Materials Today Communications 37 (2023) 107012

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Materials Today Communications

journal homepage: www.elsevier.com/locate/mtcomm

Composite of iron phthalocyanine and reduced graphene oxide with low

temperature hydrothermally grown Ti3C2Tx Mxene for ORR
catalytic application
Qihui Ding a, b, Chenshan Ji a, b, Qian Shan a, b, Chunxia Yang a, b, Wei Wu a, b, *
a
College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, PR China
b
Research Center of the Ministry of Education for High Gravity Engineering and Technology, Beijing University of Chemical Technology, Beijing 100029, PR China

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

Keywords: In this paper, Ti3C2Tx MXene was successfully prepared by a mild and environment-friendly low-temperature
Ti3C2Tx MXene hydrothermal method. On this basis, the compsites FePc-M-rGO consisting of iron phthalocyanine (FePc),
Low-temperature hydrothermal method Ti3C2Tx MXene and reduced graphene oxide (rGO) were prepared through simple mixing and used as catalysts
FePc-M-rGO
for oxygen reduction reaction (ORR). The materials were characterized by SEM, XRD and other methods. The
ORR catalysis
effects of raw material ratio, hydrochloric acid concentration, reaction temperature and reaction time on the
properties of Ti3C2Tx were studied in detail. Compared with hydrofluoric acid (HF) etching method, the Ti3C2Tx
prepared by low-temperature hydrothermal method has larger layer spacing, more complete crystal structure,
larger specific surface area and better conductivity. The influences of different ratios of each component of FePc-
M-rGO on the ORR catalytic performances were investigated. Mainly attributed to the improvement of self
stacking and uniform adhesion of FePc between Ti3C2Tx layer and graphene nanosheets, the optimized composite
material has better ORR activity than commercially available Pt-C catalysts and has good application prospects.
This work provides a new approach for the rapid and effective preparation of Ti3C2Tx Mxene, and provides new
ideas for the design of non-noble metal catalysts for ORR.

1. Introduction
MXene is a two-dimensional layered material, including two-
dimensional transition metal carbides, nitrides and carbonitrides. It is
formed by removing the "A" layer from metal carbide or nitride (MAX
phase) with alternately arranging n + 1 "M" layers and n "X" layers and
rich surface functional groups, such as -F, -OH, -O or -Cl (marked as Tx)
[1,2]. In many different configurations of MXene, Ti-based MXene,
represented by Ti3C2Tx, has attracted wide attention due to its high
conductivity, good stability, good surface hydrophilicity and large spe­
cific surface area [3–5]. In order to obtain Ti3C2Tx MXene, the Ti-Al
bond and C-Al bond with weak force in Ti3AlC2 are destroyed to sepa­
rate Al [6]. The common preparation methods include HF etching
method, in-situ HF etching method, molten salt etching method, alkali
etching method and hydrothermal method. HF etching method and
in-situ HF etching method can be carried out at room temperature, but
dangerous HF is used or synthesized during the experiment, and the
crystal structure of MXene is easily damaged due to long reaction time
[7,8]. Molten salt etching method is a fluorine-free method with high
safety, but the method requires very high temperature and huge energy
consumption, and the MXene prepared by this method shows
accordion-like structure, which is not suitable for the formation of
nanosheets [9,10]. Although alkali etchant, such as NaOH, can exfoliate
off the Al layer of MAX phase, higher temperature and higher concen­
tration of NaOH are needed to reduce the oxide and hydroxide of Al
produced in the reaction and ensure the extraction of Al layer [11,12].
There are relatively few studies on the hydrothermal etching method of
Ti3C2Tx MXene. The hydrothermal method can react in a closed envi­
ronment with short reaction time and high yield [13]. It is also suitable
for the preparation of other MXenes such as Mo2C, and has the potential
for large-scale application [14,15]. Wang et al.[16] employed a simple
one-pot hydrothermal method with etching agent (NH4F) to prepare
Ti3C2Tx, which showed higher specific capacitance and lower resistance.
Peng et al.[17] used NaBF4 and HCl as etchants to obtain Ti3C2Tx by

* Correspondence to: College of Chemical Engineering and Research Center of the Ministry of Education for High Gravity Engineering and Technology, Beijing
University of Chemical Technology, Beijing 100029, PR China.
E-mail address: wuwei@mail.buct.edu.cn (W. Wu).

