Catalysis Communications 185 (2023) 106799

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Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom

Nanocomposites of Nb2O5 and ZnO with reduced graphene oxide for

heterogeneous photocatalysis of dyes
Leonardo Zavilenski Fogaça a, *, Jean César Marinozi Vicentini a, Camila Fabiano de Freitas b,
Thais Lazzarotto Braga c, Fernando Alves da Silva d, Monique de Souza e,
Mauro Luciano Baesso e, Wilker Caetano c, Vagner Roberto Batistela f, Mara Heloisa Neves
Olsen Scaliante a
a
Department of Chemical Engineering, State University of Maringá, Colombo Avenue 5790, Zip Code 87020-900, Maringá, Paraná, Brazil
b
Department of Chemistry, Federal University of Santa Catarina, Eng. Agronômico Andrei Cristian Ferreira Street, Zip Code 88040-900, Florianópolis, Santa Catarina,
Brazil
c
Photodynamic Systems Research Center, Department of Chemistry, State University of Maringá, Colombo Avenue 5790; Zip Code 87020-900, Maringá, Paraná, Brazil
d
Department of Chemical Engineering, Federal Technological University of Paraná, Marcílio Dias St. 635, Zip Code 86812-460, Apucarana, Paraná, Brazil
e
Department of Physics, State University of Maringá, Colombo Avenue 5790, Zip Code 87020-900, Maringá, Paraná, Brazil
f
Department of Pharmacology and Therapeutics, State University of Maringá, Colombo Avenue 5790, Zip Code 87020-900, Maringá, Paraná, Brazil

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

Keywords: The removal of organic pollutants from water is a significant challenge in environmental remediation. In this
Photocatalysis study, the potential of ZnO and Nb2O5 semiconductors with the impregnation of three percentages of reduced
Reduced graphene oxide graphene oxide (rGO) as efficient photocatalysts for the degradation of methylene blue (MB) dye aqueous so­
Photoreactor
lutions was investigated in a UV mini-reactor. The heterostructures were synthesized by hydrothermal method
Niobium oxide
Zinc oxide
and characterized by analytical techniques, such as XRD, XPS, ATR-FTIR, Raman, TEM, N2 physisorption,
photoacoustic, photoluminescence, and pHZPC. Both rGONb2O5 and rGOZnO catalysts demonstrated consider­
able photocatalytic activity, resulting in the degradation of MB within a relatively short time period.

1. Introduction The Nb2O5 and ZnO are semiconductors that have been used as op­
tions in the photocatalysis process because they show similar properties
Photocatalysis is an advanced and promising oxidative treatment to TiO2, such as high oxidizing capacity [12], chemical stability, water
process to completely remove several contaminants and infectious insolubility [13] and low cost [14,15]. The Nb2O5 is the most thermo­
agents present in water [1,2]. It has high degradation efficiency and is dynamically stable state of the niobium oxides [16], and is one of the
considered eco-friendly because it can minimize the generation of most promising metal oxides in photocatalysis with a bandgap of
byproducts compared to conventional treatments [3,4]. The photo­ 2.9–3.2 eV [10]. Brazil not only holds the world’s largest niobium re­
degradation of recalcitrant organic compounds (ROCs) using semi­ serves, accounting for 80.2% of the global total but also takes the lead as
conductors such as TiO2 is openly reported in the literature, as it is a low- the largest niobium producer, contributing to over 88% of the world’s
cost operation, causes low UV light absorption, and is a nontoxic alter­ production [17]. The ZnO bandgap value (3.2 eV) [14] is also similar to
native capable of mineralizing such pollutants present in water [5–9]. TiO2 (3.2 eV) [18] and shows a low adsorption capability despite having
All the materials applied in photocatalysis systems may present char­ photo-corrosion tendency [14]. The main structure of ZnO presented is
acteristics such as high specific area, low bandgap (Eg), high conduc­ wurtzite due to its stability at ambient conditions [19]. Considering the
tivity, low electron-hole recombination, and being able to absorb UV or low cost of ZnO, the material has a large number of applications in in­
visible light to generate the oxidative species like •OH and •O−2 [10,11]. dustry, so using it as a photocatalysis is highly recommended and

* Corresponding author.
E-mail addresses: [email protected], [email protected] (L.Z. Fogaça), [email protected] (C.F. de Freitas), [email protected] (T.L. Braga), fernandoa@
utfpr.edu.br (F.A. da Silva), [email protected] (M.L. Baesso), [email protected] (W. Caetano), [email protected] (V.R. Batistela), [email protected]
(M.H.N.O. Scaliante).

https://doi.org/10.1016/j.catcom.2023.106799
Received 3 July 2023; Received in revised form 1 November 2023; Accepted 10 November 2023
Available online 15 November 2023
1566-7367/© 2023 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
L.Z. Fogaça et al. Catalysis Communications 185 (2023) 106799

