CATALYTIC PROPERTIES OF CARBON POWDER WITH DEPOSITED REDUCED GRAPHENE OXIDE IN THE ETHYLENE HYDROGENATION
Metal-free catalysts based on carbon powder modified with reduced graphene oxide (rGO) were prepared and investigated in the ethylene hydrogenation reaction. The samples were characterized by Raman and FTIR spectroscopies, SEM, TEM, thermogravimetric analysis, and N2 adsorption-desorption. SEM and T...
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| author | Nosach , Viktoriia Bucko, Igor Strizhak , Peter |
| author_facet | Nosach , Viktoriia Bucko, Igor Strizhak , Peter |
| author_institution_txt_mv | [
{
"author": "Viktoriia Nosach ",
"institution": "L.V. Pisarzhevky Institute of Physical Chemistry of the NAS of Ukraine"
},
{
"author": "Igor Bucko",
"institution": "L.V. Pisarzhevky Institute of Physical Chemistry of the NAS of Ukraine"
},
{
"author": "Peter Strizhak ",
"institution": "L.V. Pisarzhevky Institute of Physical Chemistry of the NAS of Ukraine"
}
] |
| author_sort | Nosach , Viktoriia |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:57Z |
| description | Metal-free catalysts based on carbon powder modified with reduced graphene oxide (rGO) were prepared and investigated in the ethylene hydrogenation reaction. The samples were characterized by Raman and FTIR spectroscopies, SEM, TEM, thermogravimetric analysis, and N2 adsorption-desorption. SEM and TEM analyses showed that rGO deposition leads to the formation of wrinkled graphene-derived structures covering the external surface of the carbon support. Raman spectra confirmed the presence of defect-rich sp²-hybridized carbon domains, while FTIR analysis revealed oxygen-containing functional groups associated with partially reduced graphene oxide. Textural analysis demonstrated that rGO incorporation mainly affects the external surface area without significantly changing the microporous structure of the support.
The catalytic properties of the obtained materials were studied in ethylene hydrogenation within 50–400 °C under continuous-flow conditions. The pristine carbon powder provides the highest catalytic activity, whereas deposition of rGO results in a decrease in activity compared with the unmodified support. However, within the rGO/CP series, catalytic activity increased with increasing rGO loading, reaching 18% conversion for rGO(0.1)/CP at 400 °C. At the same time, normalization of the reaction rate to the mass of deposited rGO showed a decrease in specific activity at higher rGO contents, attributed to partial restacking of graphene sheets and blocking of active surface sites.
The obtained results indicate that the catalytic behaviour of the investigated composites is governed by the balance between the intrinsic activity of carbon powder and the contribution of defect-rich graphene-derived domains. The findings highlight the importance of controlling graphene loading and surface accessibility in the design of efficient metal-free carbon catalysts. |
| doi_str_mv | 10.33609/2708-129X.92.4.2026.17-28 |
| first_indexed | 2026-06-04T01:00:20Z |
| format | Article |
| fulltext |
17
UDC 544.47:546.26-162-31:546.26-169:[542.942.5:547.313.2] doi: 10.33609/2708-129X.92.4.2026.17-28
CATALYTIC PROPERTIES OF CARBON POWDER WITH DEPOSITED
REDUCED GRAPHENE OXIDE IN THE ETHYLENE HYDROGENATION.
V.V. Nosach¹,² http://orcid.org/0000-0003-1278-9507
I.B. Bychko¹ http://orcid.org/0000-0002-4164-3024
P.Ye. Strizhak1 http://orcid.org/0000-0003-0280-8719
¹L.V. Pisarzhevskii Institute of Physical Chemistry
of National Academy of Sciences of Ukraine,
31 Nauky Avenue, 03028 Kyiv, Ukraine;
²National University of “Kyiv-Mohyla Academy”,
2 Hryhoriya Skovorody Street, 04655 Kyiv, Ukraine
e-mail: victorynosach@gmail.com
Metal-free catalysts based on carbon powder modified with reduced graphene oxide (rGO)
were prepared and investigated in the ethylene hydrogenation reaction. The samples were
characterized by Raman and FTIR spectroscopies, SEM, TEM, thermogravimetric analysis,
and N2 adsorption-desorption. SEM and TEM analyses showed that rGO deposition leads to
the formation of wrinkled graphene-derived structures covering the external surface of the
carbon support. Raman spectra confirmed the presence of defect-rich sp²-hybridized car-
bon domains, while FTIR analysis revealed oxygen-containing functional groups associated
with partially reduced graphene oxide. Textural analysis demonstrated that rGO incorpora-
tion mainly affects the external surface area without significantly changing the microporous
structure of the support.