https://doi.org/10.1016/j.mtcomm.2023.107012
Received 4 May 2023; Received in revised form 25 August 2023; Accepted 30 August 2023
Available online 1 September 2023
2352-4928/© 2023 Published by Elsevier Ltd.
Q. Ding et al.
Fig. 1. Schematic diagram of the preparation process of FePc-M-rGO composites.
hydrothermal method. Compared with the Ti3C2Tx obtained by HF
etching method, it has higher lattice parameters, larger layer spacing
and specific surface area, and shows good electrochemical perfor­
mances. However, when the reaction temperature is too high, MXene is
easy to be oxidized and the reaction energy consumption is high [18,19].
Therefore, it is necessary to develop a mild low-temperature hydro­
thermal method to prepare Ti3C2Tx MXene.
The oxygen reduction reaction (ORR) plays an important role in the
field of electrocatalysis, especially in the cathode of fuel cells and air
metal cells [20,21]. However, ORR has multiple and slow electron
transfer steps, resulting in low mass transfer efficiency and slow kinetic
speed, which limits its large-scale application [22]. It is necessary to find
suitable ORR catalysts with high stability and activity to achieve rapid
charge transfer and mass transfer [23]. The combination of carrier with
large specific surface area and materials with high ORR catalytic activity
is a strategy to prepare excellent ORR catalysts. Ti3C2Tx MXene has a
layered structure and a large specific surface area, the Ti layer has
durability in oxidizing and acidic environments, while the C layer is an
effective electron conduction channel [24,25]. When Ti3C2Tx MXene
with good conductivity is combined with other highly active but poor
conductivity materials, it can promote effective-electron charge transfer
at the electrode electrolyte interface and is considered a stable carrier
for active particles in ORR catalysts [26]. However, due to the interac­
tion of van der Waals force and hydrogen bond between Ti3C2Tx nano­
sheets, it has the problems of self stacking and agglomeration, which
makes it unable to show the best performance [27]. Reduced graphene
oxide (rGO) nanosheets have large specific surface area, high carrier
mobility and certain chemical stability [28]. Introducing rGO as a spacer
into MXene for intercalation and building a more open layered structure
is an effective strategy to reduce the stacking of nanosheets and provide
more space for electrode materials to contact with electrolyte [29–31].
Precious metal catalysts represented by platinum are common ma­
terials with high ORR catalytic activity, but also have the disadvantages
of high cost, few resources and poor stability [32]. Among many
low-cost catalysts with high ORR catalytic activity, metal phthalocya­
nine (MPc), as one of the metal nitrogen carbon (M-N-C) derivative
catalysts, has a large and fully conjugated aromatic skeleton and has
attracted the attention of scientists [33,34]. In addition to its excellent
high thermal stability, it usually shows unique optical and electro­
chemical characteristics [35], which can be used as a highly efficient
catalyst to improve electron conduction [36,37]. The electrocatalytic
performance of MPc is mainly determined by the central metal atom,
whose activity usually increases in the following order: Cu, Ni, Co and Fe
[38]. Iron phthalocyanine (FePc) has excellent ORR performance, sim­
ple synthesis method and low cost, and is considered to be one of the
most promising Pt-free ORR catalysts [39]. In FePc, there are abundant
free electrons in the FeN4 macrocycle, and O2 is easier to be adsorbed
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Materials Today Communications 37 (2023) 107012
and reduced at the FeN4 active site [40,41]. MXene-rGO can be used as
the carrier of FePc nanoparticles to make them uniformly dispersed and
overcome the poor conductivity of FePc [42–44].
In this work, Ti3C2Tx MXene was prepared by low-temperature hy­
drothermal method with HCl and LiF as etchant. The effects of raw
material ratio, hydrochloric acid concentration, reaction temperature
and reaction time on the preparation of Ti3C2Tx MXene were studied in
detail. FePc-M-rGO composites which can be used as ORR catalysts were
prepared by simple stirring method. The effects of different ratios of
each component on the catalytic performances of ORR were studied.
2. Experimental section
2.1. Materials
Titanium aluminum carbide (Ti3AlC2) and lithium fluoride (LiF)
were purchased from Macklin Company. Graphite was purchased from
Tianjin Fuchen Chemical Reagent Factory. Hydrochloric acid (HCl),
sulfuric acid (H2SO4) and hydrofluoric acid (HF) were purchased from
Beijing Tongguang Fine Chemicals Company. Tetramethylammonium
hydroxide (TMAOH) was purchased from Nantong Huanyu Chemical
Co.,Ltd. Ascorbic acid (Vc), sodium nitrate (NaNO3), potassium per­
manganate (KMnO4) and potassium hydroxide (KOH) were purchased
from Beijing Chemical Works. Ethanol (EtOH), isopropanol and N,N-
dimethylformamide (DMF) were purchased from Tianjin Zhiyuan
Chemical Reagent Co.,Ltd. All chemicals were directly used without
purification.
2.2. Synthesis
2.2.1. Synthesis of Ti3C2Tx MXene by low-temperature hydrothermal
method
A certain amount of LiF was put into hydrochloric acid solution of
different concentrations (3, 6, 9, 12 M), and then Ti3AlC2 powder (the
mass ratio of Ti3AlC2 to LiF is 1:0.75, 1:1, 1:1.25, and 1:1.5) was slowly
added into it. After stirring for 20 min, the mixed solution was put into a
polytetrafluoroethylene lined autoclave to react at different tempera­
tures (90, 100, 110, 120 ◦ C) for different hours (6, 12, 18, 24 h). Table S1
shows the synthesis parameters of MXene under different conditions.
The obtained dispersion was centrifugally washed with water until close
to neutral, and the resulting precipitate was filtered and dried to obtain
multilayer Ti3C2Tx nanosheets. In order to increase the interlayer
spacing, it was dissolved in deionized water, sonicated in N2 for one
hour and centrifuged. The supernatant was freeze-dried in vacuum to
obtain a few layers of Ti3C2Tx nanosheets.
Q. Ding et al. Materials Today Communications 37 (2023) 107012

