Adsorption of transition-metal atoms on boron nitride nanotube: A density-

functional study
Xiaojun Wu and X. C. Zeng

Citation: J. Chem. Phys. 125, 044711 (2006); doi: 10.1063/1.2218841

View online: http://dx.doi.org/10.1063/1.2218841
View Table of Contents: http://jcp.aip.org/resource/1/JCPSA6/v125/i4
Published by the American Institute of Physics.

Additional information on J. Chem. Phys.

Journal Homepage: http://jcp.aip.org/
Journal Information: http://jcp.aip.org/about/about_the_journal
Top downloads: http://jcp.aip.org/features/most_downloaded
Information for Authors: http://jcp.aip.org/authors

Downloaded 09 Mar 2013 to 142.51.1.212. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions
 THE JOURNAL OF CHEMICAL PHYSICS 125, 044711 共2006兲

Adsorption of transition-metal atoms on boron nitride nanotube:

A density-functional study
Xiaojun Wu and X. C. Zenga兲
Department of Chemistry, University of Nebraska-Lincoln, Lincoln, Nebraska 68588 and Nebraska Center
for Materials and Nanoscience, University of Nebraska-Lincoln, Lincoln, Nebraska 68588
共Received 3 April 2006; accepted 5 June 2006; published online 27 July 2006兲

Adsorption of transition atoms on a 共8,0兲 zigzag single-walled boron nitride 共BN兲 nanotube has been
investigated using density-functional theory methods. Main focuses have been placed on
configurations corresponding to the located minima of the adsorbates, the corresponding binding
energies, and the modified electronic properties of the BN nanotubes due to the adsorbates. We have
systemically studied a series of metal adsorbates including all 3d transition-metal elements 共Sc, Ti,
V, Cr, Mn, Fe, Co, Ni, Cu, and Zn兲 and two group-VIIIA transition-metal elements 共Pd and Pt兲. We
found that many transition-metal atoms can be chemically adsorbed on the outer surface of the BN
nanotubes and that the adsorption process is typically exothermic. Upon adsorption, the binding
energies of the Sc, Ti, Ni, Pd, and Pt atoms are relatively high 共⬎1.0 eV兲, while those of V, Fe, and
Co atoms are modest, ranging from 0.62 to 0.92 eV. Mn atom forms a weak bond with the BN
nanotube, while Zn atom cannot be chemically adsorbed on the BN nanotube. In most cases, the
adsorption of transition-metal atoms can induce certain impurity states within the band gap of the
pristine BN nanotube, thereby reducing the band gap. Most metal-adsorbed BN nanotubes exhibit
nonzero magnetic moments, contributed largely by the transition-metal atoms. © 2006 American
Institute of Physics. 关DOI: 10.1063/1.2218841兴

INTRODUCTION properties. This separation process poses a hindrance to fu-

ture massive application of carbon nanotubes in nanoelec-
Since the discovery of carbon nanotubes,1 tubular nano- tronics.
materials have attracted considerable attention due to their Boron nitride 共BN兲 nanotubes, another prevailing tubular
unique physical, chemical, and mechanical properties as well nanomaterial which was successfully synthesized shortly af-
as their great potential for applications. A fundamental ex- ter the discovery of the carbon nanotubes, are known to be
ample relevant to the physical and chemical properties of wide-gap semiconductors whose band gaps 共⬃5.5 eV兲 are
nanotubes is the interaction between nanotubes and metal almost independent of the tube diameter, helicity, and the
atoms. A better understanding of the metal/nanotube interac- number of walls. During the growth process, BN nanotubes
tion will have potential impacts on applications such as ca- tend to select a nonhelical or zigzag orientation. Like carbon
talysis, sensors, fabrication of core/sheath nanostructures, nanotubes, BN nanotubes also possess many unique physical
and nanoelectronics. Furthermore, a better understanding of and mechanical properties such as strong hardness, high ther-
the interaction between magnetic atoms and nanotubes can mal stability, and chemical inertness,6–9 which have pro-
be of importance to the field of low-dimensional magnetic moted increasing number of studies of this tubular nanoma-
systems. Thus far, most previous experimental and theoreti- terial. To date, fewer research work have been reported on
cal studies of metal/nanotube interactions have been mainly the BN nanotube/metal systems, compared to the amount of
work reported on the carbon nanotube/metal systems. One
devoted to the carbon nanotube/transition-metal systems.
known feature about the interaction between a BN nano-
The metal component can be a single atom, a metal cluster,
structure and metal is that the graphitelike BN surface is
or a planar metal surface.2–4 Many previous studies have
much more difficult to wet by metals than the carbon graph-
provided fundamental insights into potential applications of
ite surface. Recently, several experimental efforts have been
metal-adsorbed carbon nanotubes in various fields. The fact
made to fill the BN nanotubes with 3d transition metals, such
that the electronic properties of carbon nanotubes can be ei- as Fe–Ni Invar alloy, Co, Mo, Ni, and NiSi2.10–14 On the
ther metallic or semiconducting, depending on the tube di- theoretical side, several studies on the filling the BN nano-
ameter and helicity,5 also renders metal-adsorbed carbon tubes with transition metals have been reported, wherein
nanotubes a versatile tubular nanomaterials. On the other half-metallic behavior has been seen in some of these
hand, because of the dependence of the electronic properties systems.15,16
on the helicity and diameter, a separation process must be In this paper, we report a systematic study of the inter-
incurred to collect carbon nanotubes with uniform electronic action between the BN nanotube and all 3d transition metals
and two group-VIIIA metals using spin-polarized density-
a兲
Electronic mail: [email protected] functional theory 共DFT兲. For all DFT calculations, the indi-