The catalytic properties of the obtained materials were studied in ethylene hydrogenation
within 50–400 °C under continuous-flow conditions. The pristine carbon powder provides
the highest catalytic activity, whereas deposition of rGO results in a decrease in activity com-
pared with the unmodified support. However, within the rGO/CP series, catalytic activity
increased with increasing rGO loading, reaching 18% conversion for rGO(0.1)/CP at 400 °C.
At the same time, normalization of the reaction rate to the mass of deposited rGO showed a
decrease in specific activity at higher rGO contents, attributed to partial restacking of graphene
sheets and blocking of active surface sites.
The obtained results indicate that the catalytic behaviour of the investigated composites
is governed by the balance between the intrinsic activity of carbon powder and the contri-
bution of defect-rich graphene-derived domains. The findings highlight the importance of
controlling graphene loading and surface accessibility in the design of efficient metal-free
carbon catalysts.
Keywords: reduced graphene oxide, carbon powder, ethylene hydrogenation, carbocatalysis.
18 ISSN 2708-129X. Укр. хім. журн., 2026
CATALYTIC PROPERTIES OF CARBON POWDER WITH DEPOSITED REDUCED GRAPHENE OXIDE
IN THE ETHYLENE HYDROGENATION.PHISICAL CHEMISTRY
INTRODUCTION. The catalytic transfor-
mation of light hydrocarbons remains a key
process in modern chemical technology, where
the development of efficient and sustainable
catalysts is crucial for energy- and resource-in-
tensive industries. Ethylene, being one of the
most important platform molecules in pet-
rochemical production, is widely used in po
lymer manufacturing, fine organic synthesis,
and the fabrication of industrial intermediates.
Achieving controlled hydrogenation of alkenes
under mild conditions requires catalysts with
well-defined active sites and a surface structure
capable of selective interaction with unsatura
ted hydrocarbons [1–3].
Conventional catalytic materials for hydro-
carbon hydrogenation are typically highly-dis-
persed metals on supports such as alumina, si
lica, or metal oxides, where the role of the sup-
port is primarily associated with dispersion,
stabilization, and electronic tuning of the ac-
tive phase [4, 5]. At the same time, the growing
demand for sustainable catalytic technologies
stimulates the development of alternative cata-
lytic systems based on abundant and environ-
mentally benign materials. However, increas-
ing environmental and economic demands are
stimulating the search for metal-free catalytic
systems that combine high stability, low cost,
and the ability to operate without precious or
toxic metals [6]. In this context, carbon-based
materials have attracted growing attention due
to their structural diversity, thermal stability,
and tunable surface functionality [7].
Reduced graphene oxide (rGO) has emer
ged as a particularly promising component,
characterized by a high specific surface area,
a defect-rich architecture, and the presence
of oxygen-containing functional groups that
contribute to adsorption and activation proce
sses [8, 9]. The deposition of rGO onto carbon
powders or oxide supports leads to the forma-
tion of hybrid interfaces, where wrinkle-like
graphene fragments can alter the surface mor-
phology, modify mass-transfer pathways, and
change the distribution of active sites [10].
Depending on the rGO loading, such systems
may show different catalytic activity, as the ba
lance between accessible defects and excessive
graphene coverage can influence the efficiency
of hydrocarbon conversion.
Although numerous studies have focused
on metal-decorated graphene materials, recent
reports indicate that rGO demonstrates cataly
tic activity in hydrogenation, dehydrogenation,
and bond-activation reactions without metallic
additives [11–13]. These findings highlight the
possibility of designing functional metal-free
catalysts based on the structural characteristics
of carbon materials, in which surface defects
and residual oxygen-containing groups are key
factors influencing catalytic performance.
The aim of this work is to determine the
influence of reduced graphene oxide content,
deposited in controlled amounts onto carbon
powder, on the catalytic activity of the result-
ing composites in ethylene hydrogenation.
Structural and morphological characteriza-
tion of the obtained materials was performed
using FTIR and Raman spectroscopies, SEM
imaging, and thermogravimetric analysis. The
results provide insight into the role of rGO
loading on the formation of functional surface
regions and reveal correlations between sur-
face modification and catalytic performance in
a metal-free carbon-based system.
EXPERIMENT AND DISCUSSION OF
THE RESULTS. Samples containing rGO de-
posited onto carbon powder were prepared by
depositing an aqueous suspension of graphene
19https://ucj.org.ua
V.V. Nosach, I.B. Bychko, P.Ye. Strizhak UCJ № 4/ Vol. 92
oxide (GO) with controlled concentrations
onto the carbon support. The GO suspension
was produced by exfoliation of graphite oxide
(GrO), synthesized using a modified Hum-
mers’ method followed by ultrasonic treatment
[14]. The carbon powder (ABCR) was impreg-
nated with the GO water suspension at a ratio
of 1 mL per 1 g of support. After deposition,
the materials were dried at 60 °C for 3 h and
subsequently thermally reduced in a hydro-
gen flow at 400 °C for 2 h, yielding reduced
graphene oxide (rGO). A series of samples
containing 0.0025, 0.01, and 0.1 wt.% rGO was
prepared and designated according to rGO
loading, rGO(0.0025)/CP, rGO(0.01)/CP, and
rGO(0.1)/CP.
