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Tuning the electrochemical properties of a boron and

Cite this: J. Mater. Chem. A, 2013, 1,
14706
nitrogen codoped nanodiamond rod array to achieve
high performance for both electro-oxidation and
electro-reduction†
Yanming Liu, Shuo Chen, Xie Quan,* Huimin Zhao, Hongtao Yu and Yaobin Zhang

Received 16th August 2013
Accepted 8th October 2013
DOI: 10.1039/c3ta13243a
www.rsc.org/MaterialsA
Design of highly active metal-free electrocatalysts to replace noble metal based materials is crucial for
electrocatalysis in various applications. Here we present an efficient and multifunctional metal-free
electrocatalyst, vertically aligned boron and nitrogen codoped nanodiamond (VA-BND)/Si rod array
(RA). It can achieve high electro-oxidation activity by varying its chemical composition while maintaining
superior electro-reduction performance. Methanol oxidation was selected to evaluate its electro-
oxidation activity towards small organic molecules in fuel cells. The VA-BND3/Si RA (B/C ¼ 0.015 and
N2 ¼ 1.0%) presented superior methanol oxidation activity with a more negative peak potential
compared with commercial Pt/C. Meanwhile, the durability of VA-BND3/Si RA was highly improved
relative to that of the Pt/C catalyst. Reduction of refractory organic pollutants,
2,20 ,4,40 -tetrabromodiphenyl ether (BDE-47), was chosen to study the electro-reduction activity of VA-
BND3/Si RA. The VA-BND3/Si RA was found to be advantageous over the Pd electrode for electro-
reduction of BDE-47 in both kinetics and current efficiency at 0.8 V. The excellent electrocatalytic
performance of VA-BND/Si RA mainly originated from the doped B and N.

1. Introduction activity while decrease noble metal consumption.12,13 Mean-

Electrocatalysis is a promising technology with the advantages
of versatility, environmental compatibility and easy handling.1,2
Considerable attention has been focused on the development of
advanced electrocatalytic materials due to their importance in
energy conversion,3,4 environmental remediation,5,6 sensors7
and compound conversion.8 More importantly, electrocatalytic
materials have a major inuence on electrocatalytic efficiency.
Noble metals (Pt and Pd) are highly active electrocatalysts for
both oxidation and reduction.9,10 However, their unsatisfactory
durability and limited supply are the major bottlenecks for
application.11 Recently, addition of second metallic compo-
nents and development of advanced supporting materials for
noble metals have been proposed to promote electrocatalytic
Key Laboratory of Industrial Ecology and Environment Engineering (Ministry of
Education, China), School of Environmental Science and Technology, Dalian
University of Technology, Dalian 116024, China. E-mail: quanxie@dlut.edu.cn; Fax:
+86-411-84706263; Tel: +86-411-84706140
† Electronic supplementary information (ESI) available: Schematic diagram of a
double-compartment cell for BDE-47 electro-reduction, B and N contents of
BDD, NDD, BND1 and BND2, cyclic voltammograms of various electrodes in
KOH electrolyte, cyclic voltammograms of methanol oxidation on BND/Si RAs
(B/C ¼ 0.01 and N ¼ 0.3% or 0.5%) and Pt/C@Si RA, the in situ infrared
spectrum of methanol oxidation at BND3/Si RA, and pseudo-rst-order plots of
BDE-47 reduction on VA-BND3/Si RA and Pd electrodes. See DOI:
10.1039/c3ta13243a
while, many efforts have been devoted to metal-free carbon
materials, particularly graphitic carbon such as (heteroatom-
doped) graphene, carbon nanotubes and porous carbon. They
have been exploited as electrocatalyst supports for fuel cells,14
sensors15 and pollutant degradation,16 or as potential electro-
catalysts for oxygen reduction,17 hydrazine oxidation18 and H2O2
detection.19 Unfortunately, their stability is unsatised. The
oxidation and corrosion of graphitic carbon will be accelerated
during the electro-oxidation process or at high temperature.20
Besides, their low overpotential for hydrogen evolution will
result in low energy efficiency for contaminant removal and
compound conversion during the electro-reduction process,
such as electro-reductive dehalogenation, which should
perform at a very negative potential. Despite tremendous
efforts, search for efficient, multifunctional and stable metal-
free materials for electrocatalysis remains a great challenge.
