Thiomolybdate [Mo3S13]2- nanocluster: A molecular mimic of MoS2 active sites for highly efficient photocatalytic hydrogen evolution

Article abstract of DOI:10.1039/c7cc08178b

Thiomolybdate [Mo₃S₁₃]^2- nanoclusters, as a molecular mimic of MoS₂ edge sites, showed high efficiency in catalyzing photochemical H₂ evolution from a molecular system of Ru(bpy)₃Cl₂-ascorbic acid (H₂A) under visible light irradiation (≥420 nm), providing a turnover number of 1570 and an initial turnover frequency of 335 h^-1 for H₂ evolution based on the [Mo₃S₁₃]^2- catalyst.

Full text of DOI:10.1039/c7cc08178b

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Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
Reactivity differences of Sc
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2
-
Thiomolybdate [Mo S ] Nanocluster: A Molecular Mimic of
3
13
MoS Active Sites for Highly Efficient Photocatalytic Hydrogen
Evolution
2
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a
a
b
c
DOI: 10.1039/x0xx00000x
Yonggang Lei, Meiqun Yang, Jianhua Hou, Fang Wang, Entian Cui, Chao Kong and Shixiong
Min
*a
www.rsc.org/
2
-
Thiomolybdate [Mo
MoS edge sites, showed high efficiency in catalyzing also can be regarded as a molecular HER catalyst achieving a
photochemical
Ru(bpy) Cl -ascorbic acid (H
3 13
S ] nanocluster, as a molecular mimic of merge homogeneous and heterogeneous electrocatalysis but
2
H
2
evolution from
a
molecular system of maximum exposure of active sites. However, there are only
2
-
3
2
2
A) under visible light irradiation (≥420 few cases that reported the use of [Mo
3
S
13
]
as a cocatalyst
nm), achieving a turnover number of 1570 and an initial turnover supported on semiconductors for photo(electro)catalytic HER
2-
-
1
2-
20-24
frequency of 335 h for H
2
evolution based on [Mo
3
S
13
]
catalyst
.
and dye degradation,
3 13 2
no studies report on using [Mo S ]
nanoclusters as a HER catalyst to catalyze H
molecular system.
2
evolution from a
Artificial photocatalytic H
2
evolution via water splitting
2
-
provides an appealing solution to convert solar energy into
3
Herein, we report, for the first time, the use of [Mo S13] as
1
-3
clean fuel. Various photocatalytic H evolution systems have
2
an efficient HER catalyst in a molecular photocatalytic system
consisting of Ru(bpy) Cl as a photosensitizer and ascorbic acid
been developed yet a highly efficient and cost-effective H2
3
2
evolution catalyst is indispensable to achieve a high efficiency
(H
2
A) as a proton source and sacrificial electron donor. Under
4
,5
for large-scale H2 evolution reaction (HER). As the best-
known HER catalyst, Pt is sufficiently active but the scarcity
and high cost of Pt limit its widespread application, which in
turn largely spurred the studies for searching earth-abundant
HER catalysts. As one of the most promising candidates to
visible light irradiation (≥420 nm), a high turnover number of
-1
1
570 and an initial turnover frequency of 335 h based on
2
-
3 13
[Mo S ] catalyst could be achieved, which is much higher
than that of in-situ photochemically generated Pt, amorphous
MoSx nanoparticles, and colloidal MoS2 nanoparticles
synthesized by solvothermal method.
replace Pt, MoS in various forms loaded on a semiconductor
2
or in a photosensitized system has shown high catalytic activity
6
The thiomolybdate (NH ) Mo S ·xH O (x=0-2) crystals was
4
2
3
13
2
-13
for photocatalytic HER.
In addition to MoS , a variety of
2
(100)
molecular Mo-S complex analogues mimicking edge sites of
(
111)
MoS have also been successfully designed and employed for
2
(020)
1
4-19
2-
electrocatalytic HER.
Among them, the [Mo S ]
3 13
(001)
nanoclusters containing three distinct sulfur ligands (Fig. 1a)
can be viewed as the edge active sites of MoS2 with an
appropriate atomic structure for effective HER catalysis. In fact,
JCPDS: 76-2038
2
-
10
20
30
40
50
60
the supported [Mo S ] nanoclusters require a very small
3 13
2 θ(°)
overpotential to achieve high current density for
5,16
Raw data
Fitting curve
Background
S 2s
Raw data
Fitting curve
Background
1
2-
electrocatalytic HER.
