor.
Neither the review studies nor the numerical studies validated through experimental data
obtained from the literature have been included in Table 1.
Energies 2023, 16, 6425 12 of 24

Table 1. Main characteristics of reviewed experimental studies.

Ref. Test Bench Fuel Species Catalyst Mat. Monolith Mat. Monolith Dimensions and Structure Operating Regime or Synthetic Flow

[21] SI, 4-cylinder, - CO, HC - - - Two pre-catalysts: 20% and 40% volume of the Cold start
Izusu main CC + main CC
Chrysler Dodge CO, HC, Nearly-fresh Pd,
[22] Neon 2.0 L, - NOx Cordierite Two monoliths: D 90, L 152, 400 cpsi FTP
4-cylinder Loading 10.6 g/L

RHCC: Copper oxide 1750 rpm under no load (20 s after cold
[23] Ambassador, SI, - CO, HC RHCC: Metal RHCC: fine-meshed stainless-steel substrate; start). The required load is applied at the
4-cylinder (270 cm3 ) Primary CC
same speed.
CO, HC, MCC: 600 cpsi, WT 0.114; UCC: 400 cpsi, WT
[25] SI LPG NOx Pt/Rh Ceramic Cold-start period in CVS-75 mode
0.140. Both CCs: D 118, L 136
Catalytic carrier: Three substrates:
Ultra-low- Al2 O3 photopoly- - Diamond cell (similar to 400 cpsi); One stationary condition representing
CI, Diesel, CO, HC, gamma alumina
[26] 1-cylinder sulfur NOx merizable ceramic - Elongated diamond (similar to 400 cpsi);
diesel Precious metal: Pd slurry low loads
(2.5 wt%) - Honeycomb (baseline) 400 cpsi.
SI, 1.0 L, - - - - CCC: meets Euro 3; From no load to full load conditions
[27] 4-cylinder UCC (1500–4000 rpm)
ICE hybrid
[28] E85 gasoline
CO, HC, - Cordierite 1600 cpsi; oval (mm): 76.2 × 60.33, L 101.6, US06 City drive cycle
electric, 2016 NOx WT 0.1
Chevrolet
Micro-structured Preheated flow: 50 mL min−1 air;
[32] Reactor - CO Pd, 0.7 wt% alumina hollow L 50; GSA: 40 (equivalent to 750 cpsi)
fibers 50 mL min−1 (10% CO in 90% Ar)
Honeycomb: e = 63%, Dc = 1, SSA = 2700,
400 cpsi Simulation: EUDC
[33] TD, 1600 cm3 , - CO, HC - Cordierite;
Open cell foam and Kelvin cell structures: Validation: steady-state operating
4 in-line cylinders Foams: Al2 O3
e = 73%, Dc = 2, SSA = 1000 conditions by the OEM
All CC: L150, D80
3 types: Several typologies:
In-line OHV, CI, 2 types: Idling condition (with and without
FSE; Swaraj - CO, HC CeO2 ; - Marble clay; - Balls;
[34]
Mazda Minibus ZnO2 - Stainless steel; - Perforated disks; each CC)
- Copper sheets. - Rolled sheets.
Monolith contours: round, oval or elliptic,
[35] SI - - - Cordierite ceramic triangular, and wide oval or racetrack; Standard -
monolith: 400 cpsi, WT 0.006800
Energies 2023, 16, 6425 13 of 24

Table 1. Cont.

Ref. Test Bench Fuel Species Catalyst Mat. Monolith Mat. Monolith Dimensions and Structure Operating Regime or Synthetic Flow
Two honeycomb UCC:
CO, HC, - 400 and 600 cpsi;
SI, 4-cylinders, Pd, Rh and Pt Steady-state analysis (cold start
[36] - NOx ; Cordierite - Hydraulic diameter: 1.14 and 0.98 mm;
Proton TWC Pd > Rh > Pt not included)
- Designed for PROTON Wira 1.3 L and FIAT
Punto Selecta 1.2 L.
Several typologies:
Brass; Brass plate; - Set of perforated disks; 3 engine speeds: 1700 (idle), 2700,
[37] Motorbike engine - CO, HC (Cu 85%, Zn 15%) WT: 0.5 - Set of folded and perforated disks; and 3700 rpm
- Rolled brass plates.
5 diameters (400 cpsi): D 60, 70, 90, 105, 127;
CO, HC, 5-cell density (D 90): 100, 200, 400, 500, 600 cpsi; Bag I of the FTP and in a constant high
[39] 3.5 I, 4-cylinder - NOx Pt/Rh (40 g/ft) Metallic
2 CC designs (400 cpsi): D 118 L 40, D 60 L 150; load point
2-foil WT: 0.05, 0.04
Two-zone substrate WT 1.7, L 100, D 100:
- Middle: High cell density (500 cpsi, SSA 2995, 6 steady-state operating conditions;
[40] GDI - NO Pt Metallic e 72%); (n 3000 rpm; Torque: from 11.0 Nm
- Around: Low-cell density (400 cpsi, SSA 2728,
e 75%); to 51.3 Nm)
Heater system placed at the monolith inlet
2 types: 2 types:
CO, HC, - Ag; Synthetic gas flow similar to automobile
[41] Reactor - NOx - Alumina; -
- Pd. - Ce–Zr. exhaust gases