It is highly challenging but desirable to develop durable
electrocatalysts with high activity for both electro-oxidation and
electro-reduction. Diamond has attracted increasing interest
due to its excellent properties,21,22 such as good thermal
stability, corrosion resistance and extended lifetime. The
incorporation of B and N into diamond will greatly enhance its
conductivity and generate defect-induced active sites for elec-
trocatalysis due to the difference in the bond length and atomic
size.23,24 It has been reported that the synergistic effect between

14706 | J. Mater. Chem. A, 2013, 1, 14706–14712 This journal is ª The Royal Society of Chemistry 2013

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codoped B and N can enhance the electrocatalytic activity of
graphitic carbon nanomaterials.25,26 In our previous work,27 we
found that B and N codoped nanodiamond exhibited high
activity for oxygen reduction, but its activity for electro-reduc-
tion requiring very negative potential and electro-oxidation was
unsatised. The electronic properties of B and N codoped
nanodiamond can be tuned by varying its chemical composi-
tion, which will lead to tunable electrochemical properties.28 It
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can be expected that B and N codoped diamond will afford some
novel electro-oxidation and electro-reduction performance by
adjusting its chemical composition and achieving the syner-
gistic effect between codoped B and N. In order to maximize the
electrocatalytic activity, it is necessary to optimize the
morphology of the electrocatalyst besides composition. Nano-
diamond possesses the outstanding properties of diamond
while offering a reactive surface.29 Recently, a vertically aligned
morphology has been employed as a powerful means to improve
electrocatalytic performance,30 which provides a high aspect
ratio and enables facile charge transport. These factors have
motivated us to explore a vertically aligned B and N codoped
nanodiamond rod array (VA-BND RA) as a multifunctional
metal-free electrocatalyst.
In this work, VA-BND/Si RA with multiple electrocatalytic
functions has been designed and synthesized. The effects of B
and N on its electrocatalytic activity were studied by adjusting
the contents of doped B and N. To evaluate its electro-oxidation
activity, methanol oxidation on VA-BND/Si RA was tested. Both
its activity and stability towards methanol oxidation were
compared with those of commercial Pt/C. Meanwhile, reduction
of 2,20 ,4,40 -tetrabromodiphenyl ether (BDE-47) was selected to
investigate its electro-reduction activity. As a comparison,
reduction of BDE-47 on the Pd electrode was also carried out.
2. Experimental
2.1. Preparation of VA-BND/Si RA
VA-BND/Si RA was prepared according to our previous work.25
The typical fabrication process for VA-BND/Si RA is illustrated
in Scheme 1. Briey, the surface of p-Si (111) wafer was ther-
mally oxidized. Then a mask with a designed pattern was placed
on the SiO2 surface, followed by extreme ultraviolet photoli-
thography. Subsequently, both the SiO2 lm and Si wafer were
etched by plasma using the Bosch process. A Si RA substrate was
obtained aer removing the SiO2 lm by HF solution. In order
to enhance nucleation density during BND deposition, the Si RA
substrate was pretreated with a nanodiamond suspension.
Then, the BND lm was deposited on this substrate by micro-
wave plasma enhanced chemical vapor deposition. The
Scheme 1 The procedures for VA-BND/Si RA preparation.
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Table 1 The dopant contents of different electrocatalysts
BDD NDD BND1 BND2 BND3
N2 0 0.7% 0.7% 1.0% 1.0%
B/C 0.01 0 0.01 0.01 0.015
deposition was performed at temperature 460  C and pressure
5.8 kPa with a gas mixture of H2–CH4–B2H6–N2 (1.0% CH4). In
order to tune its electrochemical properties, three VA-BND/Si RA
electrodes were fabricated with different dopant contents
(Table 1). As a comparison, vertically aligned B-doped diamond
(VA-BDD)/Si RA and vertically aligned N-doped diamond
(VA-NDD)/Si RA were synthesized by the same method without
adding N2 and B2H6, respectively.
