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A Photoactive Catalyst Ru-g-C3N4 for Hydrogen Transfer reaction

of Aldehydes and Ketones†

Green Chemistry Accepted Manuscript

Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Priti Sharma* and Yoel Sasson
A novel heterogeneous photoactive catalyst is developed by incorporating ruthenium over a new photoactive graphite
carbon nitride (g-C3N4) support for efficient photo catalytic transfer hydrogenation of various carbonyl functional group
compunds with different alcohols. Synthesized photoactive catalyst Ru-g-C3N4 exhibits good to excellent reactivity with
high turn over number (TON) in mild reaction conditions under visible light. The physiochemical properties of the photo
catalyst were analyzed by XRD, BET analysis, TGA, FT-IR, XPS, UV-visible, ICP-OES, TEM and SEM characterization
techniquies. The main significant features of the photoactive catalyst Ru-g-C3N4 are viz; easy to handle in visible light (LED
lamp), no use of external base, solvent free, non toxic, environmentaly friendly and proceeds under very mild reaction
conditions. Further, the solid photo catalyst Ru-g-C3N4 can be recycled efficiently and reused many times, without a major
loss in reactivity.

viz; efficiency of operation under visible light, semiconductor

Introduction properties (band gap of ~2.7 eV) high stability, nontoxic, metal
free organocatalyst, environmentally benign photo catalysts
The reduction of the carbonyl functional (>C=O) group in the
and simple fabrication from cheap raw material without any
presence of alcohol as hydrogen donor is commercially 19-21
additive. Immobilization or doping of
important protocol in organic synthesis. Since, carbonyl
functional (>C=O) group conversion is frequently used as
building block in preparation of various drugs, agrochemicals,
paints and polymers.1-5 To enhance application in fine chemical
industries and organic laboratories the synthesis of these
compounds should be economically and technically feasible
and should have a broad scope for synthesis. Various different
catalysts have been reported for the hydrogen transfer
reaction, including molecular hydrogen, homogenous catalyst,
or supported catalysts on various carriers.6-9 The most
common catalysts in these reactions are based on
ruthenium.10-12 Typically these catalysts are not recyclable in
the several cases due to requirement of harsh reaction
conditions.13, 14 The development of low cost, non-toxic metal Scheme 1: Synthesis of Ru-g-C3N4.
based catalysts is nowadays the prime need in industrial and
academic research. different metals viz; Pd, Ag, Pt etc. on carbon nitride (g-C3N4)
22, 23
Furthermore, semiconductor photocatalysis has recently enhances its photocatalytic activity. Furthermore, the
emerged as a promising technology for the generation of clean regular arrangement of nitrogen atoms in the graphene like
energy and application of solar energy in catalysis, which is structure creates separated electrons and holes after visible
most economical and environmentally friendly.15-18 In the light absorption resulting in enhancement of its electronic and
same context, recently metal free semiconductors polymeric catalytic properties. Chemically, g-C3N4 itself is inert material
carbon nitride has withdrawn the attention of researchers under common acidic or basic conditions. In particular, the use
because of it’s unique, interesting physicochemical properties of g-C3N4 in photocatalysis has been extensively studied for
19, 24-28
various organic transformations. Since, the basic
conventional method of catalytic hydrogen transfer of
† Casali Center of Applied Chemistry, Institute of Chemistry, The Hebrew University carbonyl functional group (>C=O) proceeds in general under
of Jerusalem, Jerusalem 91904, Israel, E-mail: priti.sharma@mail.huji.ac.il 29-31
Electronic Supplementary Information (ESI) available: [Reaction setup, Physical
harsh reaction conditions viz; high temperature, usage of
appearance of g-C3N4, Ru-g-C3N4, XPS Quantification report, SEM-EDX images, TEM high base content, prolong reaction time. Therefore keeping in
Images, TEM–EDX, BET analysis, Pore size distribution, XRD pattern with different note mentioned key issues, in present research we considered
loading, SAED pattern]. See DOI: 10.1039/x0xx00000x