CO, HC, Copper Honeycomb

CI; - NOx , Ceramic 0%, 25%, 50%, 75%, and 100% of
[44] 1-cylinder, FSE Width: 150 mm; maximum rated load
smoke oxide
Spine: 40 mm
Motorbike (Honda - CO, HC Cu-Zn Cu-Zn CC: L 66, D 24
[45] Supra Fit 2004) inner structure: 10 tubes n: 2000 and 2500 rpm

SI, Toyota Kijang Stationary tests:

[46] LSX 1.8 series, - CO, HC Chrome-coated Metallic Honeycomb design idle conditions from 750 rpm to 5000 rpm
4-cylinder copper (CU + CR)
with a range of 250 rpm

CO, HC, Mullite (non-noble

[49] CI, FSE, 1-cylinder - NOx metal, based on Mullite Perforated mullite plate Variable engine running conditions
material limestone)
Energies 2023, 16, 6425 14 of 24

Table 1. Cont.

Ref. Test Bench Fuel Species Catalyst Mat. Monolith Mat. Monolith Dimensions and Structure Operating Regime or Synthetic Flow
Pure diesel
DI-Diesel, 3 blends: 2 nanocatalysts:
1-cylinder, FSE, CO, HC,
[50] diesel + NOx - BaO; Metal 2 CC (tubes inserted in disks) Brake Power: from o to 3.5 kW
Kirloskar TV1 biodiesel + - MgO.
CeO2

CO, HC, Blend: barium Wire mesh:

[51] CI - NOx chloride + Metallic 5 loads
zirconium oxide D 80, Dc 0.5

SI, 4-cylinder, Activated Fly ash

Fly ash (activated Idle at 700, 1000, 1500, and 2000 rpm. Air
[52] 1600 cm3 , FSE, - CO, HC
using sulfuric acid)
+ cement Several lengths (L 50, 70, 90), D 50, Dc 2
injected at 0.05, 0.1, and 0.15 MPa.
TOYOTA (adhesive)
100% Diesel; 2 CC, each with a Zeolite +
Kirloskar 5.2 kW Blend: 50% CO, HC, different Zeolite: Bentonite clay + CC casing: D 80, L 600 Brake power: 0, 1.32, 2.6, 3.9, and 5.2 kW
[53] pyrolysis oil + NOx
CI, 1-cylinder - First CC: ZSM 4A; White cement + Structure with circular holes (loads: 0, 4, 8, 12, and 16 kg)
50% Diesel - Second CC: ZSM 5A. Distilled water
CO, HC, Inlet gas, 2 tests at 400 and 700 ◦ C: lean
[57] Flow reactor - NOx Pt/Rh Ceramic Crashed ceramic substance of Pt/Rh TWC, D 15 (CO: 2500 ppm; O2 : 0.325%, 0.225%); rich
(Simulated) (7500 ppm, O2 : 0.175%, 0.255%)
4 fuels: Dual-brick system, Steady-state conditions (1600 rpm and
Daimler-Chrysler Gasoline with CO, HC, 1.23 L per brick: Daimler-Chrysler 2001 Model, 2.4 L vehicles
[58] NOx Ceramic 0.5 bar intake pressure) with
2.4 L, 4-cylinder 7, 33, 266, and - Front: Pd; with ULEV designation
500 ppm sulfur - Rear: Pt + Rh. lambda variation