2.2. Characterization
The morphology of BND/Si RA was examined by scanning
electron microscopy (SEM) on a Hitachi S-4800 microscope and
transmission electron microscopy (TEM) on an FEI-Tecnai G2
20. X-ray diffraction (XRD) was carried out on a Shimadzu LabX
XRD-6000. Raman spectroscopy was carried out using a
Renishaw Micro-Raman system 2000 spectrometer with He–Ne
laser excitation (wavelength 623.8 nm). X-ray photoelectron
spectroscopy (XPS) was performed with a VG ESCALAB 250
spectrometer using a nonmonochromatized Al Ka X-ray source
(1486.6 eV).
2.3. Electrochemical experiments
Electrochemical measurements were carried out on a standard
three-electrode cell with a PARSTAT 2273 electrochemical
system. The VA-BND/Si RA was used as the working electrode. A
platinum sheet and an Ag/AgCl (saturated KCl) electrode served
as the counter electrode and the reference electrode,
respectively.
The methanol oxidation activity of VA-BND/Si RA was eval-
uated by cyclic voltammetry with a scan rate of 50 mV s1 at
room temperature. The stability of VA-BND/Si RA was tested by
chronoamperometry at 0.20 V. Both cyclic voltammetry and
chronoamperometry were conducted in 0.1 M KOH solution
containing 1.0 M CH3OH. The performance of commercial Pt/C
(Johnson Matthey, 20 wt%) towards methanol oxidation was
also examined for comparison. The Pt/C electrode was prepared
as follows: 6 mg commercial Pt/C catalyst was dispersed in 2 mL
solution containing isopropanol and Naon, followed by soni-
cating for 30 min. The well-dispersed suspension was drop-cast
onto the Si RA substrate (dened as Pt/C@Si RA) the same as
that of VA-BND/Si RA or onto the glass carbon electrode (dened
as Pt/C@GCE) with catalyst loading 0.3 mg cm2, and then
dried in air.
Electrocatalytic reduction of BDE-47 on VA-BND/Si RA was
conducted at a double-compartment cell with a batch mode
(Fig. S1†). An initial concentration of 10 mg L1 was used in all
of the experiments with 0.05 M H2SO4 as a supporting electro-
lyte. The gap between the working electrode and the counter
electrode was 2.0 cm. The experiments were performed
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potentiostatically at 0.5 to 1.1 V. As a comparison, electro-
catalytic reduction of BDE-47 was also carried out using the Pd
electrode under the same conditions, which was prepared by
depositing Pd nanoparticles on the Si RA substrate using the
methods reported in our previous work.31 During the electro-
reduction process, BDE-47 samples collected at certain time
intervals were analyzed using an HPLC (Waters-2695) equipped
with a TC-C18 column and an ultraviolet detector. The working
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wavelength was 220 nm and the column oven was set at 30  C.
A mixture of CH3OH–H2O (90/10, v/v) was used as the mobile
phase with a ow rate of 1.0 mL min1. Quantitative determi-
nation of electro-reduction intermediates was performed using
a GC/MS (Agilent GC6890-MSD5973) equipped with an electron
impact ion source and a DB-5MS column. The temperature of
the GC column was programmed from 80  C (hold 1 min) to
265  C (hold 5 min) at a rate of 12  C min1. The other condi-
tions were as follows: injection temperature 275  C and source
temperature 280  C.
3. Results and discussion
3.1. Characterization
The SEM image clearly reveals that a vertically aligned BND/Si
rod array has been successfully synthesized, as presented in
Fig. 1a. The BND lm is deposited on the Si RA substrate
uniformly. Fig. 1b displays the magnied SEM image of the as
synthesized VA-BND/Si RA, showing that it consists of nano-
crystalline diamond. The TEM image (Fig. 1c) shows that the
particle size of the synthesized nanocrystalline diamond is
around 30–100 nm. The high resolution TEM image in Fig. 1d
reveals that the inter-planar spacing is 0.21 nm, corresponding
to the (111) planes of diamond. The XRD pattern is presented in
Fig. 2a; three diffraction peaks associated with (111), (220) and
(311) facets of cubic diamond appear at 43.9 , 75.5 and 91.5
respectively (JCPDS no. 06-0675). The quality of diamond is
evaluated by Raman spectroscopy and the result is shown in
Fig. 1 Characterization of VA-BND3/Si RA: (a) cross-sectional SEM image, (b)
high resolution SEM image, (c) TEM image, and (d) high resolution TEM image.
14708 | J. Mater. Chem. A, 2013, 1, 14706–14712
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Fig. 2 (a) XRD spectrum and (b) Raman spectrum of VA-BND3/Si RA.
