Process Safety and Environmental Protection 184 (2024) 854–880

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Process Safety and Environmental Protection

journal homepage: www.journals.elsevier.com/process-safety-and-environmental-protection

Advancements in (SCR) technologies for NOx reduction: A comprehensive

review of reducing agents
Sahar Elkaee a, Ajit Dattatray Phule a, b, Jae Hwan Yang a, b, *
a
Department of Environmental & IT Engineering, Chungnam National University, 99 Daehak-ro, Yuseong-gu, Daejeon 34134, South Korea
b
Department of Environmental Engineering, Chungnam National University, 99 Daehak-ro, Yuseong-gu, Daejeon 34134, South Korea

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

Keywords: Nitrogen oxides (NOx) are highly reactive air pollutants that cause various environmental and health concerns.
NOx reduction Selective catalytic reduction (SCR) has emerged as a vital tool for mitigating NOx emissions. This comprehensive
Selective catalytic reduction review explores the advancements in SCR technologies and their critical role in NOx reduction by investigating
Reducing agent
various reducing agents. The performance of ammonia/urea, hydrocarbons, hydrogen, and carbon monoxide as
Catalyst efficiency
Environmental impact
reductants was investigated in various SCR systems. Ammonia, which is renowned for its efficiency in SCR, was
examined for its ability to reduce NOx emissions. Urea-based SCR is a safe and low-toxicity alternative, partic­
ularly for mobile applications. Hydrocarbon-based SCR systems are versatile, enabling lower operating tem­
peratures and improved efficiency. Hydrogen-based SCR technology is an environment-friendly option for NOx
reduction, particularly in low-temperature scenarios. Carbon monoxide-SCR optimizes reduction processes,
particularly in industrial sectors like steel and coking where CO abundance is beneficial for NO removal,
addressing critical emission reduction needs. In-depth information on these reducing agents was examined, along
with information on the catalyst components, mechanisms, and important factors that affect the NOx conversion
efficiency. This study also highlights the need for research to address several challenges, future directions, and
innovations in SCR technologies, emphasizing the importance of reducing environmental impacts and enhancing
industrial processes.

1. Introduction control during combustion and measures applied after combustion.

Nitrogen oxide (NOx) emissions from various sources, including in­
dustrial facilities and automobile exhaust, have detrimental effects on
both the environment and human health. Consequently, reducing NOx
emissions has become a pressing issue in environmental science and
engineering (Cheng and Bi, 2014; Guan et al., 2021; Praveena and
Martin, 2018). The main DeNOx technologies include selective catalytic
reduction (SCR), selective noncatalytic reduction (SNCR), and
non-selective catalytic reduction (NSCR) (Cheng and Bi, 2014; Guan
et al., 2021). The primary emphasis in controlling NOx emissions from
stationary sources such as thermal power plants is on encompassing both
Post-combustion control technologies specifically target flue gas deni­
tration and utilize SNCR and SCR methods (Cheng and Bi, 2014; Guan
et al., 2021; Radojevic, 1998; Roy et al., 2009).
Among the various available emission control technologies, SCR has
emerged as a promising solution for effectively mitigating NOx emis­
sions from industrial processes, power plants, and automotive exhausts.
SCR technology employs a catalyst and appropriate reducing agents,
such as ammonia (NH3), urea, hydrocarbons (HC), hydrogen (H2), and
monoxide carbon (CO) to reduce NOx. This approach has great potential
for minimizing the environmental and health impacts of NOx emissions
(González Hernández et al., 2020; Twigg, 2007).

Abbreviations: NH2, Amino intermediates; NH3, Ammonia; NH2CONH2, Ammonium carbamate; CO2, Carbon dioxide; CO, Carbon monoxide; CeO2, Cerium oxide;
E-R, Eley− Rideal; N2, Gaseous nitrogen; HC, Hydrocarbons; H2, Hydrogen; IR, Infrared; HNCO, Isocyanic acid; L-H, Langmuir–Hinshelwood; Mn, Manganese; Mo,
Molybdenum; NOx, Nitrogen oxides; N2O, Nitrous oxide; NSCR, Non-selective catalytic reduction; PGR, Polyethylene glycol reduction; C3H6, Propene; TR, Residence
times; SCR, Selective Catalytic Reduction; SNCR, Selective noncatalytic reduction; SSITKA, Steady-state isotopic transient kinetic analysis; SO2, Sulfur dioxide; TWCs,
Three-way catalysts; W, Tungsten; WO3, Tungsten oxide; V, Vanadium; VOx, Vanadium oxide; H2O, Water; XPS, X-ray photoelectron spectroscopy.
* Corresponding author at: Department of Environmental & IT Engineering, Chungnam National University, 99 Daehak-ro, Yuseong-gu, Daejeon 34134, South
Korea.
E-mail address: yjh98@cnu.ac.kr (J.H. Yang).

https://doi.org/10.1016/j.psep.2024.02.046
Received 19 November 2023; Received in revised form 22 January 2024; Accepted 16 February 2024
Available online 17 February 2024
0957-5820/© 2024 Institution of Chemical Engineers. Published by Elsevier Ltd. All rights reserved.
S. Elkaee et al.
Using catalytic means for efficient treatment and remediation is
strategically important for improving the environment and supporting
ecologically sustainable development, especially in view of the
increasing severity of environmental pollution (Liu et al., 2024a).
Vanadium-based catalysts like V2O5-WO3/TiO2 are widely used in SCR
due to their high reactivity, but their cost and high operating tempera­
tures (300–400 ◦ C) limit broad application (Elkaee et al., 2023; Shi et al.,
2023; Huang et al., 2023; Damma et al., 2019; Jung et al., 2024). In this
regard, various low-temperature NH3-SCR catalysts, such as
ion-exchanged zeolites and transition metal oxides, have been devel­
oped (Sullivan et al., 1995; Rizzotto et al., 2018; Joshi et al., 2018). For
example, MnOx catalysts with low cost and excellent low-temperature
activity gain attention. However, challenges like thermal stability, nar­
row operation window, and poor resistance to H2O and SO2 hinder their
commercial use (Zhang et al., 2020a; Gao et al., 2018). Significant ef­
forts have been directed towards mitigating current catalyst limitations,
employing effective strategies such as introducing other transition or
rare earth metal oxides to create mixed metal oxides and optimizing the
structure–activity relationship (Liu et al., 2024a).
In recent years, notable advancements have been made in the field of
SCR, with a primary emphasis on the innovation of novel reducing
agents aimed at optimizing the effectiveness of the SCR process. Ther­
modynamically, the Gibbs free energy for NOx reduction reduces
significantly in the presence of reducing agents (Mrad et al., 2015). This
comprehensive review aims to provide an overview of the recent prog­
ress in SCR technology, with particular emphasis on the utilization of
novel reducing agents.
This review discusses the NH3/urea-, HC-, H2-, and CO-based SCR
systems to provide a comprehensive understanding of this topic.
Furthermore, the efficacies and selectivities of NH3/ urea, HC, H2, and
CO as reducing agents in SCR were compared. The efficiency of NOx
reduction under varying operating conditions was analyzed while
considering the environmental impact and byproduct formation asso­
ciated with the different reducing agents.
Finally, this review summarizes key findings and presents an outlook
on the challenges and future directions in the field of SCR using novel
reducing agents. By highlighting the latest developments and identifying
areas for further research and innovation, this review contributes to the
advancement of the SCR technology for efficient NOx emission control.
2. Ammonia/urea-based SCR systems
SCR has emerged as an exceptionally effective method for utilizing
NH3 as a reducing agent (Shi et al., 2023; Huang et al., 2023). This
method is especially suitable for stationary-source combustion units that
require superior NOx removal efficiency compared to alternatives, such
as SNCR or combustion controls. The NH3-SCR process comprises a se­
ries of essential chemical reactions (1− 5), with the initial reaction
commonly denoted as the "Standard SCR" reaction. This reaction is
distinguished by a stoichiometry that maintains an equal balance be­
tween NO and NH3. On the other hand, reaction (3) is identified as the
"Fast SCR" reaction, notable for its exceptional efficiency (Elkaee et al.,
2023).
4NO + 4NH3 + O2 → 4N2 + 6H2O (Standard SCR) (1)
2NO2 + 4NH3 + O2 → 3N2 + 6H2O (2)
4NH3 + 2NO + 2NO2 → 4N2 + 6H2O (Fast SCR) (3)
6NO + 4NH3 → 5N2 + 6H2O (4)
6NO2 + 8NH3 → 7N2 + 12H2O (5)
. cycle and a redox cycle. Brønsted acid sites associated with V5+-OH
In order to facilitate the reduction of NOx in stationary combustion
installations, the SCR unit incorporates an injection system to disperse
the chemical reductant into the high-temperature exhaust gas,
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Process Safety and Environmental Protection 184 (2024) 854–880
positioned ahead of the SCR catalyst. Ammonia serves as the baseline
reducing agent in SCR systems, converting engine-out NOx into nitrogen
molecules and water (Mehregan, 2020). Despite its superior reducing
ability for NOx, ammonia has been replaced with an aqueous solution of
urea due to concerns about toxicity, safety in storage, challenges in
detecting colorless and toxic NH3 leaks, as well as corrosion and eco­
nomic losses from NH3 salt conversion (Chen et al., 2020; Hu et al.,
2022; Elsener et al., 2021; Wang et al., 2019a, 2019a, 2019b; Baik et al.,
2004).
Urea-SCR technology, originating from NH3-SCR, addresses issues
related to ammonia. The use of urea, known for its non-toxic, clean,
odorless, non-flammable, and low corrosive properties in the form of an
aqueous solution, has become prevalent. The ammonia produced
through urea thermal decomposition is harnessed to diminish NOx in
diesel exhaust. Globally embraced and notably in China, urea-SCR rep­
resents a well-established post-processing solution for NOx reduction
(Baik et al., 2004; Qi et al., 2016; Li et al., 2022; Raza et al., 2022).
Urea-SCR system exhibits commendable NOx conversion rates at
elevated temperatures, accompanied by high efficiency, selectivity, and
cost-effectiveness. The decomposition of urea follows a sequence of re­
actions leading to NH3 generation involving the following steps (Ates
et al., 2021; Eichelbaum et al., 2010; Fang and DaCosta, 2003; Koebel
et al., 2000; Lim and Lee, 2023; Xia et al., 2023; Zhao et al., 2023):
NH2CONH2→ NH3 + HNCO (6)
HNCO + H2O → NH3 + CO2 (7)
.
The initial phase of urea hydrolysis leads to the formation of
ammonium carbamate (NH2CONH2), and is characterized by a gradual
reaction rate. In contrast, the breakdown of NH2CONH2 into NH3 and
CO2 requires significant energy input, particularly at elevated temper­
atures, facilitating accelerated decomposition within high-temperature
environments (reaction 6 and 7) (Wang et al., 2019a; Li et al., 2022;
Ma et al., 2018; Fan et al., 2018a; Zhang et al., 2017a). Importantly, NH3
can react with NOx emissions, yielding non-hazardous nitrogen gas (N2)
and H2O (Eichelbaum et al., 2010) with the possibility of solid
byproducts (Eichelbaum et al., 2010).
Comprehending the reaction mechanism is essential for influencing
the design and synthesis of SCR catalysts. Nevertheless, there exists
controversy regarding the mechanisms governing NH3-SCR reactions,
especially in diverse catalyst systems. The diversity in redox and acidic
capacities among various catalyst systems leads to the creation of unique
NHx/NOx active intermediates. These intermediates play a substantial
role in shaping the overall pathway and efficiency of the SCR reaction
(Elkaee et al., 2023; Han et al., 2019a; Gao and Peden, 2018; Forzatti,
2001; Busca et al., 1998; Guan et al., 2014). The representative mech­
anisms explaining SCR reaction pathways can be classifies as follows:
the Eley− Rideal (E-R) mechanism according to which NHx species are
adsorbed on the catalyst surface and gaseous NO(g) reacts with the
adsorbed NHx, the Langmuir− Hinshelwood (L-H) mechanism under
which both NH3 and NOx are adsorbed prior to the SCR reactions, and
the hybrid L-H and E-R mechanism in which the SCR pathways are
explained using the L-H and E-R mechanisms in sequence (Han et al.,
2019a; Gao and Peden, 2018; Forzatti, 2001; Busca et al., 1998; Guan
et al., 2014; Kijlstra et al., 1997; Li et al., 2011; Zhang et al., 2024a;
Paolucci et al., 2016, 2017).
In a pioneering study conducted by Topsøe et al. (1995), a ground­
breaking reaction mechanism was unveiled, involving a V2O5/TiO2
catalyst. This discovery was made through in-situ online FT-IR (Fourier-
transform infrared spectroscopy) experiments conducted under steady-
state conditions. They revealed two interconnected cycles: an acid
groups were found to adsorb NH3 molecules. Surface V– –O groups are
involved in activation of the adsorbed ammonia and are also found to
play an important role in the catalytic cycle. The activation involves a
S. Elkaee et al.
transfer or a partial transfer of a hydrogen and reduced V-OH groups are
produced. An intermediate product resulting from the reaction between
the activated NH3 complex and gaseous NO eventually decomposes into
N2 and H2O. The regeneration of active V5+=O groups was achieved via
the oxidation of V4+-OH sites using O2, thus completing the cycle (Fig. 1)
(Topsoe et al., 1995a, 1995b).
In a study involving microkinetic modeling conducted by Arnarson
et al. (2017), a captivating observation was made, particularly con­
cerning the reaction mechanisms of the standard SCR and fast SCR over
the VOx/TiO2(001) catalyst. At lower temperatures, a compelling sce­
nario emerged in which the speed of reduction surpassed the speed of
reoxidation. This dynamic resulted in an increased pace of the SCR re­
action. Notably, at lower temperatures, the complexity of H2O produc­
tion and desorption determined the total reaction rate. The direct
contact of NO2 with the decreased number of sites, which produced a
noticeably faster response rate, was a factor that separated the fast SCR
cycle. As a result, the catalyst capacity to promote direct NO2 reduction
at the reduced site, and the production and desorption of H2O, plays an
important role in determining the fast SCR reaction mechanism (Fig. 2)
(Arnarson et al., 2017).
In various research studies, it has been proposed that the dominant
pathway can be either the L-H or the E-R mechanism. This determination
is contingent upon specific conditions or factors, such as the type of
catalyst employed or the temperature of the reaction. For example, in
the study by Xie et al. (2020), the SCR process on Ni-Mn/TiO2 catalyst is
governed by the L-H mechanism at 200 ◦ C, contributing to enhanced
catalyst stability. In situ DRIFTS results reveal the functionality of both B
and L acid sites at 200 ◦ C, with bidentate nitrate remaining inactive. The
dominance of the L-H mechanism is confirmed at 200 ◦ C (Xie et al.,
2020). Han et al. (2019) investigated the reduction of NOx by NH3-SCR
using Fe2O3–CeO2@Al2O3. The study revealed that in the presence of
SO2, the catalyst follows the E-R reaction pathway. Active NH3 and NH+ 4 activity was observed at the accessible Ti4+ sites during the SCR reac­
species can directly react with gaseous NO, leading to enhanced SO2
tolerance, as NO does not need to competitively adsorb on the catalyst
surface as nitrates or nitrites. Additionally, the research demonstrated
that active NH2 species on Fe2O3–CeO2@na-Al2O3 monolith catalysts
participate in the E-R mechanism, further improving SO2 tolerance (Han
et al., 2019b).
A few studies suggest a combined mechanism of L-H and E-R, which
can be called the hybrid mechanism, where both the different mecha­
nisms are involved during the NOx reduction process. Kijlstra et al.
(1997) provided valuable insights by proposing that Lewis acid centers
predominantly reside at the Mn3+ sites on the MnOx/Al2O3 surface.
Their work demonstrated that the NH2 at these sites could interact with
atmospheric NO through the E-R mechanism and participate in reactions
with activated nitrite intermediates present on the catalyst surface,
following the L-H mechanism. In this study, oxygen played a pivotal role
in the formation of NH2 and the activated nitrite intermediates.
Fig. 1. Visualizing the catalytic cycle for selective catalytic reduction (SCR)
reactions on Vanadia/Titania catalysts. Adapted with permission from (Topsoe
et al., 1995b). Copyright Elsevier Inc. 1995.
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Process Safety and Environmental Protection 184 (2024) 854–880
However, notably, NH+ 4 formed on Brönsted acid centers did not
significantly contribute to low-temperature SCR reactions (Kijlstra et al.,
1997).
It was also reported that temperature is a significant factor affecting
the governing mechanism for SCR reactions; The L-H mechanism pre­
dominates at low temperatures, while the E-R mechanism becomes
prevalent at higher temperatures (Han et al., 2019a; Ye et al., 2023). For
instance, at temperatures below 250 ◦ C, Mo-doped MoxCe1− xPO4 cata­
lysts showcase NH+ 4 attached to Brønsted and NH3 from Lewis acid sites
reacting with NO(a). Simultaneously, monodentate and bidentate ni­
trates interact with adsorbed NH3 species, following to the L-H mecha­
nism. Beyond 250 ◦ C, the reaction between NH2 and NO (g) yields
NH2NO, a crucial intermediate in the subsequent decomposition leading
to the production of N2 and H2O through the E-R mechanism (Fig. 3) (He
et al., 2024). Similar pathways are proposed for MoO3 doped CeAlOx (Li
and Li, 2014), FeTiOx (Liu et al., 2011), (Fe2.8Mn0.2)1− δO4 (Yang et al.,
2011), CeO2/TiO2− ZrO2 (sulfated) (Fan et al., 2018b), Ce− W− Sb (Liu
et al., 2017), and CeW/Ti-I (Liu et al., 2021a) catalysts.
The unique redox and acidic characteristics of various oxide catalysts
play a pivotal role in generating a diverse range of essential active in­
termediates that exert a profound influence on the SCR reaction.
Notably, Zhu et al. (2017) provided crucial insights into this mechanism.
During the SCR process over the V2O5-WO3/TiO2 catalysts, their
research emphasized the reactivity between the surface NH+ 4 and NH3
species as intermediates. According to their research, surface NH3 spe­
cies displayed better SCR performance than NH+ 4 species. Within this
framework, surface VOx centers have emerged as the active centers of
choice. Among these, surface V5+ Lewis acid sites demonstrated
heightened activity in contrast to V5+ Brønsted acid sites. Conversely,
the WOx acid centers lagged considerably, displaying an order of
magnitude lower activity than the VOx acid centers. Additionally, less
tion. A key finding of their study was the decisive role of NH3 oxidative
dehydrogenation in the production of the active NH2 species. This step is
crucial for the E-R mechanism because it allows the NH2 species to
interact directly with gaseous NO and produce the crucial NH2NO in­
termediate. This intermediate then breaks down into N2 and H2O, which
significantly increases the overall efficiency of the SCR process (Zhu
et al., 2017).
Reducing N2O production is critical in NH3-SCR processes due to its
status as a potent greenhouse gas. Yang et al. (2014) elucidated the
mechanism of N2O formation. Their work highlighted that N2O may be
produced on Mn-Fe spinel catalysts via two distinct mechanisms. The
first process, also known as the L-H mechanism, involves the interaction
between the adsorbed NO-3 and adsorbed NH3 at neighboring sites. The
E-R mechanism is followed by the first mechanism, which covers the
interaction between NH species and gaseous NO. Understanding these
mechanisms is crucial for the effective reduction of N2O during the
DeNOx process, thereby mitigating its environmental impact (Fig. 4)
(Yang et al., 2014).
Researchers have diverse perspectives on the urea decomposition
mechanism and its associated by-products (Ates et al., 2021; Eichelbaum
et al., 2010; Fang and DaCosta, 2003; Brack et al., 2014; Schaber et al.,
2004; Tischer et al., 2019). Addressing undesired byproduct formation is
a key challenge in urea-SCR, necessitating effective mitigation strate­
gies. The incorporation of a suitable catalyst, particularly for HNCO
byproducts originating from urea hydrolysis, proves beneficial. By
facilitating HNCO hydrolysis, the catalyst significantly diminishes
byproduct formation (Eichelbaum et al., 2010; Fang and DaCosta, 2003;
Lundström et al., 2011; Bernhard et al., 2012; Dong et al., 2008; Nova
and Tronconi, 2014). In urea-SCR applications, anatase TiO2,
V2O5/WO3-TiO2, and zeolite-based SCR catalysts stand out as important
hydrolysis catalysts (Eichelbaum et al., 2010; Lundström et al., 2011;
Bernhard et al., 2012; Nova and Tronconi, 2014; Hauck et al., 2007;
Kleemann et al., 2000).
Regardless of the formation of byproducts on the catalyst, or the
S. Elkaee et al. Process Safety and Environmental Protection 184 (2024) 854–880