In addition, [Mo S ] nanoclusters
3 13
2
-
Terminal S
2
IV
2-
2-
are quite stable in acidic aqueous solution and can achieve a
single cluster dispersion on proper supports that not only
Mo 3d5/2
Bridging S2 /apical S
IV
Mo 3d3/2
2
36
234
232
230
228
226
224
166
164
162
160
158
Binding energy (eV)
Binding energy (eV)
2-
Fig. 1 (a) Top and side view models of a single [Mo
S. (b) XRD pattern of (NH Mo 13·xH O (x=0-2) with a reference spectrum of the
NH Mo 13·2H O crystals (JCPDS No: 76-2038). (c, d) High-resolution XPS spectra of (c)
Mo 3d and (d) S 2p for [Mo
3 13
S ] nanocluster. Blue, Mo; yellow,
4
)
2
3
S
2
(
4
)
2
3
S
2
2-
3 13 2
S ] nanoclusters.
This journal is © The Royal Society of Chemistry 20xx
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2
+
synthesized via a simple wet-chemistry method following the
reported procedures by reacting (NH Mo O with an
ammonium polysulfide ((NH solution (see detailed
Ru(bpy)3 /Pt
4
)
6
7
O24·4H
2
2+
Ru(bpy)3 /colloidal MoS2
4 2 x
) S )
2+
†
25
R
u
(
b
p
y
)
/
M
o
S
method in ESI ). The X-ray diffraction (XRD) pattern of the
obtained dark red crystals (see inset in Fig. 1b) is in good
3
x
2
+
2-
Ru(bpy)
/[Mo S ]
3
3 13
agreement with the standard
NH Mo O (JCPDS No: 76-2038). The chemical states
of Mo and S elements in [Mo
by X-ray photoelectron spectroscopy (XPS) (Fig. 1c and d). Mo
d region (Fig. 1c) can be well-fitted with a single doublet of
XRD pattern of
2+
Ru(bpy)3
(
4
)
2
3 2
S13·2H
2
-
2
-
[Mo S13]
3
3
S13] nanocluster was examined
without H A
2
3
in darkness
Mo 3d5/2 (229.35 eV) and Mo 3d3/2 (232.45 eV) with a peak
separation of 3.1 eV, indicative of Mo with a +4 oxidation
0
5
10
15
440
480
520
TON of H evolution versus catalyst
2
1
5
state. The appearance of broad S 2s peak at the higher
binding energy of the Mo 3d5/2 peak indicates multiple Fig. 2 The turnovers of H
2
evolution from different systems in a mixed solution of
2-
CH
Ru(bpy)
irradiation time is 5 h. The Pt (10 μM) and MoS
by in-situ photochemical reduction of H PtCl
3
CN/H
2
O (100 mL, 9/1). Conditions: [Mo
(100 uM); H A (100 mM); light source, Xe lamp (300 W), ≥420 nm;
(10 μM) nanoparticles were prepared
and (NH MoS , respectively. The
3 x 2
S13] , Pt, MoS , or colloidal MoS (10 μM);
coordinated states of S. The fitting of the S 2p region (Fig. 1d)
-
2
]
3
Cl
2
2
of [Mo
3
S
13
nanocluster reveals two distinct doublets (S
-
2
x
2
p3/2, S 2p1/2), which could be assigned to terminal S
2
2
6
4
)
2
4
2
2
-
ligands (162.1 eV, 163.3 eV) and bridging S
2
apical S ligand (163.4 eV, 164.6 eV), respectively. The ratio
of latter S ligands to former one is estimated to be 7.2:5.8 by
ligands and the colloidal MoS (10 μM) was prepared according to the procedures reported in ref [11].
2
-
15
evolution activity could be obtained when H
because H A can serve as both proton source and electron
donor, and can be most easily oxidized (Fig. S5, ESI ). In
addition, as a cheap alternative to Ru(bpy) Cl , the commonly
used organic dye Eosin Y (EY) was also tested as a
2
A was used
2
]
-
assuming that the single [Mo
3
S
13
nanocluster contains 13 S
3 2
Mo S13·xH O
2
†
28
atoms. The electronic absorption spectra of (NH
4
)
2
dispersed in methanol and dimethyl formamide (DMF) are well
† 15,20-22
consistent with the previous observations (Fig. S1, ESI ).
