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Applied Surface Science 469 (2019) 269–275 Contents lists available at ScienceDirect Applied Surface Science

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Applied Surface Science

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Science journal homepage: www.elsevier.com/locate/apsusc Full Length Article Controllable synthesis of nitrogen-doped

Full Length Article

Controllable synthesis of nitrogen-doped carbon nanotubes derived from halloysite-templated polyaniline towards nonprecious ORR catalysts

Wenjie Liu a , Qianxun Ru a , Shixiang Zuo a , Song Yang a , Jie Han b , , Chao Yao a ,

a School of Petrochemical Engineering, Changzhou University, Changzhou 213164, PR China b School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, PR China

T
T

ARTICLE INFO

Keywords:

Nitrogen-doped carbon nanotubes Halloysite Template Polyaniline Oxygen reduction reaction

ABSTRACT

Halloysites were applied as the template to form halloysite/polyaniline core/shell hybrids through an oxidative polymerization route, where the amount of aniline monomer could be adjusted to precisely control the shell thickness of polyaniline. The pyrolysis process was then applied to ensure the carbonization of the polyaniline to form halloysite/nitrogen-doped carbon core/shell hybrids. Finally, halloysites were removed, resulting in the formation of nitrogen-doped carbon nanotube with a uniform morphology and a controlled shell thickness. The shell thickness and pyrolysis temperature of nitrogen-doped carbon nanotubes were optimized to improve the electrocatalytic performance involved in oxygen reduction reaction. The nitrogen-doped carbon nanotubes showed good electrocatalytic activities toward oxygen reduction reaction in 0.1 mol L 1 KOH aqueous solution, making them a promising cathode catalyst for alkaline fuel cell applications.

1. Introduction

With the high degree of industrialization in the modern society, the non-renewable energy sources such as coal and oil are increasingly scarce. Fuel cells are not subject to Carnot cycles [1,2] . They convert chemical energy directly into electrical energy with high conversion e ciency and environmental friendliness. Therefore, fuel cells have become a substitute for non-renewable energy to solve the energy problem. The bipolar reaction rates of fuel cells are quite di erent. The oxygen reduction reaction (ORR) at the cathode greatly limits the performance of the fuel cells due to the slow kinetics [3] . The cathode catalyst is needed to promote the reaction. Currently, the good catalysts are still based on noble metals of typical platinum, which cannot be put into mass production due to its high price and low reserve [4] . There- fore, the development of inexpensive and stable noble metal-free ORR catalysts is of great importance in reducing the cost of fuel cells and promoting their wider use in large-scale applications. The noble metal-free ORR catalysts mainly include metal macro- cyclic compound-based catalysts [5,6] , transition metal oxide-based catalysts [7,8] , and metal-free carbon-based catalysts [9] . Recently, the metal-free carbon-based catalysts have aroused considerable interest. Wang et al. synthesized the nitrogen-doped carbon materials using melamine as the raw material, and used it to catalyze the ORR [10] . Since then, various types of ORR catalysts based on nitrogen-doped

Corresponding authors. E-mail addresses: hanjie@yzu.edu.cn (J. Han), yaochao420@163.com (C. Yao).

Received 6 August 2018; Accepted 28 October 2018

Available online 29 October 2018 0169-4332/ © 2018 Elsevier B.V. All rights reserved.

