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A silicon/zinc 2,9,16,23-tetraaminophthalocyanine coaxial coreshell nanowire array as an

efficient solar hydrogen generation photocatalyst

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2012 Nanotechnology 23 175401

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IOP PUBLISHING NANOTECHNOLOGY
Nanotechnology 23 (2012) 175401 (4pp) doi:10.1088/0957-4484/23/17/175401

A silicon/zinc 2,9,16,23-tetraamino-
phthalocyanine coaxial coreshell
nanowire array as an efficient solar
hydrogen generation photocatalyst
Zhen Liu1 , Hui Wang1 , Xue-Mei Ou1 , Chun-Sing Lee2 , Fan Li1 and
Xiao-Hong Zhang1
1
Nano-organic Photoelectronic Laboratory and Key Laboratory of Photochemical Conversion and
Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences,
Beijing 100190, Peoples Republic of China
2
Center of Super-Diamond and Advanced Film (COSDAF) and Department of Physics and Materials
Science, City University of Hong Kong, Hong Kong SAR, Peoples Republic of China

E-mail: wanghui@mail.ipc.ac.cn and xhzhang@mail.ipc.ac.cn

Received 6 January 2012, in final form 5 March 2012

Published 5 April 2012
Online at stacks.iop.org/Nano/23/175401

Abstract
In this work, we have demonstrated that a silicon nanowire (SiNW) array can be an efficient
visible light photocatalyst for hydrogen generation after being modified by the
2,9,16,23-tetraamino- phthalocyanine of zinc (ZnTAPc). A photoelectrochemical (PEC) cell
employing a ZnTAPc modified SiNW array as photoanode was found to be able to effectively
produce hydrogen at a rate of 13 mol (cm2 h)1 under 100 mw cm2 irradiation from a
xenon lamp. It is believed that the loading of ZnTAPc can enhance the efficiency of hydrogen
generation and the stability of the SiNW array. This demonstrates that the ZnTAPc modified
SiNW is a promising material for solar hydrogen generation.
S Online supplementary data available from stacks.iop.org/Nano/23/175401/mmedia
(Some figures may appear in colour only in the online journal)

1. Introduction (e.g., TiO2 or ZnO) sensitized by dyes or quantum dots were

Solar hydrogen generation offers a promising method for
clean, low-cost, and environment-friendly production of
hydrogen from solar energy. A large number of photocatalysts
have been investigated for solar hydrogen generation since
a report by Fujishima and Honda of a TiO2 anode
photoelectrochemical (PEC) cell that could split water into H2
and O2 under ultraviolet (UV) light irradiation was published
in the literature [1]. However, UV light accounts for only
approximately 4% of solar energy, whereas visible light
accounts for approximately 43% [2]. Therefore, it is now very
important in the fields of science and engineering to explore
and identify stable photocatalysts that can efficiently produce
hydrogen by using visible light [3]. So far, two strategies have
been reported. In the first approach, wide-band-gap materials
used as hydrogen generation photoanodes [4]. Although such
anodes have been extensively used in the dye-sensitized solar
cells (DSSCs), their application in hydrogen generation is,
so far, limited because the efficiency of these anodes is not
sufficiently high and the stability of many quantum dots still
needs to be improved [5]. A second strategy involved the
direct utilization of narrow-band-gap semiconductors, such as
Cu2 O, -Fe2 O3 , and WO3 [6], as photoanodes. However, their
efficiencies in absorbing visible light are also not sufficiently
high, and some of these semiconductors are susceptible to
photocorrosion [7].
Silicon is most extensively used in solar energy materials
because of its broad and strong absorption capacities of
energy in the UV and visible spectral range [8, 9]. Further,
the conduction band of Si is approximately 0.07 eV higher

0957-4484/12/175401+04$33.00 1 c 2012 IOP Publishing Ltd Printed in the UK & the USA