centrifugal washing, suction filtration, and drying. Dissolve multi-layer

Ti3C2Tx powder in water and add 1 g of tetramethylammonium hy­
droxide (TMAOH) to stir for 18 h. The resulting solution is sonicated and

Fig. 2. XRD patterns of Ti3C2Tx prepared with different MAX/LiF mass ratio.

2.2.2. Synthesis of Ti3C2Tx MXene by HF etching method

1 g of Ti3AlC2 powder was added to 20 mL of 40% HF solution and
stirred for 18 h. Multilayer Ti3C2Tx powder was obtained through Fig. 5. XRD patterns of Ti3C2Tx prepared at different reaction times.

Fig. 3. (a)XRD patterns and (b)Raman patterns of Ti3C2Tx prepared with different hydrochloric acid concentration.

Fig. 4. (a)XRD patterns and (b)Raman patterns of Ti3C2Tx prepared at different reaction temperature.

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Q. Ding et al.
Fig. 6. (a)SEM image of Ti3C2Tx prepared by HF-etching, (b)XRD, (c)BET and (d)EIS of Ti3C2Tx prepared by two different methods.
centrifuged at 3000 rpm for 10 min. The precipitate is then vacuum
freeze-dried to obtain a few layers of Ti3C2Tx nanosheets.
2.2.3. Synthesis of FePc-M-rGO composites
FePc-M-rGO composites were prepared as Fig. 1. Graphene oxide
(GO) was synthesized by the modified Hummers method [45]. Ti3C2Tx
MXene prepared by low-temperature hydrothermal method was syn­
thesized under the conditions of MAX/LiF mass ratio of 1:1.25, hydro­
chloric acid concentration of 6 M, reaction temperature of 100 ◦ C, and
reaction time of 12 h. Ti3C2Tx MXene and FePc were dispersed in DMF
by ultrasound, stirred for 20 h, filtered and washed with DMF and EtOH.
FePc-M powder was obtained by vacuum drying at 60 ◦ C. GO was dis­
solved in DMF, ascorbic acid was added and magnetically stirred at
70 ◦ C for 2 h to obtain reduced oxidized graphene (rGO). FePc-M powder
was added to the above solution and ultrasonically treated for 6 h.
FePc-M-rGO powder was obtained after centrifugation, washing and
freeze-drying.
2.3. Characterizations
The structure of samples was characterized by X-ray diffraction
(XRD) being collected from an Ultima IV X-ray diffractometer with a
scan rate of 10◦ ⋅min− 1. The morphology of samples was characterized by
scanning electron microscope (SEM, Hitachi S-4700), transmission
electron microscope (TEM, Hitachi HT-7700). The influences of
different preparation conditions on the structure of Ti3C2Tx were studied
by Raman spectra (in Via Renishaw). The sample surface functional
groups in 400–4000 cm− 1 were measured by Fourier transform infrared
(FT-IR) spectroscopy (TENSOR II). The bonding modes of each element
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Materials Today Communications 37 (2023) 107012
in the samples were characterized by X-ray photoelectron spectroscopy
(XPS, ESCALAB 250Xi). The specific surface area of the samples was
analyzed by an automatic specific surface area analyzer (Quanta-chrome
Autosorb-IQ).
2.4. Electrochemical measurements
