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N‑Doping Holey Graphene TiO2−Pt Composite as Efficient

Electrocatalyst for Methanol Oxidation
Rongli Cui, Shuaichao Liu, Xihong Guo, Huan Huang, Jiahao Wang, Bing Liu, Ying Li, Dangui Zhao,
Jinquan Dong, and Baoyun Sun*
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ABSTRACT: The nitrogen-doped holey graphene oxide/TiO2

(TiO2−NHGO) composite is synthesized as catalyst support for
Downloaded via KAROLINSKA INST on February 29, 2020 at 05:29:06 (UTC).

the Pt catalyst. The resulting catalyst, Pt−TiO2−rNHGO, shows

higher activity and stability for methanol electrooxidation than the
Pt−rGO, Pt−rHGO, and Pt−rNHGO catalysts. The enhancement
is because of the combinatory effect of nanoholes in the graphene
plane which provide more active sites and efficient mass transport,
well-distributed N-doping, and the uniform distribution of TiO2
NPs on NHGO nanosheets which facilitate to form more
uniformly dispersed Pt NPs. In addition, the strong interactions
among Pt, TiO2, and NHGO also contribute to enhance the
performance of catalyst for methanol oxidation.
KEYWORDS: nanoholes, N-doping graphene, Pt−TiO2, enhanced electrocatalysis, direct methanol fuel cells

1. INTRODUCTION doped N element can bring anchoring sites which make Pt

Direct methanol fuel cells (DMFCs) have received huge NPs better dispersed on graphene nanosheets. Furthermore, it
attention acting as promising renewable energy because of has been found that graphene embedded with N atoms greatly
enhanced the connections between Pt NPs and graphene,
their advantages of higher energy density, lower operating
which contributes to improve catalyst activity and stability.
temperature, low pollution rate, and so on.1−5 Until now, the
Nevertheless, the N-doping does not solve the π−π stacking
catalysts based on Pt nanomaterials are still the most
between graphene layers that lead to the aggregation and active
investigated catalysts for DMFCs because of their outstanding
point shielding of the loading catalyst, which would restrict the
electrocatalytic performance.4,6,7 However, the intrinsic draw-
application of graphene as catalyst support. Various strategies
backs of Pt-based catalysts, for instance, high cost, low stability,
have been put forward to solve this problem; for example, 3D
and poisoning effect, have to be resolved for the commerci-
graphene23,36 has been constructed to reduce the π−π stacking
alization of DMFCs.8−11 The catalyst poisoning is initiated by
between graphene layers.
the strong interaction of intermediate species such as CO with
To solve the corrosion shortcomings of carbon supports,
Pt nanoparticles (NPs) active sites and so decreased the
transition metal oxides, e.g., TiO2,37−39 MoOx,40 SnO2,22,41,42
catalyst activity.8,10,12 Therefore, the current research on Pt-
WO3,43 and CeO2,44,45 have been applied as substitutes for
based catalysts is focusing on how to increase their activity and
carbon supports to heighten the catalytic activity and stability
stability.
of catalysts for methanol oxidation. Among them, TiO2 is of
The past research indicated that the catalyst support plays an
particular interest because of its good corrosion resistance, low
important role in improving the catalyst performances.13,14
price, and strong interactions with Pt.46,47 However, the poor
Among multitudinous supporting materials, carbon materials
conductivity restricts its actual application in DMFCs.
(porous carbon,15−18 carbon nanotubes, 19−22 and gra- Fortunately, combining TiO2 and conducting carbon materials
phene23−28) have been extensively applied as support for Pt has been proved to be a great means for overcoming its
catalysts because of their porous structure, large surface area,
and superior electrical conductivity. However, the corrosion of
carbon support,29−31 the weak interaction with Pt,32 and π−π Received: December 5, 2019
stacking between graphene layers33 resulted in the loss and Accepted: February 19, 2020
agglomeration of Pt and hence reduced the stability of Published: February 19, 2020
DMFCs. Recently, N-doped graphene has been considered
novel support for catalyst because of its superior carrier
mobility and large specific surface area.24,34,35 Besides, the

© XXXX American Chemical Society https://dx.doi.org/10.1021/acsaem.9b02364

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Figure 1. Synthetic process of the Pt−TiO2−rNHGO composite.
disadvantage and so improve the performance of the
electrocatalyst.37,38,48 For example, Xia48 reported a Pt−
TiO2−rGO composite exhibited significantly improved cata-
lytic performance for methanol oxidation than Pt−rGO. Qin37
described the facile synthesis of the Pt/TiO2−C catalyst which
exhibited higher catalytic activity and stability than Pt/C
catalyst for methanol oxidation. Zhu38 revealed that N-doped
graphitized carbon−TiO2 showed better electrocatalytic
performance than commercial Pt/C for methanol electro-
oxidation and also showed superior CO tolerance. Despite the
above studies, it is still necessary to study the catalyst support
to further improve the performance of DMFC.