The structural and physicochemical pro
perties of the obtained composites were cha
racterized using Raman spectroscopy, Fouri-
er-transform infrared spectroscopy (FTIR),
scanning electron microscopy (SEM), trans-
mission electron microscopy (TEM), and ther-
mogravimetric analysis (TGA). Raman spectra
were recorded at room temperature using a
Raman Senterra confocal dispersive spectro
meter (Bruker Optik) equipped with a 532 nm
excitation laser operating at a power of 2 mW.
FTIR measurements were carried out using a
PerkinElmer Spectrum One spectrometer in
the range of 400–4000 cm⁻¹. Thermogravi-
metric analysis was performed on a Disco
very SDT 650 thermal analyzer under air and
nitrogen atmospheres with a heating rate of
10 °C min⁻¹, enabling the assessment of ther-
mal stability and the determination of carbon
content in the samples. The morphology and
surface elemental distribution of the composi
tes were investigated by SEM and TEM using
MIRA3 TESCAN, Quanta 3D FEG, and JEM-
1200EX microscopes. Elemental mapping was
conducted by energy-dispersive spectroscopy
(EDS) to visualize the spatial distribution of
carbon- and oxygen-rich regions associated
with the deposited rGO.
The catalytic performance of the samples
in ethylene hydrogenation was evaluated un-
der continuous flow conditions with chro-
matographic monitoring of both the reaction
mixture and its products. The analysis was
carried out using a custom-built gas chroma-
tograph equipped with a thermal conductivity
detector and a Porapak S column. The catalyst
was loaded into a fixed-bed tubular reactor
between two layers of purified quartz, which
were placed above and below the catalyst bed.
Hydrogenation of ethylene was performed
within the temperature range of 50–400 °C us-
ing a feed composed of 10% C₂H4 and 90% H₂
at a total flow rate of 20 mL/min. The mass of
catalyst used in each experiment was 0.2–0.7 g.
The rate of hydrogenation product forma-
tion was calculated according to equation (1):
rc =
Fin – Fout
mc
where Fin is the initial molar flow rate of ethy
lene (mol s-1); Fout is the molar flow rate of ethy
lene after reactor (mol s-1); m𝚌 is the mass of
the catalyst sample, g.
Figure 1a-b shows SEM images of the pris-
tine CP and rGO(0.1)/CP. SEM image of the
pristine carbon powder reveals compact parti-
cles with relatively smooth surfaces and block-
like fragments, showing only minor surface
irregularities. The material is characterized by
a predominantly monolithic morphology with
flat facets and a limited degree of microstructural
development, indicating a low level of surface
texturing and the absence of nanoscale features.
20 ISSN 2708-129X. Укр. хім. журн., 2026
CATALYTIC PROPERTIES OF CARBON POWDER WITH DEPOSITED REDUCED GRAPHENE OXIDE
IN THE ETHYLENE HYDROGENATION.PHISICAL CHEMISTRY
In contrast, the SEM image of the rGO-modi-
fied sample displays pronounced morphologi-
cal alterations. Numerous wrinkled, sheet-like
and layered structures characteristic of re-
duced graphene oxide are clearly observed on
the particle surfaces and along their edges.
Figure 1 c-d shows SEM images with car-
bon distribution maps for CP and rGO(0.1)/CP.
The elemental mapping results support the
morphological observations and reveal clear
changes in the surface chemistry after rGO
modification. For the sample containing
0.1 wt.% rGO, the composition was determined
to be 85 wt.% carbon and 15 wt.% oxygen.
In comparison, the pristine support without
rGO deposition contains 87 wt.% carbon and
13 wt.% oxygen. Oxygen-containing regions
are predominantly located in the areas where
the SEM images show film-like and layered
structures, which is consistent with the pre
sence of graphene-derived fragments on the
surface of the support. The increased oxygen
content compared to the pristine material indi-
cates the retention of functional groups within
the rGO phase and their contribution to the
formation of the surface modification.
Fig. 1. SEM images of the samples: (a) CP; (b) rGO(0.1)/CP; SEM images with carbon distribution
maps on the surfaces of: (c) CP; (d) rGO(0.1)/CP; (e) HRTEM image of CP; (f) TEM image of CP.
