Achieving uniform Pt deposition site by

tuning the surface microenvironment of

bamboo-like carbon nanotubes Meng
Jin
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 Applied Surface Science 591 (2022) 153201

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Applied Surface Science

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Full Length Article

Achieving uniform Pt deposition site by tuning the surface

microenvironment of bamboo-like carbon nanotubes
Meng Jin a, c, *, Rong Wang a, Bi Jia a, Jun Zhang a, Hui Liu d, Shi-Yu Lu a, b, *
a
College of Metallurgy and Materials Engineering, Chongqing University of Science and Technology, Chongqing 401331, China
b
BIC-ESAT & School of Materials Science and Engineering, Peking University, Beijing, 100871, China
c
Department of Chemistry, Tsinghua University, 30 Shuangqing Rd, Haidian District, Beijing 100084, China
d
Key Laboratory of Luminescence Analysis and Molecular Sensing (Southwest University), Ministry of Education, School of Materials and Energy, Southwest University,
Chongqing, 400715, China

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

Keywords: The surface microenvironment of supports, including surface state and constitution, are crucial adjective factors
Pt deposition to the dispersibility and particle size of Pt nanoparticles (NPs) on carrier, follow-up affecting their catalytic
bamboo-like CNTs activities for methanol oxidation reaction (MOR). Here an in-situ pyrolysis approach is reported for preparing
Surface microenvironment
bamboo-like N doped carbon nanotubes coupled with fewer metallic particles (M@N-CNTs (M = Co, Ni and
Methanol oxidation
Fe3C)), enabled tunable surface state and constitution of carbon layers. Combined experimental and theoretical
investigation, as fabricated Co@N-CNTs provide optimal surface of backbone for Pt deposition with narrowest
particle size distribution and minimum size by virtue of dominated pyridinic-N, enriched defect, abundant
wrinkle and fewer number of carbon layer, which exhibits superior MOR performance as well as long-lifespan.
Our findings not only exhibit some new insights for accurate modulation and optimization of carbon skelecton at
the atomic scale in fundamental, but also reveal the structural and compositive origin of the enhanced catalytic
activity towards to MOR.

1. Introduction intrinsic defects and structure in carbon skeleton can be severed as

With gaining much considerable attention to the increasing the en­
ergy crisis and environmental pollution, the utilization and development
of various energy sources with more environmentally friendly, renew­
able, and efficient are becoming an urgent problem to be solved [1–3].
Direct methanol fuel cells (DMFCs), due to the property of low operating
temperature, high energy density, and energy conversion efficiency,
have been widely deemed as the ideal energy conversion devices for
portable electronic devices and electric vehicles [4–8].
Currently, commercial catalysts utilized in fuel cell anode for MOR
are mainly Pt-based materials, which means sluggish reaction kinetics,
exorbitant costs, inferior CO tolerance and poor stability. Reasonable
and valid modulation of Pt NPs on the supports are an essential approach
to reduce the usage and promote utilization efficiency of Pt in anode
catalysts, further improving its catalytic activities towards to MOR
[9–13]. As everyone knows, the size distribution, interaction force,
morphology, and coordinate form of Pt NPs on supports are crucial
factors relative to the surface state of the carrier [14]. Nitrogen site,
eminent traps to help to absorb Pt ion and restrict it migrating on the
carrier, further contributing to nucleation and Ostwald ripening of Pt
NPs [15–17]. The nitrogen dopants not only break electroneutrality of
the original carbon skeleton, avoiding aggregation of Pt NPs, but also
provide strong interaction between Pt NPs and support, enhancing
charge transfer and catalytic activity of catalyst [19–21]. Besides,
abundant OH species offer from the N dopants are benefited to eliminate
the absorbed byproducts during the MOR process [22]. The surface
morphology of supports is highly determined by the nitrogen configu­
ration and content, such as graphitic N, pyridinic N, and pyrrolic N. Up
the to date, the role of nitrogen configuration in carbon materials
including by way of experiment and theory needs to deeper under­
standing. Furthermore, it is also highly raring to develop an electro­
catalyst with fine tunability in microenvironment for regulating Pt
deposition, as well as improving the catalytic activities towards MOR.
Herein, we elaborately design an in-situ pyrolysis approach to syn­
thesize bamboo-like N doped carbon nanotubes coupled with fewer
metallic particles (M@N-CNTs (M = Co, Ni and Fe3C)), enabled tunable