Fig. 2b. The peak around 1332 cm1 corresponds to diamond.
This sharp peak indicates the high quality of diamond.
The successful incorporation of B and N into nanodiamond
can be demonstrated from XPS data (Fig. 3). The B 1s spectrum
(Fig. 3a) shows two peaks: the main peak at about 188.9 eV is
related to the B–C bond while the peak at 189.9 eV is associated
with the B–N bond. According to the N 1s spectra (Fig. 3b), the
major component is the N–sp3C bond, which is observed at
398.2 eV. The other peaks can be assigned to the N–sp2C bond
(399.6 eV) and the N–B bond (397.1 eV). Based on the XPS
analysis, the B and N contents of VA-BND3/Si RA are 3.78 at%
and 0.96 at%, respectively. The dopant contents of other
electrocatalysts are presented in Table S1.†
3.2. Electro-oxidation activity of VA-BND/Si RA
Electrocatalysts for oxidation of small organic molecules, such
as electro-oxidation of methanol, are at the heart of energy
storage and conversion technologies.32,33 Although noble metal
based materials are proposed as active electrocatalysts for
methanol oxidation, owing to their unsatised stability and
limited supply of noble metals,34 efficient, low-cost and stable
electrocatalysts are still highly desirable. Therefore, the electro-
oxidation activity of this metal-free material, VA-BND/Si RA, was
investigated by methanol oxidation. In order to probe the effects
of B and N on electro-oxidation activity, the performance of VA-
BDD/Si and VA-NDD/Si RA towards methanol oxidation was also
investigated as a comparison. The cyclic voltammograms of
these three electrodes in 0.1 M KOH electrolyte containing
1.0 M CH3OH are shown in Fig. 4a (their cyclic voltammograms
in 0.1 M KOH electrolyte without methanol are displayed in
Fig. S2†). No oxidation peak can be observed at these electrodes
without methanol addition. Aer methanol addition, two
oxidation peaks are observed at both VA-NDD/Si RA and VA-
BND1/Si RA, while no obvious oxidation peak is observed on
Fig. 3 XPS spectra of VA-BND3/Si RA: (a) B 1s and (b) N 1s.
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Fig. 4 Cyclic voltammograms for methanol oxidation in 0.1 M KOH electrolyte
containing 1.0 M CH3OH at a scan rate of 50 mV s1 on (a) VA-BDD/Si RA,
VA-NDD/Si RA and VA-BND1/Si RA, and (b) VA-BND1/Si RA, VA-BND2/Si RA, VA-
BND3/Si RA and Pt/C@GCE (the Pt loading is 0.06 mg cm2).
VA-BDD/Si RA at potential 0.7 to 0.8 V. The forward anodic
peak is usually corresponding to methanol oxidation, while the
backward anodic peak is generally attributed to the continuous
oxidation of incompletely oxidized carbonaceous intermediates
formed in the forward scan.33,35 It shows that the forward anodic
peak potential of VA-BND1/Si RA is 0.09 V, which is obviously
more negative than that of VA-NDD/Si RA (about 0.38 V). These
results suggest that the peak potential for methanol oxidation is
negatively shied by codoping with B and N. Additionally, the
forward peak current density (If) of VA-BND1/Si RA is higher
than that of VA-NDD/Si RA. The ratio of If to the backward
anodic peak current density (Ib) is used to describe the
electrocatalyst tolerance to intermediates produced during
methanol oxidation.12,36 The If/Ib ratio of VA-BND1/Si RA is 5.4,
higher than that of VA-NDD/Si RA (2.2). It indicates that meth-
anol molecules can be more effectively oxidized by VA-BND1/Si
RA and less accumulation of residues on this electrocatalyst
surface. To investigate the performance transition for methanol
oxidation from mono-doped nanodiamond to co-doped nano-
diamond, BND/Si RAs with N content less than that of BND1/Si
RA were prepared. As shown in Fig. S3,† not only the peak
potential is positively shied but also the current density
increases gradually as the N content increases from 0% to 0.7%.
Compared with both VA-BDD/Si RA and VA-NDD/Si RA,
VA-BND1/Si RA exhibits signicantly enhanced performance for
electro-oxidation of methanol, which suggests that the electro-
oxidation activity of VA-BND1/Si RA can be greatly improved by
codoping with B and N.