3
2
2
-
2
]
-
In order to verify that the [Mo
function as the effective mimics of MoS
electrocatalytic HER activity of [Mo
3
S
13
]
nanoclusters can
active sites, the
photosensitizer for [Mo
evolution reaction from CH
containing H A or TEOA as an electron donor (Fig. S6, ESI ). The
results show that no or only trace amount of H is produced,
indicating that the EY is inactive as a photosensitizer to induce
3
S
13
catalyzed photocatalytic H
2
2
CN/H O (9/1) mixed solution
3
2
2
-
†
3
S
13
]
nanoclusters
2
-2
deposited onto carbon paper (10 nmol cm ) were firstly
†
measured (see experimental details in ESI ). As indicated in Fig.
2
†
2-
1
000
900
00
00
00
00
00
00
400
300
200
S2
.3 V vs. RHE for achieving high activity (5 mA cm ) for proton
reduction to H , indicating its high potential as a cocatalyst in
evolution from photocatalytic system.
nanocluster catalyzed
evolution reactions were performed in an
mixed solution of organic solvent and H O (100 mL) containing
Ru(bpy) Cl and H A (see experimental details in ESI ). As the
preliminary experiments, the effect of organic solvents and the
volume ratio of organic solvent to H O on the H evolution was
first optimized with the system of Ru(bpy) Cl
containing H A as electron donor. The activity of H
is highest when the mixture of CH CN and H O at a volume
ratio of 9 to 1 was used as solvent (Fig. S3 and S4, ESI ). The
solvent variation for H evolution from this system probably
3
, ESI , the [Mo S13] nanoclusters show low overpotential of
(a)
-2
0
8
2
1
00
0
7
catalyzing
H
2
a
6
0
5
10 15 20 25 30
2
]
-
-
2
]
Afterwards,
the
[Mo
3
S
13
[Mo S (ꢀM)
3
1
3
5
photocatalytic H
2
2
5
ꢀM
4
ꢀM
2
3
10
15
ꢀM
ꢀM
†
3
2
2
200
100
0
20 ꢀM
30 ꢀM
2
2
0
1
2
3
4
5
6
2
-
3
2
and [Mo
3 13
S ]
time (h)
4
3
2
1
00
00
00
00
2
2
evolution
1200
1000
800
(b)
3
2
†
00
2
200
400
600
M)
800
[
Ru(bpy) 23 +
]
(
ꢀ
results from a number of factors including solvent polarity,
stabilization of reduction intermediates, solvent coordination
6
00
400
00
25 ꢀM
5
00
00
300
400
600
800
0
ꢀM
ꢀM
ꢀM
ꢀM
ꢀM
ꢀM
ꢀM
2
-
1
2
ability to [Mo
transfer for inducing H
of the CH CN/H O ratio may be attributable to differences in
the solubility of [Mo
3
S13] , and the driving force for the electron
2
6-29
2
evolution.
Additionally, the effect
2
3
2
2
]
-
29
S
13
and H
in reaction media with different
solvent dielectric constant as the CH CN/H O ratio varies. In
2
A
and the reduction
0
3
2
0
1
2
3
4
5
6
-
3 13
potentials of [Mo S ]
time (h)
3
2
Fig. 3 (a) H
and different amount of [Mo
evolution from systems containing [Mo
amount of Ru(bpy) Cl in a mixed solution of CH
2
evolution from systems containing Ru(bpy)
3
Cl
2
(100 ꢀM), H
CN/H O (100 mL, 9/1). (b)
A (100 mM), and different
2
O (100 mL, 9/1). Light source, Xe
2
A (100 mM),
addition, the effect of various electron donors including
triethylamine (TEA), triethanolamine (TEOA), EDTA, acetic acid,
2-
3 13
S ]
in a mixed solution of CH
3
2
2-
H
2
3
S
13
]
(10 μM), H
CN/H
2
lactic acid, and H
2
A on the photocatalytic H
2
evolution activity
3
2
3
2
13] system in CH
-
from Ru(bpy) Cl /[Mo
2
3
3
S
3
2
CN/H O (9/1) mixed lamp (300 W) with a cut-off filter of 420 nm. Insets in panel (a) and (b) are the initial
2-
solution was investigated, revealing that the highest H
2
2 3 13 3 2
rate of H evolution versus [Mo S ] and Ru(bpy) Cl concentrations, respectively.