carbon nanomaterials have been studied. The in ltration of nitrogen into the graphite structure of the carbon nanomaterial changes the atomic and electronic structure of the matrix, activates the carbon-ni- trogen π-electron and the lone pair conjugated from the nitrogen do- pant [11] . The delocalized conjugated system that forms sp 2 hybrid C signi cantly improves the electrocatalytic performance. Polyaniline (PANI), as a conductive polymer material, has good electrochemical performance and chemical stability [12] , and is an ideal precursor for the preparation of nitrogen-doped nanomaterials. The reported litera- tures usually synthesized PANI and its derivative using soft templates that composed of functional doping acids and/or surfactants. For in- stance, Zhong et al. used polyvinylpyrrolidone as a soft template to prepare a graphene-like nitrogen-doped carbon material by in-situ polymerization of aniline and exhibited good catalytic oxygen reduc- tion performance in an acidic solution [13] . Similar work has also been reported by Deng et al. [14] . After pyrolysis of PANI nanotubes, they used KOH to activate the samples at di erent temperatures. N-doped nanocarbons calcinated at 700 °C exhibited the highest ORR activity. The soft template method often requires high condition control to en- sure the desired morphology. Rafael et al. used mesoporous silica as a hard template and PANI as a precursor, successfully implanted nitrogen into the structure of mesoporous carbon nanomaterials by pyrolysis [15] . The synergistic e ect of nitrogen and oxygen was used to eec- tively improve the electrocatalytic activity of the carbon nanomaterials.

W. Liu et al.

Basically, the utilization of a template for the synthesis of nitrogen- doped carbon nanomaterials derived from PANI is to ensure the synthesis of nitrogen-doped carbon nanomaterials with desired mor- phology, controllable structure and high surface area. However, from the point of practical applications, searching natural abundant nano- materials as templates towards the synthesis of highly active nitrogen- doped carbon as active ORR electrocatalysts are of great interest. As a natural magnesium aluminosilicate mineral, halloysite (Al 2 Si 2 O 5 (OH) 4 ·2H 2 O) has a wide range of sources and low prices. More interesting, it has the inherent good tubular morphology. The usage of halloysite nanotubes (HNTs) as templates for the synthesis of PANI and nally nitrogen-doped carbon shows the obvious advantages: (1) The unique hollow tube of halloysite is rich in hydroxyl groups on its sur- faces and is capable of inducing the in situ growth of PANI [1618]; (2) As a natural magnesium aluminosilicate, HNTs are resistant to organic solvents and have a high speci c surface area, providing a rich active site for nitrogen doping of carbon. Herein, HNTs were applied as templates for the synthesis of highly active ORR electrocatalysts of nitrogen-doped carbon nanotubes. Firstly, aniline and halloysite were mixed in the aqueous solution, and ammonium persulfate (APS) was then added to oxidize the aniline to obtain HNTs/PANI hybrids. The HNTs/PANI hybrids were carbonized by pyrolysis to obtain HNTs/nitrogen-doped carbon nanotubes (HNTs/ N-CNTs), and the HNTs template was then removed by hydro uoric acid etching to obtain the resulting N-CNTs. By adjusting the amount of monomer, the shell thickness of the N-CNTs can be precisely controlled. Finally, the electrocatalytic performances of N-CNTs involved in ORR were investigated.

2. Experimental

2.1. Materials and methods

HNTs were purchased from Jiangsu NDZ Technology Group Co. Ltd. All other reagents were obtained from Sinopharm Chemical Reagent Co. Ltd. Aniline was distilled under reduced pressure before use. All reagents (Sinopharm Chemical Reagent Co. Ltd. China) were of analy- tical grade and used without further puri cation. The water used in this study was deionized by milli-Q Plus system (Millipore, France), having 18.2 MΩ electrical resistivity. The pure HNTs were dispersed in 0.1 mol L 1 hydrochloric acid, and the mechanical stirring was continued for 12 h to obtain the acid- i ed HNTs. Then, a PANI layer was coated on the surface of HNTs ac- cording to a method described elsewhere [19] . The detailed synthetic procedures were as follows: 3.00 g of acidied HNTs and 450 mL hy- drochloric acid solution (pH = 0.8) were mixed into a ask and soni- cated for 30 min. A certain volume (0.5, 1, or 1.5 mL) of aniline monomer was then injected into the above mixture and stirred for 12 h. The above mixture was recorded called A. 6.8 g APS was dissolved in 100 mL hydrochloric acid solution (pH = 0.8), which was marked as solution B. After the solution A was pre-cooled in an ice-water bath for 30 min, the solution B was added dropwise into the solution A with magnetic stirring for another 30 min. Subsequently, the mixture was stirred for 12 h at room temperature. The products of dark green powers, named as HNTs/PANI hybrids, were obtained through a pro- cess of repeating centrifugation and rinsing, and drying under vacuum at 60 °C. For the purpose of distinction, the as-synthesized HNTs/PANI core/shell hybrids at the monomer amount of 0.5, 1, and 1.5 mL were denoted as HNTs/PANI-0.5, HNTs/PANI-1, and HNTs/PANI-1.5, re- spectively. The synthesized HNTs/PANI hybrids were then calcined under ni- trogen for 2 h to realize the PANI carbonization to N-doped carbon. The calcination temperature was controlled at 800, 900 or 1000 °C, re- spectively. Finally, the HNTs/N-CNTs hybrids were immersed in hy- dro uoric acid with a mass fraction of 40% overnight, washed with deionized water until neutral, the products were centrifuged at

