Catalysis Today 356 (2020) 301–311

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Catalysis Today
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Review

Catalysts based on carbon xerogels with high catalytic activity for the T
reduction of NOx at low temperatures
Esther Bailón-Garcíab,*, Ewelina Drwala, Teresa Grzybeka, Carlos Henriquesb, M. Filipa Ribeirob,*
a
AGH University of Science and Technology, Faculty of Fuels and Energy, al. Adama Mickiewicza 30, 30-059, Crakow, Poland
b
Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001, Lisboa, Portugal

A R T I C LE I N FO A B S T R A C T

Keywords: Carbon supported transition metals such as Cu, Co, Ni and Fe are proved to be active catalysts for selective NOx
NOx reduction in an oxygen-free atmosphere. In this work, metal-free carbon xerogels (CX) obtained by sol-gel
Carbon xerogel polymerization of resorcinol and formaldehyde together with Cu, Co and Fe-doped and impregnated CX were
Fe studied in the reduction of NOx in the absence and presence of an external reductant (H2). Moreover, the in-
Co
fluence of the surfactants (CTAB, Pluronic P123, Span 80) and the type of metal used as dopant on the mor-
Cu
phology and textural properties of carbon xerogels was investigated. Moderately high surface areas were ob-
tained (420−700 m2 g−1). N2 adsorption and SEM images revealed that the pore structure and morphology of
the gel were strongly affected by the type of surfactant: the most developed porous structure was obtained by
using Span 80, while the worst by Pluronic P123. Furthermore, better-defined carbon microspheres were ob-
tained in metal-doped samples when compared to the metal-free carbon xerogel, especially for Fe-doped CX in
which perfectly spherical and isolated particles were observed. However, impregnated catalysts exhibit higher
NO conversion when compared to the doped ones. Cu/CX presents the best catalytic activity among all the
samples with total NO conversion into N2 at 200 °C in the presence of H2. In addition, TGA analysis revealed that
this catalyst has a higher thermal stability in air in comparison to CX being completely stable up to 420 °C, thus,
Cu/CX is presented as optimal candidate for NOx reduction in both reductant and oxidant atmospheres with
better catalytic performance than Cu/zeolites systems

1. Introduction These technologies can lead to a substantial reduction in the overall

Municipal Solid Waste (MSW) is a complex mixture of materials
produced by households and public institutions and collected by mu-
nicipalities [1,2]. As improper collection and disposal of MSW influence
the human health and cause serious environmental problems, waste
management plays a vital role worldwide [3–5]. Globalization and the
increase of population and Gross Domestic Product (GDP) have led to
an overall increase in the global volume and variety of urban solid
wastes and consequently, an increasing awareness about an urgent need
to adopt scientific methods for safe disposal of wastes. Landfilling is
considered the most economical waste treatment option. Landfills
produce landfill gases, which may be utilized for direct thermal appli-
cations or for power generation [6,7]. However, the limited availability
of land for waste disposal has let to selecting alternative treatment/
disposal techniques to face this problem.
Waste-to-energy technologies for recovery of energy from wastes
can play a vital role in mitigating the waste management problems.
waste quantities requiring final disposal, which can be better managed
for safe disposal while meeting the pollution control standards. MSW
gasification is the most promising waste-to-energy technology, which
allows not only to reduce the amount of MSW by weight and volume,
but also enables energy recovery with high overall efficiency.
Syngas (H2 + CO) produced during MSW gasification is usually
contaminated by compounds such as tar, char, NOx, SOx or VOCs and
requires purification before utilization in a direct combustion, gas en-
gines, gas turbines or fuel cells as well as for the production of che-
micals [8]. Among all impurities present in the syngas, sulfur and ni-
trogen are the most critical pollutants because even at small quantities
may poison Fisher-Tropsch catalysts [9]. Moreover, nitrogen oxides
(NOx) are one of the main air pollutants and their presence can cause a
series of devastating effects on ecosystems, human health and the at-
mosphere, including the destruction of the ozone layer, acid rain, for-
mation of photochemical smog and even global warming. This fact
justifies the growing concern about the reduction of NOx present in the

⁎
Corresponding authors.
E-mail addresses: estherbg@ugr.es (E. Bailón-García), filipa.ribeiro@tecnico.ulisboa.pt (M.F. Ribeiro).