* Corresponding authors.
E-mail addresses: jinmeng0807@mail.tsinghua.edu.cn (M. Jin), lushiyu@cqust.edu.cn, lushiyu1990@pku.edu.cn (S.-Y. Lu).

https://doi.org/10.1016/j.apsusc.2022.153201
Received 2 January 2022; Received in revised form 20 March 2022; Accepted 24 March 2022
Available online 26 March 2022
0169-4332/© 2022 Published by Elsevier B.V.
M. Jin et al.
surface state and constitution of carbon layers. The nitrogen doping
state, thickness and defect degree of the carbon layer in bamboo-like
M@N-CNTs (M = Co, Ni and Fe3C) could be effectively tuned by using
dicyandiamide and different acetylacetone salt (Co, Ni, Fe) as the pre­
cursor. The distribution and particle size of Pt NPs on M@N-CNTs (M =
Co, Ni and Fe3C) subsequently affected by surface state and constitution
of carbon layers in N-CNTs using a simple microwave-assisted glycol
process, which further influences its MOR activity, CO tolerance ability
and durability in alkaline media. Co@N-CNTs with a high content of
pyridinic-N, enriched defect, abundant wrinkle and fewer number of
carbon layer provide excellent landing sites for Pt NPs, causing uni­
formly narrowest and minimum particle size distribution for Pt depo­
sition, which greatly enhance the activity of MOR and reduce the usage
of Pt. Pt/Co@N-CNTs exhibits high mass activity and specific activity
(1652 mA mg-1Pt and 4.82 mA cm-2Pt) with outstanding CO tolerance
ability and stability.
Fig. 1. (a) Schematic illustration for the preparation of the Pt/M@N-CNTs (M = Co, Ni and Fe3C), (b) intermediate products during the thermal treatment of
dicyandiamide, TEM images of (c, f) Co@N-CNTs, (d, g) Ni@N-CNTs and (e, h) Fe3C@N-CNTs.
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Applied Surface Science 591 (2022) 153201
2. Results and discussion
The synthesis route of the Pt/M@N-CNTs (M = Co, Ni, Fe3C) is
illustrated in Fig. 1a. The bamboo-liked M@N-CNTs (M = Co, Ni, Fe3C)
were first synthesized by using direct pyrolysis of dicyandiamide under
high temperature with the assist of acetylacetone salt. Then, Pt/M@N-
CNTs (M = Co, Ni, Fe3C) were obtained by microwave-assisted reduc­
tion process in ethylene glycol contained hexachloroplatinic acid. As
shown in Fig. 1b, there are several step in dicyandiamide decomposi­
tion, which release NH3 molecules and successively form melamine,
melem, melon, g-C3N4 and finally N-CNTs. Melem bands in products
well formed at temperature range of 400 ~ 500 ℃. Melon products
appear at ~ 500 ℃ and grows rapidly up to 600 ℃. g-C3N4 derived from
melon thermal polymerizate at the temperature range of 550 ~ 700 ℃
while translate N doped carbon higher than 700 ℃ [23]. Internal
stresses created from M metal (M = Co, Ni, Fe3C) cause a curling of the
layered g-C3N4 [24]. A typical scanning electron microscopy (SEM)
M. Jin et al.
images of M@N-CNTs (M = Co, Ni and Fe3C) presents uniformed hollow
cavity with average tubular diameters of 15–30 nm (Fig. S1). The
intrinsic microstructure of M@N-CNTs (M = Co, Ni and Fe3C) are
analyzed by transmission electron microscopy (TEM). As revealed in
Fig. 1c to 1e, bamboo-like N-CNTs are all multiwalled and encapsulated
fewer M metal nanoparticles (M = Co, Ni and Fe3C) in part of their
cavities, which clearly originate from dicyandiamide and metal pre­
cursor by growth mechanism at high temperature [25,26]. The gaseous
state of hydrocarbon derived from dicyandiamide decomposition
mutually dissolute with metal NPs reduced from metallic precursor at
high temperature, which metals and hydrocarbons continuously accu­
mulate as time goes by. When reaching saturation of carbon on the metal
surface, the carbon separated out and crystallizes to form graphite cyl­
inders. High-resolution TEM (HRTEM) images (Fig. 1f to 1 h) exhibit
increase in the carbon layer thickness when nickel acetylacetonate and
ferric acetylacetonate are used. The carbon layer thickness increased in
the following order: Co@N-CNTs＜Ni@N-CNTs＜Fe3C@N-CNTs.
Furthermore, the lattice of carbon layer in Co@N-CNTs and Ni@N-CNTs
are discontinuous compared with that of Fe3C@N-CNTs, revealing ex­