described as exhibiting good efficiency [14,20]. The limitation of these Table 1

two oxides could be attributed to the high recombination of the Characterization methods applied to the synthesized photocatalysts.
photoexcited electrons and the narrow absorption of visible light Technique Objective Methodology/Equipment
[10,21].
ATR-FTIR Identify the surface 4000 to 400 cm− 1 range;
To increase the activity of oxide semiconductors, the photocatalysts functional groups and the resolution of 4 cm− 1; 128
are generally synthesized with the addition of inert or active materials, presence of ZnO and Nb2O5. scans, with spectrometer
tending to increase the surface area, absorption capacity, and catalytic Bruker Vertex 70v.
efficiency by the minimization of photo-generated electrons [22–27]. RAMAN Investigate the bulk 532 nm excitation laser; 5
structure and the mW laser power; 60
The combination of semiconductors and carbon-based materials such as development of graphene conditions; 5 s integration
amino graphite, carbon nanotubes (CNT), graphene oxide (GO), and reduction. time; 4450 to 40 cm− 1
reduced graphene oxide (rGO) have been studied [28–31]. Recently, we range; with Bruker
impregnated rGO in TiO2 semiconductor by hydrothermal synthesis, Senterra spectrometer.
XRD Identify the impregnation of Ni-filtered CuK, λ =
with the reduction of the surface groups of GO and formation of rGO,
the graphene in the ZnO and 0.15418 nm, 40 kV, 30
and consequent rGOTiO2 heterostructure [32]. The materials were Nb2O5 nanoparticles mA, 0.02◦ resolution, and
applied in the degradation of two organic compounds in a UV-LED mini- through the crystallographic 2◦ min− 1 scanning speed
reactor. The results showed that the material with lower rGO content planes. with Shimadzu XRD-
had greater efficiency in the mineralization of the two dyes, a fact 6000.
XPS Investigate the detailed Al Kα source radiation of
attributed to the greater synergistic effect between the effective transfer chemical composition and 8.3 Å and the spectra were
of charges from the semiconductor to the rGO, due to the greater domain oxidation states of the fitted with the Doniach-
of sp2 hybridization, showing a greater presence of active sites in the elements. Sunjic model. All
semiconductors [32]. parameters were
described in [35].
In this work, the proposal is to evaluate the applicability of the
TEM Investigate the The images were taken by
impregnation of rGO in ZnO and Nb2O5 by the hydrothermal method in morphological and an electron beam with a
the same synthetic conditions as the previous work. Since Nb2O5 and arrangement distribution of 100 kV microscope JEOL
ZnO semiconductors are electron-donating agents, and carbonaceous the synthesized JEM-1011. The size
materials are relatively good electron acceptors, the synergistic effect of photocatalysts. distribution histograms
were obtained using the
these two materials tends to decrease electronic recombination [21,33].
ImageJ software (v 1.53a,
In this way, the results of the photocatalysts can be compared and National Institute of
detailed, attesting to the advantages of using these two proposed alter­ Health, USA).
natives. Additionally, we perform comparisons in terms of morpholog­ Nitrogen Determine the textural Nitrogen physisorption at
physisorption properties of the 77 K utilizing Novatouch
ical, textural, and optical characterizations and also evaluate the
photocatalysts. LX2. Specific area was
photocatalytic activity of these materials for the degradation of meth­ determined utilizing the
ylene blue dye (MB), a model dye for evaluating photocatalytic activity BET Eq. [36]. Pore volume
[19]. Another important study is to explore the applicability of the UV- was calculated at a
LED mini reactor for monitoring photocatalytic reactions with relative pressure of 0.98,
and pore size was
rGONb2O5 and rGOZnO catalysts. Among the advantages related to the
obtained from a BJH pore
use of the mini reactor, the low use of reagents and solvents, and prin­ size distribution [25,37].
ciples of green chemistry, stand out [32,34]. Photoacoustic Determine the Bandgap (Eg) 800 W Xenon lamp power;
spectroscopy values employing Eq. (1) in 13 Hz modulation
UV–Vis spectra results. frequency; by a
2. Material and methods
homemade spectrometer
[38].
2.1. Reagents and rGOZnO and rGONb2O5 catalysts synthesis Photoluminescence Investigate the emission of Catalysts water solution
spectroscopy radiation by the (1.0 g L− 1); excited in a
Graphite flake Grafimax CG12 (National of Graphite, purity 99.9%), photocatalysts. 300 nm wavelength with a
320 nm optical filter in a
HCl (Dinâmica), H2SO4 (Synth), KMnO4 (Nuclear), H2O2 (Synth), Nb2O5 Perkin Elmer, model LS-
(Brazilian Company of Metallurgy and Mining, purity 99.9%), ZnO 50B.
(Synth, purity 99.0%), Methylene Blue (B. Herzog). These materials are pHZPC Estimate the total net charge pHsalt measurement of
used in commercial form, without additional purification. The synthesis balance obtained following catalyst in a saline
Eq. (2). solution and pHwater
of rGOZnO and rGONb2O5 catalysts was similar to the one adopted by
measurement after 30 min
the rGOTiO2 catalysts [32] and is fully described in the supplementary of contact. KCl 1 mol L− 1,
material. ultrapure water, and T =
25 ◦ C [39].

2.2. Characterization
at 365 nm, luminous flux of 5–8 lm, and an illumination angle of 140◦
The catalysts were examined for several techniques such are [32,34]. This system was accoupled in the UV–Vis Cary 50 spectro­
described in Table 1, as the main technique, the objective of the char­ photometer, with a Peltier controller, coupled to a quartz cuvette (1.00
acterization, and the methodology/equipment applied. Some equations cm optical path and 4.5 mL of total volume). The experimental
used in the characterizations are presented in Eq. (1) and Eq. (2). arrangement and reaction parameters, as well as the analysis of the re­
( )
(αhv)2 = A0 hv − Eg (1) action kinetics, are fully described in supplementary material.

pHZPC = 2* pHsalt − pHwater (2) 3. Results and discussions

3.1. XRD, XPS, ATR-FTIR, and Raman studies

2.3. Photocatalysis
Fig. 1 shows the diffractograms of the rGO photocatalysts in Nb2O5
The photoreactor is composed of the UV-LED with 5 W of power, λmax

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L.Z. Fogaça et al. Catalysis Communications 185 (2023) 106799

