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Cite this: Chem. Commun., 2014,

50, 1754

A novel nickelthioureatriethylamine complex

adsorbed on graphitic C3N4 for low-cost solar
hydrogen production

Received 24th October 2013,

Accepted 9th December 2013

Donghong Wang, Yuewei Zhang and Wei Chen*

DOI: 10.1039/c3cc48141g
www.rsc.org/chemcomm

A low-cost photocatalytic system composed of earth-abundant

elements has been synthesized, with the nickelthioureatriethylamine catalyst in situ formed on the C3N4 photocatalyst, which
exhibits a comparable H2 production with a C3N4Pt photocatalytic
system and a long term photocatalytic activity.

Nickel, an earth-abundant and inexpensive metal, is found in hydrogenase enzymes, which regulate hydrogen metabolism in Nature.1
Inspired by this, hydrogenase enzymes have also been applied in the
heterosystem for enhancing the photocatalytic activity.2 However, the
complicated structures and not being easily obtainable restricted their
further application. In view of this, Zhang et al. reported an ecient
catalyst assembled from the Ni(II) salt and 2-mercaptoethanol in one
step, which exhibits an excellent quantum eciency of 24.5% at
460 nm when sensitized by erythrosin B.3 Instead, the Nithiourea
(NiTu) complex was just used as a contrast, which exhibited
an unconspicuous catalytic activity. Mechanistic4,5 and theoretical6
studies of Ni complexes suggest that the pendant amine can act as a
proton donor and the nickel functions as a hydride donor. Also,
ligands with different electronic and steric properties contribute to
different catalytic activities.3,7 Due to the available source and facile
synthesis of the NiTu complex, and the pendant amines contained in
the Tu ligand, an active molecular catalyst can be easily obtained via
exchange of ligands based on the above theories. In our research, by
using N(CH2CH3)3 (TETN) to replace several Tu ligands through a
photochemical reaction, a novel NiTuTETN complex is designed
and generated. In this complex, the TETN ligand induces a much
larger steric effect than Tu, which may result in the NH2 being close to
the Ni2+ center, allowing for the formation of the HH bond. As a
result, the Ni complex consisting of TETN and Tu is speculated to be
much more active for H2 generation than the NiTu complex.
On the other hand, graphitic-C3N4 (g-C3N4), a novel metal-free
polymeric semiconductor,8 composed of C and N elements only,
was found to perform photocatalytic water splitting in the visible
i-Lab, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of
Sciences, Suzhou, 215123, China. E-mail: wchen2006@sinano.ac.cn
Electronic supplementary information (ESI) available. See DOI: 10.1039/c3cc48141g

1754 | Chem. Commun., 2014, 50, 1754--1756

light region. The appealing electronic structure of this material, its

chemical and physical stability, and the low cost make it potentially
useful in a variety of applications.9 Our group has also made eorts
to produce porous g-C3N4 from low cost and environmentally benign
urea.10,11 Unfortunately, this metal-free material can achieve sucient eciency only when loaded with cocatalysts, such as the scarce
and expensive noble metal cocatalyst.8,10
Therefore based on the above considerations, a heterogeneous
photocatalytic system, composed of NiTuTETN and g-C3N4, is
designed. The NiTuTETN complex adsorbed on the g-C3N4 semiconductor was fabricated during the photocatalytic process in one
step, and exhibited an obvious enhancement to the H2 production.
The process of generation of a low-cost C3N4NiTuTETN
photocatalytic system is exhibited in Scheme 1. The Ni(Tu)6 complex
generated when Tu was mixed with Ni(NO3)2.12 Under irradiation,
semiconductor C3N4 absorbed solar light and the photoelectrons
and holes were created. Then, these electrons and holes migrated to
the surface, respectively. In this system, under irradiation, ligand

Scheme 1 A simple process to fabricate the NiTuTETN complex from

earth-abundant elements on the C3N4 surface for a low-cost C3N4Ni
TuTETN photocatalytic system.