Fig. 2. (a) SCR process reaction mechanism over VOx/TiO2 (001) model, (b) Reoxidation components in the selective catalytic reduction (SCR) mechanism’s NO-
activation cycle. Tubes and a ball and stick model have been used to represent the TiO2 support and active sites, respectively. Oxygen is for orange, Titanium is gray,
Vanadium is cyan, Nitrogen is blue, and Hydrogen is white. Adapted with permission from (Arnarson et al., 2017). Copyright Elsevier Inc. 2017.

deposition of aerosols containing byproducts on the catalyst, these
byproducts can still undergo catalytic hydrolysis (Nova and Tronconi,
2014). In a comprehensive study conducted by Bernhard et al. (2012),
the thermolysis and hydrolysis of byproducts resulting from the
decomposition of urea were examined. This investigation was carried
out in the presence and absence of anatase TiO2 as a catalyst, under
conditions of a flow reactor. The findings of this study demonstrated that
a temperature of approximately 200 ◦ C is sufficient to catalyze the
hydrolysis of biuret, cyanuric acid, ammelide, ammeline, and melamine
on anatase TiO2. Additionally, it has been experimentally verified that
cyanuric acid, melamine, and even melem can be hydrolyzed on Al2O3
(Bernhard et al., 2012).
Eichelbaum et al. (2010) investigated the decomposition of urea on
zeolite surfaces. This study revealed that urea undergoes breakdown
into isocyanic acid (HNCO) and NH3. At 270 ◦ C, HNCO reacted to form
CyA (cyanuric acid) and ammelide. At 500 ◦ C, most solid residues

857
S. Elkaee et al.
Fig. 3. Proposed reaction mechanisms over Mo-doped CePO4. Adapted with permission from (He et al., 2024). Copyright Elsevier Ltd. 2023.
Fig. 4. Proposed mechanisms for N2O formation on Mn− Fe Spinel. Adapted
with permission from (Yang et al., 2014). Copyright 2014 ACS.
decompose into gaseous HNCO, accompanied by the generation of green
photoluminescent heptazines like melem and melon in small amounts.
These species subsequently transform into gaseous HNCO and cyanogen
at temperatures >625 ◦ C. The presence of zeolites significantly accel­
erates urea decomposition, thereby lowering the temperatures required
for pyrolysis and CyA decomposition. Steam in the purge gas has a
minimal impact on urea decomposition alone but prevents solid residue
formation when combined with zeolites. Zeolites are believed to prevent
HNCO accumulation and the production of solid byproducts by accel­
erating the hydrolysis of HNCO into NH3 and CO2 (Fig. 5) (Eichelbaum
et al., 2010).
The effectiveness of SCR systems is significantly influenced by the
catalyst material. Extensive research has been conducted on several
types of catalysts, including metal oxide catalysts, such as VOx-, MnOx-,
CeO2-, Fe2O3-, and CuO-based catalysts, specifically for NH3-SCR. In
addition, research has been conducted on acidic chemical catalysts such
as vanadate, phosphate, and sulfate. Fe- and Cu-exchanged zeolite cat­
alysts are two examples of ion-exchanged zeolite catalysts that have
attracted considerable interest. Furthermore, metal-organic frameworks
(MOFs) and catalysts derived from MOFs exhibit significant promise in
NH3-SCR applications. These diverse catalytic materials offer a wide
array of options, each with unique advantages and characteristics,
enabling tailored solutions for SCR applications (Table 1) (Elkaee et al.,
2023; Shi et al., 2023; Han et al., 2019a; Shan et al., 2021; Song et al.,
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Process Safety and Environmental Protection 184 (2024) 854–880
2023a, 2023b, 2024).
Vanadium oxide (VOx)-based SCR catalysts are among the many
available catalysts and are well-known for their effectiveness. Particu­
larly in lower temperatures (below 300 ◦ C), these VOx-based catalysts
have consistently shown NOx reduction rates of 90% (Elkaee et al., 2023;
Shi et al., 2023; Zhang et al., 2020b). In reaction to stricter emission
criteria, extensive research efforts have been concentrated on enhancing
the performance of specific formulations, such as V2O5/WO3-TiO2 and
V2O5-MoO3/TiO2, which have emerged as promising candidates to meet
these elevated environmental requirements (Wu et al., 2021a; Kobaya­
shi and Hagi, 2006; Kwon et al., 2019; Nova et al., 2001; Phule et al.,
2018; Kim et al., 2018; Phule et al., 2021). The V2O5-MoO3/TiO2 cata­
lyst stands out for its remarkable low-temperature performance and
robust resistance to SO2 due to the addition of molybdenum (Mo), which
produces V-O-V bonds and efficiently prevents the reaction between SO2
and VOx (Zhang et al., 2019a). This catalyst has garnered commercial
interest owing to its advantages; however, certain challenges remain.
One limitation is the relatively narrow operating temperature range of
the catalyst, which necessitates precise control during application.
Additionally, the catalyst exhibited high activity for oxidizing SO2 to
SO3, which can be problematic in certain settings. The formation of
nitrous oxide (N2O) is another problem at elevated temperatures (Han
et al., 2019a). To some extent, these concerns have limited the industrial
applications of V-Mo-Ti catalysts. The presence of Mo, which is benefi­
cial in several respects, can significantly increase N2O production at
higher temperatures, thus demanding further optimization (Wang et al.,
2015a). Another challenge of V2O5-WO3(MoO3)/TiO2 catalysts is their
thermal stability. The sintering of TiO2 occurs at high temperatures,
along with a phase change from the active anatase phase towards the
less active rutile phase. V and tungsten (W) species may separate or even
volatilize because of this thermal stress, making measures to increase the
durability of these catalysts important (Nova et al., 2001). In SCR sys­
tems, the V2O5/WO3-TiO2 catalyst has emerged as a prominent choice,
primarily because of its remarkable hydrothermal stability. This stability
enables the catalyst to generate low-valence V species, which in turn
facilitates the reduction process. The incorporation of tungsten oxide
(WO3) serves to augments electron transfer within the system. This, in
combination with the formation of robust acidic sites, significantly en­
hances the redox performance (Elkaee et al., 2023).
Manganese (Mn)-based catalysts have received substantial attention
in the field, primarily because of their low-temperature SCR activity.
They are valued for their diverse labile oxygen species, variable valence
states (Mn2+, Mn3+, and Mn4+), and exceptional redox capabilities.
Manganese-based catalysts primarily exist in three forms: MnO2, Mn2O3,
and MnO, with their respective activity levels following the order of
S. Elkaee et al.
Fig. 5. Key reactions, intermediates, and end products diagram for neat urea pyrolysis and hydrolysis at 20–750 ◦ C. Adapted with permission from (Eichelbaum
et al., 2010).Copyright Elsevier B.V. 2010.
MnO2 > Mn2O3 > MnO. However, it is important to acknowledge that
these catalysts have their limitations, including challenges with N2
selectivity, sensitivity to sulfur dioxide (SO2), humidity, and relatively
low level of thermal stability, especially in pure MnOx catalysts.
Currently, research projects are concentrating on adding different dop­
ants to these catalysts to address and improve their performance in
response to these difficulties (Elkaee et al., 2023; Shi et al., 2023; Han
et al., 2019a; Wu et al., 2021b). Mn-based catalysts are commonly
enhanced by doping with transition metal elements like Ce, Sm, Fe, and
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Process Safety and Environmental Protection 184 (2024) 854–880
W, as well as rare earth elements such as lanthanum and cerium, to
optimize their performance (Zhang et al., 2024b; Xu et al., 2021).
Cerium oxide (CeO2)-based catalysts have attracted substantial
attention in the field of NH3-SCR owing to their nontoxic properties and
exceptional capabilities for oxygen storage and release (Elkaee et al.,
2023). A significant obstacle to improving the SO2 tolerance of Ce-based
catalysts is CeO2’s sensitivity to sulfation (Gao et al., 2010; Chen et al.,
2022). Currently, efforts are focused on reducing CeO2 sulfation by
suppressing SO2 adsorption and oxidation, or the insertion of promoters,
S. Elkaee et al. Process Safety and Environmental Protection 184 (2024) 854–880