respectively. This result indicates that zinc remains ZnO even after the
synthesis of the rGOZnO nanocomposite [46,47], with its oxidation state
remaining Zn2+. The C 1 s spectra for the rGOZnO photocatalysts have
been deconvoluted into four peaks: sp2 bonded carbon at 284.6 eV (C −
C), epoxy/hydroxyl groups at 286.5 eV (C − O), carbonyl groups at
288.6 eV (C=O) [48], and a minor peak at 290.4 eV (π − π*) indicative
of a conjugated satellite related to modified aromatic ring domains [49].
This provides evidence for the presence of a modified π structure, which
is only observed in the formation of the rGOZnO structure. The O 1 s
spectrum has also been deconvoluted, revealing three main peaks. The
peak at 530.6 eV corresponds to lattice oxygen of the crystalline zinc
oxide (Zn − O), while the peak at 532.3 eV can be attributed to adsorbed
oxygen molecules or oxygen vacancies (C − OH/Zn − OH or Ov), and
the peak at ~534 eV may be associated with the presence of C − O
groups originating from the graphene surface [46,48].
To analyze the effects of adding different mass ratios of rGO to the
catalysts, data were collected on the integrated areas of the bonds in the
C 1 s and O 1 s spectra. Examination of the individual bonds in the C 1 s
spectra of rGONb2O5 shows that the C–C bonds account for 64.1%,
75.4%, and 73.6% for the photocatalysts with 1, 5, and 10% rGONb2O5,
respectively. Similarly, C − O bonds account for 19.9%, 17.2%, and
Fig. 1. X-ray diffractograms of a) rGONb2O5 and b) rGOZnO photocatalysts. 15.0%, while C– – O bonds represent 16.0%, 7.4%, and 11.4% for 1, 5,
and 10 rGONb2O5, respectively. In the O 1 s spectrum, Nb − O bonds
and ZnO. For commercial Nb2O5 and its supported catalysts, the 2θ re­ constitute 84.9%, 83.7%, and 80.9%, and Nb − O − Nb bonds make up
gion from 23◦ to 27◦ is prominent. The commercial Nb2O5 presents the 15.1%, 16.3%, and 19.0% for 1, 5, and 10 rGONb2O5, respectively.
characteristic signs at 23.9o, 24.5o, and 25.6o which are related to a Comparing the individual bonds in the C 1 s spectra of rGOZnO, we
crystalline structure similar to the monoclinic H phase, being its phase find that C − C bonds account for 62.6%, 59.8%, and 67.7% for the
considered the most stable from the thermodynamic point of view [16]. photocatalysts with 1, 5, and 10% rGOZnO, respectively. Similarly, C −
This structure is obtained from the calcination of Nb2O5 at temperatures O bonds account for 19.8%, 22.3%, and 17.52%, C– – O bonds account for

above 1000 ◦ C [40]. The diffractograms of the rGONb2O5 photocatalysts 9.8%, 11.7%, and 9.18%, and π − π* bonds account for 7.8%, 6.1%, and
show the typical signals of Nb2O5 and an additional peak at 25.0◦ , 5.5% for the photocatalysts with 1, 5, and 10 rGOZnO, respectively.
characteristic of rGO (Fig. 1S), which overlaps the peaks of 24.5o and Analysis of the O 1 s spectra shows no significant variations in the
25.6o as the percentage of rGO in the photocatalyst increases, the peak binding fractions with the increase in rGO mass within the structure.
shown are more intense [25]. Moreover, the presence of the small signal By the ATR-FTIR for GO in Fig. 3, the bands in i) the region of
in 43.8o (Fig. S1), also confirms the presence of rGO in Nb2O5 photo­ 1050–1100 cm− 1 attributed to the C–O alkoxy group were identified; ii)
catalysts. The slight broadening of the peaks in rGONb2O5 catalysts is a shoulder in the region of 1220–1230 cm− 1 attributed to the vibration of
result of the incorporation of rGO [41]. Moreover, the presence of the the C-O-C epoxy groups; iii) 1565–1665 cm− 1 band assigned to
connection C– – C of the GO plans; iv) 1680–1760 cm− 1 band associated
rGO signal indicates that there was a favoring for rGO crystallinity
during the synthesis process in Nb2O5. with C–– O, the vibration of carbonyl groups [50].

The XRD signals of the photocatalysts in ZnO are all similar showing Fig. 3 (a) shows the ATR-FTIR of the rGONb2O5 in the spectral region
the most typical signals of ZnO 31.8◦ , 34.4◦ , and 36.2◦ referring to the of 2000 to 400 cm− 1. The spectra of all catalysts show the presence of the
wurtzite crystal structure [14,42]. From these diffractograms, it is characteristic bands of Nb2O5 in the region of 950 to 500 cm− 1 [51], and
inconclusive to describe the interaction between rGO and ZnO semi­ the bands associated with GO centered at 1737, 1579, 1226 and 578
conductor that confirms the synthesis of the desired photocatalyst only cm− 1, characteristic of stretching vibrational of C– – O groups, C − C

by XRD. Other authors reported a similar problem probably due to the skeletal with remaining sp2 carbon, the C − O epoxy groups [52], and
low content of rGO [42,43], and the lower crystallinity of the carbo­ probably to OH out of plane bend [53], respectively. The 562 cm− 1 band
naceous. However, the coincidence in diffraction peaks of the photo­ of Nb2O5 corresponds to the stretch of the Nb − O − Nb bonding [51],
catalysts with commercial ZnO form indicates that the lattice of ZnO which was slighted broadening by the presence of rGO. The decrease
remains unchanged because of surface hybridization [21]. suggests the principal point of interaction of the active phase with the
Fig. 2 presents the XPS results, with the C 1 s and O 1 s spectra for the different functional groups of the rGO sheets.
(a) rGONb2O5 and (b) rGOZnO photocatalysts. Additionally, Fig. 2S il­ Fig. 3 (b) shows the ATR-FTIR of the rGOZnO photocatalysts. It ap­
lustrates the Nb 3d and Zn 2p XPS spectra. pears that the three photocatalysts have the typical ZnO bands in the
In Fig. 2S (a), the Nb 3d XPS spectrum shows prominent peaks at region of 600 to 400 cm− 1, including the 550 cm− 1 of the Zn–O
207.1 and 209.8 eV, corresponding to Nb 3d5/2 and Nb 3d3/2, respec­ stretching [54]. The three photocatalysts present the band at 1737 cm− 1,
tively. These values align with the binding energy characteristic of Nb5+ associated with rGO, and also present the band at 1579 cm− 1, slightly
oxidation state [12,44,45]. The C 1 s spectra for rGONb2O5 have been displaced to the region of lowest wavenumber. The peak of 1579 cm− 1
deconvoluted into three distinct peaks, each associated with different could indicate the successful reduction of GO and growth of the ZnO
carbon species: sp2 bonded carbon at 284.6 eV (C − C), epoxy/hydroxyl particles [15]. It was also found that the three photocatalysts present the
groups at 286.5 eV (C − O), and carbonyl groups at 288.6 eV (C=O) band at 1226 cm− 1, associated with C − O epoxy groups, which appears
[13,44]. The O 1 s spectrum for rGONb2O5 has been deconvoluted into more intense with the rGO amount. The intensity of the bands in 1737,
two peaks, one attributed to niobium‑oxygen bonding within the 1579, and 1226 cm− 1 increase as the percentage of rGO also increases.
semiconductor at 530 eV (Nb − O), and the other to the presence of Nb To complement the ATR-FTIR analysis, the Raman technique was
− O − Nb bonding at 532 eV [12,13]. performed, their spectra are shown in Fig. 4. It was used to evidence the
In Fig. 2S (b), the Zn 2p XPS spectrum reveals two major peaks at composite formation of rGO and the semiconductor oxides and to
1022.2 and 1045.33 eV, corresponding to Zn 2p3/2 and Zn 2p1/2 levels monitor variations in signals related to the mass percentage of the cat­
alysts. The rGO spectrum shows characteristic bands G, due to plane

