Photocatalytic oxidation of organic compounds in a hybrid system composed of a molecular catalyst and visible light-absorbing semiconductor

Article abstract of DOI:10.1039/c4dt02945c

Photocatalytic oxidation of organic compounds proceeded efficiently in a hybrid system with ruthenium aqua complexes as catalysts, BiVO₄ as a light absorber, [Co(NH₃)₅Cl]²⁺ as a sacrificial electron acceptor and

Full text of DOI:10.1039/c4dt02945c

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Photocatalytic Oxidation of Organic Compounds in a
Hybrid System Composed of Molecular Catalyst and
Visible Light-Absorbing Semiconductor
Cite this: DOI: 10.1039/x0xx00000x
a
a
b
a
a
a,c
Received 00th January 2012,
Accepted 00th January 2012
Xu Zhou, Fei Li,* Xiaona Li, Hua Li, Yong Wang and Licheng Sun*
DOI: 10.1039/x0xx00000x
www.rsc.org/
Photocatalytic oxidation of organic compounds was they suffered from serious desorption from the surface of
11
semiconductive oxide in aqueous solution.
efficiently proceeded in a hybrid system with ruthenium
On the other hand, photoactive semiconductors are chemically
stable to light irradiation and have the advantage of easily forming
thin film photoelectrode. Combinations of pꢀtype semiconductors
with suitable molecular catalysts have been shown to improve the
aqua complexes as catalysts, BiVO as a light absorber,
4
2
+
[
Co(NH ) Cl] as a sacrificial electron acceptor and water
3 5
as an oxygen source. The photogenerated holes in
semiconductor are used to oxidize molecular catalysts into hydrogen evolution from water and the reduction of CO , where
2
IV
-
the high-valent Ru =O intermediates for 2e oxidation.
molecular catalysts compensate for the kinetic limitations of
12ꢀ14
semiconductors on water splitting.
Though no precedent on
Solar water splitting inspired by natural photosynthesis is a photocatalytic oxidation of organic compounds with such a
2
+
promising approach for sustainable conversion of solar energy into combination in water, we reason that replacing [Ru(bpy)
]
with
3
+
ꢀ
chemical fuels. To date, the 4H /4e process of water oxidation more stable and cheap semiconductor materials should be applicable.
remains a major obstacle to overall water splitting driven by As a proofꢀofꢀconcept, in this work, a sacrificial system composed of
sunlight. An alternative approach for artificial photosynthesis is photoactive nꢀtype semiconductor as a light absorber and ruthenium
1
coupling the proton reduction with photochemical oxidation of complex as a catalyst was developed. With water as both the solvent
hydrocarbons by activation of water using transition metal and the oxygen source, the hybrid system shows promising
2
complexes. Such a system integrating sunlight and water is thought efficiency and selectivity in alcohol and sulfide oxidation. The
to greatly benefit the environment without using hazardous chemical utilization of photostable light absorber leads to an unexpected
oxidants for organic transformations. However, in spite of great ligandꢀdependent reactivity towards sulfoxidation, which was not
2+
efforts towards photochemical oxidation of water to oxygen, observed by using [Ru(bpy)
]
as the photosensitizer. Futhermore,
3
catalytic oxidation of organic compounds by visible light and water the photocatalytic formation of the highꢀvalent metalꢀoxo
has been rare. In literature, the available examples are operated in intermediates by PCET from ruthenium complexes to photoexcited
homogeneous aqueous solutions. Employing the molecular semiconductor was demonstrated.