Since codoping B and N in nanodiamond can improve its
electro-oxidation activity, we further increase the B or N content
of VA-BND1/Si RA individually to tune its electro-oxidation
activity and clarify which component is effective for enhancing
the electro-oxidation activity. Fig. 4b shows that If of VA-BND2/
Si RA is obviously higher than that of VA-BND1/Si RA, which is
resulted from the increased N content. When the mole ratio of
B/C is increased, If of VA-BND3/Si RA is also signicantly
improved compared with that of VA-BND2/Si RA. It shows that
both B doping and N doping on VA-BND/Si RA can contribute to
its enhanced electro-oxidation activity.
The methanol oxidation performance of VA-BND3/Si RA was
compared with that of commercial Pt/C (Fig. 4b). During the
positive scan, the peak potential for methanol oxidation on
VA-BND3/Si RA is at 0.12 V, more negative than that on
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Journal of Materials Chemistry A
Pt/C@GCE (0.02 V), which suggests that VA-BND3/Si RA is
more favorable for methanol oxidation compared with
commercial Pt/C. Although the If value of VA-BND3/Si RA is
slightly lower than that of Pt/C@GCE, VA-BND3/Si RA is
comparable to commercial Pt/C for methanol oxidation,
demonstrating the excellent electro-oxidation activity of
VA-BND3/Si RA. It should be noted that the If/Ib value of VA-
BND3/Si RA is 9.6, which is greater than that of Pt/C@GCE. This
indicates that VA-BND3/Si RA is superior in poison resistance
compared to commercial Pt/C. Since the performance of BND
was tested on Si RA, methanol oxidation on Pt/C@Si RA was also
performed as a reference (Fig. S4†). The VA-BND3/Si RA
outperforms Pt/C@Si RA in peak potential, peak current density
and poison resistance. These results reveal that VA-BND3/Si RA
can achieve high electro-oxidation activity by tuning its B and
N contents.
The mechanism of methanol oxidation at BND3/Si RA was
studied using the in situ infrared spectrum (Fig. S5†). The peaks
at 1680 cm1 and 1450 cm1 can be assigned to COads and C–H
bending vibrations of CH3OHads, respectively, while the peaks
at 1350 cm1 and 1580 cm1 are attributed to COOH. The
intermediates are not detectable until the potential is more
positive than 0.3 V. At potential 0.3 V to 0.1 V, peaks related
to COads and COOH are clearly observed. The nal products,
CO2 (2350 cm1) and CO32 (1390 cm1), have been detected at
potential more positive than 0.1 V. Based on these results and
the mechanism reported in alkaline solution, methanol oxida-
tion at BND/Si RA mainly proceeds as follows (M represents
BND/Si RA):
M + OH / M–OHads (1)
M + CH3OH / M–CH3OHads (2)
M–CH3OHads + 4OH / M–COads + 4H2O + e (3)
M–COads + M–OHads + OH / M + CO2 + H2O + e (4a)
or
M–COads + M–OHads / M–COOHads (4b-1)
M–COOHads + OH / M + CO2 + H2O + e (4b-2)
CO2 + 2OH / CO32 + H2O (5)
When B and/or N atoms are bonded with a carbon frame-
work, they induce uneven charge distribution and introduce
defects in the nearby sites, which may increase the number of
electrocatalytic sites. The doped B atoms are positively charged
owing to the larger electronegativity of C related to B, and N
doping generates positive charges in neighboring C atoms
because the high electronegativity of N polarizes the adjacent C
atoms. These positive charges are favorable to adsorb hydroxyl
and methanol onto the catalyst, and then the equilibrium of
eqn (1) and (2) will shi toward the right. This results in high
OHads and CH3OHads coverage, which can facilitate methanol
oxidation.
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Fig. 5 Chronoamperometry curves of methanol oxidation at 0.20 V in 0.1 M
KOH electrolyte containing 1.0 M CH3OH.