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Applied Surface Science 469 (2019) 269–275

8000 rpm, washed with ultrapure water and dried at 80 °C to obtain N- CNTs. For the purpose of distinction, the resulting N-CNTs are denoted N-CNTs(x)-y, where x means the calcination temperature and y means the monomer amount during the polymerization of aniline.

2.2. Electrochemical tests

Electrochemical test was carried out with a standard three electrode system. A Pt foil was used as the counter electrode and a saturated calomel electrode (SCE) was used as the reference electrode. The glass carbon (GC) substrate was coated with di erent catalysts and applied as the working electrode, which was conned in a rotating ring-disk electrode (RRDE, Pt ring and GC disk, 6.25 mm in disk diameter). To prepare the working electrode, 5.0 mg catalysts were dispersed in so- lution containing 950 μ L of 2-propanol and 50 μL of 5 wt% Na on so- lution (Sigma-Aldrich). The suspension was ultrasonically dispersed to form a homogeneous ink. After that, 6 μL of the ink was pipetted onto the GC electrode and then was naturally dried for 2 h to form a thin catalyst layer on the GC electrode. A certain volume of catalyst ink was then pipetted onto glassy carbon surface to result in a 0.15 mg cm 2 loading for all samples including commercial Pt/C (20 wt%, Johnson Matthey). The tests were conducted on a computer-controlled potentionstat/ workstation at room temperature. The supporting electrolyte was 0.1 mol L 1 KOH aqueous solution, which was purged with Ar or O 2 (Air Product, purity 99.995%) for at least 30 min prior to testing and maintained under Ar or O 2 atmosphere during the test. Cyclic voltam- mograms were recorded from 0.2 to 0.8 V versus SCE in Ar- and O 2 - staurated 0.1 mol L 1 KOH electrolyte solutions with a scan rate of 20 mV s 1 . Rotating disk electrode (RDE) was performed in O 2 -stau- rated 0.1 mol L 1 KOH at 1600 rpm with a sweep rate of 5 mV s 1 . All potentials were reported with reference to the reversible hydrogen electrode (RHE) potential scale. In 0.1 mol L 1 KOH solution, the po- tential of SCE was calibrated as +0.990 V with respect to RHE.

2.3. Characterization

Morphologies were characterized with a transmission electron mi- croscopy (TEM, Tecnai-12 Philip Apparatus Co., United States) and a high resolution transmission electron microscopy (HRTEM, Tecnai G2 F30 S-Twin TEM, FEI, Holland). The Fourier transform infrared spec- trometry (FTIR) spectra (Bruker Tensor 27, Bruker, Germany) were recorded in the range of 400 4000 cm-1. The samples were prepared in a pellet form with spectroscopic grade KBr. The speci c surface area and pore size were studied by using a Beishide 3H- 2000PS2 analysis instrument. The surface area was determined from the adsorption iso- therm using the multipoint Brunauer-Emmett-Teller (BET) method. The desorption isotherm were used to determine the average pore size and distribution by the Barrett-Joyner-Halenda (BJH) method. X-ray pho- toelectron spectroscopy (XPS) data were recorded on a Thermo ESCALAB 250 using a nonmonochromatized Al K α X-ray (1486.6 eV) as the excitation source and choosing C 1s as the reference line.