2
| J. Name., 2012, 00, 1-3
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0
.6 (a)
0.6 (b)
2-
0
5
ꢀ
M
M
0
mM
[
H A]
[Mo S13]
3
2
0
.5
.4
.3
.2
.1
.0
0.5
0.4
0.3
0.2
0.1
0.0
0
ꢀ
100 mM
0
0
0
0
5
00 550 600 650 700 750 800
500 550 600 650 700 750 800
Wavelength (nm)
Wavelength (nm)
2-
Scheme 1 Proposed reaction mechanism for the [Mo
3
S
13
]
catalyzed photocatalytic H
2
3 2 2
evolution from a molecular system of Ru(bpy) Cl and H A under visible light irradiation.
3 2
Fig. 4 Quenching of PL emission of Ru(bpy) Cl (20 ꢀM) excited at 450 nm by
2-
2 3 13
adding different amounts of (a) H A and (b) [Mo S ] catalyst.
catalyst concentration.
To gain an insight into the electron transfer process and the
reaction mechanism for photocatalytic H evolution from the
system, the photoluminescence (PL)
properties of the Ru(bpy) Cl in CH CN/H O (9/1) solution were
studied, as shown in Fig. 4. With the addition of different
amounts of H A (Fig. 4a), PL emission of Ru(bpy) Cl at 607
an efficient H
2
evolution might due to the incompatibility of EY
with H A and weak interaction between excited state EY and
2
2
2
-
2
-
3 2 3 13
Ru(bpy) Cl /[Mo S ]
[
Mo
Ru(bpy)
visible light was continuous during the 5 h reaction. The
3
S
13] nanoclusters. Under optimum reaction conditions of
Cl /H A system, the H evolution over time under
2
2
2
3
2
3
2
3
2
-
2
3
2
~
turnover of H
2
3 13
evolution reaches 508 versus the [Mo S ]
nm by the light excitation of 450 nm is quenched following
†
linear Stern-Volmer behavior (Fig. S9, ESI ) with a rate constant
catalyst within 5 h of irradiation. Control experiments indicate
2
-
that the Ru(bpy)
are all essential for H
yielded unobservable to trace amount of H
3
Cl
2
photosensitizer, [Mo
evolution; the absence of any of them
(Fig. 2). These
could serve as an efficient
evolution from a molecular
system under visible light. In addition, we compared the
3 2
S13] , H A, and light
7
-1 -1
k
q
of 1.984
2
×10 M ·s , which is consistent with that H A can
2
-
act as a proton source and its ascorbate anion (HA ) can
2
2
-
function as
2
a
reductive quencher for excited-state of
+ 11
results suggest that the [Mo
3 13
S ]
+
2-
Ru(bpy)
3
to Ru(bpy)
3
.
3 13
Notably, [Mo S ] catalyst can also
HER catalyst in catalyzing the H
2
2
+
effectively quench the excited state of Ru(bpy)
3
via a
2
-
oxidative quenching pathway (Fig. 4b). It is also noted that the
fitting of the combined Stern-Volmer plot shows two linear
catalytic H
amorphous MoS
Ru(bpy) Cl /H
nanoparticles were prepared by in-situ photochemical
reduction and only show 7 and 10 turnovers for H evolution,
respectively, which is much lower than that of [Mo
Moreover, the colloidal MoS nanoparticles synthesized by
solvothermal method exhibits the lowest turnover (ca. 2) for
2
evolution activity of [Mo
3
S
13
]
with that of Pt,
x
,
and colloidal MoS
2
nanoparticles in
2
-
regions with a transition point at 0.5
†
ꢀ
ESI ), from which two rate constants are extracted. Both rate
M [Mo
3 13
S ] (Fig. S10,
3
2
2 x
A system. The Pt and amorphous MoS
1
2
12
-1 -1
constants (4.04×10 and 1.18×10 M ·s ) are more than five
orders of magnitude faster than that for H A and approach the
diffusion-controlled limit, indicating the higher dispersion of
2
2
-
3
S13] .