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43, 44
ruthenium metal loading over chemically, thermally stable the conjugated aromatic system (Fig. 1.b,c). The diffraction
carbon nitride g-C3N4 as a promising support for enhanced of (002) plane of Ru-g-C3N4 shows less intensity compared to
photo catalytic activity and can be established as the ideal the g-C3N4 material, probably due to partial loading of
catalyst for both environmental and economic perspectives. ruthenium (Fig. 1.b,c).
In a remarkable approach, J.E. Bäckvall and his co-workers Synthesis of g-C3N4 from urea and ruthenium loaded Ru-g-
reported notably activity of base and different homogeneous C3N4 is well characterized by FTIR spectroscopy and visualized
ruthenium catalysed in the hydrogen transfer reaction of in figure 2 (a) Urea, (b) g-C3N4, (c) Ru-g-C3N4. The absorption
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different ketones at higher temperature (82°C) in various
reports and strongly states that no hydrogenation occurs in
32-36
the absence of base. Furthermore, few groups
demonstrated potential of iron and other metal complexes in
-1
bands at 3429, 3346, 1453, 1580 cm are characteristics
absorption bands of urea and disappeared after
transformation into g-C3N4 by heating urea at 550°C for 3 h
(Fig. 2.a,b,c). The well-resolved and strong IR absorption bands

Green Chemistry Accepted Manuscript

37-39
homogeneous system for hydrogen transfer reactions.
However, these catalytic systems face the drawback viz; high
temperature, high usage of base content and no catalyst
recovery was possible. In the same context, we decided to
establish the protocol, under visible light, room temperature,
and base free by using Ru-g-C3N4 heterogeneous photo
catalyst for hydrogen transfer along with in order to recycle
the catalyst. the Herein, we report an efficient and reusable
ruthenium supported on graphite carbon nitride Ru-g-C3N4
heterogeneous photo catalyst for hydrogen transfer of
carbonyl functional group with alcohols as hydrogen donors by
in figure 2 revealed a typical existence molecular structure of
g-C3N4. In the typical FTIR spectrum of g-C3N4, the broad bands
around 3100 cm-1 are indicative of N-H stretching vibrations,
the peaks at 1248 cm-1 and 1624 cm-1 correspond to the C–N
and C=N stretching vibrations, respectively (Fig. 2.b,c).27
*
*
* *
* *

Intensity (a.u.)
* *
* * a
using simple procedure under visible light (9 W LED domestic
(002)
ceiling lamp) at room temperature and interestingly without 27.2
use of any base additive, which is considered essential for the (100)
13.2
hydrogen transfer reaction to initiate.36, 40, 41 The incorporation
of ruthenium chloride over graphitic carbon nitride (g-C3N4) b
provides both the benefits i.e. enhanced photo catalytic
activity owing to the synergistic effect of both components and c
facile recovery and in addition recycling of the heterogeneous
catalyst (Scheme 1). To the best of our knowledge, this is the
10 20 30 40 50 60 70
first report on ruthenium incorporated photo catalyst Ru-g-
C3N4 for hydrogen transfer of carbonyl functional group (>C=O) 2 Theta (°)
with alcohol as hydrogen donor under visible light condition. Figure 1. XRD pattern: (a) Urea, (b) g-C3N4, (c) Ru-g-C3N4.

a
Results and discussion 3429
3346
Graphitic semiconductor support g-C3N4 is fabricated via the
42
known reported procedure by Wei Chen. Further,
Tranmittance (%)

heterogeneous photoactive catalyst Ru-g-C3N4 was synthesized b 3263 717

by stirring ruthenium chloride (RuCl3) with g-C3N4 in ethanol in 1149
round bottom flask at 50°C till dry in 6 h (Scheme 1). The c 1453
1580
obtained material Ru-g-C3N4 is well characterized by various
physiochemical characterization techniques. 1409