3. Results and discussion

3.1. Synthesis and characterization of N-CNTs

The synthesis of nitrogen-doped carbon nanotubes is shown in Scheme 1 . The structural changes of N-CNTs during the preparation were monitored by TEM images. PANI could be generated in situ by adding APS to the mixed solution of HNTs and aniline, due to the in- duction of HNTs surface hydroxyl groups. Fig. S1 a shows the TEM image of HNTs, where the hollow tube structure of halloysite can be clearly seen. Fig. S1b shows the rough surface of halloysite, indicating that the PANI coating is successfully formed, with a thickness of ap- proximately 20 nm. After calcination, it can be clearly seen from Fig.

W. Liu et al.

Applied Surface Science 469 (2019) 269–275

W. Liu et al. Applied Surface Science 469 (2019) 269–275 Scheme 1. Schematic representation of the

Scheme 1. Schematic representation of the preparation processes of N-CNTs.

representation of the preparation processes of N-CNTs. Fig. 1. (a) TEM and (b and c) SEM

Fig. 1. (a) TEM and (b and c) SEM images of N-CNTs(900)-1. (d, e, f) SEM-EDS maps of (e) C and (f) N of N-CNTs(900)-1.

S1 c that the composite material maintains a good nanotubular struc- ture. When the HNTs are removed, the nitrogen-doped carbon with a hollow tubular structure can be seen from Fig. 1 a with a diameter of about 35 nm and a tube length of between 0.2 and 0.4 μm. The shell thickness of N-CNTs is about 7 nm (inset in Fig. 1 a). The tubular mor- phology of the catalyst material was further conrmed by the corre- sponding SEM image ( Fig. 1 b), showing the tubular cross-section of the N-CNTs ( Fig. 1c). In addition, the SEM-EDS surface scan clearly shows the presence of C and N elements ( Fig. 1df).

3.2. Structural characterization

The shell thickness N-CNTs could be tuned by controlling the amount of aniline. The shell thicknesses of N-CNTs(900) are 10 nm ( Fig. 2 a) and 7 nm ( Fig. 2 b) when the aniline used were 1.5 mL and 1 mL, respectively. It was reported that the thinner wall thickness favors the adsorption and desorption of O 2 and the electron transfer during ORR [20 22] . When the aniline used was decreased to 0.5 mL, the shell thicknesses of N-CNTs(900) was further decreased to 5 nm, but the

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thin and broken shells collapsed and supported with each other ( Fig. 2 c). The calcination temperature also aects the resulting tubular morphology of N-CNTs, where high calcination temperature leads to thinner shell thickness of N-CNTs ( Fig. S2a and b). In comparison, the nitrogen-doped carbon materials prepared in the same manner without using HNTs as the template shows the irregular particulates ( Fig. S2 c). The chemical structures of products during the preparation pro- cesses of N-CNTs were monitored by FTIR spectra. Fig. 3 a shows the FTIR spectra of HNTs, where the Oe H stretching vibration at 3696 and 3621 cm 1 , the stretching of in-plane Si eO at 1100 and 1023 cm 1 can be observed. The peak at 537 cm 1 is assigned to the vibration of Al eO eSi and 469 cm 1 is assigned to bending vibration of Si e O [19] . As for HNTs/PANI core/shell composites, the characteristic peaks at 1568, 1487, 1302 and 1246 cm 1 ( Figs. 3 b and S3a) that assigned to PANI [23] , are detected: the peak at 1568 cm 1 is attributed to the characteristic vibrational peak of the PANI quinoid structure, the peak at 1487 cm 1 is attributed to the characteristic vibration peak of the phenylene structure of polyaniline, the peak at 1302 cm 1 is attributed to the C e N stretching vibration peak of the PANI skeleton and the peak

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Applied Surface Science 469 (2019) 269–275

W. Liu et al. Applied Surface Science 469 (2019) 269–275 Fig. 2. TEM images of (a)

Fig. 2. TEM images of (a) N-CNTs(900)-1.5, (b) N-CNTs(900)-1, (c) N-CNTs(900)-0.5.