Synthetic gas similar to gasoline exhaust

Pd/Zr-doped CeO2 , 4 gases: Propane (390 ppm) + CO
Reactor - CO, HC,
[59] NOx Zr concentrations (5, Cordierite Honeycomb: L 20, D 10, 400 cpsi (0.56 vol%) + NOx (1002 ppm) + O2
10, 15, and 20 mol%) (0.56 vol%) + CO2 (11 vol%) + Ar
(balance), from 100 to 600 ◦ C.
Pt/Rh or UCC: 400 cpsi;
3.8 L sequential. CO, HC, Pt/Pd/Rh;
[60] - NOx wash coat: alumina
Ceramic front brick 81 × 145 oval, L 152; FTP
Port fuel injection rear brick 81 × 145 oval, L 127
ceria
CCC: Pd, 75 g/ft3 ; CCC: D 3.6600 round, L 300 ; Reactor for lean and stoichiometric
CO, HC,
[61] SI, 3.8 L -
NOx UCC (two bricks): Pt Cordierite ceramic UCC: front brick 3.1800 × 6.6800 oval, L 600 ; light-off activity and lean and
18.3, Rh 1.3 g/ft3 rear brick: 3.1800 × 6.6800 oval, L 500 stoichiometric warm-up activity at 600 ◦ C
Energies 2023, 16, 6425 15 of 24

Table 1. Cont.

Ref. Test Bench Fuel Species Catalyst Mat. Monolith Mat. Monolith Dimensions and Structure Operating Regime or Synthetic Flow
Unleaded CO, HC, Made in 1997 according to Euro II: Engine operating cycle range
IC, 4-cylinder gasoline with MTBE, Ceramic (zirconia n = 1000–2500 rpm and
[62] OPEL 1.6 L 11% w/w CH4 , 0.4% w/w Pt/Rh (5:1) and alumina) BET surface area: 8.29 m2 g−1 ; average pore torque = 0.1–40 lbf ft; one experiment
MTBE Ethylene radius: 47.40 A◦ duration = 3900 s

2 fuels: low Two 2.5 L substrates in series with and Steady-state speeds (40, 70, and 70 mph)
(4 ppm) and Pt-alumina zeolitic without wash coats: and 3% grade. Transient effects from 40
Light-duty diesel wash coat (5 mg/cm3 - Contour: round;
[64] truck, 1997, 2.5 L, high (350 ppm) PM Cordierite to 70 mph. Wind speed from 25 to
precious - 62 cells/cm2 ;
DI/TCI, Euro II sulfur metal loading) - D 144, L 152; 70 mph. Air temperature 20 ◦ C. Relative
diesel fuel - WT 0.0017. humidity from 15% to 50%.
Four CC:
SI: Front brick Pt/Rh
(5/1); Rear Four CC manufactured in 1998 for:
Pd/Rh (9/1); - Ford Fiesta van 1.3 L (Gasoline); EUDC driving cycle for
[65] SI and CI - - SI: Single brick Pd/Rh -
- Ford Fiesta van 1.1 L (Gasoline); light-duty vehicles
(9/1) with CCC; - Seat Ibiza 1.9 L (Diesel) 2 samples.
Two CI CC: Single
brick Pt (1.29 g)
Energies 2023, 16, 6425 16 of 24