2
2
2
-
[
3 13
Mo S ] catalyst at lower concentrations, while the smaller
~
1
2
-1 -1
2-
2
-
k
q 3 13
of 1.18×10 M ·s obtained with higher [Mo S ]
H
2
evolution. The high catalytic activity of the [Mo
3 2
S13] for H
concentrations suggests a strong interaction probably derived
2
evolution could be mainly attributed to the high activity of
-
+
2
]
from the electrostatic force between cationic Ru(bpy)
30
3
and
uncoordinated S edge sites of [Mo
3
S
13
along with its
2
-
anionic [Mo
3
S13] nanoclusters.
molecular dispersion feature in reaction media that render the
+
maximum exposure of active sites for H reduction to H .
2
2
A and [Mo S13] catalyst
-
Above results suggest that when H
2
3
2
-
coexist in the system, both reductive and oxidative quenching
may involve and compete in the electron transfer process for
In the system of Ru(bpy)
fixed concentrations (100 μM), the initial rate of H
exhibits a first-order dependence on the concentration of
3
Cl
2
/[Mo
3
S
13
]
with Ru(bpy)
3 2
Cl at
2
evolution
2
+
H
2
evolution from excited state of Ru(bpy)
3
. However, the
would dominate
for oxidative quenching than k
for reductive quenching even though higher concentration of
2
+
2
-
2-
oxidative quenching of excited Ru(bpy)
because of the much larger k
3
[Mo
3 13 3 13
S ] (Fig. 3a). At 2 μM [Mo S ] this system exhibits
exceptionally high activity, a turnover number of 1570 versus
2
q
q
-
[
Mo
3 13
S ] after 5 h reaction and an initial turnover frequency
2
]
-
-1
H
2
A (100 mM) is used relative to [Mo
3
S
13
catalyst (10
Moreover, it should also be
evolution induced by electron transfer
ꢀM)
(
TOF) of 335 h for H evolution could be achieved (Fig. S7,
2
†
ESI ). With the increasing [Mo
3
1,32
2-
]
under H
2
evolution conditions.
3
S
13
concentrations, the
inferred that the H
*
from the Ru(bpy)
2
2+
amount of H evolved is gradually increased, but the TON does
2
2-
]
to [Mo
3
S
13
catalyst via a oxidative
not follow the linear relationship with catalyst concentration,
and the initial TOF reaches a plateau at higher catalyst
3
quenching pathway would be more feasible since there is a
strong electrostatic force between positively charged
concentrations. When the concentration of Ru(bpy)
3 2
Cl is
*
2+
2-
]
Ru(bpy)
3
and negatively charged [Mo
3
S
13
nanoclusters,
increased from 25 to 800 μM at a fixed concentration of
2
-
which would expect to render a fast electron transfer from
[
Mo
reaches a maximum at 400 μM Ru(bpy)
with a rapid decrease in TON versus Ru(bpy)
which indicates that at this concentration of Ru(bpy)
3
S
13
]
(10 μM), both TON and initial TOF versus catalyst
2
+
2-
excited state of Ru(bpy)
3
to [Mo
3
S
13] catalyst. Above results
evolution reaction from the
molecular system most likely
3
Cl (Fig. 3b), together
2
†
indicate that the photocatalytic H
2
3
Cl
2
(Fig. S8, ESI ),
Cl the H
2
2
+
2-
Ru(bpy)
3 3 2
/[Mo S13] /H A
3
2
proceed via a oxidative quenching mechanism, as shown in
evolution activity of the system becomes limited by the
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Scheme 1. Under visible light irradiation (
2
≥
absorbs visible light photon to form excited state
420 nm), the
Notes and references
+
Ru(bpy)
*
3
1
2
A. Kudo and Y. Miseki, Chem. Soc. Rev., 2009, 38, 253.
X. Chen, S. Shen, L. Guo and S. Mao, Chem. Rev., 2010, 110
6503.
Y. Ma, X. Wang, Y. Jia, X. Chen, H. Hai and C. Li, Chem. Rev.,
014, 19, 9987.
J. Yang, D. Wang, H. Han and C. Li., Acc. Chem. Res., 2013, 46
900.
X. B. Li, Y. J. Gao, Y. Wang, F. Zhan, X. Y. Zhang, Q. Y. Kong, N.
J. Zhao, Q. Guo, H. L. Wu, Z. J. Li, Y. Tao, J. P. Zhang, B. Chen,
C. H. Tung and L. Z. Wu, J. Am. Chem. Soc., 2017, 139, 4789.
X. Zong, H. Yan, G. Wu, G. Ma, F. Wen, L. Wang and C. Li, J.
Am. Chem. Soc., 2008, 130, 7176.