https://doi.org/10.1016/j.cattod.2020.03.004
Received 19 January 2019; Received in revised form 1 February 2020; Accepted 2 March 2020
Available online 03 March 2020
0920-5861/ © 2020 Elsevier B.V. All rights reserved.
E. Bailón-García, et al.
exhaust gases of the combustion sources.
Selective catalytic reduction (SCR) of NO with NH3 is widely used
for the reduction of NOx emissions from stationary sources of pollution
such as energy production plants based on the burning of gas, fuel or
coal. The catalysts commonly used are based on vanadium oxide since it
has a high catalytic activity and a high resistance to poisoning by SO2
and H2O. Therefore, the most commonly used catalyst for NH3-SCR in
the industry consist of well dispersed vanadium oxide supported on
titanium dioxide with WO3 or MoO3 as promoters (V2O5–WO3/TiO2
and V2O5-MoO3/TiO2, respectively) [10–12]. However, due to narrow
operating temperature window, N2O formation and poor thermal sta-
bility, other catalysts received attention, especially Fe and Cu-based
zeolites and metal-based oxides catalysts (mainly Mn, Fe, Cr, Cu and Ce-
based oxides) [13,14] and transition-metal promoted (Cu, Fe, Mn etc)
activated carbons [15,16]. As an example, the study of Baran et al. [17]
showed that Cu2.0SiBEA and Cu2.0HAIBEA zeolites in NH3-SCR process
achieved NO conversion higher than 80 % and N2 selectivity above 95
% at 350 °C.
The potential application of carbonaceous materials in the pur-
ification of exhaust gases has motivated the study of NOx-carbon re-
action. Activated carbon by itself can reduce NOx to N2 without the
addition of an external reducing agent, but temperatures above 500 °C
are needed and the reaction is strongly dependent on the porous texture
and surface chemistry of the carbonaceous material [18]. A significant
reduction of this temperature can be achieved by the addition of metals
(such as Cr, Fe, Co, Ni or Cu). It is observed that during the NO/carbon
reaction, the metal participates in the redox mechanism, being oxidized
by NO and reduced by carbon. Therefore, the catalytic behaviour is
related to: i) the initial state of oxidation of the metal, ii) its affinity to
NO and iii) its redox properties, that is, the tendency to be oxidized by
the NO and the tendency of the resulting oxide to be reduced by carbon
[18].
In this sense, carbon xerogels are presented as optimal candidates
for NOx reduction, due to their high purity, which avoids interferences
of the inorganic impurities of the conventional activated carbons in the
catalytic results and in addition to the advantage of their nano and
macro-scale design, that is, its porous texture can be controlled and
designed at nanoscale, as well as its morphology (powder, pellets,
foams, coatings). Therefore, these materials present a great versatility
in many applications. In addition, active phases can be highly dispersed
in the carbonaceous matrix during synthesis, minimizing metallic sin-
tering [19].
With the above-mentioned background, in this work the preparation
of metallic catalysts (Fe, Co, Cu) dispersed on carbon xerogels, by im-
pregnation of previously synthesized supports or by doping during the
synthesis, is considered. The activity of these materials in the reduction
of NOx is studied both in the presence and absence of an external re-
ducer (H2, the main component of the syngas) and the results will be
discussed based on the textural and chemical characteristics of the
catalysts and compared with usually used Cu/zeolite catalysts. The
main aim of this work is to discern between a high battery of catalysts
for the NO reduction in order to select the most appropriate catalyst to
analyse their catalytic performance in real syngas atmospheres.
2. Experimental
2.1. Support preparation
Carbon xerogels were obtained by sol-gel polymerization of re-
sorcinol (R) and formaldehyde (F) in the presence of three surfactants:
hexadecyltrimethylammonium bromide (CTAB, cationic), Pluronic
P123 (non-ionic) or Span 80 (non-ionic), so that three types of supports
were prepared, denoted as: XC, XP and XS, respectively.
Briefly, 500 ml of n-heptane together with the proper amount of
surfactant were heated to 65 °C under reflux and stirring (450 rpm) in a
three-neck round bottom flask. Then, a mixture containing resorcinol,
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Catalysis Today 356 (2020) 301–311
formaldehyde (37 %) and water (molar ratio: R/F = 1/2 and R/W = 1/
14), denoted as R-F mixture, was prepared and added dropwise into the
heated solution. The gel was aged for 24 h under stirring at 65 °C and
then filtered. In order to exchange water within the pores and prevent
the structure from shrinkage and collapse, the obtained solid orange gel
was placed in acetone for 5 days (changing the acetone once a day).
After that time, acetone was filtered out and the gel was dried in a
microwave oven under nitrogen atmosphere at 300 W in periods of
1 min until constant weight. Finally, the xerogel was carbonized at
900 °C under nitrogen flow for 1 h at a low heating rate of 2 °C min−1 to
enable soft release of gases.
2.2. Catalysts preparation
Cu, Co and Fe-based catalysts (4 wt. %) were prepared by two
methods: i) incipient wetness impregnation of the prepared supports
(described above) and ii) doping during the synthesis of the carbon
xerogel. In such a way, in the former, the support (carbon xerogel) was
first prepared and then the adequate amount of metallic acetate to
obtain catalysts with 4 wt.% of metal was dissolved in water and added
drop wise to the support. Finally, the catalyst was dried at 100 °C for
12 h and pre-treated in a flow of 5% H2/Ar (5 °C min−1) at 400 °C for