21https://ucj.org.ua
V.V. Nosach, I.B. Bychko, P.Ye. Strizhak UCJ № 4/ Vol. 92
Figure 1e–f shows HRTEM and TEM ima
ges of the carbon powder (CP). The HRTEM
analysis Fig. 1e reveals a disordered carbon
structure composed of densely packed nano-
scale domains. No clear lattice fringes corre-
sponding to crystalline graphitic planes are
observed, indicating a predominantly amor-
phous or poorly ordered turbostratic structure.
The material is characterized by a developed
surface with nanoscale heterogeneities. The
TEM images Fig. 1f show irregularly shaped
particles with a broad size distribution, form-
ing agglomerates up to several micrometres in
size. The particles have non-uniform morpho
logy with diffuse boundaries and no well-de-
fined geometric shape, indicating a fragment-
ed structure. TEM analysis was also performed
for rGO-modified samples; however, no dis-
tinct graphene-derived structures could be
reliably identified due to the low rGO loading
and insufficient contrast between rGO and the
carbon powder surface
Fig. 2. FTIR (a) and Raman (b) spectra of rGO (0.0025)/CP, rGO (0.01)/CP, rGO (0.1)/CP;
(с) thermogram of rGO(0.1)/CP in nitrogen atmosphere.
Figure 2a presents the FTIR spectra of
carbon powder samples modified with diffe
rent loadings of reduced graphene oxide. All
spectra show weak-to-moderate absorption
features typical of carbon-based materials
containing residual oxygen functionalities.
A broad band near 3400 cm⁻¹ is common-
ly associated with O–H stretching vibrations
of hydroxyl groups and adsorbed moisture
[23]. Weak bands in the 2850–2950 cm⁻¹ re-
gion can be assigned to C–H stretching vibra-
tions originating from aliphatic fragments or
residual organic species [24]. A distinct band
at approximately 1700–1720 cm⁻¹ is generally
attributed to C=O stretching of carbonyl and
carboxyl groups, while the absorption close to
~1600 cm⁻¹ is usually linked to C=C stretch-
ing within sp²-hybridised carbon structures
[25]. Bands appearing in the 1400–1200 cm⁻¹
region are commonly associated with C–OH
and C–O vibrations, and signals in the ~1100–
1000 cm⁻¹ range are indicative of C–O–C
stretching modes related to epoxide and ether
functionalities that may remain in partially re-
duced graphene oxide [26]. The band observed
near ~2350 cm⁻¹ can be attributed to atmos-
pheric CO₂ [27]. Comparison of the spectra
suggests that oxygen-related bands become
slightly more pronounced with increasing rGO
content, indicating progressive enrichment
of the surface with rGO-derived functional
groups.
22 ISSN 2708-129X. Укр. хім. журн., 2026
CATALYTIC PROPERTIES OF CARBON POWDER WITH DEPOSITED REDUCED GRAPHENE OXIDE
IN THE ETHYLENE HYDROGENATION.PHISICAL CHEMISTRY
Figure 2b shows the Raman spectra of
carbon powder samples modified with diffe
rent loadings of reduced graphene oxide. All
rGO-containing samples have two character-
istic bands of sp²-hybridised carbon materi-
als: the D band at 1350 cm⁻¹, associated with
disorder-induced scattering, and the G band
in the 1580–1600 cm⁻¹ region, correspond-
ing to the in-plane vibration of graphitic car-
bon atoms. With increasing rGO content, the
D band becomes more pronounced relative to
the G band, indicating an increase in the defect
density and structural disorder within the car-
bon framework [28]. In addition to the main
D and G bands, a weak D′ band is observed at
around 1620–1630 cm⁻¹, which is commonly
associated with defect-related modes in gra-
phitic structures. A broad 2D band is observed
at 2680–2720 cm⁻¹ and remains of low inten-
sity, with only a minor enhancement at higher
rGO loadings [29]. Overall, the evolution of
the Raman spectra suggests that incorporation
of rGO increases the degree of structural disor-
der in the carbon powder, consistent with the
introduction of defect-rich graphene-derived
domains.
Figure 2c shows the thermogravimetric be-
haviour of the carbon powder/rGO sample in
an inert nitrogen atmosphere, demonstrating
a stepwise mass loss typical for carbon-based
materials. At temperatures up to 120 °C, the
sample loses 5% of its mass, mainly due to the
desorption of physically adsorbed moisture and
residual volatiles. Further heating to 300 °C re-
sults in an additional mass loss of 4%, which
can be attributed to the thermal decomposition
of oxygen-containing surface functional groups
associated with rGO and the carbon support.
In the 300–500 °C range, the mass change re-
mains minimal (~0.48%), indicating relatively
high thermal stability of the carbon framework.