istence of defect in Co@N-CNTs and Ni@N-CNTs. Obviously, the carbon
layers in Co@N-CNTs is highly curved-evidence of its superthin
character.
Fig. 2a shows the powder X-ray diffraction (XRD) pattern of the as-
synthesized M@N-CNTs (M = Co, Ni and Fe3C). An obvious sharp
diffraction peak at about 2θ = 26◦ is observed in Co@N-CNTs, Ni@N-
CNTs and Fe3C@N-CNTs, which is corresponded to the (0 0 2) plane of
graphite. The other diffraction peaks can be ascribed to the cobalt metal
(PDF#15–0806), nickel metal (PDF#04–0850) and iron carbide
(PDF#85–0871) for Co@N-CNTs, Ni@N-CNTs and Fe3C@N-CNTs,
respectively. The XRD patterns of Pt/M@N-CNTs (M = Co, Ni and Fe3C)
Fig. 2. (a) The XRD patterns of M@N-CNTs (M = Co, Ni and Fe3C), (b) Pt/M@N-CNTs, (c) FTIR spectra of M@N-CNTs and (d) Raman spectra of M@N-CNTs.
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Applied Surface Science 591 (2022) 153201
are presented in Fig. 2b. The location of diffraction peaks for Pt/M@N-
CNTs (M = Co, Ni and Fe3C) are similar with their original M@N-CNTs
(M = Co, Ni and Fe3C), but relative intensity of carbon and metallic
phase are totally different, indicated partly dissolution of metallic phase
under Pt loading process. The diffraction peak located at ~ 39.8◦ relate
to the (1 1 1) plane of Pt (PDF#04–0802). The ratio of carbon peak
strength and metal peak strength of Pt/Co@N-CNTs and Pt/Ni@N-CNTs
are significantly enhanced, revealed that partial dissolution of metal
under Pt loading process, while only the diffraction peaks of carbon and
Pt can be discerned in Pt/Fe3C@N-CNTs, attributing to the greatly
dissolution of Fe3C under Pt loading process. The texture specific surface
area and pore size distribution of M@N-CNTs (M = Co, Ni and Fe3C) are
investigated by using N2 adsorption–desorption isothermal analysis. The
N2 adsorption–desorption isotherm measured for all samples are typical
IV-type with H3-type hysteresis loops (Fig. S2), indicating the presence
of mesopores in three supports. Noticeably, the Brunauer-Emmett-Teller
(BET) specific surface area of Co@N-CNTs, Ni@N-CNTs and Fe3C@N-
CNTs are 48.1, 136.1 and 87.7 m2 g− 1, respectively. Remarkably, in the
region with high relative pressure (P/P0), N2 adsorption–desorption
isotherm loops of Co@N-CNTs is higher than that of Ni@N-CNTs and
Fe3C@N-CNTs, indicated that a large number of mesoporous exist in
Co@N-CNTs [27,28]. The pore size distribution curve calculated based
on the BJH method further illustrates the existence of the mesoporous
structure of the support materials. It also proves that the pore size of
Co@N-CNTs is larger, which is conducive to the transport of methanol
molecules [29].
In Fourier Transform Infrared (FTIR) spectroscopy (Fig. 2c), the
three obvious peaks located at 890, 1070 and 1600–1650 cm− 1 reflect
vibrations of N-H bonds, C-N bonds and C = N bonds, which are assigned
to pyrrolic nitrogen, graphitic nitrogen and pyridinic nitrogen in M@N-
M. Jin et al.
CNTs, respectively [30,31]. In addition, the peak at ~ 1392 cm− 1 is
corresponding to the N-O (pyridinic oxide) bonds while the two peaks at
~ 2360 cm− 1 correspond to C = O bonds. Furthermore, Co@N-CNTs and
Ni@N-CNTs show two new small peaks at ~ 2917 cm− 1, which are
related to the C-H stretching. The formation of C-H bonds may improve
the hydrophilicity of M@CNTs (M = Co, Ni and Fe3C). Raman spectra
are obtained for M@N-CNTs (M = Co, Ni and Fe3C) in the frequency
range from 1000 to 3000 cm− 1 using 514 nm excitation (Fig. 2d). Two
characteristic peaks at ~1350 and ~1590 cm− 1 are renowned to D band
and G bands in the carbon structure, respectively. The D band reflect to
disordered sp2 carbon and the G band represent ordered graphitic sp2
carbon. By comparison of spectra, in Co@N-CNTs nanocomposite the
intensity ratio of ID/IG (~1.02) is higher than that of Ni@N-CNTs
(~0.91) and Fe3C@N-CNTs (~0.85), which may be attributed to the
domination of disordered structure of Co@N-CNTs. Moreover, the order
peak at ~ 2680 cm− 1 is renowned to 2D band. The intensity ratio of 2D
band to G band (I2D/IG) has been reported to a valuable approach to