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L.Z. Fogaça et al. Catalysis Communications 185 (2023) 106799

Fig. 2. XPS spectra of (a) rGONb2O5 and (b) rGOZnO nanocomposites.

vibrational of the sp2 carbons in 1592 cm− 1, band D refers to the pres­ in Figs. 4 (a) and (b), respectively. Compared to rGO, the D band of the
ence of defects in the rGO structure at 1345 cm− 1, and another addi­ rGONb2O5 catalysts showed a slight decrease in the intensity, and to the
tional band in 2D refers to the second resonance of the second order of G band, a slight increase in the intensity. This modification can be
Raman scattering across the zonal border at 2700 cm− 1 [55]. Here, the analyzed by the ID/IG peak intensity ratio, which uses the size of the sp2
Raman spectra of the rGONb2O5 and rGOZnO photocatalysts are shown domains and is a measure of the disorder degree in the graphene

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L.Z. Fogaça et al. Catalysis Communications 185 (2023) 106799

Fig. 3. Attenuated total reflectance Fourier Transformed Infrared spectra (ATR-FTIR) of a) rGONb2O5 and b) rGOZnO photocatalysts.

Fig. 4. Raman spectra of a) rGONb2O5 and b) rGOZnO photocatalysts.

materials [21,56]. From Fig. 3S, the intensity of ID/IG ratios are 0.95 for For the three photocatalysts 1rGONb2O5, 5rGONb2O5, and
GO, 1.04 for rGO, and from Fig. 4 (a) the 1rGONb2O5, 5rGONb2O5, and 10rGONb2O5 Raman spectra, it was observed in Nb2O5 and rGO the
10rGONb2O5 photocatalysts were 0.93, 0.92, and 0.94, respectively. presence of their characteristic peaks, which further suggests that the
The intensity ID/IG ratios of 1rGONb2O5, 5rGONb2O5, and 10rGOZnO material obtained has the two species on the same surface [25]. All three
photocatalysts were 0.98, 0.99, and 0.98, respectively. This implies that photocatalysts 1rGOZnO, 5rGOZnO, and 10rGOZnO had very prominent
all rGONb2O5 catalysts have ID/IG lower than the pure GO and rGO, and and intense bands referring to rGO. They also showed the characteristic
all rGOZnO catalysts have an ID/IG between the GO and rGO values. ZnO bands in the three main peaks at 101, 327, and 437 cm− 1. These
After hydrothermal synthesis of the catalysts, there is a decrease in in­ peaks correspond to the hexagonal wurtzite phase of ZnO [50], and the
tensity in band D concerning band G for all photocatalysts. This decrease results were consistent with the XRD data for the phase identification.
in intensity indicates the reduction of some functional groups, such as The presence of all main peaks of both rGO and ZnO in all photocatalysts
hydroxyl and epoxy, in addition to reducing the existence of defects in also confirms the composite formation [21]. The D and G bands
the structure of the rGO sheets [57], as discussed in FTIR-ATR analysis. remained with similar intensity even with the mass variation of rGO,
In Table 3 all the results at the empirical size of the sp2 domains are contrary to what is demonstrated for the rGONb2O5 and in our previous
described (La). rGOTiO2 photocatalysts published work [32].

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L.Z. Fogaça et al. Catalysis Communications 185 (2023) 106799