Holey graphene oxide (HGO), a structural derivative of
graphene oxide, has amounts of holes distributed on the
graphene nanosheets.49 The nanometer-sized or even larger
holes could afford new properties for the applications of
graphene. For example, the rich functional groups in the hole
edge of HGO provide more active sites which increase its
reactivity.49−51 In addition, the existence of holes can facilitate
the mass transfer across the plane, thereby making the mass
transfer efficiently.51,52 Furthermore, holes weaken the π−π
interactions between graphene layers and thus reduce their
agglomeration.
Therefore, in this study, we constructed N-doped holey
graphene oxide (NHGO) with deposited TiO2 NPs as
functional catalyst support for the oxidation of methanol.
The Pt−TiO2−rNHGO catalyst was prepared via a polyol
method and behaved higher catalytic activity and stability than
Pt NPs loaded on rGO, rHGO, and rNHGO supports (Pt−
rGO, Pt−rHGO, and Pt−rNHGO) for methanol oxidation
reaction. The enhancement can be ascribed to the synergetic
effects among nanoholes, N-doping, and TiO2, which are
discussed in the following.
2. EXPERIMENTAL SECTION
2.1. Materials. The 5 wt % Nafion dispersion was purchased from
Alfa Aesar, natural graphite powder (99.9%) was from Qingdao
Hensen Graphite Co., Ltd., commercial Pt/C (20%) was from
Shanghai Hesen Electric Co., Ltd., and HNO3 (BV-III) was from
Beijing Chemical Reagent Research Institute Co., Ltd. All other
chemicals were purchased from Sinopharm Chemical Reagent Co.,
Ltd. Deionized (DI) water was used.
2.2. Material Synthesis. 2.2.1. Synthesis of Holey Graphene
Oxide (HGO) and N-Doped Holey Graphene Oxide (NHGO). GO
was synthesized by the method described in ref 53. HGO was
synthesized as follows: 10 mL of GO (1 mg/mL) solution was
sonicated for 2 min, and then 10 mL of H2O2 (30%) was added. The
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mixture was reacted for 3.5 h under vigorous stirring at 100 °C.
NHGO was synthesized by adding 10 mL of H2O2 (30%) and 10 mL
of ammonia hydroxide (25%) to the GO dispersion (10 mL, 1 mg/
mL) and stirred at 100 °C for 10 min. It is worth noting that
nanoholes and N are simultaneously introduced into the GO layer
under these reaction conditions. The final products were centrifuged
and washed with DI water four times and then dried by freeze-drying.
2.2.2. Synthesis of TiO2−NHGO Supports. TiO2−NHGO (TiO2,
25 wt %) was prepared by a two-step process. First, in the hydrolysis
reaction, typically 10 mg of as-prepared NHGO was dissolved in
EtOH/water (75 mL/5 mL) with ultrasonics for 2 min. Then we
heated the suspension to 80 °C and slowly added the solution
containing Ti(BuO)4 (10 mg) and H2SO4 (0.075 mL) in 5 mL of
EtOH. The above mixture was kept under stirring for 12 h at 80 °C.
The composite was centrifuged and washed with water. In the second
step, the washed composite was dispersed in water/DMF (25 mL/0.5
mL) with ultrasonics, and then the mixture was transported to a 50
mL Teflon stainless steel autoclave for hydrothermal reaction at 180
°C for 12 h. The final product was washed with water several times
and then dried under vacuum for 12 h. For comparison, TiO2−HGO
were synthesized by using a similar procedure with HGO as substrate.