(a) (b) N=Q=N -OH C-H N-B-N Al-O M-O C-N N-H Si-O (c) (d) 4000 3500
(a)
(b)
N=Q=N
-OH
C-H
N-B-N
Al-O
M-O
C-N N-H
Si-O
(c)
(d)
4000
3500
3000
2500
2000
1500
1000
500
Intensity (a.u)

Wavenumber (cm -1 )

Fig. 3. FTIR spectra of (a) HNTs, (b) HNTs/PANI-1, (c) HNTs/N-CNTs(900)-1, and (d) N-CNTs(900)-1.

at 1246 cm 1 is attributed to the C e N stretching vibration peak of the doped PANI. As for HNTs/N-CNTs, the characteristic peaks of PANI disappear in the infrared spectra. The broad peak appearing around 1590 cm 1 is attributed to the vibration of the C ] N bond in the uorene ring and the benzene ring, and the broad peak near 1236 cm 1 is attributed to the C e N and C e H stretching vibrations of the carbo- nized benzene and anthracene rings (Fig. 3 c). After further etching the HNTs, the characteristic peaks belonging to HNTs completely disappear ( Fig. 3 d), which proves that the template in the synthesized N-CNTs has been completely removed [24] . As shown in Fig. 4 a, the degree of graphitization of N-CNTs was characterized by Raman spectra. Normally, the degree of graphitization is qualitatively compared with the intensity ratio of the D band to the G band (I D /I G ), where the D band represents defective and amorphous of carbon nanostructures [25,26] while the G band represents the in-plane stretching vibration of ordered sp 2 hybridized carbon atoms [26,27] . Comparing the Raman spectra of N-CNTs(800)-1.5, N-CNTs(900)-1.5 and N-CNTs(1000)-1.5, the D and G bands at 1377 and 1587 cm 1 , respectively, were observed. The I D /I G value decreases as the calcina- tion temperature increases. It means that higher calcination tempera- ture leads to fewer defects and increased graphite crystallites in the N- CNTs. Increasing the degree of graphitization is benecial for im- proving the conductivity of N-CNTs. The conductivity of the materials plays a decisive role in the ORR when the electrical conductivity of the

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material di ers greatly [28] . Comparing the Raman spectra of N-CNTs (900)-1.5, N-CNTs(900)-1 and N-CNTs(900)-0.5, it was found that the I D /I G value increased with decreasing shell thickness, indicating the degree of disorder of the material increases, the defect increases [28] . Detection of N-CNTs(900)-1 by HRTEM clearly shows the shbone-like graphite structure, which can expose more graphite edges ( Fig. 1 a) [29] . XPS spectra were then applied to reveal the elemental composition and chemical environment of the materials (Fig. S3b) The N atomic percentage of N-CNTs(800)-1.5, N-CNTs(900)-1.5, N-CNTs(1000)-1.5, N-CNTs(900)-1 and NCNTs(900)-0.5 were 7.45%, 6.10%, 4.87%, 6.00% and 2.74%, respectively (Fig. 4 b). Normally, the thermal treat- ment of nitrogen contained precursor leads to reduction of nitrogen content as the treatment temperature increases. The e ect of N with di erent con gurations on the ORR performance is of great sig- nicance. Fig. 4 c shows the N 1s spectra of N-CNTs(900)-1, where the N 1s spectra can be tted into three peaks, corresponding to pyridinic N (398.6 eV), pyrrolic N (400.5 eV) and graphitic N (401.3 eV). The N 1 s spectra of di erent catalysts were also analysized (Fig. S3 c). The con- tents of di erent N have been given in Fig. 4 d. It has been reported that the pyridinic N content determines the onset potential, whereas the graphitic N content in uences the limiting current density for ORR [30] . The speci c surface area and pore diameter of N-CNTs were ana- lyzed by N 2 adsorption-desorption curves. The adsorption-desorption curves of all the samples belong to the type IV adsorption-desorption curves, which proves the mesoporous structure of the samples (Fig. 5 a). The specic surface area corresponding to N-CNTs(800)-1.5, N-CNTs (900)-1.5, N-CNTs(1000)-1.5, N-CNTs(900)-1, and N-CNTs(900)-0.5 are 68, 338, 261, 322 and 101 m 2 g 1 , respectively. It can be seen that when calcined at 1000 °C, the tubular structure of the nitrogen-doped carbon nanomaterials slightly collapse, and the pipes shrink sig- nicantly ( Fig. S2a). This is the reason why the specic surface area of N-CNTs (1000)-1.5 is decreased. The average pore diameters calculated by the BJH method from the desorption curves were 8.97, 9.53, 11.23, 9.09 and 11.32 nm, respectively ( Fig. 5 b).