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Scheme 2

Fig. 1 (a) The methyl, methylene and amino region in the 1H NMR
spectrum of the NiTuTETN complex (solvent: CHCl3); (b) cyclic voltammograms of NiTu (0.5 mM) in the C3N4NiTuTEOA system before
irradiation and NiTuTETN (0.5 mM) generated in the C3N4NiTu
TEOA system after irradiation for 30 min using a glassy carbon working
electrode with a scan rate of 100 mV s 1 (pH is about 9).

exchange occurred and the Ni(I) complex was formed, with several
Tu ligands being replaced by TEOA.13 Then the active Ni(I) can
reduce TEOA [N(CH2CH2OH)3] which was dehydroxylated to
N(CH2CH3)3 (TETN). Therefore, complex NiTuTETN was produced. The composition of the complex was studied using the
proton NMR spectrum, as shown in Fig. 1a. The proton NMR
spectra of the reactants, Tu and TEOA, are presented in Fig. S1a
and b (ESI), and also the proton NMR spectrum of TETN is
presented in Fig. S1c (ESI). Through comparing these signals with
that of the Ni-complex, it is observed that TEOA changed to TETN
during photocatalysis. The 1H NMR spectra also reveal that the
ligands of the Ni complex are composed of Tu (NH2CSNH2) and
TETN (N(CH2CH3)3), and the ratio of the two ligands is calculated to
be 3 : 2. The coordination is reasonable, due to the large steric effect
arising from TETN ligands or C3N4 structure.4,14,15
Electrocatalytic properties of the complexes were investigated in
order to obtain insight into the reaction mechanism. The cyclic
voltammogram (CV) (black curve) of the NiTuTETN complex in
Fig. 1b displays an irreversible reduction wave at around 0.84 V
(vs. Ag/AgCl), which should be associated with the reduction of Ni(II) to
the reactive Ni(I),3 the resultant Ni(I) would have a larger driving force
for hydride formation and hence the H2 generation. However, no
Ni(II)/Ni(I) reduction peak is observed for the NiTu complex. The
results can predict that the NiTuTETN complex has a larger capacity
for receiving the photoelectrons from the C3N4 than the NiTu complex,
and thus displays a higher activity than that of the NiTu complex.
Dierent electrocatalytic properties of the NiTuTETN complex
from those of NiTu are expected on the basis of the structural
differences. The proposed structure change is shown in Scheme 2.
During the photocatalytic process, ligands exchanged through a
photochemical reaction. The reaction occurred on the surface of
C3N4, because it needs the photoelectrons from the C3N4 photocatalyst. Thus the interaction between the C3N4 and Ni played an
important role, in which the N in C3N4 may serve as a ligand for the
Ni metal.14 For TETN, the three ethyl groups are three-dimensional,
which will induce a large steric effect. The sheet structure of C3N4
and the steric hindrance of TETN will force the configuration of Tu

This journal is The Royal Society of Chemistry 2014

Proposed structure change from NiTu to NiTuTETN.

to change, enabling the NiSQC bond to curve, so the NH2 amine is

much near the metal center, as shown in Scheme 2. A key feature of
highly efficient electrocatalysts has shown that the presence and
positioning of the nitrogen bases near the metal center facilitate the
heterolytic cleavage or formation of the HH bond,46,16 and H2
production is associated with the heterolytic cleavage of the HH
bond and formation/cleavage of NiH and NH bonds. Thus, the
NiTuTETN complex is designed for the H2 evolution.
The photocatalytic reaction occurred at room temperature; in this
case, Tu could not decompose to give S2 , which means NiS could
not appear in our system, as revealed in the TEM images and UV-vis
absorption spectra. TEM images of C3N4NiTuTETN in Fig. S2
(ESI) only show a typical porous morphology of g-C3N4 powders
produced from urea, a two-dimensional structure consisting of small
flat sheets. No particles attributed to NiS crystals are observed on the
C3N4 sheets.17 Also, the optical properties of the C3N4Nicomplex
solids were characterized as shown in Fig. S3 (ESI). The Ni complex
has little effect on the absorption of C3N4. The absence of absorption
level enhancement further excludes the presence of NiS.17
Fig. 2a shows the time course of hydrogen evolution over the
low-cost C3N4NiTuTETN system. The experimental parameters
including the amount of Ni2+ ions, Tu content and TEOA content
have been optimized, as shown in Fig. S4 (ESI). The optimal dosage
of Ni2+ was found to be 0.05 mmol. And the optimal volume of TEOA
was 20 mL for its dual roles, sacrificial reagents and sources for
TETN. It is found that the optimal C3N4NiTuTETN system can
efficiently produce 410 mmol of hydrogen gas in the first 8 h of
irradiation of solar light, corresponding to a high average production
rate of 51 mmol h 1. Furthermore, our system performs accumulated
photocatalytic water splitting for at least 24 h, as shown in Fig. 2a.
For most hydrogenase catalysts, after several hours of continuous
illumination, little or no further accumulation of H2 appeared, as
those in ref. 2a,b and 18. Due to the porous structure of C3N4, and
the large amount of pyridine N (possessing lone pair electrons)
contained in C3N4,10,11 the urea-derived C3N4 will promote hybridization between the orbitals of N at the porous sites and the metal
atoms.19 The binding energy can reach 4 eV for Ni metal,19 the
rather strong binding energy may overcome the steric hindrance
caused by the ligands. Thus the interaction can promote the
anchoring of the Ni-complex and further maintain charge transfer
from the photocatalyst into the Ni metal ions.20 The interaction
between the metal ion and the nitrogen in C3N4 contributes to the
stability.21,22 Other metals were also complexed with Tu and TETN,
as shown in Fig. 2b. Overall, the complex of Ni2+ exhibits much
better activity than those of Co2+, Fe2+ and Cu2+.

