Using the hydrogen and oxygen in water directly for hydrogenation reactions and glucose oxidation by photocatalysis

Article abstract of DOI:10.1039/c5sc03178h

Direct utilization of the abundant hydrogen and oxygen in water for organic reactions is very attractive and challenging in chemistry. Herein, we report the first work on the utilization of the hydrogen in water for the hydrogenation of various organic compounds to form valuable chemicals and the oxygen for the oxidation of glucose, simultaneously by photocatalysis. It was discovered that various unsaturated compounds could be efficiently hydrogenated with high conversion and selectivity by the hydrogen from water splitting and glucose reforming over Pd/TiO₂ under UV irradiation (350 nm). At the same time, glucose was oxidated by the hydroxyl radicals from water splitting and the holes caused by UV irradiation to form biomass-derived chemicals, such as arabinose, erythrose, formic acid, and hydroxyacetic acid. Thus, the hydrogen and oxygen were used ideally. This work presents a new and sustainable strategy for hydrogenation and biomass conversion by using the hydrogen and oxygen in water.

Full text of DOI:10.1039/c5sc03178h

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DOI: 10.1039/C5SC03178H
Journal Name
ARTICLE
Using hydrogen and oxygen in water directly for hydrogenation
reactions and glucose oxidation by photocatalysis
Received 00th January 20xx,
Accepted 00th January 20xx
Baowen Zhou, Jinliang Song,* Huacong Zhou, Tianbin Wu and Buxing Han*
DOI: 10.1039/x0xx00000x
Direct utilization of the abundant hydrogen and oxygen in water for organic reactions is very attractive and challenging in
chemistry. Herein, we report the first work on the utilization of the hydrogen of water for hydrogenation of various
organic compounds to form valuable chemicals and the oxygen for the oxidation of glucose simultaneously by
photocatalysis. It was discovered that various unsaturated compounds could be efficiently hydrogenated with high
www.rsc.org/
conversion and selectivity by the hydrogen from water splitting and glucose reforming over Pd/TiO
2
under UV irradiation
(350 nm). At the same time, glucose was oxidated by the hydroxyl radicals from water splitting and the holes caused by UV
irradiation to form biomass-derived chemicals, such as arabinose, erythrose, formic acid, and hydroxyacetic acid. Thus, the
hydrogen and oxygen were used ideally. This work presents a new and sustainable strategy for hydrogenations and
biomass conversion by using the hydrogen and oxygen in water.
chemicals or H . Exploration of new processes for glucose
2
Introduction
Efficient utilization of hydrogen and oxygen in water is one of
the most attractive but challenging technologies for the
sustainable development of our society. Photocatalytic water
utilization is a long term task.
Hydrogenation is an important approach for producing
various chemicals. Current hydrogenation processes usually
suffer from harsh reaction conditions and lower selectivity.
1
0-12
Moreover, H used is mainly derived from fossil resources.
2
splitting offers a fascinating means for the production of H
2
1
,2
Furthermore, reduction processes that use stoichiometric
reductants generally form large amounts of environment-
and O from water. Over the past decades, considerable
2
efforts have been devoted to this area, and great progress has
1
3-15
3
unfriendly wastes.
In recent years, photocatalytic reduction
been made. However, many challenging problems are still
has been reported to be an alternative method for the
traditional hydrogenation process with high selectivity under
unsolved, such as low energy efficiency, environment-sensitive
reaction systems, separation of H2 and O , and efficient
storage, transportation and combustion of H , etc. Therefore,
it is highly attractive to develop effective and novel routes for
the utilization of hydrogen and oxygen from water splitting.
Using the abundant hydrogen and oxygen in water directly for
hydrogenation and oxidation is a desirable strategy.
2
16,17
18
milder reaction conditions. Triethanolamine,
isopropanol,
2
19
and oxalic acid, etc., are usually used as electrons and protons
donors, which makes the process less sustainable.
Use of cheap and abundant resources in the
hydrogenation of organic compounds and transformation of
biomass into value-added chemicals is of great importance.