characterize the number of carbon layer in carbon nanotubes and gra­
phene [32,33]. Hence, lowest values of I2D/IG suggest that Co@N-CNTs
(~0.09) forms N-CNTs with the relatively small thickness of walls fol­
lowed by Ni@CNTs (~0.18) and Fe3C@N-CNTs (~0.25), which also is
consistent with directly observation in HRTEM images (Fig. 1f to 1 h).
The TEM images of Pt/M@N-CNTs (M = Co, Ni and Fe3C) are
depicted in Fig. 3a-3c to analysis the size and distribution of Pt NPs on
M@N-CNTs (M = Co, Ni and Fe3C). The Pt NPs uniformly disperse both
in Pt/Co@N-CNTs and Pt/Ni@N-CNTs, while greatly aggregate in Pt/
Fe3C@N-CNTs. High-resolution TEM (HRTEM) (Fig. 3d to 3f) reveals
that well-crystalline structure of Pt NPs with smaller particle size uni­
formly monodisperse in Pt/Co@N-CNTs. Poor distribution of Pt NPs in
Pt/Fe3C@N-CNTs reveals relatively perfect carbon layer of Fe3C@N-
CNTs is not suitable to help to the nucleation and anchoring of Pt NPs.
The HAADF-STEM images of Pt/Co@N-CNTs catalyst and the corre­
sponding EDS elemental mapping displays the homogeneous distribu­
tion of C, N, Co and Pt elements in the whole nanotubes (Fig. S3). The
lattice pattern with interplanar spacing of ~ 0.221 nm attribute to (1 1 1)
plane of the face-centered cubic Pt (Fig. 3d and 3e). The average par­
ticle size of Pt NPs (Fig. S4a to 4c) in Pt/Co@N-CNTs, Pt/Ni@N-CNTs
Fig. 3. (a-c) The low-resolution TEM images, (d-f) high-magnification TEM images of Pt/M@N-CNTs (M = Co, Ni and Fe3C).
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Applied Surface Science 591 (2022) 153201
and Pt/Fe3C@N-CNTs are 1.65, 1.73 and 9.27 nm, respectively. Pt NPs
with smaller size and well uniformly distribution in Pt/Co@N-CNTs
improve the utilization rate of Pt, reduce unnecessary side reactions,
and enhance the catalytic activity towards MOR [14,34].
The composition and nature of coordination environment of M@N-
CNTs and Pt/M@N-CNTs (M = Co, Ni and Fe3C) are also character­
ized by using X-ray photoelectron spectroscopy (XPS). Fig. 4a exhibits
Co 2p, Ni 2p and Fe 2p core level spectra of Co@N-CNTs, Ni@N-CNTs
and Fe3C@N-CNTs, respectively. For spectra of Co 2p, the centered
peaks at binding energy of 779.0 eV and 794.3 eV are accorded with Co
2p3/2 and Co 2p1/2, respectively [35]. The doublet peaks at 780.8 eV and
795.8 eV are associated to Co (II) state, while the peaks located at higher
binding energy of 783.5 eV and 802.7 eV correspond to satellite peaks of
Co 2p [36]. As displayed in the spectra of Ni 2p, the two peaks observed
at 853.7 eV and 871.4 eV can be attributed to Ni 2p3/2 and Ni 2p1/2,
respectively, indicating that primarily exist Ni (0) [37,38]. Meanwhile,
the peaks at 855.3 eV and 873.6 eV represent Ni (II). The spectra of Fe 2p
shows the peaks around at 707.8 eV and 720.3 eV corresponding to the
Fe 2p3/2 and Fe 2p1/2, respectively, demonstrating the presence of Fe
(0). In addition, the peaks at 710.8 eV and 723.8 eV are discovered,
which are consistent with iron carbide [39]. The XPS spectra of Co 2p of
Pt/Co@N-CNTs, Ni 2p of Pt/Ni@N-CNTs and Fe 2p of Pt/Fe3C@N-CNTs
are separately exhibited in Fig. 4b. The peak intensity of Co 2p in Pt/
Co@N-CNTs, Ni 2p in Pt/Ni@N-CNTs and Fe 2p in Pt/Fe3C@N-CNTs
weaker than that of fresh M@N-CNTs, which is consistent with XRD
pattern (Fig. 2b). Above results indicate that a vast of metal species in
M@N-CNTs (M = Co, Ni and Fe3C) will dissolve after Pt deposition
process while a small amount of metallic matter remained in Pt/M@N-
CNTs (M = Co, Ni and Fe3C).
Pt 4f spectra of Pt/M@N-CNTs (M = Co, Ni and Fe3C) are shown in
Fig. 4c. The Pt 4f spectra mainly shows two peaks at 70.9 eV and 74.1
eV, which are consistent with Pt 4f5/2 and Pt 4f7/2, respectively. More­
over, the peaks located at 72.1 eV and 76.0 eV are also observed, cor­
responding to Pt (II) [40]. The Pt 4f peak of Pt/Co@N-CNTs have
significantly negative shift relative to Pt/Ni@N-CNTs and Pt/Fe3C@N-
CNTs, manifesting the stronger interaction between Pt NPs and support
[19]. At the same time, the negative shift of Pt 4f also means that Pt NPs
M. Jin et al. Applied Surface Science 591 (2022) 153201