2.2.3. Synthesis of Pt−TiO2−Reduced NHGO (Pt−TiO2−rNHGO)
Catalyst. Pt−TiO2−rNHGO catalysts (Pt, 20 wt %) were prepared
by a polyol method. Typically, TiO2−NHGO (10 mg) was dispersed
in water/EG (10 mL/40 mL) through sonication for 10 min. Then
upon addition of 625 μL of K2PtCl6 solution (10 mg/mL), the
mixture was reacted for 18 h under reflux conditions at 120 °C. The
resulting Pt−TiO2−rNHGO hybrids were centrifuged, washed, and
dried under vacuum.
The whole process of Pt−TiO2−rNHGO catalyst synthesis is
schematically shown in Figure 1. NHGO was first prepared, then
TiO2 NPs were deposited uniformly on the surface of NHGO, and
last Pt NPs were deposited on the TiO2−NHGO support which
simultaneously reduced NHGO to rNHGO nanosheets. For
comparison, Pt−rGO, Pt−rHGO, Pt−rNHGO, and Pt−TiO2−
rNHGO were synthesized by using a similar procedure with GO,
HGO, NHGO, and TiO2−NHGO as supports, respectively.
2.3. Characterization. Atomic force microscopy (AFM) (Bruker,
Dimension Edge) was applied with tapping mode to obtain AFM
images. An X-ray powder diffractometer (Bruker, D8-Advance, λ =
1.5406 Å) was taken to characterize the X-ray diffraction (XRD)
patterns of the catalysts. Raman spectra were recorded on a confocal
Raman microscope (Jobin Yvon, LabRam ARAMIS) with a 532 nm
laser beam. Transmission electron microscopy (TEM) was charac-
terized by a Tecnai F20 operated at 200 kV. The X-ray photoelectron
spectroscopy (XPS) measurement was performed in an AXIS-Ultra
instrument (Kratos Analytical, monochromatic Al Kα radiation hυ =
1486.6 eV). Inductively coupled plasma mass spectrometry (ICP-MS)
(PerkinElmer, Nexlon 300D) was used to measure the loading of Pt
and Ti in as-prepared catalysts.
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2.4. Electrochemical Measurements. A CHI660D electro-
chemical workstation with a three-electrode system was taken in all
electrochemical experiments. A glassy carbon electrode (GCE) (5
mm diameter) coated with as-prepared catalyst, an Ag/AgCl
electrode, and a platinum wire were exploited as the working
electrode, reference electrode, and counter electrode, respectively.
Twenty microliters of catalyst ink (1 mg/mL, 0.05 wt % Nafion) was
dropped-coated on the cleaned GCE. The cyclic voltammetry (CV)
and chronoamperometry were measured in a mixing solution
containing 1 M CH3OH and 0.5 M H2SO4 with a scan rate of 50
mV s−1. High-purity nitrogen was used to drive out the oxygen of
electrolyte solutions prior to the measurement.
3. RESULTS AND DISCUSSION
AFM and TEM were applied to characterize the morphologies
of as-prepared samples. As shown in Figure 2 and Figure S1d,
Figure 2. AFM images of GO (a) and NHGO (b).
nanoholes could be clearly observed on NHGO and HGO
nanosheets compared to GO. The height of GO, NHGO, and
HGO nanosheets was about 1 nm, respectively, indicating the
nanosheets of GO, NHGO, and HGO were all a single layer.
Moreover, the nanosheets of NHGO and HGO were well
dispersed and not aggregated. The TEM images of NHGO and
HGO also demonstrated a lot of nanoholes on the nanosheets
compared to GO (Figure S1a−c), which further certified the
existence of nanoholes on NHGO and HGO nanosheets.
Raman spectra of as-prepared GO, HGO, NHGO, and
TiO2−NHGO are shown in Figure S2. The peak around 1340
cm−1 was the D band, matched with the disorder sp3 carbon,
while the peak at 1590 cm−1 was the G band of the carbon
materials, corresponding to the first-order G mode of the
regular sp2 graphitic network. ID/G was commonly used to
characterize the defect density in graphene. It was observed
that the ID/IG ratio was 0.91, 0.98, 1.05, and 0.82 for GO,
HGO, NHGO, and TiO2−NHGO, respectively. The results
suggested that introduction of nanoholes and N-doping both
increased the defects in graphene, while for TiO2−NHGO, the
ID/IG ratio was 0.82, which was smaller than the ratio of
NHGO. The result implied that the process of loading TiO2
NPs on NHGO reduced partial defects of NHGO.