Herein, we report the first work of using water to provide
hydrogen and oxygen for hydrogenation of organic compounds
and oxidation of biomass into value-added chemicals
simultaneously by photocatalysis. In this approach, the
hydrogen in water is utilized for hydrogenation of different
organic compounds, and at the same time the oxygen in water
involved in the oxidation of glucose to generate a series of
biomass-derived valuable chemicals as shown Scheme 1, in
which the main products are provided.
Lignocellulosic biomass is an abundant and renewable
4
resource. Glucose can be obtained from depolymerization of
cellulose, which is a main component of lignocellulosic
5
biomass. Conversion of glucose into various value-added
6
chemicals and fuels has received much attention.
Furthermore, H2 can also be generated from glucose by
7
various routes, including photocatalytic process, catalytic
8
9
reforming, and enzymatic procedures. Up to now, attention
has been mainly focused on transformation of glucose into
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Colloid
and Interface and Thermodynamics, Institute of Chemistry, Chinese Academy of
Sciences, Beijing 100190 (China)
E-mail: songjl@iccas.ac.cn; hanbx@iccas.ac.cn.
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
Scheme 1. Photocatalytic water splitting for hydrogenation of various organic
compounds and conversion of glucose to valuable chemicals.
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proved that high molar ratio of glucose to substrate was
beneficial for the reaction.
Results and discussion
View Article Online
DOI: 10.1039/C5SC03178H
Selective hydrogenation of nitrobenzenes containing other
reducible groups provides a convenient route to produce
functionalized anilines, which are high-value intermediates for
various fine chemicals. Thus, photocatalytic reduction of
functionalized nitrobenzenes was selected to study the
reaction in aqueous solution of glucose by UV-light (350 nm).
Pd/TiO , which was effective for photocatalytic hydrogenation
2
20,21
of the nitro group in the presence of various alcohols,
utilized as the catalyst. Transmission electron microscope
TEM) examinations indicated that the difference between the
was
(
size of the Pd nanoparticles (PdNPs) in the Pd/TiO catalysts
2
with Pd loadings of 1 wt%, 2 wt%, and 3 wt% was not
considerable (Fig. S1). Fig.1 (a-c) shows the influence of Pd
contents in the Pd/TiO catalysts on photocatalytic reduction
2
of 4-nitroacetophenone to 4-aminoacetophenone. It was
found that the catalyst with 2 wt% Pd had better catalytic
performance than those with 1 wt% and 3 wt% Pd. The main
reason is that the loading amount of Pd affected the reaction
in opposite ways. In the catalytic cycle, Pd nanoparticles
served as electron sinks and provided active sites for forming
H-PdNPs, which is the active species for the reduction of the
nitro group. On the other hand, excessive loading of Pd
nanoparticles could reduce the photocatalytic activity because
22
Pd could also act as charge carrier recombination centers,
and shielded 3the incident light absorption by the Fig. 1. Effect of the Pd contents in the Pd/TiO catalysts (a-c) and the molar ratio
2
2
of glucose to substrate (d-f) on the photocatalytic reduction of 4-
semiconductor. The competition of the above factors
nitroacetophenone to 4-aminoacetophenone. Reaction conditions: 4-
resulted in the best performance of the catalyst with 2 wt% Pd
nitroacetophenone, 0.1 mmol; water, 1 mL; 0.025 g Pd/TiO with various Pd
2
2
2
content. The 4-nitroacetophenone could be completely contents; UV-light (350 nm, 4 mW/cm ); illuminated area, 2 cm ; temperature,
o
2
5 C. The molar ratio of glucose to substrate was 5 in a-c; Pd/TiO
2
with 2 wt% Pd
converted in 12 hours (Fig. 1a) with a 4-aminoacetophenone
selectivity of 98% (Fig. 1b).
was used in d-f.