Fig. 4. (a) The XPS spectra of Co 2p of Co@N-CNTs, Ni 2p of Ni@N-CNTs and Fe 2p of Fe3C@N-CNTs. (b) The XPS spectra of Co 2p of Pt/Co@N-CNTs, Ni 2p of Pt/
Ni@N-CNTs and Fe 2p of Pt/Fe3C@N-CNTs. The XPS spectra of (c) Pt 4f and (d) N 1 s of Pt/M@N-CNTs (M = Co, Ni and Fe3C).

can obtain electrons from the Co@N-CNTs support, thus changing the d-
band center of Pt. According to the d-band center theory, the CO
adsorption energy of Pt would weaken with the decrease of the d-band
center, which is also advantageous to the removal of COads intermediates
on the catalyst surface [41,42]. As is well known, Pt (0) is deemed to
provide more active sites for MOR than Pt (2 + ), which is crucial for the
realization of high catalytic performance [18,43]. The content of Pt (0)
in Pt/Co@N-CNTs is obviously higher than that of Pt/Ni@N-CNTs and
Pt/Fe3C@N-CNTs (Table S1), indicating that the Pt/Co@N-CNTs could
provide more active sites for methanol oxidation. The high-resolution
XPS spectra of the N1s (Fig. 4d) confirms the presence of three
nitrogen functional groups in Pt/M@N-CNTs, including pyridinic N
(397.5 eV), pyrrolic N (399.7 eV) and graphitic N (401.4 eV). Notably,
the positive shift of N1s in Pt/Co@N-CNTs reveal the occurrence of
electron transfer from N to Pt NPs. Generally speaking, pyridinic N is
recognized as promote electron transfer, meanwhile, graphitic N can
improve the conductivity of the catalyst [44,45]. The percentage of
pyridinic N and graphitic N in Pt/Co@N-CNTs are highest among all
catalysts (Table S2), which might be vital to enhance the catalytic ac­
tivity. The C 1 s spectrum (Fig. S5) could be fitted into four peaks at
284.3 eV (sp2-sp2 C), 285.5 eV (N-sp2 C), 286.2 eV (N-sp3 C) and 288.4
eV (π-π*) [42]. The deconvoluted XPS spectra of O 1 s (Fig. S6)