0021-9606/2006/125共4兲/044711/7/$23.00 125, 044711-1 © 2006 American Institute of Physics

Downloaded 09 Mar 2013 to 142.51.1.212. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions
044711-2 X. Wu and X. C. Zeng J. Chem. Phys. 125, 044711 共2006兲

FIG. 1. 共Color online兲 The optimized structure of a pristine 共8,0兲 zigzag

single-walled BN nanotube.

vidual metal atom is placed on the outer surface of a 共8,0兲

zigzag single-walled BN nanotube. Configurations corre-
sponding to the local minima 共including the most stable con-
figuration兲 of the metal atoms on the BN nanotubes, the cor-
responding binding energies, and the modified electronic
structures of BN nanotubes due to metal adsorption are cal-
culated. We found that the binding energies can vary signifi-
cantly with different metal atoms, but change little at differ-
ent adsorption sites for a given metal. The adsorption of one
metal atom per supercell can induce impurity states within
the band gap of the pristine BN nanotube, thereby causing
the band gap reduction. With different transition metals, the
BN nanotube can exhibit a magnetic moment ranging from 0
共for Ni兲 to 5.0␮B 共for Mn兲. Our calculations show that some
metal atoms can strongly bind to the BN nanotube. Thus, the
BN nanotube may be covered 共or wet兲 by metal atoms,
which may lead to potential applications in future molecular
electronics.

MODELS AND METHODS

The DFT calculations were carried out using linear com-
bination of atomic orbitals density-functional method imple-
mented in the DMOL3 package.17 All-electron calculations
were performed with the double numerical basis sets plus
polarization functional 共DNP兲 and the generalized-gradient
approximation 共GGA兲 with the Perdew-Burke-Ernzerhof
共PBE兲 functional.18 The DNP basis sets are comparable to
6-31G** Gaussian basis sets.19 Delley et al. showed that the
DNP basis sets are more accurate than the Gaussian basis
sets of the same size.17 For the 5d transition metals Pd and
Pt, scalar relativistic effect is taken into account when deal-
ing with their core electrons. The real-space global cutoff
radius was set to be 5.5 Å. Spin-unrestricted DFT was used
to obtain all the results presented in this work. Without los-
ing generality, we chose the 共8,0兲 zigzag single-walled BN
nanotube as a prototype model system since the electronic
properties of BN nanotubes are weakly dependent on the
tube diameter and helicity. A tetragonal supercell is used,
whose size is 20⫻ 20⫻ 8.64 Å3, with the length of c 共in the
axial or z direction兲 being twice of the periodicity of the 共8,
0兲 BN nanotube. The supercell contains 32 B and 32 N atoms FIG. 2. 共Color online兲 Local minima configurations of the 3d transition-
as well as a single metal atom. With the periodic conditions, metal atom 关共a兲–共j兲兴 adsorbed on the outer surface of the 共8,0兲 BN nanotube.