Electrochemical measurements were performed using a glassy car­
bon rotating ring disk electrode (RRDE, Taizhou Yinhe Instrument
Factory) with a diameter of 3 mm, connected to a CHI660e electro­
chemical workstation in a standard three-electrode cell with a platinum
wire as the counter electrode and Ag/AgCl electrode as the reference
electrode. Electrolytes used in these tests were 0.1 M KOH. The catalyst
ink was prepared by dispersing 2 mg catalyst in 10 μL of Nafion (5 wt%
from Aldrich), 800 μL of deionized water and 200 μL of isopropanol, and
then dispersed for 30 min in an ultrasonic bath. 5 μL of catalyst ink was
evenly coated on the glassy carbon electrode to prepare the working
electrode. Electrochemical measurements were performed at room
temperature. All potential values are converted to RHE values for easy
comparison. Electrochemical measurements include cyclic voltammetry
(CV), linear sweep voltammetry (LSV) and electrochemical impedance
spectroscopy (EIS). The scanning rate of CV is 50 mV/s and the scanning
rate of LSV is 5 mV/s. The experimental and computational details of
these methods are provided in the "Supporting Information".
Q. Ding et al. Materials Today Communications 37 (2023) 107012

Fig. 7. SEM image (a), TEM image (b), XRD patterns (c) and BET (d) of FePc-M-rGO.

Fig. 8. XPS spectra of FePc-M-rGO: (a) full spectra, (b) N 1 s spectra, (c) Fe 2p.

3. Results and discussion
3.1. Effects of different preparation condition on Ti3C2Tx MXene
In order to obtain better conditions for preparing Ti3C2Tx MXene, the
influences of the mass ratio of MAX/LiF, the concentration of hydro­
chloric acid, reaction temperature and reaction time were studied.
3.1.1. Effects of different MAX/LiF mass ratios
Firstly, the Ti3C2Tx MXene prepared at different MAX/LiF mass ratios
(1:0.75, 1:1, 1:1.25 and 1:1.5) are characterized. Other experimental
conditions are hydrochloric acid concentration of 6 M, reaction tem­
perature of 100 ◦ C, and reaction time of 12 h. When the MAX/LiF mass
ratio is below 1:1, the MAX phase is partially etched, and Ti3C2Tx is still
a large structure without obvious layering, which means that the
amount of etchant added is not enough to completely etch Al (Fig. S1(a,
b, e, f)). When the mass ratio of MAX/LiF is 1:1.25, the obtained Ti3C2Tx
has obvious nanosheet structure and clear edges (Fig. S1(c, g)). When
more LiF is added, Ti3C2Tx nanosheets are folded and stacked, and the
layered structure is obviously damaged (Fig. S1(d, h)). Fig. 2 is the XRD
patterns of Ti3C2Tx prepared with different MAX/LiF mass ratios. After
hydrothermal reaction, the characteristic peak of Al in Ti3AlC2 at 39◦
disappears, the peak at 9.5◦ shifts to the left and becomes lower, indi­
cating that the interlayer spacing of the product Ti3C2Tx becomes larger
[16]. Meanwhile, a series of new characteristic peaks appear in the
product. The characteristic peaks near 25◦ , 51◦ and 58◦ correspond to