5
M. Jin et al.
demonstrated existence of carboxyls (530.8 eV) and hydroxyls (532.5
eV) in electrocatalyst.
Fig. 5a displays the cyclic voltammograms (CVs) of Pt/M@N-CNTs
(M = Co, Ni and Fe3C) and commercial Pt/C in 1 M KOH. The electro­
chemically surface area (ECSA) can be calculated by the hydrogen
desorption region (-0.8 V ~ -0.5 V) of CVs. The Pt/Co@N-CNTs has the
largest ECSA (34.3 m2 g− 1) in all catalysts (Fig. 5d), indicating that Pt/
Co@N-CNTs provides more catalytic active sites in electrocatalytic
process. The catalytic properties of Pt/M@N-CNTs (M = Co, Ni and
Fe3C) towards methanol oxidation are investigated in 1 M KOH and 1 M
CH3OH (Fig. 5b). The mass activity of Pt/Co@N-CNTs is 1652 mA mg-
1
Pt, which is 1.16, 1.97 and 2.19-fold larger than that of Pt/Ni@N-CNTs,
Pt/Fe3C@N-CNTs and commercial Pt/C, respectively (Fig. 5e). Mean­
while, the specific activity of Pt/Co@N-CNTs (4.82 mA cm-2Pt) is 1.13,
1.24 and 1.41 times higher than that of Pt/Ni@N-CNTs, Pt/Fe3C@N-
CNTs and commercial Pt/C, respectively. The ratio of the peak current
density for forward (If) and backward (Ib) scans (If/Ib) can be used to
evaluate the CO tolerance of the catalysts (Table S3). Traditionally, a
lower If/Ib value reveals weaker tolerance to intermediate carbon spe­
cies, which means incompletion of methanol oxidation [46,47]. The If/Ib
ratios of Pt/Co@N-CNTs, Pt/Ni@N-CNTs, Pt/Fe3C@N-CNTs and Pt/C
calculated from Fig. 6b are 5.51, 5.24, 4.32 and 5.12, respectively. It is
demonstrated that Pt/Co@N-CNTs possess the enhanced anti-poisoning
ability, which might be attributed to the uniform and dense dispersion of
Pt NPs on the surface of Co@N-CNTs. The dense and uniform distribu­
tion of Pt NPs mean that the distance between Pt and Pt is relatively
close, which is facilitating the removal of the COads intermediate by OH
adsorbing on adjacent Pt. Obviously, Pt/Co@N-CNTs also displays the
much lower oxidation potential in MOR at the same oxidation current
density (Fig. 5c) than other catalysts (Fig. 5f), implying that methanol
can be more easily oxidized on the Pt/Co@N-CNTs.
We used DFT calculations of models to optimal anchoring sites of Pt4
cluster on the N-CNTs supports. As presented in Fig. 6a, the substitution
of carbon atom with a nitrogen atom in hexatomic ring can form three
nitrogen bonding configurations, which are graphitic N, pyridinic N and
pyrrolic N, respectively. To understand the effect of N on the stability of
Pt NPs, the adhesion energy of Pt, Eadh was calculated with the following
equation:.
Eadh = (Eslab+Pt4 − Eslab − EPt4 )
Fig. 5. CVs of Pt/M@N-CNTs (M = Co, Ni and Fe3C) and commercial Pt/C in (a) 1 M KOH and (b) 1 M KOH + 1 M CH3OH at 50 mV s− 1. LSV curves of all catalysts in
(c) 1 M KOH + 1 M CH3OH at a step rate of 1 mV s− 1; corresponding histogram of the (d) ECSA, (e) mass activity and specific activity, (f) onset potential.
6
Applied Surface Science 591 (2022) 153201
Where Eslab+Pt4, Eslab and EPt4 are the total energy of Pt4 cluster with
substrate, the energy of free-standing substrate, the energy of Pt4 cluster.
As shown in Fig. 6b, N doped can significantly decrease the adhesion
energy of each Pt atom, from − 0.57 eV in Pt4@C system to − 0.68 eV in
Pt4@graphitic N and then to − 1.39 eV in Pt4@pyridinic N (Fig. S7-S8,
Fig. 6c-6e, Table S4-S5 and Table 1). Analyzing the results of the cal­
culations, indicating the formation of Pt-N bonds, in agreement with the
XPS spectra. Thus, the systematic binding energies simulation in DFT
methods revealed that Pt-group metals preferentially interacts with
pyridinic nitrogen (Npyr) [48]. As listed in Fig. 6c-6e and Table 1, the Pt
atom prefers to form a bridge in the centers of three pyridinic nitrogen. It
can be attributed to the number and stability of generated bonds inter­
action between Pt-group metals and vacancy Npyr atoms, which is not
only break C-C bonds in the hexatomic ring and symmetry, but also can
further improve catalytic activity and stability of MOR. We also calcu­
lated the charge density differences (Fig. S9) and DOS (density of states,
see Fig. S10) of Pt4/C, Pt4/graphitic N, and Pt4/pyridinic N models,
respectively. The d band center of Pt moves upwards after bonding with
N atoms because of the stronger electronic accumulation of Pt4 clusters
after interacting with pyridinic nitrogen (Npyr).
The steady-state chronoamperometry of Pt/M@N-CNTs (M = Co, Ni
and Fe3C) and commercial Pt/C are measured in 1 M KOH and 1 M
CH3OH (Fig. S11). Conspicuously, the Pt/Co@N-CNTs exhibits the
highest initial current density and slowest deterioration rate during the
entire test time in comparison with other catalysts, indicating an
excellent CO tolerance during the methanol oxidation processes.
Continuous CV tests of all catalysts are conducted in 1 M KOH
(Fig. S12). After 1000 cycling, the ECSA of Pt/Co@N-CNTs remained at
53 % relative to the initial ECSA, which is highest retention rate among
all catalysts. The CO stripping measurement of Pt/M@N-CNTs (M = Co,
Ni and Fe3C) and commercial Pt/C are conducted (Fig. S13). The onset
potential of Pt/Co@N-CNTs (-0.475 V) is more negative than that of Pt/
Ni@N-CNTs (-0.399 V), Pt/Fe3C@N-CNTs (-0.352 V) and commercial
Pt/C (-0.363 V). Specifically, the Pt/Co@N-CNTs also displays the
smallest peak potential (-0.114 V) among all catalysts. Above results
illustrate superior CO tolerance of Pt/Co@N-CNTs. All of Pt/M@N-CNTs
(M = Co, Ni and Fe3C) exhibit three peaks at the potential ranging from
− 0.4 to 0 V, compared with commercial Pt/C, revealing that the CO
oxidation occurs on different active sites [49,50]. All of these
M. Jin et al. Applied Surface Science 591 (2022) 153201