3.2. Morphological and textural analysis showed 8.68 ± 3.24 nm and 2.49 ± 0.91 nm to 10rGOZnO and
10rGONb2O5, respectively. To explain this experimental observation, it
The morphological characteristics of rGONb2O5 and rGOZnO pho­ can be assumed that the increase in the concentration of rGO in the
tocatalysts are described by transmission electronic micrographs (TEM) medium allows a better distribution of the oxide nanoparticles along the
shown in Fig. 5. The particle size distribution to all photocatalysts is rGO sheets. The best distribution will limit growth induced by hydro­
shown in Figs. 4S and 5S. thermal conditions. In other words, there is a greater number of active
Firstly, the micrographs depicted in Fig. 5a and e, reveal that the sites to be occupied by ZnO and Nb2O5 along the rGO sheets.
oxide exhibited a nanometric scale, average size of 3.46 ± 1.09 nm to Pure rGO exhibited multilayer N2 adsorption without complete
ZnO and 2.38 ± 1.05 nm to Nb2O5. Furthermore, the incorporation of saturation over relative pressure (not shown). This is commonly
the niobium and zinc oxides during the hydrothermal process with GO observed in non-porous isothermal profiles [61]. Low volumes of
can be inferred from the micrographs presented in Figs. 5b-d and f-h, adsorbed N2 were obtained for pure Nb2O5, suggesting that this pure
respectively. The creased translucent films are the rGO sheets and the support has a low specific surface area and porosity, as confirmed by the
darker points are the Nb2O5 and ZnO nanoparticles. The wrinkles shown values in Table 2. Hysteresis was also observed between the adsorption
in rGO sheets confirm the 2D structure of rGO [21]. All the micrographs and desorption isotherms, likely due to N2 condensation on the capil­
show aggregation of the active phase in rGO sheets, which indicates the laries over a wider relative pressure range. However, since rGO appears
formation of conglomerated heterostructures. Other authors reported to be a non-porous material, the increase in average pore size after
the same characteristics [21,48]. incorporation of 1rGO could be due to the mesoporous blocking effect of
For the 1rGONb2O5 (Fig. 5b) and 1rGOZnO (Fig. 5f), the difference in Nb2O5 caused by rGO.
the agglomerated structure of the active phase in rGO sheets. The lower Comparing the isotherms of the Nb2O5 and 1rGONb2O5, there was a
rGO content showed the proximity of semiconductor particles in rGO reduction in hysteresis and a decrease in the average pore size, while the
sheets. With the increase of rGO load to 5% (Fig. 5c and g) and 10% specific surface area increased. This suggests that rGO incorporation
(Fig. 5d and h), there is a distancing of the semiconductor oxide particles preferably occurred in the mesopores of Nb2O5, or even that rGO
and greater dispersion of these particles in the rGO sheets. contributed to the formation of more micropores on the support. In the
A very interesting aspect is associated with the pattern observed in same way, 5rGONb2O5 and 10rGONb2O5 also exhibited a higher for­
the size of the impregnated oxide nanoparticles. In general, it is mation of micropores, as confirmed by the increased volume of N2
observed for the lowest concentration of rGO (1rGO) that the nano­
particles of both oxides were greater to the respective precursors, 12.06
± 4.40 nm and 7.69 ± 4.91 nm, to 1rGOZnO and 1rGONb2O5, respec­ Table 2
tively. This experimental observation indicates a growth of nano­ Textural parameters of rGONb2O5 and rGOZnO photocatalysts obtained by N2
physisorption at 77 K.
particles during the hydrothermal process, a method widely used to
obtain such oxides [58,59]. In this scenario, at the lowest rGO per­ Photocatalyst SBET Average Micropore Pore External
(m2 g Pore Area (m2 Volume Surface
centage, there will be a certain level of proximity or even agglomeration − 1
) Radius g− 1) 10− 2 (cc Area (m2
of the initial oxides along the rGO sheets. This proximity, associated (nm) g− 1) g− 1)
with hydrothermal processing conditions, allows the growth of nano­
rGO 113.11 > 58 *
particles, as observed by other authors but not over-discussed
– – –
*
[10,21,26,60]. Nb2O5 1.21 8.16 0.00 0.34 1.21
Furthermore, it is observed that this tendency decreases as the rGO 1rGONb2O5 2.12 6.84 0.00 0.52 2.12
percentual increases (1rGO > 5rGO > 10rGO). Thus, for 5rGO, slightly 5rGONb2O5 6.65 2.73 1.34 0.74 5.31
10rGONb2O5 18.89 1.89 3.66 1.57 15.23
smaller oxide nanoparticles are observed for both ZnO and Nb2O5, 9.81
ZnO 5.86 5.95 0.00 1.28 5.86
± 3.83 nm and 7.46 ± 4.70 nm to 5rGOZnO and 5rGONb2O5, respec­ 1rGOZnO 7.13 7.09 0.00 1.83 7.13
tively. In this sense, at the highest percentual of rGO (10rGO), it is 5rGOZnO 8.27 10.70 0.00 3.12 8.27
observed that the oxide nanoparticles in the nanocomposites have small 10rGOZnO 10.0 10.75 0.00 3.93 10.0
sizes in comparison to the pure oxides (Fig. 5a and e). The results *
Calculated by the DFT (Density Functional Theory) method.

Fig. 5. TEM images of the photocatalysts of a) Nb2O5, b) 1rGONb2O5, c) 5rGONb2O5, d) 10rGONb2O5; e) ZnO, f) 1rGOZnO, g) 5rGOZnO, and h) 10rGOZnO.

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L.Z. Fogaça et al. Catalysis Communications 185 (2023) 106799

physisorbed (Fig. 6), as well as the reduction in the average pore size and However, the type of pore obtained depends on the interactions of rGO
larger specific surface areas, as shown in Table 2. with the oxide. For rGOZnO catalysts, there is a synergistic effect that
Isotherms of ZnO and rGOZnO catalysts containing 1, 5, or 10 rGO contributes to the formation of mesopores, while for rGONb2O5, this
exhibited a profile that indicated a presence of micropores, as the effect corresponds to the formation of micropores.
amount of adsorbed N2 remained low over a wide range of relative
pressures, with the complete pore filling occurring only towards the end 3.3. Photoacoustic spectroscopy (PAS) and Photoluminescence (PL)
of the isotherm (Fig. 7). This increase in adsorbed volume may also be
associated with the presence of mesopores in the samples. However, no In Fig. 8 we show the overlapping spectra of photoacoustic and
hysteresis was observed between the adsorption and desorption curves, photoluminescence. The continuous line demonstrates the photo­
indicating the absence of capillary condensation of the adsorbate. This luminescence data, and the dashed line, the photoacoustic data.
effect is commonly observed in materials with primarily mesoporous Comparing Fig. 8a and b the photocatalysts showed that the amount
morphology, suggesting a higher presence of micropores rather than of rGO affects the PL spectra, but opposite to rGONb2O5 against the
mesopores in the samples [61]. rGOZnO. To rGONb2O5 photocatalysts, the lower amount of rGO pre­
The different rGO w/w% led to an increase in the volume of adsorbed sented a lesser PL intensity. For rGOZnO photocatalysts, as the per­
nitrogen, in the order of 1rGO < 5rGO < 10rGO. Consequently, the centage of rGO increases, the intensity of the PL decreases,
addition of rGO contributed to enhancement in the specific surface area demonstrating that the transfer of photoelectrons to the rGO sheets
of the catalysts, as also evidenced in Table 2. The increase in specific occurs. This effect is primarily attributed to the inhibition of recombi­
surface area was accompanied by an increase in the average pore radius. nation in charge carriers, characteristic of the carbonaceous materials
The pore size distribution for pure ZnO and rGOZnO catalysts appeared [26]. Since the PL phenomenon is the result of the recombination of
to be multimodal, extending into the mesoporous region (between 2 and photo-excited electrons and holes, lower intensities of the PL spectrum
50 nm). Thus, despite the isotherms displaying a Type I behavior indicate less electronic recombination [62]. The 1rGONb2O5 presented
(indicative of microporous materials), there was also evidence of mes­ the lesser photoluminescence recombination, which indicates that 1rGO
opore formation as confirmed by the increase in N2 physisorbed and the showed a better quality to be an electron acceptor, characteristic of the
average pore size. Furthermore, the formation of mesoporosity was carbonaceous materials.
favored with the incorporation of rGO in the samples, as the number of In previous works, some authors have discussed the results of Pho­
mesopores (i.e., the shift of the average pore size distribution towards toluminescence (PL) with those of Electrochemical Impedance Spec­
the mesoporous region) increased with the amount of rGO, as observed troscopy (EIS). It is based on the interpretation of the radius of the
in Table 2. impedance-related arc in the Nyquist plot, which relates the charge
These results suggest that rGO acts as a pore agent in the catalysts, transfer rate between the photocatalysts and the electrolyte [41,63]. In
leading to an increase in specific surface area and pore volume. these results, the EIS technique demonstrates that ZnO and Nb2O5

Fig. 6. N2 physisorption of rGONb2O5 photocatalysts.