At higher temperatures, the mass loss becomes
more pronounced, reaching 11% between 500
and 800 °C and a further 7% between 800 and
1000 °C. The total mass loss of approximately
28% at 1000 °C confirms that a substantial frac-
tion of the carbon framework remains intact
under non-oxidising conditions.
Table 1.
Textural characteristics of CP and rGO/CP samples.
Specific surface
area, S,
m² g⁻¹
Total pore volume,
Vₚ,
cm³ g⁻¹
Micropore volume,
Vₘ,
cm³ g⁻¹
t-Plot External
Surface Area,
m² g⁻¹
CP 1880 1.46 0.62 150
rGO (0.0025)/CP 1930 1.45 0.62 620
rGO (0.01)/CP 1720 1.46 0.62 670
rGO (0.1)/CP 1920 1.48 0.62 690
The textural parameters of the CP and
rGO-modified CP samples are summarized in
Table 1. The pristine CP exhibits a specific sur-
face area of 1880 m² g⁻¹, a total pore volume
of 1.46 cm³ g⁻¹, and a micropore volume of
0.62 cm³ g⁻¹. The incorporation of rGO leads
to slight variations in the specific surface area
depending on its loading. The highest value
among the modified samples is observed for
rGO(0.0025)/CP (1930 m² g⁻¹), while a more
23https://ucj.org.ua
V.V. Nosach, I.B. Bychko, P.Ye. Strizhak UCJ № 4/ Vol. 92
pronounced decrease to 1720 m² g⁻¹ occurs
at the intermediate loading (rGO(0.01)/CP),
followed by an increase to 1920 m² g⁻¹ for
rGO(0.1)/CP. A similar trend is observed for
the total pore volume, which remains in the
range of 1.45–1.48 cm³ g⁻¹ for all samples. In
contrast, the micropore volume remains con-
stant at 0.62 cm³ g⁻¹ for both pristine and
rGO-modified materials, indicating that the
introduction of rGO does not significantly al-
ter the microporous fraction. The substantial
increase in observed t-plot external surface
area from 150 m² g⁻¹ for CP to 620-690 m² g⁻¹
for rGO-deposited samples is a consequence
of several effects. Mainly, a contribution of
additional surface area, formation of carbon–
rGO gaps, and increased surface roughness
and fractality due to the introduction of addi-
tional corrugation and defects, increasing the
geometric complexity of the outer surface as a
consequence of rGO deposition.
These results suggest that rGO incorpora-
tion mainly affects the external surface and
mesoporous structure rather than generating
additional microporosity. Overall, rGO modi
fication does not lead to a substantial increase
in surface area compared to pristine CP, but
significantly increases surface area, which is
not associated with micropores.
Fig. 3. (a) Temperature dependence of ethylene conversion in the process of ethylene
hydrogenation within the temperature range of 50-400 °C, total flow rate 20 mL/min;
Conversion of ethylene for ■ – rGO(0.0025)/CP; ● – rGO(0.01)/CP; ▲ – rGO(0.1)/CP; ▼ – CP.
(b) Reaction rate diagrams of ethylene hydrogenation over CP, rGO (0.0025)/CP,
rGO (0.01)/CP, rGO (0.1)/CP, recalculated per catalyst mass at 400oС.
rc – rate of ethylene hydrogenation normalized to the mass of the catalyst.
Figure 3a shows the temperature dependence
of ethylene conversion over pristine carbon
powder (CP) and rGO-modified CP catalysts.
For the CP sample, conversion starts at 2% at
60 °C and gradually increases to 14% at 200 °C.
Upon further heating, a sharp rise is observed,
with conversion reaching 28% at 250 °C and
exceeding 30% at temperatures above 300 °C.
24 ISSN 2708-129X. Укр. хім. журн., 2026
CATALYTIC PROPERTIES OF CARBON POWDER WITH DEPOSITED REDUCED GRAPHENE OXIDE
IN THE ETHYLENE HYDROGENATION.PHISICAL CHEMISTRY
The maximum conversion of 35% is achieved
at 350 °C, followed by a slight decrease to 32%
at 400 °C. For the rGO(0.0025)/CP catalyst,
ethylene conversion remains below 1% over
the investigated temperature range, reaching a
maximum of 1% at 400 °C. The rGO(0.01)/CP
catalyst becomes active already at 80 °C, pro-
viding an ethylene conversion of 1%, and shows
a continuous increase in the low- and inter-
mediate-temperature region. The conversion
reaches 3% at 150 °C and attains its maximum
value of 7% at 250 °C. At higher temperatures,
a gradual decrease is observed, with conver-
sion declining to 6% at 300 °C, 6% at 350 °C,
and 5% at 400 °C. In contrast, the rGO(0.1)/CP
catalyst remains inactive up to 140 °C. With in-
creasing temperature, the conversion rises pro-
gressively to 3% at 200 °C and 6% at 250 °C,
followed by a more pronounced increase in
the high-temperature region. The conversion
reaches 11% at 300 °C and increases further to
16% at 350 °C, achieving a maximum of 18%
at 400 °C.