Fig. 6. (a) Schematic diagram of different N structures in N doped CNTs, (b) the variation of calculated adhesion energies of Pt in different N structures, (c-e) top and
side views of models for Pt cluster anchored to pyridinic N-doped CNTs. Color code: C, gray; N, blue; Pt, cyan.

Table 1
Pt-CH3OH + OH– → Pt-CH3O + H2O + e- (1)
The adhesion energy for Pt cluster anchored to pyridinic N-doped CNTs (Model 1
and 3). –
Pt-CH3O + OH → Pt-CH2O + H2O + e -
(2)
Model EPt4 (eV) Eslab (eV) Eslab+Pt4 (eV) Eadh (eV) Eadh/4 (eV)
Pt-CH2O + OH– → Pt-CHO + H2O + e- (3)
1 − 13.09 − 450.29 − 467.12 − 3.75 − 0.94
2 − 13.09 − 450.29 − 468.93 − 5.55 − 1.39 –
Pt-CHO + OH → Pt-CO + H2O + e -
(4)
3 − 13.09 − 450.29 − 465.86 − 2.48 − 0.62
–
Pt-CO + Pt-OH + OH → 2Pt + CO2 + H2O + e -
(5)

consequences provide clear evidence of the remarkable electrocatalytic
activity and good catalytic stability of Pt/Co@N-CNTs for MOR. The Pt/
Co@N-CNTs is more competitory than those of recent methanol oxida­
tion electrocatalysts in alkaline medium (Table S6).
More importantly, electrochemical impedance spectroscopy (EIS)
can be used to estimate the activity of catalysts. The Nyquist plots of Pt/
M@N-CNTs (M = Co, Ni and Fe3C) and commercial Pt/C are depicted in
Fig. 7a. The smaller semicircle diameter of Nyquist plots indicates the
lower charge transfer resistance [51]. Pt/Co@N-CNTs has the smallest
semicircle diameter, and hence Pt/Co@N-CNTs has the fastest rate in
methanol oxidation. To further investigate the kinetics of methanol
oxidation in Pt/Co@N-CNTs, the Nyquist plots at different potentials are
shown in Fig. 7b to 7d. Manifestation of approximatively straight lines
in EIS spectra below − 0.4 V reveals no occurrence of methanol oxidation
lower − 0.4 V, agreeing with the CV data [43]. From − 0.4 V to − 0.2 V,
an obvious clockwise loop at low frequencies centered on the fourth
quadrant reveals behavior of pseudocapacitance and the semicircle
diameter of Nyquist plots decreases with potential increasing. Above
results illustrates the process that adsorbed CO intermediate species
dehydrogenized from methanol (Equation (1) to (4)) oxidize to CO2 to
removal from catalyst (Equation (5)). More active site freshly exposing
due to oxidation removal of COads from Pt/Co@N-CNTs, the kinetics of
the methanol oxidation reaction facilitate [52].
As the potential goes by, the semicircle diameter of EIS first increases
at potential from − 0.2 V to − 0.15 V. Then the impedance profile sud­
denly exhibits negative values at − 0.1 V, turned to the second quadrant
(Fig. 7c). Owing to formation of the chemisorbed OH species, the rate-
determining step of MOR turned into the oxidation removal of COads
intermediates from methanol dehydrogenation [53,54]. As shown in
Fig. 7d, further increase the potential beyond 0.1 V, the impedance arc
tries back to the first quadrant with large resistance. Over-high potential
caused excessively strong adsorption of OH species on the surface of Pt/
Co@N-CNTs, which inhibit happening of methanol oxidation reaction.
3. Conclusion
In summary, we have successfully tuned microstructure of carbon
layer in M@N-CNTs (M = Co, Ni and Fe3C) via acetylacetone salt. After
Pt loading, the distribution of Pt NPs in Pt/M@N-CNTs are strongly
depend on surface state and constitution of carbon layer in M@N-CNTs,