Downloaded 09 Mar 2013 to 142.51.1.212. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions
044711-3 Adsorption of metals on boron nitride nanotubes J. Chem. Phys. 125, 044711 共2006兲

Sc atom will spontaneously relocate to take one of the three

stable configurations. At the BA site, the B–Sc and N–Sc
bond lengths are 2.31 and 2.15 Å, respectively. At the BZ
site, the two bond lengths are 2.24 and 2.16 Å, close to those
at the BA site. At the H site, the Sc atom locates right above
the center of the B3N3 hexagonal ring at the height of
⬃1.8 Å. The three B–Sc bonds lengths are 2.30, 2.72, and
2.73 Å, and three N–Sc bonds lengths are 2.27, 2.69, and
2.67 Å, respectively. The results show that the Sc atom tends
to locate closer to the three N atoms than B atoms. The
calculated binding energies range from 1.06 to 1.18 eV for
the three stable configurations. The positive binding-energy
value indicates that the chemical adsorption process is exo-
thermic. Note also that the binding energies as well as the
B–Sc and N–Sc bond lengths change little at the three ad-
sorption sites.
Among other nine transition-metal elements considered,
the Ti, V, Cr, Mn, Fe, Co, and Ni atoms can be chemically
FIG. 3. The binding energies Eb 共at the most stable configuration of metal adsorbed on the BA, BZ, and H sites as well, whereas the
atoms兲 vs the number of d electrons Nd of the first-row transition metals.
adsorption on the B or N site is unstable. The B – M 共M
= Ti, V, Cr, Mn, Fe, Co, and Ni兲 bond lengths range from
the nearest distance between two BN nanotubes is no less 2.05 to 2.52 Å while the N – M bond lengths range from
than 14.0 Å. The Brillouin zone is sampled by 1 ⫻ 1 ⫻ 3 spe- 1.85 to 2.40 Å. In contrast, at the H site, six of the seven
cial k point using the Monkhorst-Pack scheme.20 Test calcu- metal atoms can no longer locate above the center of the
lation showed that results are not changed upon increasing B3N3 hexagonal ring but either near the B–N bond that is
the k points. parallel to the tube axis 共for Ti, Cr, and Fe兲, or near the B
atom 共for Mn and Co兲 or the N atom 共for V兲; only the Ni
RESULTS AND DISCUSSION
atom can locate right above the center of the B3N3 hexagonal
Ten 3d transition metals 共Sc, Ti, V, Cr, Mn, Fe, Co, Ni, ring at the height of 1.6 Å. More different from the Sc case,
Cu, and Zn兲 and two group-VIIIA transition metals 共Pd and Cu atom can only be chemically adsorbed at the BA and BZ
Pt兲 have been considered to be the adsorbate on the outer sites, while Zn atom can only be physically adsorbed above
surface of the 共8,0兲 BN nanotube. For each type of the ad- the B site at a height of ⬃3.7 Å. Again, as in the case Sc
sorbate, five different initial adsorption sites were selected to adsorption, the calculated binding energies as well as the
examine the nanotube/metal interaction. The five sites are 共1兲 B – M and N – M bond lengths change little at different ad-
the top site of the boron atom 共B兲, 共2兲 the top site of the sorption sites for nearly all the 3d transition metals.
nitrogen atom 共N兲, 共3兲 the hollow site of the B3N3 hexagon In Fig. 3, we plot the binding energies corresponding to
ring 共H兲, 共4兲 the bridge site over an axial BN bond 共BA兲, and the most stable configurations Eb versus the number of d
共5兲 the bridge site over a zigzag BN bond 共BZ兲, all shown in electrons Nd of the ten 3d transition-metal elements. Interest-
Fig. 1. To ensure that the most stable adsorption configura- ingly, the trend in the variation of Eb vs Nd is mostly similar
tion can be achieved, the initial distance between the metal to that in the cases of adsorption of the 3d transition-metal
atom and the sidewall surface was adjusted several times atoms on the carbon nanotubes, while the values of the bind-
from 1.5 to 3.0 Å. Full structural relaxation was then per- ing energies are slightly smaller than those of 3d transition-
formed with each initial metal-tube distance. metal atoms adsorbed carbon nanotubes.2 Here, there are two
In Figs. 2共a兲–共j兲, configurations corresponding to the lo- maxima in the Eb vs Nd curve, one at Nd = 2 and the other at
cal minima are displayed for each of the ten 3d transition Nd = 8, and the curve shows a minimum at Nd = 5 共Cr兲. The
metals adsorbed on the BN nanotube 共BNNT兲. The binding binding energy of Ni 共Nd = 8兲 is the highest among the ten 3d
energies for all stable configurations are summarized in transition-metal elements. As shown in Fig. 3, some atoms
Table I. Here, the binding energies are given by the equation such as Sc, Ti, and Ni can bind strongly with the BN nano-
tube 共with the binding energies ⬎1.0 eV兲, and some others
Eb = ET共BNNT兲 + ET共A兲 − ET共BNNT + A兲, 共1兲
such as V, Fe, and Co can still be chemically adsorbed on the
where ET共BNNT兲 denotes the spin-polarized total energy sidewall but with modest binding energies 共ranging from
共per supercell兲 for the pristine BN nanotube, ET共A兲 is the 0.62 to 0.92 eV兲. The binding between Mn or Cu atom and
energy of a single atom A, and ET共BNNT+ A兲 is the total the BN nanotube is only marginal with the binding energy
energy of the BN nanotube with the adsorbed A atom 共per ⬍0.50 eV. Two unusual cases are Zn and Cr. The former
supercell兲. metal atom cannot be chemically adsorbed on the BN nano-
Using the Sc case as an example 关Fig. 2共a兲兴, for which tube, for which the binding mainly stems from the van de
three stable configurations at the BA, BZ, and H sites are Waals interaction. For Cr, although a stable adsorption con-
obtained, whereas the adsorption at the B and N sites is figuration on the BN nanotube can be achieved, the calcu-
unstable. Upon structural relaxation at the B and N sites, the lated binding energy suggests that the adsorption process is