The crystalline structures of Pt−rGO, Pt−rHGO, Pt−
rNHGO, and Pt−TiO2−rNHGO catalysts were analyzed by
XRD. The obtained diffraction peaks (Figure 3) located at 2θ
values of ca. 39.6°, 46.2°, and 67.5° could be ascribed to the
face-centered cubic (fcc) Pt structure of (111), (200), and
(220) crystalline plane, respectively. The wide diffraction peak
at ca. 23.9° corresponded to the (002) plane of carbon, which
indicated shorter distance between rGO layers. For the Pt−
TiO2−rNHGO catalyst, the new diffraction peaks observed at
25.3°, 37.8°, 48.0°, 55.0°, and 62.7° could be assigned to
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Figure 3. XRD patterns of as-prepared catalysts: (a) Pt−rGO, (b)
Pt−rHGO, (c) Pt−rNHGO, and (d) Pt−TiO2−rNHGO.
anatase structure of (101), (004), (200), (211), and (204),
which indicated that TiO2 on Pt−TiO2−rNHGO only
contained the anatase phase. It has been reported that anatase
had better electrical conductivity than rutile.54 Moreover, it
was considered that anatase was more catalytically active than
rutile on methanol oxidation reaction.55
Figure 4 shows the typical TEM micrographs and the
corresponding size distribution histogram of Pt−rGO, Pt−
rHGO, Pt−rNHGO, and Pt−TiO2−rNHGO catalysts. It
could be seen that the Pt NPs were deposited on the GO,
HGO, NHGO, and NHGO−TiO2 supports. TiO2 NPs were
uniformly deposited on NPGO nanosheets with an average
size of 14.5 nm in Pt−TiO2−rNHGO catalysts. The size
distributions of Pt were collected from the TEM images with
more than 100 particles. It indicated that the average particle
sizes were 2.99, 2.52, 2.54, and 2.37 nm for the Pt−rGO, Pt−
rHGO, Pt−rNHGO, and Pt−TiO2−rNHGO catalysts, re-
spectively. Pt NPs deposited on GO were not as uniform as
that on HGO, NHGO, and NHGO−TiO2 supports, and some
Pt NPs were agglomerated. The average particles size and size
distribution of the Pt−TiO2−rNHGO catalyst was the smallest
in the prepared four catalysts. Pt NPs of Pt−rNHGO and Pt−
rHGO catalysts have a similar average size, which was also
smaller than Pt on the Pt−rGO catalyst. The results showed
that the introduction of nanoholes improved the dispersion
and uniform of Pt NPs on supports.
The TEM observations indicated that the TiO2−NHGO
support could facilitate the preparation of well-dispersed
nanocatalysts and reduce their size. Nanoholes on graphene
nanosheets, which provided more active sites in graphene for
Pt anchoring, contributed to the distributions of Pt NPs and
reduced the size. In addition, the N atoms were also
introduced simultaneously with the generation of nanoholes
on the nanosheets. The doping of N afforded the graphene
nanosheets strongly bonded to Pt, thus also facilitating the
distributions of Pt NPs, reducing the dimension of Pt NPs, and
hindering the agglomeration of Pt NPs. HRTEM images
(Figure 4b,e,h,k) clearly showed the regular lattice stripes with
a spacing of 0.227 and 0.35 nm, which were highly matched
with the plane of (111) Pt and (101) anatase TiO2,
respectively. The results were identical with the XRD results.
The surface composition of as-prepared samples was
characterized with XPS. Figure 5a exhibits the overall spectrum
of Pt−TiO2−rNHGO, revealing the presence of Pt, Ti, N, C,
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Figure 4. TEM images and corresponding particle size distribution histograms of Pt−rGO (a−c), Pt−rHGO (d−f), Pt−rNHGO (g−i), and Pt−
TiO2−rNHGO (j−l) catalysts.