To evaluate the durability of VA-BND3/Si RA towards meth-
anol oxidation, chronoamperometric measurement was
performed at 0.20 V in 0.1 M KOH electrolyte containing 1.0 M
CH3OH (Fig. 5). It is obvious that the current decay for methanol
oxidation on VA-BND3/Si RA is much slower than that on
commercial Pt/C. The current density decreases rapidly on Pt/C
due to the poisoning of intermediate species produced during
methanol oxidation reaction. Besides, VA-BND3/Si RA shows
much higher current density than commercial Pt/C, which is in
good agreement with the results of cyclic voltammetry. These
results suggest that VA-BND3/Si RA possesses better electro-
oxidation activity and stability for methanol oxidation than
commercial Pt/C.
3.3. Electro-reduction activity of VA-BND/Si RA
Recently, considerable effort has been devoted to the develop-
ment of cost-effective ways for remediation of toxic and recal-
citrant organic pollutants,1 such as BDE-47. It is resistant to
oxidative treatment due to the strong electron-withdrawing
ability of its bromine substituent. However, electro-reduction is
a promising method for BDE-47 removal, which can convert
BDE-47 to lower toxic and more biodegradable products by the
cleavage of C–Br bonds.37 The reported cathodes with high
electro-reduction activity include graphite, noble metals and
composites based on these active species.38 Owing to their low
overpotentials for water electrolysis and the limited supply of
noble metals, an alternative material has been actively pursued.
Herein we proposed an efficient metal-free material, VA-BND/Si
RA, for electro-reduction of BDE-47. Fig. 6 shows the linear
sweep voltammogram of VA-BND3/Si RA in the absence and
presence of BDE-47. When the potential is more negative than
Fig. 6 Linear sweep voltammogram of VA-BND3/Si RA in the absence and
presence of BDE-47 containing 0.05 M H2SO4.
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Fig. 7 BDE-47 concentration as a function of time (a) on VA-BND3/Si RA at
0.5 V, 0.8 V and 1.1 V and (b) on VA-BND3/Si RA and Pd electrodes at 0.8 V.
0.40 V, the current density is signicantly increased aer the
addition of BDE-47, which originates from electro-reduction of
BDE-47 by VA-BND3/Si RA. It also reveals that the onset poten-
tial for electro-reduction of BDE-47 on VA-BND3/Si RA is
0.40 V. Based on the results of linear sweep voltammogram,
electro-reduction of BDE-47 was investigated under constant
potentials 0.5 V, 0.8 V and 1.1 V. Fig. 7a displays the
evolution of the BDE-47 concentration as a function of elec-
trolysis time. The reduction rate of BDE-47 increases when
applied potential is more negative. 90%, 99.7% and 100% of
BDE-47 are electrochemically reduced in 2 h at potential 0.5 V,
0.8 V and 1.1 V respectively. The electro-reduction reaction is
found to follow pseudo-rst-order kinetics based on the linear
correlation between ln(C0/Ct) and t (C0 is the initial concentra-
tion of BDE-47 and Ct is the concentration of BDE-47 at time t).
The kinetic constants are 0.020 min1, 0.029 min1 and 0.046
min1 at 0.5 V, 0.8 V and 1.1 V, respectively (Fig. S6†).
As a comparison, the Pd electrode, one of the most active
electro-reduction materials reported, was selected for electro-
reduction of BDE-47 at 0.8 V (Fig. 7b). It shows that the electro-
reduction rate of BDE-47 on VA-BND3/Si RA is greater than that
on the Pd electrode. As presented in Table 2, the kinetic
constant for BDE-47 reduction on VA-BND3/Si RA is 1.45 times
as great as that on the Pd electrode (Fig. S7†). The current
density related to electro-reduction of BDE-47 (dened as
effective current density) was obtained by subtracting the
current density measured in the absence of BDE-47 from that
measured in the presence of BDE-47. The higher effective
current density on VA-BND3/Si RA can explain its much greater
kinetic constant. The ratio of effective current density to total
current density is 41.4% on VA-BND3/Si RA, which is 2.25 times
as great as that on the Pd electrode (18.4%). These results
suggest that VA-BND3/Si RA exhibits higher electro-reduction
activity and efficiency than the Pd electrode under the experi-
mental conditions applied.