Downloaded 09 Mar 2013 to 142.51.1.212. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions
044711-4 X. Wu and X. C. Zeng J. Chem. Phys. 125, 044711 共2006兲

TABLE I. Calculated binding energies 共Eb兲 of a single metal atom 共per supercell兲 adsorbed on the 共8,0兲 BN
nanotube at three stable binding sites, the corresponding boron-metal, nitrogen-metal bond distances, and
boron-metal-nitrogen angle, the net magnetic moment of the metal atom/total system, and the charge transferred
共C兲 from the metal atom to BN nanotube. 共M denotes the metal atom and B and N atoms are labeled in Fig. 1.兲

Atom Site BondB–M 共Å兲 BondN–M 共Å兲 ⬔B–M–N 共°兲 Eb 共eV兲 ␮M / ␮total 共␮B兲 C 共e兲

Sc BA 2.31 2.15 40.3 1.08 0.88/ 1.0 0.35

BZ 2.24 2.16 43.9 1.06 0.90/ 1.0 0.35
H 2.30,a,2.72,b2.73c 2.27,d2.69,e2.67f 77.4g 1.18 0.94/ 1.0 0.32

Ti BA 2.50 2.35 42.6 1.18 3.39/ 4.0 0.12

BZ 2.22 2.15 35.2 1.19 1.96/ 2.0 0.28
H 2.25,2.44,2.98 2.34,2.34,2.93 76.0 1.19 1.87/ 2.0 0.30

V BA 2.52 2.19 35.7 0.85 4.39/ 5.0 0.08

BZ 2.51 2.19 36.5 0.92 4.34/ 5.0 0.08
H 2.90,2.74,2.74 2.22,2.98,2.98 66.5 0.79 4.29/ 5.0 0.05

Cr BA 2.19 2.04 42.1 −0.22 4.08/ 4.0 0.32

BZ 2.18 2.03 44.5 −0.23 4.05/ 4.0 0.32
H 2.20,2.95,2.08 2.20,2.95,2.07 79.8 −1.17 2.12/ 2.0 0.39

Mn BA 2.19 2.31 38.8 0.47 4.99/ 5.0 0.20

BZ 2.19 2.34 39.7 0.46 4.99/ 5.0 0.19
H 2.21,2.98,2.98 2.74,2.72,2.72 69.4 0.42 4.98/ 5.0 0.21

Fe BA 2.17 2.37 37.8 0.62 3.87/ 4.0 0.10

BZ 2.23 2.29 39.2 0.62 3.86/ 4.0 0.10
H 2.12,2.01,2.88 2.15,1.97,2.87 82.1 −0.27 2.20/ 2.0 0.22

Co BA 2.15 2.30 38.7 0.64 2.90/ 3.0 0.08

BZ 2.16 2.40 38.3 0.62 2.81/ 3.0 0.09
H 2.14,3.19,3.02 3.03,2.78,2.57 64.7 0.65 2.79/ 3.0 0.10

Ni BA 2.05 1.85 44.9 1.30 0.00/ 0.0 0.11

BZ 2.10 1.85 45.2 1.27 0.00/ 0.0 0.11
H 2.21,2.40,2.41 1.98,2.50,2.51 83.8 0.81 0.00/ 0.0 0.09

Cu BA 2.33 2.27 36.8 0.46 0.78/ 1.0 0.06

BZ 2.27 2.36 37.7 0.44 0.76/ 1.0 0.10
H → BA

Zn ⬃3.7 ⬃4.0 0.16 0.00/ 0.0

Pd BA 2.21 2.14 39.9 1.33 0.00/ 0.0 0.22

BZ 2.28 2.13 40.4 1.32 0.00/ 0.0 0.22
H → BA

Pt BA 2.19 1.98 42.4 1.80 0.00/ 0.0 0.12

BZ 2.43 1.96 38.7 1.71 0.00/ 0.0 0.11
H → BA
a
B1 – M.
b
B3 – M.
c
B5 – M.
d
N2 – M.
e
N4 – M.
f
N6 – M.
g
⬔B3 – M – N6.

endothermic. In summary, based on the calculated binding of the electronic structures of the BN nanotube by the chemi-
energies, we speculate that those metals that can bind cal adsorption of 3d transition-metal atoms. Based on the
strongly with the BN nanotube might form a uniform cover- spin unrestricted calculation, the band structures of the pris-
age on the tube sidewall, while those cannot are more likely tine 共8,0兲 BN nanotube as well as those of the nine BNNT/
to form clusters on the sidewall as the number of the metal metal systems 共except BNNT/Zn兲 with the metal atom at the
atoms grows. BA, BZ, and H sites are calculated. Both the plus and minus
In addition to the binding energies and local-minimum spins 共labeled with “⫹” and “⫺” in Fig. 4兲 were considered.
