Materials Letters 141 (2015) 104–106

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Synthesis of FeS2 (pyrite) nanotube through sulfuration

of Fe2O3 nanotube
Xiaoguo Shi a, Ang Tian a, Xiangxin Xue a,n, He Yang a, Quan Xu b
a
Liaoning Provincial Key Laboratory of Metallurgical Resources Circulation Science, Northeastern University, Shenyang 110819, China
b
Institute of New Energy, State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China

art ic l e i nf o a b s t r a c t

Article history: Pyrite (FeS2) has been widely used in the photovoltaic field due to its various advantages. In this study,
Received 7 October 2014 FeS2 nanotube arrays were successfully synthesized by sulfuration of the precursor Fe2O3 nanotube
Accepted 16 November 2014 arrays. The microstructure, crystalline phase and optical characteristics of FeS2 nanotube arrays were
Available online 26 November 2014
investigated. It was found that the precursor with tubular nano-topography could effectively accelerate
Keywords: the diffusion rate of sulfur atoms and make the sulfuration more complete. The structure of FeS2
FeS2 nanotube nanotube could enlarge the optical absorption area and enhance the scattering of incident light which
Optical property would extend the travel path of photon in the nanotube coating and ultimately promoted the optical
Nanocrystalline absorption. The bandgap of FeS2 nanotube arrays was 1.24 eV.
Microstructure
& 2014 Elsevier B.V. All rights reserved.
Band gap

1. Introduction of TiO2 nanotube would lead to the narrower forbidden band gap
which could be attributed to the quantum confinement [14]. On
Since the photoelectric characteristics of the natural pyrite were the basis of the works mentioned above, we successfully prepared
discovered, lots of research works about preparation, crystal struc- FeS2 (pyrite) nanotube array by sulfuration of the precursor Fe2O3
ture, morphology and photoelectric property of FeS2 were reported nanotube arrays. The microstructure, optical absorption property
[1,2]. The optical absorption capacity of pyrite (α4105 cm 1) is two and bandgap of FeS2 nanotube coating were also investigated.
orders of magnitude higher than that of the monocrystalline Si [3]
and pyrite has appropriate band gap of 0.95 eV. With these
excellent properties, pyrite has been widely used as the photoanode 2. Experimental
[4], sensitizer for the energy conversion [5] and solar cells [6].
However, the S/Fe ratio in natural pyrite does not fully comply with Preparation of precursor Fe3O4 and TiO2 nanotube coating: The
the stoichiometric ratio. Therefore, various preparation methods commercial Fe foils (1 mm thick, purity 99.5%) were anodized at
have been applied for the preparation of FeS2, such as, chemical 70 V in the electrolyte solution containing ethylene glycol, 0.9 wt%
vapor deposition (CVD) [7], flash evaporation [8], magnetron NH4F and 3 vol% H2O for 20 min at 10 1C. Subsequently, the
sputtering and ion sputtering [9], sulfuration of Fe, Fe2O3 or Fe3O4 amorphous samples were annealed at 400 1C for 2 h in air to
[10,11], etc. Among these methods, sulfuration of the precursor obtain the precursor Fe3O4 nanotube. In order to explore the effect
Fe2O3 can effectively avoid the formation intermediate phases (e.g. of nanotube's morphology on the optical absorption, TiO2 nano-
FeS, Fe1 xS). tube array with similar morphology was prepared as the control
It is known that TiO2 nanotube arrays could be used as the group. The cleaned Ti foil was anodized at 40 V for 6 h in the
photoanode of the solar cell [12,13] with larger special surface area electrolyte solution containing ethylene glycol, 5 wt% NH4F and
to absorb dye molecule and highly ordered structure which could 2 vol% hydrofluoric acid. Then the TiO2 nanotube sample was
accelerate transmission of photoelectronics. The optical absorption annealed at 450 1C for 1 h in air.
property of nanotube arrays could be tuned by geometry size of Sulfuration of precursor Fe3O4 nanotube coating: The precursors
nanotube such as inner radii, wall thickness and the length of were sealed in the quartz tube (vacuum tube furnace) with the
nanotube [14,15]. For example, the increase of the wall thickness sulfur pressure of 80 kPa. Filling and evacuating the quartz tube
with nitrogen for 5 times to ensure the residual gas pressure was
less than 1  10 2 Pa before annealing at 400 1C for 5 h. The
n
Corresponding author. control sample of FeS2 micro-particles coating (FeS2 sheet) was
E-mail address: Xuexx@mail.neu.edu.cn (X. Xue). prepared at 600 1C for 10 h with the Fe substrate.

http://dx.doi.org/10.1016/j.matlet.2014.11.084
0167-577X/& 2014 Elsevier B.V. All rights reserved.
 X. Shi et al. / Materials Letters 141 (2015) 104–106 105