3.3. Electrocatalytic performances of N-CNTs

The ORR electrocatalytic activity of N-CNTs(800)-1.5, N-CNTs (900)-1.5, N-CNTs(1000)-1.5, N-CNTs(900)-1 and N-CNTs(900)-0.5 was rstly studied by cyclic voltammetry (CV) experiment ( Fig. S4 ae). It can be seen that the reduction current in N 2 -saturated electrolyte is almost negligible, whereas the reduction current in O 2 -saturated elec- trolyte increases signi cantly, demonstrating that the material can be used to catalyze oxygen reduction. As can be seen from Fig. 6 a, the N- CNTs(900)-1 showed the best oxygen reduction performance. The peak potential of N-CNTs(900)-1 (0.74 V) is much higher than that of other catalysts. In addition, the linear-sweep voltammetry (LSV) curves for di erent catalysts at 1600 rpm were shown in Fig. 6b. The ORR activity (limiting current density) follows the sequence of N-CNTs(900)-1 > N- CNTs(900)-1.5 > N-CNTs(900)-0.5 > N-CNTs(800)-1.5 > N-CNTs

W. Liu et al.

D G (a) I D /I G =0.93 N-CNTs(800)-1.5 I D /I G =0.90 N-CNTs(900)-1.5
D
G
(a)
I
D /I G =0.93
N-CNTs(800)-1.5
I
D /I G =0.90
N-CNTs(900)-1.5
I
D /I G =0.87
N-CNTs(1000)-1.5
I D /I G =0.95
N-CNTs(900)-1
I D /I G =0.97
N-CNTs(900)-0.5
500
1000
1500
2000
2500
3000
3500
Intensity (a. u.)

Roman shift(cm -1 )

(c) graphitic N pyridinic N pyrrolic N 392 394 396 398 400 402 404 406
(c)
graphitic N
pyridinic N
pyrrolic N
392
394
396
398
400
402
404
406
Intensity(a.u.)

Binding energy(eV)

Applied Surface Science 469 (2019) 269–275

12 N content(%) (b) 10 8 6 4 2 0 N-CNTs(800)-1.5 N-CNTs(900)-1.5 N-CNTs(1000)-1.5 N-CNTs(900)-1
12
N content(%)
(b)
10
8
6
4
2
0
N-CNTs(800)-1.5
N-CNTs(900)-1.5
N-CNTs(1000)-1.5
N-CNTs(900)-1
N-CNTs(900)-0.5

100

90

80

70

60

50

(d) 16.87 17.10 18.94 19.33 21.56 Pyridinic N Pyrrolic N Graphitic N N-CNTs(800)-1.5 N-CNTs(900)-1.5
(d)
16.87
17.10
18.94
19.33
21.56
Pyridinic N
Pyrrolic N
Graphitic N
N-CNTs(800)-1.5
N-CNTs(900)-1.5
N-CNTs(1000)-1.5
N-CNTs(900)-1
N-CNTs(900)-0.5

Fig. 4. (a) Raman spectra of N-CNTs. (b) The analyzed result of N element in N-Carbon nanotubes. (c) N 1s XPS spectra of N-CNTs(900)-1. (d) Relative ratios of various nitrogen types in N-CNTs.