configurations, we have also examined possible modification For the pristine BN nanotube, the band structures for the plus

Downloaded 09 Mar 2013 to 142.51.1.212. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions
044711-5 Adsorption of metals on boron nitride nanotubes J. Chem. Phys. 125, 044711 共2006兲

FIG. 4. The band structures of metal-adsorbed BN nanotube. The plus and minus spin electronic structures are distinguished with “⫹” and “⫺.” The Fermi
level is plotted with the dotted line. The ⌫ and X represents two highly symmetric points in the Brillouin zone of the supercell, that is, 共0, 0, 0兲 and 共0, 0, 0.5兲,
respectively.

and minus spins are the same, showing a direct band gap of structures, however, there is a band gap of ⬃1.0 eV. Again,
3.65 eV that is nearly the same as previous results.5,6 As the band structures of BNNT/ M 共M = Sc, Cr, Co, and Ni兲
shown in Fig. 4, it can be seen that in all nine systems the change little with different adsorption sites.
chemical adsorption of the 3d transition-metal atoms induces The electron-charge analysis using the Hirshfeld method
certain impurity states within the band gap of the pristine BN is summarized in Table I. Note that the Hirshfeld charge
nanotube, thereby causing the band gap reduction. In most analysis is based on the deformation electron density, which
cases, the band gap is no greater than 1.0 eV. The results of seems less sensitive to the selected basis sets than the Mul-
projected density of states 共PDOS兲 show that these impurity liken charge analysis, although the Hirshfeld charge analysis
states are mainly due to the d and s electrons of the transition generally underestimates the atomic charges.21 With the 3d
metals. To some extent, the p electrons also contribute to the transition-metal atoms adsorbed on the sidewall of BN nano-
density of states near the Fermi level, but the contribution is tube, the Hirshfeld analysis indicates that certain amount of
much less than that from the d and s electrons. The BN charge is transferred from the metal atoms to the BN nano-
nanotube contributes little to the density of states near the tubes. As a result, a net magnetic moment may emerge, rang-
Fermi level. It is worthy to note that when Fe atoms are ing from 5.0␮B 共for Mn兲 to 0 共for Ni兲. The net spin mainly
adsorbed at the BA site, the calculated band structures sug- locates on the metal atoms. Understandably, because the
gest that this particular BNNT/Fe configuration is possibly a ground state of the pristine BN nanotube is nonmagnetic, the
half-metal. A band crossing at the Fermi level occurs with net spin should origin from the magnetism of the adsorbed
little dispersion in the plus-spin band structures, due mainly metal atoms. Note also that in the case of transition-metal
to the s electrons of the Fe atoms. In the minus-spin band atoms adsorbed on the graphite or carbon nanotubes, previ-