Characterization: The morphology and crystallinity of the sam- crystalline phase of the TiO2 nanotube was anatase mixed with rutile
ples were evaluated by field emission scanning electron micro- (Fig. 1e). Fig. 1c shows the morphology of FeS2 micro-particles with the
scopy (FE-SEM, ZEISS ULTRA) and X-ray diffraction (XRD, Rigaku D/ least diameter of 200 nm. The corresponding XRD pattern showed
Max 2500). The transmission electron microscopy (TEM, JEM- that the intermediate phase (FeS and Fe1 xS) also exist with pyrite
2100) was used to characterize the single nanotube's morphology (Fig. 1f). The tubular structure of FeS2 nanotube could be clearly
and crystallinity. Optical absorption spectra of the samples at observed in Fig. 2a. The diffraction spots' lattice spacing of 0.164 nm,
ambient temperature were recorded at wavelength between 400 0.189 nm and 0.315 nm corresponded to the d value of (311), (220) and
and 1100 nm with UV-2550 spectrophotometer which spectral (111) crystal planes of FeS2 (pyrite), respectively (Fig. 2b). It meant that
resolution is 0.1 nm. the nanotube had the cubic crystal and single crystal characterization.
As shown in Fig. 3a, the absorption curve could be divided into
three stages: weak absorption region in the range below 1.25 eV;
3. Result and discussion abrupt absorption region in the range of 1.25–2.0 eV and the stable
absorption region in the range above 2.0 eV. Among the three
The morphologies of different samples were shown in Fig. 1a. The samples, the stable optical absorption coefficient of FeS2 micro-
vertically-aligned FeS2 nanotubes were highly ordered arranged and particles is 1.8  105 cm 1 and FeS2 nanotube has the maximum
the caliber, length and wall thickness were 90710 nm, 2.570.2 μm absorption coefficient of 4.6  105 cm 1. The pattern of the abrupt
and 1572 nm respectively. The XRD pattern of FeS2 nanotube was absorption region indicated that all of the samples possessed
index to represent the pyrite phase (PDF Card 99-0087) (Fig. 1d). The classical semiconductor properties [16]. The excellent absorption
diffraction peak of Fe also appeared in the pattern because of the Fe performance of the FeS2 nanotube could be attributed to the
substrate. The TiO2 nanotube had the caliber, length and wall thickness morphology of nanotube. The nanotube array has larger surface
of 100710 nm, 370.1 μm and 2072 nm, respectively (Fig. 1b). The area which could effectively increase the diffusion rate of sulfur

Fig. 1. SEM and XRD of different samples: morphology of (a) FeS2 nanotube (b) TiO2 nanotube (c) FeS2 microparticles; XRD pattern of (d) FeS2 nanotube (e) TiO2 nanotube
(f) FeS2 microparticles.

Fig. 2. TEM of single FeS2 nanotube: (a) morphology (b) diffraction pattern.
106 X. Shi et al. / Materials Letters 141 (2015) 104–106

Fig. 3. Optical absorption property of different samples: (a) photo absorption coefficient α. (b) Plots of (αhν)1/2 vs. hν. Inset: zoom magnified picture of TiO2 nanotubes'
absorption coefficient.

atoms and complete the sulfuration, eventually leading to the FeS2 nanotube coating showed better optical property than FeS2
better optical property than the FeS2 micro-particles mixed with micro-particles which could attribute to the morphology effect that
FeS or Fe1 xS [17]. In addition, compared with micro-particles, the the nanotube enhanced the scatter of light and promoted the optical
nanotubes with hollow tubular structure could enable more lights absorption.
to be irradiated inside the cavity and promote the light refraction
[18] as well as the subsurface scattering [19], therefore, the
absorption was increased. Similarly, the weak optical absorption Acknowledgments
of TiO2 nanotube (1.5  104 cm 1) in visible region might be
attributed to the photonic band generated from nanotube topo-
This work is supported by the National Natural Science Foun-
graphy and multiple scattering of light [20].
dation of China (U1261120, 51002027), Post Doctoral Foundation
The indirect band gap of FeS2 could be concluded from the
of China (2013M530930), Scientific Foundation of Educational
curve of (αhν)1/2 vs. photoelectron energy in Fig. 3b. The optical
Department of Liaoning Province (L2012084), Project of Ministry
absorption of indirect semiconductor was caused by the transi-
of Education of Basic Scientific Research (N130402001).
tions of electrons from the valence band to the conductive band as
well as assisting phonons [21]. The band gap of FeS2 micro-
particles was 0.88 eV and the bandgap of FeS2 nanotube arrays References
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