Table 1
Summary of ammonia-based selective catalytic reduction (NH3-SCR) research for NOx removal.
Catalyst Reaction condition NO conversion (%) Temperature (◦ C) ref

NO/NH3(ppm) O2 (%) GHSV (h ¡1

)

Mn-Ce 1:1 5 6,4000 100 100–250 (Liu et al., 2013b)

Mn-Ce-Ti 1:1 5 6,4000 90 150–350 (Liu et al., 2014)
Sm-Zr-Mn-Ti 1:1 5 30,000 100 125–275 (Sun et al., 2018a)
MnCoOx-HNT 1:1 8 90,000 80.1 150 (Shi et al., 2021)
Mn/CeO2-TiO2 1:1 8 60,000 90 180–250 (Lee et al., 2012)
CeCu 1:1 5 28,000 90 160–220 (Guo et al., 2014)
Cu-Ce-W 1:1 5 36,000 90 240–390 (Shi et al., 2019)
Fe-Ce-W 1:1 2.5 20,000 90 200–500 (Stahl et al., 2017)
Ce/Al2O3 1:1 5 25,000 90 220–370 (Guo et al., 2013)
W-Ce/TiO2 1:1 3 28,000 90 200–400 (Chen et al., 2010)
Fe2O3 1:1 3 47,000 96 200–250 (Liu et al., 2013c)
Fe2O3/CNTs 1:1 3 30,000 80 180–350 (Qu et al., 2014)
Fe-ZSM-5 1:1 5 190,000 80 300–800 (Li et al., 2010a)
Fe-SSZ-13 1:1 14 200,000 80 320–550 (Gao et al., 2015)
Cu-SAPO-34 1:1 5 600,000 80 260–440 (Wang et al., 2014a)
Cu-SSZ-16 1:1 10 42,500 90 200–500 (Fickel et al., 2011)
Cu-ZSM-5 1:1 9.5 90,000 70 235–425 (De La Torre et al., 2012)
2Mn-1Fe-BTC-MOF 1:1 5 36,000 90 60–270 (Song et al., 2023a)
quasi-Mn-BTC 1:1 5 36,000 90 120–330 (Song et al., 2023b)
IPA50-Mn-BTC 1:1 5 36,000 90 120–270 (Song et al., 2024)

which results in the emergence of new sacrificial sites. According to the
most recent study by Huo et al. (2022), SO2 has a significantly less
negative impact on the fast SCR process than on standard SCR. This
phenomenon was due to increased nitrate production from NO2
adsorption, rapid NH4HSO4 breakdown, and enhanced interactions
among NO, surface nitrates, and adsorbed NH3. These methods signifi­
cantly reduced the inhibition of the fast SCR system by SO2 (Huo et al.,
2022).
Fe2O3-based catalysts have long been a subject of interest for NH3-
SCR reactions, primarily because of their environmentally friendly at­
tributes, exceptional tolerance to SO2 at elevated temperatures (>300
◦
C), remarkable thermal stability, favorable N2 selectivity, and
commendable medium-to-high SCR activity. It is crucial to stress that a
specific temperature range is required for pure Fe2O3 catalysts to work
most effectively. To overcome this limitation, significant studies have
been devoted to improving the crystalline phases and facets, modifying
the nanostructures, and enhancing the thermal stability and acidity/
redox characteristics by modifying or doping strategies (Han et al.,
2019a).
The catalytic activity of the pure CuOx oxide catalysts was confined
to a narrow temperature range (Dzwigaj et al., 2009a). As a result of its
ability to exist in different valence states (Cu2+/Cu1+), CuOx is
commonly used as a promoter in Mn- or Ce-based oxide catalysts (Yan
et al., 2018; Guo et al., 2014; Kang et al., 2006). Cu-based catalysts are
primarily based on Cu-exchanged zeolites, leveraging the presence of
highly active sites, including isolated Cu ions and dimeric Cu species
(Centi and Perathoner, 1995; Moretti et al., 2005).
Acidic compound catalysts are characterized by high acidity,
remarkable redox properties, and superior SCR performance over a wide
temperature range. Notably, vanadate, phosphate, and sulfate com­
pounds, which exhibit moderate acidity and specific redox attributes,
have been the focus of exploration for SCR applications. Specifically,
within the realm of extensive research, catalysts like FeVO4 and CePO4
have demonstrated an impressive ability to operate effectively over a
broad temperature window, highlighting their significance in SCR pro­
cesses (Han et al., 2019a; Huang et al., 2014; Liu et al., 2013a; You et al.,
2018; Ma et al., 2010).
Ion-exchange zeolite catalysts, defined by their outstanding thermal
stability and divided into three varieties depending on their relative pore
diameters—micropores, mesopores, and macropores—have been
essential for the advancement of catalytic research (Elkaee et al., 2023).
The ZSM-5 zeolite was discovered in 1986, which was a crucial turning
point in this field and a notable breakthrough (Shi et al., 2023). For the
SCR, Fe- or Cu-exchanged zeolites such as ZSM-5, SAPO-34, Beta,
SSZ-13, FAU, MOR, and USY have attracted considerable attention (Han
et al., 2019a). Fe zeolite catalysts are typically active at medium to high
temperatures (Qi et al., 2008). Cu-based zeolites have demonstrated
excellent low-temperature catalytic efficacy (<300 ◦ C). However,
challenges related to poor resistance to SO2 and high-temperature ac­
tivity persist as critical issues that require resolution, although they
show better activity than Fe-zeolite, especially at low temperatures
(Elkaee et al., 2023; Shi et al., 2023).
MOFs and their derived catalysts offer flexibility in adjusting pore
diameters, functionality, and mesoporous/microporous structures
(Zhang et al., 2024a). These crystalline materials, resulting from the
self-assembly of metal ions and organic ligands, show considerable po­
tential, particularly in NH3-SCR applications. Despite their adjustable
pore size and active sites, MOFs face challenges in thermal stability,
limiting their use in catalytic de-NOx. Current applications involve
calcining MOFs into metal oxides, but this approach has limitations in
enhancing catalytic activity due to the destruction of the MOF skeleton
(Song et al., 2023a, 2023b, 2024). Song et al. (2023) conducted a study
to enhance NH3-SCR performance by synthesizing Mn− Fe− BTC cata­
lysts with varying Mn and Fe ratios. The 2Mn-1Fe-BTC catalyst, with a
2:1 molar ratio, exhibited exceptional low-temperature de-NOx perfor­
mance, surpassing 90% NO conversion between 60 and 270 ◦ C. It also
demonstrated resilience to H2O and SO2 poisoning, maintaining 88%
NO conversion at 150 ◦ C with 100 ppm of SO2 and/or 6% H2O (Song
et al., 2023a). Additionally, another study introduced a novel
quasi-Mn-BTC nanorod to address poor SO2 tolerance in Mn-based cat­
alysts. This innovation consistently maintained over 90% NOx conver­
sion between 120 and 330 ◦ C, even with an increased SO2 concentration
from 100 ppm to 200 ppm over 36 hours (Song et al., 2023b).
NH3-SCR and urea-SCR, aimed at reducing NOx emissions, encounter
challenges like limited catalyst temperature range, sensitivity to impu­
rities, N2O formation, deactivation, high costs, and sustainability issues.
Research is crucial for improving catalyst resistance, optimizing condi­
tions, minimizing N2O, and exploring alternative NH3 reductants. Urea-
SCR, seen as a solution for diesel engines, faces complexities in urea
handling and lacks infrastructure. Despite potential, practical imple­
mentation in mobile applications is hindered by NH3 handling chal­
lenges. Ongoing research on V-based catalysts like V2O5 and WO3 shows
promise, but issues such as HNCO toxicity, urea freezing points, and by-
products require further exploration for advancing urea-based SCR in
mobile applications.

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3. Hydrocarbon-based SCR systems
NOx emissions from different stationary and mobile sources can be
reduced using widely used methods, such as SCR (Cheng and Bi, 2014;
Mrad et al., 2015; Gómez-García et al., 2005; Skalska et al., 2010). While
traditional SCR systems primarily utilize NH3-based reducing agents
such as urea or aqueous NH3 solutions, there has been growing interest
in exploring alternative reducing agents, particularly HCs, owing to
their potential advantages in terms of availability, gas mixture utiliza­
tion, handling, and storage. HCs are promising reducing agents for SCR
systems (Cheng and Bi, 2014; Praveena and Martin, 2018; Mrad et al.,
2015; Gómez-García et al., 2005; Gholami et al., 2020).
Although NH3-SCR has significant drawbacks, HC-based SCR (HC-
SCR) is a viable technique for removing NOx from flue gas
(Hernández-Terán et al., 2022; Xu et al., 2019a). The Gibbs free energy
was significantly reduced when reducing chemicals were used, and this
reduction was further reduced in the presence of oxygen. Additionally,
the introduction of oxygen further contributes to a reduction in free
energy. Due to these characteristics, these reactions have practical ap­
plications (Cheng and Bi, 2014; Mrad et al., 2015; Gholami et al., 2020;
Chen et al., 2004). Iwamoto et al. (1990) conducted a pioneering study
on the SCR of NOx using HCs that laid the foundation for subsequent
research in this field (Iwamoto and Yahiro, 1994). Since then, metal
ion-exchanged zeolites, such as Cu-ion-exchanged ZSM-5, have been
extensively investigated as catalysts for HC-SCR (Cheng and Bi, 2014;
Iwamoto and Yahiro, 1994; Lee et al., 2021a).
The comparative analysis of NH3-SCR (Yu et al., 2014) and C3H6-SCR
(Gao et al., 2021) over Cu/SAPO-34 underscores distinctive advantages
and challenges inherent in each catalytic process. NH3-SCR demon­
strates commendable overall activity within the temperature range of
120− 600 ◦ C, relying on isolated Cu2+ species as active sites and
ammonia nitrites as intermediates. However, its efficacy diminishes
above 300 ◦ C due to NH3 oxidation, impacting NO conversion negatively
(Yu et al., 2014). In contrast, C3H6-SCR, leveraging predominantly iso­
lated Cu cations at lower loadings, excels in activating C3H6 and exhibits
enhanced performance at medium and low temperatures (below 400
◦
C). The activation of C3H6 is further enhanced by the presence of CuO
species; however, this is followed with a decrease in activity due to
accelerated nonselective oxidation at high temperatures. Notably, the
study suggests that tuning the proportion of various copper species al­
lows tailoring the active temperature window for HC-SCR, offering a
strategic approach for optimizing Cu/SAPO-34 catalysts based on
application-specific needs. These findings provide beneficial insights
into the detailed design of highly efficient Cu-based zeolite catalysts,
underlining the potential benefits of C3H6-SCR in achieving targeted
catalytic performance (Gao et al., 2021).
To reduce NOx emissions, extensive research has been conducted on
HC-SCR. Based on a comprehensive literature review, three distinct
types of catalysts are commonly employed in HC-SCR: metal oxides, ion-
exchanged zeolites, and noble metal catalysts (Table 2). HCs such as
propene, octane, decane, ethanol, isopropyl alcohol, and acetone are
commonly used as metal oxide catalysts. The choice of reducing agent
having proper carbon number plays a crucial role in influencing the
activity of the metal oxide catalyst (Liu and Ihl Woo, 2006). For
instance, with an increase in carbon number, the activity window of the
Ag/Al2O3 catalyst shifts towards lower temperature regions (Shimizu
et al., 2000). Zeolite-based catalysts primarily utilize ethylene, propene,
propane, and decane (Cheng and Bi, 2014).
To address the narrow operating temperature window observed in
certain catalysts, particularly Ag/γ-Al2O3, researchers have explored the
use of low concentrations of H2 to activate the HC-SCR reaction
(Hernández-Terán et al., 2022; Hernández-Terán and Fuentes, 2014;
Satokawa, 2000). When H2 was used in Ag/Al2O3 catalysts for
H2-C3H6-SCR, Lee et al. (2021) found that low-temperature de-NOx
processes performed admirably. Complete conversion of NOx occurred
between 285 and 370 ◦ C, which was influenced favorably by the pres­
ence of H2 (Lee et al., 2021a). The effect of H2 on SCR has been inves­
tigated for various compounds, including alcohols, ketones, aliphatic
HCs, and aromatic HCs, the effect of H2 on the SCR reaction has also
been investigated (Hernández-Terán et al., 2022; Hernández-Terán and
Fuentes, 2014; Gu et al., 2015; Kalamaras et al., 2017; Satsuma et al.,
2005; Shibata et al., 2004a, 2004a; Yan et al., 2023). Although the exact
mechanisms underlying the effects of H2 are not yet fully understood,
they are believed to be influenced by a combination of structural and

Table 2
Summary of hydrocarbon-based selective catalytic reduction (HC-SCR) research for NOx removal.
Catalyst Reaction condition NO Conversion (%) Temperature (◦ C) Ref.