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L.Z. Fogaça et al. Catalysis Communications 185 (2023) 106799

Fig. 7. N2 physisorption of rGOZnO photocatalysts.

Fig. 8. Photoacoustic and photoluminescence spectra of a) rGONb2O5 and b) rGOZnO photocatalysts.

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L.Z. Fogaça et al. Catalysis Communications 185 (2023) 106799

materials exhibit the largest radius, thus contributing to higher PL 10− 3 min− 1 for Nb2O5 (Table 4). This pseudo-first order constant value
emission intensities, which are directly associated with reduced electron for the photodegradation of MB by ZnO is consistent with the previously
transport [63]. When these materials are modified with the addition of reported literature of 97.4 ± 7.4 × 10− 3 min− 1 [34], indicating high
varying amounts of rGO, they exhibit smaller radius in the EIS reliability in the mini-photoreactor for carrying out photocatalysis ex­
[25,64,65], indicating an increased charge transfer rate. Consequently, periments. However, significant degradation of MB within the 400-min
the emission intensities of PL also decrease, suggesting reduced photo­ photocatalytic reaction was not observed for pure rGO.
induced electron recombination on the catalyst surface [66]. Addition­ Concerning ZnO, the 1rGOZnO photocatalyst presented the highest
ally, certain reports based on EIS results indicate that the increasingly kinetic rate constant, 109.72 × 10− 3 min− 1, slightly higher than 99.70
high amount of rGO can cause an enlargement in the arc radius. Despite × 10− 3 min− 1. For 5rGOZnO and 10rGOZnO the values were compar­
the crucial role played by rGO in charge transfer, an excess of rGO can atively ~3× and ~ 7.5× smaller than 1rGOZnO. For those photo­
introduce resistance due to its semiconductor properties, leading to a catalysts supported in Nb2O5, the 1rGONb2O5 showed the fastest kinetic,
reduction in charge transfer efficiency [25,63]. while 5rGONb2O5 and 10rGONb2O5 were ~ 1.1× and ~ 1.9× slower
According to the results presented in Table 3, the Eg values of the than pure Nb2O5. In this case, a noteworthy aspect is that the presence of
pure semiconductor oxides are consistent with the literature, for Nb2O5 1% rGO promoted a ~ 3× increase in the rate constant in pure Nb2O5,
is 2.98 eV (416 nm), and for ZnO is 3.18 eV (390 nm) [12,14,67]. The Eg indicating that this small modification improves its photocatalytic
values slightly increased as the rGO content increased in both oxides, properties and can make it more attractive for commercial purposes.
according to Table 3. For the rGONb2O5 photocatalysts, the values are From Table 4, it can be observed that pure ZnO showed a higher MB
between 3.01 and 3.03 eV; and for rGOZnO, between 3.21 eV and 3.26 photodegradation rate compared to pure Nb2O5. Despite ZnO presenting
eV, in both cases considering the rGO amount increment. All the values a higher bandgap, this result can be attributed to the higher surface area
indicate that the UV-LED source (λmax = 365 nm) can excite all the in this photocatalyst, compared to the Nb2O5 one (Table 2). Here, it can
photocatalysts The increase in Eg values was also verified in the cata­ also be inferred that a higher bandgap did not bring photocatalyst ac­
lyst’s color, which became darker from 1 to 10% rGO, implying more tivity down for MB decomposition. Thus, MB photodegradation depends
light absorption [32]. on both bandgap and surface area, as for MB interactions with surface
The LA empirical values usually applied to discuss the largest size of photocatalysts.
sp2 domains in the rGO sheets were very close for each class of photo­ However, for both systems, it was found that 1rGO promoted the
catalyst. This indicates that the ID/IG ratio is also very similar for all highest rate constant for MB photodegradation. In this case, there is a
rGONb2O5 and rGOZnO photocatalysts, and it is inconclusive to discuss combination of surface area and bandgap effects that act to favor dye
the better charge transference between active phase to rGO sheets. In degradation. Two other important factors are LA, empirical sp2 domains
our previous work, the 1rGOTiO2 showed large sp2 domains, and the [32,68], EU, and Urbach’s Energy, related to the energy of semi­
results converged to better photocatalytic activity [32]. conductor heterostructures [69]. In our previous work with rGOTiO2
photocatalysts, in the same conditions as the present photocatalytic
3.4. Photocatalytic activity system mini-reactor, we discussed that the photocatalytic effect of rGO
supported on TiO2 is greater than for the pure TiO2 [32]. The electrons
The photocatalytic performance of the rGO supported in ZnO and were photoexcited on TiO2 and migrated to rGO sheets, which can
Nb2O5 was monitored in a mini-photoreactor, which has the advantages effectively separate these charges and stop the recombination, thus
of using less photocatalyst and solvents and real-time monitoring in a extending the photocatalytic activity [46,70,71]. In this new work, the
UV–Vis spectrophotometer with the possible acquisition of 1 reading at same conclusion is derived from the results of rGONb2O5 and rGOZnO
λmax per minute, by the principles of Green Chemistry [32,34]. Also, it photocatalysts, due to the less photoexcited electrons recombination. By
has efficiency in directly illuminating samples, safe use of ultraviolet TEM images it can be concluded that when the semiconductor was
radiation, and environmental aspects related to LED sources [32,34]. combined with small percentages of rGO, the sheets acted capturing the
The kinetic curves of the photodecomposition of MB as present in Fig. 9a electrons in the conduction band, and decreasing the recombination
and b for rGONb2O5 and rGOZnO photocatalysts, respectively. And, in [19], following the photoluminescence and the Urbach’s energy results.
Fig. 9c and d, the pseudo-first-order kinetic rate constants are also As can be seen from Table 2 and Table 3, higher rGO loading in both
presented for rGONb2O5 and rGOZnO photocatalysts, respectively. supports increased surface area and bandgap (except for 10rGOZnO,
From the literature, the photolysis of MB is 8% in 300 min, in the which showed a lower bandgap compared to 5rGOZnO). However, it
same experimental conditions [32]. The kinetic curves presented in was verified a negative effect on the rate constant of these photo­
Fig. 9a and b were fitted by the pseudo-first-order kinetic model and the catalysts. The lower rate constants show that the photodegradation oc­
values of the coefficient of determination (R2) were very close to unity curs on specific active sites and not all surface area. So, the
(Table 4). From Figs. 9a-9d, the actions of ZnO and Nb2O5 pure photo­ incorporation of more rGO content on supports might cover the Nb2O5
catalysts were very different. The photodegradation of MB reached or ZnO active sites. A large amount of rGO sheets can influence the
100% in 200 min for pure ZnO photocatalyst, while that promoted by synthesis process, which affects active site dispersion on Nb2O5 and
pure Nb2O5 was only 20% at the same time. Even in 400 min, the ZnO. Thus, higher rGO content caused lower electron availability in the
photodegradation was only 40% for pure Nb2O5 photocatalyst. In these conduction band. Thus, a partial blocking effect of the UV irradiation on
cases, the rate constant was 99.70 × 10− 3 min− 1 for ZnO and 1.17 × the semiconductor might have occurred, consequently providing fewer
radicals to photodegrade the MB dye. This was also observed by pHZPC
(Table 3), which showed a displacement to lower values compared with
Table 3
Physicochemical parameters of rGOZnO and rGONb2O5 photocatalysts.
the heterostructure photocatalysts with rGO and pure ZnO and Nb2O5.
So, the incorporation of higher amounts of rGO interfered in MB pho­
Photocatalyst Eg (eV) EU (eV) LA (nm) pHZPC
todegradation, towards lower adsorption effects.
Nb2O5 2.94 0.17 – 4.69 The XPS results demonstrated that rGOZnO exhibited a π-π* transi­
1rGONb2O5 3.01 0.18 4.7 5.06 tion, suggesting that the molecular-level interaction of these species may
5rGONb2O5 3.03 0.19 4.7 5.11
10rGONb2O5 3.03 0.20 4.6 4.72
have been the most intense. Furthermore, the π-π* transition with the
ZnO 3.18 0.09 – 8.08 highest relative area was associated with the photocatalyst 1rGOZnO.
1rGOZnO 3.21 0.10 4.4 4.76 This combination of the presence of π-π* and the higher distribution of
5rGOZnO 3.26 0.08 4.3 5.19 semiconductor particles in the rGO sheets, as demonstrated by TEM
10rGOZnO 3.22 0.24 4.4 5.63
images, at a 1% rGO ratio in both materials. Since charge transfer