4. Numerical Research to Improve CC Knowledge

Numerical simulations are utilized in research in the field of exhaust emissions after
treatments because they offer a low-cost analysis of the influence of one or more parameters
on the efficiency of catalytic converters and, consequently, on exhaust emissions. The
physical and chemical phenomena involved in the performance of CCs can be described
using mass, momentum, and energy transport, as well as chemical reaction models.
In general, conducting very accurate simulations is not easy because the complexities
of the physical–chemical phenomena involved in the conversion process hinder their
practical use in the design of CCs. Simplified models offer reasonable accuracy while
preserving the models’ simplicity and computational efficiency.
The reports gathered in this review reveal intense research in developing fast esti-
mation tools with reasonable accuracy. Revised models and simulations usually focus
on conditions critical for the performance of CCs, such as cold starts (transient CCs and
light-off behavior), conversion (chemical reactions and CC oxygen storage interaction), and
flow distribution. Several explain coupled models that consider heat-mass transfer and
the chemical reaction. In this sense, the reports summarized here complement the results
presented in the previous Section 3.
The studied simulations exhibited differences, mainly in one or more of the following
strategies:
• Equations or set of coupled equations to solve: Some authors focused on a specific
phenomenon, such as the temperature distribution, and, therefore, solved one trans-
port equation (heat, mass, or momentum). In contrast, other scholars solved coupled
models to estimate the light-off and/or the conversion of CCs.
• Assumptions: The simplifications applied and the boundary conditions considered,
as well as the methods used to determine the required equation coefficients.
• Temporal and spatial discretization: Compared to static models, dynamic models
include temporal discretization. Spatial discretization is usually applied to the length
of a CC (1D models) or a longitudinal section of a CC (2D models).
• System parameters and computed responses: Among the most studied parameters are
the geometry of the CC, A/F flow rate, and engine operating conditions. The responses
computed are temperature, conversion efficiency, and drop pressure, among others.
Table 2 lists the specific simulation works included in this review, with the descriptions
focused on their mathematical and numerical features. Most works are related to estimating
species conversion, mainly in the transient warm-up during the vehicle’s cold start, and use
one-dimensional approximations. These studies address the flow maldistribution faced by
simulations of the entire monolith (three-dimensional) using different approximations to
reduce computational efforts, such as single-channel models, porous media, and alternative
strategies. Nevertheless, they do not include realistic kinetic equations.
In the following paragraphs, we describe the details and specific results achieved
using the models and simulations in relation to the research questions (Section 1). Starting
with the topic of cold starts, Shen, Shamin, and Sengupta [66] used their model to estimate
the light-off temperature of CCs during an FTP test and claimed that at least a substrate
temperature of 600 ◦ C is required for reducing cold-start emissions. The simple CC model,
proposed by Sanketi, Hedrick, and Kaga [67] to control emissions during cold starts,
provided the CC conversion rate function of the air/fuel ratio and substrate temperature.
Finally, Yun [25] developed a one-dimensional model of an exhaust system with SAI to
identify the optimal operating conditions for reducing the light-off time and HC and CO
emissions (Section 3.1).
Regarding the models that focused on species conversion, as shown in Table 2, the re-
viewed methods generally combined heat and mass transfer models with reduced reaction
schemes. An example of coupled heat-mass transfer and chemical reaction is the solution
presented by Psyllos and Philippopoulos [68]. Using this model, they noted that conversion
depends on the volumetric rate according to the length of the CC, gas inlet temperature,
and gas pollutant inlet concentration. On the other hand, for a Pe number greater than 250,
Energies 2023, 16, 6425 17 of 24