1 h. The catalysts are named as the support followed by the metal, for
example XSCu means that Cu is dispersed on the carbon xerogel pre-
pared using Span 80 as surfactant. In the latter, the metal-doped carbon
xerogels were prepared by adding the proper amount of metal precursor
into the R-F solution, i.e. before polymerization of resorcinol and for-
maldehyde, and subjected to ultrasound for 30 min for ensure the
complete solution of the salt before to be added to the 3-neck flask. The
amount of each salt was calculated to obtain 4 wt. % of Cu, Co or Fe in
the final carbon product, considering a complete reaction of R and F
and a weight loss of 50 wt. % during the carbonization [20,21]. In the
case of doped catalysts, the name is preceded by the prefix "d", for
example, dXSCu indicates that 4 % of Cu was deposited by doping (d)
on the carbon xerogel support with Span 80 used as surfactant (XS).
Cu-impregnated on BEA zeolite (from Zeolyst) was also prepared by
incipient wetness impregnation following the same procedure described
for carbon xerogels and was used as reference catalyst.
2.3. Textural and chemical characterization
The morphology of the samples was analysed by field emission
scanning electron microscopy (FESEM) using a JEOL 7001 F micro-
scope. The textural characterization was carried out by adsorption of N2
at -196 °C using an Autosorb-1 equipment from Quantachrome. The
BET equation was used to determine the surface area (SBET) and the
Dubinin-Radushkevich equation for the determination of the volume
(W0) and width (L0) of micropores. The volume of nitrogen adsorbed at
P/P0 = 0.95 is considered as the total volume of pores. The mesopore
volume (Vmeso) was given by the difference V0.95 – W0.
The dispersion and the average metal particle size were analysed by
transmission electron microscopy (TEM) using a Hitachi 8100 micro-
scope and by X-ray diffraction (XRD) using a Bruker D8 Advance dif-
fractometer with CuKα radiation. The crystal size (dXRD) was de-
termined using the Scherrer equation. To obtain the average particle
size by TEM (dTEM), TEM images were analysed by the appropriate
software (IJ.JAR, from Java) and a minimum of 500 particles were
analysed from different images and their diameter calculated assuming
spherical shape.
The thermal stability of the samples in oxidizing atmosphere was
followed by thermogravimetric analysis in air using a Setsys Evolution
TGA-DTA/DSC from Setaram.
2.4. Catalytic tests
The catalytic activity of carbon xerogels (doped and impregnated)
E. Bailón-García, et al.
for NO reduction, with and without hydrogen was measured. The ex-
periments were carried out in a fixed bed reactor with 2.2 cm of dia-
meter, using 150 mg of catalysts and blank samples. First, the catalyst
was pre-treated in situ in 5 % H2 in Argon flow (250 mL min−1) at
400 °C for 1 h. Then, two types of catalytic tests were performed: one
with a reagent gas mixture containing 500 ppm NO in Argon as bal-
ancing gas and the second with 500 ppm NO and 1 % H2 in Ar flow
(total flow rate in both cases was 250 mL min−1). The experiments
were performed in the temperature range of 30–450 °C and with a
heating rate of 5 °C min−1. Tests were also carried out under isothermal
conditions at selected temperatures up to equilibrium was reached.
The reactor outflow was analysed simultaneously by a chemilumi-
nescence NOx analyser (Thermo Electron 42C NO-NO2-NOx high level),
a mass spectrometer (Pfeiffer Vacuum GSD 301) and an IR analyser for
CO/CO2 (ABB EL 3020).
3. Results and discussion
3.1. Morphological and textural properties
Three types of carbon xerogel supports were prepared by inverse
emulsion synthesis using different surfactants (CTAB, Pluronic P123
and Span 80). A different appearance between the samples is clearly
observed both in organic and carbon gels (Fig. 1a and b, respectively),
which manifests an important influence of the type of surfactant used
during the synthesis on the morphology and textural properties.
Effectively, it can be observed that the type of surfactant strongly
affects the morphology of the samples (Fig. 1 C–F); the use of Span 80
generates spherical-shaped particles (Fig. 1E and F), agglomerates with
spherical holes are obtained using CTAB (Fig. 1C), while the use of
Pluronic P123 gives rise to thin sheets (Fig. 1D). These morphologies
could be ascribed to the different type of micelles formed by the dif-
ferent surfactant in the organic medium. The non-ionic surfactant Span
80 forms vesicles inside which R-F polymerization occurs obtaining
spherical-shaped particles [22,23], whereas using cationic CTAB, in-
verse micelles are formed around which R-F condensate generating that
spherical void after the removal of the surfactant. Conversely, rod-like
micelles are obtained in some conditions with Pluronic P123 [24,25]
which could justify the distribution in thin films.
The morphology was also clearly affected by the addition of metal
during the synthesis (Fig. 1G-I). Spherical-shaped particles were ex-
pected due to the application of Span 80 as surfactant, but significant
differences were observed as compared to the pure support (XS). Better-
defined spheres were obtained in metal-doped samples, especially in
dXSFe in which perfectly spherical and isolated particles are observed.
This effect can be related with the presence of metal. As it was already
mentioned in the introduction, the sol-gel polymerization of R-F solu-
tion is a quite flexible process, which enables to synthesize carbon gels
in various formats (powder, pellets, coatings, monoliths or thin films)
[26]. R-F sols behave as fluids before gelation, thus, can be emulsified
to produce microspheres of different sizes. The ability to obtain an