5
Q. Ding et al.
Fig. 9. EIS (a), CV (b) and LSV (c) curves of four catalysts compounded according to different mass ratio (scanning rate of CV: 50 mV/s, scanning rate of LSV: 5 mV/s,
same as below).
the by-product AlF3 [46,47]. The reason may be that LiF produces some
fluoride salts that cannot be thoroughly washed, which affect the purity
of Ti3C2Tx. It can be seen from the comparison that when the mass ratio
of MAX/LiF is 1:1.25, the characteristic peaks of by-products are the
lowest, and the (002) peak of product Ti3C2Tx is the highest.
3.1.2. Effects of different concentration of hydrochloric acid
Fig. S2 shows the morphology of Ti3C2Tx prepared with different
concentration of hydrochloric acid. Other experimental conditions are
MAX/LiF mass ratio of 1:1.25, reaction temperature of 100 ◦ C, and re­
action time of 12 h. When the concentration of hydrochloric acid is 3 M
(Fig. S2(a, e)), the surface of blocky MAX phase becomes soft, and
layered structure appears at the edge, but most of the MAX phase has not
been etched. When the concentration is 6 M (Fig. S2(b, f)), a relatively
smooth large-area sheet structure appears. When the concentration is
further increased (Fig. S2(c, d, g, h)), the size of Ti3C2Tx nanosheets is
uneven and turns into fragments, indicating that Ti3C2Tx nanosheets are
excessively etched.
From the XRD patterns in Fig. 3(a), it can be seen that when the
concentration of hydrochloric acid is 3 M, the characteristic peak of
Ti3AlC2 at 39◦ still exists, there is only partial etching effect. When the
concentration increases to 6 M, the characteristic peak of Al basically
disappears, and the (002) peak shifts to the left and becomes stronger,
indicating that the layer spacing is further enlarged. When the concen­
tration reaches 12 M, the (002) peak almost disappears, indicating that
the structure of Ti3C2Tx nanosheets have been destroyed at this time.
Fig. 3(b) shows the Raman spectra of Ti3C2Tx prepared at different hy­
drochloric acid concentration. When the concentration of hydrochloric
acid is 3 M, the Raman peaks of Al atoms at 185 and 272 cm− 1 disap­
pear, indicating that the amount of Al has greatly decreased and may not
have been detected. The peaks of Carbon atoms at 633 and 665 cm− 1
merge and move down to 580 cm− 1, which is related to the vibration of
Carbon atom in Ti3C2Tx [48]. The peaks at 200, 387 and 1572 cm− 1
correspond to the characteristic absorption Raman peaks of Ti3C2Tx, of
which the peak at 200 cm− 1 is the strongest, indicating that it is the
Raman vibration mode of anatase phase, and the symmetry is Eg [49].
When the concentration of hydrochloric acid is 6 M, the Raman peak of
Ti3C2Tx is the strongest, indicating that the purity of Ti3C2Tx is the
highest at this time.
3.1.3. Effects of different reaction temperatures
Fig. S3 shows the SEM and TEM images of Ti3C2Tx prepared at
different reaction temperatures. Other experimental conditions are
MAX/LiF mass ratio of 1:1.25, hydrochloric acid concentration of 6 M
and reaction time of 12 h. Ti3C2Tx prepared at 90 ◦ C (Fig. S3(a, e)) is still
blocky as a whole, and the layered trend at the edge is gradually
obvious. When the reaction temperature is 100 ◦ C (Fig. S3(b, f)), the
nanosheet with smooth surface appears, and the size is above micro­
meter level. When the reaction temperature is continuing to rise to
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Materials Today Communications 37 (2023) 107012
110 ◦ C or 120 ◦ C (Fig. S3(c, d, g, h)), Ti3C2Tx nanosheets produce a
certain degree of wrinkles and accumulation, and some nanoparticles
appear on the surface, indicating that the Ti3C2Tx might be oxidized
under the high hydrothermal temperature.
It can be seen from the XRD pattern in Fig. 4(a) that after etching, the
strongest Al characteristic peak (104) peak in the MAX phase disappears,
and the characteristic (002) peak of Ti3C2Tx moves to a low angle,
indicating that the Al atomic layer in the MAX phase has been success­
fully etched. As the reaction temperature increases, the degree of
oxidation of the samples increases, and the intensity of the (002) peak
decreases [50] until the (002) peak disappears at 120 ◦ C. In the Raman
spectrum of Fig. 4(b), the peak at 197 cm− 1 corresponds to the out of
plane vibration of A1g (Ti, C and O) and Ti3C2Tx. The wide peak near
370 cm− 1 shows the in-plane vibration of surface group (Tx) interacting