Fig. 1 (d-f) illustrates the influence of the molar ratio of
glucose to substrate on photocatalytic hydrogenation of 4-
Water splitting accompanied with glucose reforming
nitroacetophenone with different reaction times. It can be continuously proceeded over Pd/TiO2 under UV-light
seen that the conversion of 4-nitroacetophenone (Fig. 1d), the illumination, releasing protons and electrons for photocatalytic
selectivity (Fig. 1e) and yield (Fig. 1f) of 4-aminoacetophenone hydrogenation. As shown in Fig. 2 and Table 1, 0.13 mmol of
increased with the increasing molar ratio of glucose to glucose were consumed for total conversion of 0.1 mmol of 4-
substrate. In the reaction process, glucose performed as the nitroacetophenone to 4-aminoacetophenone, as was known
scavenger of the photoexcited holes to inhibit the from HPLC analysis with a refractive detector (Shimadzu RID-
recombination of the electron-hole pairs on TiO . More 10A). Simultaneously, a series of biomass-derived chemicals,
2
importantly, photocatalytic reforming of glucose with the aid including arabinose, erythrose, formic acid, and hydroxyacetic
of hydroxyl radical from water splitting could release protons, acid were formed from the consecutive photoxidation of
which could be reduced by photoinduced electrons to form glucose by the oxygen in the form of hydroxyl radicals from
the active H-PdNPs species, which will be discussed in detail in water and the holes on TiO caused by UV irradiation. In order
2
the subsequent sections. Therefore, increasing the molar ratio to confirm that the hydrogen in water took part in the reaction,
of glucose to substrate facilitated the elimination of the holes we carried out the control experiment using D O to replace
2
and promoted the formation of H-PdNPs species, which was H2O with a reaction time of 12 hours and other conditions
beneficial to the photocatalytic reduction. Our control were the same as that shown in Fig. 1b. The -NO was reduced
2
experiment showed that the hydrogenation reaction could be to -NH , -NDH, and -ND with the -NH :-NDH:-ND ratio of
2
2
2
2
prohibited by the addition of 2,2’,6,6’-tetramethylpiperidine 0.60:0.32:0.08, indicating that 24% hydrogen was from water
N-oxyl (TEMPO, 100 mg), which could remove hydrogen atom in the reaction. This indicates that the hydrogen for the
24
from the metal surface, indicating the formation of H-PdNPs. reduction was derived from both water splitting and glucose
In addition, when the molar ratio of glucose to substrate was reforming. Our experiment showed that the reaction did not
increased to 100/1, the reaction time for the complete occur without glucose, indicating that to use the hydrogen of
conversion of 4-nitroacetophenone was reduced to 4 hours water for the hydrogenation reaction, the oxygen of water
with a 4-aminoacetophenone selectivity of 98%, which further must be consumed in oxidation of glucose simultaneously,
2
| J. Name., 2012, 00, 1-3
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which will be discussed in the following sections. In addition,
ARTICLE
Photocatalytic reduction of nitrobenzenes VwiewithArtivclaerOionliunes
hydrogenation did not occur in dark or when the wavelength substituted reducible groups was perforDmOeI:d1,0.a10n3d9/tCh5eSCr0e3s1u78ltHs
of incident light was >420 nm. The reason was that the are presented in Table 1. It was found that all the
electron-hole separation resulting from the wide band gap of nitrobenzenes examined could be converted to the
TiO (3.2 eV) could not be induced, which was the first key step corresponding anilines in the water-glucose system. The
2
for the subsequent photoredox reactions. Furthermore, only activity order of para-, meta- and ortho-substituted
very little amount (about 2%) of 4-aminoacetophenone was nitroacetophenone (Entries 1-3, Table 1) was para- > meta-
produced upon simulated sunlight because UV light energy >ortho- caused mainly by the steric hindrance. Meanwhile, 4-
only contributed to little proportion (about 4%) of solar energy. iodo-nitrobenzene (Entry 8, Table 1) and 4-chloro-
These results suggested that UV-light was the driving force of nitrobenzene (Entry 9, Table 1) showed lower selectivity
the reaction when Pd/TiO was used as the catalyst.
because of the dehalogenation reaction occurred in the
reaction process. In addition, nitroethane (Entry 11, Table 1)
could be reduced to ethylamine with a selectivity of 97% with
a prolonged reaction time (48 h), indicating that our reaction
system could also be used to reduce nitroalkanes.
2
Table 1. Photocatalytic selective reduction of various nitro compounds in water-
a
glucose system.
Time
h)
Nitroarenes
Anilines
Glu. cons.
Entry
Substrate
b
c
d
(
Con.(%)
Sel.(%)
(mmol)
H3COC
NO2
1
2
3
4
5
6
7
8
9
12
12
12
11
10
16
18
16
16
20
48
>99
92
99
89
96
98
99
93
96
88
90
96
97
0.11
0.13
0.12
0.13
0.11
0.12
0.12
0.13
0.13
0.12
0.20
Fig. 2. The dependence of amounts of the products from glucose reforming in
water on time at the reaction conditions of Fig. 1b.