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L.Z. Fogaça et al. Catalysis Communications 185 (2023) 106799

Fig. 9. Photodegradation of MB. Kinetic curves promoted by a) rGONb2O5, and b) rGOZnO photocatalysts. Pseudo-first order kinetic constant promoted by c)
rGONb2O5 and d) rGOZnO photocatalysts.

efficient with 1rGONb2O5 compared to TiO2/Nb2O5/RGO containing

Table 4
10% rGO, also obtained with the hydrothermal method. However, pa­
Kinetic parameters for the photodegradation of MB with rGOZnO and rGONb2O5
rameters such as light intensity and dosage must be better evaluated.
photocatalysts.
The ZnO with rGO application is much more common due to higher
3
Photocatalyst k x 10− (min− 1) t ½ (min) R2 photocatalytic action. For ZnO, in Table 5, the use of different synthesis
ZnO 99.70 ± 9.54 6.95 0.9899 methodologies of impregnation of rGO can be verified, such as chemical
1rGOZnO 109.72 ± 8.39 6.31 0.9934 reduction, sonochemistry, and hydrothermal, among others. In one
5rGOZnO 35.65 ± 1.16 19.44 0.9996
study, ~99% degradation of MB was obtained in 60 min with 7.7% ZnO-
10rGOZnO 14.70 ± 1.64 47.15 0.9991
Nb2O5 1.79 ± 0.11 387.84 0.9995 rGO, a 300 W Mercury-Xenon lamp, and dosage of 1 g L− 1, which are
1rGONb2O5 5.21 ± 0.07 133.11 0.9999 7.7×, 60×, and 5× higher, respectively, than what we used [46]. The
5rGONb2O5 3.10 ± 0.09 223.69 0.9997 difference between the hydrothermal synthesis methodology compared
10rGONb2O5 3.51 ± 0.22 197.70 0.9982 to our work was the utilization of ethanolamine reagent, otherwise, we
used only deionized water. Another study applied a simple mixing to
depends on the high availability of active sites in the semiconductors produce ZnO-RGO and it reached 97% degradation with 3 w/w % ZnO-
and their closer proximity or interaction with sp2 domains originating RGO only in 180 min of irradiation [72]. Towards the simplified
from rGO, this could indicate that the activity of the rGOZnO hetero­ impregnation method, they applied a 500 W halogen lamp and a 2.5×
structure was significantly higher than rGONb2O5. higher dosage that we use in the present work.
In Table 5, results involving rGO supported on zinc oxide and For the degradation of MB, the best result reported was for the
niobium oxide, published in the last five years are presented. From the catalyst obtained by chemical reduction, reaching >99% degradation of
literature study, we conclude that for the optimal degradation of organic the dye in 60 min, with UV and Vis lamps (not mentioning the potency
pollutants, the formulation of heterostructure like rGO-semiconductor is or λmax) [73]. This synthetic method uses polyvinyl alcohol, sodium
much more attractive to photocatalysis applications. In general, lower hydroxide, and sodium borohydride, to obtain a photocatalyst with 25%
activity of rGO catalysts supported on Nb2O5 can be seen than on ZnO. w/w rGO supported. Compared to the results of this work, we were able
The utilization of Nb2O5 in photocatalysis is uncommon due to its low to obtain 97% MB removal in 90 min, using 1% rGO and a 5 W UV-LED.
efficiency when used as a standalone material [12]. However, when In this case, the synthesis of 1rGOZnO was performed with less energetic
niobium is combined with substances like graphene, the resulting het­ reagents and conditions. In another study, MB degradation was inves­
erostructure shows greater promise and warrants further utilization tigated using RGO@ZnO prepared by sonication [74]. Here, a dye
[13,44]. The studies in Table 5 only involve ternary structures for cat­ degradation of 90.72% was achieved in only 2× longer time, with a
alysts based on Nb2O5. For example, MB degradation was slower and less 100× W higher Xe lamp for the 3× w/w amount of rGO amount, and 5×