Figure 3b shows the reaction rate values for
ethylene hydrogenation at 400 °C over carbon
powder (CP) and rGO/CP catalysts. The pris-
tine carbon powder has the highest activity,
with a reaction rate of 1.3·10⁻⁶ mol·g(cat)⁻¹·s⁻¹.
Deposition of rGO decreases the reaction rate
compared to pristine CP. The sample containing
0.0025 wt.% rGO has a reaction rate of ethy
lene hydrogenation 4.4·10⁻⁸ mol·g(cat)⁻¹·s⁻¹,
which increases to 1.4·10⁻⁷ mol·g(cat)⁻¹·s⁻¹
for 0.01 wt.% rGO, and reaches 3.5·10⁻⁷ mol·
·g(cat)⁻¹·s⁻¹ for the catalyst with 0.1 wt.% rGO.
These results indicate that although rGO in-
corporation does not outperform the pristine
carbon powder under the studied conditions,
higher rGO loading partially improves the
activity within the composite catalyst series.
Overall, the obtained data demonstrate that
the catalytic behaviour of the carbon/rGO
composites strongly depends on rGO load-
ing. While pristine CP remains the most active
material at 400 °C, the reaction rate within the
rGO-modified series increased progressively
with increasing rGO content.
The obtained results demonstrate that the
catalytic behaviour of the investigated materi-
als in ethylene hydrogenation is governed pri-
marily by the activity of the CP. SEM analysis
reveals that rGO forms wrinkled, sheet-like,
and layered domains covering the surface of
the carbon particles, which is consistent with
t-plot analysis. Such coverage leads to partial
blocking of the outer surface of carbon sup-
port, whereas the main surface of CP is loca
lized in the micropores. Therefore, it can be
proposed that active sites on the surface of CP
are localized on the outer surface of CP parti-
cles, whereas the surface of CP that is localized
in the micropores contains a minor fraction of
active sites. Analysis shows that since the mi-
cropore volume remains essentially constant
for all samples, diffusion limitations associated
with high microporosity can be excluded for
the observed catalytic behavior. This indicates
that, for the studied reaction, the overall sur-
face area is not the determining factor, and the
reaction rate is governed by a combination of
factors.
The catalytic activity of graphene-derived
carbon materials in hydrogenation reactions,
and particularly in ethylene hydrogenation,
was demonstrated previously [30]. Whereas
the detailed mechanism remains undefined,
the surface structural defects, such as vacan-
cy-type defects, are considered as adsorption
sites for hydroden dissociative adsorption, and
ethylene is proposed to be activated by a π-π
25https://ucj.org.ua
V.V. Nosach, I.B. Bychko, P.Ye. Strizhak UCJ № 4/ Vol. 92
stacking. This means that in the rGO/CP sys-
tem, there are two catalytically active phases,
the CP and rGO. Whereas deposition of rGO
on CP results in the decrease of catalytic ac-
tivity of CP due to the blocking of active sites,
the increase of the ethylene hydrogenation rate
with the increase of rGO content shows that
rGO remains catalytically active after its dep-
osition on CP. An increase of rGO content by
4 times, from 0.0025 wt.% to 0.01 wt.%, leads
to an increase in the ethylene hydrogenation
rate by 3.2 times. This indicates that deposited
rGO in very small amounts does not restack
and allows for the approximation of a rate of
ethylene hydrogenation associated with rGO.
The obtained rate is 1.3·10⁻5 mol·g(rGO)⁻¹·s⁻¹,
which is consistent with the ethylene hydro-
genation rate on rGO reported previously in
such conditions [30]. Deposition of higher
amounts of rGO by 10 times, from 0.01 wt.% to
0.1 wt.%, leads to an unproportional increase
in ethylene hydrogenation rate by 2.5 times,
which can be caused by a significant restacking
of rGO sheets during its deposition in this con-
centration range.
Therefore, the catalytic performance of the
investigated metal-free carbon-based systems
is non-additive and determined by a combi-
nation of the active sites of the carbon powder
and introducing additional defect-rich rGO
through surface modification. In the present
composites, rGO deposition predominantly
leads to partial deactivation of an intrinsically
active carbon support due to site blocking.