Downloaded 09 Mar 2013 to 142.51.1.212. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions
044711-6 X. Wu and X. C. Zeng J. Chem. Phys. 125, 044711 共2006兲

atoms can be chemically adsorbed at the BA and BZ sites,

but the adsorption at the H, B, and N sites is unstable. The
B – M and N – M 共M = Pd and Pt兲 bond lengths range from
1.96 to 2.43 Å, nearly independent of the adsorption site.
The calculated binding energies are 1.33 and 1.23 eV for Pd
at the BA and BZ sites, and 1.80 and 1.71 eV for Pt at the
BA and BZ sites, respectively. Like in the case of first-row
transition-metal adsorption, the adsorption of Pd or Pt atoms
can induce six impurity states within the band gap of the BN
tube 共Fig. 6兲. One of the six impurity states is unoccupied,
while the other five are occupied. As such, the band gap of
the BNNT/ M systems 共M = Pd and Pt兲 is about 2.10 eV. The
PDOS analysis indicates that the unoccupied state origins
mainly from the s electrons of the metal atoms and the oc-
FIG. 5. 共Color online兲 Local minima configurations of a 共a兲 Pd and 共b兲 Pt cupied states mainly origin from the d electrons of the metal
atom 共in the supercell兲 adsorbed on the 共8,0兲 BN nanotube. atoms. Moreover, both the BNNT/Pd and BNNT/Pt systems
exhibit zero magnetism moment.
ous studies have shown distinct deduction of the local mag-
netic moment on the transition-metal atoms due to the pro-
motion of the 4s electrons into 3d orbitals.2,3,22 However, in CONCLUSION
the case of transition-metal atoms adsorbed on the BN nano-
tubes, the deduction of the magnetic moment is not as much. Using the density-functional theory, the adsorption of
Consequently, the local magnetic moments of many transition-metal atoms on the 共8,0兲 zigzag single-walled BN
transition-metal atoms are close to those of freestanding nanotube has been systemically studied. Ten 3d transition
transition-metal atoms. Moreover, the net spin depends only metals 共from Sc to Zn兲 and two group-VIIIA elements, Pd
weakly on the location of the adsorption site for many tran- and Pt, were considered. We found that most transition met-
sition metals, a unique feature that could be exploited for als can be chemically adsorbed on the sidewall of BN nano-
making molecular magnets with the metal-covered BN nano- tube and the adsorption process is typically exothermic. Sev-
tubes. Three exceptions are Ti, Cr, and Fe, for which the eral metal atoms such as Sc, Ti, Ni, Pd, and Pt can be
magnetic moment can vary with the location of the adsorp- chemically adsorbed with relatively high binding energy
tion site. One possible reason for the exceptions is that the 共greater than 1.0 eV兲. The Mn atom can only form a weak
obtained adsorption configuration is only a local minimum chemical bond with the BN nanotube while Zn atoms cannot
with different magnetic moments. Interestingly, this variation be chemically adsorbed on the BN nanotube at all. In most
of the magnetic moment seems also correlate with the charge cases, the binding energies are less sensitive to the adsorp-
transfer from the metal atoms to the BN nanotube 共see the tion sites. On the electronic structures, the adsorption of
last two columns of Table I兲. metal atoms generally induces some impurity states within
Lastly, the interaction between two group-VIIIA the band gap of the pristine BN tube. These impurity states
transition-metal element, Pd and Pt, and the BN nanotube is are mainly due to the s and d electrons of the metal atoms.
studied because these two metals are popular catalysts. The transition-metal adsorbed BN nanotubes are all semicon-
Local-minimum configurations of the Pt and Pd atom on the ductors with reduced band gaps except the Fe-adsorbed BN
BN nanotube are shown in Figs. 5共a兲 and 5共b兲. Both metal nanotube 共on the BA site兲 which may result in a half-metal.