The typical X-ray diffraction (XRD) pattern (a) Urea, (b) g-

C3N4 and (c) Ru-g-C3N4 materials are visualized in figure. 1.
Transformation of urea into g-C3N4 after calcination at 550°C 1624
for 3 h distinguished clearly with emergence of intense peak at 1553 810
1248
27.20 and with disappearance of urea characteristics
4000 3500 3000 2500 2000 1500 1000 500
background peaks (Fig. 1.a,b). For the pure g-C3N4, the two
distinct diffraction peaks at 13.20 and 27.20 are in good Wavenumber (cm-1)
43
agreement with reported procedure that corresponding to Figure 2. FTIR spectra: (a) Urea, (b) g-C3N4, (c) Ru-g-C3N4.
(100) and (002) diffraction plane of the graphitic g-C3N4
materials, respectively (Fig. 1b). In the pure g-C3N4 and Ru-g- It should be noted that the broad bands at around 3100
-1
C3N4 samples, the (002) reflection is more intense than the cm are indicative of N-H stretching vibration modes.
other reflection (Fig. 1.b,c). The intense XRD peak at 27.2° Additionally, the characteristic breathing mode of the triazine
-1
corresponds to the (002) plane and is attributed to stacking of units at 810 cm , related to the s-triazine ring absorption band

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45
vibrations well observed in fabricated g-C3N4 (Fig. 2.b,c). The and 405.6 eV (Fig. 4E). The intense increase in peak at 405.6,
-1
intense bands at 1624, 1553, 1409 and 1248 cm were which belongs to the terminal amino groups (-NH2) might be
assigned to typical stretching vibration modes of triazine due to the transformation of bulk g-C3N4 transformed into
derived repeating units (Fig. 2.b,c). The similar mode vibration simpler flakes or simpler unit which develops more terminal
was also present in Ru-g-C3N4, clearly indicate all mode of amino groups (-NH2) during metal incorporation process in
47
vibration preservation after ruthenium incorporation and ethanol solution (Fig. 4E).
without disturbing the typical molecular structure of g-C3N4 XPS spectrum of Ru-3d exhibit peaks centered at 278.7 and
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(Fig. 2c). 282.8 eV corresponds to metallic Ru phase which is highly

The optical properties of synthesized material, g-C3N4 and overlapped by the C1s peaks (Fig. 4F). The Ru 3p XPS spectrum
Ru-g-C3N4 were analyzed by UV-Vis spectroscopy. Absorption of Ru-N-C shows a major peak centered at 464.5 eV. As shown
in the visible light range (from 400 to 700 nm), which is an in figure 4G, the main peak (doublet) of the spectrum can be

Green Chemistry Accepted Manuscript

important condition for the photocatalytic activity of g-C3N4 deconvoluted into two doublets of ruthenium 3p3/2 and Ru
under visible light (Fig. 3A). Both the synthesized materials g- 3p1/2, which leads to two binding energies (Bes) at 464.5 and
C3N4 and Ru-g-C3N4 show maximum absorption below 550 nm 485.3 eV, corresponds to ruthenium oxide species.48
(visible range), which corresponds transition from the valence
band (VB) to the conduction band (CB) (Fig. 3. A,B). As per Tauc 60000 N1s A B CPS
(N-C=N)
plots, the band gap for g-C3N4 and Ru-g-C3N4 is found at ~2.84 50000

Intensity (a.u)
(N-(C)3

Intensity (a.u)
eV, ~3.00 eV respectively, in good agreement with reported 40000 (NH2)
literature.19, 46 The absorption edge of the g-C3N4 to Ru-g-C3N4 30000 C1s
underwent blue shift, indicating an increased band gap from 20000 O1s
~2.84 eV to ~3.0 eV (Fig. 3. A,B). 10000