CONCLUSIONS. Therefore, the results in-
dicate that the strategy of enhancing catalytic
performance through deposition of active rGO
onto an activated carbon support may not al-
ways lead to the expected synergistic effect,
due to the non-additive behavior of the system
components. The pristine carbon powder ex-
hibited the highest catalytic activity, achieving
an ethylene conversion of 32% and a reac-
tion rate of 1.3·10⁻⁶ mol·g(cat)⁻¹·s⁻¹ at 400 °C.
Within the rGO/CP series, the catalytic ac-
tivity increased with increasing rGO loading,
reaching a maximum conversion of 18% for
the rGO(0.1)/CP sample. At the same time,
normalization of the reaction rate to the mass
of deposited rGO showed a decrease in speci
fic activity at higher rGO loadings, which was
attributed to partial restacking of rGO sheets
and blocking of active surface sites. These fin
dings highlight the sensitivity of surface-active
sites and suggest that partial coverage of the
outer surface plays a key role.
Importantly, these observations open up
clear directions for improved catalyst design.
Future efforts can focus on the deliberate in-
troduction of chemically distinct active sites
or on optimizing graphene-derived materials
in combination with suitable supports, where
surface modification promotes the formation
of new reactive centers rather than limiting
access to existing ones. This approach offers
a promising pathway toward achieving en-
hanced catalytic performance through more
targeted material engineering.
AUTHOR CONTRIBUTIONS:
V. V. Nosach: investigation, methodology,
data curation, formal analysis, visualization,
writing – original draft.
I. B. Bychko: conceptualization, methodo
logy, writing – review & editing.
P. Ye. Strizhak: conceptualization, supervi-
sion, writing – review & editing, funding ac-
quisition.
All authors have read the results of the study
and approved the final version of the manu-
script.
26 ISSN 2708-129X. Укр. хім. журн., 2026
CATALYTIC PROPERTIES OF CARBON POWDER WITH DEPOSITED REDUCED GRAPHENE OXIDE
IN THE ETHYLENE HYDROGENATION.PHISICAL CHEMISTRY
CONFLICT OF INTEREST. The authors
declare no conflict of interest.
FUNDING. This work was carried out
with financial support from a grant provi
ded by the Simons Foundation (ID: SFI-PD-
Ukraine-00014577 (2025)).
ACKNOWLEDGMENTS. Raman spec-
troscopy, thermogravimetric analysis
(TGA), and scanning electron micro
scopy with elemental mapping (SEM–
EDS) were performed at Nicolaus Co-
pernicus University. The authors would
like to thank Prof. Wojciech Kujawski,
PhD, DSc, for his support.
КАТАЛІТИЧНІ ВЛАСТИВОСТІ ВІДНОВЛЕНОГО
ОКСИДУ ГРАФЕНУ, НАНЕСЕНОГО НА
ВУГЛЕЦЕВИЙ ПОРОШОК, У РЕАКЦІЇ
ГІДРУВАННЯ ЕТИЛЕНУ
В. В. Носач¹,², І. Б. Бичко¹,
П. Є. Стрижак¹
¹Інститут фізичної хімії
ім. Л. В. Писаржевського
Національної академії наук України,
просп. Науки, 31, Київ, 03028, Україна;
²Національний університет
«Києво-Могилянська академія»,
вул. Григорія Сковороди, 2, Київ 04655,
Україна
е-mail: victorynosach@gmail.com
Неметалеві каталізатори на основі вугле-
цевого порошку з нанесеним відновленим
оксидом графену (rGO) з різним вмістом
було синтезовано та досліджено в реакції
гідрування етилену. Отримані зразки оха-
рактеризовано методами раманівської та
ІЧ-Фур’є-спектроскопії (FTIR), скануваль-
ної електронної мікроскопії (SEM), транс
місійної електронної мікроскопії (TEM) і
термогравіметричного аналізу. Вихідний
вуглецевий порошок продемонстрував
найвищу каталітичну активність, тоді як
нанесення rGO призводить до зниження
ступеня перетворення етилену та швидко-
сті реакції порівняно з немодифікованим
носієм. Водночас у серії rGO/CP активність
зростає зі збільшенням вмісту rGO, причо-
му найвищі показники спостерігаємо для
зразка з 0,1 мас.% rGO. Швидкості реакції
у перерахунку на масу нанесеного rGO по-
казали зменшення каталітичної активності
зі зростанням його вмісту. Припускаємо,
що нанесення rGO на активний вуглецевий
носій може призводити до часткового бло-
кування активних центрів.
Ключові слова: відновлений оксид гра-
фену, вуглецевий порошок, гідрування ети-
лену, карбокаталіз.
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Стаття надійшла: 28.03.2026.
Статтю прийнято до друку: 10.05.2026.