Nanotechnology 23 (2012) 175401
Figure 1. (a) SEM image of a SiNW array. (b) TEM image of a ZnTAPc modified SiNW. (c) HRTEM image of a ZnTAPc modified SiNW.
than the energy required for hydrogen generation from water
(pH = 7). Although the band gap of Si (1.1 eV) is slightly
smaller than the energy requirement for water splitting
(1.23 eV), a model using two photocatalysts to produce
H2 and O2 , respectively, under the mediation of a redox
couple (e.g., I /IO 3 , S /SO3 , or Ce /Ce ), could be
2 2 3+ 4+
introduced to solve this problem [10]. However, one challenge
that persists with regard to the utilization of Si as a photoanode
for hydrogen generation is its unstable surface [11].
In this work, we have demonstrated that a silicon
nanowire (SiNW) array could be a stable and efficient
visible light photocatalyst for hydrogen generation after being
modified by the 2,9,16,23-tetraaminophthalocyanine of zinc
(ZnTAPc). The coating of ZnTAPc is believed to enhance
both the efficiency of hydrogen generation and the stability of
the SiNW array. A PEC cell employing a ZnTAPc modified
SiNW array as photoanode was found to be able to effectively
produce hydrogen at a rate of 13 mol (cm2 h)1 under
100 mw cm2 irradiation from a xenon lamp with I as the
sacrificial agent and a stable photocurrent of 1.1 mA cm2
was obtained. These performance parameters are among
the best reported in photocatalyzed hydrogen production
systems [12].
2. Experimental methods
ZnTAPc was synthesized and characterized according to
the reference method (supporting information S1 available
at stacks.iop.org/Nano/23/175401/mmedia). The SiNW array
was prepared in HF aqueous solution with Ag nanoparticles
as catalyst (supporting information S2 available at stacks.iop.
org/Nano/23/175401/mmedia) [5]. The product was etched
with 10% HF aqueous solution for 10 min at room
temperature and then washed with ethanol and acetone to
remove the HF aqueous solution before drying in vacuum.
Acetone solution containing 0.03 mg ml1 ZnTAPc was
dripped onto the surface of the SiNW array (the amount
of ZnTAPc solution for a 1 cm2 SiNW array was 0.5 ml),
and then the array was dried in vacuum for 5 min. This
process was repeated until about 0.3 mg of ZnTAPc was
loaded on a 1 cm2 SiNW array (supporting information S3
available at stacks.iop.org/Nano/23/175401/mmedia). After
measuring the visible absorption spectra (Varian Carry 5000),
partly modified SiNWs were scratched off and dispersed
2
Z Liu et al
in water, and a drop of the dispersion was put on a
carbon-coated copper TEM sample grid for examination
(JEOL JEM-2100, operated at 200 kV). Photoelectrochemical
analysis was conducted with a 500 W xenon lamp as
excitation source. The intensity of the illumination at the
surface of the electrode was 100 mW cm2 . A PEC cell
containing a ZnTAPc modified SiNW array as working
electrode (1 cm2 area, 20 m thickness), a Pt net as counter
electrode, and a saturated calomel electrode as reference
electrode were immersed in 0.8 M KI aqueous solution
(pH = 3, adjusted with dilute hydrochloric acid) to monitor
the photoelectrochemical process with a electrochemical
workstation (CHI660A). The solution was stirred rapidly
and purged with argon gas to remove oxygen. To study the
incident photon-to-electron conversion efficiency (IPCE) of
the PEC cell, a monochromator (AH-IMS) was used to adjust
the wavelength. The formation of H2 at the cathode of the cell
was confirmed by gas chromatography (Shimadzu GC-2014).
3. Result and discussion
ZnTAPc was first coated on an array of n-type SiNWs to
form a coreshell structure (several to tens of nanometers for
the ZnTAPc shell, as shown in figure 1) [13]. ZnTAPc was
used as a shell because its bandgap matches the energy level
of Si. Hence, ZnTAPc is expected to increase the separation
efficiency of electronhole pairs in the core/shell structures.
Moreover, some phthalocyanines have been reported to serve
as stable photocatalysts for hydrogen generation, with I as
sacrificial agent [14].
The absorption spectra of the modified SiNW array
revealed that a new absorption peak for the ZnTAPc-coated
SiNWs appears at 728 nm (figure 2). A small red shift of
approximately 20 nm for this new peak from the absorption
peak of the ZnTAPc film could be attributed to the interaction
(e.g., electron transfer) between the ZnTAPc and the SiNWs.
Unlike the widely used dye-sensitized nanowire anodes, the
narrow-band-gap SiNWs used in the current study do not
require sensitization.
A schematic diagram of the hydrogen production PEC
cell is shown in figure 3. A ZnTAPc modified SiNW array
was used as the anode (area = 1 cm2 ), a saturated calomel
electrode (SCE) was the reference electrode, and a Pt net
was the cathode. The three electrodes were immersed in
Nanotechnology 23 (2012) 175401
Figure 2. Visible absorption spectra of the ZnTAPc modified SiNW
array, an unmodified SiNW array, and ZnTAPc film.
A photoelectrolysis cell during onoff cycles of illumination. In both
e- h+
Pt
Modified Si NWs array
Figure 3. Schematic diagram of the hydrogen production PEC cell.
0.8 M KI aqueous solution (pH = 3, adjusted with dilute
hydrochloric acid). Upon illumination, the photogenerated
electronhole pairs were separated by a spacecharge layer at
the interface between the ZnTAPc and the SiNWs. The holes
stayed at the anode and reacted with I , whereas the electrons