2
+
2+
polypyridyl ruthenium complexes such as [Ru(bpy)3] (bpy = 2,2'ꢀ
Ruthenium complex [Ru(tpa)(H
2
O)
2
]
(1, tpa
=
tri(2ꢀ
bipyridine) as a photosensitizer to capture photons, ruthenium and pyridylmethyl)amine) (Scheme 1) bearing two aqua ligands has
manganese aqua complexes have been demonstrated to catalyze the shown to be efficient catalysts in conversion of alcohol to aldehyde
3a
oxidation of alcohol and alkene with visible light in the presence of a with water and light. Under visible light irradiation by a 300 W Xe
2
+ 3ꢀ7
sacrificial electron acceptor such as [Co(NH ) Cl] . Furthermore, lamp equipped with a cutꢀoff filter (λ > 400 nm), we found that the
3
5
molecular assemblies based on ruthenium photosensitizerꢀcatalyst catalytic oxidation of benzyl alcohol by complex 1 selectively
dyads have been reported for photocatalytic oxidation of alcohol and afforded benzaldehyde in 22% yield (based on substrate) in the
8
ꢀ10
2+
2+
sulfide.
of [Ru(bpy) ]
[
In these cases, the oxidative quenching of the exited state presence of [Ru(bpy)
3
]
and [Co(NH
by sacrificial electron acceptor results in buffer (Table 1, entry 1). With this result in mind, we examined the
Ru(bpy)3] with thermodynamic driving force for extracting possibility of replacing ruthenium sensitizer with photoactive
electrons from catalyst. Water serves as the oxygen source to semiconductors in photocatalytic oxidation. Initially, BiVO was
generate highꢀvalent metalꢀoxo species by virtue of protonꢀcoupled chosen as a visible light absorber due to its narrow bandgap energy
3 5
) Cl] in a pH 4.7 phosphate
2+
3
3
+
4
15
electron transfer (PCET), which is successively used for the (2.4 eV) and a good response to visible light. In a heterogeneous
oxidation of various organic molecules. However, ruthenium system including 0.04 mM complex 1, 15 mg BiVO and 25 mM
Cl] , selective photoꢀconversion of benzyl alcohol into
4
2
+
polypyridyl dyes have a couple of drawbacks: They are costly and [Co(NH )
3 5
are not sufficiently stable under longꢀterm light irradiation. Grafted benzaldehyde was smoothly proceeded with a turnover number
on the electrode of a dyeꢀsensitized photoelectrochemical (PEC) cell, (TON) of 73 and a yield of 29%, which are comparable to the values
obtained by us and others using molecular sensitizer (Table 1, entry
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DOI: 10.1039
J
/
o
C
u
4DrnT0
a
2
l
9
N
4
a5Cme
3
a,9a
2
).
In the absence of molecular catalyst or BiVO , negligible 110
were
achieved
(Table
1,
entry 7).
Complex
4
2
+
amount of benzaldehyde was obtained, indicative of both [Ru(tpy)(bpy)(H O)] (2, tpy = 2,2':6',2''ꢀterpyridine) (Scheme 1)
2
components are indispensible for efficient photoꢀoxidation (Table 1, bearing one aqua ligand was also found to be active under the
entries 3 and 4).
present reaction conditions (Table 1, entry 9). It is worth noting that
replacing BiVO with other nꢀtype semiconductors such as WO and
4
3
αꢀFe O3 also exhibited comparable activities in the oxidation of
2
alcohol to aldehyde (entries 11 and 12). Therefore,
semiconductor/molecular complex hybrid represents a popular
strategy for solar conversion of hydrocarbons.
As for a green and sustainable process, it would be more
interesting to use water as the oxygen source for oxygen atom
transfer reaction. In this regard, sulfide oxygenation was selected as
a model reaction due to its emerging importance in the areas of
18
pharmaceutical chemistry and asymmetric catalysis. Table 2 shows
photocatalytic oxygenation of thioanisole in the absence of catalyst
affords the corresponding sulfoxide with a low yield of 10% (entry
Scheme 1. The molecular structures of ruthenium catalysts.