with Ti atoms and the peak near 600 cm− 1 is related to the vibration of
Carbon atoms [51]. It can be seen that when the reaction temperature is
100 ◦ C, the vibration of Ti and C atoms is stronger, in the mean time, the
crystal form of Ti3C2Tx is more complete, the layer spacing is larger,
which is more conducive to electron transfer, and the sample purity is
the highest.
3.1.4. Effects of different reaction time
Fig. 5 shows the XRD of Ti3C2Tx prepared at different reaction times.
Other experimental conditions are MAX/LiF mass ratio of 1:1.25, hy­
drochloric acid concentration of 6 M and reaction temperature of
100 ◦ C. Compared with the (002) peak of Ti3C2Tx, when the reaction
time increases from 6 h to 12 h, the peak intensity of Ti3C2Tx becomes
stronger and the degree of crystallization becomes higher. Further
increasing the reaction time to 18 h and 24 h, the crystallinity of Ti3C2Tx
becomes lower and the impurities appear. Fig. S4 shows the morphology
of Ti3C2Tx prepared at different reaction time. The relatively short re­
action time can only partially etch the MAX phase (Fig. S4(a, e)). When
the reaction time reaches 12 h, some wrinkles appear on the surface of
Ti3C2Tx nanosheet, and the size of the prepared nanosheet is large
(Fig. S4(b, f)). In Fig. S4(c, d, g, h), further increasing the reaction time,
the Ti3C2Tx nanosheets were over etched, and the large nanosheets
turned into small slices, and stacked to a certain extent.
3.2. Comparison with samples prepared by HF etching method
Fig. 6(a) is the SEM image of Ti3C2Tx prepared by HF etching
method. It can be seen that after HF etching, Ti3C2Tx is in accordion
structure with certain layer spacing but still remains large block. As
shown in Fig. 6(b), the (002) peak of Ti3C2Tx obtained by hydrothermal
method is at 6.4◦ , the corresponding layer spacing is 1.38 nm, and the
(002) peak of Ti3C2Tx obtained by HF etching method is at 7.04◦ , the
corresponding layer spacing is 1.25 nm, the (002) peak shifts to the left,
and the peak intensity is relatively weak. In addition, the Ti3C2Tx pre­
pared by hydrothermal method has few impurity peaksshowing good
Q. Ding et al.
Fig. 10. CV (a) and LSV (b) curves of different catalysts, (c)LSV curves of FePc-M-rGO at different rotating speeds, (d)K-L curves at different electrode potentials and
(e)LSV curve of FePc-M-rGO after 1000 cycles.
stability. As shown in Fig. 6(c), the specific surface area of Ti3C2Tx
nanosheets obtained by HF etching is 13.07 m2/g, while that of Ti3C2Tx
nanosheets obtained by hydrothermal etching is 50.62 m2/g. A larger
specific surface area and wider interlayer spacing are conducive to the
uniform distribution of active sites in Ti3C2Tx, which can synchronously
improve electron/ion transfer kinetics and greatly enhance electro­
chemical performance [52,53]. Fig. 6(d) is the electrochemical
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Materials Today Communications 37 (2023) 107012
impedance spectrum (EIS) of the samples. It can be seen that the slope of
the straight line is large, and the diameter of the semicircular diagram of
Ti3C2Tx MXene prepared by hydrothermal method is smaller. It indicates
that the material has smaller charge transfer impedance, faster electron
transfer rate and better conductivity, which lays a foundation for its
application in ORR [54,55]. Compared with the common HF etching
method, the low-temperature hydrothermal method used in this article
Q. Ding et al.
Fig. 11. (a) CV curves and (b) LSV curves of FePc-M-rGO and FePc-M-rGO-HF.
Fig. 12. Diagram of the structure of FePc-MXene and FePc-M-rGO.
has a shorter reaction time and avoids the direct use of dangerous HF in
a closed environment [17,56]. The hydrothermal reaction is relatively
uniform, and the water used as a solvent is in a subcritical state, which
has a certain intercalation effect and can spontaneously insert into the
interlayer of MXene [57]. At this point, Ti3C2Tx MXene nanosheets with
high exfoliating degree, thin layers, complete structure, and larger size
can be obtained [58,59]. Meanwhile, the low-temperature hydrother­
mal method avoids the oxidation of MXene at excessively high tem­
peratures, reduces energy consumption, and provides a new and
effective method for the simple preparation of Ti3C2Tx MXene [60].
3.3. Characterizations of FePc-M-rGO
The morphology and structure of the synthesized FePc-M-rGO were