1000 800 600 400 200 410 405 400 395

4 A g-C3N4 1200 B Binding energy (eV.)
Binding energy (eV.)
Ru-g-C3N4
Absorbance (a.u.)

1000 288 eV 35000 N1s

Ru 3p1/2
4000 C D

Ru 3p3/2
3 800 30000
(αhν)2

C1s

Intensity (a.u)
Intensity (a.u)

a 25000 O1s
3000
600 b 20000
2 2000 15000
400

Cl 2s
b
284.8 eV 10000
C3N4 1000 Cl 2p
200 5000
a Ru-C3N4
1 0
0 0
400 500 600 700 800 1.5 2.0 2.5 3.0 3.5 4.0 -5000
300 295 290 285 280 1200 1000 800 600 400 200 0
wavelength (nm) Energy (eV) Binding energy (eV.) Binding energy (eV.)
Figure 3.(A)Tauc plots, (B)UV-Vis spectra:(a)g-C3N4, (b)Ru-g- CPS CPS
E Ru 3d 5/2 (Ru) F
C3N4. N-C=N
N-(C)3 Ru 3d 3/2 (Ru)
Intensity (a.u)

Intensity (a.u)
Ru 3d 5/2 (RuO2)
XPS spectroscopy technique was employed to determine the NH2 Ru 3d 3/2 (RuO2)
electronic state of the elements present (Fig. S3) in the C 1s (CH)
C 1s (C-O)
synthesized materials. In order to analyze the surface chemical C 1s (C=O)
C 1s (COOH)
properties and to confirm formation of g-C3N4 and
incorporation of ruthenium over g-C3N4 support, XPS analyses
of g-C3N4 and Ru-g-C3N4 material was carried out. Accordingly, 410 408 406 404 402 400 398 396 300 295 290 285 280 275
C1s spectrum shows two characteristic peak components due Binding energy (eV.) Binding energy (eV.)
to the C–C and N=C–N at 284.8 and 288 eV; respectively in G 3p3/2 Ru 3p
both the prepared g-C3N4 and Ru-C3N4 material (Fig. 4. C,F).24 3p1/2 464.5
Intensity (a.u)

In case of Ru-g-C3N4 material C (carbon) characteristic peaks 485.3

are highly overlapped by Ru 3d (ruthenium) peaks (Fig. 4F).

High resolution N1s spectrum of g-C3N4 the N1s spectra can be
deconvoluted into three peaks centered at 399.9, 401.3 and
405.6 eV, respectively. The peak at 399.9 eV is assigned to the
presence of pyridine-N species [sp2-hybridized nitrogen 520 500 480 460 440 420
Binding energy (eV.)
(C=N−C)], through which, each nitrogen (N) atom is bonded to
two carbon atoms from aromatic ring located at edges of the
graphite planes (g-C3N4). The peak at 401.3 eV corresponds to Figure 4. XPS spectra: (A) Full scan g-C3N4, (B) high resolution
N (nitrogen) atoms trigonally bonded with sp2-C or sp3-C XPS spectra in the N 1s region g-C3N4, (C) in the N 1s region of
carbon atoms of amino functional groups (C−N−H) (Fig. 4B). g-C3N4, (D) Ru-g-C3N4 full scan, (E) High resolution XPS spectra
Whereas, the peak at 405.6 eV describes the terminal amino in the N 1s region of Ru-g-C3N4, (F) Ru 3d and C 1s overlapped
groups (-NH2). Similarly the N1s spectrum of Ru-g-C3N4 region of Ru-g-C3N4, (G) Ru 2p region of Ru-g-C3N4.
material can be deconvoluted into three peaks 399.9, 401.3

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The stability of the synthesized materials, g-C3N4 and Ru-g-

C3N4 was measured by thermo gravimetric analysis (TGA)
under air atmosphere from 30°C to 750°C temperature range.
As visualized from figure 5; the g-C3N4 material shows stability
up to 500°C under air atmosphere. This materials show its
initial decomposition temperature at 500°C and complete
decomposition was observed at ~650°C. In the case of Ru-g-
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C3N4 composite material, the decomposition temperature

starts earlier, ~420°C, than that of pure g-C3N4. This is due the
presence of ruthenium metal in the g-C3N4, which might
catalyze the oxidation of support (g-C3N4) under air