which further influences their catalytic ability and stability towards to
MOR. The state-of-art Pt/Co@N-CNTs exhibits superior both mass and
specific activity towards to MOR in alkaline medium than that of com­
mercial Pt/C. Proper tuning of N configuration, thickness and defect of
carbon layer not only endow more active site to well- disperse Pt NPs
deposition, but also provide strong interaction to prevent migrating and

7
M. Jin et al.
Fig. 7. Nyquist plots of (a) Pt/M@N-CNTs (M = Co, Ni and Fe3C) at − 0.2 V in 1 M KOH + 1 M CH3OH. Nyquist plots of (b-d) Pt/Co@N-CNTs in 1 M KOH + 1 M
CH3OH solution at electrode potentials from − 0.6 V to 0.3 V.
excellent charge/electron transport ability, further improving stability
and catalytic activity in electrochemical process. This work not only
provide a new viewpoint to develop novel carbon/metal oxide com­
posite with desired surface state and constitution, but also open an
approach for design and construct of nanomaterials for energy storage
and conversation.
CRediT authorship contribution statement
Meng Jin: Writing – original draft, Investigation, Methodology.
Rong Wang: Formal analysis, Software. Bi Jia: Investigation. Jun
Zhang: Investigation. Hui Liu: Methodology. Shi-Yu Lu: Conceptuali­
zation, Funding acquisition, Writing – review & editing, Investigation,
Methodology.
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.
Acknowledgement
This work was financially supported by Talent Introduction of
Chongqing University of Science and Technology (No. ckrc2021050),
“Young scholar in engineering science” post-doctoral project of BIC-
EAST (Peking University) and Project funded by China Postdoctoral
Science Foundation (No.2020M670021). The authors acknowledge
Beijng PARATERA Tech CO.,Ltd. for providing HPC resources that have
contributed to the research results reported within this paper. URL:
https://paratera.com/
8
Applied Surface Science 591 (2022) 153201
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.apsusc.2022.153201.
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Another random document with
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produced no other interest than would have arisen from the appearance of a
gull, or any other aquatic bird.

[9] When the steward was informed of his sentence, he asked Comstock
how long a time he would give him to make his peace with God?
—"Fourteen seconds!" was the reply.

[10] Tamon, High Chief.

[11] Called the Reef Chain Tide Islands.

[12] Lay witnessed the execution of a man during his residence at the
Mulgraves. I do not remember the nature of his offence. He was not bound,
or in any way confined; but, after it was determined that he should die,
several men attacked him with spears and stones. He fought desperately to
the last, although his situation was altogether hopeless, freely bestowing
upon his enemies the epithets of cowards and murderers. Even when he
could no longer resist, his spirit was unconquered,—and he breathed his
last, with expressions of scorn and hatred on his lips.

[13] Lay frequently saw the people, who performed the execution I have
mentioned in a former note, throw away portions of their food, as an
offering to the spirit of him they had slain.

[14] Crimacu, as it is pronounced by the natives. The missionaries write his

name Karaimoku.
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