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L.Z. Fogaça et al. Catalysis Communications 185 (2023) 106799

Table 5
Summary of photocatalytic degradation promoted by rGO supported on Nb2O5 and ZnO.
Photocatalysts rGO loading (w/w Synthesis method Experimental condition Ref.
%)
Catalyst Pollutant Light source Irradiation time Degradation
dosage (g L-1) (min) efficiency (%)

rGOZnO 1, 5 and 10 Hydrothermal 0.2 Methylene Blue 5 W UVA LED 90 97 with 1 wt present
work
ZnOrGO 3.6, 5.2 and 7.7 Hydrothermal 1 Methylene Blue 300 w Mercury- 60 99 with 7.7 wt [46]
Xenon lamp
ZnO-rGO 1, 2, 3 and 4. Simple mixing 0.5 Methylene Blue 500 W Halogen 180 97 with 3 wt [72]
lamp
ZnO-rGO 25 Chemical 0.1 Methylene Blue UV and Visible 60 > 99 [73]
Reduction lamp
RGO@ZnO 1, 2, 3 and 4 Sonochemical 1 Methylene Blue 300 W Xenon 180 90.72 with 3 wt [74]
lamp
qZnO-rGO 50, 33, 25 and 20 Solvothermal 0.12 Safranin O 100 W UV lamp 30 100 with 25 wt [21]
rGO-ZnO 0.01, 0.10, 0.50, Microwave 0.5 Rhodamine B Solar simulator 90 > 95 with 2.00 wt [75]
1.0 and 2.0
RGO-ZnO 2, 5 and 10 Deep Eutetic 0.33 Rhodamine B 500 W Xenon 150 100 with 5 wt [76]
Solvents lamp
rGO-ZnO 0.01 with ΔT (70, Sol-gel 0.01 Phenol Sunlight 20 86 at 70 ◦ C [77]
80 and 90 ◦ C)
rGONb2O5 1, 5 and 10 Hydrothermal 0.2 Methylene Blue 5 W UVA LED 300 75 with 1 wt present
work
TiO2/Nb2O5/RGO 10 Hydrothermal – Methylene Blue 300 W Xenon 240 97 [78]
lamp
Sr doped Nb2O5/ – Co-precipitation 0.025 Benzophenone- UV lamp 120 94.6 [45]
rGO 3
MoO3 doped 47.5, 45 and 42.5 Ultrasonication 0.04 Ciprofloxacin 300 W Tungsten 60 85.4 with 45 wt [41]
Nb2O5/RGO lamp

higher dosage. Methodology, Formal analysis. Camila Fabiano de Freitas: Writing -

Finally, it is important to highlight that in our work we explored the review & editing, Formal analysis. Thais Lazzarotto Braga: Validation.
use of the UV-LED mini-reactor developed in our laboratory with ach­ Fernando Alves da Silva: Writing - review & editing, Formal analysis.
ieved reliable and reproducible results. The UV-LED system had only 5 Monique de Souza: Data curation, Formal analysis. Mauro Luciano
W, and the reaction volume was limited to only 3.0 mL in real-time Baesso: Formal analysis, Resources. Wilker Caetano: Formal analysis,
monitoring, without the need to remove aliquots (in situ analysis). By Resources. Vagner Roberto Batistela: Supervision, Resources, Writing
employing a reaction volume lesser than reported by other authors, this – review & editing. Mara Heloisa Neves Olsen Scaliante: Project
research was able to minimize the consumption of reagents and generate administration, Resources, Writing – review & editing, Supervision,
less waste in comparison to the photocatalytic activity. Funding acquisition.

4. Conclusions Declaration of Competing Interest

An effective hydrothermal synthesis was reported to produce the The authors declare that they have no known competing financial
rGONb2O5 and rGOZnO photocatalysts. The GO, rGO, and nano­ interests or personal relationships that could have influenced the work
composites were successfully obtained, and the formation of the mate­ reported in this paper.
rial was confirmed by XRD, XPS, FTIR-ATR, Raman, TEM, PA, and PL
results. The TEM images demonstrated the interaction and formation of Data availability
nanocomposites despite the rGO amount and how it probably affects the
dispersibility of semiconductors on rGO sheets, which directly affects Data will be made available on request.
the growth and homogeneity of the nanocomposite.
Despite the rGO obtained not improving light absorption in the Acknowledgments
visible region, it was very efficient in the application with Nb2O5 and
ZnO with UV-LED, and under the same conditions as our previous work The authors would like to thank Higher Education Personnel
with rGOTiO2 photocatalysts. The rGO sheets affect the photoactivity of Improvement Coordination (CAPES), Brazil’s National Council for Sci­
zinc and niobium oxides as photocatalysts. There is a verifiable entific and Technological Development (CNPq), and Araucária State of
improvement in the rate constant of photodegradation of MB with 1% of Parana Research Foundation (Fundação Araucária) for financial support
rGO, whose photocatalysts present large homogeneity and dispersibility and the utilization of the Complex of Research Support Center of the
of the particles in rGO sheets. The 1rGONb2O5 showed three times faster State University of Maringá (COMCAP-UEM), the Laboratory of
kinetic than the pure Nb2O5, providing important improvement in the Adsorption and Ion Exchange of the State University of Maringá (LATI-
photocatalytic action of this semiconductor. The action of 1rGOZnO was UEM) for realization of XRD analysis, and to LAMAP-UTFPR for the
very similar to the ZnO, resulting in a faster photocatalyst to photo­ realization of N2-physisorption isotherms. Finally, we would like to
degrade MB. thank Professor PhD Richard Landers, from IFGW-UNICAMP, for the
realization of the XPS analysis.
CRediT authorship contribution statement
Appendix A. Supplementary data
Leonardo Zavilenski Fogaça: Conceptualization, Investigation,
Validation, Data curation, Writing – original draft, Visualization, Formal Supplementary data to this article can be found online at https://doi.
analysis. Jean César Marinozi Vicentini: Writing - review & editing, org/10.1016/j.catcom.2023.106799.

11
L.Z. Fogaça et al. Catalysis Communications 185 (2023) 106799

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