Green Chemistry Accepted Manuscript

atmosphere. The decomposition of Ru-g-C3N4 materials end at
~475°C with residual weight fraction of ~8%, which may be
due to the formation of oxide of ruthenium metal. This
residual weight loss of Ru-g-C3N4 material is in good
agreement with the XPS and ICP analysis result for ruthenium
loading over g-C3N4 (Fig. S3).
The morphologies of g-C3N4 and Ru-g-C3N4 material are
visualized by SEM analysis. The monomer unit of g-C3N4
appeared to aggregate along with sheet structure, each
particle agglomerates of many small pieces in g-C3N4, whereas
Ru-g-C3N4 shows smaller unit of agglomeration and dense
morphology upon further solvent reaction process (Fig. 6).
Moreover, the EDX pattern of g-C3N4 and Ru-g-C3N4 indicates
the presence of ruthenium in the synthesized photoactive
catalyst Ru-g-C3N4 (Fig. S4).
110
g R
-
C u
N g
3-
4C
Figure 6. SEM Images: (A) g-C3N4, (B) Ru-g-C3N4.
The morphologies of representative material (g-C3N4 and Ru-g-
C3N4) are determined by TEM analysis technique. TEM images
of g-C3N4 material at 0.5 µm, 100 nm and 20 nm (Fig. 7A, B and
C) scale show crumbled sheets, multilayer with a graphitic
alike structure. Further in case of photo catalyst Ru-g-C3N4
TEM images at 0.5 µm and 50 nm show nearly similar pattern
of crumbled sheet like structure with darker spotted area,
corresponding to the ruthenium loading over g-C3N4 support
(Fig. 8A,B) but do not show much morphological deference
(Fig. 8A,B). EDX obtained from TEM analysis and ICP-AES
analysis confirms the presence of elemental ruthenium in the
heterogeneous photo catalyst Ru-g-C3N4 [Fig. S6.I,II].
Furthermore, the SAED pattern shows a broad ring with lower
intensity, might be due to the amorphous nature of the
synthesized g-C3N4 and Ru-g-C3N4 materials (Fig. S5.C). After

100 thorough TEM analysis it could be concluded that, there is not

-
N
3
4

90 much change in morphology of g-C3N4 and Ru-g-C3N4 (Fig. S5,

80 S6).
Weight Loss %

70
60
50
40
30
20
B A
10
0
-10
0 100 200 300 400 500 600 700 800 Figure 7. TEM Images of g-C3N4 at different magnification: (A)
Temperature (%) at 0.5µm g-C3N4, (B) at 100 nm g-C3N4, (C) at 20 nm g-C3N4.
Figure 5. TGA graph: (A) g-C3N4, (B) Ru-g-C3N4.

The surface textural properties of the synthesized samples are

determined by with the help of the BET multilayer adsorption
and desorption analysis. The BET surface area (SBET), total
pore volume (Vp) and mean Pore size (Radius) Dv(r) of g-C3N4
are found to be 15.203 m2g−1, 0.013 cc/g, and 15.366 nm,
respectively, however for Ru-g-C3N4 material these values are
found to be 32.121 m2g−1, 0.029 cc/g and 15.356 nm,
respectively. An increase in the surface area of the photo
catalyst Ru-g-C3N4 from 15.203 to 32.121 m2g−1 after
incorporation of ruthenium chloride is mainly due to the
transformation into monolith sheets from bulk g-C3N4 (Fig. S7). Figure 8. TEM Images of Ru-g-C3N4 at different magnification:
(A) at 0.5µm Ru-g-C3N4, (B) at 50 nm Ru-g-C3N4.