1
). Unlike the oxidation of alcohol, no improvement on sulfoxidation
could be made by addition of complex 1 (entry 2). However, using
complex 2 as catalyst, nearly quantitative conversions of thioanisole
and pꢀmethoxy thioanisole to the corresponding sulfoxides were
achieved (entries 3 and 5). The excellent catalytic activity and
selectivity of 2 were further evidenced by spending all electron
acceptor in the presence of excess sulfide (entries 4 and 6), where
oxygen evolution was found to be significantly suppressed. The
a
Table 1. Photocatalytic oxidation of benzyl alcohol to benzyl aldehyde.
b
c
Entry Photosensitizer
Catal
Substrate
Yield%
TON
yst
1
d
1
2
3
4
5
6
7
8
9
[Ru(bpy)
3
]Cl
2
benzyl alcohol
benzyl alcohol
benzyl alcohol
benzyl alcohol
benzyl alcohol
4ꢀmethylbenzyl
alcohol
4ꢀmethoxybenzyl
alcohol
4ꢀchlorobenzyl
alcohol
22
29
1
2
ꢀ
55
73
ꢀ
ꢀ
ꢀ
BiVO
BiVO
ꢀ
4
1
-
1
1
4
kinetics of simultaneous formation of methyl phenyl sulfoxide and
e
2+
BiVO
BiVO
4
the consumption of [Co(NH ) Cl] based on the UVꢀVis absorption
3 5
4
1
31
77
spectral changes is shown in Figure S4, from which the efficiency of
18
sulfide oxygenation is decided to be 96%. With H O as the solvent
BiVO
4
4
1
1
44
12
110
30
18
+
for photocatalysis, PhCH S O (m/z =143, [M+H] ) was identified
3
by mass spectrum as the dominant product, confirming that water is
the unique source of oxygen atom (Figure S5).
BiVO
BiVO
BiVO
4
2
1
1
1
benzyl alcohol
benzyl alcohol
benzyl alcohol
benzyl alcohol
23
30
24
26
58
75
60
65
f
1
0
4
Table 2. Photocatalytic oxidation of sulfide to sulfoxide with BiVO
absorber.
4
as light
1
1
1
2
WO
2 3
αꢀFe O
3
a
a
b
c
Reaction conditions: Semiconductor powder 15 mg, catalyst 0.04 mM, Entry
Catalyst Substrate
Product
Methyl phenyl 11
sulfoxide
Methyl phenyl 10
sulfoxide
Methyl phenyl 97
sulfoxide
Methyl phenyl 48
sulfoxide
Methyl
Yield%
TON
ꢀ
2+
benzyl alcohol 10 mM and [Co(NH
phosphate buffer was irradiated with 300 W Xe lamp equipped with a 400
nm cutꢀoff filter for 5 h. Yields were calculated as the percentage
conversion of benzyl alcohol to benzyl aldehyde. TONs were calculated as
3
)
5
Cl] 25 mM in a 10 mL pH 4.7
1
2
3
4
5
ꢀ
Thioanisole
Thioanisole
Thioanisole
Thioanisole
b
1
2
2
2
ꢀ
c
d
2+
(
mol of product)/(mol of catalyst). 0.08 mM [Ru(bpy)
3
]
was used as
243
120
245
e
photosensitizer. Reaction was conducted in oxygen saturated solvent in the
absence of [Co(NH
used.
2+
f
d
3
)
5
Cl] . BiVO
4
recovered from catalytic system was
pꢀMethoxy
pꢀ 98
thioanisole
methoxy
Phenyl
sulfoxide
Methyl
methoxy
Phenyl
sulfoxide
Although BiVO has been known as a photocatalyst for water
4
16
2+
oxidation, less than 10% [Co(NH ) Cl] was involved in oxygen
3
5
production in the present conditions. Since essentially identical
amounts of oxygen were produced regardless of the presence of
catalyst or substrate (Figure S1), we proposed the oxidation of water
d
6
2
pꢀMethoxy
thioanisole
pꢀ 50
125
takes place on the surface of BiVO and the oxidation of alcohol is
4
selectively catalyzed by 1. The poor kinetics for oxygen evolution
here were thought to offer ruthenium complex the chance to capture
a
Reaction conditions: BiVO
4
15mg, catalyst 0.04 mM, substrate 10 mM, and
2+
[
Co(NH ) Cl] 25mM in a 10 mL pH 4.7 sodium phosphate buffers was
3 5
the holes generated by photoexitation of BiVO and eventually act as
b
4
irradiated with 300 W Xe lamp with a 400 nm cutꢀoff filter for 5 h. Yields
were calculated based on the percentage conversion of sulfides to sulfoxides.