organic gel of the desired shape depends on the gelation time, whose
determination requires knowledge of the rheological properties of the
R-F sols used in the synthesis [27,28]. This is particularly important in
the preparation of organic microspheres by inverse emulsion of the R-F
sols [28,29]. As it has been previously commented, metals catalyse the
polymerization of R-F and affect the gelation time and rheological
properties after the complete dissolution of the metal precursor on the
R-F mixture before its addition to the preheated reactor, and conse-
quently, different-defined spheres were obtained.
These morphological differences strongly affect the textural prop-
erties. N2-adsorption isotherms and textural data are collected in Fig. 2
and Table 1, respectively. Regarding supports, XP sample (where
Pluronic P123 was used) presents a type I isotherm according to IUPAC
classification which is characteristic of microporous materials, while XS
(where Span 80 was used) and XC (where CTAB was used) samples
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Catalysis Today 356 (2020) 301–311
present a type I and type IV hybrid isotherms characteristic of micro-
mesoporous materials in which the strong N2-adsorption at inter-
mediate relative pressures and the hysteresis loop denote the presence
of mesopores. All supports have a similar adsorbed amount of N2 at low
relative pressures and therefore a very similar micropores volume
(Table 1). It is well known that carbon gels are formed by inter-
connected primary particles forming a coral-like structure in which the
meso and macroporosity is related to the inter-particle structure, while
the microporous structure is ascribed to the intra-particle pores. The
fact that all the samples present a similar volume of micropores shows
that, using the inverse emulsion synthesis, the surfactant does not really
affect the intra-particle structure but rather their ordering. It means that
the surfactant forms micelles in which or out of which the poly-
merization take place without affecting the intra-particle structure. In
this way, the distribution in sheets generates a compact structure, ex-
clusively microporous, while its arrangement in spheres or agglomer-
ates with spherical voids generates a certain macro-mesoporosity.
Moreover, the meso-macroporous structure of XC and XS is very dif-
ferent as is also observed by SEM images. The high and fast N2 ad-
sorption obtained at high relative pressures with the XC sample denotes
capillary condensation in macropores (the observed spherical voids)
whereas a high mesopore volume is obtained in XS sample (Table 1).
The hysteresis loop is also different; a H2 type is obtained for XS
sample, which is characteristic for condensation in mesopores with
narrow entrances, such as ink-bottle pores, whereas H3 is observed in
XC, indicating slit-like pores. Note also that in XS sample the loop ap-
pears at 0.3-0.4 relative pressure while in XC appears at higher relative
pressures (0.6-0.7) indicating the presence of narrower mesoporosity in
the former. Moreover, it should be noted that moderately high surface
areas are obtained in all samples (650−700 m2/g), but the XS sample is
the one with the most developed porosity, and this is why Span 80 was
selected as surfactant to prepare metal-doped samples.
Regarding N2 adsorption isotherms of impregnated catalysts, it is
observed that the deposition of metal particles by impregnation pro-
duces a blockage of the porosity of the samples due to the deposition of
metallic nanoparticles on the surface (Fig. 2a and Table 1). All catalysts
present smaller pore volumes and surface areas than their corre-
sponding supports, indicating a certain pore blockage by the deposition
of metal particles. This blockage of porosity may be due to the de-
position of metal particles on the external surface which block the N2
diffusion into the pores or due to a homogenous distribution of nano-
particles along the pore walls. From Fig. 2a, it can be observed that this
porosity blockage is more significant in the mesoporosity range for XS
sample, while for XC and XP samples, the blockage occurs mainly in
micropores. This suggest a homogeneous distribution of metal particles
along the pore walls in the case of XS sample. On the other hand, in XP
and XC samples (with lower mesoporosity than XS), nanoparticles are
probably mainly localized on the external surface, blocking the mi-
cropores entrances.
However, the addition of metal precursors during the synthesis af-
fects both its morphology and its porous texture. The presence of the
metallic precursor catalyses the polymerization reaction and, therefore,
textural characteristics of the transition-metal-containing carbon gels
depend on the nature of the metal [28]. A big difference in the iso-
therms shape (Fig. 2b) can be observed. All samples present a type I and
IV hybrid isotherms, characteristic of micro-mesoporous materials, but
for dXSCo and dXSCu, the last points of the isotherm rise significantly,
most likely due to the presence of macropores. The hysteresis loop is
also clearly different; a H2 type is obtained for XS and dXSFe samples,
which is characteristic for condensation in mesopores with narrow
entrances, such as ink-bottle pores, whereas H3 is observed in dXSCu
and dXSCo, indicating slit-like pores. All this manifests that metals
really participate in the R-F polymerization, thus affecting the primary
particle sizes and the connection between them (intra and inter-
particular structure). From Table 1 it may be seen that dXSFe has the
smallest specific surface area and micro and mesopores volumes,
E. Bailón-García, et al. Catalysis Today 356 (2020) 301–311