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Photo catalytic hydrogen transfer reaction using
heterogeneous catalyst Ru-g-C3N4: Typically, the hydrogen
transfer reaction need high temperature, high base content,
30, 40
and prolong reaction time period. Here we tried to
develop simple, easy protocol under ambient photo catalytic
reaction conditions viz; without base usage, room temperature
and under optimal reaction time period for photo catalytic
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hydrogen transfer reaction of the carbonyl functional group
(>C=O) in the presence of alcohols as hydrogen donor.
The synthesized heterogeneous photo catalytic Ru-g-C3 N4
catalyst was investigated for photo catalytic hydrogen transfer
reaction using 4-nitrobenzaldehyde and isopropanol as a
standard substrates under optimized reaction conditions viz;
heterogeneous catalyst Ru-g-C3N4 (30 mg), isopropanol (5 mL),
4-nitrobenzaldehyde (1 mmol) at room temperature under
visible light [(9W domestic LED ceiling lamp) visible light
source] with magnetic stirring speed of ~500 rpm (Scheme 2).
To monitor the progress of reaction, samples were withdrawn
periodically from the reaction mixture and analyzed by GC.
Photo catalytic hydrogen transfer reaction was performed on
three different ruthenium loaded (by weight % ratio) catalysts
6%, 8% and 10% over g-C3N4 support. The conversions of 4-
nitrobenzaldehyde with respect to ruthenium loading were
found to be 55%, 80% and 80% respectively after 8 h of
reaction time period. The reaction proceeds at the active
ruthenium metal centre. Since reaction progress with 8% and
10% loaded ruthenium is compatible, further reaction were
investigated using 8% ruthenium loaded catalyst Ru-g-C3N4 for
minimal to maximum use of ruthenium metal in
heterogeneous Ru-g-C3N4 photo catalyst (Fig. S8).
Scheme 2: Hydrogen transfer reaction model reaction using 4-
nitrobenzaldehyde and isopropanol.
Herein, we performed hydrogen transfer reaction under visible
light (9W domestic LED lamp) at room temperature with 8 cm
height distance from the visible light source LED lamp to
reaction mixture in conical flask to avoid heating impact (Fig.
S1, S2).
To demonstrate the catalytic activity of synthesized photo
catalyst Ru-g-C3N4 blank reaction was carried out in the
absence of the Ru-g-C3N4 photo catalyst. There is no product
formation was observed even after 24 h visible light irradiation
using 4-nitrobenzaldehyde and isopropanol as a standard
substrate under optimized reaction conditions (see SI, Table
S1, entry 9). Similarly to prove significance of visible light in the
hydrogen transfer reaction a controlled reaction was
performed under dark using similar optimized reaction
conditions in presence of Ru-g-C3N4 catalyst and 4-
nitrobenzaldehyde and isopropanol as substrate. The result of
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controlled experiment shows quite poor result with <10%
corresponding product formation even after 24 reaction time
period (see SI, Table S1, entry 7). Interestingly under visible
light heterogeneous photo catalyst Ru-g-C3N4 delivered
excellent reactivity to give corresponding product under
optimized reaction condition (using substrate 4-
nitrobenzaldehyde and isopropanol) (see SI, Table S1, entry 8).
Whereas at the same time, independently pure g-C3N4 and
ruthenium chloride (RuCl3) do not show any satisfactory result
in terms of corresponding products yield in dark/visible light
irradiation under optimized reaction conditions (see SI, Table
Green Chemistry Accepted Manuscript
S1, entries 1,2,5 and 6 ).
For the base usage in the model reaction, was performed
reaction with pure RuCl3, under dark/light condition with/
without base (KOH) at room temperature (see SI, Table S1,
entries 3, 4). It is evident from the obtained results (table S1);
the reaction is not proceeding well without the photoactive
material g-C3N4 at room temperature even in presence of
foreign base (KOH) (see SI, Table S1, entries 3, 4, 8). From all
these experiments it is clear that a combination of support, g-
C3N4, dispersed ruthenium chloride (RuCl3) and visible light is
necessary to conduct these experiments (see SI, Table S1).
In order to explore photo catalytic activity of synthesized Ru-g-
C3N4 for hydrogen transfer reaction, various substrates were
evaluated under visible light optimized reaction conditions.
Results with various substrates of alcohol and substituted
aldehyde group are summarized in table 1. Different alcohols
were tested as hydrogen donors for the reduction of
benzaldehyde (mono or disubstituted) to the corresponding
alcohol (Table 1). Monosubstituted aldehyde and ketone, such
as cyclohexanone, acetophenone, benzaldehyde with
isopropanol gave 19%, 29%, 21% yields of corresponding
alcohols respectively (Table 1 entries 1, 2, 3) under
photochemical irradiation. Whereas, in case of substituted
aldehyde viz; 4-nitrobenzaldehyde, 4-chlorobenzaldehyde
affords faster rate of reaction completion with isopropanol to
give 73%, 80% yields selectively and efficiently to their
corresponding alcohols respectively with good TON. From the
table 1 it is evident that the presence of electron withdrawing
groups (-Cl, -NO2) at the benzene ring increased the rate of
reaction (Table 3 entries 3,5,). Electron withdrawing groups (-
Cl, -NO2) attached to aldehyde group shows enhanced rate of
reaction with all type of hydrogen donor alcohols (primary,
secondary, tertiary) selectively and efficiently to their
corresponding alcohols (Table 3 entries 5-10). Whereas in case
of mono-substituted aldehyde shows relatively faster rate of
reaction with isopropanol as a hydrogen donor alcohol (Table
3 entries 3). But rate of reduction was lower when primary
alcohols like 1-propanol were used (Table 3 entry 4) as
hydrogen transfer agent under visible light. From the obtained
result (Table 1) it is clearly evident that the synthesized photo
catalyst Ru-g-C3N4 efficiently affords moderate to good yield of
corresponding products for hydrogen transfer reaction.
Green Chemistry, 2016, 00, 1-3 | 5