(1000)-1.5. N-CNTs(900)-1 exhibited the highest half-wave potential of 0.72 V (0.769 V, commercial Pt/C-20%), better than that of recently reported carbon-based materials (Table S1). As shown in Fig. 6 c, the calculated start potential of N-CNTs(900)-1 is also the highest as com- pared to other N-CNTs. Fig. 6 d is a calculated Koutecky-Levich (K-L) plot at a potential of 0.3 V (see support information for details), showing a linear relationship between j 1 and ω 1/2 where j is the limiting current density, ω is the electrode rotating speed. The slope of the K-L curve linearly tted at 0.3 V (versus RHE) by the N-CNTs(900)-1 electrode was the smallest whereas the kinetic current obtained at the intercept was the largest of all the catalysts studied in this study ( Fig. 6 e). The number of electrons transferred ( n) is calculated based on ring current and disk current (Eq. 4 in the supporting information ). The n -value of N-CNTs(900)-1 is stable at 3.99, indicating the four-

electron pathway of ORR ( Fig. S5b). This result is basically consistent with the K-L curve calculation result. To further conrm the oxygen reduction process, we performed the RRDE measurement ( Fig. S5b) to assess the formation of peroxide species (HO 2 ) during the ORR pro- cess. It can be found that the percentage of HO 2 formation for N-CNTs (900)-1 is less than the others (Fig. S5c). Stability of the catalyst in practical application is an important parameter. The stability of the catalyst was tested by potentiometric cycling from 0.3 to 1.2 V at 20 mV s 1 in 0.1 mol L 1 KOH saturated with O 2 atmospheres. As shown in Fig. 6f, after 1000 cycles, the half- wave potential of N-CNTs(900)-1 exhibited only a negative 10 mV shift, signi cantly lower than the commercial 20% Pt/C catalyst (18 mV). The corresponding ORR electrocatalytic characteristics of di erent catalysts were summarized in Table 1 , where N-CNTs(900)-1 exhibits

1000 N-CNTs(800)-1.5 (a) (b) N-CNTs(900)-1.5 N-CNTs(1000)-1.5 800 0.3 N-CNTs(900)-1 N-CNTs(900)-0.5 600 0.2
1000
N-CNTs(800)-1.5
(a)
(b)
N-CNTs(900)-1.5
N-CNTs(1000)-1.5
800
0.3
N-CNTs(900)-1
N-CNTs(900)-0.5
600
0.2
N-CNTs(800)-1.5
N-CNTs(900)-1.5
400
N-CNTs(1000)-1.5
0.1
N-CNTs(900)-1
N-CNTs(900)-0.5
200
0.0
0
0.0
0.2
0.4
0.6
0.8
1.0
10
100
Relative pressure(P/P 0 )
d(nm)
Volumn absorbed(cm 3 g -1 )
Volumn absorbed(cm 3 g -1 )

Fig. 5. (a) N 2 adsorption-desorption isotherms and (b) pore size distribution of N-CNTs.

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Applied Surface Science 469 (2019) 269–275

W. Liu et al. Applied Surface Science 469 (2019) 269–275 Fig. 6. (a) CV pro fi
W. Liu et al. Applied Surface Science 469 (2019) 269–275 Fig. 6. (a) CV pro fi
W. Liu et al. Applied Surface Science 469 (2019) 269–275 Fig. 6. (a) CV pro fi
W. Liu et al. Applied Surface Science 469 (2019) 269–275 Fig. 6. (a) CV pro fi
W. Liu et al. Applied Surface Science 469 (2019) 269–275 Fig. 6. (a) CV pro fi