NO (ppm) O2 (%) Reducing agent H2O (%) H2 (%)

Ag/Al2O3 800 10 1714 ppm C3H6 1 100 295–530 (Xu et al., 2017)
Ag/Al2O3 720 4.3 620 ppm toluene 7.2 70 250–275 (Stere et al., 2014)
Ag/Al2O3 200 13 1200 ppm C12H26 5 58 315 (Gu et al., 2015)
Ag/Al2O3 500 10 1500 ppm EtOH 98 290–415 (Gunnarsson et al., 2017)
Ag/Al2O3 800 10 1565 ppm C2H5OH 10 90 400 (Xu et al., 2018)
Ag/γ-Al2O3 300 10 150ppm C12H26 10 50 200 (Lee et al., 2023)
Ag/γ-Al2O3 3000 21 3000 ppm C3H6 90 300–600 (Kummari et al.,)
Ag/γ-Al2O3 300 9.7 257ppm C7H16 3 100 350–450 (Lee et al., 2017)
Ag/Al-SBA-15 500 10 2500 ppm C2H6O 35 350 (Boutros et al., 2009)
La0.8Sr0.2MnO3/αAl2O3 1000 1200 ppm CH4 90 900 (Teng et al., 2018)
La0.8Sr0.2MnO3/αAl2O3 1000 1 1200 ppm CH4 >90 900 (Teng et al., 2018)
FeAl2O3/CM 500 1000 ppm C2H6 97 500 (Zhou et al., 2017)
FeAl2O3/CM 500 1 1000 ppm C2H6 97 600 (Zhou et al., 2017)
CuSiBEA 1000 2 1000 ppm C2H6O 40 380 (Dzwigaj et al., 2009a)
CuSiBEA 1000 2 2000 ppm C3H8 20 380 (Dzwigaj et al., 2009a)
Cu-TNU-9 500 12 835 ppm C3H8 80 350 (Moreno-González et al., 2017)
Fe-PCH 1000 2 5000 ppm C3H6 96 400 (Yuan et al., 2018)
Fe/SiO2/CM 500 500 ppm C3H8 100 500–600 (Zhou et al., 2018)
Fe/SiO2/CM 500 1 500 ppm C3H8 100 550–600 (Zhou et al., 2018)
Pt/Ce1− xZrxO2-δ 150 2.5 5000 ppm C3H8 92 220 (Kalamaras et al., 2017)
2% Pt/MCM-41 1000 14 3000 ppm C3H6 94 200 (Komatsu et al., 2006)
2% Pt/B-MPS 1000 14 3000 ppm C3H6 100 160 (Komatsu et al., 2006)
2% Pt/MPS 1000 1 10000 ppm C3H6 100 400 (Komatsu et al., 2006)
In/H-BEA 600 6 600 ppm CH4 90 550 (Pan et al., 2017)
Pd-SBA-Imp 150 7 1500 ppm CH4 98 300 (Boutros et al., 2014)
AuPd/TiO2 720 4.3 620 ppm toluene 70 275 (Hamill et al., 2014)
HAIBEA 1000 2 1000 ppm C2H6O 62 450 (Dzwigaj et al., 2009a, 2009b

861
S. Elkaee et al. Process Safety and Environmental Protection 184 (2024) 854–880

chemical factors. The specific reasons behind the observed impact of H2
on catalytic reactions are still the subject of ongoing research and
investigation (Satokawa, 2000; Breen et al., 2005; Chansai et al., 2010;
Satokawa et al., 2003; Sazama et al., 2005).
3.1. C3H6-SCR
The C3H6-SCR process is a highly effective method that has been
extensively studied to reduce NOx emissions from various combustion
sources (Table 3). This includes the use of the reducing agent propene
(C3H6) in conjunction with a catalyst to transform NOx into the inert N2,
H2O, and carbon dioxide (CO2) (Praveena and Martin, 2018).
One significant advantage of the C3H6-SCR process is its ability to
operate at lower temperatures than traditional NH3-based SCR systems.
This characteristic makes it suitable for applications in which high
temperatures can be detrimental, such as automotive exhaust after­
treatment systems and small-scale stationary sources (Gao et al., 2021).
Multiple factors influence the performance of C3H6-SCR, including
the temperature, space velocity, C3H6/NOx ratio, oxygen concentration,
pH, catalyst nature, and synthesis procedure. Optimizing these param­
eters is crucial for achieving a high NOx conversion efficiency while
minimizing undesirable byproducts such as NH3 or NO2 (Kummari et al.,
).
In the C3H6-SCR process, choosing an appropriate catalyst is a crucial
step. Transition metal oxides, such as V, W, and Mo, supported on
various materials, such as zeolites and metal oxides, are only a few of the
diverse catalyst types that have been investigated. By promoting the
reaction between C3H6 and NOx molecules, which produces N2, H2O,
and CO2, these catalysts aid in the reduction of NOx (Gao et al., 2021).
Among these catalysts, ZSM-5 stands out for its remarkable DeNOx ac­
tivity, selectivity, and cost-effectiveness, making it the most suitable
candidate for HC-SCR reactions, as noted by various researchers (Gao
et al., 2021; Grinsted et al., 1993).
While Mn-based catalysts show remarkable activity in NH3-SCR,
their catalytic efficiency is notably restricted in C3H6-SCR (Xu et al.,
2021; Nam et al., 2017). Interestingly, the microporous H-type ZSM-5
zeolite, characterized by high acid sites, displays a synergistic effect
when combined with Mn. Moreover, the widespread practice of incor­
porating rare earth elements like lanthanum and cerium is common for
catalytic modification (Xu et al., 2021). Tang et al. (2022) used the
coprecipitation method to prepare MnOx/ZSM-5-H2RF-100W catalysts,
activated by H2 RF plasma. Achieving over 99% NO conversion at 200
–300 ◦ C, the catalyst’s efficacy is attributed to H2 RF plasma impacting
Mn(OH)2, promoting electron transfer, generating active Mn2O3 species,
and enhancing C3H6-SCR redox processes. The catalyst’s exceptional
performance also stems from stable Brønsted acidity and improved
dispersion caused by the H2 RF plasma, leading to enhanced
low-temperature C3H6-SCR catalytic activity (Tang et al., 2022). Tange
et al. (2023) studied the impact of lanthanum doping on C3H6-SCR in
another recent investigation. The study revealed that lanthanum doping
increased NOx conversion by 15% within the range of 150–250 ◦ C.
Doping with lanthanum was observed to decrease the adsorption of
C3H6 while increasing the ability of NO and NO2 to bind to active
manganese sites. The increased charge nonlocalization caused by

Table 3
Summary of hydrogen-based selective catalytic reduction (H2-SCR) research for NOx removal.
Catalyst Reaction condition NO conversion Temperature Ref
(%) (◦ C)
NO (ppm) or H2 (ppm) or O2 Other gases GHSV (h¡1),
(%) (%) (%) (gscm¡3)

Pt–MnOx 0.048 (%) 0.1 (%) 5 78,000 ( h− 1) 64 100 (Park et al., 2011)
Pt/SiO2 0.072 (%) 1 (%) 5 36,000 (h− 1) 78 130 (Zhou et al., 2002)
Pt/HZM-5 1000 (ppm) 5000 (ppm) 10 36,000 ( h− 1) 71.4 120 (Xue et al., 2018)
Pt/ZSM-35 1000 (ppm) 5000 (ppm) 6.7 80,000 (h− 1) 81 120 (Yu et al., 2010a)
Pt/Zr–SiO2 0.048 (%) 0.08 (%) 5 10,000 (h− 1) 95 75 (Park et al., 2012)
Pt (PZ-1–168) 2760 (ppm) 0.9 (%) 0.91 1100 (h− 1) 91 166 (Jones et al., 1971)
Pt/Cr/ZSM-35 1000 (ppm) 5000 (ppm) 6.7 80,000 (h− 1) 95 120 (Yu et al., 2010b)
Pt/Ce1-xZrxO2- δ 150 (ppm) 800 (ppm) 2.5 33,000 (h− 1) 90 100–300 (Kalamaras et al.,
2017)
Pt/ZrO2@C (Zr-MOF) 0.1 (%) 0.5 (%) 4 72,000 ( h− 1) 100 90 (Wang et al., 2019c)
Pt/Ti–MCM-41 1000 (ppm) 5000 (ppm) 6.7 80,000 (h− 1) 90 50–300 (Li et al., 2010b)
2% Pt/SDB 1000 (ppm) 1 (%) 3.2 3000 ( h− 1) 90 45 (Fu and Chuang,
1989)
1%Pt/Al2O3 1000 (ppm) 0.4 (%) 6 0.03 (gscm− 3) 75 120 (Burch and
Coleman, 2002)
3% Pt/ZrO2 + H-ZSM-5 1000 (ppm) 1 (%) 2 0.12 (gscm− 3) 100 127 (Nanba et al., 2003)
(1:3)
− 1
Pd/CeO2 0.05 (%) 1 (%) 10 50,000 (h ) 67 230 (Alghamdi et al.,
2020)
− 1
Pd/SiO2 0.05 (%) 0.05 (%) 2 80,000 (h ) 46 175 (Yu et al., 2010c)
Pd/FeTi 2000 (ppm) 8000 (ppm) 5 60,000 (h− 1) 94 100–135 (Zhang et al., 2021a)
Pd/MFI 1000 (ppm) 0.8 (%) 2 0.02 (gscm− 3) 70 100 (Wen, 2002)
Pd–Ir/TiO2 1000 (ppm) 0.3 (%) 5 60,000 h− 1 80 140–200 (Li et al., 2012)
Pd-Ni/TiO2 0.02 (%) 0.2 (%) 1.5 36,000 (h− 1) 99 200 (Hu et al., 2020)
Pd/WOx/ZrO2 500 (ppm) 2000 (ppm) 6 80,000 (h− 1) 80 50–400 (Leicht et al., 2012)
Pd/TiO2/ZSM-5 0.1 (%) 0.5 (%) 10 60,000 (h− 1) 80 260 (Borchers et al.,
2023)
Pd/V2O5/TiO2/SBA-15 50 (ppm) 2000 (ppm) 1.5 46,000 h− 1 95 100–380 (Wang et al., 2016)
0.5% Pd/LaCoO3 2500 (ppm) 1 (%) 5 0.09 (gscm− 3) 100 150 (Chiarello et al.,
2007)
5% Rh–Zn/SiO2 1000 (ppm) 0.6 (%) 5 20 (ppm) SO2, 6 0.0267 (gscm− 3) 55 300 (Hasegawa et al.,
(%) H2O 2005)
− 1
Zn-ZSM-5 0.05 (%) 0.2 (%) 1.5 12,000 (h ) 40 250 (Wang et al., 2014b)
1
PrCeMnPdO3@Ni 0.108 (%) 1.08 (%) 4 32,000 (h− ) 93 200 (Ma et al., 2021)
1
Ir/SBA-15 0.005 (%) 0.2 (%) 1.5 46,000 (h− ) 72 250 (Yin et al., 2015)
1
NiO, NiCo2O4, Co3O4 0.034 (%) 1.5 (%) 3 90,000 (h− ) 99 200–250 (Wang et al., 2015b)
1
LaNixFexO3 0.05 (%) 3.5 (%) 8 72,000 (h− ) 95 350 (Wang et al., 2014b)
1
LaFeCoPdO3 0.15 (%) 0.5 (%) 3 45,000 (h− ) 90 433 (Zhou et al., 2002)

862
S. Elkaee et al.
lanthanum doping was confirmed by X-ray photoelectron spectroscopy
(XPS), which is a key factor for enhancing the oxidation of active sites
and facilitating the conversion of NO to NO2. Favorable oxidation of
C3H6 with NO to CH3NO2/CH3CN was demonstrated by computational
studies examining the C3H6 oxidation pathway, where NO2 acted as a
better oxidant for O2 and NO. This study also established a strong cor­
relation between temperature-programmed experiments and the barrier
associated with the C3H6-SCR pathway, emphasizing the significance of
the initial oxidation of C3H6 and the formation of amino intermediates
(NH2) in influencing the low-temperature activity of C3H6-SCR (Tang
et al., 2023). Xu et al. (2021) synthesized Mn-based microporous zeolite
ZSM-5 co-doped with rare earth metals La and Ce (MnxLayCez/ZSM-5)
by using the co-impregnation method. Within the temperature range of
180 ◦ C to 270 ◦ C, the catalyst, specifically Mn0.2La0.07Ce0.05/ZSM-5,
demonstrated over 90% NO conversion and selectivity. This success was
attributed to the robust synergistic interactions among manganese,
lanthanum, and cerium (Xu et al., 2021).
The development of Ag/-Al2O3 catalysts by wet impregnation and
single-step sol-gel methods was examined in a recent study by Kummari
et al. (2023). The study focused on exploring the effect of varying pH
values on the catalysts, where C3H6 was used as the reducing agent to
conduct the catalytic tests in the temperature range of 200–600 ◦ C. With
conversion rates exceeding 90%, the findings showed that increased pH
levels had a favorable effect on NOx conversion. Furthermore, due to
Fig. 6. NOx and C3H6 conversion over Ag/Al catalysts at various HC/NOx ratios (a), (d) HC/NOx = 1, (b), (e) HC/NOx = 4, and (c), (f) HC/NOx = 8. Adapted with
permission from (Lee et al., 2021a). Copyright Elsevier B.V. 2020.
863
Process Safety and Environmental Protection 184 (2024) 854–880
increased C3H6 availability, raising the C3H6:NO ratio from 0.9 to 2.2 led
to a notable improvement in NOx conversion, from 65% to 99% at 400
◦
C. It was found that extra oxygen maintained high catalytic activity and
NOx conversion at high temperatures. Additionally, the catalyst per­
formed well at an elevated GHSV (Gas hourly space velocity) of
120,000 h− 1. These findings clearly demonstrate that the optimized Ag/
γ-Al2O3 catalysts achieved exceptional NOx conversions across a wider
temperature range, even under conditions similar to real diesel exhaust
with higher space velocities and excess oxygen concentrations (Kum­
mari et al.,).
Lee et al. (2021) investigated the effect of C3H6/NOx ratio on Ag/
Al2O3. This study demonstrated that increasing the HC/NOx ratio led to
a corresponding increase in NOx conversion. Specifically, the highest
observed ratio of HC/NOx, 8 resulted in a shift towards lower temper­
atures and improved NOx conversion. Thus, the study concluded that
impregnation with Ag enhanced C3H6-SCR, and that a higher concen­
tration of HC was beneficial for enhancing NOx conversion (Fig. 6) (Lee
et al., 2021a).
Gao et al. (2021) studied Cu/SAPO-34 catalysts and their perfor­
mance in C3H6-SCR. The performance of the Cu/SAPO-34 catalysts was
compared with that of H-SAPO-34 catalysts without copper. The study
revealed that a higher Cu loading led to improved de-NOx performance,
particularly at low and medium temperatures where the Cu loading had
a significant impact. The CuO species enhanced the activation of C3H6,
S. Elkaee et al. Process Safety and Environmental Protection 184 (2024) 854–880

converting it into a highly active CxHyOz species that effectively reduced
NOx. However, at temperatures >400 ◦ C, higher Cu loadings resulted in
a decrease in deNOx activity owing to increased non-selective oxidation
of C3H6. This decline was attributed to the higher CuO content. Addi­
tionally, a higher CuO content leads to an increased NO2/NO ratio,
which inhibits the HC-SCR process as the generation of NO2 hinders the
overall reduction of NOx (Gao et al., 2021).
Chaieb et al. (2013) found that catalysts with more Ag loading per­
formed better in converting C3H6 at lower temperatures and enhanced
NOx conversion below 375 ◦ C. However, the oxidation of C3H6 increases
at higher temperatures, which reduces NOx conversion. This phenome­
non has been attributed to the dispersion of Ag, which results from the
creation of larger Ag2O clusters. These clusters can change into Ag0
particles through HCs, and these active Ag0 particles cause the undesired
complete oxidation of propene. This study also revealed a correlation
between the optimal surface density of Ag and the catalytic performance
in the C3H6-SCR of NOx, specifically in terms of NOx conversion to N2.
When the surface density of Ag exceeded 0.7 Ag/nm2, a decline in the
catalytic performance of C3H6-SCR was observed. Conversely, the lower
surface density of Ag results in an increase in the catalytic performance
of C3H6-SCR (Chaieb et al., 2013).
3.2. C3H8-SCR
Al2O3-sphere in C3H8-SCR. Furthermore, the absence of N2O or NO2
detection, as indicated by the analyzer, suggests the effective conversion
of NO to N2 (Yang et al., 2023).
Zhou et al. (2018) examined the effects of oxygen on a monolithic
iron-based C3H8-SCR catalyst. In the absence of oxygen, the findings
revealed 100% NOx conversion and 95% N2 selectivity at temperatures
between 450 and 600 ◦ C. In the presence of oxygen, similar results were
obtained, with a shift of approximately 50◦ C towards higher tempera­
tures (Fig. 7) (Zhou et al., 2018).
HC-SCR, a promising NOx reduction technology, faces challenges and
limitations. Selecting suitable HC reductants is a challenge due to
varying reactivities and selectivities towards NOx conversion. Factors
like temperature, space velocity, and presence of other exhaust gases
affect HC-SCR efficiency. Undesirable byproducts like unburned HCs or
NH3 can pose environmental concerns. Additionally, the longevity and
stability of the catalysts used in HC-SCR systems remain limited because
catalyst deactivation over time can decrease the overall efficiency.
Furthermore, the operational range of the HC-SCR may be constrained
by the need for specific temperature conditions, making it less effective
under transient or low-temperature exhaust conditions. Overcoming
these challenges and optimizing the HC-SCR technology is vital for
broader NOx reduction and achieving more sustainable air quality and
environmental goals.