there is negligible thermal conduction along the axial direction. Additionally, radiation
influences the solid phase temperature; the maximum temperature is attained at 85% of the
length of the CC. The model proposed by Aimard, Li, and Sorine [69] enables long-term
simulations and can be used to design A/F controllers. It is worth mentioning the discus-
sion by Koltsakis, Konstantinidis, and Stamatelos [56] on the limitations of approaches
focused on emissions estimation during a complete driving cycle: a large amount of input
data are required, as well as knowledge of the HC composition as a function of the engine
temperature and operating condition and accuracy of the light-off and oxygen storage
simulation for estimating CO and HC conversion. Besides estimating emissions in TWCs,
the authors claimed that their model can be applied to the design of systems for improving
the cold start of CCs, investigating the influence of flow distribution on the efficiency of
CCs during steady-state operation, and evaluating the behavior of aged CCs. On the other
hand, Koltsakis and Stamatelos [70] extended the previous approach using submodels for
the main dynamic phenomena (oxygen storage and water–gas reaction) and concluded that
compared to the experimental data, the extended model could explain the phenomena bet-
ter than quasi-static ones. It could demonstrate that the air–fuel ratio oscillation improved
CO and HC conversion in rich environments and NO conversion in lean environments, and
that the air–fuel scan direction (from rich to lean environments or vice versa) influenced
the conversion efficiency. Kumar et al. [71] described a reduced-order model designed for
the control and diagnosis of TWCs with the ability to estimate oxidation in TWCs through
two parameters: fractional oxygen storage and total oxygen storage capacity. The authors
explained that this solution helps assess the age of TWCs and can result in adequate fuel
control. Instead of modeling a CC as an independent component, Onorati, D’Errico, and
Ferrari [72] integrated a 1D fluid dynamic engine model with a 1D thermal and chemical
CC submodel. According to the authors, this solution enables the estimation of the gas
composition in the exhaust system and the evaluation of the interaction between the en-
gine and the CC, which can be helpful in exhaust system design. Regarding the chemical
models, Pontikakis and Stamatelos [73] explained a method for determining the kinetic
parameters of reduced reaction schemes using genetic algorithms. Unlike non-stochastic
procedures, the proposed method provides a global optimum, leading to more accurate
results. More recently, Bedi and Chauhan [74] presented a model for predicting methane
oxidation and used it to compare two different catalysts and the effect of aging. The Pt/δ-
Al2O3 catalyst showed faster conversion and better behavior during aging compared to
the CuO/δ-Al2 O3 catalyst.
The simulation of flow distribution is also a common topic due to the effect of maldis-
tribution on the performance of CCs. The reviewed reports usually employ Computational
Fluid Dynamics (CFD) models. For example, Jeong and Kim [75] used a CFD simulation to
study the flow distribution in CCs considering pulsating exhaust gases, noting that mald-
istribution depends on the height and angle of the cones used to join the substrate to the
exhaust system. Diffuser geometry was also studied using a CFD model by Khalil et al. [76],
who found that an optimum inlet angle impacts the pressure drop and flow distribution.
Martin et al. [77] studied the relationship between flow distribution simulations and mea-
sured the conversion and light-off. They concluded that the maldistribution produced
by a small inlet pipe diameter reduces the conversion efficiency of CCs in some stages of
the tested driving cycles (especially for NOx ), and aging fosters this effect. On the other
hand, they did not observe an acceleration in the light-off time. In addition to the external
geometry, the internal shape of CCs influences their performance. In this sense, a study by
Hayes et al. [38] presented a CFD model coupled with thermal-mass transfer and chemical
schemes. The authors concluded that the substrate cell density affects the flow and temper-
ature distribution, the resulting chemical reactions, and the pressure drop. Furthermore,
an increase in the cell density increases the pressure drop but reduces maldistribution.
Sun et al. [78] studied dual monoliths and also noted better uniformity for high-density
cells when the gap width between substrates was increased. They also evaluated the effect
of the length ratio of the front/rear monoliths on flow uniformity and conversion efficiency.
Energies 2023, 16, 6425 18 of 24

The authors found that a longer front length improved uniformity and accelerated the light-
off. Cornejo, Nikrityuk, and Hayes developed a series of reports [79–82] using various fast
CFD models to understand flow distribution before and after the monolith. Reference [79]
focused on a multiscale scheme that extends the turbulence decay in one channel to the
converter scale and improves flow prediction after the monolith. In a related report [80], the
substrate was modeled as a continuum (porous media), and the authors defined a Reynolds
number, depending on the monolith’s wall thickness, to determine when the flow became
turbulent (below a value of 100, the flow was mainly steady). This study was followed
by two works considering multi-zone models [81,82]. The multi-zone solutions consisted
of two and three permeability regions, respectively, and the authors claimed that these
multi-zone models were in better agreement with the experimental results compared to
the conventional permeability model (one single porous medium). Recently, using a CFD
single-channel model, Cornejo et al. [10] explored the effect of cell geometry (cross-sections:
square, hexagonal, and triangular) on pressure drop.

Table 2. Main characteristics of reviewed simulation studies.