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Scheme 3: Probable Mechanism of Photo catalytic hydrogen
transfers reaction.
Mechanism of Photo catalytic hydrogen transfers reaction:
Based on previous reported mechanism,49, 50 the most
probable path of reaction mechanism might be followed by
reaction like as shown in scheme 3. Carbon nitride (g-C3N4),
having π-conjugated system due to the presence of nitrogen
atoms, which works as a semiconductor. Apart from this,
doping of ruthenium may be a hetero-junction between the g-
C3N4 π-electron. After absorption of visible light >420 nm
mediated electron transfer (previous literature, the band gap
~2.70 to ~2.8 eV)19, 20, 24 the transfer of electron in the hetero
junction from the semiconductor Ru-g-C3N4, and g-C3N4
enriches the electron density over ruthenium active centre.
In further step, holes and electron (due to hetero-junction
between the g-C3N4 π-electron), are capable of oxidizing the
easily absorbed alcohol (due to -NH- and -NH2 active site of g-
C3N4) on the surface of carbon nitride and able to reduce
absorbed aldehyde simultaneously. The activation of alcohol
hydrogen and hydrogenation of aldehyde may occur in a
conjugative process with acetone (or similar product) as
byproduct formed during the reaction, which remains into the
reaction mixture.
100
80
Yield (%)
60
40
20
0 Fresh cycle I Recycle II Recycle III Recycle
Number of Recycle
Figure 9. Recycling study of heterogeneous photo catalyst Ru-
g-C3N4 catalyst
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Long-term stability and reusability is quite important
characteristic feature in terms of heterogeneous catalyst.
Heterogeneous catalysts are well preferred over homogeneous
catalysts due to ease of reusability, good compatibility with
flow reactors, facilitating the efficient production of chemicals
in continuous processes. Recycling test was performed under
optimized reaction condition [room temperature, visible light
(LED lamp visible light source), 500 rpm] for hydrogen transfer
reaction using 4-nitrobenzaldehyde (1 mmol) and isopropanol
(5mL) as a model substrates. After the reaction, the
Green Chemistry Accepted Manuscript
heterogeneous photo catalyst Ru-g-C3N4 was recovered by
simple filtration, washed with methanol, dried (overnight in
oven at 80°C) and reused in further experiments for six runs.
No significant loss was observed in the activity of the recycled
photo catalyst Ru-g-C3N4 and the product yield remained
almost unchanged even after six recycling experiments, which
confirmed that the catalyst is stable and the true
heterogeneous nature of synthesized heterogeneous photo
catalyst Ru-g-C3N4 remains active (Fig. 9).
Conclusions
In concluding remarks, an efficient, sustainable and simple
protocol has been developed for the hydrogen transfer
reaction of carbonyl functional group (>C=O) using a
heterogeneous photoactive catalyst Ru-g-C3N4, the reaction
occurs efficiently at room temperature in presence of visible
light using different alcohols as a hydrogen source. The
considerable catalytic performance was observed without use
of foreign base enrollment, high temperature or solvent. The
photoactive catalyst Ru-g-C3N4 is able to produce moderate to
good yield of corresponding products, makes the newly
developed protocol as clearly novel green process for
hydrogen transfer reaction using various alcohol as hydrogen
source. The salient added feature of the Ru-g-C3N4 catalyst is
remains active under photochemical conditions even over
several reaction cycles.
Experimental
The material used in the experiments such as Urea, Alcohols,
Ruthenium chloride, Deionized water, Aldehydes, Ketones
chemicals were purchased from commercial firms (Sigma
Aldrich and reliable resources) and used without further
purification. LED lamp (9W domestic ceiling downlight Epistar
LED ceiling lamp) used as a visible light source. GC analyses
were performed using Focus GC from Thermo Electron
Corporation, equipped with low polarity ZB-5 column. GC
analyses were performed using Trace 1300 Gas
Chromatograph model from Thermo Scientific, equipped with
IV Recycle V Recycle VI Recycle the Rxi-1ms (crossbond 100% dimethyl polysiloxane) column.
Conversion based on GC area. The ruthenium (Ru) content of
product was determined by an Inductively Coupled Plasma
Mass Spectrometry (ICPMS) spectrometer (Agilent 7500 cx).
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Graphitic Carbon nitride (g-C3N4) and Ru-g-C3N4 Synthesis: Acknowledgements