traveled through the external circuit and reached the cathode
(Pt net) to reduce the hydrogen ions (H+ ). The formation of
hydrogen at the cathode of the PEC cell was confirmed by gas
chromatography.
Figure 4 shows the short-circuit photocurrent response
curve with zero potential bias (versus SCE) [15]. A typical
steady-state anodic current density of 1.1 mA cm2 was
generated when the modified SiNW array was irradiated
at a power density of 100 mW cm2 with a xenon lamp
(supporting information S5 available at stacks.iop.org/Nano/
23/175401/mmedia). The current density sharply decreased
to 10 A cm2 in the dark. The onoff light-switching
experiment was continued for 90 min, and the cell showed
no observable decay in performance.
For comparison, the photocatalytic properties of an
unmodified SiNW array were also studied. The initial
anodic current density was only 0.63 mA cm2 . The current
also rapidly decreased to 0.27 mA cm2 after 5 min of
irradiation (figure 4) and to 0.04 mA cm2 after nine
cycles of switching. The current density continued to decay
regardless of the irradiation of the PEC cell. The unstable
3
Z Liu et al
Figure 4. The short-circuit photocurrent response of the ZnTAPc
modified and unmodified SiNW arrays in the three-electrode
cells, the electrolyte was 0.8 M KI (pH = 3) and the light intensity
from the xenon lamp was 100 mW cm2 .
Figure 5. IPCE of the PEC cell in the wavelength range of
430780 nm with zero applied potential bias (versus SCE).
photovoltaic property may be attributed to the gradual
oxidation of the surface of the SiNW array. In comparison,
the good stability of the ZnTAPc modified SiNW array
demonstrated that this array can be a stable photocatalyst for
hydrogen generation after suitable surface passivation.
The IPCE is a widely used parameter for the
characterization of photoelectrodes. The IPCE of our PEC cell
over the wavelength range of 410780 nm is shown in figure 5.
Up to 12% the IPCE was observed to be in the range of
590610 nm. The absorption of ZnTAPc is relatively low in
this spectral region, and is considered to serve as a window
layer [16], allowing light to penetrate the single crystalline
SiNWs. This phenomenon decreases the recombination of
electronhole pairs on the surface of the ZnTAPc shell, and
thereby increases the IPCE. Another IPCE peak appeared at
728 nm, which corresponded to the absorption peak of the
ZnTAPc layer. Comparison of the IPCE of ZnTAPc films, a
Nanotechnology 23 (2012) 175401
Figure 6. The rate of hydrogen production as a function of time by
the use of ZnTAPc modified or unmodified SiNW array anodes. The
experimental conditions were the same as in figure 4.
SiNW array and a ZnTAPc-coated SiNW array is shown in
supporting information S6 (available at stacks.iop.org/Nano/
23/175401/mmedia).
Long-time irradiation experiments were conducted under
the same conditions to monitor the production of hydrogen.
As shown in figure 6, the amount of hydrogen produced
by PEC cells with modified and unmodified SiNW array
photoanodes was recorded every 15 min. PEC cells employing
modified SiNW arrays as photoanodes showed an initial
hydrogen production rate of 13 mol (cm2 h)1 and
a mild decrease after 75 min of continuous operation. In
contrast, PEC cells employing unmodified SiNW arrays as
photoanodes showed an initial hydrogen production rate of
4 mol (cm2 h)1 and this decreased rapidly. The results
indicated that the coating of ZnTAPc could enhance both
the photocatalytic hydrogen generation efficiency and the
operational stability of the SiNW array.
The efficient and stable photocatalytic activity of the
ZnTAPc-coated SiNW array may be attributed to four reasons.
First, the interface between the ZnTAPc film and the n-type
SiNWs could promote electronhole separation due to the
0.1 eV energy difference between the highest occupied
molecular orbital (HOMO) of ZnTAPc (5.0 eV) [17] and
the valence band of Si (5.1 eV) (see figure S6 available at
stacks.iop.org/Nano/23/175401/mmedia). Second, H+ could
be reduced to H2 by the electrons from the conduction band
of the silicon at the cathode (Pt), whereas I is oxidized
to I3 on the HOMO of the ZnTAPc. Third, the surfaces
of the SiNWs are well coated by a ZnTAPc film, which
could increase the area of heterojunctions and shorten the
carrier diffusion distance. Consequently, the carrier collection
efficiency is increased [18]. Fourth and last, the ZnTAPc
layer could protect SiNWs from oxidation and promote their
stability.
4. Conclusions
We have demonstrated that SiNW can be an efficient
visible light photocatalyst for hydrogen generation after being
Z Liu et al
modified by ZnTAPc. It was found that a PEC cell employing
a ZnTAPc modified SiNW array as photoanode can effectively
produce hydrogen at a rate of 13 mol (cm2 h)1 with zero
potential bias (versus SCE) under 100 mw cm2 irradiation
using I as a sacrificial donor. The coating of ZnTAPc is
believed to enhance the efficiency of hydrogen generation
and the stability of the SiNW array. This demonstrates that
the ZnTAPc modified SiNW is a promising material for solar
hydrogen generation.
Acknowledgments
This work was partially supported by the National Ba-
sic Research Program of China (973 Program) (Grant
Nos 2010CB934500, 2012CB932400), and the National
Natural Science Foundation of China (Grant Nos 50825304,
50972190, 20971128, 51172246).
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