2+
3+
*
2+
32
Ru(bpy)
3
3 3
, which (E(Ru(bpy) / Ru(bpy) )=-0.79 V vs. SCE)
,
was then oxidatively quenched by direct transferring electrons
-
2
to the [Mo
3
S
13
]
nanoclusters and then to the
3
4
5
+
undercoordinated S active sites, where the H are reduced to
2
+
,
2 2
H (E(H /H )=-0.10 V vs. SCE). At the same time, the oxidative
1
3
+
3+
2+
32
Ru(bpy)
3
3 3
(E(Ru(bpy) /Ru(bpy) )=+1.33 V vs. SCE) is
·
-
reduced back to its ground state by H
2
A (E(HA /HA )=+0.47 V vs.
SCE) , thereby complete the catalytic cycles.
In addition, the H evolution stability of the Ru(bpy)
2
8
2
+
6
2
3
-
2
-
†
[
Mo
that the H
The same system is then evacuated and subject to light
irradiation; however, no observable H formation could be
detected (not shown). Subsequently, when 100 μM Ru(bpy)
was added into above system, the H evolution could be
revived but the efficiency is decreased by 50%, implying that
the deactivation of the system is most likely because of the
3
S
13] -H
2
A system is examined. Fig. S11 in the ESI shows
7
8
S. Min and G. Lu. J. Phys. Chem. C., 2012, 116, 25415.
Q. Xiang, J. Yu and M. Jaroniec, J. Am. Chem. Soc., 2012, 134
6575.
2
evolution reaction ceases after 6 h light irradiation.
,
9
1
1
C. G. Morales-Guio, S. D. Tilley, H. Vrubel, M. Gratzel and X.
Hu, Nat. Commun., 2014, , 3059.
0 H. Yu, P. Xiao, P. Wang and J. Yu, Appl. Catal. B. Environ.,
016, 193: 217.
1 X. Zong, Y. Na, F. Wen, G. Ma, J. Yang, D. Wang, Y. Ma, M.
Wang, L. Sun and C. Li, Chem Commun., 2009, 30, 4536.
2
2
+
5
3
2
2
~
2
+
†
2-
degradation of the Ru(bpy)
catalyst is more stable. In fact, the UV-vis spectra of [Mo
catalyst aged in CH CN/H
absence of H A shows no any obvious change after 24 h in
darkness, and the aged [Mo
same H evolution activity as the fresh [Mo
S13 and S14, ESI ). In the third run, the system only produce
trace amount of H even although additional fresh 100 μM
3
(Fig. S12, ESI ) and the [Mo
3
S
13
]
12 X. Zong, Z. Xing, H. Yu, Y. Bai, G. Lu and L. Wang, J. Catal.,
014, 310, 51.
3 X. B. Li, Y. J. Gao, H. L. Wu, Y. Wang, Q. Guo, M. Y. Huang, B.
Chen, C. H. Tung and L. Z. Wu, Chem Commun., 2017, 53
606.
catalyst shows nearly the 14 H. I. Karunadasa, E. Montalvo, Y. Sun, M. Majda, J. R. Long, C.
2
]
-
2
3
S
13
1
3
2
O (9/1) solution in the presence or
,
2
5
2
]
-
3
S
13
2
-
S
13] catalyst (Fig.
J. Chang, Science 2012, 335, 698
5 J. Kibsgaard, T. F. Jaramillo and F. Besenbacher, Nat. Chem.,
014, , 248
6 Y. N. Shang, X. Xu, B. Y. Gao and Z. F. Ren, ACS Sustainable
Chem. Eng., 2017, , 8909.
might eventually decompose and convert to certain species 17 Z. Huang, W. Luo, L. Ma, M. Yu, X. Ren, M. He, S. Polen, K.
.
2
3
†
1
1
2
6
.
2
2
+
2-
Ru(bpy)
3
3 13
was added. This imply that the [Mo S ] catalyst
5
that is inactive in catalyzing H
2
evolution. Attempts to isolate
Click, B. Garrett, J. Lu, K. Amine, C. Hadad, W. Chen, A.