Fig. 1. Photographs of organic (A) and carbon (B) gels and SEM images of supports and metal-doped XS catalysts. XC (C), XP (D), XS (E, F), dXSCu (G), dXSCo (H) and
dXSFe (I).

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E. Bailón-García, et al. Catalysis Today 356 (2020) 301–311

Fig. 2. Nitrogen adsorption-desorption isotherms of supports and catalysts. a) supports (continue line) and Cu-impregnated catalysts (dashed line) and b) metal-
doped catalysts.

whereas dXSCo is characterized by a well-developed porous texture,

more open, with wide micropores (1.01 nm of diameter). The latter
sample has high mesopore volume (Vmeso) and large amount of mac-
ropores (fast absorption at high relative pressures).

3.2. Thermogravimetric studies (Thermal stability in air)

Thermogravimetric studies were performed to determine the

thermal stability of carbon xerogels in the presence of air, as well as to
estimate the metal content in carbon xerogels (Fig. 3). The weight loss
below 200 °C (2–7 %) can be mainly attributed to the physically ad-
sorbed water in the xerogel [30]. The presence of metals affects the
thermal stability of materials in an oxidizing atmosphere. It can be
observed that combustion of carbon gel (XS) started at around 500 °C,
while the presence of metals, especially cobalt, catalyses the combus-
tion process, decreasing the light-off temperature by c.a. 150 °C. This is
in good agreement with previous studies which confirmed that cobalt
oxide is a catalyst for carbon oxidation [31]. However, if the metal is
added by doping (i.e. before the polymerization resorcinol and for-
maldehyde), the reduction of the combustion temperature was lower
than in the case of the impregnated samples, possibly because part of
the metal particles are embedded in the carbonaceous matrix and are
inaccessible to air. For Cu-containing samples, much higher tempera-
ture, around 800 °C, was needed to the complete carbon combustion,
indicating better thermal stability in air (Fig. 3b).
The metal content (Table 1) was also analysed by TG. The obtained
contents in impregnated samples are very similar in all cases
Fig. 3. a) TGA and b) DSC profiles in air of the carbon xerogels and catalysts.
(3.8 ± 0.2 wt.%) and are very close to the assumed (theoretical) value
Impregnated catalysts (dashed lines) and doped ones (continuous lines).
(4 wt.%). Nevertheless, the metallic percentages obtained in doped
samples (4.8 ± 0.1 wt.%) are slightly higher than the theoretical (4
%), because the weight loss obtained during the carbonization is
slightly higher than 50 % that was assumed in the metal precursor

Table 1
Textural properties of the carbon xerogels supports and catalysts.
Sample Metal content (%) SBET (m2 g−1) W0 (N2) (cm3 g−1) L0 (N2) (nm) Smicro (m2 g−1) V0.95 (cm3 g−1) Vmeso (cm3 g−1)

Support XC – 671 0.259 0.65 602 0.470 0.211

XP – 639 0.252 0.56 682 0.259 0.014
XS – 695 0.261 0.73 569 0.552 0.290
Impregnated samples XCCu 3.9 630 0.243 0.65 569 0.452 0.209
XPCu 3.8 591 0.232 0.50 626 0.244 0.011
XSCu 4.1 661 0.253 0.78 531 0.495 0.242
XSCo 3.7 682 0.265 0.84 535 0.520 0.256
XSFe 3.6 635 0.245 0.86 490 0.493 0.247
HBCu 4.0 812 0.323 1.01 595 1.142 0.822
Doped samples dXSCu 4.9 622 0.243 0.68 550 0.411 0.168
dXSCo 4.7 642 0.250 1.01 496 0.577 0.327
dXSFe 4.9 421 0.161 0.80 334 0.329 0.169
Where: SBET – specific surface area, W0 – micropore volume, L0 – micropore width, Smicro – micropore surface area, V0.95 – total pore volume and Vmeso – mesopore volume

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E. Bailón-García, et al. Catalysis Today 356 (2020) 301–311

Fig. 4. TEM images of impregnated and doped catalysts on different carbon xerogel supports.

calculations. Thus, NOx activity can be compared because similar Table 2

amounts of active phase are present in all cases. Metal particle size determined by XRD (dXRD) and TEM (dTEM).
Sample dTEM (nm) dXRD (nm)
3.3. Metal dispersion
HBCu – 12
XCCu 21 33
TEM and XRD analysis were performed in order to characterize the XPCu 16 31
metal dispersion and particle size. TEM images and XRD data are shown XSCu 14 28
XSCo 10 n.d.
in Fig. 4 and Fig. 5, respectively and data collected in Table 2. The XRD
XSFe 7 n.d.
reflections in Fig. 5 clearly show the presence of reduced Cu and Co dXSCu 29 34
(reflections at 2θ = 43.6°, 50.8°, 74.4° for Cu and 2θ = 44.2°, 51.5° for dXSCo 19 n.d.
Co). Only for Fe-based catalysts a mixture of Fe(0) (reflections at dXSFe 10 n.d.
2θ = 44.6, and 65.2°) and Fe(III) (at 2θ = 43.5°) are detected.
Regarding Cu-impregnated samples on the different supports n.d.: not determined due to the low intensity caused by the high metal dis-
persion.
(XCCu, XSCu and XPCu), a better Cu dispersion is observed in XSCu
sample compared with XPCu and XCCu ones. Moreover, XSCu sample
exhibits the lowest size of crystallites (14 nm) when compared to XCCu

Fig. 5. X-Ray diffraction patterns of a) impregnated and b) doped catalysts.