NOx emissions from combustion engines and industrial sources can 4. Hydrogen-based SCR system
be effectively reduced using propane-SCR (C3H8-SCR), commonly
known as propane SCR. Using C3H8 as the main reducing agent signif­ The introduction of H2-SCR systems constitutes an important shift in
icantly alters the SCR procedure. Utilizing propane, C3H8-SCR offers a this field compared to the HC-SCR and NH3-SCR systems. Introducing H2
compelling alternative to conventional SCR systems, providing
improved performance and efficiency (Dzwigaj et al., 2009a;
Hernández-Terán et al., 2022; Moreno-González et al., 2017; Zhou et al.,
2018; Yang et al., 2023).
The operational principles of C3H8-SCR closely align with those of
other SCR systems, enabling seamless integration into existing setups
(Yang et al., 2023). Furthermore, this innovative process exhibited
remarkable thermal stability, allowing it to maintain optimal catalytic
activity across a wide temperature range and ensure efficient NOx
reduction (Hernández-Terán and Fuentes, 2014; Yang et al., 2023).
In the context of C3H8-SCR, the conversion of C3H8 involves two
distinct processes: C3H8 oxidation and C3H8-SCR. These processes are
known to be competitive, and C3H8 oxidation can be further categorized
into partial and complete oxidations. Partial oxidation generates active
intermediates that play crucial roles in promoting NOx removal during
C3H8-SCR, whereas complete oxidation is considered less beneficial
(Yang et al., 2023). In a different study, Hernández-Terán et al. (2014)
examined the catalytic behavior of Ag/-Al2O3 and the role of reductants.
This study found that NO conversion occurs via two different chemical
routes. The immediate decrease in NO observed upon C3H8 oxidation
suggests that it serves as a reducing agent. The starting temperature of
the C3H8 reactivity was lowered by the presence of H2. Notably,
although the low-temperature conversion of NO decreased, there was no
corresponding decrease in the temperature at which C3H8 reacted. The
conversion of C3H8 commenced at approximately 120◦ C and steadily
increased until complete consumption at approximately 500 ◦ C. Inter­
estingly, in the H2-C3H8-SCR system, the initiation temperature for the
C3H8 reaction was approximately 40 ◦ C higher than the onset temper­
ature for NO conversion (Hernández-Terán and Fuentes, 2014).
Yang et al. (2023) explored particular catalysts for C3H8-SCR, using
Al2O3-sphere and Al2O3-flake catalysts. These findings revealed that at
low temperatures, C3H8 exhibited minimal NO conversion because of its
stability as an alkane. However, when the temperature increased, the
catalysts started to show catalytic activity, with Al2O3-flake converting Fig. 7. NO conversion and N2 selectivity on iron-based monolithic catalysts
NOx at 550 ◦ C at a rate of 95% and Al2O3-sphere at 550 ◦ C at a rate of with various supports under different reaction conditions: (a) 0.05% NO, 0.05%
75%. Interestingly, beyond 550 ◦ C, NO conversion started to decrease. C3H8, GHSV = 15,000 mL g− 1 h− 1, (b) 0.05% NO, 0.3% C3H8, 1% O2, GHSV =
The study concluded that the Al2O3-flake demonstrated higher catalytic 15,000 mL g− 1 h− 1.Adapted with permission from (Zhou et al., 2018). Copy­
efficiency and a wider operational temperature range compared to the right Elsevier Ltd. 2018.

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S. Elkaee et al.
as a potent reductant not only offers a novel approach but also has the
potential to revolutionize NOx abatement strategies. H2’s intrinsically
ecofriendly nature, characterized by clean combustion that produces
only water vapor, highlights its appeal as a sustainable and clean fuel
source (Gholami et al., 2020; Amiridis et al., 1996; Hu and Yang, 2019;
Mondragón Rodríguez et al., 2010; Park et al., 2011; Luo et al., 2014;
Muhammad Farhan et al., 2024).
H2-SCR is a preferred technique for the SCR of NOx, especially under
low-temperature conditions, compared to HC and NH3 (Muhammad
Farhan et al., 2024). The use of H2 offers several advantages over its use
as a simple reductant. H2 enhances catalyst activity and mitigates
catalyst poisoning that could hinder the reaction, thereby improving the
overall efficiency of the SCR process. Furthermore, its unique charac­
teristics position it as a favorable alternative reductant for H2-SCR,
aligning well with the need to adhere to stringent emission limits while
minimizing the generation of secondary pollutants (Guan et al., 2021;
Xu et al., 2019b).
The effectiveness of H2 as a reducing agent for the SCR in the pres­
ence of high oxygen levels has been extensively studied (Table 3). The
technique has drawn a lot of interest as an ecologically friendly tech­
nology because of its excellent efficiency, capacity to reduce the
necessary reaction temperatures to below 200 ◦ C, great selectivity to­
wards nitrogen (N2), and exclusive creation of water vapor as a
byproduct. Numerous studies have documented the remarkable efficacy
of utilizing H2 as a reductant in SCR reactions, especially in in absence of
oxygen, leading to a substantial reduction of NOx emissions (Gholami
et al., 2020; Tu et al., 2017).
Researchers have investigated several processes to conduct
comprehensive study on the effectiveness of H2-SCR catalysts. They
divided the H2-SCR reaction mechanism into three separate groups: NO
adsorption/dissociation L-H mechanism, NO oxidation-reduction, and
dual/bifunctional processes (Muhammad Farhan et al., 2024; Liu et al.,
2012). The following simple statement summarizes the understanding of
the H2-SCR reaction mechanism (Hu and Yang, 2019; Muhammad Far­
han et al., 2024; Yu et al., 2010c; Liu et al., 2012; Ravishankara et al.,
2009; Jong Kim et al., 2023; Olympiou and Efstathiou, 2011):
2 NO + 4H2 + O2 → N2 + 4H2O (Primary reaction) (8)
. NOad + NO → N2O + Oad
Reaction (8) is the primary reaction essential for achieving the
desired outcome, exemplifying green chemistry, with N2 and H2O as the
sole products. Nonetheless, prior research has revealed suboptimal
performance and reduced N2 selectivity owing to the concurrent re­
actions described in reactions (9) and (10).
2 NO + 3H2 + O2 → N2O + 3H2O (Undesired byproducts) (9)
2 NO + H2 → N2O + H2O (Undesired byproducts) (10)
. Gioria et al. (2019) examined the removal of NO via H2 reduction
Reaction (11) reveals another potential by-product, NH3, under
specific conditions.
NO + 5/2H → NH3 + HO (Alternative byproduct) (11)
.
Notably, N2O is a potent greenhouse gas known to deplete the ozone
layer. Furthermore, in "Fast H2-SCR," the reactivity of NO2 outperforms
that of NO, and it assumes a pivotal function (Reaction (12)):
NO + 1/2 O2 → NO2 (Fast reaction) (12)
. kinetic effects in the synthesis of suboxides and activating oxide cata­
Moreover, in Reaction (13), the catalytic reaction occurred at lower
temperatures under oxygen-enriched conditions.
H2 + 1/2O2 → H2O (Efficient reaction) (13)
. the metal support in the catalyst interface area. More precisely, the NOx
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Process Safety and Environmental Protection 184 (2024) 854–880
According to the L-H model, the main processes in the adsorption-
dissociation mechanism may be summed up as follows, with "X*"
standing in for the active site on the noble metal or metal oxide catalyst
element. According to reactions (14–22), NO adsorption on the catalyst
surface results in NO species, which are then converted into N and O
molecules at the active sites on the catalyst surface, initiating NO
reduction on the catalyst. The dissociation of NO is the rate-determining
step in the synthesis of N2. This process is temperature- and H2(g) partial
pressure-dependent because of the beneficial influence of adsorbed
hydrogen on NO dissociation. In the subsequent interaction between the
newly formed N and NO species, by-products such as N2O were pro­
duced in the reaction combination. The active sites of the catalyst effi­
ciently adsorb and break down O2 and H2, producing atomic oxygen (O)
and hydrogen atoms (Had). The reaction between O and H species at
these active sites produces OH, which reacts with Had to create H2O (Hu
and Yang, 2019; Liu et al., 2012; Papp and Sabde, 2005; Frank et al.,
1998).
L-H Mechanism is as follows:
NO + X* ↔ NOad (14)
H2 + 2 X* ↔ 2Had (15)
O2 + 2 X* ↔ 2Oad (16)
2Nad → N2↑ + 2 X* (17)
NOad + Nad → N2O↑ + 2 X* (18)
Oad + Had → OHad + 2 X* (19)
OHad + Had → H2O + 2 X* (20)
.
The co-adsorption of NO on the surfaces from which the original
NOad dissociates can likewise be influenced by adsorbed hydrogen. The
following equation illustrates the probability of N2O production (Liu
et al., 2012):
N2O generation mechanism is as follows:
NOad + Had → Nad + OHad (21)
(22)
.
Another approach is the NO oxidation-reduction cycle. Catalytic
reduction employs this technique to reduce NO to nitrogen-based in­
termediates, which are then transformed into N2 and H2O. In an atmo­
sphere with excess oxygen, NO can be oxidized by reacting with O2 and
then adsorbing onto the catalyst surface. This process produces reactive
compounds such as NH3, NO2, NO3, and other dynamic substances
required for the H2-SCR reaction (Muhammad Farhan et al., 2024).
over Cu/SiO2. In the presence of a reducing agent, metallic Cu creates
active sites during the redox cycle. NOx was absorbed and broken down
on the catalyst, generating NO and CuO. The active site was predomi­
nantly composed of metallic Cu, which was discovered through
comprehensive characterization procedures and survived the reaction as
a CuO or Cu-O adsorbent (Fig. 8) (Gioria et al., 2019).
Kim et al. (2003) examined the ability of CuO to reduce utilizing H2
in their research. First-principles density functional simulations and
time-resolved X-ray diffraction were used to investigate the reaction
process. These findings suggest that H2 converts CuO to Cu without
generating intermediate molecules or suboxides. The significance of
lysts has also been clarified (Kim et al., 2003).
Costa et al. (2007) examined a Pt/MgO-CeO2 catalyst and provided a
reaction pathway. The experimental results revealed the presence of two
distinct transient NOx species with various structural characteristics on
S. Elkaee et al. Process Safety and Environmental Protection 184 (2024) 854–880

Fig. 8. NO reduction using Cu/SiO2 catalysts and H2. Adapted with permission from (Gioria et al., 2019).

species around the dynamic NOx species with various configurations studies, including two unique and active chemisorbed NOx molecules.
underwent excessive H2 reduction to convert into N2. However, an These included nitrosyls (NO+) co-adsorbed with irreversibly chem­
overabundance of H2 causes a decrease in NOx species close to NOx with isorbed bidentate (bridge) nitrate on the MgO support surface and
the same structure, resulting in the synthesis of N2 and N2O (Costa and reversibly chemisorbed nitrate NO3 species on the CeO2 support surface
Efstathiou, 2007a). (Fig. 10) (Costa and Efstathiou, 2007a, 2007b).
The H2-SCR mechanism is a distinctive catalytic process that relies For H2-SCR, Qi et al. (2006) discovered a noteworthy spillover
on the interaction between a noble metal catalyst and either a reducible phenomenon in which H2 migrates from the noble metal to the support
or oxidizable support in conjunction with acid promoters. This process, surface, exerting a significant influence on the reaction activity. In
also referred to as a dual or bifunctional mechanism, combines these addition, they observed a reverse spillover effect of NOx from the
elements to facilitate reduction reactions (Dhainaut et al., 2007). Shi­
bata et al. (2004) investigated Pt-based catalysts for NO removal and
proposed a dual-function reaction mechanism for H2-SCR. The two
primary parts of this system are as follows: first, when NO and H2
interact, an intermediate product named NHx is formed on the surface of
Pt; and second, the surfaces of the Pt atoms underwent H2 and NO
splitting, which initiated the formation of NH3(g). Gaseous NH3 is then
adsorbed onto the B-acid sites of the support, where it finally de­
composes into NH+ 4 . NH4 actively participates in SCR, which produces
+

N2 as a consequence (Fig. 9) (Shibata et al., 2004b).

Costa et al. (2007) examined the mechanism of H2-SCR on a Pt/MgO-
CeO2 catalyst using in situ DRIFTS and steady-state isotopic transient
kinetic analysis (SSITKA). Their research showed that the Pt/MgO-CeO2
catalyst’s interface between the MgO and CeO2 supports was where the Fig. 10. Histogram of the bifunctional catalysis on the Pt/MgO/CeO2 catalyst.
Adapted with permission from (Costa and Efstathiou, 2007a). Copyright
reaction occurred most often. The nitrogen (N) pathways of the Pt/MgO-
2007 ACS.
CeO2 catalyst were clarified using a combination of DRIFTS and SSITKA

Fig. 9. Proposed H2 over Pt catalyst selective catalytic reduction (SCR) mechanism. Adapted with permission from (Shibata et al., 2004b). Copyright 2004 ACS.