and O in the catalyst. The N 1s could be divided into three
types of N peaks (Figure 5b): graphitic-N (401.0 eV), pyrrolic-
N (399.8 eV), and pyridinic-N (398.3 eV).56 The Pt 4f signals
were ascribed to Pt(0) and Pt(II). The binding energy of Pt
4f7/2 of Pt (0) for the Pt−rNHGO catalyst was 71.2 eV, while
the binding energy for the Pt−TiO2−rNHGO catalyst was
71.8 eV. The binding energy of Pt for Pt−TiO2−rNHGO
shifted higher compared with Pt−rNHGO, reflecting strong
metal−support interactions between Pt and TiO2.38 In
addition, the binding energies of Ti 2p1/2 and 2p2/3 of Pt−
TiO2−rNHGO (464.6 and 458.9 eV, Figure S3b) were also
higher than the corresponding binding energy of TiO2 (464.2
and 458.5 eV), also indicating the strong interactions between
NHGO, TiO2, and Pt.57
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The C 1s spectrum for Pt−TiO2−rNHGO (Figure S3a)
could be deconvolved into five peaks (C−C, C−N, C−O, C
O, and O−CO, respectively). The presence of a C−N peak
indicated that N was successfully doped into graphene
nanosheets. It could be seen that after the reduction of Pt by
ethylene glycol the contents of oxygenated functional groups
all decreased, and the carbon−carbon skeleton was recovered
(Figure S3c,d). Therefore, the conductivity of support was
improved, which was beneficial to the improvement of the
electrocatalytic activity of the catalyst.
The CVs for Pt−rGO, Pt−rHGO, Pt−rNHGO, and Pt−
TiO2−rNHGO catalysts were measured in 0.5 M H2SO4
solution vs Ag/AgCl (Figure 6a). It could be seen from the
CV profiles that all as-prepared catalysts exhibited hydrogen
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Figure 5. XPS spectra of Pt−TiO2−rNHGO (a), N 1s (b), the Pt 4f of Pt−TiO2−rNHGO (c), and Pt−rNHGO (d).

Figure 6. (a) CV of Pt/C, Pt−rGO, Pt−rHGO, Pt−rNHGO, and Pt−TiO2−rNHGO catalysts in 0.5 M H2SO4 purged with N2. (b) and (c) are
the CO-stripping CVs of Pt/C and Pt−TiO2−rNHGO catalysts in a solution of 0.5 M H2SO4 at a scan rate of 50 mV s−1.

adsorption/desorption (−0.20 to 0.10 V), a flat double layer
(0.1−0.5 V), and oxide formation/stripping wave peaks
(0.50−1.00 V). Pt−TiO2−rNHGO has higher peak current
density than Pt−rGO, Pt−rHGO, and Pt−rNHGO, illustrating
more exposed reactive sites during the surface redox process.
The electrochemical surface areas (ECSAs) of as-prepared
catalysts could be calculated by eq 1.
ESCA = Q H/(mPt × 0.21) (1)
where QH is the total charge (mA) for hydrogen desorption in
low potential region (from −0.2 to 0.1 V) of the CVs, and 0.21
mC cm−2 is the charge required to desorb the adsorbed
hydrogen on the Pt surface; mPt is the Pt loading (mg) in
catalyst on GCE. The ECSA is 42.3, 24.1, 42.5, 79.9, and 113.4
m2 g−1 Pt for Pt/C, Pt−rGO, Pt−rHGO, Pt−rNHGO, and
Pt−TiO2−rNHGO catalysts, respectively.