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E. Bailón-García, et al.
and XPCu (21 nm and 16 nm, respectively). This is in good agreement
with the different pore blockage observed by N2-adsorption. In XS
sample, a high porosity blockage is observed, mainly in the meso-
porosity range, due to the best dispersion of Cu nanoparticles (favoured
by the higher mesopore volume and well-developed porosity), while in
XP and XC samples, Cu-nanoparticles are mainly localized on the ex-
ternal surface and consequently, a worst dispersion is observed. It
should be noted that larger particles were obtained by XRD diffraction
because particles lower than 4 nm cannot be detected by this technique.
However, the conclusions obtained from XRD data are similar to those
from TEM (Fig. 4 and Table 2). Again, a better dispersion was obtained
in XS sample in comparison to XC and XP ones. Consequently, XS
support was selected for the preparation of Co and Fe-impregnated
catalysts. Regarding Cu, Co and Fe/XS impregnated catalysts, a similar
pore blockage was observed, independently of the metal (Table 1),
denoting a similar metal distribution (and consequently similar metal
dispersion) along the porosity of the samples. However, better disper-
sions were achieved following the order Fe > Co > Cu, which was
corroborated by XRD and TEM analysis. On the other hand, the best
dispersion was obtained using β-zeolite as support due to, in part, the
highest surface area (800 m2 g−1).
Regarding metal-doped catalysts, it could be observed that metals
are predominantly embedded within the carbon matrix, as confirmed
by TEM. The metal particles can be clearly observed in Fig. 4, but the
dispersion depends on the metal. High metal dispersion can be observed
for Co and Fe-doped samples, while large particles are present for Cu-
doped one. It should be noted that in the latter case, many particles are
not embedded in the carbon matrix. The mean metal particle size fol-
lows the sequence: Fe < Co < Cu, which is also corroborated by XRD,
and again respects the same trend observed for impregnated samples.
However, it should be considered, that large particles are easily mea-
sured by TEM, while small particles are not easily identified, so, in the
case of dXSCu sample, a good agreement between both techniques
(XRD and TEM) was obtained due the bad Cu dispersion. On the other
hand, e.g. for dXSCo, only the small fraction of large particles (20 nm)
were identified by TEM, while the most part of them are very small and,
as a consequence, were not easily identified from TEM images due to
the high density of the carbon particles. Thus, only this small fraction of
large particles is identified by XRD and so, the intensity of the dif-
fraction peaks is very low regarding dXSCu sample. The presence of Co
and Fe metallic nanoparticles inside the organic matrix have catalysed,
during the carbonization process, the development of graphite clusters
(Fig. 4) around them, especially in Fe-doped samples in which graphitic
lines can be clearly observed. This partial graphitization of the carbon
xerogel structure has also been observed in previous works [32] with
Co, Fe and Ni as doping metals. The presence of these graphitic clusters
was also corroborated by XRD (Fig. 5) as a broad reflection at around
26°. This reflection was registered for dXSFe sample and dXSCo one,
while it is not present in dXSCu diffractograms. The latter could be
expected considering that no graphitic clusters were observed by TEM.
The extent of graphitization was found to be higher in case of dXSFe
than in dXSCo sample which is in agreement with the intensity of the
reflections.
Comparing these results with those obtained for the impregnated
samples, it should be concluded that metal dispersions obtained for
metal-doped samples are lower and, moreover, part of metal aggregates
are embedded inside the carbon matrix, which may result in lower
amount of active sites accessible for reactants. Thus, lower catalytic
activities can be expected when using metal-doped catalysts. On the
other hand, the impregnated samples can deactivate more easily than
metal-doped catalysts due to metal leaching and/or sintering.
3.4. NOx catalytic reduction
NOx catalytic reduction experiments were performed with 500 ppm
of NO in absence of external reductant, in order to study the role of the
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Catalysis Today 356 (2020) 301–311
carbon and metal particles in NO reduction and in presence of 1 % of
H2, an external reductant and the main component of the syngas ob-
tained from MSW gasification. The evolution profiles are shown in
Fig. 6 and Figure S1 for impregnated and doped catalysts, respectively.
As expected, the metal-free carbon xerogel has low catalytic activity
both in presence and absence of H2 (3.4 % and 6.9 % at 450 °C, re-
spectively). The NO profile shows a sharp decay at low temperature in
all cases, which is associated with a process of physisorption on the
carbon surface. With increasing temperature, physisorption is avoided,
while the reaction between both phases is favoured. Different profiles
are observed for the studied catalysts. For XS and XSCu, this adsorption
is similar due to the similar textural properties of both samples, while in
case of XSFe and XSCo a higher decay is observed due to the production
of N2O at this temperature, which is not observed for Cu and metal-free
samples. According to Illán-Gómez et al. [33] transition-metal carbon-
based catalysts appear to enhance NO chemisorption and participate in
the redox cycles to a different extent, depending on the nature of the
chemical species involved. Especially in the case of very active cata-
lysts, NO reduction process (up to 500 °C) reveals two stages: i) first
stage (≤300 °C) in which N2 and/or N2O are the only products, while
oxygen is retained on the catalyst/carbon surface; ii) second stage
(300–500 °C) in which NO reduction is enhanced, while N2 continues to
evolve and CO2 release occurs. This can explain N2O formation in the
first stage in case of XSCo and XSFe catalysts, while for metal-free
carbon xerogel and XSCu the first stage disappeared, and NO reduction
occurs only after CO2 release. In the absence of H2, N2 and CO2 are
obtained as major products in all catalysts. The observed increase in
CO2 coincides with the decrease in NO concentration and is accom-
panied by the production of N2. Taking into account that no other re-
action products are detected in this temperature range and that CO2 is
the only carbon-containing product, the NO reaction can be described
globally as: 2NO + C → CO2 + N2. The catalytic activity follows the
trend Cu > > Co ∼ Fe despite very similar textural properties of the
samples and even the worst Cu dispersion. This fact could be related to
the redox potential of the metal and thus, the ability of the metal to be
subjected to progressive cycles of oxidation by NO and reduction by the
carbonaceous matrix. It is observed that during the NO/carbon reac-
tion, the metal participates in the redox mechanism, being oxidized by
NO and reduced by carbon. Thus, the catalytic behaviour is related to: i)
the initial state of oxidation of the metal, ii) its affinity to the NO, iii) its
redox properties, that is, the tendency to be oxidized by the NO and the
tendency of the resulting oxide to be reduced by carbon matrix [18].
In the presence of H2 (Fig. 6, right), the profiles of the impregnated
catalysts completely change. In all of them, a complete NO conversion
is achieved due to the reducing nature of H2, resulting in N2 as the only
reaction product. This indicates that, in this case, the carbon matrix is