characterized. Fig. 7(a, b) shows that the composite material is in the
shape of a thin sheet. The bent and folded rGO is inserted between the
layers of Ti3C2Tx, while the granular FePc nanoparticles are dispersed
between the layers of Ti3C2Tx and rGO, with a diameter of about 10 nm
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Materials Today Communications 37 (2023) 107012
[61]. As shown in Fig. 7(c), the characteristic diffraction peaks of FePc
(27.18◦ ) and Ti3C2Tx appear, indicating that FePc nanoparticles are
successfully loaded on Ti3C2Tx and rGO. The characteristic peaks of rGO
are not obvious because of its small crystallinity. In addition, when
Ti3C2Tx is compounded with rGO, the (002) peak shifts from 6.62◦ to
6.32◦ , indicating that the stacking degree of Ti3C2Tx becomes smaller
and the layer spacing becomes larger during the composite process. As
shown in Fig. 7(d), the original Ti3C2Tx MXene and the FePc-M-rGO
composites show Type IV isotherms with obvious hysteresis loops,
which are caused by the mesoporous voids between the nanosheets. The
specific surface area of FePc-M-rGO is 111.36 m2/g, which indicates that
the specific surface area of the composites increase after being com­
pounded by FePc and rGO.
XPS can further reveal the element composition and valence state of
FePc-M-rGO. It can be seen that the elements of Fe, Ti, C, N and F exist in
FePc-M-rGO in Fig. 8(a), where the elements Fe and N come from π
conjugated FePc molecules. The peaks of 398.28 eV and 400.27 eV
observed in the N 1 s XPS spectrum of the sample in Fig. 8(b) correspond
Q. Ding et al.
Fig. 13. Schematic diagram of ORR reaction mechanism.
to the pyrrole N structure (Fe-Nx) and graphite N structure of meso­
porous metal Fe in FePc [62]. As shown in Fig. 8(c), the peaks at 710 eV
and 723 eV correspond to Fe2+, and the peaks at 712 eV and 725 eV
correspond to Fe3+. This is because the spin orbit coupling leads to the
2p3/2 and 2p1/2 transition splitting [63].
3.4. ORR performances of FePc-M-rGO
It can be seen from Fig. 9(a) that after the combination of MXene
with FePc and rGO, the slope of the linear part in the EIS diagram in­
creases and the diffusion resistance decreases. The charge transfer
impedance (Rct) of MXene is reduced from 14.37 Ω to 5.37 Ω after being
compounded, the electron transfer rate is accelerated and the conduc­
tivity is enhanced, which strongly proves that MXene can be used as a
good conductive substrate loading electrocatalysts. In order to explore
the different effects of FePc, Ti3C2Tx MXene and rGO on improving the
ORR activity, Fig. 9(b, c) show the ORR performances of the FePc-M-rGO
with different ratio of each component. It can be seen that when the
addition of FePc increased, the oxygen reduction peak potential and
limiting current density of FePc-M-rGO211 were significantly higher than
those of other catalysts, and the ORR activity increased. In addition,
FePc-M-rGO111 catalyst also shows good ORR activity. This is because
rGO and MXene play a synergistic role in inhibiting accumulation and
aggregation, and increase the dispersion of FeN4 active substances in
FePc.
In order to evaluate its ORR electrocatalytic performance, FePc-M-
rGO211 was compared with commercial Pt-C catalyst. As shown in
Fig. 10(a), pure MXene has almost no ORR activity due to lack of active
sites, and the ORR activities of FePc and rGO materials are low. The
oxygen reduction peaks of FePc, MXene and rGO appear at 0.79 V,
0.54 V and 0.74 V respectively, while that of FePc-M-rGO is 0.94 V,
indicating that ORR catalytic performance of FePc-M-rGO was signifi­
cantly improved. Fig. 10(b) shows the LSV curves of FePc-M-rGO211 at
1600 rpm. It can be seen that the starting voltage of MXene, rGO and
FePc-M-rGO is gradually increasing, and the limiting current density is
also gradually increasing. The limiting current density and half-wave
voltage of FePc-M-rGO are slightly better than Pt-C. It can be seen
from Fig. 10(c, d) that JL increases with the increase of speed, and this
reaction is the first-order reaction kinetics of dissolved oxygen concen­
tration. The electron transfer number of ORR reaction catalyzed by
FePc-M-rGO is 3.94, following the 4e- oxygen reduction process. O2 is
mainly reduced to OH-, indicating the high efficiency[64]. In addition,
cyclic stability testing was conducted on FePc-M-rGO, as shown in