Asthagiri and Y. Wu, Angew. Chem. Int. Ed., 2015, 54, 15181.
18 B. R. Garrett, K. A. Click, C. B. Durr, C. M. Hadad and Y. Wu, J.
Am. Chem. Soc., 2016, 138, 13726.
the deactivated catalyst is failed and further studies is ongoing
2
-
to unravel the deactivation mechanism of the [Mo
catalyst during the visible-light-induced H evolution processes.
In summary, we have shown that [Mo
an effective mimic of edge sites of MoS
catalyzing evolution reaction from
photocatalytic system of Ru(bpy)
irradiation. The single cluster dispersion feature of [Mo
in a proper solvent render a maximum exposure of active sites
3 13
S ]
2
1
9 B. R. Garrett, S. M. Polen, M. Pimplikar, C. M. Hadad and Y.
Wu, J. Am. Chem. Soc., 2017, 139, 4342.
2
]
-
3
S
13
nanoclusters is
crystals in efficiently 20 D. Yue, X. Qian, Z. Zhang, M. Kan, M. Ren and Y. Zhao, ACS
Sustainable Chem. Eng., 2016, , 6653
21 D. Yue, Z. Zhang, Z. Tian, T. Zhang, M. Kan, X. Qian and Y.
Zhao Catal. Today 2016, 274, 22.
2
4
.
H
2
a
molecular
2
+
3
-H A under visible light
2
,
2
-
3 13
S ]
2
2 D. Yue, T. Zhang, M. Kan, X. Qian and Y. Zhao, Appl. Catal. B.
Environ., 2016, 183, 1.
2
-
at molecular level, thus [Mo
have higher activity for H
amorphous MoS , and colloidal MoS
not only shows the capability of [Mo
highly active H
3
S
13] nanoclusters were found to 23 Y. Hou, Z. Zhu, Y. Xu, F. Guo, J. Zhang and X. Wang, Int. J.
Hydrog. Energy 2017, 42, 2838.
2
evolution than the most-active Pt,
2
2
4 M. Kan, J. P. Jia and Y. X. Zhao, RSC Adv., 2016,
5 A. ller, E. Krickemeyer, A. Hadjikyriacou and D.
Coucouvanis, Inorganic Syntheses, Wiley, 2007, 27, 47.
evolution catalyst in the molecular systems for 26 29 E. D. Cline, S. E. Adamson and S. Bernhard, Inorg. Chem.,
6, 15610.
x
2
nanoparticles. This work
M
ü
2
-
3 13
S ] nanoclusters as a
2
solar to chemical fuel conversion, but also provides a new
insight to understand the relationship of Mo-S based
homogeneous and heterogeneous HER catalysts. Our
continuous efforts are now focused on the immobilization of
2008, 47, 10378.
2
2
7 30 P. W. Du, J. Schneider, G. G. Luo, W. W. Brennessel and R.
Eisenberg, Inorg. Chem., 2009, 48, 4952.
8 31 F. Y. Wen, X. L. Wang, L. Huang, G. J. Ma, J. H. Yang and C.
Li, ChemSusChem 2012, 5, 849.
2
-
[
Mo
materials to construct recoverable, more stable, and efficient
photocatalytic H evolution systems for long-term application.
3
S
13
]
on the conductive substrates or photoactive 29 W. N. Cao, F. Wang, H. Y. Wang, B. Chen, K. Feng, C. H. Tung
and L. Z. Wu, Chem. Commun., 2012, 48, 8081.
0 J. Dong, M. Wang, P. Zhang, S. Yang, J. Liu, X. Li and L. Sun, J.
Phys. Chem. C 2011, 115, 15089.
1 Z. Han, W. R. McNamara, M.-S. Eum, P. L. Holland and R.
Eisenberg, Angew. Chem. Int. Ed., 2012, 51, 1667.
3
3
2
This work is supported by the National Natural Science
Foundation of China (Grant No. 21763001, 21463001), the Key
Scientific Research Projects of the Higher Education 32 Y. Na, P. C. Wei and L. Zhou, Chem. Eur. J., 2016, 22, 10365.
Institutions of Ningxia Hui Autonomous Region (Grant No.
NCX2017143), and the Key Scientific Research Projects in 2017
at North Minzu University (Grant No. 2017KJ20).
4
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