It could be observed from the data that the ECSA of Pt−
TiO2−rNHGO and Pt−rNHGO catalysts were higher than the
commercial Pt/C catalyst. Furthermore, the ECSA of Pt−
rHGO was about doubled compared with GO, which indicated
that nanoholes play a significant role. In addition, N-doping
E https://dx.doi.org/10.1021/acsaem.9b02364
increased the ECSA of Pt−rNHGO by 88% compared with
Pt−rHGO. Moreover, it was found that the introduction of
TiO2 NPs also improved the ECSA by 42% by comparing Pt−
rNHGO with Pt−TiO2−rNHGO. Therefore, Pt−TiO2−
rNHGO had the highest ECSA compared with Pt−rGO,
Pt−rHGO, and Pt−rNHGO because of nanoholes in the
graphene plane, uniform distribution of Pt NPs, N-doping, and
intense interactions among NHGO, TiO2, and Pt. The CO-
stripping voltammetry test was executed in 0.5 M H2SO4 to
compare the CO tolerance of research catalysts (Figure 6b,c
and Figure S4). The onset potentials of Pt−TiO2−rNHGO
and commercial Pt/C catalyst are 0.486 and 0.619 V,
respectively. The negatively shifted onset potential revealed
that Pt−TiO2−rNHGO catalyst had better CO tolerance than
Pt/C catalyst and other catalysts in Figure S4. The high CO
tolerance might result from the following reasons. First, the
strong interactions between Pt NPs and support (especially Pt
with doped-N and Pt with TiO2) enhanced the synergistic
effect and so weakened the binding energy of Pt−COads.35,47
Therefore, CO intermediates could be easily removed. Second,
N-graphene and TiO2 in TiO2−NHGO support could
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ACS Applied Energy Materials
facilitate water activation and dissociation to make sufficient
OHads species which helped effectively electro-oxidize removal
of poisoning intermediates absorbed on the Pt surface.58−64
To evaluate the catalytic activity of Pt−rGO, Pt−rHGO,
Pt−rNHGO, and Pt−TiO2−rNHGO catalysts, CV was
measured in deaerated mixing solution of 1 M CH3OH and
0.5 M H2SO4. As shown in Figure 7, the CV curves incorporate
Figure 7. CVs of methanol oxidation on Pt/C, Pt−rGO, Pt−rHGO,
Pt−rNHGO, and Pt−TiO2−rNHGO catalysts in deaerated mixing
solution of 1 M CH3OH and 0.5 M H2SO4.
two peaks for methanol oxidation. The forward peak current
densities for Pt−rGO, Pt−rHGO, Pt−rNHGO, and Pt−
TiO2−rNHGO are 302.1, 349.7, 390.2, and 591.0 mA mg−1,
respectively. By contrast, the current density of the Pt−TiO2−
rNHGO electrocatalyst is the highest and about 1.96, 1.69, and
1.51 times higher than that of Pt−rGO, Pt−rHGO, and Pt−
rNHGO and 1.70 times more than commercial Pt/C (347.0
mA mg−1). These results indicated that Pt−TiO2−rNHGO
had the highest catalytic activity among studied catalysts,
which was consistent with the results of ECSA.
The chronoamperometry (CA) curve was applied to assess
the stability of the as-prepared electrocatalysts, and Figure 8
shows the corresponding i−t curves. Apparently, it could be
observed that all as-prepared catalysts and commercial Pt/C
catalyst had an initial rapid current decay in the first 20 s,
Figure 8. Chronoamperometry (CA) curves of Pt/C, Pt−rGO, Pt−
rHGO, Pt−rNHGO, and Pt−TiO2−rNHGO in the mixing solution
(1 M CH3OH and 0.5 M H2SO4) recorded at 0.70 V for 3600 s.
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which was because of catalyst surface poisoning caused by the
absorption of carbonaceous intermediates and the reduced
methanol concentration. At this stage, amounts of free Pt
active sites were occupied by CO intermediates. As a result,
further adsorption and oxidation of methanol at the Pt site
were prevented. After that, the currents decreased slowly,
which was due to the relative balance of the adsorption and
oxidation of poisonous species on Pt sites. Throughout the
measurement, although the current continued to decline
gradually, the Pt−TiO2−rNHGO catalyst showed a higher
current density compared to those of other as-prepared
catalysts and commercial Pt/C catalyst, indicating its excellent
CO tolerance and higher electrocatalytic activity for methanol
oxidation.
The improved activity and stability of Pt−TiO2−rNHGO
were probably due to the following factors. First, nanoholes in
graphene planes provided more active sites and efficient mass
transport, which is beneficial for methanol oxidation. More-
over, nanoholes made the N-doping and the distribution of
TiO2 NPs more uniform on NHGO nanosheets, which
facilitated to form the small size and uniformly dispersed Pt
NPs on the TiO2−rNHGO support. Second, the more uniform
doping of nitrogen induced by nanoholes in the graphene
plane would bring more even C−N defects, which are
favorable to activate water and generate OHads. Moreover,
the abundant −OH groups around Pt NPs can promote the
oxidation of COads at the Pt sites. Besides, N-doping could
increase the electron density of graphene, which brings
stronger interactions between Pt NPs and TiO2−rNHGO
supports. Third, the existence of well-dispersed TiO2 NPs
provided rich −OH species and increased the oxidation of the
poisonous CO-like intermediates into CO2 and minimized the
oxidation of Pt−OH on the surface. Fourth, the thus-induced
strong metal−support interaction, which was confirmed by a
positive shift of Pt 4f peaks in XPS, resulted in lower CO
coverage and bonding strength and so enhanced methanol
oxidation on the Pt surface.