NO2
COCH3
NO2
Experiments were also conducted to examine the
reusability of Pd/TiO . In each cycle, Pd/TiO was recovered by
H3COC
98
2
2
o
OHC
NO2
centrifugation and washed by ethanol. After dried at 60 C
under vacuum for 12 hours, the catalyst was reused for the
next run. The conversion of 4-nitroacetophenone and the yield
and selectivity of 4-aminoacetophenone are shown in Fig. 3. It
was found that there was no considerable decrease in the
conversion, selectivity, and yield after four cycles, indicating
>99
>99
98
NC
NO2
H2C=HC
NO2
that Pd/TiO was stable in the reaction. Meanwhile, Pd/TiO2
HC
I
C
NO2
2
>99
97
recovered after reused four times was characterized by TEM,
and the result indicated that the size of the Pd particles was
not changed obviously (Fig. S4).
NO2
Cl
NO2
95
C2H5OOC
NO2
1
1
0
1
98
NO2
95
a
Reaction conditions: substrates, 0.1 mmol; glucose, 0.5 mmol; water, 1 mL;
o
2
temperature, 25 C; 0.025 g Pd/TiO
illuminated area, 2 cm . Con.=Conversion. Sel.=Selectivity. Glu. cons.= Glucose
consumption.
2
with2 wt% Pd; UV-light (350 nm, 4 mW/cm );
2
b
c
d
From Table 1, it was found that the substituted
nitrobenzenes with other reducible groups could be reduced
to the corresponding anilines with good to excellent (88-99%)
selectivity by economic consumption of glucose. The high
selectivity can be attributed mainly to two reasons. The first is
Fig. 3. Reusability of Pd/TiO
in glucose aqueous solution. Reaction conditons: 4-nitroacetophenone, 0.1 mmol;
2
for photocatalytic reduction of 4-nitroacetophenone
o
glucose, 0.5 mmol; water, 1 mL; temperature, 25 C; reaction time, 12 h; 0.025 g that the nitro group prefers to be absorbed on the catalysts in
2
10
2
Pd/TiO with 2wt% Pd; UV-light irradiation (350 nm, 4 mW/cm ); illuminated area,
comparison with other reducible groups,
which was
2
2
cm .
beneficial to selective reduction of the nitro group. A kinetic
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experiment was conducted to prove this. When the mixture of
nitrobenzene (0.1 mmol) and benzyaldehyde (0.1 mmol) was
used as the reactants, it was found that nitrobenzene was
preferentially hydrogenated in the process, while the
reduction of benzyaldehyde was inhibited completely in the
presence of nitrobenzene (Fig. S2). Secondly, the nitro group
has stronger electron-withdrawing ability than other
View Article Online
DOI: 10.1039/C5SC03178H
16
substituted groups, exhibiting better electrophilicity, which is
favorable to the reduction of the nitro group by the active H-
PdNPs species compared with other reducible groups. We
designed and carried out the control experiments to find
evidence to support this argument. In the experiment, the
photocatalytic hydrogenation of nitrobenzene (0.1 mmol),
benzyaldehyde (0.1 mmol) and acetophenone (0.1 mmol) were
performed separately in 2 mol/L glucose aqueous solution
with a reaction time of 6 hours under UV-light (350nm), and
the results are illustrated in Fig. S3. It was found that the nitro
group had a higher reaction rate than the aldehyde and
carbonyl groups. This suggests that the nitro group had a high
intrinsic catalytic activity than other reducible groups.
Fig. 4. Possible pathways of photocatalytic selective reduction of functionalized
nitroarenes to anilines.
Generally, there are two possible pathways for
hydrogenating nitrobenzenes to anilines (Fig. 4). As shown by
HPLC analysis, there were no azoxybenzene and azobenzene
produced during the entire catalytic process. In contrast,
nitrosobenzene and hydroxyamine were formed. These results
indicated that the photocatalytic reduction of nitrobenzenes to
the corresponding anilines was through the pathway A in our
Fig. 5. Proposed mechanism of photocatalytic water splitting and glucose
reforming for selective reduction of nitrobenzenes to anilines catalyzed by
reaction system (Fig. 4). On the basis of the experimental Pd/TiO
2
.