Cold Start Conversion Flow Distribution Other Topics

Conversion in TWCs; CC mass transfer [83]; TWC
Exhaust system with SAI Oxygen Storage [56,69,71]; temperature for CC
Turbulence [79–81]; Pressure
(LGPi engine) [25]; Conversion in TWCs [70,73]; drop [10,82]; Flow control [84]; Temperature
Modeled Model for cold-start Performance of CCs [68]; distribution [75–78]; Flow distribution in the exhaust
control [67]; Exhaust system (SI and temperature system [85]; Influence of
Transient performance of 4-cylinder engine) [72]; distribution [38] engine misfiring on thermal
CCs [66] Oxidation of VOCs [74] behavior of CC [86]
Energy Eq. [25,66,67] [56,68–74] [38] [84–86]
Mass Eq. [25,66] [56,68–74] [10,38,76–82] [83,86]
Moment Eq. - [72] [10,38,76–82]
Kinetic (13-step reaction
mechanism); Oxygen
storage (9-step reaction
scheme) [66]; Oxygen storage
Empirical Wiebe Reduced-order exothermic
model [56,69,71]; Langmuir– First-order kinetic [38]; CO
Chemical Eq. oxidation [78] reaction kinetics [84]; CO,
profiles [67]; C3 H6 , H2 oxidation [86]
Hinshelwood [70,72,73]
7-step global
chemical reactions
(Langmuir–
Hinshelwood) [25]
Transient [68,69,71–74]; Dynamic [84];
Behavior Transient [25,66] Quasi-Steady [56] - Quasi-steady [85];
Dynamic [70] Transient [86]
3D (Porous medium +
turbulence BC after CC) [81];
Dimension 1D [25] 1D [68,69,71–74]; 3D (Porous 1D [83,85,86]
2D [56,70]
medium) [38,79,82]; 3D
single channel [10,80]
Scheme Finite differences [66] Finite differences [72] Finite volumes Finite differences [86]
ANSYS Fluent [10,79–82];
STAR CCM [76]; COMSOL
GASDYN [72]; CTRAN [73]; Multiphysic [38];
Software AMEsim [25] Matlab [74]
PHOENICS and
STAR-CD [77]
Length of turbulence zone
Engine conditions [66]; Re · Sc [83]; Engine
Temperature, A/F ratio [67]; A/F ratio [69,70,72]; Engine Re [81]; Diffuser inlet
Parameters conditions [85]; Axial
angle [76]; Axial distance, misfiring, catalyst
SAI air-flow rate, supply conditions [69,73]
distance [77,78,80]; r/R [79];
time [25] Channel geometry [10] content [86]

Emissions [66,67]; Temperature [56,68,72]; Turbulence [79–81]; Pressure

Responses Cumulative drop [10,76,82]; Flow
emissions [25,66]; Pressure [72]; Sh [83]; Temperature [85,86]
Temperature [25] Conversion [56,68–74] uniformity index [76,78]
Energies 2023, 16, 6425 19 of 24

Regarding the “other topics” category (Table 2), at least three reviewed works deal
with temperature estimations. Oh [86] modeled the thermal behavior of the CC during
misfiring. The wall temperature is influenced by misfiring, and below 40%, the melting
point of the CC is not attained. The solution by Shailer and Hayden [85] for estimating
the thermal behavior of exhaust and after-treatment system components under steady
and transient conditions can help design the layout and location of these elements. The
authors developed correlations to describe the heat transfer process between the gas and
walls. The model enables parametric studies, that is, the effect of operating conditions and
dimensions on the temperatures. The recent work of Shah, Premchand, and Pedro [84]
proposed a physics model that, through reduced schemes and gas–solid phase-energy
balances, estimates the temperature of the CC in real time and, according to the authors,
improves estimation accuracy compared to empirical methods. On the other hand, Santos
and Costa [83] evaluated different mass transfer correlations and defined a characteristic
Sherwood (Sh) number that depends on the chemical species to convert. According to the
authors, chemical and internal diffusion limitations can explain the previous dependence
and influence the performance of the CC.
Considering the above discussion, further efforts are critical for understanding the
influence of factors different from conventional engine conditions that affect the perfor-
mance of CCs. The internal geometry of a CC is a clear example of a factor that needs to
be considered in future studies. In this sense, additive manufacturing could be critical
in future investigations due to its ability to produce prototypes with complex shapes at
affordable costs.

5. Conclusions
Much of the research related to CCs is focused on reducing cold-start emissions, as
they account for up to 80% of total pollutant emissions. Active and passive methods are
used to decrease cold-start emissions. Active methods include the use of electrical heaters,
fuel burners, air injection, and hydrogen injection. Passive methods include the use of a
pre-catalyst, thermal management, and placing the CC closer to the exhaust manifold. All
of these systems must be appropriately designed to avoid excessively high temperatures
that can lead to durability problems.
The geometrical characteristics and the material of the monolith significantly influence
the efficiency of the CC. Some geometrical factors influencing the performance of the
CC include the geometric configuration of the substrate channel, such as the hydraulic
diameter, channel length, cell density, and wall thickness. The geometry of the whole
monolith cross-section also influences the efficiency of the CC. Circular or nearly circular
monolith contours have several advantages regarding durability, temperature, and uniform
pressure distribution.
New ceramic hollow fiber and foam substrates provide advantages compared to
regular ceramic and metallic substrates. Additive manufacturing technologies allow for the
production of complex geometries for substrates, resulting in a significant improvement in
the light-off temperatures for CO, THC, and NO compared to a conventional honeycomb
catalyst design.
Although researchers have achieved significant improvements in emissions reduction
through alternative catalyst materials, more effort is required to reach the conversion
efficiency levels provided by noble metals.
Other topics studied relate to oxygen storage and catalyst deterioration. According to
the reviewed works, the oxygen storage capacity (OSC) of some materials (mainly cerium
oxides) present in the wash coating, together with the use of a lambda sensor for the
determination of the O2 concentration, allows the engine control unit to vary the air–fuel
ratio (lambda number, λ) to achieve optimal efficiency in the conversion of CO, HC, and
NOx . The influence of the OSC and air–fuel ratio on the performance of a CC is known and
critical in CC design. On the other hand, knowing the CC’s deactivation modes is critical
for defining accurate and affordable diagnosis tools.
Energies 2023, 16, 6425 20 of 24