not acting as a reducer, but predominantly as a support. Temperature of
complete NO conversion (T100 %) depends on the metal used and again
increases in the sequence of Cu < Co < Fe (T100 % =230 °C, 330 °C
and 420 °C for Cu, Co and Fe, respectively). NO is reduced on the metal
surface which at the same time is oxidized and later reduced by H2.
Thus, the activity is closely related to the ability of the metal to be
subjected to progressive cycles of oxidation by NO and reduction by H2.
Copper has the highest ability to undergo redox cycles of the studied
metals (Cu, Co and Fe) and consequently, it presents the best catalytic
behaviour. In addition, this catalyst has a high thermal stability under
air (Fig. 3), so at these reaction temperatures (150–200 °C) the com-
bustion of the catalyst in oxidant atmospheres (in the presence of O2) is
limited because carbon matrix starts to burn only at temperatures
higher than 420 °C, according with TGA results. Thus, carbon Cu/xer-
ogel catalysts can be good candidates for NOx reduction in both re-
ductant and oxidant atmospheres at low temperature.
Another interesting observation has been made regarding NO re-
duction over XSCo in the presence of hydrogen. As can be seen in Fig. 6,
only in case of impregnated cobalt catalyst, small amounts of methane
were produced during the test. Cobalt and iron are two conventionally
E. Bailón-García, et al.
Fig. 6. Evolution of NO, N2, N2O, CO and CO2 concentrations during TPSR measurements for metal-free and metal-impregnated carbon xerogels in absence (left) and
presence (right) of H2.
used catalysts for the Fisher-Tropsch reaction [34], however Riedel
et al. [35] found that cobalt catalysts may shift the process into me-
thanation with an increasing concentrations of CO2 and respectively
decreasing concentrations of CO in Syngas. This could explain the for-
mation of CH4 over cobalt catalyst and the absence of CO2 (because it
was consumed during the reaction).
The same trend in activity is observed in the case of the doped
samples (Figure S1). However, as shown in Fig. 7, lower activity was
registered as compared to the impregnated samples, which can be re-
lated to the lower metal dispersion of those catalyst samples, together
with the lower accessibility of the metal particles. As described above,
part of the metal particles are embedded in the carbonaceous matrix. In
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Catalysis Today 356 (2020) 301–311
the presence of H2, at 370 °C total NO conversion was achieved only for
dXSCu, while it was 83.3 % and 74.1 % at 450 °C for dXSCo and dXSFe,
respectively.
The role of the carbon matrix was clearly pointed out when com-
pared with Cu/zeolite (Fig. 8a) in the absence of H2. A profile similar to
that of XSCu is obtained up to 400 °C and then a loss of activity is ob-
tained progressively for CuBEA whereas an enhancement of activity is
observed for XSCu. This could be explained on the base of the ability of
carbon matrix to reduce oxidized Cu nanoparticles. Concerning the
behaviour of CuBEA sample in absence of H2, it showed a decrease of
NO concentration during a short time (from 40 to 70 min) and then the
NO conversion began to decrease. The apparent activity of this sample
E. Bailón-García, et al.
Fig. 7. NO conversion in isothermal conditions at different temperatures in the
presence of H2. Dashed line: impregnated catalysts (XSM) and continuous line:
doped catalysts (dXSM).
can be attributed to the presence of Cu nanoparticles that initially are
oxidized by NO, but due the lack of reducer agent the process is in-
terrupted and the catalyst is not able to continue the mechanistic redox
cycle. On the other hand, in XSCu sample, those particles are again
reduced by the carbon matrix and the activity increases. A change of
slope is observed in this case at around 400 °C indicating that carbon
matrix is not able to reduce the Cu nanoparticles until this temperature
is reached. In addition, it is important to highlight that in spite of the
lower Cu dispersion, XSCu is much more active than CuBEA zeolite (83
% and 35 % of conversion respectively). In the presence of H2 (Fig. 8b),
Cu nanoparticles are reduced at lower temperature by the H2 rather
than carbon matrix, but this reducibility is improved in catalysts pre-
pared using carbon xerogel as support as compared to zeolites, due to
the intimate contact between carbon and copper which favours the
reducibility in a more reducing environment.
The influence of the type of carbon support, and consequently the
metallic dispersion was also pointed out in the absence of H2 (Fig. 9). A
linear relationship between the activity and the Cu particle size is ob-
tained. Increasing the particle size, two factors must be taken into ac-
count: i) a decrease of the number of active metallic sites for the NO
reduction and ii) a decrease of the carbon-metal interphase and thus, a
worst metal reducibility by the carbon matrix. Both factors contribute
to the decrease of the activity in the reduction of NO in absence of H2.
Finally, bibliographic results using Cu supported on different carbon
materials have been included in Table 3. Note that NO conversion and
N2 selectivity obtained with the XSCu catalysts are much better than the
obtained using activated carbon and other carbon xerogels as supports
or even, using advanced carbon materials such as carbon nanotubes
(CNT) or ordered mesoporous carbons (OMC).
Fig. 8. Evolution of NO concentrations with the time during TPSR measurements performed with XSCu and CuBEA samples in a) absence and b) presence of H2.
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Catalysis Today 356 (2020) 301–311
Fig. 9. Evolution of NO concentrations with the time during TPSR measure-
ments in absence of H2 for Cu-impregnated catalyst on different carbon sup-
ports.
4. Conclusions
Carbon xerogels were prepared by inverse emulsion polycondensa-
tion of resorcinol and formaldehyde using different surfactants. The
textural and morphological characterization shows that the surfactant
mainly affects the interparticular structure of the gel primary particles,
while the intraparticular structure (volume of micropores) remains
unchanged. The sample prepared with Span 80 that presents the most
developed porosity was, thus, used as a support to prepare Co, Cu and
Ni-based catalysts by impregnation and by doping during its synthesis.
These catalysts were used in the reduction of NO both in the absence
and in the presence of H2. In the absence of H2, N2 and CO2 were de-
tected as main products and the observed increase in the amount of CO2
coincides with the decrease in NO concentration and it is accompanied
by the production of N2, which indicates that the carbonaceous matrix
is acting as reductant of metal particles. In the presence of H2, higher
activity was obtained and N2 was the main product, so that, in this case
the carbon matrix is acting mostly as a support. The temperature at
which the complete conversion of NO was obtained depends greatly on
the used metal, decreasing in the following order: Cu (230 °C) < Co
(330 °C) < Fe (420 °C). The highest activity and selectivity were ob-
tained with Cu-based catalysts, which is related to its ability to undergo
progressive cycles of oxidation by NO and reduction by the carbon
matrix or H2. However, the catalytic activity was lower for the doped
than for impregnated materials which can be related to the lower metal
dispersion, as well as the lower accessibility to the active sites, since
part of the metal particles are embedded inside the carbon matrix.
E. Bailón-García, et al. Catalysis Today 356 (2020) 301–311