866
S. Elkaee et al.
support to the noble metal catalyst, especially at lower temperatures.
This study emphasized the importance of NH+ 4 as a key intermediate
species in reduction processes, particularly with Brønsted acid sites.
Adding V2O5 significantly increased the effectiveness of the Pd/TiO2/
Al2O3 catalyst, expanding the reaction temperature range and high­
lighting the benefits of including V2O5 in the catalyst composition. N2
and N2O are the ultimate products of this process, which involves the
adsorption and dissociation of H2 and NO on the metallic Pd surfaces.
Notably, the rate of NO dissociation has been shown to be the rate-
limiting factor at lower temperatures, but the in situ production of
NHx species is critical at higher temperatures (Qi et al., 2006).
Various methods for preparing H2-SCR catalysts have the potential to
affect the catalytic activity of the reaction. Typically, researchers
exploring H2-SCR have employed techniques such as impregnation,
hydrothermal, and sol-gel methods to fabricate these catalysts (Kala­
maras et al., 2017; Luo et al., 2014; Xue et al., 2018; Leicht et al., 2012;
Wang et al., 2016; Wu et al., 2010; Xu et al., 2016). In order to reduce
NO using H2 and C3H6, Kalamaras et al. (2017) developed a
Pt/Ce1-xZrxO2-δ catalyst employing the sol-gel method. The catalytic
characteristics of these materials were extensively studied using
SSITKA-mass spectrometry-DRIFTS, in situ DRIFTS, and H2
temperature-programmed desorption techniques. Furthermore, NO
removal was conducted to measure the performance of the catalyst,
which demonstrated increased catalytic activity during the process
(Kalamaras et al., 2017). Park et al. (2011) successfully applied an
impregnation method, which resulted in exceptional activity and high
N2 output. In their thorough investigation, infrared (IR) examination
supported the formation of NH3 via NO and H2 interactions with the
Pt-MnOx catalysts. Molecular NOx species and dissociatively adsorbed
NOx species interact with H atoms on the catalysts, resulting in the
production of NH3. Due to the secure retention of NH3 on MnOx,
approximately 100% of the NO in the gas mixture was converted in the
temperature range of 100–125 ◦ C, revealing the enormous potential of
these Pt-MnOx catalysts for NO conversion (Park et al., 2011). Ti (SO4)2
and Fe (NO3)3 were used as precursor materials to synthesize an in­
ventive Pd/FeTi catalyst via a hydrothermal method. According to their
research, the hydrothermal method improved H2-SCR’s efficiency by
maximizing the effects of both titanium and iron, resulting in an
astonishing 94% NOx conversion rate in the temperature range of
100–135◦ C (Zhang et al., 2021a).
The effectiveness of three different preparation methods—poly­
ethylene glycol reduction (PGR), impregnation, and deposition-precip­
itation—was examined by Zhang et al. (2019) to determine the catalytic
efficiency of Pd/TiO2 in H2-SCR. They demonstrated that the PGR
method produced the most effective NOx reduction. In conclusion, the
study highlighted the importance of the preparation process on the Pd/
TiO2 catalyst’s performance in H2-SCR (Zhang et al., 2019b).
Catalysis includes active components such as metals, nonmetals, or
metal oxides. Modifying the surface features and interactions with the
catalytic support offers active sites for reactions and considerably in­
fluences the activity, selectivity, and stability of the catalyst. Designing
efficient catalysts for various applications requires a thorough under­
standing of their function (Zhang et al., 2019b; Yang et al., 2017). Noble
metals, such as Pd, Pt, and Rh, are key elements in H2-SCR for reducing
NOx emissions. They excel because of their unique structures, resistance
to deactivation, and efficient NO decomposition, forming active species
that reduce NOx. Among these catalysts, Pt and Pd are particularly
effective at low temperatures. Their significant roles in SCR research
continue to make them important subjects of study (Huai et al., 2016;
Ryou et al., 2017; Zhang et al., 2013; Polychronopoulou and Efstathiou,
2012).
Granger et al. (2006) used supported Pt-, Rh-, and Pd-based catalysts
to study H2-SCR activity. The following activity sequences were
discovered for several noble metals: Pd/Al2O3, followed by Rh/Al2O3.
According to previous studies, the best N2 selectivity was demonstrated
for Pd-based catalysts. With noble metals, the rate-determining step
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Process Safety and Environmental Protection 184 (2024) 854–880
changed. While Pt catalysts favored a reaction between nearby N atoms,
Pd and Rh catalysts preferentially produced N2 through a reaction be­
tween N atoms and the adsorbed NO molecules. The H2 + O2 reaction
competition affects the rate of conversion of NO. Stronger NO adsorp­
tion, which prevents H2 dissociation, is believed to be the cause of Rh/
Al2O3’s reduced activity. The production of NHx species and NO disso­
ciation are aided by H2 dissociation, which increases the overall reaction
activity (Granger et al., 2006). For Pt/Al2O3 and Pd/Al2O3 catalysts,
Nanba et al. (2003) observed two unique temperature zones of activity
at 350 and >450 K. The reduced and oxidized states of the Pt and Pd
catalysts correspond to these areas, indicating that the nature of the
noble metal may affect the temperature range of the catalytic activity
(Nanba et al., 2003).
Using a Pt-K/Al2O3 catalyst, Castoldi et al. (2010) investigated the
use of H2 to reduce NOx. Their research showed that nitrates accumu­
lated on Pt-K/Al2O3 at 350 ◦ C. The NH3 produced by this procedure
interacts with the remaining nitrates to form N2, according to transient
reactivity studies and FT-IR spectroscopy (Castoldi et al., 2010).
Pt/TiO2-ZrO2, which had been prepared with H2 and O2 at 400 ◦ C, un­
derwent a comparative examination of its catalytic performance by
Achida et al. (2001). Their research showed that the highest conversion
for the oxidized catalyst was 40% lower than that for the reduced
catalyst and that the first NO reduction for the oxidized catalyst did not
occur below 100 ◦ C. These findings highlight the much greater activity
of metallic Pt species than that of oxidized Pt species (Machida et al.,
2001). The high cost associated with noble metal catalysts poses a sig­
nificant barrier to their practical utilization in engineering, despite their
remarkable efficiency in NO removal through H2. Consequently,
numerous researchers have shifted their focus towards investigating
non-noble metal catalysts as viable and cost-effective alternatives for the
H2-SCR of NOx.
Wang et al. (2015) successfully prepared catalysts with ordered
mesoporous structures in their research, including Co3O4, NiO, and
NiCo2O4. They performed this synthesis using a hard template, meso­
porous KIT-6. Of these catalysts, NiCo2O4 stood out because it removed
more than 70% of NO with H2 at temperatures ranging from 50 to 400
◦
C. This exceptional performance is attributed to both the ordered
mesoporous structure of NiCo2O4 and its large surface area, which al­
lows the delivery of more active oxygen and reducing chemicals. This
enhances SCR efficiency at lower temperatures (Wang et al., 2015b).
Valiheikki et al. (2014) investigated the well W-promoted CeO2-ZrO2
catalysts reduced NOx emissions in H2-SCR. Two catalysts were used: W-
ZrCe (Zr-rich) and W-CeZr (Ce-rich). At 250–350 ◦ C, W-ZrCe out­
performed W-CeZr with outstanding NOx conversion (30%–55%) and
good N2 selectivity (85%–92%). Both catalysts contained WOx clusters,
with W-ZrCe having Zr-rich compositions, revealing W species in the
WOx clusters, according to UV–vis/DRS studies. This work emphasized
the function of WOx as an active site for the production of NHx,
increasing the SCR activity of the W-ZrCe catalysts (Fig. 11) (Väliheikki
et al., 2014).
Perovskite catalysts can be prepared as described by Luo et al.
(2014). For the purpose of H2-SCR applications, they specifically
developed LaNi1xFexO3, where x had values of 0.0, 0.2, 0.4, 0.7, and 1.0.
The findings of this study showed that adding Fe to LaNiO3 not only
improved the NOx removal effectiveness but also improved the stability
of the perovskite structure. An important step in the NO reduction
process is the successful reduction of Ni3+ to Ni2+ because of its elevated
catalytic activity in H2-SCR (Luo et al., 2014).
Another noteworthy advancement in the development of H2-SCR
catalysts is the development of bimetallic systems that combine noble
and transition metals. This area of research has been extensively
explored by numerous investigators (Duan et al., 2019; Dimick et al.,
2010; Sun et al., 2018b). PtNi/C catalysts for H2-SCR were studied by Tu
et al. (2017) in fixed-bed and gas-diffusion reactors. Pt0.65Ni0.35 had the
best performance, removing 95% of NO between 120 and 300 ◦ C and
indicating potential for low-temperature SCR. A Pt-rich top layer with Ni
S. Elkaee et al. Process Safety and Environmental Protection 184 (2024) 854–880

Fig. 11. In terms of NOx conversion (XNOx,%), H2 conversion (XH2,%), N2-selectivity (SN2), and N2O creation (ppm) at various reaction temperatures, W-ZrCe and
W-CeZr catalysts perform well for hydrogen-based selective catalytic reduction (H2-SCR). Adapted with permission from (Väliheikki et al., 2014).Copyright Elsevier
B.V. 2014.

underneath was shown by XPS analysis, improving catalytic efficiency
per mass. In a new gas diffusion reactor, these PtNi/C catalysts func­
tioned remarkably well, efficiently removing NO at temperatures <95
◦
C (Fig. 12) (Tu et al., 2017).
H2-SCR is a promising technology for reducing NOx emissions from
various combustion processes, particularly in the context of hydrogen-
rich fuel sources such as hydrogen fuel cells or hydrogen-enriched nat­
ural gas. Although H2-SCR offers several advantages, it has its own set of
challenges and limitations. This necessitates a high H2/NO molar ratio,
which increases operating expenses. Industrial exhaust gases frequently
contain high quantities of CO2 and H2O, which may cause the catalysts
to lose their effectiveness and produce NH3. The hydrogenation of NOx
may be preferred over N2 or N2O reduction in the presence of H (–OH)
species on the support. In addition, CO2 in the flue gas competes with
NOx for adsorption sites and slows the reactions. Furthermore, in H2-SCR
systems, the H2 combustion rates over Pt and Pd surfaces can exceed the
primary NOx reduction stages.
5. CO-based SCR system
The SCR reaction benefits significantly from alternative reducing
agents like NH3/urea, CxHy, H2, and CO, showcasing notable effective­
ness (Akil et al., 2022). A pioneering approach, termed CO-SCR, in­
tegrates catalysts to optimize the reduction process’s efficiency,
demonstrating immense potential in de-NOx applications within flue gas
environments (Kim et al., 2023; Li et al., 2024a; Bai et al., 2024). Con­
trolling industrial emissions, particularly in sectors like steel and coking,
necessitates the removal of NO, especially in the presence of CO abun­
dance in flue gas. The incorporation of CO-SCR technology not only
elevates reduction efficiency but also addresses the critical need to
mitigate NO emissions in these industrial settings (Li et al., 2023a; Song
et al., 2021; Pan et al., 2023; Heo et al., 2020; Lan et al., 2023).
CO-SCR proves particularly advantageous in industries where CO, a
common toxic byproduct of incomplete combustion, exceeds NOx con­
tent in flue gas (Lan et al., 2023; Zhang et al., 2021b). This method
presents a viable alternative to NH3-SCR, offering energy savings and
simultaneous removal of unburned carbon and NOx (Pan et al., 2023;
Heo et al., 2020).

Fig. 12. Various PtxNiy/C catalysts’ chemical reactions and catalytic abilities. Adapted with permission from (Tu et al., 2017). Copyright 2017 ACS.

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S. Elkaee et al. Process Safety and Environmental Protection 184 (2024) 854–880

Illustrating the primary NO-CO reaction process through reactions
(23) and (24), it is notable that reaction (24) generates a certain amount
of N2O. Subsequently, N2O undergoes further reaction with CO, result­
ing in the formation of N2 and CO2, as observed in reaction (25) (Wang
et al., 2022a).
2 NO + 2 CO → N2 + 2 CO2 (23)
2 NO + CO → N2O + CO2 (24)
N2O + CO → N2 + CO2 (25)
.
Many researchers have suggested potential mechanism to improve
understanding of the nature of the reaction. Catalytic reactions typically
adhere to either the Langmuir-Hinshelwood (L-H) or Eley-Rideal (E-R)
mechanisms. However, the specific reaction mechanisms tend to vary
depending on the catalyst employed (Li et al., 2024b, 2023b; Wang
et al., 2023). Some researchers have also suggested the Mars van Kre­
velen (M-K) mechanism in addition to the L-H and E-R mechanisms.
According to a study by Hirakawa et al. (2020), the M-K mechanism has
been proposed to be responsible for the reduction of NO on
Cu0.05Ni0.95Al1.8Cr0.2O4 in the presence of O2. In this mechanism,
interaction occurs between the reactant and the lattice oxygen ion of the
catalyst during the reaction. The first step on Cu0.05Ni0.95Al1.8Cr0.2O4 is
the reaction of CO with the catalyst surface, which creates oxygen va­
cancies. O2 in the gas phase also rapidly adjusts to these vacancies at the
same time. The next process involves NO being adsorbed onto the sur­
face, where it is reduced with the help of oxygen vacancies (Hirakawa
et al., 2020).
The catalyst selectively adsorbs NO molecules on its surface, causing
them to dissociate into N and O radicals when exposed to a mixture of

Fig. 13. Mechanistic investigation of the surface reaction pathways. Adapted with permission from (Salker and Desai, 2016).Copyright Elsevier B.V. 2016.