Chem. Commun., 2014, 50, 1754--1756 | 1755

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reduction of Ni(II)/Ni(I) is absent, proved by the CV spectrum, and

the amines are away from the Ni center for protonation. Therefore,
the H2 generation process clearly illustrates that replacing several
Tu with TETN can promote the activity of the Ni-complex.
In conclusion, the low-cost C3N4NiTuTETN system composed
of earth-abundant elements shows outstanding photocatalytic
efficiencies for hydrogen evolution under solar light. Further
work is underway for a more efficient NiligandTETN complex.
This work was supported by the Natural Science Foundation for
Distinguished Young Scientists of Jiangsu Province (BK2012008), the
Hong Kong, Macao and Taiwan Science & Technology Cooperation
Program of China (2012DFH50120), the National Natural Science
Foundation of China (21373263, 11204350, 51303204), and the
National Basic Research Program of China (2010CB934700).
Fig. 2 (a) Time course of photocatalytic hydrogen evolution over the
C3N4NiTuTETN system under solar light (0.05 mmol Ni, 3 mmol Tu
and 20 mL TEOA); (b) different metalTuTETN (Fe, Co, Ni and Cu)
molecular catalyst for H2 generation under solar light (0.05 mmol metal
ion, 3 mmol Tu and 10 mL TEOA); (c) photocatalytic hydrogen evolution
over the C3N4NiTuTETN composites and C3N4NiTu using
10 mL lactic acid as the sacrificial reagent; (d) hydrogen production by
C3N4NiTuTETN and 3 wt% Pt loaded C3N4.

A previous report suggests that the NiTu complex also shows a

certain effect for promoting H2 evolution;3 in order to highlight the
impact of TETN ligands, control experiments were performed, under
the condition of using lactic acid as the sacrificial reagent. The
C3N4NiTuTETN powders were collected by filtration and washed
with water and ethanol several times. TEOA, TETN and Tu are
soluble in water, so the washing process can remove these species
except for the adsorbed NiTuTETN complex on the C3N4 surface.
As shown in Fig. 2c, the C3N4NiTu system shows negligible
photocatalytic activity, while the C3N4NiTuTETN system exhibits
a much higher H2 production. The PL spectra can provide a clear
proof for the obviously different photocatalytic activities. As shown
in Fig. S5 (ESI), the weaker PL intensity is contributed from the low
recombination of photo-generated electrons and holes. Compared
with the NiTu complex, the adsorption of the NiTuTETN complex
onto the C3N4 surface greatly suppressed the recombination of
photogenerated electrons and holes, which in return provided active
sites for H2 production. In our previous reports, the naked ureaderived C3N4 exhibits a negligible H2 production. However, the
production gets enhanced to 59 mmol h 1 (per 100 mg catalyst)
after loading 3 wt% Pt as the cocatalyst, as shown in Fig. 2d. And the
catalytic activity of the NiTuTETN complex (51 mmol h 1) was
found to be comparable with that of the Pt cocatalyst. The Q.E. is
about 0.2% measured at 420 nm, which is close to that of C3N4/Pt8
(about 0.1% measured at 420460 nm).
The proposed H2 evolution process is shown in Scheme S1
(ESI); the molecular catalyst in the H2 production system first
receives an electron and is reduced to an active species,3,23 in our
system, active Ni(I)TuTETN generated. Protonation occurs to get
the electron from the Ni+ center, and the proton bonded with Ni is
reduced to H2.5 After the release of H2, the molecular catalyst is
recovered to Ni(II)TuTETN. However, in the Ni(II)Tu complex, the

1756 | Chem. Commun., 2014, 50, 1754--1756

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This journal is The Royal Society of Chemistry 2014