10, 25, 26
results and some related reports,
we propose a possible
mechanism about photocatalytic selective reduction of
nitrobenzenes to anilines in water-glucose system over
Pd/TiO , which is shown in Fig. 5 and Fig. 6. Firstly, electron-
2
hole separation on TiO occured under UV-light irradiation (Fig.
2
5
).Then, water splitting accompanied with photocatalytic
reforming of glucose was induced by the photogenerated
holes to release protons and hydroxyl radicals (Fig. 5). The
hydroxyl radical involved photocatalytic reforming of glucose.
A series of biomass-derived chemicals were formed through
C1-C2 cleavage from the continuous photoxidation of glucose
by the hydroxyl radicals from water splitting and the holes on
TiO2 caused by UV irradiation (Fig. 6). Subsequently, the
+
photoinduced electrons could readily reduce H from water
splitting and glucose reforming on PdNPs to form the active H-
PdNPs species (Fig. 5). Finally, the nitro group of nitrobenzenes
is preferably absorbed on the catalyst, and predominantly Fig. 6. Proposed routes of photocatalytic water splitting and glucose reforming
2
over Pd/TiO .
reduced to the functionalized anilines by the H-PdNPs species
through the Pathway A shown in Fig. 4.
Inspired by the results obtained from the selective
photocatalytic reduction of nitrobenzenes, we explored
hydrogenation of other kinds of unsaturated organic
compounds using the same method, and the results were
illustrated in Table 2. It was found that the hydrogen from
water splitting and glucose reforming could be used for
efficiently
hydrogenating
benzyaldehdye
and
hydroazobenzene to the corresponding saturated products
with high yields. The products from glucose were also mainly
arabinose, erythrose, formic acid, and hydroxyacetic acid.
4
| J. Name., 2012, 00, 1-3
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ARTICLE
Control reactions conducted in D O showed that the contents analyzed by HPLC with Shimadzu LC-15C pump, Shimadzu UV-
2
View Article Online
o
Vis SPD-15C detector, and a Hypersil ODDOS2I: 1
c
0
o
.1
l
0
u
3
m
9/
n
C5
a
S
t
C0
3
3
5
178
C.
H
of deuterohydrogen in the products were 39% and 30%,
Methanol/water solution (60/40 V/V) was used as the mobile
phase at a flow rate of 1.0 mL/min. The chemicals in the
reaction mixture were identified by GC-MS (QP-2010) as well
as by comparing retention times to the respective standards in
HPLC traces.
respectively. This result further proved that the hydrogen for
the reductions originated from both water and glucose.
Table 2.Photocatalytic water splitting and glucose reforming for various
a
hydrogenations.
Con.
Yield
(%)
89
Hydrogen
from water
39%
Reusability of Pd/TiO2
Entry
1
Reactant
CHO
Product
t (h)
24
b
(
%)
96
In the experiments to test the reusability of Pd/TiO , the
catalyst was recovered by centrifugation, and washed with
ethanol. After drying under vacuum at 60 C for 12 h, the
catalyst was reused for the next run.
2
CH2OH
o
NH NH
2
NH2
10
100
90
30%
a
Reaction conditions: substrates, 0.1 mmol; glucose, 0.5 mmol; water, 1 mL;
o
temperature, 25 C; 0.025 g Pd/TiO
2
with 2 wt% Pd; UV-light (350 nm, 4
conversion.
Acknowledgements
We wish to thank the financial supports from the National
Natural Science Foundation of China (21173234, U1232203,
2
2 b
mW/cm ); illuminated area, 2 cm . Con.
=
2
1321063), Chinese Academy of Sciences (KJCX2.YW.H16,
KJCX2.YW.H30).
Conclusions
In summary, direct utilization of the hydrogen and oxygen of
water for organic reactions was realized by photocatalysis. It
was discovered that nitrobenzenes with different reducible
groups could be efficiently reduced to the corresponding
anilines with high selectivity by the hydrogen from water
splitting and glucose reforming in the presence of Pd/TiO2
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