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S. Elkaee et al. Process Safety and Environmental Protection 184 (2024) 854–880

CO and NO gasses. An essential stage in the NO + CO reaction, the

dissociation of NO is facilitated by the presence of oxygen vacancies
(Gholami et al., 2021; Yao et al., 2013a, 2013b; Deng et al., 2015; Xiong
et al., 2014). There are two types of oxygen vacancies: surface oxygen
vacancies (SOVs) and surface synergistic oxygen vacancies (SSOVs).
Whereas SSOVs are typically found on multi-metal oxides, SOVs are
typically prevalent on single-metal oxides (Wang et al., 2022a; Li et al.,
2024b). The concentration of oxygen vacancies is widely recognized as a
crucial factor influencing the deNOx reaction (Li et al., 2024b; Du et al.,
2020). An explanation was given by Salker et al. (2016), according to
which CO and NO first adsorb onto the surface of the catalyst. Following
this, CO reacts with the oxide’s lattice oxygen to produce CO2 and ox­
ygen vacancies on the surface of the catalyst. At the same time, the
catalyst is reduced, and NO fills the oxygen vacancies (which, in the
presence of O2, can also be filled by O2). The N-O bond must break for N
and O atoms to form, which is an essential stage in the reaction. The
catalyst is oxidized when the produced N atoms unite to form N2.
Furthermore, the catalyst may react with an additional NO that has been
Fig. 15. NO removal reaction pathway over Cu1.2FeMg2.8-LDO Catalyst.
adsorbed to create the byproduct N2O (Fig. 13) (Salker and Desai, 2016).
Adapted with permission from (Liu et al., 2022). Copyright Elsevier Ltd. 2020.
Gholami et al. (2020) carried out a study that examined Cu–Ce cat­
alysts supported on carbon nanotubes for the elimination of NO by CO.
adsorbed NO, creating oxygen vacancies and forming N2 or N2O. This
NO species desorb or dissociate as the reaction temperature rises,
L–H mechanism involves CO adsorption, oxygen vacancy formation, NO
creating more active sites for CO adsorption. CO adsorption is enhanced
adsorption, and subsequent bond division, generating separated N
because, at the same time as Cu–O–C species are reduced by CO, a large
atoms. Concurrently, new lattice oxygen forms on the catalyst surface
number of Cu+ species and oxygen vacancies are produced. When CO
(Li et al., 2014).
molecules are adsorbed on Cu+ species on the catalyst surface, oxygen
The selective catalytic reduction of NOx by CO (CO-SCR) faces
radicals that are created by NO dissociation react with them. N radicals
challenges, including low denitration efficiency, susceptibility to O2
have the ability to combine with NO molecules to make N2O or with
levels in flue gas, insufficient toxicity, and limited catalyst durability,
other N radicals to form N2. There is always reduced Cu+ present on the
hindering its widespread application (Pan et al., 2022). Addressing these
catalyst surface due to the redox equilibrium (Cu2+ + Ce3+ → Cu+ +
issues requires the development of low-temperature SCR catalysts
Ce4+). The NO + CO reaction is enhanced by the supplementary effects
characterized by high denitration performance, stability, and suitability
of Cu+ species and oxygen vacancies (Fig. 14) (Gholami and Luo, 2018).
for oxygen-enriched conditions. This obstacle in CO-SCR technology
The presence or absence of oxygen concentration results in distinct
advancement has prompted extensive research by numerous scholars,
reaction mechanisms, attributed to the competition between O2 and NO
exploring various catalysts to enhance the overall performance of
in their reaction with CO (Gholami et al., 2021). Liu et al. (2020)
CO-SCR (Table 4).
discovered that the Cu1.2FeMg2.8 layered double oxide
Extensive research has been conducted on catalysts supported by
(Cu1.2FeMg2.8-LDO) catalyst exhibits distinct reaction mechanisms
noble metals for CO-SCR, primarily driven by their remarkable catalytic
under different conditions. In the absence of O2, the interaction between
performance, elevated activity, and superior selectivity. However, their
the adsorbed CO species (Cu+–CO and Fe2+–CO) and the adsorbed NOx
widespread adoption is hindered by challenges such as prohibitively
species (bridged nitrate and bidentate nitrate) adheres to L-H mecha­
high costs, inadequate resistance to SO2, and compromised thermal
nism at low temperatures. However, at elevated temperatures, the re­
stability (Gholami et al., 2021; Liu et al., 2021b; Lee et al., 2021b). In
action mechanism shifts to the E-R mechanism (Fig. 15) (Liu et al.,
addition, extensive studies have delved into the thorough investigation
2022).
of Mn- and Fe-based catalysts (Table 4).
Li et al. (2014) proposed a reaction mechanism for NOx reduction by
Following in-depth investigations, it has become evident that cata­
CO in the presence of O2 at 700 ◦ C. Their mechanism involves O2
lysts founded on transition metal oxides have attracted considerable
adsorption on the oxidized catalyst surface, hindering NO adsorption.
interest, due to their cost-effectiveness and heightened activity in redox
Introduction of CO consumes O(s), initiating NO adsorption and forming
reactions (He et al., 2022). Among the catalysts explored for the selec­
N(s) and O(s). Reduction of O(s) by CO leads to CO2 formation, and two
tive catalytic reduction of NOx by CO, Cu-supported catalysts stand out
N(s) combine to produce N2. At low temperatures, CO–SCR on metal
as particularly promising (Jin et al., 2024; Lv et al., 2024; Liu et al.,
oxide catalysts adheres to the L–H mechanism. Adsorbed CO reacts with
2024b). The understanding of active sites in Cu-supported catalysts for
CO and NO interaction has evolved from initial identification of Cu2+ as
the active site to considering co-existing Cu2+ and Cu+ as active centers.
Recently, Cu+ as the pivotal active site, employing the L-H mechanism
for activating both CO and NO. Additionally, there is a suggestion that
Cu0/Cu+ coexisting species are crucial for NO dissociation, involving
partial reduction of Cu2O under reaction conditions (Huang et al.,
2022). In a study conducted by Dai et al. (2018), it was demonstrated
that CuO-CeO2 achieved 100% NOx conversion at 150 ◦ C (Dai et al.,
2018). Additionally, Bai et al. (2019) reported a noteworthy 90% con­
version at 300 ◦ C in CO-SCR (Bai et al., 2019). Enhancing the support
structure is a viable strategy for boosting the activity and N2 selectivity
of Cu-based catalysts (Gholami et al., 2021).
In brief, CO-SCR is a promising solution for reducing NO emissions in
Fig. 14. Potential mechanism by which CO reduces NO over the Cu:Ce/CNT CO-rich industrial flue gas. It enhances NO reduction efficiency, offering
catalyst. Adapted with permission from (Gholami and Luo, 2018). Copyright
an energy-saving alternative to NH3-SCR. Research on catalysts,
2018 ACS.

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S. Elkaee et al. Process Safety and Environmental Protection 184 (2024) 854–880

Table 4
Summary of CO-SCR research for NOx removal.
Catalyst NO (ppm) or (%) CO (ppm) or (%) GHSV NO conversion (%) Temperature (◦ C) Ref

CuO-CeO2 5 (%) 10% 90,000 (mL/ 100 250 (Deng et al., 2021)
g•h)
− 1
CuFe − N/C 1000 (ppm) 2000 (ppm) 30,000 (h ) 100 225 (Ding et al., 2021)
1
CuCo-CeO2 500 (ppm) 1000 (ppm) 40,000 (h− ) 100 200 (Liu et al., 2024c)
1
Cu/CeO2-Fe2O3 800 (ppm) 1600 (ppm) 30,000 (h− ) 95 150 (Cheng et al., 2018)
1
6Cu1Al-BTC 500 (ppm) 1000 (ppm) 30,000 (h− ) 100 325 (Shi et al., 2020)
1
Cu1.2FeMg2.8-LDO 600 (ppm) 1200 (ppm) 60,000 (h− ) 100 225 (Liu et al., 2022)
1
MnOx/TiO2 400 (ppm) 400 (ppm) 50,000 (h− ) 95 299 (Boningari et al., 2018)
1
Mn-Cu-CeOx/ 300 (ppm) 5 (%) 25,000 (h− ) 98 200 (Wang et al., 2022b)
γ-Al2O3
Fe0.5Ni0.5Ox 1000 (ppm) 2000 (ppm) 15,000(mL/g•h) 100 130 (Du et al., 2019)
10%Fe2O3/TiO2 5000 (ppm) 500 (ppm) 75,000 (h− 1) 50 500 (Sierra-Pereira and Urquieta-González,
2014)
Fe@CeO2-ZIF-8 500 (ppm) 1000 (ppm) 22,800 (h− 1) 99 250 (Li et al., 2023a)
Fe-Ba/ZSM-5 0.1 (%) 0.2 (%) 5,000 (h− 1) 100 375 (Zhang et al., 2017b)
Ce0.08-OMS-2 0.05 (%) 0.1 (%) 15000 (h− 1) 100 175–300 (Cai et al., 2023)
CeO2-CuOx 3000 (ppm) 3000 (ppm) 12,000 (h− 1) 95 400 (Bahrami et al., 2017)
Rh0.05Co2.95O4 5 (%) 5 (%) 5000 mL.h− 1 90 250 (Salker and Desai, 2016)
LaCu0.5Mn0.5O3 5 (%) 10 (%) 60,000 (mL/ 100 300–600 (Wu et al., 2020)
g•h)
LaNi0.5Cu0.5O3 5 (%) 10 (%) 36,000 (mL/ 100 375–300 (Yi et al., 2019)
g•h)
IrRu/Al2O_30.5 h 50 (ppm) 0.7 (%) 100,000 (h− 1) 90 175 (Cho et al., 2023)

especially Cu-supported ones, has improved our understanding of the
NO-CO reaction. Challenges drive ongoing efforts for improved low-
temperature SCR catalysts. Despite obstacles, recent studies show Cu-
supported catalysts effectively reduce NOx at lower temperatures.
Continued research aims to advance CO-SCR technology for efficient NO
emission reduction in industries.
6. Comparative evaluation of reducing agents
This section discusses the comparative evaluation of various
reducing agents in the context of the SCR of NOx emissions. Under­
standing the influence of the reductant type and temperature is crucial
for optimizing NOx reduction in various applications, including envi­
ronmental remediation and industrial processes.
The pioneering work of Abdulhamid et al. (2004) (Abdulhamid et al.,
2004) and their subsequent study in 2006 (Abdulhamid et al., 2006)
provided essential insights into reducing agents in the SCR process. They
emphasized the influence of the reductant type and temperature, high­
lighting the superior performance of hydrogen and carbon monoxide in
NOx reduction, particularly at higher temperatures (Table 5). These
findings emphasize the importance of selecting an appropriate reducing
agent for optimizing SCR systems. Moreover, the formation of NH3 and
N2O based on the reductant type and temperature adds complexity to
the SCR process. Additionally, the superior adsorption capabilities of
alcohols compared to HCs offer a promising avenue for enhancing SCR
technologies. Recent in situ DRIFTS experiments further highlighted the
role of the reductant adsorption capacity in generating reactive in­
termediates, deepening the understanding of the underlying mecha­
nisms (D’Agostino et al., 2022; Frobert et al., 2013; Chansai et al.,
2014).
In their initial study, Abdulhamid et al. (2004) explored the reduc­
tion of NOx and its dependence on reductant type (H2, CO, C3H6, and
C3H8) and temperature (350, 250, and 150 ◦ C) over a Pt/BaO/Al2O3
catalyst. They found that H2 and CO are highly effective in reducing
NOx, outperforming C3H6 and C3H8, especially at 350 ◦ C. H2 exhibited
improved NOx reduction at 250 ◦ C, while CO showed rapid initial
reduction. They discovered the unexpected fact that at any temperature,
C3H8 did not exhibit any NOx reduction ability for NOx stored in Pt/
BaO/Al2O3. NH3 formation was observed exclusively with H2 and was
found to be temperature-dependent, decreasing at lower temperatures.
Notably, when CO was used as the reductant at 350 ◦ C, significant N2O
formation occurred, with traces detected when C3H6 was used at 250 ◦ C.

Table 5
Performance of Rh/BaO/Al2O3, Pt/BaO/Al2O3, and Pd/BaO/Al2O3 Catalysts in NOx Reduction and NH3/N2O Formation from H2, CO, C3H6, and C3H8 at 150◦ C, 250◦ C,
and 350◦ C (Abdulhamid et al., 2006).
Temperature

350 ◦ C 250 ◦ C 150 ◦ C

H2 CO C3H6 C3H8 H2 CO C3H6 C3H8 H2 CO

Rh/BaO/Al2O3 NOx reduction rate (ppm/s) 3.45 3.65 3.21 - 0.23 2.18 - - - -
Maximum NOx reduction (ppm) 422 438 372 - 40 274 - - - -
NH3 formation after 150 s reduction (ppm) 44 0 0 0 20 0 0 0 0 0
Average N2O formation during reduction (ppm) 0 0 0 0 3 28 0 0 0 0
Pt/BaO/Al2O3 NOx reduction rate (ppm/s) 2.63 2.45 2.12 - 3.85 5.12a 1.79 - 1.48 -
Maximum NOx reduction (ppm) 357 355 277 - 419 -b 253 - 183 -
NH3 formation after 150 s reduction (ppm) 218 0 0 0 113 0 0 0 0 0
Average N2O formation during reduction (ppm) 0 8.6 0 0 0 38 21 0 3.7 0
Pd/BaO/Al2O3 NOx reduction rate (ppm/s) 3.53 3.40 3.04 0.85 3.28 2.95 1.72 - - -
Maximum NOx reduction (ppm) 453 468 416 190 427 356 316 - - -
NH3 formation after 150 s reduction (ppm) 221 0 0 0 209 0 0 0 0 0
Average N2O formation during reduction (ppm) 0 6 0 13 0 98 25 0 0 0
a
The reduction rate was calculated for the first 40 s to show the effect of the reducing agent.
b
No maximum reduction value was calculated because of the irregular reduction behavior.