Статтю опубліковано: 25.05.2026.
|
| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-776 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-23T01:14:35Z |
| publishDate | 2026 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| resource_txt_mv | ucjorgua/22/5b4ed7d569b6959d27a284603853a522.pdf |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-7762026-07-22T08:23:57Z CATALYTIC PROPERTIES OF CARBON POWDER WITH DEPOSITED REDUCED GRAPHENE OXIDE IN THE ETHYLENE HYDROGENATION Nosach , Viktoriia Bucko, Igor Strizhak , Peter reduced graphene oxide, carbon powder, ethylene hydrogenation, carbocatalysis. Metal-free catalysts based on carbon powder modified with reduced graphene oxide (rGO) were prepared and investigated in the ethylene hydrogenation reaction. The samples were characterized by Raman and FTIR spectroscopies, SEM, TEM, thermogravimetric analysis, and N2 adsorption-desorption. SEM and TEM analyses showed that rGO deposition leads to the formation of wrinkled graphene-derived structures covering the external surface of the carbon support. Raman spectra confirmed the presence of defect-rich sp²-hybridized carbon domains, while FTIR analysis revealed oxygen-containing functional groups associated with partially reduced graphene oxide. Textural analysis demonstrated that rGO incorporation mainly affects the external surface area without significantly changing the microporous structure of the support. The catalytic properties of the obtained materials were studied in ethylene hydrogenation within 50–400 °C under continuous-flow conditions. The pristine carbon powder provides the highest catalytic activity, whereas deposition of rGO results in a decrease in activity compared with the unmodified support. However, within the rGO/CP series, catalytic activity increased with increasing rGO loading, reaching 18% conversion for rGO(0.1)/CP at 400 °C. At the same time, normalization of the reaction rate to the mass of deposited rGO showed a decrease in specific activity at higher rGO contents, attributed to partial restacking of graphene sheets and blocking of active surface sites. The obtained results indicate that the catalytic behaviour of the investigated composites is governed by the balance between the intrinsic activity of carbon powder and the contribution of defect-rich graphene-derived domains. The findings highlight the importance of controlling graphene loading and surface accessibility in the design of efficient metal-free carbon catalysts. V.I.Vernadsky Institute of General and Inorganic Chemistry 2026-05-25 Article Article Physical chemistry Физическая xимия Фізична xімія application/pdf https://ucj.org.ua/index.php/journal/article/view/776 10.33609/2708-129X.92.4.2026.17-28 Ukrainian Chemistry Journal; Vol. 92 No. 4 (2026): Ukrainian Chemistry Journal; 17-28 Украинский химический журнал; ##issue.vol## 92 ##issue.no## 4 (2026): Ukrainian Chemistry Journal; 17-28 Український хімічний журнал; Том 92 № 4 (2026): Ukrainian Chemistry Journal; 17-28 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/776/409 Copyright (c) 2026 Viktoriia Nosach , Igor Bucko, Peter Strizhak https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Nosach , Viktoriia Bucko, Igor Strizhak , Peter CATALYTIC PROPERTIES OF CARBON POWDER WITH DEPOSITED REDUCED GRAPHENE OXIDE IN THE ETHYLENE HYDROGENATION |
| title | CATALYTIC PROPERTIES OF CARBON POWDER WITH DEPOSITED REDUCED GRAPHENE OXIDE IN THE ETHYLENE HYDROGENATION |
| title_full | CATALYTIC PROPERTIES OF CARBON POWDER WITH DEPOSITED REDUCED GRAPHENE OXIDE IN THE ETHYLENE HYDROGENATION |
| title_fullStr | CATALYTIC PROPERTIES OF CARBON POWDER WITH DEPOSITED REDUCED GRAPHENE OXIDE IN THE ETHYLENE HYDROGENATION |
| title_full_unstemmed | CATALYTIC PROPERTIES OF CARBON POWDER WITH DEPOSITED REDUCED GRAPHENE OXIDE IN THE ETHYLENE HYDROGENATION |
| title_short | CATALYTIC PROPERTIES OF CARBON POWDER WITH DEPOSITED REDUCED GRAPHENE OXIDE IN THE ETHYLENE HYDROGENATION |
| title_sort | catalytic properties of carbon powder with deposited reduced graphene oxide in the ethylene hydrogenation |
| topic_facet | reduced graphene oxide carbon powder ethylene hydrogenation carbocatalysis. |
| url | https://ucj.org.ua/index.php/journal/article/view/776 |
| work_keys_str_mv | AT nosachviktoriia catalyticpropertiesofcarbonpowderwithdepositedreducedgrapheneoxideintheethylenehydrogenation AT buckoigor catalyticpropertiesofcarbonpowderwithdepositedreducedgrapheneoxideintheethylenehydrogenation AT strizhakpeter catalyticpropertiesofcarbonpowderwithdepositedreducedgrapheneoxideintheethylenehydrogenation |