Finally, this review has revealed a large number of publications devoted to developing
models with the aim of improving our understanding of the aforementioned topics. In
general, these efforts, whose main characteristics are synthesized in Table 2, highlight the
interest in improving estimations in a reasonable computational time.

Author Contributions: Conceptualization, R.D.-V., E.T.-J. and L.L.; methodology, L.R.-L., R.D.-V. and
E.T.-J.; investigation, L.R.-L., R.D.-V., E.T.-J., G.B. and L.L.; resources, G.B. and L.L.; data curation,
L.R.-L., R.D.-V., E.T.-J., G.B. and L.L.; writing—original draft preparation, L.R.-L., R.D.-V. and E.T.-J.;
writing—review and editing, L.R.-L., R.D.-V., E.T.-J., G.B. and L.L.; visualization, R.D.-V. and E.T.-J.;
supervision, R.D.-V. and E.T.-J.; project administration, R.D.-V. and E.T.-J.; funding acquisition, R.D.-V.
and E.T.-J. All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by the Consejería de Universidad, Investigación e Innovación de
la Junta de Andalucía, grant number ProyExcel-00662, within the framework of the
FEDER-Andalucía 2014–2020 program. Eloísa Torres-Jiménez and Rubén Dorado Vicente are grateful
for the Research Mobility Grants from the University of Jaén—Acción 1a and 1b del Plan Operativo
de Apoyo a la Investigación de la Universidad de Jaén (2021–2022).
Conflicts of Interest: The authors declare no conflict of interest. The funders had no role in the design
of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript; or
in the decision to publish the results.

Abbreviations
The following abbreviations are used in this manuscript:

Ag Silver
AM Additive manufacturing
Ar Argon
BC Boundary condition
CC Catalytic converter
CCC Close-coupled (light-off) catalytic converter
Ce Cerium
CI Compression ignition
CO Carbon monoxide
CO2 Carbon dioxide
cpsi Cells per square inch
Cu Copper
D Catalytic converter diameter (mm)
Dc Diameter of one catalytic converter cell (mm)
DCCS Dynamic catalytic converter system
DI Direct injection
DOC Diesel oxidation catalyst
e Porosity
EGR Exhaust gas recirculation
EUDC Extra-urban driving cycle
F&E Filling and emptying
FOS Fractional oxidation state
FSE Four-stroke engine
FTP Federal test procedure
GDI Gasoline direct injection
GSA Geometric surface area m2 /m3
HC Hydrocarbons
ICE Internal combustion engine
λ lambda number
L Catalytic converter length (mm)
LCA Life-cycle assessment
LPG Liquefied petroleum gas
MCC Manifold catalytic converter
n Engine rotational speed
Energies 2023, 16, 6425 21 of 24

NOx Nitrogen oxides

OEM Original equipment manufacturer
OHV Overhead valve
OSC Oxygen storage capacity
PCM Phase change material
Pd Palladium
Pe Peclet dimensionless number
Pt Platinum
PtG Power-to-gas
PtL Power-to-liquid
QSF Quasi-static flow
RAT Rapid aging test
Rh Rhodium
RHCC Resistance-heated catalytic converter
SAI Secondary air injection
Sc Schmidt number
SCR Selective catalytic reduction
SI Spark ignition
Sh Sherwood number
SSA Specific surface area m2 /m3
TCI Turbocharged intercooled
TD Turbocharged diesel
THC Total hydrocarbons
TOSC Total oxygen storage capacity
TWC Three-way catalytic converter
UCC Underbody (Underfloor) catalytic converter
VOC Volatile organic compound
VCI Variable-conductance isolation
WT Wall thickness (mm)
Zn Zinc

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