the reaction sites for alcohol oxidation. In a control experiment,
2
+
c
d
[
Co(NH ) Cl] was removed and the reaction was carried out in
3 5
TONs were calculated as (mol of product)/(mol of catalyst). 10 mM
2+
oxygen saturated solvent. The reaction showed no aldehyde [Co(NH
formation (Table 1, entry 5), thus excludes the possibility of O2
3 5
) Cl] was used.
serving as an oxidant or electron acceptor and suggests a distinct
mechanism from that of extensively investigated photoactive conversion of sulfide were not observed when [Ru(bpy)3] was used
In sharp contrast, the ligand dependence in photocatalytic
2
+
1
7
semiconductor/O system.
as the photosensitizer. Related experiments in the presence of 1 or 2
2
Other factors were also found to influence the reactivity of hybrid were found to produce sulfoxide in similar yields (Table S2). This
system. Higher or lower pH values resulted in lower yields (Table means the existence of other species that are catalytic active for
2+
S1). By employing benzyl alcohols with an electronꢀdonating sulfoxidation. Since the instability of [Ru(bpy)3] under longꢀterm
substituent as the substrate, conversions up to 44% and TONs up to light illumination has been documented and the decomposition of
2
| J. Name., 2012, 00, 1-3
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DOI: 10
C
.
O
10
M
39
M
/C
U
4D
N
T
I
0
C
2
A
94
T
5
I
C
ON
3
+
19
9,21
[
Ru(bpy)3] was found to result in ligand loss species, we electrochemically formed 4 (Figures 1d and S8).
To the best of
proposed that these decomposition products compete with 1 and 2 to our knowledge, we provide evidence for the first time that the
catalyze the oxygenation. This speculation was identified by the fact photocatalytic formation of the highꢀvalent rutheniumꢀoxo
2+
that irradiation of a reaction solution of thioanisole, [Ru(bpy) ] and complexes in water mediated by a semiconductor sensitizer.
3
2
+
[
Co(NH ) Cl] with either a 300 W Xe lamp (λ > 400 nm) or an Addition of thioanisole into the above phosphate buffer of inꢀsituꢀ
3 5
AM 1.5G solar simulator yielded considerable amounts of sulfide generated complex 4, complex 2 regenerated in 80% yield within 5
comparable to those received in the presence of 1 or 2 (Table S2). In min, as observed by the recovery of its characteristic absorption
hybrid system, the stability issue is resolved by using semiconductor band at 460 nm (Figure 2b). In contrast, the absorption spectrum
II
photosensitizer. Though the precipitation of Co complexes on the remained unchanged after adding thioanisole into the solution of
surface of BiVO during photoirradiation reduces the lightꢀabsorbing complex 3 (Figure 2a). These observations are in agreement with the
4
efficiency, BiVO4 could be recoverd by treatment with HOAc results of photocatalytic oxygenation, which underline the crucial
IV
aqueous solution and be reused without decrease in activity (Table 1, role of Ru =O in oxygen atom transfer. Though the reasons for the
entry 10).
reactivity differences exhibited by 3 and 4 are not clear, according to
previous study on the catalytic properties of pentadentate and
tetradentate ligandꢀbased iron complexes, this is possibly due to a
smaller energy 2+barrier of the oxygen transfer for
IV
[
[
Ru (tpy)(bpy)(O)]
with
respect
to
that
for
IV
2+ 22
.
Ru (tpa)(O)(OH)]
IV
Figure 2. UV-Vis spectral changes of in situ generated Ru =O complexes
3 (a) and
(b) before (black) and after (red) the addition of 1 mM thioanisole. The spectra
4
of (a) and (b) are shown in dashed lines for comparison.