871
S. Elkaee et al.
These findings highlight the critical influence of reductant choice and
temperature on NOx reduction and offer valuable insights for applica­
tions in environmental remediation and industrial optimization
(Abdulhamid et al., 2004). In a subsequent study, Abdulhamid et al.
(2006) explored the effects of different reducing agents (H2, CO, C3H6,
and C3H8) on stored NOx reduction over PM/BaO/Al2O3 (PM:Pt, Pd, or
Rh) at temperatures of 350, 250, and 150 ◦ C. Among the catalysts tested,
Pd/BaO/Al2O3 exhibited the highest reduction and storage capacities.
However, these capacities decreased with decreasing temperatures.
Interestingly, this catalyst effectively reduced stored NOx using C3H8 at
350 ◦ C due to Pd’s unique ability to activate saturated HCs.
Pt/BaO/Al2O3 showed a slightly lower reduction efficiency than
Pd/BaO/Al2O3 and Rh/BaO/Al2O3 but had a superior storage capacity.
Moreover, Pt/BaO/Al2O3 could reduce stored NOx using H2 even at a
lower temperature of 150 ◦ C due to Pt’s ability to activate H2. On the
other hand, Rh/BaO/Al2O3 had limited NOx storage capacity, resulting
in high reduction efficiency but low storage, diminishing at 250 ◦ C. NH3
formation depended on the precious metal and temperature, with
Rh/BaO/Al2O3 showing the least NH3 formation. Finally, N2O formation
during reduction was linked to the precious metal type, and maximum
occurred at 250 ◦ C with CO as the reducing agent (Table 5) (Abdulhamid
et al., 2006).
Seneque et al. (2015, 2016) investigated urea-SCR and NH3-SCR,
emphasizing the importance of catalyst composition and urea residence
time in achieving efficient NOx reduction. Their findings guide future
SCR catalyst development for enhanced sustainability and emission
control (Seneque et al., 2016, 2015).
The former study explored urea as a reductant for NOx conversion in
standard-SCR, finding temperature-dependent variations in conversion
rates. NH3 showed similar trends, indicating comparable reductant
utilization. At 500 ◦ C, NH3 oxidation by O2 increased the (NH3 con­
version/NOx conversion) ratio. The study validated the microscale setup
for simulating DeNOx behavior influenced by temperature and reductant
type. The effectiveness of urea-SCR could be compromised in actual
exhaust systems due to the shorter residence times typical of such en­
vironments. Altering residence times (tR = 6.1 s and tR = 4.0 s) revealed
reduced NOx conversion at shorter tR, particularly at 350–400 ◦ C. The
(NH3 conversion/NOx conversion) ratio changed notably at 350–400 ◦ C
Fig. 16. (a) Comparative standard-SCR activity using gaseous NH3 as a Reductant over aZr (pink line) and Fe-zeo (grey line) Catalysts: NOx Conversion (A) and NH3
Conversion (B), (b) Impact of urea residence time on ’Standard-SCR’ conditions, contrasted with gaseous NH3 utilization (pink box), for aZr (A) and Fe-zeo (B)
Catalysts (Green box: Tr = 5.2 s; Blue box: Tr = 4.0 s). Adapted with permission from (Seneque et al., 2016). Copyright Springer 2016.
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Process Safety and Environmental Protection 184 (2024) 854–880
for tR = 4.0 s. The NO2/NOx ratio varied, with a lower tR (4.0 s) causing
delayed NO2 appearance until 350 ◦ C, peaking at 17% at 450 ◦ C (Sen­
eque et al., 2015).
The latter study compared urea-SCR and NH3-SCR using different
catalyst prototypes. They found that DeNOx efficiency depends on the
reductant and catalyst composition. The impact of urea residence time
was more significant for acidic zirconia oxide (aZr) than for iron-
exchanged zeolite. The aZr catalyst showed suboptimal NOx conver­
sion with aqueous urea due to limited NH3 availability, attributed to
weak HNCO hydrolysis activity. This limitation, especially for shorter
urea residence times, was observed under various inlet conditions. In
contrast, the Fe-zeolite catalyst did not have these drawbacks, empha­
sizing the need for catalysts tailored for effective urea use. The results
also indicate that HNCO is more reactive towards oxidation than NH3
when using an acidic zirconia catalyst (Fig. 16) (Seneque et al., 2016).
D’Agostino et al. (2022) emphasized the significance of reductant-
catalyst affinity, measured by the T1/T2 ratio, in achieving optimal
NOx conversion rates, particularly at low temperatures. Their research
underscores the importance of understanding reductant properties and
their interactions with catalyst surfaces for informed selection of
reducing agents in SCR applications. By exploring how reductant mol­
ecules interact with catalyst surfaces, a deeper understanding of the
principles governing SCR performance and the reduction process
emerges. Their study, using Ag/Al2O3 catalysts, integrated catalytic
testing and T1/T2 NMR studies, revealing that higher affinity of reducing
agents for the catalyst surface correlates with lower activation temper­
atures and higher NOx conversion rates. This critical link between
adsorption properties of reactive species and catalyst performance
provides a valuable screening tool for selecting reducing agents in SCR,
applicable not only to Ag-based catalysts but also to Pt-based catalysts
using a similar methodology (D’Agostino et al., 2022).
Farhan et al. (2024) emphasized H2-SCR as a promising alternative to
NH3-SCR and conventional HC-SCR systems. H2-SCR utilizes abundant
hydrogen sources from industrial by-products and fuel without requiring
additional setup. Its practicality is highlighted by the growing demand
for hydrogen in various industries, offering lower toxicity risks and
fewer byproducts. H2-SCR catalysts exhibit notable NOx reduction per­
formance at lower exhaust temperatures, making them suitable for
S. Elkaee et al.
urban driving and cold-start scenarios. The attraction of H2-SCR is
increased by their greater resistance to catalyst deactivation as
compared to NH3-SCR. Additionally, H2-SCR systems are simple,
compact, and potentially cost-effective, particularly for stationary ap­
plications. This summary succinctly outlines H2-SCR’s advantages over
NH3-SCR and HC-SCR systems, including reduced emissions, enhanced
efficiency, and streamlined system design (Muhammad Farhan et al.,
2024; Borchers et al., 2023; Hu et al., 2021).
In summary, the studies presented in this section provide an unpar­
alleled understanding of the complexities surrounding reducing agents
in SCR applications. These insights have profound implications for
environmental protection, industrial emission control, and the
advancement of SCR technology. Delving into the intricate interplay
between reductant properties, catalyst performance, and the molecular
intricacies of NOx reduction equips us to refine and optimize SCR
technologies for a cleaner and more sustainable future. This section is
crucial for understanding the role of reducing agents in the ongoing
battle against NOx emissions.
7. Challenges and future directions
Addressing NOx emissions from industries and vehicles is vital for
improving air quality and public health. Technologies, such as NH3/
Urea-SCR, HC-SCR, H2-SCR, and CO-SCR, face distinct challenges. Re­
searchers are actively striving for cleaner and more sustainable solu­
tions, emphasizing the need for innovation to meet environmental
standards and improve global health.
The challenges and future directions for NH3/Urea SCR technologies,
widely employed for NOx reduction across various industries, are
multifaceted and demand innovative solutions. NH3-SCR encounters
issues such as NH3 slip, temperature sensitivity, and catalyst durability.
For instance, migration and agglomeration of metal oxides in the cata­
lyst can diminish their accessibility and efficacy in the SCR reaction and
increased NH3 slip. In terms of industrial-scale applications, the Mn or
Fe-based catalysts would be more promising than V-based catalysts, for
the former can achieve higher NOx conversion rate at lower temperature
ranges that is advantageous to save the operational cost for deNOx
processes. However, their susceptibility to sulfur sensitivity poses a
challenge in terms of SO2 resistance. There is a pressing need to improve
both selectivity and operating conditions, prompting efforts to develop
new manganese-based catalysts that are tolerant to sulfur or to explore
regeneration methods. To address these challenges, advanced catalysts,
control strategies, and thermal management systems are essential.
Additionally, novel materials and regeneration techniques are required
to enhance durability and improve NOx conversion, especially under
200 ◦ C. Management of NH4NO3 deposition and improved urea
decomposition are crucial aspects. Future regulations may necessitate a
focus on reducing N2O emissions. Moreover, achieving hydrothermal
stability, resistance to hydrocarbon and SO2 poisoning and efficient NH3
storage/release demand exploration of advanced systems and solid-state
storage materials. In the automotive sector, urea-SCR faces challenges in
urea decomposition, catalyst poisoning, and system integration. Regu­
latory compliance, amidst stringent emission standards, requires opti­
mized catalyst designs, poison-resistant materials, and innovative
distribution solutions like smart dosing systems.
HC-SCR as reducing agents for NOx reduction, encounters unique
challenges. The presence of volatile organic compounds (VOCs) in this
process contributes to air pollution and ground-level ozone formation,
necessitating the mitigation of VOC emissions while preserving effective
NOx reduction. A key focus for future research lies in developing low-
VOC or non-VOC hydrocarbon alternatives. Ongoing research in HC-
SCR technology focuses on enhancing catalyst sensitivity for improved
effectiveness. The exploration includes developing robust, versatile
catalysts with multifunctional features and advanced materials. Chal­
lenges involve selecting optimal hydrocarbons for NOx reduction,
leading to research on diverse hydrocarbons and real-time sensing.
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Process Safety and Environmental Protection 184 (2024) 854–880
Future efforts emphasize bifunctional catalysts for simultaneous NOx
and VOC removal, optimizing distribution ratios for enhanced redox
activity. Understanding the synergistic mechanisms of acid and redox
active sites is crucial for guiding catalyst development. Catalyst struc­
ture design, such as core-shell and hollow structures, significantly in­
fluences performance. Practical experimentation in flue gas conditions
aims to create more effective designs, considering reaction tempera­
tures, VOC removal efficiency, and catalyst resistance. Achieving eco­
nomic viability involves rationalizing production costs by minimizing
precious metal usage and exploring low-cost alternatives.
In the context of H2-SCR, the paramount concern of mitigating high
explosion hazards associated with hydrogen storage necessitates
comprehensive attention. Recognizing the potential risks is imperative,
emphasizing the critical importance of safe storage practices. Specif­
ically, the exploration of challenges related to hydrogen storage be­
comes a dedicated focus when contemplating the industrial applications
of H2-based SCR. To effectively address these challenges, a thorough
discourse is indispensable, encompassing innovative storage solutions,
safety protocols, and technological advancements. The examination
should notably extend to the feasibility assessment of solid-state and
high-pressure storage options, aiming for a cohesive integration of ef­
ficiency and safety in the storage and distribution of hydrogen.
Furthermore, the discourse should seamlessly transition into consid­
ering potential applications across various industries, incorporating a
critical examination of safety measures and strategies for risk
mitigation.
CO-SCR encounters challenges in catalyst development, requiring
achievement of high activity, selectivity, and thermal stability. Under­
standing intricate reaction kinetics and ensuring a reliable CO source are
also crucial, alongside adapting to varying operational conditions.
Future directions encompass exploring nanostructured catalysts, utiliz­
ing in situ characterization techniques, integrating with other emission
control technologies, and adopting renewable CO sources for sustain­
ability. Advanced computational modeling, real-time monitoring, and
efforts towards commercialization and standardization are pivotal for
enhancing the effectiveness and widespread adoption of CO-SCR tech­
nology in addressing nitrogen oxide emissions from diverse sources. In
the context of the three reactions, the presence of oxygen typically in­
hibits catalytic performance, influencing oxygen vacancy and the
chemical nature of metal active sites, as observed in CO-SCR of NOx. The
flue gas often contains H2O and SO2, necessitating intensive research on
catalyst activity and durability in their presence. While some inhibiting
mechanisms in the presence of co-present gases have been speculated,
further work is desirable to fully understand poisoning mechanisms
using in-situ techniques and DFT calculations, specifically studying the
effect of O2, H2O, and SO2 on the adsorption and activation of NO, N2O,
and CO, as well as the reaction routes.
In summary, reducing NOx emissions is imperative for both envi­
ronmental and public health. As we navigate through the challenges of
various NOx reduction technologies, innovations in catalysts, materials,
and control strategies have become paramount. Achieving sustainability
through cleaner solutions and reducing adverse environmental impacts
are the ultimate goals. The commitment to these endeavors will lead us
towards a cleaner and healthier future.
8. Conclusion
This review has collectively provided a comprehensive understand­
ing of different reducing agents for SCR systems to mitigate NOx emis­
sions from industrial and transportation sources.
Ammonia/urea-based SCR systems effectively reduce NOx emissions,
with urea addressing safety concerns. Understanding SCR catalysis
principles is crucial, exploring pathways like E-R, L-H, and hybrids.
Cutting-edge research on V2O5/TiO2 catalysts unveils breakthrough acid
and redox cycles. While catalysts like VOx, manganese-based, cerium
oxide, and zeolites show promise, challenges include N2O formation and
S. Elkaee et al.
urea byproducts.
Hydrocarbon-based SCR shows potential in reducing NOx emissions,
particularly with propane and propene as effective reducing agents
operating at lower temperatures (below 400 ◦ C) than NH3-SCR
(120–600 ◦ C). The selection of catalysts and key parameters, including
C3H6/NOx ratio, oxygen concentration, pH, and catalyst preparation
methods, plays a crucial role in enhancing NOx conversion efficiency.
The optimization of catalysts like Cu/SAPO-34 and Mn-based zeolites
contributes to improved NOx conversion.
Hydrogen-based SCR systems signify a notable advancement in NOx
reduction, displaying superior performance, especially at low tempera­
tures, characterized by outstanding efficiency, reduced reaction tem­
peratures (below 200 ◦ C), and the exclusive generation of water vapor as
a byproduct. However, challenges persist, such as the requirement for a
high H2/NO molar ratio, vulnerability to CO2 and H2O, and the potential
formation of undesired byproducts.
CO-SCR is a breakthrough in NOx reduction, particularly in CO-rich
industries, producing N2 and CO2. Researchers investigate mechanisms
like L-H and E-R, accounting for catalyst-specific variations. Cu-
supported catalysts, despite facing challenges like low denitration effi­
ciency, show promise for high NOx conversion at lower temperatures,
emphasizing the potential of CO-SCR in reducing NO emissions in in­
dustries. Ongoing research aims to enhance low-temperature SCR
catalysts.
Understanding SCR systems and their reducing agents is vital for
future innovation. Overcoming challenges like enhancing catalyst
durability and minimizing byproducts is crucial for cleaner environ­
ments. Advancements in SCR technology promise further NOx emission
reductions, contributing to better air quality and public health. This
review serves as a foundational resource for researchers and industry
professionals in the pursuit of a cleaner, more sustainable future.
CRediT authorship contribution statement
Sahar Elkaee: Conceptualization, Writing - Original Draft, Writing -
Review & Editing, Visualization. Ajit Dattatray Phule: Review &
Editing. Jae Hwan Yang: Investigation, Writing - Review & Editing,
Visualization, Supervision.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgement
This research was financially supported by the Basic Science
Research Program through the National Research Foundation of Korea
(NRF) funded by the Ministry of Education (2021R1I1A3050146 & RS-
2023–00249553), the Ministry of Science and ICT (MSIT) (No. RS-
2023–00218203), and Korea Ministry of Environment (MOE) as Waste
to energy recycling Human resource development Project.
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