Table 3
Bibliographic data using Cu/carbons catalysts.
Sample Conversion (%) Selectivity to N2 (%) Reductor % Cu Ref

XSCu 100 (300 °C) 100 (300 °C) H2 4 Present work

94 (220 °C) 100 (220 °C)
Cu/CA form coconut shell 64 (200 °C) n.d. HC 8 [36]
Cu/CA from palm kernel shell 58 (200 °C) n.d. HC 8 [36]
Cu/carbon xerogel (X-525) 48 (220 °C) n.d. NH3 3.6 [37]
Cu/carbon xerogel (X-560) 47 (220 °C) n.d. NH3 3.2 [37]
Cu/carbon xerogel (X-625) 29 (220 °C) n.d. NH3 2.9 [37]
Cu/CNT ≈ 5 (200 °C) n.d. CO 3 [38]
Cu/Ce ≈ 5 (200 °C) n.d. CO 3 [38]
Cu3Ce1/CNT ≈ 70 (200 °C) n.d. CO 3 [38]
Cu1Ce1/CNT ≈ 80 (200 °C) n.d. CO 1 [38]
Cu1Ce3/CNT ≈ 82 (200 °C) n.d. CO 1 [38]
Cu1Ce3/AC ≈ 40 (220 °C) n.d. CO 1 [38]
CNT ≈ 20 (200 °C) n.d. CO 0 [39]
Cu25Fe25/CNT ≈ 52 (200 °C) n.d. CO 25 [39]
Cu5Mn5/OMC 85 (250 °C) 92 (250 °C) NH3 5 [40]
(Self-Assembly Synthesis)
Cu5Mn5/OMC 59 (250 °C) 85 (250 °C) NH3 5 [40]
(Ultrasound-Assisted Impregnation)
Cu5Mn5/OMC 45 (250 °C) 60 (250 °C) NH3 5 [40]
(Mechanical Mixing)

Declaration of Competing Interest 1996.0179.

The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
This research is supported by the FCT (ERANETMED SOL-CARE
project). EBG acknowledges a postdoctoral fellowship from the
University of Granada,” perfeccionamiento de doctores” programme.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.cattod.2020.03.004.
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