4. CONCLUSIONS
In conclusion, an efficient electrocatalyst Pt−TiO2−rNHGO
for methanol fuel cells was synthesized by loading TiO2 NPs
and Pt NPs on the surface of reduced NHGO. Pt NPs
deposited on the TiO2−rNHGO support showed evenly
dispersion and smaller average particle size of 2.37 nm. The
Pt−TiO2−rNHGO catalyst revealed remarkably improved
catalytic activity and stability toward the methanol oxidation
compared with Pt−rGO, Pt−rHGO, and Pt−rNHGO
catalysts. This was attributed to the produced nanoholes on
graphene nanosheets which could provide more active sites
and efficient mass transport, the induced more uniform N-
doping to graphene, the rich active −OH species on TiO2−
NHGO support, and the strong metal−support interactions
among Pt, TiO2, and rNHGO. This work might provide some
directions for further development of efficient electrocatalysts
for direct methanol fuel cells.
■ ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsaem.9b02364.
TEM images of GO, NHGO, and HGO; AFM image of
HGO; Raman spectra of GO, HGO, NHGO, and
ACS Appl. Energy Mater. XXXX, XXX, XXX−XXX
ACS Applied Energy Materials
TiO2−NHGO; XPS spectra of C 1s, Ti 2p of Pt−TiO2−
rNHGO, C 1s comparison of GO, Pt−rGO, Pt−rHGO,
Pt−rNHGO, and Pt−TiO2−rNHGO, and GO, HGO,
and NHGO; CO-stripping CVs of Pt−rGO, Pt−rHGO,
and Pt−rNHGO catalysts (PDF)
■ AUTHOR INFORMATION
Corresponding Author
Baoyun Sun − CAS Key Laboratory for Biomedical Effects of
Nanomaterial & Nanosafety, Institute of High Energy Physics,
Chinese Academy of Science (CAS), Beijing 100049, China;
orcid.org/0000-0003-1542-4642; Email: sunby@
ihep.ac.cn
Authors
Rongli Cui − CAS Key Laboratory for Biomedical Effects of
Nanomaterial & Nanosafety, Institute of High Energy Physics,
Chinese Academy of Science (CAS), Beijing 100049, China
Shuaichao Liu − College of Chemistry and Chemical
Engineering, Inner Mongolia University, Huhhot 010021,
China
Xihong Guo − CAS Key Laboratory for Biomedical Effects of
Nanomaterial & Nanosafety, Institute of High Energy Physics,
Chinese Academy of Science (CAS), Beijing 100049, China
Huan Huang − CAS Key Laboratory for Biomedical Effects of
Nanomaterial & Nanosafety, Institute of High Energy Physics,
Chinese Academy of Science (CAS), Beijing 100049, China
Jiahao Wang − CAS Key Laboratory for Biomedical Effects of
Nanomaterial & Nanosafety, Institute of High Energy Physics,
Chinese Academy of Science (CAS), Beijing 100049, China
Bing Liu − CAS Key Laboratory for Biomedical Effects of
Nanomaterial & Nanosafety, Institute of High Energy Physics,
Chinese Academy of Science (CAS), Beijing 100049, China
Ying Li − CAS Key Laboratory for Biomedical Effects of
Nanomaterial & Nanosafety, Institute of High Energy Physics,
Chinese Academy of Science (CAS), Beijing 100049, China
Dangui Zhao − CAS Key Laboratory for Biomedical Effects of
Nanomaterial & Nanosafety, Institute of High Energy Physics,
Chinese Academy of Science (CAS), Beijing 100049, China
Jinquan Dong − CAS Key Laboratory for Biomedical Effects of
Nanomaterial & Nanosafety, Institute of High Energy Physics,
Chinese Academy of Science (CAS), Beijing 100049, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsaem.9b02364
Author Contributions
R.C. and S.L. contributed equally to this work.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported financially by the National Key
Research and Development Program of China (No.
2018YFA0703504), the National Basic Research Program of
China (No. 2016YFA0203200), the National Natural Science
Foundation of China (Nos. 21971242, U1632113, 21402202,
11505191, and 11705211), and the Young Scientist Innovative
Foundation of IHEP (No. 542019IHEPZZBS11220).
■
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