Fig. 10(e), after 1000 cycles, the E1/2 of FePc-M-rGO is 0.86 mV, indi­
cating a certain long-term stability.
9
Materials Today Communications 37 (2023) 107012
In order to further test the differences in practical applications of
Ti3C2Tx prepared by the two methods, two types of Ti3C2Tx prepared by
low-temperature hydrothermal method and HF etching method were
used as raw materials to prepare FePc-M-rGO composite materials, and
their catalytic performance of oxygen reduction reaction was tested, as
shown in Fig. 11. The CV curves show that the oxygen reduction peak of
FePc-M-rGO-HF appears at 0.84 V, while the oxygen reduction peak of
FePc-M-rGO appears at 0.94 V, The LSV curves show that the JL of FePc-
M-rGO-HF is 4.42 mA/cm2, while the JL of FePc-M-rGO is 5.01 mA/cm2.
The high oxygen reduction peak potential and JL indicate that FePc-M-
rGO has better oxygen reduction performance, which is due to the
larger, thinner, and more complete crystal structure of Ti3C2Tx prepared
by hydrothermal method, which improves its electronic conductivity
and activity, and improves its electrochemical performance [65].
Fig. 12 is a diagram of the structure of FePc-M-rGO. FePc and rGO
have similar benzene ring structures, and hydrogen bonding or van der
Waals force interactions occur between them, which facilitates the for­
mation of FeN4 sites [66,67]. At the same time, there is an interaction
between the functional groups of MXene and rGO, which prevents the
accumulation of MXenes [68], while the uniform adhesion of FePc be­
tween layers prevents the aggregation of FePc [69]. In addition, the
self-supporting structure and good conductivity of rGO also play an
important role [70,71].
Fig. 13 is a schematic diagram of ORR reaction mechanism. The ORR
activity of FePc-M-rGO catalyst is significantly enhanced, which may be
due to the combination of abundant "-O" and "-OH" functional groups on
the surface of MXene with part of Fe(II) in FeN4, weakening the Fe-N
bond. The lower local electron density and higher spin state of Fe(II)
center greatly promote the electron transfer, and O2 is easier to be
adsorbed and reduced at the active site of FeN4 [72]. On the other hand,
the coupling of rGO and FeN4 accelerates the electron transfer between
the active site FeN4 and the reactant/intermediate, thus improving the
ORR performances [73].
4. Conclusions
In this paper, Ti3C2Tx MXene was successfully prepared by low-
temperature hydrothermal method using LiF and HCl as etchants. This
method has low energy consumption, short reaction time, avoids direct
use of HF in a closed environment, and makes MXene difficult to be
oxidized. Compared with HF etching method, Ti3C2Tx prepared by low-
temperature hydrothermal method under optimized process conditions
has larger layer spacing, more complete crystal structure, larger specific
surface area and better conductivity. On this basis, Ti3C2Tx MXene was
composed with FePc and reduced graphene oxide, and a variety of FePc-
M-rGO composites were obtained by changing their mass ratios. The
addition of rGO may increase the specific surface area of the complex
and inhibit the stacking of MXene. FePc with high ORR catalytic activity
was evenly distributed between MXene and rGO layers, promoting the
adsorption of O2 and the formation of active sites. FePc-M-rGO211
showed better ORR activity than commercial Pt-C catalyst and potential
for large-scale industrial preparation. This work provides new insights
into the design of efficient non-noble metal catalysts for oxygen reduc­
tion reactions.
CRediT authorship contribution statement
All data reported in this article were obtained from our experiments
and have not been published anywhere. All authors agree to publish this
paper in Materials Today Communications.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Q. Ding et al.
Data Availability
The data that has been used is confidential.
Acknowledgment
This work was supported by the National Natural Science Foundation
of China (No. 21676023).
Supporting information
The synthesis parameters of MXene under different conditions. The
experimental and computational details of these method; SEM images
and TEM images of Ti3C2Tx Mxene prepared by low-temperature hy­
drothermal method under different process conditions.
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.mtcomm.2023.107012.
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