Graphitic carbon nitride (g-C3 N4) was synthesized by a known
42 Author acknowledges the financial support from the Israel
method as reported by J. by Wei Chen. In a typical
Science Foundation (Grant No. 1727/212)
experiment, 5 g of urea (99%) was placed in a ceramic crucible,
and then loaded into the central region of furnace. The
furnace was heated to 550°C in air and maintained at 550°C for
Notes and references
3 h (10°C/min rate), and then allowed to cool to room
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temperature naturally. In the end of process pale yellow

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Green Chemistry Accepted Manuscript

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Table 1: Reactivity of photoactive catalyst Ru-g-C3N4 for catalytic

hydrogen transfer reaction.
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S.No. Carbonyl Alcohol Product Time Yield TON

group (h) (%)
Reaction conditions: Ru-g-C3 N4 (30 mg),

Green Chemistry Accepted Manuscript

1. 20 19 833 Alcohol (5 mL), Carbonyl functional group
(>C=O) (1 mmol), Isolated yields, visible light
irradiation >420 nm (9 W LED domestic
ceiling lamp), room temperature, Conversion
and product yield based on GC area.
2. 20 29 1271

3. 20 21 921

4. 20 15 651

5. 6 73 3201

6. 6 80 3508

7. 6 70 3070

8. 6 91 3991

CHO

9. 6 85 3728

Cl

10. 6 80 3508

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Graphical Abstract:
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