Fig. 6. (a) CV pro les (scanning rate of 20 mV s 1 ) of all the samples in O 2 -saturated 0.1 mol L 1 KOH solutions. (b) LSV curves of all the samples recorded at 1600 rpm in O 2 -saturated 0.1 mol L 1 KOH solution. (c) The di erential plots of I versus E constructed from the LSV curves. From the sharply increased slope of the plots, the onset potential indicative of the start of the ORR can be clearly seen. (d) K-L plots of di erent catalysts at 0.3 V. (e) Kinetic current of dierent samples for O 2 reduction at 0.3 V. (f) Stability tests of N-CNTs(900)-1 and 20% Pt/C catalysts through 3000 potential cycles between 0.3 and 1.2 V at 5 mV s 1 .

Table 1 Summary of N content, surface area and electroactivity for the synthesized catalysts a .

Samples

N atomic percentage (at.%)

Pyridinic N content (at.%)

Speci c surface area (m 2 g 1 )

I s (mA cm 2 )

E onset (V)

E half (V)

n

N-CNTs(800)-1.5

7.45

16.87

68

3.54

0.82

0.67

3.22

N-CNTs(900)-1.5

6.10

17.10

338

4.24

0.82

0.68

3.54

N-CNTs(1000)-1.5

4.87

19.33

261

3.58

0.75

0.60

3.88

N-CNTs(900)-1

6.00

21.65

322

5.03

0.87

0.72

3.99

N-CNTs(900)-0.5

2.74

18.94

101

4.11

0.83

0.69

3.23

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the best overall performance. It has been reported that the pyridinic nitrogen and graphite nitrogen are the main con gurations that a ect the catalytic performance of ORR in N-doped carbon. When the ni- trogen atomic percentage is less than 2.8%, the di erence of con- ductivity between graphite nitrogen and pyridinic nitrogen is small. The activity of catalytic ORR depends on the di culty of the O 2 pro- tonation step, and graphite nitrogen shows higher catalytic ORR ac- tivity than pyridinic nitrogen. On the contrary, if the nitrogen atomic percentage is high (> 2.8%), the di erence of conductivity between graphite nitrogen and pyridinic nitrogen is large [26,31 35] . The electron transport properties of graphite nitrogen become the main determinants of ORR activity, so pyridinic nitrogen has a higher cata- lytic activity. Moreover, making nanostructured ORR catalysts with high surface area that ensuring abundant accessible active sites toward ORR is benecial for improvement in the catalytic activity. It can be seen that N-CNTs(900)-1 has the highest pyridinic nitrogen content and the large speci c surface area and thus exhibits the best electrocatalytic performance.

4. Conclusion

Through the template strategy as started from natural abundant HNTs, uniform N-CNTs can be successfully fabricated. The shell thick- ness, specic surface area and chemical composition of N-CNTs can be easily adjusted by changing the amount of aniline monomer and cal- cination temperature, which have a signi cant impact on the electro- catalytic properties of ORR. The N-CNTs(900)-1 catalyst with a speci c surface area of about 322 m 2 g 1 and a pyridinic N content of 21.65% showed the best ORR performance in alkaline medium and an overall quasi 4-electron transfer (3.99), including a good long-term stability. The strategy developed here not only provides an economical route to highly uniform N-CNTs with excellent ORR catalytic activity, but also will be instructive to the rational design of other advanced catalysts involved in energy storage and conversion applications.

Acknowledgements

The authors gratefully acknowledge nancial support from the National Natural Science Foundation of China (21673202), Qing Lan Project and the Priority Academic Program Development of Jiangsu Higher Education Institutions, Advanced Catalysis and Green Manufacturing Collaborative Innovation Center, Changzhou University, Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology (BM2012110). We would also like to acknowledge the technical support received at the Testing Center of Yangzhou University.

Appendix A. Supplementary material

Supplementary data to this article can be found online at https:// doi.org/10.1016/j.apsusc.2018.10.225 .

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