1
2
Figure 1. Visible absorption spectra of 0.04 mM complexes
1
(a) and
2
(c) in 0.1
and 5 mM
Cl] before (black) and after (red) light irradiation for 15 min (BiVO
was removed for UV-Vis analysis and the spectra were corrected for the
M phosphate buffer solutions (10 mL, pH 4.7) containing 15 mg BiVO
4
2+
[
Co(NH
3
)
5
4
Combining the results obtained from catalytic and spectroscopic
studies apparently suggests a mechanism for hybrid system (Scheme
): Photoꢀinduced charge separation occurs in semiconductor
2
+
absorption of [Co(NH
complexes (b) and
3
)
5
Cl] ) and visible absorption spectra of 0.04 mM
(d) before (black) and after (red) electrochemical
2
1
2
IV
nanoparticles upon light irradiation. This triggers the electron
transfer from exogenous ruthenium complexes to the valence band
oxidation into their corresponding high-valent Ru -oxo species (red) in 0.1M
phosphate buffer solutions (20 mL, pH 4.7). The insets in (b) and (d) show cyclic
IV
of semiconductor and form Ru =O complex by PCET oxidation.
voltammograms of
potentials (noted by blue lines) used for electrolysis are 1.0 V vs. NHE for
.1 V vs. NHE for , respectively.
1 and 2 in the solutions for electrolysis. The applied
1
and Meanwhile, the photogenerated electrons in the conduction band are
III
IV
1
2
consumed by Co . Finally, Ru =O is subject to nucleophilic attack
IV
by the sulfide, the oxygen atom transfer from Ru =O to sulfide reꢀ
II
7,9,23
In order to gain more insight into the reactivity induced by produces Ru complex and releases sulfoxide as the product.
ruthenium complexes, a reaction sample containing 1, BiVO and Herein, the wellꢀseparated functions of the inorganic and organic
Co(NH ) Cl] was irradiated for 15 min. BiVO4 powder was components enable the ready alteration of the properties of hybrid
4
2
+
[
3 5
removed by filtration and the UVꢀVis absorption spectrum of the system by structural variations of catalysts, providing significant
resulted solution was recorded in Figure 1a. It was found that a new advances in constructing a PEC cell. Recently, an iron complex
species appears with an absorption band at 470 nm. On the basis of a based on nonꢀheme ligand was attached on WO
photoanode for
3
rich chemistry that already built for the highꢀvalent rutheniumꢀoxo photoelectrochemical water oxidation. However, the active species
2
4
complexes, this species was attributed to a paramagnetic S = 1 responsible for oxygen evolution has not yet been clarified. Based
IV
IV
+
Ru =O complex [Ru (tpa)(O)(OH)] (3), as has been previously on the findings here, it is very likely that molecular species are
3
a,20
described in homogeneous solutions.
According to the energy involved in surface OꢀO bond formation.
levels provided in Figure S6, the valence band of BiVO is positive
4
enough to oxidize 1 to the highꢀvalent species 3 and the conduction
band of BiVO is thermodynamically able to reduce the electron
4
2
+
acceptor by transfer electrons to [Co(NH ) Cl] . For further
3
5
identification, electrochemical oxidation of 1 into its oxo form was
carried out at a constant potential of 1.0 V vs. NHE, the UVꢀVis
IV
absorption spectrum of electrochemically formed Ru =O (Figures
1
b and S7) is consistent with that formed by light. Similarly,
complex 2 is oxidized by photoexcited semiconductor to its
IV
IV
2+
corresponding Ru =O species [Ru (tpy)(bpy)(O)] (4) (S = 1) in
water, showing a featureless spectrum (Figure 1c) identical to that of
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DOI: 10.1039/C 294
Jou4DrnT0al Na5Cme
2
3
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In summary, we have developed a robust system that can give
photocatalytic oxidation of organic substrates such as alcohol
and sulfide with an inorganic semiconductor as the
photosensitizer, ruthenium aqua complexes as the catalyst and
water as an oxygen source. The holes generated in inorganic
semiconductor by visible light irradiation could be trapped by
6
7
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4386ꢀ4387.
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Electronic Supplementary Information (ESI) available: Experimental
1
8
details of photocatalytic oxidation, mass spectrum of Oꢀlabeling
experiment and the data of control experiments. See
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DOI: 10.1039/C4DT02945C
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Photocatalytic oxidation of organic compounds was carried out in water using a
molecular catalyst and a semiconductor photosensitizer.