In order to determine the electro-reduction pathway of BDE-
47, the intermediates generated during the electro-reduction
process on VA-BND3/Si RA (0.8 V) were analyzed by GC/MS and
their concentrations as a function of electrolysis time are pre-
sented in Fig. 8. The intermediates detected include tri-BDEs
(BDE-28 and BDE-17), di-BDEs (BDE-15, BDE-8 and BDE-4),
mono-BDEs (BDE-3 and BDE-1) and biphenyl ether, which are
conrmed by comparing their GC/MS chromatograms with
those of standard samples. The main intermediates are tri-BDEs
and di-BDEs aer electro-reduction for 15 min; further
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Table 2 Parameters of VA-BND3/Si RA and Pd electrodes towards electro-
reduction of BDE-47 at 0.8 V
Kinetic Current density Current density
constant without BDE47 with BDE47 I  I0
[min1] [I0, mA cm2] [I0, mA cm2] [mA cm2] (I  I0)/I
BND 0.029 2.04 3.48 1.44 41.4%
Pd 0.021 4.26 5.22 0.96 18.4%
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Fig. 8 The intermediate product concentrations as a function of electrolysis
time.
electro-reduction (50 min) results in the concentration increase
of tri-BDEs and di-BDEs and the formation of mono-BDEs.
When the electro-reduction has been carried out for 90 min, the
concentrations of tri-BDEs decrease, while the concentrations
of di-BDEs and mono-BDEs increase. The main intermediates
are di-BDEs (BDE-15 and BDE-8) and mono-BDEs (BDE-3).
Meanwhile, the completely debrominated product, diphenyl
ether, has been detected. At 120 min, both the concentrations of
tri-BDEs and di-BDEs decrease, while the concentrations of
mono-BDEs and diphenyl ether are further increased. Based on
the above results, the electro-reduction mechanism of BDE-47 is
proposed as follows. As illustrated in Fig. 9, electro-reduction of
BDE-47 is a stepwise debromination process. Firstly, BDE-47 is
debrominated to tri-BDEs (BDE-28 and BDE-17) through elec-
tro-reduction by VA-BND3/Si RA. These tri-BDEs are subse-
quently debrominated to di-BDEs (BDE-15, BDE-8 and BDE-4).
The produced di-BDEs are transformed to mono-BDEs (BDE-3
and BDE-1) by further electro-reduction. Finally these lower
brominated intermediates are debrominated completely, and
the nal product is diphenyl ether.
Based on the above results, it is believed that the good
performance of VA-BND/Si RA for both electro-oxidation and
electro-reduction can be achieved by tuning the contents of
Fig. 9 Schematic electro-reduction pathway of BDE-47 on VA-BND3/Si RA.
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Journal of Materials Chemistry A
doped B and N. When B and/or N atoms are bonded with a
nanodiamond framework, they induce uneven charge distri-
bution and introduce defects in the nearby sites due to the
difference in the bond length and atomic size, and thereby
increase the number of electrocatalytic sites. Besides, the carrier
density of nanodiamond can be greatly improved aer doping,39
which will increase the electron transfer rate between VA-BND/
Si RA and reactant and then decrease the kinetic barrier.
Meanwhile, the conductivity of nanodiamond will be signi-
cantly improved by B and N doping. The uniformly deposited
BND lm and its high surface area could provide more active
sites for reactants. In addition, the vertically aligned
morphology provides a path for charge transport between
VA-BND/Si RA and the external circuit, and thus the produced
charges can be immediately and efficiently transported.
4. Conclusion
In summary, VA-BND/Si RA with multiple electrocatalytic
functions has been successfully synthesized. It exhibited
excellent performance for methanol electro-oxidation as well as
BDE-47 electro-reduction aer tuning its electrochemical
properties. VA-BND/Si RA outperformed the commercial Pt/C
catalyst in both peak potential and stability for electro-oxidation
of methanol. Moreover, VA-BND/Si RA was also efficient for
electro-reduction of BDE-47 with much greater kinetic constant
and efficiency compared with the Pd electrode under the
experimental conditions applied. The greatly enhanced elec-
trocatalytic activity mainly originated from the incorporated B
and N. These attractive electrocatalytic performances suggest
promising applications of VA-BND/Si RA as a highly active and
multifunctional metal-free material in energy conversion,
environmental remediation, sensors, compound conversion or
biomedicine. This work could provide new insights into the
design of next-generation multifunctional metal-free
electrocatalysts.
Acknowledgements
This work was supported by National Basic Research Program of
China (2011CB936002) and National Nature Science Founda-
tion of China (no. 21077018).
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