FIG. 6. The band structures of the Pd-

and Pt-adsorbed 共8,0兲 BN nanotubes.
The Fermi level is plotted with the dot-
ted line. The plus and minus spin band
structures are distinguished with ⫹ and
⫺.

Downloaded 09 Mar 2013 to 142.51.1.212. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions
044711-7 Adsorption of metals on boron nitride nanotubes J. Chem. Phys. 125, 044711 共2006兲

Finally, the adsorption of the transition-metal atoms can give 035427 共2003兲.
9
A. Loiseau, F. Willaime, N. Demoncy, G. Hug, and H. Pascard, Phys.
rise to a variety of net magnetic moments, ranging from
Rev. Lett. 76, 4737 共1996兲.
5.0␮B to 0. 10
Y. B. Li, P. S. Dorozhkin, Y. Bando, and D. Golberg, Adv. Mater. 共Wein-
heim, Ger.兲 17, 545 共2005兲.
11
ACKNOWLEDGMENTS W. Q. Han, P. Redlich, F. Ernst, and M. Rühle, Appl. Phys. Lett. 75, 1875
共1999兲.
We are grateful to valuable discussions with Professor J. 12
R. Z. Ma, Y. Bando, and T. Sato, Chem. Phys. Lett. 350, 1 共2001兲.
13
L. Yang. This work is supported by grants from the DOE C. C. Tang, Y. Bando, D. Golberg, X. X. Ding, and S. R. Qi, J. Phys.
共DE-FG02-04ER46164兲, the Nebraska Research Initiative, Chem. B 107, 6539 共2003兲.
14
D. Golberg, F. F. Xu, and Y. Bando, Appl. Phys. A: Mater. Sci. Process.
and by John Simon Guggenheim Foundation and the Re- 76, 479 共2003兲.
search Computing Facility at University of Nebraska- 15
H. J. Xiang, J. L. Yang, J. G. Hou, and Q. S. Zhu, New J. Phys. 7, 39
Lincoln. 共2005兲.
16
Z. Zhou, J. J. Zhao, Z. F. Chen, X. P. Gao, J. P. Lu, P. v. R. Schelyer, and
1
S. Iijima, Nature 共London兲 354, 56 共1991兲. C.-K. Yang, J. Phys. Chem. B 110, 2529 共2006兲.
17
2
E. Durgun, S. Dag, V. M. K. Bagci, O. Gülseren, T. Yildirim, and S. B. Delley, J. Chem. Phys. 92, 508 共1990兲; Int. J. Quantum Chem. 69,
Ciraci, Phys. Rev. B 67, 201401 共2003兲. 423 共1998兲; J. Chem. Phys. 113, 7756 共2000兲; Phys. Rev. B 65, 085403
3
Y. Yagi, T. M. Briere, M. H. F. Sluiter, V. Kumar, A. A. Farajian, and Y. 共2002兲; A. Kessi and B. Delley, Int. J. Quantum Chem. 68, 135 共1998兲.
18
Kawazoe, Phys. Rev. B 69, 75414 共2004兲. J. P. Perdew, K. Burke, and M. Ernzerhof, Phys. Rev. Lett. 77, 3865
4
C.-K. Yang, J. J. Zhao, and J. P. Lu, Phys. Rev. B 66, 41403 共2002兲. 共1996兲; 78, 1396共E兲 共1997兲.
5 19
R. Saito, M. Fujita, G. Dresselhaus, and M. S. Dresselhaus, Phys. Rev. B W. J. Hehre, L. Radom, P. v. R. Schlyer, and J. A. Pople, Ab Initio
46, 1804 共1992兲. Molecular Orbital Theory 共Wiley, New York, 1986兲.
20
6
A. Rubio, J. L. Corkill, and M. L. Cohen, Phys. Rev. B 49, 5081 共1994兲. H. J. Monkhorst and J. D. Pack, Phys. Rev. B 13, 5188 共1976兲.
21
7
E. Bengu and L. D. Marks, Phys. Rev. Lett. 86, 2385 共2001兲. F. L. Hirshfeld, Theor. Chim. Acta 44, 129 共1977兲.
22
8
H. J. Xiang, J. L. Yang, J. G. Hou, and Q. S. Zhu, Phys. Rev. B 68, D. M. Duffy and J. A. Blackman, Phys. Rev. B 58, 7443 共1998兲.

Downloaded 09 Mar 2013 to 142.51.1.212. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions